ester carboxy ketals, methods of manufacture and use thereof.

专利摘要:
i! ster carboxy ketals, methods of manufacture and use thereof this disclosure addresses the compound of formula (1) where: r1 is a c7_18 alkyl, r2 is a hydrogen or a c1_3 alkyl, each r3, r4, r5 , r6 and r7 is, independently, a hydrogen or a c1-e alkyl, a is 2-3 and b is 0-1, its preparation method and its uses in hydronic coating compositions, cleaning compositions, fragrances and hygiene compositions folks.
公开号:BR112015012471B1
申请号:R112015012471
申请日:2013-11-27
公开日:2020-05-19
发明作者:J Yontz Dorie；Richard Rieth Lee
申请人:Segetis Inc；
IPC主号:

专利说明:

ESTER CARBÓXI KETALS, MANUFACTURING METHODS AND USE OF THE SAME
CROSS REFERENCE TO RELATED ORDER
This application claims the benefit under 35 USC 119 (e) of provisional patent application serial number US 61/731, 194, filed on November 29, 2012, the contents of which are incorporated herein by reference in their entirety .
FUNDAMENTALS
[0001] This disclosure relates to acetal carboxy ester compounds and a variety of compositions, including waterborne fragrance coating compositions and personal care compositions comprising acetal carboxy ester compounds, methods for making compounds and compositions and uses of the compositions.
[0002] The selection of the solvent for the foregoing and other uses is guided by considerations such as solubility, reactivity, volatility, toxicity, environmental profile, stability and cost. Although numerous solvents are available and in commercial use, there is still a need in the art for new solvents that offer a favorable combination of these characteristics. There is still a specific need for solvents of renewable origin that offer an advantageous combination of one or more attributes such as solubility with one or more components, reactivity, volatility, toxicity, environmental profile and cost for waterborne coating compositions, cleaning compositions , fragrance or personal care compositions are in continuous demand.
RESUME
[0003] A compound of formula (1) is presented in this document.
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(D where
R ¹ is C ₇ alkyl. ₁₈
R ² is hydrogen or alkyl .3, each R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ is, independently, a hydrogen or C 1-6 alkyl, a is 2-3 and b is O-1.
[0004] Also presented in this document is a method for creating the aforementioned compound of the formula (1), the method comprising coming into contact with a keto acid ester of the formula (2).
R .
OR ⁸ • I (2) with a diol of formula (3)
R ³
R ³
Effective HO
OH
R ⁵
R ⁷ (3) under reaction conditions formula (4).
to form a compound of
OR®
R ²
Ό
R ³
R ⁴ b R ⁹
OR ⁷ R® (4) where R ⁸ is a C 4 alkyl group; and transesterification of the formula of the group R ⁸ (4) with an alcohol of the formula R ¹ -OH to form the compound of the formula (1).
[0005] Compositions comprising the compound of formula (1) are also described, in particular coating compositions
3/135 carried by water comprising water; a polymer binder; and a compound of the formula (1).
[0006] In another embodiment, a latex coating composition comprises water; a latex polymer binder; and the compound of formula (1).
[0007] In another embodiment, a water-reducible coating composition comprises water; a latex polymer binder; and the compound of formula (1).
[0010] In yet another aspect, a method of coating a substrate comprises contacting the aforementioned coating composition with a surface of a substrate to form a coating; and drying the coating.
[0011] In another aspect, a coated substrate is made by the aforementioned method of coating a substrate.
[0012] In yet another aspect, a cleaning composition comprises a cleaning or personal care component; and the compound of formula (1).
[0013] In yet another aspect, an aromatic composition comprising: at least one aromatic component; and the compound of formula (1).
[0014] In yet another aspect, a cleaning composition comprises a cleaning component; and the compound of formula (1).
[0015] The aforementioned modalities and other modalities are further described in the detailed description that follows.
DETAILED DESCRIPTION
[0016] The inventors of the present have discovered long chain acetal adducts of ketocarbon esters, especially levulinate esters. Such carboxy-ester acetal adducts offer a combination of properties that make them useful as solvents for a variety of uses. There is still a need in the art for solvents from
4/135 renewables that offer an advantageous combination of one or more attributes such as solubility with one or more components, reactivity, volatility, toxicity, environmental profile and cost. It will also be an advantage if such solvents could be easily modified to adjust the chemical and physical properties of the solvent to meet the needs of a specific application. It would be advantageous if the solvents from a renewable source provide a waterborne coating composition, for example, a paint, dye, adhesive, sealant, clear-coat coating or caulking composition, cleaning compositions, an aromatic composition or personal care compositions that meet one or more customer needs as applicable to the specific composition.
[0017] Ketocarboxy ester acetals, sometimes mentioned in this document as adducts of acetals, are compounds that have the general formula (1):
.OR 'where
R ¹ is C ₇ alkyl. ₁₈
R ² is hydrogen or C 4 alkyl, each R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ is, independently, a hydrogen or C 4 alkyl and, a is 2-3 and b is 0-1.
[0018] More specifically, R ¹ is a C7.18 alkyl, R ² is methyl, each R ³ , R ⁴ , and R ⁵ is independently hydrogen or a C-1-3 alkyl, R ⁶ is hydrogen or a C ^ alkyl , R ⁷ is hydrogen, a is 2-3, and b is 0-1.
[0019] Even more specifically R ¹ is C ₇ alkyl. ₁₈ , R ² is methyl, each R ³ , R ⁴ , and R ⁵ is hydrogen, R ⁶ is hydrogen or a C ^ alkyl, R ⁷ is
5/135 hydrogen, a is 2, and b is 0.
[0020] In a specific embodiment R ¹ is C ₇ alkyl. ₁₈ , R ² is methyl, R ³ is hydrogen, R ⁶ is hydrogen, methyl, or ethyl, R ⁷ is hydrogen, a is 2, and b is 0.
[0021] Preferably, the acetal adduct of formula (1) is the adduct
1,2-propanediol of a levulinic acid ester, having the formula (1a):
(la>
wherein R ¹ is as defined above, and is specifically a C ₇ alkyl. ₁₈ , which can be straight or branched. Where R ¹ is an ethylhexyl group 2 in formula (1a), 2-ethylhexyl levulinate propylene glycol ketal (2EHLPK) is obtained. Where R ¹ is a 1-nonyl group in the formula (1a), 1-nonyl levulinate propylene glycol acetal (1N-LPK) is obtained. Where R ¹ is a group
3,5,5-trimethylhexyl in formula (1a), 3,5,5-trimethylhexyl levulinate propylene glycol acetal (355TMH-LPK) is obtained.
[0022] The acetal adducts of formula (1) can be obtained by the acid-catalyzed reaction of the corresponding ketoadic ester of formula (2) with a diol of formula (3):
(2)
wherein each of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ , and the integers a and b are as defined above. The reaction conditions are described in WO 09/032905, for example. Alternatively, the acetal adducts of formula (1) can be obtained by transesterification of acetal ester (4) (obtained as described in WO 09/032905, for example)
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wherein each of R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ and the integers a and b are as defined above, and R ⁸ is a C 4 alkyl group, for example, a methyl group or ethyl. In transesterification, acetal (4) comes in contact with alcohol R ¹ OH comprising the substituent of R ¹ in which R ¹ is as described in formula (1). A catalyst (for example, a metal oxide or metal complex as described in WO 09/032905) can be used to accelerate the reaction, in the presence of excess alcohol. Catalysts include, for example, those where the metal is Sn, Zn, Ge (ll), Cu (ll), Ni (ll), Fe (ll), Fe (lll), Al (lll), Pt (IV), V (IV) or V (V), specifically Sn, Zn, Ni, Al and Pt as oxides or complexes with, other binders such as sulfides or acetates. In one embodiment, the metal complex is a dialkyl metal oxide, and the alkyl groups on the dialkyl metal oxide are C- | to C ₁₀ , alternatively C ₂ to C ₄ alkyl groups, alternatively n-butyl groups, for example, a tin alkoxide such as dibutyl tin oxide (DBTO). Transesterification can be carried out at elevated temperatures, for example, about 160 to about 220 ° C, with concomitant removal of R ¹ OH.
[0023] Many of the compounds that fall within the scope of formulas (2) and (3) may come from renewable sources. Acetal adducts thus provide an entry point for a wide variety of solvents from renewable sources. For example, levulinic acid is produced by the thermochemical treatment of various carbohydrates such as cellulose; Subsequent esterification with alkanols from renewable sources and levalinate ester acetalization with polyhydroxy compounds such as glycerol or propylene glycol produces a bioderivative solvent.
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[0024] Acetal adducts are especially useful in waterborne coating compositions. Waterborne coating compositions cover a wide variety of coating compositions, including water-reducible coating compositions and latex compositions. Latex resin coatings are waterborne dispersions of sub-micrometer polymer particles. The dispersions are formed by polymerization of the emulsion, and can then be further formulated for a variety of applications. Latex coating compositions, for example, latex paint compositions, can be formulated with a variety of additives, including a coalescing or coalescing solvent. Coalescent solvents promote film formation. The coalescence solvent serves as a plasticizer, softening the resin particles by reducing the glass transition temperature (Tg) of the particles and allowing them to melt in a continuous film. For example, a latex paint composition containing a coalescing solvent is coated on a substrate and then cured by coalescence, where water and the coalescing solvent are removed sequentially or simultaneously. During the formation of the film, the coalescing solvent softens the particles of polymer binder, melting them together in a polymer film interlaced so that the polymer binder will not redissolve in the water / solvent that was originally transported.
[0025] Water-reducible coating compositions are produced using traditional polymerization techniques instead of emulsion polymerization and generally contain a water-miscible organic solvent. The polymer binder is generally modified to make it compatible with the water / organic solvent system. The modification may involve a hydrophilic comonomer, such as an organic acid that can transmit water reducibility to the binders
8/135 oligomencos or polished lerals. Another modification is to disperse the binder in an aqueous phase with the use of a surfactant, which in some cases, can be chemically incorporated into the polymer binder during the synthesis of the binder. In each case, the resulting polymers are subsequently mechanically dispersed in the aqueous phase. When polymer particles (liquid or solid) are formed in water, the water-reducible coating compositions are an emulsion (for liquid polymers) or a dispersion (for solid polymers). Another version of water-reducible coating composition is based on the polymer binder being soluble in the organic solvent / water mixture or partially soluble in the organic solvent / water mixture, since the polymer chains form aggregates that are dispersed in the liquid aqueous phase. The solvent is divided between the polymer aggregates and the water. Thermoset acrylics, epoxies, polyesters, epoxy esters and alkyds are examples of binders used in water-reducible coating compositions.
[0026] Although the water-borne coating compositions contain a polymer binder and water, the different properties of the binders result in different formulation requirements. As mentioned above, water-reducible compositions are generally initially dissolved in a non-aqueous solvent to reduce viscosity and aid dispersion in water. The compositions can additionally be formulated with a variety of additives, within them a coalescing solvent to promote film formation. The coalescing solvent smooths out the particles of the polymer binder by reducing the glass transition temperature (Tg) of the particles to below the processing temperature and allowing them to melt with a continuous film. Therefore, when a water-reducible coating composition containing a coalescence solvent is coated on a substrate, the coating cures by coalescence, where the
9/135 water and the coaescence solvent evaporate sequentially and simultaneously. During the evaporation of the solvent or water, the concentration of dispersed latex particles or microemulsion droplets increases to the point where the microemulsion particles or droplets come into contact with the coaescence solvent that bonds and the coalescent softens the polymer binder particles , allowing the particles to fuse into an interlaced polymer mesh film. In some cases, the coalescent does not evaporate and can serve as a plasticizer for the final film. Chemical curing through a crosslinking agent or an oxidative process can take place after the film is significantly cured by solvent evaporation mechanism.
[0027] There remains a need for solvents, preferably solvents derived from renewable sources, that can be used in a waterborne coating composition, for example, a paint, dye, adhesive, sealant, clearcoat coating or caulk composition that meets a or more customer needs as applicable for the specific coating composition such as hydrolytic stability, good viscosity, balanced drying time or good flow and leveling in the coating composition; or good adhesion of a dry film, good resistance to displacement, durability, impact resistance, flexibility, water resistance, chemical resistance, stain resistance, gloss or hardness in the resulting coating. It would be of added advantage if solvents derived from renewable sources provide a waterborne coating composition with a minimum low film-forming temperature and low content of volatile organic compounds with appreciable storage stability.
[0028] It has been found that acetal adducts (1), specifically (1a), find use in waterborne coating compositions. Without being bound by theory, it is believed that acetal adducts
10/135 function primarily as a coalescing solvent during film formation. However, it is believed that acetal adducts may have more than one function, including one or more solubilization, solvent coupling, reduction of VOC content, reduction of film formation temperature, plasticization and the like. In an advantageous feature, the selection of groups R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ and b in the acetal adducts of formula (1) allows the chemical and physical properties of the acetal adducts to be adjusted to achieve the desired combination of properties, for example, hydrolytic stability and VOC reduction.
[0029] In a specific modality of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ and whole numbers a and B are selected to provide a desired coalescence activity, that is, the capacity of the acetal adduct to plasticize the polymer binder and assist in the formation of a coating film. When necessary, the presence of ester and ether functionally allows the interaction of the acetal adduct with different types of functional groups of polymer binders.
[0030] Acetal adducts (1), specifically (1a), are additionally advantageous in the sense that the structure of the compounds can be adjusted to alter the volatility of the compounds. Volatility itself manifests itself in a number of key properties for coalescing solvents, including, but not limited to, vapor pressure, relative evaporation rate, flammability, odor and volatile organic compound (VOC) content. The desired volatility profile of a solvent varies considerably by application, and there are generally conflicting considerations. For example, highly volatile solvents require less energy to remove after use, however, in many cases it also requires special handling due to the higher flammability. The appropriate choice of groups R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ and integers a and b can additionally provide a selected volatility. In particular, 2EH
11/135
LPK, 1N-LPK and 355TMH-LPK have low acceptable volatility and low flammability (for example, have an evaporation point of about 99 ° C (210 ° F) or more) and have high coalescence efficiency, while decreasing concentrations of VOC in the coating formulas to a level below about 5.0 to about 10g VOC per liter of the coating composition.
[0031] Water-borne coating compositions comprise water; a polymer binder; and an acetal adduct (1). Coating compositions can be formulated (for example, the type and amount of polymer binder, water, other co-solvents if present, and additives), such as a paint, adhesive, sealant, coloring, clear-coat coating composition , caulking or tincture. Advantageously, water-borne compositions can maintain a pH for more than about 1 week, specifically more than about 2 weeks, and more specifically more than about 4 weeks within a range of about 7.5 for about 10, or about 7.5 to about 9.0 or about 8.5 to about 9.5, or about 8.5 to about 9.5. In another embodiment, water-borne compositions can maintain a stable initial pH that is in the range of about 7.5 to about 10, or about 7.5 to about 9.0, or about 8.5 to about 9.5, specifically about 9.0, for more than about 1 week, specifically more than about 2 weeks, and more specifically more than about 4 weeks. For example, the initial pH of waterborne compositions, for example, latex dye compositions comprising an adduct (1a) specifically acetal (1), varies by less than 0.5 pH units at 23 ° C, specifically less than 0.2 pH units at 23 ° C pH, above about 1 week, above about 2 weeks or above about four weeks, or even more.
[0032] In one embodiment, the coating composition
Waterborne 12/135 is a latex coating composition comprising a latex polymer binder, water and an acetal adduct (1), specifically (1a).
[0033] The latex polymer binder can be selected from a variety of polymers known in the art of latex coating compositions, specifically latex dye compositions, latex adhesive compositions, latex sealant compositions, caulking compositions latex, latex coloring compositions and latex dye compositions. For example, the latex polymer binder can be derived from monomers comprising vinyl acetate or at least one acrylic monomer such as acrylic acid, acrylic acid Ο _νιο alkyl esters, methacrylic acid or Ct alkyl esters. ₁₀ of methacrylic acid, optionally copolymerized with one or more of styrene, hydroxyethyl acrylate, hydroxypropyl acrylate, α-methyl styrene, vinyl chloride, acrylonitrile, methacrylonitrile, ureido methacrylate, vinyl acetate, vinyl esters or monocarboxylic acids branched (eg vinyl esters of versatile acid (referred to as vinyl versatates) commercially available under the VeoVa® brand by Shell Chemical Company or sold as Exxar® Neo Vinyl Esters by ExxonMobil Chemical Company), itaconic acid, crotonic acid, maleic acid , fumaric acid and ethylene. It is also possible to include C4-8 conjugated dienes such as 1,3-butadiene, isoprene and chloroprene. In one embodiment, the monomers include one or more n-butyl acrylate, methyl metracrylate, styrene and 2-ethylhexyl acrylate.
[0034] Pure acrylics can be used (comprising acrylic acid, methacrylic acid, an acrylate ester and / or a methacrylate ester as the main monomers); styrene-acrylics (comprising styrene and acrylic acid, methacrylic acid, an acrylate ester, and / or a methacrylate ester as the main monomers); vinyl-acrylics (comprising vinyl
13/135 acetate and acrylic acid, methacrylic acid, an acrylate ester and / or a methacrylate ester as the main monomers); and acrylated ethylene vinyl acetate copolymers (comprising ethylene, vinyl acetate and acrylic acid, methacrylic acid, an acrylate ester and / or a methacrylate ester as the main monomers). The monomers can also include other major monomers such as acrylamide and acrylonitrile, optionally with one or more monomers such as itaconic acid and ureido methacrylate.
[0035] The latex polymer binder is present in water in the form of an aqueous dispersion and can include about 2 to about 85 weight percent (% wt) in solids, specifically about 5 to about 75% in weight of solids (for example, the weight percentage of the dry latex polymer based on the total weight of the aqueous latex coating composition). Latex can be present in a wide variety of particle sizes, for example, a latex particle size of about 10 to about 1,000 nanometers (nm), specifically about 50 to about 800 nm. The particle size distribution can be mono-modal or multimodal, for example, bimodal. The acetal adduct (1), specifically (1a) is present in the latex coating composition in an amount effective for its purpose, for example, film coalescence, solubilization and the like. Such amounts can be determined by a person skilled in the art and can be, for example, from about 0.1 to about 30% by weight, specifically about 1 to about 20% by weight, based on the total weight of the product. dry weight of the latex polymer binder. The balance of latex coating compositions is water and other optional additives known in the art.
[0036] In a specific embodiment, acetal adducts (1), specifically (1a) are used in latex dye compositions and can reduce or replace other organic solvents in latex paint compositions. In particular, 2EH-LPK can be used with a solvent of
14/135 green coalescence in latex paint compositions, and in special paints used in architectural and light industrial applications. Thus, in one embodiment, a latex paint composition comprises a latex polymer binder, water, an acetal adduct (1), specifically (1a) and a pigment. The paint compositions can be a primer, cocoate-based, top-coat, color coat.
[0037] In an alternative embodiment, acetal adducts (1), specifically (1a) are used in latex coloring compositions, latex adhesive compositions, latex sealant compositions, latex caulking compositions, latex compositions latex mastic or latex dye compositions. Thus, in another embodiment, a latex coating composition comprises at least one latex polymer binder, water, an acetal adduct (1), specifically (1a), and optionally a pigment, and that the coating composition of latex is a latex adhesive composition, latex sealant composition, latex caulking composition, latex coloring composition, latex mastic compositions or latex dye composition and the latex polymer binder is selected with respect specific function of the latex coating composition.
[0038] A wide variety of latex polymer binders can be used in the preceding latex coating compositions, including those described for latex paint compositions. Acrylics can be specifically mentioned, formed from one or more of acrylic acid, methacrylic acid, an alkyl acrylate ester _10, an alkyl ester methacrylate Ci. ₁₀ monomers or vinyl versatate. Styrene acrylics formed from styrene and at least one of acrylic acid, methacrylic acid, a C C o alkyl acrylate ester or C C o alkyl methacrylate ester monomers can be used. Other latex products include vinyl-acrylics formed from vinyl acetate and at least one of acrylic acid, methacrylic acid, an acrylate ester
15/135 here! C1.10 or a C106 alkyl methacrylate ester monomer. Acrylated ethylene vinyl acetate copolymers can be used and formed, for example, from ethylene, vinyl acetate and at least one of acrylic acid, a C C ^ alkyl acrylate ester or a C C C methacrylate ester monomers ^ q. The preceding polymers can also include other monomers such as acrylamide, acrylonitrile, itaconic acid and ureido methacrylate.
[0039] A pigment can be present in latex coating compositions. The term pigment as used herein includes solids that do not form films, such as extenders and fillers, for example, an inorganic pigment TiO ₂ (in anatase and rutile forms), clay (aluminum silicate), CaCO ₃ ( in both floor and precipitate forms), aluminum oxide, silicon dioxide, magnesium oxide, talc (magnesium silicate), barites (barium sulfate), zinc oxide, zinc sulfite, sodium oxide, potassium oxide , solid organic latex particles (high Tg) added to modify the surface hardness or roughness or (as in the case of hollow latex particles) to replace TiO ₂ , and a combination comprising at least one of the preceding. Representative combinations include mixtures of metal oxides such as those sold under the MINEX® brands (silicon, aluminum, sodium and potassium oxides commercially available from Unimin Specialty Minerals), CELITES® (aluminum oxide and silicon dioxide commercially available from Celite Company ), ATOMITES® (commercially available from Imerys) and ATTAGELS® (commercially available from BASF). Specifically, the pigment includes TiO ₂ , CaCO ₃ , or clay.
[0040] Generally, the average particle sizes are from about 0.01 to about 50 micrometers. For example, the TiO ₂ particles used in the aqueous coating composition generally have an average particle size of about 0.15 to about 0.40 micrometers.
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The pigment can be added to the aqueous coating composition as a powder or as a mixture.
[0041] Latex coating compositions may contain additional additives, as are known in the art, to modify the characteristics of latex coating compositions and provide the desired functionality, provided that the additives do not significantly adversely affect the desired properties of the composition. These additives can include a plasticizer, drying retardant, dispersant, surfactant or wetting agent, rheology modifier, foam remover, thickener, biocide, fungicide, colorant, wax, perfume, pH regulator or co-solvent. Additives are present in the amount commonly used in latex coating compositions, and specifically in latex paint compositions, latex adhesive compositions, latex sealant compositions, latex caulking compositions, latex mastic compositions and latex dye. In one embodiment, the latex coating composition essentially consists of a latex polymer binder, water, an optional pigment and an acetal adduct (1), specifically (1a). As used in this document, the phrase essentially consists of covers the latex polymer binder, water, optional pigment and acetal adduct, and optionally, one or more additives defined in this document, however, excluding additives that significantly adversely affect desired properties of the latex coating compositions or the dry coating derived therefrom.
[0042] The latex polymer binder may be present in the latex composition in an amount of dry weight of about 5 to about 80% by weight, and more specifically about 8 to about 60% by weight of the composition latex coating, based on the total weight of the latex coating composition.
[0043] When present, a pigment can be used in
17/135 latex coating composition in an amount of about 5 to about 75% by weight, specifically about 10 to about 55% by weight, of the total solids in the latex composition.
[0044] The acetal adduct (1), specifically 1 (a), can be present in the latex coating composition in an amount of about 0.1 to about 30% by weight, about 0.5 to about from 20% by weight, about 1 to about 15% by weight, about 1 to about 10% by weight, about 1 to about 8% by weight, and more specifically about 1 to about 7% by weight, based on the dry weight of the polymer binder.
[0045] Although most of the water is present in the latex dispersion and other components of the latex composition, the water can be added separately from the latex composition. Generally, the latex composition includes about 10 to about 85% by weight and more specifically about 20 to about 80% by weight of water, for example, the total solids content of the latex composition is about 15 to about 90% by weight, more specifically about 20 to about 80% by weight of the total composition. The compositions are generally formulated in such a way that the hardened (dry) coatings comprise at least about 5% by volume (% vol.) Of dry polymer solids, and, when present, about 5 to about 90% by volume of non-polymeric solids in the form of pigments. In addition to dry polymer solids and non-polymeric solids in the form of pigments, the hardened (dry) coatings may comprise an acetal adduct amount (1), specifically (1a), in an amount of about 35 vol%. after drying, and this amount decreases to essentially zero over time.
[0046] In another embodiment, a latex caulking composition comprises a latex polymer binder, water, an acetal adduct (1), specifically (1a), and a caulking additive, for example, fillers such as like talc and calcium carbonate, fungicides,
18/135 biocides, pigments and pesticides. The polymer bonding agent for the caulking composition can be selected from a wide variety of polymers known in the art of latex coating compositions, for example, those described above for latex paint compositions. Additives include filler materials, such as talc and calcium carbonate, fungicides, biocides, foam-removing agents, anti-freeze agents, pigments and pesticides. The amounts of latex polymer binder and acetal adducts (1), specifically 1 (a) effective to form a latex caulking composition can be determined by one skilled in the art, and can be, for example, about 5 to about 80% by weight of the polymer binder solids, based on the total weight of the latex caulking composition, and about 0.1 to about 30% of the acetal adduct, more specifically between about 0.1 and about 10% (1), specifically 1 (a), based on the total weight of the latex caulking composition.
[0047] In another embodiment, a latex sealant or adhesive composition comprises a latex polymer binder, water, an acetal adduct (1), specifically (1a) and an adhesive sealant or additive, for example, a pigment . The polymer binder of the sealant or adhesive can be selected from a wide variety of polymers as are known in the art or latex coating compositions, for example, those described above for latex paint compositions. Additives include filler materials, such as talc and calcium carbonate, fungicides, biocides, foam-removing agents, anti-freeze agents, tackiness agents and pesticides. The amounts of latex polymer binder and acetal adducts (1), specifically 1 (a) effective to form a latex sealing composition or adhesive composition can be determined by one skilled in the art, and can be, for example, about from 5 to about 80% by weight of the polymer binder solids, based on
19/135 in the dry weight of the caulking composition, and about 0.1 to about 30%, specifically between about 0.1 and about 10%, and more specifically about 0.1 to about 5% of the adduct of acetal (1), specifically 1 (a), based on the total weight of the sealing, mastic or adhesive composition composition.
[0048] In another embodiment, a latex dye composition comprises a latex polymer binder, water, an acetal adduct (1), specifically (1a), a pigment and, optionally, a dye additive, for example, a wax. The latex polymer binder can be selected from a wide variety of polymer as known in the art of latex dye compositions, for example, those described above for latex dye compositions. Additives include greases, dyes, foam-removing agents, anti-freezing agents, surfactants and plasticizers. The amounts of latex polymer binder and acetal adducts (1), specifically 1 (a) effective to form a latex dye composition can be determined by one skilled in the art, and can be, for example, about 5 to about 80% by weight of the polymer binder solids, based on the dry weight of the dye composition, and about 0.1 to about 30% of the acetal adduct (1), specifically 1 (a), based in the total weight of the latex dye composition.
[0049] In another embodiment, a water-reducible coating composition comprises a water-reducible polymer binder, water, and the acetal adduct represented by formula (1), specifically (1a). The water-reducible polymer binder can be selected from a wide variety of polymers known in the art of water-reducible coating compositions, specifically water-reducible paint compositions, and may include, for example, acrylics that are produced using techniques traditional polymerization processes in water-miscible organic solvent, polyesters, polyurethanes,
20/135 aikids, alkyds modified by silicone, epoxies, epoxy esters and alkyds. In a specific embodiment, the binder is a polyurethane, for example, an aliphatic polyurethane, an alkyd, an acrylic or combinations or hybrids thereof. The water-reducible polymer binder can be present in water composition as a true solution (for example, the volume of the solution is equal to the sum volume of the water-reducible polymer binder), an emulsion, a duplex emulsion ( for example, a water-in-oil in water (W / O / W) emulsion, a dispersion or a suspension (for example, a coarse dispersion)). The various types of polymer binders can be made reducible in water by neutralizing groups of residual free acids attached to the polymer structure with a base, for example, an organic amine, ammonium hydroxide or another base. Exemplary acrylic or alkyd binders can have acid numbers from about 20 to about 100.
[0050] The polymer binder can be thermoset, in which case any curing agent used for each polymer binder will depend on the nature of the specific polymer and its curing mechanism. Thus, polyester and alkyd polymers having hydroxyl, carboxyl or amide functionality or any combination of such functionalities, crosslinking or curing can be effective by means of urea formaldehyde, melamine formaldehyde and methoxylated, ethoxylated or butoxylated forms thereof. Blocked isocyanate crosslinking agents are also known in the art. Catalysts can also be used to promote the healing reaction, such as peroxides. In addition to catalysts, promoters and activators for promoting the healing reaction can be used.
[0051] Some polymer binders, for example, curable polyurethane binders, include two components: an aqueous component including a component containing active hydrogen (for example, a polyol or amino functional compound) in one part and a polyisocyanate
21/135 aqueous elsewhere. The polyol can be a water-soluble or dispersible polyol, optionally having a carboxyl group, one or amino functional hydroxyoligourethane and / or oligurethane, and the polyisocyanate can be modified with polyoxyalkylene ethyl ether to be soluble in water or dispersible in water.
[0052] Epoxy binders include derivatives of diglicidyl ether / bis-phenol compounds such as bisphenol A (DGEBA), for example, polyether diepoxide derivatives that are obtained by the polymeric addition of bisphenols with the bisphenol diglycidyl ether. Epoxies can be soluble in water by reacting with phosphoric acid and then neutralizing the resulting, acidic products, ester, and reaction products that comprise glycol with a base. If the base is a fugitive base, such as ammonium or a volatile amine, the water-neutralized and neutralized polymer can be converted to a high-performance thermoset polymer, insensitive to evaporating water, heating to disrupt ammonium saline groups and expelling ammonia (or amine) and cure. Conventional curing agents capable of reacting with acidic groups and / or hydroxyl alcoholic groups can be incorporated with the uncured polymer. Epoxy binders can also be made with a surfactant to aid dispersion. In some cases, the surfactant may have reactive groups so that the surfactant is chemically incorporated into the polymer system.
[0053] As indicated above, the water-reducible polymer binder can be present in completely dissolved water, for example, in the form of a solution, in the form of aggregates or an aqueous dispersion and can include about 5 to about 85% of solids, specifically about 10 to about 75% by weight of solids (e.g., the weight percentage of the polymer binder based on the total weight of the water-reducible coating composition). It is observed that the higher the concentration of the dispersed phase, the greater the viscosity.
22/135
As used in this document, solids refer to the 100% binder in any form, such as a solid or liquid. The polymer binder can be present in a wide variety of particle sizes, for example, an average polymer binder particle size of about 10 to about 1,000 nanometers (nm), specifically about 50 to about 800 nm . The particle size distribution can be mono-modal or multimodal, for example, bimodal.
[0054] The acetal adduct (1), specifically (1a) is present in the water-reducible coating composition in an amount effective for its purpose, for example, film cohesion, solubilization and the like. Such amounts can be determined by a person skilled in the art and can be, for example, from about 0.1 to about 30% by weight, or about 0.5 to about 30% by weight, specifically about 1 to about 20% by weight or about 1 to about 10% by weight, each based on the total weight of the water-reducible coating compositions. The balance of water-reducible coating compositions is water, polymer binder, and other optional additives, including cosolvents known in the art.
[0055] In a specific embodiment, acetal adducts (1), specifically (1a), are used in water-reducible paint compositions, coloring compositions or clear-coat compositions and can reduce or replace other organic solvents in compositions reducible in water. EtLPK in particular can be used as a green / non-toxic coaescence solvent in water-reducible paint, coloring, or clear-coat coating compositions, and in particular such compositions used in architectural and light industrial applications. Because EtLPK evaporates more slowly than water, the drying time is slower. However, the volatility of EtLPK is such that none or very little remains on the completely dry film, thereby avoiding a sticky film.
23/135
[0056] Therefore, in one embodiment, a water-reducible ink, coloring or clear-coat composition comprises a water-reducible polymer binder composition, optionally a pigment and an acetal adduct (1), specifically (1a ). A wide variety of water-reducible polymer binders can be used, including those described above. When the polymer binder is thermoset, the binder compositions comprise the uncured polymer and one or more of a curing agent, catalyst, initiator or promoter, if used.
[0057] A pigment can be present in ink composition or water-reducible coloring. The term pigment as used in this document includes non-film solids, such as extenders and fillers, for example, an inorganic pigment, aluminum oxide, barites (barium sulfate), CaCO ₃ (both in floor and precipitated), clay (aluminum silicate), chromium oxide, cobalt oxide, iron oxides, magnesium oxide, potassium oxide, silicon dioxide, talc (magnesium silicate), TiO ₂ (both in the forms of anastase and rutile), zinc oxide, zinc sulfite, an organic pigment such as solid (high Tg) organic latex particles added to modify the hardness or (as in the case of hollow latex particles) to replace TiO ₂ , carbon black and a combination comprising at least one of the preceding. Representative combinations include mixtures of metal oxides, such as those sold under the MINEX® brands (silicon, aluminum, sodium and potassium oxides commercially available from Unimin Specialty Minerals), CELITES® (aluminum oxide and silicon dioxide commercially available from Celite Company), ATOMITES® (commercially available from English China Clay International), and Attagels® (commercially available from Engelhard). Specifically, the pigment includes TiO ₂ , CaCO ₃ , or clay.
[0058] Generally, the average particle sizes of the
24/135 pigments are from about 0.01 to about 50 micrometers. For example, the TiO ₂ particles used in the aqueous coating composition generally have an average particle size of about 0.15 to about 0.40 micrometers. The pigment can be added to the aqueous coating composition as a powder or as a mixture.
[0059] A dye may be present in an ink composition or water-reducible coloring, in addition to or instead of a pigment. The term dye as used in this document includes organic compounds generally soluble in the compositions, which impart color to the compositions.
[0060] The water-reducible ink, coloring or clear-coat composition may contain additional additives, as are known in the art, to modify the characteristics of the water-reducible composition, provided that the additives do not significantly adversely affect the desired properties of the paint, coloring or clear-coat, for example, viscosity, drying time or other characteristic. These additives can include a plasticizer, drying retardant, dispersant, surfactant or wetting agent, rheology modifier, foam remover, thickener, biocide, fungicide, colorant, wax, perfume, pH regulator or co-solvent. Additives are present in the amount commonly used in water-reducible ink, coloring or clear-coat compositions. In one embodiment, the water-reducible ink, coloring or clearcoat composition essentially consists of a water-reducible polymer binder, an optional pigment, an optional dye and an acetal adduct (1). As used in this document, the phrase essentially consists of encompassing the polymer binder reducible in water, water, optional pigment and acetal adduct, and optionally, one or more additives defined in this document, however, excluding additives that significantly adversely affect the desired properties of the water-reducible compositions or the
25/135 dry coating derived from this.
[0061] The water-reducible polymer binder can be present in the water-reducible ink composition in an amount of about 2 to about 60% by weight, and more specifically about 4 to about 40% by weight of the composition of water-reducible ink, based on the dry weight of the water-reducible polymer binder.
[0062] When present, the pigment can be used in water-reducible ink composition in an amount of about 2 to about 50% by weight, specifically about 5 to about 40% by weight of the total solids in the composition water-reducible ink.
[0063] The water-reducible polymer binder can be present in the water-reducible chlorination composition in an amount of about 0.1 to about 50% by weight, and more specifically about 0.5 to about 30% by weight of the water-reducible paint composition, based on the dry weight of the water-reducible polymer binder.
[0064] When present, the pigment or dye can be used in a water-reducible coloring composition in an amount of about 0.1 to about 40% by weight, specifically about 0.5 to about 30% by weight of total solids in the water-reducible coloring composition.
[0065] When present, the coloring can be used in ink composition or water-reducible coloring in an amount of about 0.001 to about 10% by weight, specifically about 0.005 to about 5% by weight of the total solids in the composition of ink or water-reducible coloring.
[0066] The acetal adduct (1), specifically 1 (a), more specifically 1 (b), can be present in an amount of about 0.1 to about 30% by weight, specifically about 1 to about 10% by weight, more specifically about 1 to about 8% by weight, and even more specifically about 1 to about 7% by weight based on weight
26/135 dry of the polymer binder.
[0067] The water-reducible ink composition can include about 5 to about 85% by weight and more specifically about 35 to about 80% by weight of water, for example, the total solids content of the ink composition water-reducible can be from about 15 to about 95% by weight, more specifically about 20 to about 65% by weight of the total composition. The compositions can be formulated in such a way that the hardened (dry) coatings comprise at least about 2 to about 98% by volume (% vol.) Of polymer solids and, if present, the acetal adduct (1), specifically (1a), and about 2 to about 98% vol. of non-polymeric solids in the form of pigments or a combination of a pigment and a dye, together with other additives (if present).
[0068] The water-reducible coloring composition can include about 10 to about 95% by weight and more specifically about 25 to about 90% by weight of water, for example, the total solids content of the coloring composition water-reducible can be from about 5 to about 75% by weight, more specifically about 10 to about 75% by weight of the total composition. The coloring compositions are generally formulated in such a way that the hardened (dry) coatings comprise at least about 1% by volume, for example, about 5 to about 98% by volume of polymer solids, if present, the acetal (1), specifically (1a) and about 0.1 to about 99% by volume of non-polymeric solids in the form of pigments and / or dyes, and other additives (if present). A wood-colored coating can penetrate the wood substrate to some degree.
[0069] The water-reducible coating composition can include about 10 to about 95% by weight and more specifically about 25 to about 90% by weight of water, for example, the total solids content of the coating composition reducible in water can be about 5 to
27/135 about 75% by weight, more specifically about 10 to about 75% by weight of the total composition. The compositions are generally formulated in such a way that the hardened (dry) coatings comprise about 1% by volume of polymer solids, for example, about 1 to about 100% by volume of polymer solids, if present, the acetal (1), specifically (1a) and 0 to about 10% by volume of non-polymeric solids. For example, in clear-coat compositions certain additives (for example, calcium carbonate, talc or silica) can be used that do not transmit color, on the contrary, they serve primarily to reduce cost, modify gloss levels or the like.
[0070] A method for preparing any of the preceding waterborne coating compositions comprises the combination of water, the polymer binder, the acetal adduct (1), specifically (1a) and any optional additives, for example, a pigment to form water-borne coating compositions. The components can be combined in any suitable order.
[0071] For example, a method for preparing a latex coating composition comprises the combination of aqueous latex polymer binder emulsion, acetal adducts (1), specifically (1a), and any optional additives, for example, a pigment to form a latex coating composition. The acetal adducts and additives can be added in any order suitable for the polymer latex, the additives or combinations thereof, to provide these additives in aqueous coating composition. In the case of latex paint compositions, the aqueous coating composition has a pH of about 7 to about 10. Alternatively, the acetal adducts (1), specifically (1a), may be present during the polymerization of the latex polymer. A method for preparing a latex paint composition comprises combining the aqueous dispersion of the Binder
28/135 latex polymer, the acetal adducts (1), specifically (1a), the pigment and any optional additives to form the latex paint composition.
[0072] In another embodiment, a method of preparing a water-reducible coating or paint composition, coloring or clear-coating coating comprises combining the polymeric binder, the acetal adducts (1), such as, for example, (1a) , aqueous phase (e.g., water and any cosolvents if present), and any additives, if present, to form a water-reducible coating composition. Components can be added in any order to provide the water-reducible coating composition. The polymer binder can be combined with an acetal adduct after the polymer binder synthesis is complete. Thus, the acetal adduct can be added to the polymer binder or water before the binder is combined with water to form the coating composition. Adding the acetal adduct to the polymer for the polymer binder before adding the composition in water can improve processing due to a decrease in the viscosity of the polymer / acetal combination. Alternatively, the acetal adduct can be admixed after the binder is combined with water. Where the binder is neutralized, the acetal adduct can be combined with the binder before neutralization or after neutralization. For example, the acetal adduct and polymer binder can be combined after the binder is neutralized, to avoid the side reaction of the acetal adduct and the base used for neutralization. In the case of water-reducible ink compositions, the aqueous coating composition has a pH of about 5 to about 8.5.
[0073] In another embodiment, the water-reducible coating composition components, for example, a paint, coloring or clear-coat composition, are provided in two parts that are immediately combined before use. For example, a first part
29/135 of a water-reducible coating composition includes an epoxy dispersion and a second part includes an amine crosslinker. The parts are mixed at a predetermined ratio to provide the epoxy system. Acetal esters and other additives are generally present in the epoxy dispersion. Similarly, a first part of the water-reducible alkyd composition includes an alkyd binder and a second part includes a melamine crosslinker. A first part of the water-reducible polyurethane coating composition includes hydroxyl functional polyurethane dispersion and a second part includes an isocyanate prepolymer. The parts are mixed at a predetermined ratio to provide the polyurethane system. Acetal esters and other additives are generally present in the polyurethane dispersion.
[0074] A method of use, that is, coating a substrate with a waterborne coating composition is also described. The substrate can be a wide variety of materials, such as paper, wood, concrete, metal, glass, ceramics, plastics, plaster, ceiling substrates such as asphalt coatings, ceiling felts, foam polyurethane insulation, roofing membranes of polymers and masonry substrates such as brick, concrete block and cement layers, including external building cladding systems such as EIFS (External Insulation Finishing Systems). Substrates include painted, primed, coated, worn or weathered substrates. The method comprises contacting a substrate surface with a water-borne coating composition to form a film and drying the film to harden it. The water-borne coating composition can be applied to materials by a variety of techniques well known in the art such as curtain, sponge, brush, roller, broom, air-assisted or airless spray, electrostatic spray and the like. In a
30/135 modality, the ink composition does not significantly penetrate or impregnate the substrate. In one embodiment, the clear-coat composition does not significantly penetrate or impregnate the substrate. Stains are generally made to partially or completely impregnate the substrate after coating. In one embodiment, the substrate is completely impregnated by a coloring composition, so that the formed film fits inside the coated substrate and can be continuous or discontinuous.
[0075] Hardening occurs through loss of water and solvent, by evaporation under atmospheric conditions at room temperature or with heating to assist in the drying rate. Curing can be carried out before drying, during drying or after drying or any combination thereof. Chemical curing through a crosslinking agent or an oxidative process can take place after the film is significantly cured by solvent evaporation mechanism.
[0076] According to another embodiment, a substrate coated with a dry coating is provided, characterized by the fact that the coating comprises the polymer binder in the form of a film. Some amount of acetal adduct (1), specifically (1a) may be present. In one embodiment, the acetal adduct can be chemically combined with the polymer binder. For example, acetal adducts (1), specifically (1a), can be present in the coating in an amount of about 1 per million by weight (ppm) to about 15% by weight, specifically about 0.1 to about 15% by weight, each based on the total weight of the dry coating. For example, where the acetal adduct performs a plasticizer function, the adduct can be present in larger amounts, for example, about 0.25 to about 15% by weight, based on the total weight of the dry coating.
[0077] The dry coating is arranged on a surface of the
31/135 substrate, in the form of a film that can partially or completely cover the surface. The coating may be disposed directly on the surface, or one or more intermediate layers (for example, a primer) may be present between the coating and the surface of the substrate. In a further embodiment, the dry coating can be a dry paint coating that comprises the polymer binder in the form of a film. The dry paint coating additionally contains one or more additional additives as discussed above, for example, a pigment. The dry coating or dry paint coating can be significantly free of one or more of water, other coalescing agents or other organic solvent. In addition, or alternatively, as described above, the coating can be partially or completely impregnated within the substrate and adapt to the internal surfaces of the substrate. In these embodiments, the acetal adducts (1), specifically (1a), can be present in the coating in an amount of about 1 part per million by weight in about 15% by weight, specifically about 0.1 to about 15% by weight, each based on the total weight of the dry coating. Again, where the acetal adduct performs a plasticizer function, the adduct can be present in larger amounts, for example, about 0.25 to about 15% by weight, based on the total weight of the dry coating. If any of the foregoing modalities, it is also possible to dry the coating and / or substrate sufficiently to remove the acetal adducts (1), specifically (1a) below the detectable limits on the films.
[0078] The water-borne coating composition exhibits comparable or improved coalescence compared to similar compositions that do not have acetal adducts (1), specifically (1a).
[0079] The waterborne coating composition has a minimum and low temperature of film formation (MFFT).
32/135
Specifically, the acetal adducts of formula 1, specifically of formula (1a), lower the minimum film formation temperature to below about 10 ° C (50 ° F), specifically, to below about 5 ° C ( 41 ° F) as measured using ASTM Method D2354. The minimum temperature of film formation is an indicator of coalescence efficiency. The minimum film-forming temperature is the minimum temperature at which water-borne synthetic latex will coalesce when applied to a substrate such as a thin film. At a temperature lower than the minimum film-forming temperature, a powdery cracked layer will form instead of a film.
[0080] Additionally, the water-borne coating composition provides a coating of commercially acceptable properties, while significantly reducing or eliminating the need for VOCs within the coating composition. The water-borne coating composition, in particular the latex paint composition, advantageously comprises less than about 250 g / l of VOCs, and most advantageously does not comprise significant VOCs content. As such, the latex paint composition can be produced that has lower VOC levels than conventional latex paint compositions and is more environmentally desirable than conventional coatings. In one embodiment, the waterborne coating composition, especially the latex paint composition, has a VOC content of less than about 150 g / l, less than about 100 g / l, less than about 50 g / l, or still significantly zero, for example, less than about 10 g / l, as determined using the ASTM D3960 Method. Alternatively, a component of a composition can be defined as being a VOC if its initial boiling point is less than or equal to about 250 ° C, measured at a standard pressure of 101.3 kPa according to EU Directive 2004 / 442 / EC. The VOC content of a coating composition is the
33/135 mass of VOC compounds, expressed in g / l in the composition in its ready-to-use condition and can be measured by ISO 11890-2.
[0081] Although Method ASTM D3960 is applicable to determine the VOC content expressed as the mass of VOC per volume of coating unit, Method ASTM D2369 is used to obtain a weight percentage of non-volatile matter by difference to determine volatiles emitted by coatings. In one embodiment, the acetal adduct of formula (1a) used in the latex paint composition retains more than about 50% by weight, specifically greater than about 55% by weight, and more specifically greater than about 60% by weight of the acetal adduct based on an initial amount of acetal adduct as determined by Method ASTM D2369. This indicates that a water-borne composition comprising an acetal adduct of formula (1a) according to the coalescing solvent has an extremely low contribution of VOC content due to the coalescing solvent
[0082] Furthermore, the water-borne composition, for example, paint compositions such as latex paint composition has improved hydrolytic stability. Water-borne compositions, for example, ink compositions are usually stored at a relatively high alkaline pH, for example, at a pH of about 7.5 to about 10. In highly alkaline environments, hydrolysis of esters can occur in a significant rate and the coalescence efficiency of an ester functionalized coalescence solvent decreases. Without being bound by theory, it is believed that ester hydrolysis produces carboxylic acids that lower the pH of paint compositions, specifically latex paint compositions. In one embodiment, waterborne compositions, for example, latex paint compositions comprising an acetal (1), specifically adduct (1a), can maintain a pH for more than 1 week, specifically for more than 2 weeks, and more specifically more than about 4 weeks in
34/135 of a range of about 7.5 to about 10, or about 7.5 to about 9.0 or about 8.5 to about 9.5 or about 8.5 to about 9.5 at a temperature of 10 ° C to 25 ° C. In another embodiment, waterborne compositions, for example, ink compositions such as latex ink compositions comprising a ketal (1), specifically adduct (1a), can maintain a stable initial pH that is in the range of about 7, 5 to about 10, or about 7.5 to about 9.0, or about 8.5 to about 9.5, specifically about 9.0, for more than about 1 week, specifically more than about 2 weeks, and more specifically more than about 4 weeks at a temperature of 10 ° C to 25 ° C. For example, the initial pH of waterborne compositions, for example, latex paint compositions comprising an acetal (1), specifically adduct (1a), ranges from less than 0.5 pH units at 23 ° C, specifically less than 0.2 pH units at 23 ° C pH, above about 1 week, above about 2 weeks, or above about four weeks, or even more at a temperature of 10 ° C to 25 ° C .
[0083] In addition, water-borne coating compositions, specifically paint compositions can have very good overall performance, in particular one or more of viscosity, drying times, drop resistance, flow and leveling, hardness, specular gloss , dry film adhesion, impact flexibility, dilute alkaline resistance, water resistance, stain resistance, solvent resistance, resistance to hydraulic fluid, resistance to weather conditions and good heat storage stability.
[0084] In a specific embodiment, a latex paint composition comprises an acrylic vinyl emulsion, water, pigment and 2EH-LPK. Acrylic vinyl emulsions are especially suitable for indoor and outdoor architectural coatings. The composition can exhibit excellent pigment binding, scouring resistance, resistance to
35/135 coloring, external durability, resistance to scale and resistance to grain breakage. The composition can also have good gloss and gloss as well as excellent thickening performance. In addition, the composition may show low contribution to VOC content, high hydrolytic stability at a high level of alkaline pH and low minimum temperature of film formation.
[0085] In a specific embodiment, a latex paint composition comprises an acrylic vinyl emulsion, water, pigment and 2EH-LPK. Acrylic emulsions are especially suitable for wall paints and paints with internal / external architectural finishes. The composition can exhibit excellent moisture and dry adhesion on a chalky surface and aged alkyd substrates, resistance to blistering, resistance to grain breakage and shade retention. The composition can have excellent exterior durability and very good flowering and alkaline resistance. In addition, the composition has excellent resistance to loss of gloss, corrosion, fading, chalk, chemicals and solvents. In addition, the composition shows no significant contribution to the VOC content, high hydrolytic stability at a high level of alkaline pH and low minimum temperature of film formation.
[0086] The inventors also found that acetal adducts of long chain esters that ketocarbon (1) offer a combination of properties that make them useful in a wide variety of cleaning compositions. In particular, ketal adducts (1) have low volatility. Under normal conditions of manufacture, storage and use, they are not reactive with many of the other materials that are usually found in personal care or cleaning formulas. Another advantage is that ketal adducts (1) are stable under basic conditions. In addition, certain ketal adducts (1) can be derived from biological raw materials.
[0087] Exemplary cleaning compositions include, but are not
36/135 are limited to laundry detergents, washing machine cleaning formula, hard surface cleaners, soft surface cleaners, glass cleaner compositions and stove cleaners. Exemplary cleaning compositions also include removal compositions such as paint removal formulas, graphite removal, dye cleaning and removal, adhesive removal, mastic removal, photoresist removal, wax removal, asphalt removal, concrete cleaning , shape cleaning, mold cleaning, hand cleaning, body cleaning, sap / tar removal, oil paint cleaning and removal, parts grease removal and engine grease removal. The acetal adducts of formula (1), specifically (1a) have an excellent combination of properties for use in these applications, including solubilization activity, low flammability, long working times, biodegradability, without corrosivity and low odor. The cleaning compositions can be in the form of a solid, a gel, a liquid, an emulsion. A single composition can have more than one in use, for example, a single composition can be used both as a paint and dye remover, as a paint, oil or grease remover.
[0088] And one embodiment, the cleaning compositions contain only acetal adducts of the formula (1), specifically (1a), and 0 to 1% by weight of water, based on the total weight of the removal compositions. Such cleaning compositions can be removal compositions, for example, an paint remover, graphite remover, dye remover, adhesive remover, mastic remover, photoresist remover, wax remover, asphalt remover, concrete cleaner, cleaner shape, sap remover, oil remover or grease remover.
[0089] In another embodiment, the cleaning compositions comprise the acetal adducts of the formula (1), specifically (1a); 0 to 1% by weight of water, based on the total weight of the
37/135 removal; and one or more additional components, for example, a cosolvent and / or other components such as a plurality of abrasive particles, an organic amine, antioxidant, biocide, colorant, corrosion inhibitor, foam remover, dye, enzyme, light stabilizer, odor masking agent, plasticizer, preservative, rust inhibitor, surfactant, thickener or a combination comprising at least one of the foregoing.
[0090] In yet another embodiment, the cleaning compositions comprise 20 to 99% by weight, water, 0.1 to 40% by weight, the acetal adducts of formula (1), specifically (1a) and 0 , 1 to 20% by weight of at least one surfactant. In yet another embodiment, the cleaning compositions comprise from 20 to 99% by weight, of water, from 0.1 to 40% by weight of acetal adducts of formula (1), specifically (1a) and from 0.1 to 45 % by weight of at least one surfactant and one or more additional components, for example, a cosolvent and / or other components such as a plurality of abrasive particles, an organic amine, antioxidant, biocide, colorant, corrosion inhibitor, foam remover , dye, enzyme, light stabilizer, odor masking agent, plasticizer, preservative, rust inhibitor, surfactant, thickener, soil suspending agent, building or chelating agent, bleach, bleach activator, bleach stabilizer and control agent pH, hydrotope and tissue softening ingredient.
[0091] Exemplary co-solvents include:
aliphatic hydrocarbons, for example straight chain, branched, cyclic or aliphatic C6-30 hydrocarbons, which are specifically liquid at room temperatures and which have a boiling point of at least about 100 ° C, for example mineral oil (also called liquid petrolatum or liquid paraffin), mineral spirits (also called ligroin or petroleum spirits), and dot cuts
38/135 low glow distillate o and niorocarbon (for example, Conosol® ΟΙ 45 (mainly C10-13 cycloparaffinic and isoparaffinic hydrocarbons), Conosol® C-170 (composed mainly of C10-15 cycloparaffinic and isoparaffinic hydrocarbons), Conosol® C-200 (composed mainly of C12-16 and isoparaffinic cycloparaffinic hydrocarbons) and Conosol® 215 (composed mainly of C12-15 and isoparaffinic cycloparaffinic hydrocarbons) from Calumet Specialty partners);
aromatic hydrocarbons, eg naphthalene, C1-8 alkyl derivatives of benzene and C1-8 alkyl derivatives of naphthalene, specifically toluene, xylene (o, m or p), cumene, ethylbenzene, mesitylene, durene, sec-amylbenzene, n-butylbenzene, naphthalene and methylnaphthalene;
terpenes, for example, turpentine, alpha-pinene, beta-pinene and dlimonene;
sulfur-containing organic compounds, such as sulfoxides, for example, dimethyl sulfoxide (DMSO);
dormant solvents, for example, dormant C1-6 aliphatic compounds such as allyl chloride, carbon tetrachloride, chloroform, 1,1-dichloroethane, dichloroethyleter, 1,2-dichloroethylene, dichloroisopropyl ether, ethyl chloride, ethylene dichloride, chloride isopropyl, methyl chloride, perchlorethylene, propylene dichloride, 1,1,2-trichloroethane, trichlorethylene 1,2,3 trichloropropene and methylene chloride (dichloromethane or DCM);
alcohols, for example amyl alcohol, n-butanol, 3-butoxyethyl-2-propanol, benzyl alcohol, benzyloxyethanol, diethoxyethanol, diisobutyl carbinol, dimethyl heptanol, ethanol, 2-ethylhexanol, ethylene glycol, glycerin, 1-hexanol, isobutanol, isopropanol, methanol, methyl amyl alcohol, 2-methyl-1-butanol, 1 pentanol, 1-propanol, propylene glycol and 2,2,4-trimethyl-1,3-pentanedial monoisobutyrate (commercially available as UCAR FILMER ™ IBT from Dow Chemical Co .);
39/135 glycol ethers, for example, diethylene glycol meth! ether, glycine diethylene! mono-n-butyl ether (commercially available as Dow's Butyl CARBITOL), diethylene glycol monoethyl ether (commercially available as Dow's CARBITOL), diethylene glycol monohexyl ether (commercially available as Dow's Hexyl CARBITOL), diethylene glycol monomethyl ether (commercially available such as Methyl CARBITOL from Dow), diethylene glycol monopropyl ether (commercially available as Propyl CARBITOL from Dow), diethylene glycol n-butyl ether acetate (commercially available as Butyl CARBITOL ™ Acetate from Dow), dipropylene glycol monobutyl ether (commercially available as DOWANOL ™ DPnB from Dow), dipropylene glycol mono-methyl ether (commercially available as DOWANOL DPM from Dow), dipropylene glycol monopropyl ether (commercially available as DOWANOL DPnP from Dow), dipropylene glycol tert-butyl ether, ethylene glycol methyl ether acetate (available commercially as Dow's Methyl CELLOSOLVE Acetate), ethylene glycol monobutyl ether (commercially available as B util CELLOSOLVE from Dow), ethylene glycol monohexyl ether (commercially available as Hexyl CELLOSOLVE from Dow), ethylene glycol monopropyl ether (commercially available as Propyl CELLOSOLVE from Dow), ethylene glycol n-butyl ether acetate (commercially available as Butyl CELLOSOLVE Acetate from Dow ), ethylene glycol phenyl ether (commercially available as DOWANOL ™ EPh from Dow), heptaethylene glycol monobenzyl ether, heptaethylene glycol monophenyl ether, hexaethylene glycol monobenzyl ether, hexaethylene glycol monophenyl ether, pentaethylene glycol monobenzyl ether, pentaethylene glycol ether, propylene glycol methyl ether acetate (commercially available as DOWANOL ™ PMA from Dow), propylene glycol monobutyl ether (commercially available as DOWANOL PnB from Dow), propylene glycol monomethyl ether (commercially available as DOWANOL PM from Dow), propylene glycol monopropyl ether (commercially available as Dow's DOWANOL PnP), propylene
40/135 glycol phenyl ether (commercially available as DOWANOL PPh from Dow), tetraethylene glycol monobenzyl ether, tetraethylene glycol monophenyl ether, Methylene glycol methyl ether, triethylene glycol monobenzyl ether, triethylene glycol monophenyl ether, tripropylene glycol methyl EAN (commercially available) TPM from Dow) and tripropylene glycol n-butyl ether (commercially available as DOWANOL TPnB from Dow);
water soluble ethoxylates of propylene glycol monophenyl ether (specifically containing an average of at least 2 oxyethylene fractions per molecule);
polymeric amines soluble in water or dispersible in water such as poly (ethyleneimine);
amides, such as acetamidophenol, Ν, Ν-dimethyl formamide (DMF) and acetanilide and cyclic amides, such as 1-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-cyclohexyl -2-pyrrolidone, 2-hydroxyethyl2-pyrrolidone, N-dimethylaminopropyl-2-pyrrolidone, vinylpyrrolidone and 2pyrrolidone;
amines such as 2- (2-aminoethoxy) ethanol, 2-acetyl-1-methylpyrrole, 2-amino-2methyl-1-propanolalkanolamines (for example, n-butyldiethanolamine, diethanolamine, diisopropanolamine, dimethylethanolamine, ethanolamine, isopropanolamine, methylisopropanolamine, phenyl diethanolamine and triethanolamine), cyclic amines (for example, N-methyl pyrrolidine, Nmethylpyrrole, morpholine and oxazolidines), n-butylaminoethanol, diethylaminoethanol, diglycolamine, 2-methylamineethanol and trialkylamines (for example, triethylamine);
ketones and cyclic ketones such as isobutyl heptyketone, isophorone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, diacetone alcohol, acetophenone, methyl n-amyl ketone, cyclohexanone and cycloheptanone;
dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate and dibutyl carbonate;
cyclic carbonates such as propylene carbonate and ethylene carbonate;
41/135 monoesters such as amyl acetate, benzyl acetate, benzyl benzoate, butyl acetate, ethyl acetate, ethyl propionate, ethyl lactate, isobutyl acetate, isopropyl acetate, n-butyl propionate, n- propionate pentyl, n-propyl acetate, n-propyl propionate, butyl lactate, C1-4 alkyl esters of C6-22 saturated or unsaturated carboxylic acids, such as C6-14 unsaturated fatty acid methyl ester, fatty acid glycerol ester, including derivatives of vegetable oils such as flaxseed, coconut, palm, soy, cotton, peanut, sunflower, rapeseed, sesame, olive, corn, safflower, palm kernel, castor oil, peanut, fish, lard, mustard seed, poppy seed , turpentine and tall oil and ethyl 3ethoxypropionate (commercially available as UCAR ™ EEP Ester from Dow Chemical Co.);
dibasic esters such as dimethyl adipate, dimethyl succinate, dimethyl glutarate, dimethyl malonate, diethyl adipate, diethyl succinate, diethyl glutarate, dibutyl succinate, dibutyl glutarate and products available under the trade names DBE ™, DBE- Invista 3, DBE4, DBE-5, 6-DBE, DBE-9, DBE-IB and DBE-ME;
alkoxylated aromatic alcohols described in US Patent No. 7179775, in particular alkoxylated aromatic alcohols containing at least one aromatic ring per molecule and alkoxylated units of the general formula - (CR ¹ -R ³ CR ² R ⁴ -O) _n R ⁵ where: R ¹ , R ² , R ³ and R ⁴ are independently hydrogen or methyl; R ⁵ is hydrogen, C 1-6 alkyl or phenyl; and n is 2-10, where the alkoxylated units are attached to the aromatic ring directly or through an ether (oxygen) or an (-CHR ⁸ O-) oxymethylene bond, where R ⁸ is hydrogen or C1-4 alkyl. A combination comprising one or more of the aforementioned cosolvents can be used.
[0092] In one embodiment, the cosolvent is NMP.
[0093] The ratio between ketal adducts of formula (1), specifically (1a) and the cosolvent can vary widely depending on the ketal adducts of formula (1), the cosolvent and the intended use and can be 1:99
42/135 to 99: 1, specifically from 10:90 to 90:10, more specifically from 20:80 to 80:20, from 30:70 to 70:30 or from 40:60 to 60:40, all in volume .
[0094] It is understood that a single additive may have more than one function and that the characterization of an additive as having that function (for example, as a cosolvent) does not exclude the additive from performing another function. The concentrations of the individual additives in the cleaning compositions may vary depending on the components of the cleaning composition, the type of material to be removed and the rate at which the material removal is to be carried out. Optimal concentrations for a specific application can easily be determined by one skilled in the art using standard experimental methods and the guidelines set out below.
[0095] Organic amine accelerators may include those listed above as cosolvents. Accelerators are believed to enhance the performance of the composition by chemically attacking the organic binder of a coating and thereby weakening the adhesion and cohesion of the coating. Exemplary amine accelerators include ethanolamine, diethanolamine, ethylene diaminetetraacetic acid, morpholine, triethanolamine, triethylamine and 2- (N, N'-diethylamine) ethanol). When used as an additive, the amine accelerator can be present in an amount of 0.1 to 20% by weight or from 1 to 10% by weight, although these amounts are merely illustrative.
[0096] Exemplary organic acid accelerators include carboxylic acids 01-22 (eg, formic acid, acetic acid, propionic acid, oleic acid, oxalic acid and hydroxyacetic acid). When used as an additive, the organic acid accelerator can be present in an amount of 0.1 to 20% by weight or from 1 to 10% by weight, although these amounts are merely illustrative.
[0097] Corrosion inhibitors may be present, particularly, where the composition is supplied in a metal container or when an acid accelerator is present. Inhibitors of
43/135 corrosion can be, for example, a molecule that has an oil-soluble part and a water-soluble part, such as an amphoteric surfactant that contains an amine functionality in an amount of about 0.05% to about 2 % by weight, specifically about 0.25% to about 1.0%, as disodium N-lauryl immunodipropionate esters available as DERIPHAT® amphoteric surfactants from Cognis Corporation. Other corrosion inhibitors include fatty acid amine soaps and fatty alkanolamides, such as C ₈ to C ₁₈ fatty alkanolamides, examples of which include STAND AMID® alkanolamides available from Cognis Corporation. These corrosion inhibitors can also be used for anti-corrosion effects after application on surfaces that will rust or corrode due to the presence of water in the cleaning compositions, such as metallic surfaces, such as iron, steel and the like.
[0098] Cleaning compositions may also contain an effective amount of odor-masking agents, such as essential oils, aromatic chemicals, perfumes and the like, for example, gray amber, borneol and its esters, carvone, castoro, algalde, cinnamaldehyde , citrus, clove oil, galbanum, jasmine, limonene, linalool and its esters, pinenes (alphas, betas, etc.), rosemary oil, sandalwood, terpineols, terpinenes and the like, benzaldehyde, benzoin, isoamyl acetate (banana); isobutyl propionate (rum); methyl anthranilate (grape); benzyl acetate (peach), dipentene, methyl butyrate (apple); ethyl butyrate (pineapple); octyl acetate (orange); n-propyl acetate (pear); phenylethyl acetate (honey) and the like. An effective amount of such odor-masking agents will be readily determinable by those skilled in the art, for example, from about 0.25% to about 2.50% by weight, the removal composition specifically about 0.4% to about 1.0%.
Exemplary plasticizers include phthalate esters, for example, dibutyl phthalate, diethylhexyl phthalate and diethyl phthalate; aliphatic diesters, for example dioctyl adipate; terephthalate esters, for
44/135 example, dioctyl terephthalate; citrate esters, for example, triethyl acetyl citrate and tri-n-butyl acetyl citrate; plasticizers based on ketal such as those described in PCT Application WO 2010/151558 or a combination comprising at least one of the aforementioned items. When used, the plasticizer is present in an amount of about 0.1 to about 10% by weight based on the total weight of the removal composition.
[0100] A wide variety of surfactants can be used, depending on the application, and they can be amphoteric, anionic, cationic, non-ionic or zwitterionic. A surfactant or a combination of surfactants may be present in order to improve the wetting of the dirt or coating to be removed and to accelerate the penetration of the active components. In addition, a surfactant can facilitate washing with water and cleaning the substrate with water after removing dirt or coating. Exemplary amphoteric surfactants include amine oxide compounds with the formula RR'RN—> 0 where each R, R 'and R is independently an alkyl, aryl or arylalkyl group (C-iC24) which can optionally contain one or more heteroatoms P , O, S or N. Exemplary amphoteric surfactants also include betaine compounds of the formula ΡΡΉΝ ⁺ (ΟΗ ₂ ) _η Ο (Ο) Ο where each R, R 'and R is independently an alkyl, aryl or arylalkyl group 0) - 024) which can optionally contain one or more heteroatoms P, O, S or N and n is about 1 to 10. A combination comprising at least one of the above items can be used.
[0101] Exemplary anionic surfactants include water-soluble salts of alkylbenzene sulfonates as the isopropylamine salt of a C ₁₀ -4 alkyl alkyl sulfonic acid and / or a Ce-14 fatty alcohol sulfate> alkyl sulfates, sulfates of polyethylene alkyl ether, paraffin sulfonates, alpha-olefin sulfonates and sulfosuccinates, alpha-olefin sulfocarboxylates and their esters, alkyl glyceryl ether sulphonates, fatty acid monoglyceride sulphates, polyethoxy ether alkyl sulphates, salts
45/135 water soluble or esters of alpha-suifonated fatty acids that contain about 6 to 20 carbon atoms in the fatty acid group and about 1 to 10 carbon atoms in the ester group and the like. When present, the anionic surfactant may be present in the composition in an amount of about 0.1 to about 15% by weight, from about 3 to 12% by weight and more specifically from about 5 to about 10% by weight weight based on the weight of the composition. A combination comprising at least one of the previous items can be used.
[0102] In addition, instead of an anionic surfactant, a short chain surfactant may be present, for example, alcohols, glycols and ethers of C ₃ -C ₆ glycol such as propylene glycol n-butyl ether, pyrrolidones, esters of glycolic ether and the like. A combination comprising at least one of the previous items can be used.
[0103] Exemplary cationic surfactants include quaternary amine compounds with the formula RR'RR'N ⁺ X where R, R ', R and R' are independently a C-1-C24 alkyl, aryl or arylalkyl group) that may contain , optionally, one or more heteroatoms P, O, S or N, and X is F, Cl, Br, I or an alkyl sulfate. A combination comprising at least one of the previous items can be used.
[0104] Exemplary non-ionic surfactants include alcohol ethoxylates (eg C ₆ -C ₂₄ or C ₆ -C ₁₆ alcohol ethoxylates) having 1 to about 20 ethylene oxide groups (for example, about 9 to about 20 ethylene oxide groups), alkylphenol ethoxylates (eg, C ₆ -C ₂₄ or C ₈ -C ₁₀ alkylphenol ethoxylates) with 1 to about 100 ethylene oxide groups (for example, about 12 to about 20 ethylene oxide groups), alkyl polyglycosides (for example, C ₆ -C ₂₄ alkyl or C ₆ -C ₂₀ alkyl _{polyglycosides} ) with 1 to about 20 glycoside groups (for example, about 9 to about glycoside groups). A combination comprising at least one of the previous items can be used.
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[0105] As a general guide, the amount of surfactant can be about 0.1 to about 20%, about 0.1 to about 15% or about 2 to about 15% of the total weight of the composition cleaning.
[0106] In one embodiment, the disclosure includes a composition comprising a surfactant described above and the ketal adducts of formula (1), specifically (1a). In these modalities, the ratio between the surfactant and the ketal adducts of formula (1), specifically (1a), can vary from 50: 1 to 1:50, preferably 20: 1 to 1:10. These compositions can be prepared as intermediates for use in final formulations, such as for cleaning products.
[0107] Thickeners may be present to adjust the rheological properties of the cleaning compositions. For example, the removal of partially dry paint from automotive paint booths is usually accomplished by spraying a cleaning composition as a paint remover in the paint booth. The coating remover should be thin enough to spray easily, but it should quickly build up in viscosity in low-shear conditions to effectively adhere to vertical surfaces. A higher viscosity formulation is generally desired if the coating remover is painted while a low viscosity formulation that does not contain any added thickeners can be used where the coated substrate is soaked in a tank. Thickeners can also serve to increase the effectiveness of coating removers by decreasing the rate of evaporation of volatile components after application to a coated substrate. The use of a thickener in the composition allows the composition to be applied to vertical surfaces without any dripping or inherent flow and also inhibits the dissipation of the composition on porous substrates such as brick or concrete.
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[0108] Exemplary thickeners are natural or synthetic clays including bentonite, hectorite, smectite and other silicates such as available grades of BENTOLITE ™, CLAYTONE ™ and GELWHITE ™ bentonites, PERMON ™ smectites, CLOISITE ™ magnesium aluminum silicates, LAPONITE ™ silicates and GARAMITE ™ silicates (all available from Southern Clay Products, Inc.) and available grades of OPTIGEL ™ bentonites, hectorites, smectites and other clays (all from the Sued Chemie Group); stearates of clay compounds such as tetraalkyl ammonium bentonite; gums and other polysaccharides such as carrageenan gum (eg, GENUVISCO ™ X-906-02 (from CP Kelco)), cassia gum, diutane gum (eg, GEOVIS ™ XT, KELCO-CRETE ™ 80, KELCOCRETE 200 and KOC617 (all from CP Kelco)), gelano (for example, KELCOGEL ™, KELCOGEL F and KELCOGEL LT 100 (all from CP Kelco)), guar gum, arabic gum, tragacanth gum, locust bean gum, whelan gum and xanthan gum (by example, KELZAN ™, KELZAN AR, KELZAN ASX, KELZAN ASX T, KELZAN CC, KELZAN HP, KELZAN RD, KELZAN S, KELZAN ST, KELZAN T, KELTROL ™, KELTROL T and KELTROL TF (all from CP Kelco) and VANZAN ™ and VANZAN D (both from RT Vanderbilt co.)); hydrocolloids such as NOVEGUM ™ C865, NOVEGUM C866 and NOVEGUM G888 (all from Noveon, Inc); alginates such as agar; cellulose ethers such as ethylcellulose, hydroxyethylcellulose, hydroxyethyl ethylcellulose, methylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose and other commercially available alkyl or hydroxyalkyl cellulose ethers, for example, as METHOCEL ™ K15MDGSE, METHOCEL K4MELGH, METHOCEL K4MELG from Dow), cellulose ether XDS 8898.5 (from Dow) and KLUCEL ™ H, KLUCEL M or KLUCEL G (all from Ashland Inc.); acrylic acid homopolymers or copolymers, for example, those that can be neutralized with a salt that includes associative or non-associative thickeners such as acrylate polymers ACUSOL ™ 801s, ACUSOL 810, ACUSOL 810A, ACUSOL 820, ACUSOL
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823 and ACUSOL 830 (all from Rohm & Haas Co.) or those that can be cross-linked (for example, with a polyalkenyl polyether) including CARBOPOL ™ 674, CARBOPOL 676, CARBOPOL ETD 2691, CARBOPOL ETD 2623, CARBOPOL EZ-3, CARBOPOL EZ-3A, CARBOPOL EZ-4 and CARBOPOL ULTREZ ™ 21 (all from Noveon, Inc); PEMULEN ™ 1622 copolymer (from Noveon, Inc); polyethylene oxides (for example, high molecular weight polyethylene oxides) such as polyethylene glycols and methoxypolyethylene glycols; polyvinyl alcohols; polyvinylpyrrolidone; starches; polyurethanes including RHEOLATE ™ 266 (from Elementis Specialties, Inc.) and available grades of OPTIFLO ™ associative thickeners (all available from Sud-Chemie Group); and methyl vinyl ether / maleic anhydride copolymers. Other possible thickeners include hydrophobic modified ethoxy urethane thickeners (HEUR), hydrophobic modified alkaline soluble emulsion thickeners (HASE), hydrophobic modified hydroxyethylcellulose thickeners (HMHEC) and HEUR-ASE thickeners combined. A combination comprising at least one of the previous items can be used.
[0109] The thickener can be used in an amount of about 0.1 to about 30% by weight, specifically from about 2 to about 20% by weight and more specifically from about 3 to about 10% by weight. weight based on the total weight of the cleaning composition.
[0110] A detergent builder is commonly present in laundry detergents, hard surface cleaners and dishwashing liquids and may be present in cleaning compositions in this disclosure. Examples of such builders include Ndiethylene glycol-N, N-diacetic acid (DID A) polyphosphates (eg potassium pyrophosphate), nitrilotriacetates (eg Na ₃ NTA), tetraacetic ethylenediamine acid (EDTA), sodium etienethiaminentaacetate, sodium citrate, sodium carbonate, sodium metasilicate and zeolites, for example, zeolites with a cation exchange capacity (measured as CaCO ₃ ) of 200 mg or more
49/135 per gram of zeóiite. Enzymes such as proteases and amylases are also frequently present in cleanser compositions, especially laundry detergent and prewash products.
[0111] The cleaning composition may contain a bleach such as sodium hypochlorite, sodium perborate, diperoxidodecanedioic acid, sodium dichloroisocyanurate, m-chloroperoxybenzoic acid and peroxide-based bleaches. An advantage of this disclosure is that alkyl ketal esters are stable in bleach solutions and, thus, can add good solvency to oily dirt in a bleach containing composition. A bleach-containing composition of the disclosure can also contain one or more bleach activators such as tetra acetyl ethylene diamine and sodium nonanoyloxybenzene sulfonate.
[0112] The cleaning composition may also contain one or more agents that suspend subject such as sodium carboxymethyl cellulose; one or more bleach stabilizers such as sodium diethylenetriamine-pentamethylenophosphonate and sodium diethyl enetriaminopentaacetate; one or more hydrotropes such as sodium toluene sulfonate, cumene sodium sulfonate and potassium xylene sulfonate; one or more fabric softening ingredients such as smectite clay and tallow-dimethyl-ammonium chloride.
[0113] In a specific embodiment, the cleaning composition is a liquid laundry detergent that can be hand or machine washed and that comprises 50 to 95% by weight of water; 0.1 to 25% by weight of ketal adducts of formula (1), specifically (1a); 0.1 to 45% by weight of a surfactant; and a builder, a chelating agent, a chlorine bleach, a chlorine-free bleach, abrasives, an abrasive, an anti-deposit agent, a bleaching agent or a combination comprising at least one of the preceding items. In liquid clothing products, the ketal adducts of formula (1), specifically (1a), can perform any or all of the various functions, such as solubilization or
50/135 emulsification of surfactant or other ingredients and acting as an active cleaning agent.
[0114] For example, a liquid formulation for clothing may contain, in percentage of the total formulation weight: a) water: 50-95; b) ketal adducts of formula (1), specifically (1a): 0.1-50, more typically 1-25%, specifically 1-10%; c) one or more surfactants: 0.1-45%, specifically, 1-40%, more specifically, 1-35%, even more specifically 1-10%, but in some cases, more specifically, 15-35%; where the surfactants are advantageously (1) at least one anionic surfactant, (2) a nonionic surfactant, (3) a mixture of at least one nonionic surfactant and at least one anionic surfactant, (4) one or more an β alkyl glycoside, alkyl betaine or a sulfosuccinate salt or (5) a mixture of (4) with (1), (2) or (3); h) one or more builders or chelating agents, particularly a chelating agent such as EDTA or DIDA: 0-30%, specifically, if present, 0.130%, more specifically, if present, from 1 to 25% and even more specifically, if present , 1-10%; i) one or more bleaches including, for example, a chlorine bleach such as sodium hypochlorite or a chlorine-free bleach: 0-10%, specifically, if present, 0.1-5%; o) one or more abrasive products: 0-30%, specifically if present 1-20% p) one or more anti-redeposition additives, such as carboxymethyl cellulose salts and polymeric cellulose acetate agents, 0-5%, specifically if present 0.1 to 2%; eq) brightening agents, including optical brightening agents, fluorescent brightening agents and fluorescent bleaching agents including, for example, sulfonated triazine-stilbenes, coumarins, imidazolines, diazoles, triazoles, benzoxazolines and stybene biphenyls, 0-3, specifically if present 0.1 to 1.
[0115] In addition, a liquid clothing product may contain any optional component for the cleaning compositions described in this document, alone or in any combination of two or
51/135 more. Any or all of the optional components can be omitted in any specific liquid clothing formulation.
[0116] Here are some liquid formulations for exemplary clothing in accordance with the disclosure. The percentages indicated are percentages by weight based on the total weight of the formulation. The function of these ketal adducts of formula (1), specifically (1a), in liquid laundry formulations is similar to those described above with respect to the hard surface cleaners set out below.
Amount
Sodium hydroxideSodium chlorideNonionic surfactant (eg ethoxylated alcohol)Anionic surfactant (eg, benzenesulfonic acid, alkylated)BuildersAnti-redeposition agentProteolytic enzymesWhitener (fluorescent agent) Buffers 0-1% Ketal adducts of formula (1), specifically (1a) Water (balance of total formulation) 0-1%about 1%0-20, specifically 0.1-6% 1-20, specifically 1-10%0-10%0-1%0-2%0-5%0.1-80% Aqueous Stain Remover for Clothes Amount Protein enzymeSurfactantChelating agentKetal adducts of formula (1), specifically (1a) Water (balance of total formulation) 0- <1% 10-20% 0.5-1.5% 0.1-80% Aqueous Dry Cleaning Composition Amount Water Polyacrylates Mixed glycolic esters Ketal adducts of the formula (1), specifically (1a) Surfactant (s) 1,2-Octaenediol 60-95%0.2-0.5%0-30%0.1-80%<0.1% 0-5%
[0117] Any liquid formulations for the aforementioned laundry clothes can be prepared in a concentrated manner, reducing the amount of water and, correspondingly, increasing the concentration of at least the surfactant and advantageously the concentration of the ketal adducts of the formula (1), specifically (1a), and the surfactant. This formulation of the concentrated hard surface cleaner may contain,
52/135 by weight, up to 50% combined with water and / or volatile organic compound and, more typically, contains no more than 40%. This concentrated formulation often contains 5 to 70% or 10 to 50% by weight of at least one ketal adduct of formula (1), specifically (1a), as described in this document and from 5 to 90%, 5 to 70%, or 10 to 50% by weight of at least one surfactant.
[0118] In another specific embodiment, the cleaning composition is a hard surface cleaner with a general formulation known in the art and which can be formulated for industrial, institutional, office or domestic use. It can be formulated as, for example, general purpose hard surface cleaners, bathroom cleaners, disinfectant shower / bath / tile cleaners, soap foam removers, mold removers, glass / mirror cleaners or stain removers. Many of these cleaners are formulated as diluted solutions or emulsions and many are applied by spraying. A hard surface cleaner can include at least 20% by weight, at least 50% by weight or as much as 99% by weight of water; up to 50% by weight, 0.1% by weight to 50% by weight, 1% by weight to 25% by weight, 3% by weight to 15% by weight, or 1% by weight to 10% by weight of adducts ketal of formula (1), specifically (1a); and 0.01-40% by weight of a surfactant, in particular an anionic or nonionic surfactant, each of which is based on the total weight of the composition. The ketal adducts of formula (1), specifically (1a), can perform any or all of the various functions, such as (1) dissolving and / or removing dirt; (2) compatibility of ingredients, particularly moderately water-soluble ingredients; (3) formation of a co-solvent mixture in which one or other ingredients are dissolved or dispersed, (4) elimination or reduction of surfactants and / or organic or other solvents. The surfactant can include one or more materials
53/135 derived from plant sources, such as one or more alkyl glycosides, alkyl betaine or a sulfosuccinate salt.
[0119] In specific embodiments, a hard surface cleaner formulation may comprise, as percentages of the total formulation weight: a) water: 20-99%, more typically 50-95%; b) one or more ketal adducts of formula (1), specifically (1a): 1-50, more typically 1-25% or 1-10; c) one or more surfactants: 0.01-20, specifically, 0.115, more specifically 0.25-10, even more specifically 1-7% and, in some cases, 1-5; with surfactants being specifically (1) at least one anionic surfactant, (2) at least one nonionic surfactant, (3) a mixture of at least one nonionic surfactant and at least one anionic surfactant or nonionic surfactant , (4) one or more alpha, beta alkyl glycosides, alkyl betaine or a sulfosuccinate salt or (4) a mixture of (4) with (1), (2) or (3).
[0120] The formulation may also comprise d) one or more propellants which are generally hydrocarbons such as low boiling point such as butane, pentane, hexane and cyclohexane or dormant and / or fluorinated hydrocarbons having boiling temperatures of -10 C to 50 ° C; e) one or more water-miscible organic solvents in moderation: generally 0-10, specifically, if present, 0.1-5%. It can be, for example, one or more long-chain alcohols, glycolic ethers, hydrocarbons, halogenated hydrocarbons, aromatic Οβ-9 alkyl compounds, olefins, terpenes, terpene oxides, terpenoids, oils and natural oil derivatives. The formulation may also comprise f) one or more highly water-miscible organic solvents, such as a lower alcohol (eg, ethanol and 1-propanol), acetone, glycols and glycolic ethers: 0-10, specifically, if present, 0, 1-5; g) one or more antimicrobial agents, 0-5, specifically, if present, 0.1-2, some examples include quaternary ammonium chlorides such as C-12-16 alkyl dimethyl benzyl ammonium chloride and various phenylphenol compounds; h) one or more
54/135 builders or queuing agents, particularly a queuing agent such as a phosphate salt, a citrate salt, EDTA or DIDA: 0-30%, specifically, if present, 0.05-10% and more specifically, if present, from 0.5 to 1%, even more specifically, if present, from 2-8% and even more specifically, if present, from 2-6; i) one or more bleaches including, for example, a chlorine bleach such as sodium hypochlorite or a chlorine-free bleach such as hydrogen peroxide or other peroxy compound: 0-10%, specifically, if present, 0.1-5%; j) one or more pH controlling agents (for example, acids, bases, pH buffers): 0-2%, if specifically present 0.05 to 1%; k) one or more dyes: 05%, specifically if present 0.1-2%; I) one or more water-soluble inorganic salts such as sodium sulfate: 0-10%, specifically if 0.1-5% is present; m) one or more viscosity thickeners including, for example, a water-soluble polymer: 0-10%, specifically if 0.1-5% is present; n) one or more proteolytic enzymes, 0-5%: specifically if present 0.1-1% o) one or more abrasive products; and p) one or more fragrances. The components b) and d) -p) described above can be present in any combination of two or more. Any or all of the components e) - n) can be omitted in any particular hard surface cleaner formulation. Component d) is typically present in a spray cleaner formulation. It has been noted earlier that in some cases, a single material can perform several functions in a hard cleaner formulation. Component j) is often present to provide pH 3.5 or higher, specifically 6 to 10.
[0121] A method of preparing a cleaning composition comprises a combination of the ketal adducts of formula (1), specifically (1a), and any cosolvent or other component to form the cleaning composition. The order of addition is not particularly limited. The ketal adducts of formula (1), specifically (1a), and additives
55/135 can be added in any order appropriate to the additional components present in the composition to provide the cleaning composition.
[0122] When used with cosolvents or other components, cleaning compositions can be supplied as a concentrate. Concentrates are generally diluted with water for use as a functional water-based cleaning composition. In one embodiment, a two-part concentrate package can be provided, which normally comprises Part A and Part B, where each part contains a component susceptible to react with the other part, for example, the ketal and a amine in Part A and an inorganic base in Part B.
[0123] The cleaning compositions can alternatively be formulated in other forms useful for removal or cleaning compositions, for example, gels, wipes, aerosols and the like. Removal compositions can be formulated as a gel by adding an effective amount of a gelling agent such as pyrogenic silica, organic gums, polymers, copolymers, paraffin wax, bentonite clay and commercially available cellulose ethers such as methylcellulose and hydroxypropylmethylcellulose such as METHOCEL® cellulose ethers, from Dow Chemical. The wipes are usually a piece of natural or synthetic fabric impregnated with the liquid or gel removal composition. When used as an aerosol, cleaning formulations are formulated under pressure with a propellant known in the art.
[0124] A cleaning method, for example, that removes a material such as a coating, dirt and / or stain from a substrate comprises contacting the material with a composition comprising ketal adducts of formula (1), specifically (1a) , under conditions that effect removal, for example, for an effective time to dissolve and / or lift the material; and separating the dissolved and / or lifted material from the substrate. As used in this document, the term dissolved includes the
56/135 partial dissolution of a material, often referred to as softening, so that the material can still be removed from the substrate by washing or mechanical action. Of course, the cleaning composition can also be at least partially removed by separating the material.
[0125] Cleaning compositions can be used to remove a wide variety of materials, usually those that are soluble or can be softened by organic solvents. Examples include materials such as dirt, stains, grease, dyes for all types of substrates, including paper, wood, plastic, metal, textiles, ceramics, stone, leather and for indoor or outdoor use; adhesives and sealants, for example, silicone, polyurethane, epoxy, polyvinyl acetate (including copolymers with ethylene), phenolic, amino resin, cyan acrylate, polyester, polyamide, rubber (styrene-butadiene and natural) or acrylic adhesives and sealants; mastics; photoresist; waxes, for example, floor wax, car wax or beeswax; asphalts; juices (those used in this document include tar, pitch, tar and natural resins such as tree sap); residual materials left in forms or molds, for example, polymers such as alkyds, polyacetals, polyacrylates, polyacrylics, polyamides, polycarbonates, polyesters, polyethers, polyethylenes, polyamides, polystyrenes, polyurethanes, polyvinyls, silicones, natural and synthetic rubbers and the like and additives polymer; greases, for example, silicone and petroleum-based greases; oils, including machine oil; and paints, finishes and other coatings, for example, alkyd enamels, acrylic enamels, polyesters, polyurethanes, epoxy resin coatings, latex paints, oil based paints, shellac, phenolic coatings, gum varnishes, silicone coatings, polyvinyls, polyvinyl cinnamates, polyamides, polyimides, polyalkyl acrylates, polyalkyl methacrylates, drying oils, polyvinyl acrylates and cellulosic resins.
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[0126] The substrates that are treated with the cleaning compositions are reasonably resistant to the cleaning compositions, including natural and synthetic fabrics, wood, cardboard and coated paper, especially if treated with a wax or other protective material, glass, thermoset resins, thermoplastic resins, ceramics, stone, masonry substrates, cement or metals (eg aluminum alloys, zinc alloys, stainless steel or galvanized steel). The cleaning compositions can also be used for a part of the human body, for example, hands or hair, as well as in animals.
[0127] Although methods of contacting the surface with the cleaning composition can be carried out in several ways, for example, in the form of an aerosol or other spray medium such as standard spray nozzles; brush application; diving; coating; gel application of a compress bottle or brush and the like, but dipping and spraying can be specifically mentioned. If the surface to be cleaned is readily accessible then spraying can be used. The spray pressure will generally be 1.3 bars to 8.0 bars of absolute pressure. The mechanical strength of the impact removal composition facilitates material removal. On the other hand, if the surface to be cleaned has recesses or other shapes that are not easily accessible, immersion can be used. Obviously, the two methods can be used in combination and / or varied in apparent ways to those skilled in the art. During or after contact, mechanical action, such as scraping, peeling, friction, cleaning and the like, can be used to increase contact and / or assist in dissolution and / or lifting.
[0128] The contact time required to produce an effective degree of dissolution and / or lifting of the material from a surface will depend on the nature and thickness of the material, the composition of the cleaning composition, including ingredient concentrations, temperature of the
58/135 composition and other factors. With some materials and under some conditions, contact times from a few minutes (eg 2-3 minutes) to an hour may be sufficient. The operating temperature when using the removal compositions can be 0 to 180 ° C or higher, specifically 15 to 90 ° C or 21 to 55 ° C. The treatment is most conveniently carried out at room temperature, but the lifting time can be reduced as desired by heating the cleaning compositions and / or substrate. Heating can be achieved by applying local heat, such as with a heat gun, or a more general application of heat, such as with an electric heater, infrared heater and the like. It is understood, however, that those skilled in the art can determine ideal conditions for particular removal applications by minimal experimentation. Higher temperatures generally increase the rate at which material is removed from the surface.
[0129] The separation of ketal adducts from formula (1), specifically (1a), and the dissolved material from the substrate may include mechanical action such as scraping, flaking, friction, cleaning and the like, or washing the substrate with removal composition additional or other solvent, including mixing water or aqueous water with an organic solvent.
[0130] The ketal adducts of formula (1), specifically (1a), are also useful in perfume and flavoring formulations (hereinafter referred to together as fragrance compositions). Ketal adducts (1) offer a combination of properties that make them useful in a wide variety of fragrance compositions. In particular, ketal adducts (1) have low volatility. Under normal conditions of manufacture, storage and use, they are not reactive with many other materials that are commonly found in fragrance compositions or in formulations in which fragrance compositions are used.
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Another advantage is that cetai (1) adducts are stable under basic conditions. In addition, certain adducts of cetai (1) can be derived from biological raw materials. Thus, ketone adducts (1) can be advantageously used both as solvents as well as fixatives in fragrance compositions. Efforts continue to be made to find improvements in the performance of fragrance compositions, including the life of the product, its delivery effectiveness and its longevity or substantivity on various substrates. For example, during use, a substantial amount of perfume in a cleaning product is lost with the rinse water or during drying. It is desirable to have the ability to overcome these process conditions and to ensure that the perfume material left on the substrate provides a maximum odor effect for the minimum amount of material. In one embodiment, cetai adducts (1) can effectively function as a fragrance fixative, prolonging the effect of the fragrance composition and thus extending the life of the fragrance. In another modality, adducts (1) can work effectively to make fragrance composition compatible with waxes.
[0131] The fragrance composition comprises at least one fragrance compound (also referred to herein as a fragrance molecule). The fragrance molecule is also called an aromatic compound. The fragrance molecule can be a naturally occurring molecule or a synthetic molecule (for example, a molecule that is synthesized in a laboratory from ingredients that are not naturally occurring). Naturally occurring molecules are those that derive, directly or indirectly, from living beings (for example, animals, plants, fruits, flowers and the like). Naturally occurring molecules include products of naturally occurring molecules and synthetic molecules. Fragrance molecules can be found in food, wine, spices, perfumes, scented oils and essential oils. For example,
60/135 many are formed biochemically during the ripening of fruits and other crops. In wines, most form as by-products of fermentation.
[0132] Naturally occurring molecules include essential oils derived from plants. Essential oils are concentrated hydrophobic liquids that contain volatile fragrance molecules from plants. Essential oils are also known as ethereal, volatile oils or simply as the oil from the plant from which it was extracted, such as clove oil. An oil is essential in the sense that it has a distinctive plant scent or essence. Essential oils do not have the specific chemical properties in common other than imparting characteristic fragrances. Some essential oils like lavender, mint and eucalyptus are distilled by steam. The vegetable raw material comprising flowers, leaves, wood, bark, roots, seeds or skin is placed in a distillation apparatus over water. As the water is heated, the steam passes through the plant material, vaporizing the volatile compounds. The vapors flow through a coil where they condense into the liquid, which is then collected in the receiving vessel.
[0133] Essential oils are derived from berries, allspice, juniper, seeds, almond, anise, celery, cumin, nutmeg oil, bark, cassia, cinnamon, sassafras, wood, camphor, cedar, paurosa, sandalwood, agarwood , rhizome, galangal, ginger, leaves, basil, bay leaf, cinnamon, common sage, eucalyptus, lemongrass, melaleuca, oregano, patchouli, mint, pine, rosemary, mint, tea tree, thyme, wintergreen, resin, frankincense, myrrh, flowers, cannabis, chamomile, sage, cloves, fragrant geranium, hops, hyssop, jasmine, lavender, manuka, marjoram, rose, rosemary, basil, lemongrass, blood-brain, skin, bergamot, grapefruit, lemon , lime, orange, tangerine, root, valerian, mango or similar
61/135 or a combination comprising at least one of the items previously exposed.
[0134] Examples of fragrance molecules are alcohols (eg furaneol (strawberry), 1-hexanol (herbaceous, woody), cis-3hexen-1-ol (fresh cut grass), menthol (mint), or the like or a combination comprising at least one of the aforementioned alcohols); aldehydes (eg, acetaldehyde (pungent), hexanal (grassy, green), cis-3-hexenal (green tomatoes), furfural (burnt oats) or the like or a combination comprising at least one of the above aldehydes); esters (eg fructon (fruit, similar to apple), hexyl acetate (apple, floral, fruity), methylphenylglycidate (strawberry) methyl formate, methyl acetate, methyl butyrate, methyl butanoate, ethyl acetate, butyrate ethyl, ethyl butanoate, isoamyl acetate, pentyl butyrate, pentyl butanoate, pentyl pentanoate, benzoin (extracted from benjoeiro resin); black pepper (from the piper nigrum plant of the piperaceae family), cajepute oil (from the cajuputi melaleuca) , caraway, carrot seeds, coriander, cypress, dill, fennel, helichyrsum, lavandin, lemon verena, lemon balm (essential oil extracted from lemongrass extracted from melissa officinalis of the labiatae family), niaouli, palmarosa, petitgrain, tagetes, vetiver or the like or a combination comprising at least one of the preceding esters); ketones (eg, dihydrojasmone (floral woody fruity), oct-1-in-3-one (similar to bloody metallic mushroom), 2-acetyl-1-pyrroline (fresh bread, jasmine rice), 6-acetyl2,3 , 4,5-tetrahydropyridine (fresh bread, tortillas, popcorn), or the like or a combination comprising at least one of the preceding ketones); lactones (γ-decalactone (intense peach flavor), γ-nonalactone (coconut odor, popular in tanning products), δ-octalactone (creamy note, jasmine lactone peach and fruity, greasy and potent apricot) massoia lactona (powerful creamy coconut, lactona wine sweet coconut odor) sotolon (maple syrup, curry, fenugreek), or similar or a combination that
62/135 comprises at least one of the preceding lactones); thiols (etanetiol (commonly called ethyl mercaptan) mercaptan from grapefruit (grapefruit), methanethiol (commonly called methyl mercaptan), 2-methyl-2-propanethiol (commonly called tertiary butyl mercaptan)); linear terpenes (for example, mircene (woody, complex), geraniol (pink, flowery) nerol (sweet, flowery), citral, limonal, geranial, neral (lemon, lemon myrtle, lemongrass), citronellal (lemon, herb) lemongrass), citronelol (lemon, lemongrass, rose, pelargonium), linalool (floral, sweet, woody, lavender), nerolidol (woody, fresh bark), or similar or a combination comprising at least one of the previous linear terpenes; cyclic terpenes (for example, limonene, camphor, terpineol, ionone, thujuon or the like, or a combination comprising at least one of the preceding cyclic terpenes); aromatic species (for example, benzaldehyde, eugenol, cinnamaldehyde, ethyl maltol, vanillin, anisol , anethole, estragol, thymol or the like or a combination comprising at least one of the preceding aromatic species); amines (for example, thiethylamine, trimethylamine, cadaverine, pyridine, indole, eschatol or similar or a combination comprising at least one of the a preceding mines) or the like, or a combination comprising at least one of the preceding fragrance molecules.
[0135] Additional examples of fragrance molecules are geraniol, geranyl acetate, linalool, linalyl acetate, tetrahydrolinalol, citronelol, citronyl acetate, dihydromyrcenol, dihydromyrcenyl acetate, tetrahydromyrcenol, terpineol acetate, terpenyl acetate, terpenyl acetate, terpenyl acetate, terpenyl acetate nopil, 2-phenylethanol, 2-phenylethyl acetate, benzyl alcohol, benzyl acetate, benzyl salicylate, benzyl benzoate, styryl acetate, amyl salicylate, dimethylbenzyl carbinol, trichloromethylphenylcarbinyl acetate, p-tert-butyl acetate cyclohexyl, isononyl acetate, vetiveryl acetate, vetiverol, alpha-n-amylcinamic aldehyde, alpha-hexylcinamic aldehyde, 2-methyl-3- (p-tercbutylphenyl) -propanol, 2-methyl-3- (p-isopropylphenyl) - propanal, 3- (p-tert-butylphenyl)
63/135 propanal, tricyclodecenyl acetate, tricyclodecenyl propionate, 4- (4-hydroxy-4-methylpentyl) -3-cyclohexene, carbaldehyde, 4- (4-methyl-3-pentenyl) -3cyclohexene, 4-acetoxy-3-pentiletetrahydropyran , methyl-dihydrojasmonate, 2n-heptylcyclopentanone, 3-methyl-2-pentylcyclopentanone, n-decanal, 9decenol-1, phenoxyethyl isobutyrate, phenylacetaldehyde dimethyl acetal, phenylacetaldehyde diethyl acetal, cedanitrile, acetonitrile, citronitrile, citronitrile ether, isolongifolanone, aubepine nitrile, aubepine nitrile, aubepine, heliotropin, coumarin, eugenol, vanillin, diphenyl oxide, hydroxycitronal, ionones, methionones, isomethioniones, irones, cis-3-hexenol and their esters, musk, musk, musk isochroman musk, macrocyclic ketones, macrolactone musk, ethylene brassylate, aromatic nitro-musk.
[0136] Exemplary fragrance molecules include bergamot oil, coriander oil, dimethyl heptanol, dimethyl benzylcarbinyl acetate, geranyl acetate, citronyl acetate, synthetic rose, bourbon geranium, hedione, iso-eugenol, methyl acetate and sterile styrene, stemone, laevo pink oxide, undecyclic C-11 aldehyde, 2,6-dimethyl-2-alkoxy octan-7-ol derivatives, vertivert oil, vetiverol, vetiveryl, acetate, quaiac wood oil, esters anthranilic acid, benzyl salicylate, benzyl benzoate, oak moss, eugenol, p-tert-butyl cyclohexyl acetate and coumarin.
[0137] In one embodiment, an additional solvent can be used in the fragrance composition in addition to the ketal adducts of formula (1), specifically (1a). Polar solvents such as water, propylene carbonate, ethylene carbonate, butyrolactone, acetonitrile, benzonitrile, nitromethane, nitrobenzene, sulfolane, dimethylformamide, N-methylpyrrolidone, glycolic ethers, methyl acetate, ethyl acetate, methanol, acetonitrile, nitromethane, nitromethane, propanol, isopropanol, butanol, benzyl alcohol, butoxyglycol, 1,2-propanediol (propylene glycol), 1,3-propanediol, ethoxyiglycol, hexylene glycol and dipropylene glycol, triethylene glycol, hexylene glycol,
64/135 diethylene glycol, ethylene glycol, propylene glycol, 1,2-butylene glycol or the like or combinations comprising at least one of the foregoing solvents mentioned are generally desirable. Non-polar solvents such as benzene, toluene, methylene chloride, carbon tetrachloride, hexane, diethyl ether, hexane, tetrahydrofuran or the like, or combinations comprising at least one of the preceding non-polar solvents can also be used. Co-solvents comprising at least one polar solvent and at least one non-polar solvent can also be used to modify the compatibility capabilities of the solvent and thereby adjust the clarity and opacity characteristics of the fragrance composition. Exemplary solvents are methyl acetate, ethyl acetate, glycolic ethers and water. Glycolic ethers and alcohols can also be used to make the ketal adducts of formula (1), specifically (1a), compatible with water, if desired. Exemplary solvents are water and ethyl alcohol.
[0138] In one embodiment, the fragrance composition may optionally comprise a radical scavenger or a source of a radical scavenger. As used in this document, the term radical scavenger refers to a species that can react with a carbonate radical to convert the carbonate radical, through a series of rapid reactions, into a less reactive species, that is, a carbonate radical scavenger .
[0139] Radical scavengers can be selected from the classes of alkanolamines, amino sugars, amino acid esters and mixtures thereof. For example, the following compounds can be used as radical scavengers: ethylamine, monoethanolamine, 2-methoxyethylamine, 3-amino-1-propanol, 4-amino-1-butanol, 5-amino-1pentanol, 1-amino-2- propanol, 1-amino-2-butanol, 1-amino-2-pentanol, 1 amino-3- pentanol, 1-amino-4-pentanol, 3-amino-2-methylpropan-1-ol, 1 amino-2- methylpropan- 2-ol, 3-aminopropane-1,2-diol, glucosamine, N
65/135 acetiigiucosamine, glycine, arginine, lysine, proline, glutamine, histidine, sarcosine, serine, glutamic acid, tryptophan, morpholine, piperidine, or the like, or a combination comprising at least one of the previous radical scavengers.
[0140] The fragrance composition can optionally comprise a polymer. It is generally desirable that the polymer be soluble in the ketal adducts of formula (1), specifically (1a) and / or in the co-solvent used with the ketal adducts of formula (1), specifically (1a). In one embodiment, the polymer is soluble in water. In another embodiment, the polymer is not soluble in water and exists as a dispersion in the fragrance composition.
[0141] It is desirable that the polymer be an organic polymer. The polymer can be a thermoplastic polymer, thermoset, or a combination of a thermoset polymer with a thermoplastic polymer. In one embodiment, the polymer can be an oligomer, a homopolymer or a copolymer. The copolymer can be a block copolymer, a star block copolymer, a random copolymer, an alternative block copolymer, a dendrimer, an ion block copolymer, a polyelectrolyte, or the like, or a combination comprising at least one of the foregoing polymers .
[0142] Examples of polymers that are soluble in water are polyvinyl alcohol, polyacrylamides, polyvinylpyrrolidone, polyamides, hydroxyalkyl celluloses, such as hydroxyethylcellulose and hydroxypropylcellulose, polyacrylic acid, or the like, or a combination comprising at least one of the water-soluble polymers above.
[0143] Examples of polymers that are not soluble in water are polymethyl methacrylates, polyacrylates, polyesters, polyimides, polyethers, polyolefins, polyethercetones, polyether ether ketones, polyether ketone ketones, polycarbonates, polyether ethyl ethers, epoxides, polyoxyethersides, polyoxides, polyoxides , polynorbornylene, polysiloxanes, polyvinyl chlorides,
66/135 fluoropolymers, liquid crystalline polymers, ionomers, or the like, or combinations comprising at least one of the foregoing water-soluble polymers.
[0144] Polymers can be used as rheology modifiers, dispersants, stabilizers, promoters, or antimicrobials, and the like; in industrial product applications, such as textiles (processing, finishing, printing and coloring aids, washable protective surface coatings, manufacture of synthetic leather by saturation of non-woven fabrics, and the like; manufacture of fabrics, non-woven fabrics, fibers natural and synthetic and similar); water treatments (waste water, cooling water, drinking water purification, and the like); chemical spill arrestors (acid spill absorber, and the like); leather and skin processing (processing aids, finishing, coating, embossing, and the like); paper and papermaking (surface coatings, such as pigmented coatings, antistatic coatings, and the like, pulp binders, surface sizing, dry and wet strength enhancers, wet layer felting, and the like); printing (inks, jet printer inks with anti-capillary dye, thickeners for dye formulations containing cationic dyes to print acrylic fabrics, and the like); dyes (pigment and wear additive, crosslinking agent for epoxy latex emulsions, particulate suspension aid for clays, pigments, and the like); industrial plant effluent treatment (flocculants for phenolics in paper mill effluent, and the like); metal work (acid caustic cleaners, low pH metal coatings, pickling agents in cold rolled steel processing, and the like); adhesives (clear adhesives, adhesion promoters for metal, plastic, wood, and the like, non-woven float adhesive bond coatings, bonding, and the like); forest preservation; and
67/135 industrial construction products for buildings and roads (cement plasticizers, low pH asphalt emulsion stabilizers, acid caustic products for cement, concrete consistency modifiers, mortar, almond, and the like).
[0145] The polymer has an average molecular weight number of less than or equal to about 1,000,000 grams per mole, specifically less than or equal to 500,000 grams per mole, specifically less than or equal to about 50,000 grams per mole, and more specifically less than or equal to about 5,000 grams per mole.
[0146] Other additives can also be added to the fragrance composition to form a fragrance composition. These additives are optional. Suitable additives are antioxidants, antiozonants, antibacterial agents, humectants, colorants, dyes, pigments, food additives, pheromones, musks, a carbonate ion source, an alkalizing agent, a pH buffer, a conditioning agent, a chelator, an agent auxiliary, solvents (for example, a co-solvent), surfactants (such as cleaning agents, emulsifying agents, foam enhancers, hydrotropes, solubilizing agents and suspending agents), non-surfactant suspending agents, emulsifiers, hair conditioning agents ( emollients, humectants, moisturizers, and the like), hair conditioning agents, hair fixers, film-forming agents, skin protectors, binders, chelating agents, antimicrobial agents, antifungal agents, anti-dandruff agents, abrasives, adhesives, absorbents, dyes, deodorant agents , before antiperspirants, opacifying and pearlescent agents, preservatives, propellants, aids dispersing agents, sunscreen agents, skin tanning accelerators, ultraviolet light absorbers, pH adjusting agents, botanical products, hair dyes, oxidizing agents, reducing agents, skin lightening agents, pigments, agents
68/135 physiologically active, anti-inflammatory agents, topical anesthetics, fragrance and fragrance solubilizers, a polymer, and the like, in addition to the previously discussed ingredients that may not appear in this document. Oral care products, for example, may contain anti-caries, anti-tartar and / or anti-plaque agents, in addition to surfactants, abrasives, humectants, flavorings, or the like, or a combination comprising at least one of the above additives.
[0147] In one embodiment, in a method of manufacturing the fragrance composition, a fragrance composition, the ketal adducts of formula (1), especially (1a), as described above, an optional solvent, an optional active agent, an optional surfactant, an optional thickening agent, an optional compatibilizer and desired additives are mixed in the desired amounts in a reactor. The reactor can be a batch or continuous reactor. It is desirable for the reactor to be equipped with a mechanism for stirring the fragrance composition. The fragrance composition can be heated if desired to evaporate some of the solvent or to further guide the compatibility between the fragrance compositions, the ketal adducts of formula (1), specifically (1a) and the optional solvent.
[0148] In another embodiment, in another method of manufacturing the fragrance composition, the ketal adducts of formula (1), specifically (1a) can be used as an extraction solvent to extract a fragrance composition, such as essential oils of naturally occurring substances. The ketal adducts of formula (1), specifically (1a) can be maintained with the essential oil and further processed to form a desired fragrance composition. Essential oils can be extracted through steam extraction, supercritical extraction or solvent extraction. The ketal adducts of formula (1), specifically (1a) can be used in conjunction with steam, supercritical solvents, or normal solvents (solvents that do not
69/135 are in a supercritical state) to perform the extraction of essential oils. The ketal adducts of formula (1), specifically (1a) can also be used, in themselves, to extract essential oils.
[0149] Steam extraction is normally environment friendly and uses only water to perform the extraction. Water, however, is not a good solvent for all essential oils. The ketal adducts of formula (1), specifically (1a) can be used in conjunction with water to extract additional essential oil from a naturally occurring substance than would be extracted using only steam for extraction. The use of the ketal adducts of formula (1), specifically (1a) in steam extraction, would continue to produce the environment-friendly process, while at the same time it would be effective in extracting additional oil from the naturally occurring substance.
[0150] Supercritical extraction is usually carried out with carbon dioxide, but it can also be carried out with other solvents. A mixture of supercritical carbon dioxide and the ketal adducts of formula (1), specifically (1a), can be used to extract essential oils for the fragrance composition. Liquid carbon dioxide (which is not in a supercritical state) mixed with the ketal adducts of formula (1), specifically (1a), can also be used for extraction. Other supercritical fluids can also be mixed with the ketal adducts of formula (1), specifically (1a), to extract essential oils.
[0151] Hexane extraction is generally used to extract a variety of essential oils. The ketal adducts of formula (1), specifically (1a), can be mixed with hexane (or other solvents) to facilitate improved extraction. Ethanol is often used to direct the secretion of a target hexane molecule after extraction. In one embodiment, although the ketal adducts of formula (1), specifically (1a), are used to facilitate the extraction of an essential oil together with hexane, they can also be used to
70/135 facilitate a segregation of a moiécuia aivo from hexane. By changing the ratio of the quantity of ketal adducts of formula (1), specifically (1a), the mixture of the target molecule and hexane and / or temperature, the target molecule can be secreted after extraction. Other solvents can be used in conjunction with the ketal adducts of formula (1), especially (1a), to facilitate the segregation of the target molecule.
[0152] In yet another embodiment, the ketal adducts of formula (1), specifically (1a) itself, can be used to facilitate the extraction of various essential oils from naturally occurring substances. The ketal adducts of formula (1), specifically (1a), can be mixed with the naturally occurring substance and, under suitable combinations of temperature and pressure, can facilitate the extraction of an essential oil from the naturally occurring substance. The resulting product can then be subjected to purification processes, such as filtration, decantation, distillation, and the like, to obtain a purified mixture of the essential oil and the ketal adducts of formula (1), specifically (1a). The mixture of essential oil and ketal adducts of formula (1), specifically (1a), can then be mixed with other suitable ingredients to produce the desired fragrance composition. Thus, the ketal adducts of formula (1), specifically (1a), can be used not only to extract the essential oil, but can serve as a solubilizing solvent and / or a fixative in the fragrance composition.
[0153] The mixture to form the fragrance composition or the fragrance composition can be carried out by dry mixing, melting mixing, mixing in solution, or a combination comprising at least one of the above forms of mixing. The dry mix encompasses the mixture without the use of solvents and is generally conducted to mix two or more fragrance compositions. Fusion mixing occurs when the mixing temperature is conducted
71/135 above the melting point of some of the ingredients and the wet mixing is generally conducted in the presence of solvents.
[0154] Mixing the formulation involves the use of shear form, stretching force, compressive force, ultrasonic energy, electromagnetic energy, thermal energy or combinations comprising at least one of the previous forces or energy forms and is conducted in the processing equipment , where the forces mentioned above are exerted by a single screw, multiple screws, co-rotating or counter-rotating coupling screws, co-rotating or counter-rotating non-coupling screws, reciprocal screws, bolt with pins, cylinders with pins, rollers, battering rams, helical rotors, or combinations comprising at least one of the above.
[0155] Mixtures involving the aforementioned forces can be conducted on machines, such as single screw or multi-screw extruders, Buss kneader, Henschel, helicones, Ross mixer, Banbury, roller mills, molding machines, such as machines injection molding machines, vacuum forming machines, blow molding machines, boilers, boilers with distillation and / or condensation columns, or the like, or combinations comprising at least one of the previous machines.
[0156] The fragrance composition can be used in a variety of articles and applications. It can be used in body lotions, shampoos, massage oils, as a chemical identifier (for example, odorless chemicals or toxic or dangerous chemicals), to mask odor, in perfume sticks and tubes, air fresheners, candles, paints , varnishes, furniture, insect repellents, in polymers, cleaning products, detergents, cosmetics, personal care products, cosmetic and beauty products, personal care and cleaning products applied to the skin, hair, scalp and nails of humans and animals. Fragrance compositions are used in a variety of
72/135 air purifiers, such as, for example, spray, gel, (for example, an electric air purifier or spheres), a paper substrate (for example, car air purifiers suspended in rear view mirrors) or liquid (for example, air diffusers or with electric air purifiers).
[0157] The term personal care products, as used in this document, includes pharmaceuticals, pharmaceuticals, oral care products (mouth, teeth), eye care products, optical care products and over-the-counter products and applications, such as bandages , plasters, dressings and the like, and medical devices externally applied or applied within humans and animals to improve a medical or health-related condition, to maintain, in general, hygiene or well-being, and the like. The term body includes the keratinous (hair, nails) and non-keratinous areas of the entire body (face, trunk, limbs, hands and feet), the tissues of the body and eye openings, and the term skin includes the scalp and mucous membranes. The term household care products, as used in this document, includes products used in a household to clean surfaces, control or mask odor, or biocidal cleaning products to maintain sanitary conditions, such as in the kitchen and bathroom, household laundry for cleaning and care of fabrics, air purifiers, air disinfectants, air deodorants / odor removers, candles, and the like. These products can be used at home, in the workplace or in institutional settings.
[0158] The fragrance composition or fragrance composition is generally added as a concentrate to an article to produce a desired sensory effect on the article. The ratio of the fragrance composition to the ketal adducts of formula (1), specifically (1a), used in the fragrance composition can vary from article to article, depending on the composition of the article. In addition, the amount of the
73/135 fragrance can also vary from article to article, depending on the usefulness of the article.
[0159] In one embodiment, the fragrance composition can be added to organic polymer formulations to give the organic polymer a specific odor or to mask an undesirable odor. Examples of polymers to which the fragrance composition can be added are polyolefins, polyvinyl acetates, cellulose polystyrene acetates, acrylonitrile butadiene styrene, polyacrylics, polycarbonates, polyamides, polyurethanes, epoxies, and polyesters. _i
[0160] The ketal adducts of formula (1), specifically (1a), are also useful in personal care compositions. As used in this document, personal care compositions have a wide scope and include cosmetic compositions (ie, makeup). Exemplary personal care compositions include bath or bathroom products, including various hair and body cleansers; eye care products; ~ cosmetics; a fragrance; treatment formulation, including hair coloring formulation; a capillary straightening or permanent waving formulation; a nail care formulation; an oral hygiene formulation, including toothpaste and mouthwashes; a hair removal cream; a skin care formulation; a formulation of care against the sun; a lip care formulation; an antiperspirant; or a foot care formulation. Personal care compositions are used interchangeably with personal care formulations. It is contemplated that some personal care compositions, such as hand cleaning and body cleaning formulations, are also within the scope of the cleaning compositions disclosed in this document.
[0161] The ketal adducts of formula (1), specifically (1a), can be used to increase the solubility of an active agent in a personal care formulation. Depending on the native solubility of
74/135 active agent in the formulation and the type of formulation, the ketal adducts of formula (1), specifically (1a), can be used as a co-solvent with water, as a compatibilizer with water and an organic solvent, as a co-solvent with an organic solvent, such as an emulsifier, or a combination comprising any one or more of the above. As is known to those skilled in the art of formulating personal care products, an individual ingredient may have more than one type of function, for example, the ketal adducts of formula (1), specifically (1a), would function as a co-ingredient. solvent and as a compatibilizer.
[0162] The presence of such a ketal adduct can allow the concentration of the active agent to be increased, often without the presence of volatile organic compounds (VOCs), such as ethanol, isopropanol, acetone, ethyl acetate, and the like in the formulation, or with reduced amounts of these VOCs. The result in some cases may be a low, more concentrated VOC formulation. The ketal adducts of formula (1), specifically (1a), can also perform additional functions, such as compatibilization, or solubilization of certain organic materials in an oil phase, and emulsification of an oil phase in an aqueous phase.
[0163] The ketal adducts of formula (1), specifically (1a), can act as emulsifiers, compatibilizers, or solubilizers for ingredients other than the active agent, or as a coemulsifier, co-compatibilizer, or co-solubilizer for those ingredients other than the active agent. In addition, the incorporation of the ketal adducts of formula (1), specifically (1a), can lead to a less fatty formulation with a lighter or heavier feeling, especially compared to many other naturally derived ingredients.
[0164] In cases where the active agent is slightly soluble or highly soluble in an alcohol or an alcohol-water mixture, the adducts
75/135 cetai of formula (1), specifically (la), may, in some cases, function as a co-solvent, both with alcohol and with an alcohol-water mixture. Cetai adducts of formula (1), specifically (1a), may, in some cases, allow an increase in the concentration of the active agent in an alcoholic or alcohol-water phase. In other cases, this may allow the proportion of alcohol in the co-solvent mixture to be decreased, which has the benefit of reducing VOCs in the formulation and, in some cases, lessening the drying effect that the formulation has on the skin. . In some cases, the keto adducts of formula (1), specifically (1a), can lead to a less fatty formulation with a lighter or heavier feeling.
[0165] In formulations containing active agents that are oily or oil-soluble and sparingly soluble (if not insoluble) in water, the cetai adducts of formula (1), specifically (1a), may, in some cases, allow the active agent becomes dissolved in an aqueous phase and, in other cases, together with one or more other co-solvents. In some cases, a mixture of keto adducts having different solubility / solubilization characteristics may be present in order to effect the dissolution of the active agent. Alternatively (or in addition), the cetai adducts of formula (1), specifically (1a), can assist in the dissolution or compatibilization of such active agent in an organic phase, or to help to compatibilize or emulsify an organic phase containing the agent active with an aqueous phase, forming, in this case, an emulsified formulation that can be, for example, a cream or lotion. As before, cetai adducts of formula (1), specifically (1a), in some cases, may allow the level of emollient materials to be reduced or improve the sensation characteristics of the formulation.
[0166] Whether an active agent is present or not, cetai adducts of formula (1), specifically (1a), may, in some cases, mutually assist incompatible materials to be formulated in
76/135 a stable formulation. Thus, the ketal adducts of formula (1), specifically (1a), are a valuable ingredient in many emulsified formulations, such as lotions and creams, which include water-in-oil or oil-in-water emulsion. In many cases, this can be achieved while reducing or eliminating other ingredients in the formulation. For example, volatile organic compounds or emulsifiers can be eliminated or used in small quantities. The presence of the ketal adducts of formula (1), specifically (1a), can improve the feeling of a personal care product, giving the formulated formulation a less oily, lighter feel, while preserving its function and performance . In many cases, the formulation's viscosity is reduced, which can contribute to a lighter and less greasy feeling.
[0167] Due to the fact that the ketal adducts of formula (1), specifically (1a), are a good solvent for a wide range of materials, they are very useful for making concentrates, which can be left as an oil , an alcohol or other thinner to provide a personal care composition.
[0168] In one aspect, the personal care composition contains the ketal adducts of formula (1), specifically (1a), and one or more active agents selected from organic anti-aging agents, organic anti-acne agents, organic skin lightening, organic ultraviolet light absorbing agents, organic tanning agents, organic anti-alopecia agents, antifungal agents and / or anti-dandruff agents, antimicrobial agents, organic medicines, depilatory compounds, hair dyes, or organic insect repellents. In some embodiments, the ketal adducts of formula (1), specifically (1a), form part of a mixture of co-solvent with water, oils, or with another organic solvent miscible with the ketal adducts of formula (1) , specifically (1a), in proportions relative to those that are
77/135 present in the formulated personal care formulation, and the active agent is dissolved in the co-solvent mixture. The active agents are present in amounts effective to achieve the desired activity, which can vary widely, depending on the active agent and the product. Thus, an active agent can be present in the formulation in amounts as low as 0.001% by weight, 0.01% by weight, or 0.1% by weight, up to 30% by weight. The amount of water used in the formulation can also vary widely based on the active agent and the product, from anhydrous products as described above, for the products to have 2 to 90%, 80%, 70%, 60%, 50%, 40 %, 30%, 20%, or 10% by weight of water, based on the total weight of the formulation.
[0169] Thus, in some embodiments, the formulated personal care formulation includes a compound selected from alpha hydroxy acids, such as lactic acid, 2-hydroxydecanoic acid, 2-hydroxyoctanoic acid and glycolic acid, beta hydroxy acids, such as beta-hydroxy salicylic acid, avobenzone, coenzyme Q10, benzoate-4-methylbenzylidene, cinoxate, dioxibenzone, homosalate, menthyl anthranylate, mexoril SX, drometrizole trisiloxane, octocrylene, octyl methoxy benzine, amine oxide; PABA), phenylbenzimidazole sulfonic acid, sulisobenzone, titanium trolamine salicylate, salicylic acid, retinoic acid (including the fully trans isomer known as tretinoin), benzoyl peroxide, hydroquinone, arbutin (including plant extracts containing it), kojic acid, azelaic acid, glycyrrhetic acid, levulinic acid, 2-cyano-3,3-diphenylacrylic acid, sodium benzotriazolyl butylphenol sulfonate, ethyl-2-cyan-3,3-diphenyl lacrylate, 2-tbutyl-6- (5-chloro-2H-benzotriazol-2-yl) -p-cresol, 2- (2-H-benzotriazol-2-yl) -4methylphenol, benzophenone-12, bornelone, or 2 -benzotriazolyl-4-tert-octylphenol. These compounds work as anti-aging, anti-acne, skin lightener and / or UV absorbers; formulations that contain them are useful as
78/135 anti-aging or anti-wrinkle formulations, acne treatments, skin lighteners and / or sunscreens.
[0170] In some embodiments, a personal care formulation includes a tanning agent, such as dihydroxyacetone, erythrulose, dihydroxyacetone-ortho-ethyl-acetate, canthaxanthin, or afamelanotide. These compounds work as tanning agents, and in personal care formulations that contain them in sufficient quantities are effective tanning formulations (skin darkeners).
[0171] In some embodiments, the personal care formulation includes a compound selected from minoxidil and 5-alpha reductase inhibitors, such as dutasteride and ketoconazole. These compounds work as anti-alopecia agents (preventing hair loss); in that sense, the personal care formulations that contain them are useful in some cases to prevent hair loss.
[0172] In some embodiments, a personal care formulation includes a compound selected from zinc pyrithione, selenium sulfide, clotrimazole, tea tree oil, or pyroctone olamine. These compounds function as antifungal agents, and the personal care formulations that contain them in sufficient quantities are effective topical antifungal treatments (such as Tinea pedis or Tinea cruris) and / or as anti-dandruff formulations.
[0173] In some embodiments, a personal care formulation includes a compound selected from an amphetamine, an antihistamine, methylphenidate, oxymetazoline, tetrahydrolizoline hydrochloride, or psilocybin. These compounds work as vasoconstrictors in some cases and the personal care formulations that contain them in sufficient quantities are effective as redness reducers (such as eye drops and anti-redness or anti-puffiness creams).
[0174] In some embodiments, a personal care formulation includes a compound selected from calcium thioglycolate,
79/135 sodium thioglycolate, thioglycolic acid, ammonium thioglycolate, butyl thioglycolate, ethanolamine thioglycolate, glyceryl thioglycolate, isooctyl thioglycolate, isopropyl thioglycolate, magnesium thioglycolate, tioglycolate, magnesium tioglycolate, tioglycolate, magnesium thioglycolate. These compounds work to modify hair fibers, breaking the S-S bonds in keratin; the personal care formulations that contain them in sufficient quantities are used in depilatory formulations, permanent waxes, relaxers, hair straighteners and hair stylers.
[0175] In some embodiments, a personal care formulation includes a selected compound of aluminum tetrachlorohydrex glycine and zirconium, aluminum hydrochloride, or aluminum chloride. These agents are antiperspirants and the personal care formulations that contain them are often effective as deodorants and antiperspirants.
[0176] In some embodiments, a personal care formulation includes a selected compound of resorcinol (resorcin), 1naphthol, p-aminophenol, p-phenylenediamine (and its salts), 4-amino-2hydroxytoluene, and the like. These active agents are effective hair dyes; and the personal care formulations that contain them are often effective as hair dyes or hair dye concentrates.
[0177] In some embodiments, a personal care formulation includes a compound selected from phenoxyethanol, N, N-diethyl-methanoluamide, p-menthane-3,8-diol (active agent in lemon eucalyptus essential oil), nepetalactone (oil catnip oil), citronella oil, permethrin oil, neem oil, or marsh myrtle extract. These active agents are effective insect repellents; and the personal care formulations that contain them are often effective as insect repellents.
[0178] In some modalities, the formulation of personal care comprises from 0 or 0.001 to 15% by weight of water, specifically, 0 or
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0.01 to 12% by weight of water, 0.1 to 10% by weight of water, 0.5 to 8% by weight of water, or 1 to 5% by weight of water, each urn based on the total weight formulation. In some embodiments, the personal care formulation is essentially anhydrous, containing no more than 3% by weight of water, no more than 2% by weight of water, more specifically no more than 1% by weight of water. In essentially anhydrous personal care formulations, the amount of water can be 0%, as low as 0.001%, or 0.01%, or 0.1% by weight, each based on the total weight of the personal care formulation .
[0179] In another aspect, for use in a wax formulation, for example, a lipstick, lip gloss, lip balm formulation, or a cuticle cream, which contains a wax, an emollient, and ketal adducts are provided of formula (1), specifically (1a). In specific interest modalities, the lipstick, lip gloss, lip balm, or cuticle cream formulation contains 0.1 to 10% by weight of water, specifically 0.5 to 5% by weight of water, each based on total weight of the personal care formulation. These formulations are in stick form or in another solid form. In another aspect, a personal care formulation formulated in the form of an emulsion is provided. The emulsion can have a continuous phase and a dispersed phase, one of which is an aqueous phase, and the other of which is an oil phase. Alternatively, the emulsion can have at least two co-continuous phases, again where at least one of the co-continuous phase is an aqueous phase and at least one of the co-continuous phases is an oil phase. The oil phase contains at least one of (a) a paraffinic, naphthenic or aromatic mineral oil, or seed oil (b) a nonionic organic compound having a melting temperature of less than 45 ° C, a molecular weight of at least 190 Daltons, a starch or ester group, an alkyl chain containing at least 8 carbon atoms, and a water solubility of not more than 1 part in 99 parts of water by weight; (c) in non-ionic organosilicone compound having
81/135 a melting temperature of less than 45 ° C and a solubility in water of not more than 1 part in 99 parts of water by weight; (d) a long chain alcohol; and (e) a wax. The emulsion further comprises the ketal adducts of formula (1), specifically (1a). The ketal adducts of formula (1), specifically (1a) can be present in a continuous phase, a dispersed phase, a continuous phase and a dispersed phase, or at the interface between a continuous and a dispersed phase. Additional ingredients may also include emollients, such as vegetable oils and animal fats and derivatives thereof; non-ionic organosilicone compounds, such as dimethicone and cyclopentasiloxane; co-solvents, as described in this document above; natural, synthetic or modified organic polymers; surfactants, as described in this document above; natural or synthetic fragrances; botanical extracts; natural or synthetic dyes; pigments or pearls; pH adjusters / buffers and chelating agents; inorganic particles; nonhydrocarbon propellants; preservatives, and a combination comprising at least one of the above.
[0180] Formulations and personal care products can take the physical form of solids (sticks, bars, powders, etc.), solutions (including solutions containing enough showy or thickening compounds to provide a gel-like consistency), ointments, dispersions (including pastes or scrubs), or emulsions (including gels, ointments, lotions, creams or the like). They can be sprayable, in particular, solutions, dispersions and powders.
[0181] Many personal care formulations are combinations of two or more of the formulation forms. For example, some personal care formulations contain an aqueous phase that contains a dissolved active agent, and also include an oil phase that may be present, for example, to provide emollients and / or humectants, or to produce a specific formulation. (cream, lotion and the like).
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In such cases, it is possible to include two or more ketal adducts within the formulation to perform different functions. Thus, for example, a completely water-miscible ketal adduct may be present in the aqueous phase to help dissolve the active agent, and a partially or moderately water-miscible ketal adduct may be present within the oil phase to reduce its viscosity. or make its components compatible. Any of these ketal adducts can also perform some emulsifying or compatibilizing function between the aqueous and oil phases.
[0182] In addition, the ketal adducts of formula (1), specifically (1a), can perform multiple functions within a personal care formulation, such as dissolving an active agent in an aqueous or oil phase, compatibilization, or emulsifying an aqueous phase with an oil phase.
[0183] The ketal adducts of formula (1), specifically (1a), can reside in an aqueous phase, an alcoholic or alcohol-water phase, or an oil phase of a personal care formulation, depending on the specific formulation and of the specific ketal adduct. In many cases, the ketal adducts of formula (1), specifically (1a), can be distributed between the aqueous and oil phases of a personal care formulation, due to their solubility in both phases. In some cases, the ketal adducts of formula (1), specifically (1a), may reside at the limit of the aqueous and oil phases.
[0184] The amount of ketal adducts of formula (1), specifically (1a), present in a personal care formulation depends on the function of the ketal adducts of formula (1), specifically (1a), of the other ingredients in the formulation of personal care, the specific form of personal care formulation, and similar considerations. In general, the formulation comprises 0.001 to 90% by weight, 0.01 to 80% by weight, 0.1 to 70% by weight, or 0.1 to 50% by weight of the
83/135 ketal adducts of formula (1), specifically (1a), based on the total weight of the formulation, although a more typical amount is 0.5 to 25% by weight, and in many cases, from 1 to 10 % by weight of the total weight of the formulation.
[0185] Anti-aging, anti-acne, skin lightening and sun protection formulations may contain 0.001 to 50% by weight of the active agent, specifically 0.01 to 40% by weight, based on the total weight of the formulation . Anti-aging and anti-acne formulations can be formulated in aqueous and / or ethanolic solutions, or in lotions or creams. Sun protection formulations can take the form of clear, low-viscosity liquids (as is typical for spray formulations, which are often ethanolic or ethanol-based), or are lotions or creams. Spray sunscreen formulations can be aqueous and / or ethanolic solutions or diluted emulsions. Many of the active anti-aging, anti-acne, skin lightening and sun protection agents are soluble in the measure of at least 5 parts per 95 parts of the ketal adducts of formula (1), specifically (1a), in the formulation. These include, for example, avobenzone, coenzyme Q10, hydroquinone, oxybenzone, and salicylic acid, all of which are soluble to the extent of at least 5 parts per 95 parts of the ketal adducts of formula (1), specifically (1a). In these cases, the presence of the ketal adducts of formula (1), specifically (1a), often allows the amount of ethanol to be reduced, and / or the amount of the active agent to be increased in a constant ethanol content, leading to a formulation that is less dry for the skin. In some cases, the ketal adducts of formula (1), specifically (1a), can be used to replace a heavy-feeling material that solubilizes the asset.
[0186] An anti-aging, anti-acne, skin whitening, or sun protection formulation may contain additional UV-absorbing agents, particularly inorganic compounds, such as titanium dioxide or
84/135 zinc dioxide. These materials are solid particles that are normally dispersed in a lotion or cream formulation.
[0187] Sun protection formulations, such as sunscreens, often contain a mixture of organic UV absorbing agents, often to expand the range of UV light wavelengths that are absorbed. Such a mixture of organic UV agents can include two or more of avobenzone, octylmethoxy cinnamate, oxybenzone and ethylhexyl salicylate. These can, in aggregate, make up from 0.1 to 50% of the weight of the sunscreen formulation and more specifically make up from 2 to 25% by weight.
[0188] The tanning formulation can contain from 1 to 25% by weight, for example, from 2 to 10% by weight of one or more tanning agents as previously described. Tanning formulations are often formulated in a cream or lotion. Spray tanning formulations can be aqueous and / or ethanolic solutions.
[0189] Tanning formulations may contain organic UV active agents, as described above, as well as inorganic UV agents, such as titanium dioxide or zinc oxide. As is the case with sunscreen formulations, organic UV active agents can constitute 0.1 to 50% by weight, specifically 0.1 to 30% by weight of a tanning formulation and more specifically 2 to 25% by weight. A mixture of organic UV additives may be present, including a mixture of two or more among avobenzone, octylmethoxy cinnamate, oxybenzone and ethylhexyl salicylate.
[0190] Anti-dandruff formulations can contain from 0.1 to 25% by weight, specifically from 0.5 to 10% by weight of one or more of an anti-fungal agent, as previously described. The formulation form can be an aqueous solution, aqueous gel or diluted emulsion containing mainly the aqueous phase. An anti-dandruff formulation can
85/135 contain one or more surfactants, particularly one or more anionic surfactants. Sulfosuccinate, lauryl sulfate and lauride sulfate surfactants and the various fatty acid betaines or fatty acid amide propyl betaines are preferred types, although others, particularly other anionic surfactants, can be used. Surfactants can make up 0.1 to 10% by weight of an anti-dandruff formulation. Surfactants can function as cleaning agents and / or emulsifiers in the formulation. An anti-dandruff agent can contain hair conditioners and other materials as well.
[0191] Anti-alopecia formulations can contain 0.1 to 25% by weight, for example 1 to 10% by weight of one or more of the anti-alopecia agents. Formulations of these types are generally formulated in fluids with a low to medium viscosity, which can contain a propellant and be sprayable, which can be clear solutions in the case of anti-alopecia formulations or opaque emulsions in the case of anti-dandruff formulations. These formulations can contain propylene glycol, ethanol and / or water as a cosolvent mixture, although it is an advantage of this invention that the levels of propylene glycol and / or ethanol can in some cases be reduced due to the presence of the ketal adducts of the formula (1 ), specifically (1a).
[0192] Chemical treatment formulations for hair include formulations for hair straighteners, relaxers, and perms, which may contain one or more materials that smooth the hair, possibly breaking the sulfur-sulfur bonds in keratin or some other hair component; among these are the depilatory agents described above. They can constitute up to 10% by weight of an active agent for chemical hair treatment. Chemical treatment formulations for hair can take the form of fluids, lotions, creams or gels with low viscosity.
[0193] A hair styling formulation can contain one or
86/135 plus hair fixers, which kill hair in a restyled position. Some of these fixatives can also function as thickeners in a formulation to smooth and shape hair strands. The hair fixative can be from 0.25 to 25% by weight, for example from 0.5 to 15% by weight of the formulation. The hair styling formulation can take the form of an aqueous and / or ethanolic solution, a gel or a lotion.
[0194] Antiperspirant formulations contain one or more antiperspirants as described above. Antiperspirant formulations can take the form of a gel, a viscous liquid (for roll-on applications) or a bar.
[0195] A bar or roll-on antiperspirant may contain a little water, which may make up 2 to 60% of the formulation's weight and at least 5%, up to 30% by weight of the antiperspirant.
[0196] Topical pharmaceutical formulations may contain one or more medicinal agents such as amphetamine, antihistamine, methylphenidate, oxymetazoline, tetrahydrolzoline hydrochloride, psilocybin, clotrimazole, tea tree oil, pyroctone olamine, chlorhexidine, octenidine, triclosine, triclosine, triclosine , Sodium 5-dibromo-4-hydroxybenzenesulfonate (Dibromol), quaternary ammonium salts such as benzalkonium chloride, cetyl trimethylammonium bromide, cetylpyridinium chloride and benzethonium chloride and the like. These formulations can be formulated in low viscosity fluids (which can be sprayed), gels, lotions, ointments, creams or ointments. Low viscosity fluid formulations can be aqueous and / or ethanolic; lotions and creams can be emulsions containing a continuous aqueous phase and a dispersed or co-continuous phase containing an emollient.
[0197] Hair dye formulations can include hair dyes like those described above. Hair whitening formulations may contain a peroxide bleaching agent such as peroxide
87/135 of hydrogen, in an effective amount, for example, 0.1 to 5% by weight of the total weight of the formulation in the case of dyes; and 1 to 20% by weight in the case of bleaches. A bleaching formulation may, in addition, contain an inorganic oxidant such as a persulfate salt, in an amount between 0.1 to 5% by weight of the formulation. Hair dye and bleach formulations can take the form of low viscosity fluids, lotions, creams or gels. They can also be prepared in the form of a water-dilutable concentrate. A hair dye or bleach formulation may contain one or more agents that can function as emulsion stabilizers, or as a detergent.
[0198] Depilatory formulations can contain one or more depilatory agents as described above, for example an amount of 1 to 20% by weight, based on the weight of the formulation. Depilatory formulations can be in the form of lotions, creams or gels.
[0199] In another aspect, a waxy solid formulation containing a wax, an emollient and the ketal adducts of formula (1), specifically (1a), is provided. The waxy solid formulation may contain from 0.5 to 20% by weight, 15% by weight, 10% by weight, 8% by weight, 5% by weight, 4% by weight or 3% by weight of water. These formulations can be supplied in bars or in another solid form. They can contain at least 20% by weight of an oil such as castor oil, a wax (as defined below) and at least 0.5% by weight of ketal adducts of formula (1), specifically (1a). The ketal adducts of formula (1), specifically (1a) can be present in amounts up to 25% by weight, 20% by weight, 15% by weight or 10% by weight of the formulation. The ketal adducts of formula (1), specifically (1a) can be a ketal adduct partially or totally miscible with water, as defined below, when the waxy solid formulation contains more than 0.5% by weight of water. Such formulations include formulations for the lips as a
Lipstick, briiho iabiai or lip balm; cuticle creams; and the like.
[0200] Several waxy formulations, including lip care formulations, include a mixture of one or more waxes with one or more oils and, in the case of lipsticks, one or more pigments. Lipstick and lip balm formulations, as well as cuticle creams, tend to be malleable solids at 25 ° C, while lip gloss tends to be a viscous or pasty liquid. A lip care formulation can contain, for example, 1 to 30% by weight of a wax; between 30-95% by weight of one or more different hydrophobic materials, among which castor oil is usually an important component; and from 1 to 30% by weight of one or more pigments. In some embodiments, the lipstick or lip balm formulation contains a ketal adduct of formula (1). In addition to the personal care formulations containing the active agents, a significant number of personal care formulations do not contain any of the active agents mentioned above, but exist in the form of emulsions. Emulsions can be of the water-in-oil type, of the '<t oil-in-water type, or of the type containing co-continuous aqueous and oily phases. These formulations generally take the form of low viscosity fluids (where the dispersion phase, which is generally an oil phase, constitutes a small proportion, typically 35% or less, or 10% or less, by weight of the formulation), lotions or creams. These formulations include, for example, hair conditioners, aftershave lotions, various body cleansing products, various hand and skin lotions, creams and the like, which do not contain specific active agents as described above. Emulsion formulations of these types typically contain 0.1 to 50% by weight of ketal adducts of formula (1).
[0201] Additional ingredients that can be included in the personal care formulations of this disclosure include paraffinic, naphthenic or aromatic mineral oil; an organic compound not
Ionic 89/135, having a melting temperature less than 45 ° C, a molecular weight of at least 190 Daltons, a starch or ester group and a chain containing at least 8 carbon atoms and a solubility in water not exceeding 1 part for 99 parts of water; a non-ionic organosilicone compound with a melting temperature of less than 45 ° C and a solubility in water of not more than 1 part for 99 parts of water; a long-chain alcohol (eight or more carbon atoms), a wax or a combination comprising at least one of the above. The additional ingredients also include emollients like vegetable oils and animal fats and their derivatives; nonionic organosilicone compounds, such as dimethicone and cyclopentasiloxane; co-solvents, as described above in this document; natural, synthetic or modified organic polymers; surfactants, as described above in this document; natural or synthetic fragrances; botanical extracts; natural or synthetic dyes; pigments or pearls; pH adjusters / buffers and chelating agents; inorganic particles; non-hydrocarbon propellants; preservatives, and a combination comprising at least one of the above.
[0202] Formulations containing ketal adduct of formula (1) have been identified as excellent cosmetic (makeup) removers, particularly if the formulation contains at least 5% by weight and more specifically at least 8% of ketal adduct. The ketal adduct can constitute up to 75% by weight, up to 60% by weight or up to 50% by weight of a cosmetic remover formulation. A cosmetic remover can include, in addition to the ketal adduct, water, an alcohol such as ethanol, isopropanol or 1,2 or 1,3-propane diol; one or more of the above components. This cosmetic remover can also be free of surfactants, or contain a low concentration (less than 2% by weight) of surfactants.
[0203] The ketal adducts of formula (1), especially (1a),
X x
90/135 are also efficient solvents for polymers that are generally present in nail polishes, such as nitrocellulose, cellulose acetate propionate, cellulose acetate butyrate, styrene / acrylates copolymers, acrylates copolymers, polyethylene terephthalate and resin resins tosylamide / formaldehyde, and thus find benefit as a solvent in nail polish removers, nail strengthening formulations, and / or nail polish.
[0204] The personal care formulations described in this document satisfy certain continuing needs in the art for form ingredients. The ketal adducts of formula (1), especially (1a) can be used in a wide range of formulation forms and in a wide variety of specialized applications. Although these various types of formulations differ enormously, as do the conditions under which they are used, the ketal adducts of formula (1), especially (1a), can be used in the formulation of many of them, which greatly simplifies the process of formulation.
[0205] In addition, formulating personal care formulations often addresses simultaneously the needs of formulations that are often competing and are sometimes even contradictory. For example, many personal care formulations contain an active agent that lends a particular functional attribute to the formulation. It may be desirable to increase the concentration of the active agent in a given formulation, or to produce a formulation that contains the active agent in a specific formulation form (such as a solution, dispersion, lotion, cream, bar, gel or the like), but the formulator is limited by the solubility of the active agent in the other ingredients in the formulation. Approaches to address solubility include the use of various types of emulsifiers, oils, co-solvents and the like, but it often occurs that other requirements, such as the specific formulation, are incompatible with the presence of such materials in
91/135 quantities needed for effectiveness. Use of the ketal adducts of formula (1), especially (1a) allows a greater concentration of active agent in a wide variety of forms of formulation specific to personal care. The ketal adducts of formula (1), especially (1a) are additionally compatible with many other ingredients in personal care formulations.
[0206] In other cases, the presence or absence of a specific ingredient that can be an aid to solubility is important. For example, it may be desirable to reduce or eliminate volatile organic compounds (VOCs) from a personal care formulation. Some ingredients, such as ethanol, can dry out the skin and, in some cases, should be avoided for this reason, or for other reasons, such as VOC regulations in some jurisdictions. On the other hand, there are other cases where ethanol and / or other relatively volatile material is desired, so the formulation dries quickly when applied, for example. In some modalities, use of the ketal adducts of formula (1), especially (1a) results in formulations with reduced levels of VOCs and, in some cases, there are no volatile organic compounds. In one embodiment, the formulations and products described in this document may have a low VOC as defined below.
[0207] The use of ketal adducts of formula (1), especially (1a) in personal care formulations can increase compatibility between the various ingredients in the formulations. Many personal care formulations contain hydrophilic and hydrophobic components. These ingredients tend not to mix with each other. To create a formulation that does not quickly separate into oil-rich and water-rich layers, thickeners, emulsifiers or cosolvents can be included to make it kinetically stable. These emulsifiers, thickeners and cosolvents often play a small role in the formulation's function or performance (that is, they are not
92/135 active agents), although they can affect the spread and sensation characteristics of the skin. Mostly, they are present to allow the various functional ingredients to coexist in a stable formulation form or to provide a desired feel or consistency to the formulation. The inclusion of certain compatibilizing ingredients (such as volatile or drying organic solvents, for example), as described above, can be more specifically omitted from some formulations. The need to include these compatibilizers can increase the complexity of the formulation. Formulations that require compatibility can be very sensitive to small formulational changes. Small changes to a formulation often destabilize, requiring a new balance of ingredients.
[0208] The ketal adducts of formula (1), especially (1a) can act as emulsifiers, oils, co-solvents, compatibilizers and similar materials. In an additional advantage, the ketal adducts of formula (1), especially (1a) improve the spread of the formulation, and / or do not become dense or greasy. Use of ketal adducts of formula (1) especially (1a) can provide simplified formulations for personal care formulations that still have the necessary functions and attributes of formulations. In other cases, the use of ketal adducts of formula (1), especially (1a) can reduce the quantities of the various components of the form and thus reduce costs and simplify the formulation. This can allow a formulator to maintain a simplified inventory of the raw material and thereby reduce associated costs. Use of the ketal adducts of formula (1), especially (1a) can also result in personal care formulations that are more resistant to formulation changes.
[0209] The following non-limiting examples serve to further illustrate various embodiments of the present invention.
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EXAMPLES
Example 1
[0210] 2-ethylhexyl levulinate propylene glycol cetai (2EH-LPK) was prepared by combining 708.0 grams of EtLPK with 729.2 grams of 2-ethylhexanol (99%) in a two-liter, four-necked round bottom flask, equipped with Dean Stark condenser, with stirring shaft and heating cover. The mixture was stirred at 100 ° C, 60 torr until the water content was below 100 ppm by Karl Fischer titration (24 hours). A nitrogen blanket was applied and 0.33 grams of tin octoate catalyst was added to the reaction mixture with a syringe. The stirred reaction mixture was heated to 190 ° C for 6.5 hours; displaced ethanol was collected in the trap. The remaining reaction mixture was transferred to a round bottom flask equipped with a stir bar, fractionation column (Vigreaux), distillation head and oil bath. The reaction mixture underwent fractional distillation under reduced pressure, producing 605.9 grams of 99.2% purity 2-ethylhexyl levulinate propylene glycol (by GC-FID).
[0211] 1-nonanyl levulinate propylene glycol keta (1N-LPK) was prepared by combining 166.0 grams of EtLPK with 189.9 grams of 1nonanol (98%) in a one-liter, round, three-necked flask, equipped with a Dean-Stark condenser with a stirring shaft, thermoelectric and heating cover. The mixture was stirred at 100 ° C, 60 torr until the water content was below 100 ppm by Karl Fischer titration. A nitrogen blanket was applied and 0.065 ml of tin octoate catalyst was added to the reaction mixture with a syringe. The stirred reaction mixture was heated to 190 ° C for 3.5 hours; displaced ethanol was collected in the trap. The same deep, round liter liter flask was equipped with a stir bar, distillation head and oil bath. The reaction mixture underwent fractional distillation under reduced pressure, producing 146.2 grams of 1-nonanil levulinate keti
-saw
94/135 propiienogiicol with 97.1% purity (by GC FID).
[0212] 3,5,5-trimethylhexyl levulinate propiienogiicol cetal (355TMHLPK) was prepared by combining 166.1 grams of EtLPK with 190.4 grams of 3,5,5-trimethylhexanol (> 85%) in a flask with three bottlenecks of one liter, deep and round, equipped with a DeanStark condensing device with agitation axis, thermoelectric and heating cover. The mixture was stirred at 100 ° C, 60 torr until the water content was below 100 ppm by Karl Fischer titration. A nitrogen blanket was applied and 0.065 ml of tin octoate catalyst was added to the reaction mixture with a syringe. The stirred reaction mixture was heated to 190 ° C for 4 hours; displaced ethanol was collected in the trap. The same deep, round liter liter flask was equipped with a stir bar, distillation head and oil bath. The reaction mixture underwent fractional distillation under reduced pressure, producing 188.1 grams of ketal 3,5,5-trimethylhexyl levulinate propylene glycol with 88.1% purity (by GC-FID).
Example 2
[0213] Latex coating formulations were prepared using three different latexes: vinyl-acrylic latex (UCAR ™ 379G commercially available from Arkema, Inc.), acrylic latex (UCAR ™ 625 commercially available from Arkema, Inc.) and another acrylic latex (MAINCOTE ™ 54D commercially available from The Dow Chemical Company). Acrylic latex UCAR ™ 625 has an acrylic copolymer content of 30% to 60% by weight and water content from 30% to 60% by weight, based on the weight of the latex and pH 9; and MAINCOTE ™ 54D acrylic latex has an acrylic copolymer content of 41% to 42% by weight and water content from 58% to 59% by weight based on the weight of the latex and pH of 7.2 to 7.8.
[0214] Latex coating formulations for minimum film forming temperature tests
95/135 temperature, MFFT) were prepared by adding 20 grams of latex-binding polymer (UCAR 379G, LICAR 625 and Maincote HG - 54D), 0.04 grams of Rhodoline 643 defoamer (commercially available from Rhodia) and 0 , 2 or 0.4 grams of coalescent in a small bottle. The resulting mixture was stirred vigorously by hand to produce a stable latex coating composition.
[0215] Formulations are shown in Table A.
Table A.
Formulation latex Latex Qty (gr) Coalescent Coalescent Qty (gr) Rhodoline 643 Qty (gr) Control UCAR 579G 20.0 0.04 TPM 1 UCAR 379 (i 20.0 TPM 0.2 0.04 TPM 2 UCAR 579G 20.0 TPM 04 0.04 ElLPK 1 UCAR 579G 20.0 ElLPK 02 0.04 ElLPK 2 UCAR 379G 20.0 ElLPK 0.4 0.04 ÍPrLPKl UCAR 579G 20.0 iPrl.PK 02 0.04 iPrlPK. 2 UCAR579G 20.0 iPrIJ’K 0.4 0.04 2EH4PK 1 UCAR 579 (i 20.0 2EILLPK 0.2 0.04 2E1I-LPK2 UCAR 379G 20.0 2E11-LPK 0.4 0.04 Control UCAR 615 20.0 0.04 TPM 1 UCAR 625 20.0 TPM 0.2 0.04 TPM 2 UCAR 625 20.0 TPM 0.4 0.04 ElLPK 1 UCAR 625 20.0 EdJ »K 0.2 0.04 Etl.PK 2 UCAR 625 20.0 EtLPK 0.4 0.04 iPrLPKI UCAR 625 20.0 iPrLPK 0.2 0.04 iPrl.PK2 UCAR 625 20.0 iPrlPK 0.4 0.04 2E1I-IPK 1 UCAR 625 20.0 2EU4PK 0.2 0.04 2EH-IJPK 2 UCAR 625 20.0 2EH4.PK 0.4 0.04 Control Maincote HG54Í) 20.0 0.04 TPM 1 Maincote IIG54D 20.0 TPM 0.2 0.04 TPM 2 Maincote IIG541) 20.0 TPM 0.4 0.04 ElLPK 1 Mamcote IIG54D 20.0 EtLPK 0.2 0.04 ElLPK 2 Mamcote HG54D 20.0 ElLPK 0.4 0.04 iPrJJ’KJ Maiucotc IKi.MD 20.0 iPrLPK 0.2 0.04 iPri-PK 2 Maincote IIG54D 20.0 iPri-PK 0.4 0.04 2Ε11ΈΡΚ 1 MaiiKote HG54D 200 2EHLPK 0.2 0.04 2E4LLPK2 Maincote IIG54D 20.0 2EU4PK 0.4 0.04
[0216] MFFT studies have been carried out using various coalescent solvents to establish their relative coalescence efficiency. The minimum film-forming temperature of the 2-ethylhexyl levulinate propylene glycol (2EH-LPK) adduct was compared to the coalescent solvents of cetyl ethyl levulinate propylene glycol (EtLPK) and isopropyl levulinate propylene glycol (iPrLK 2) , 2,4-trimethyl-1,3-pentanedial monoisobutyrate (reference mark TPM, available as TEXANOL ™ from Eastman Chemical Company). THE
96/135 minimum film-forming temperature of a pure latex control formulation with no coalescent was also measured.
[0217] Table 1 shows the minimum film-forming temperature for formulations with different latex fillers (the percentage weight of coalescing solvent based on the weight of the latex formulation) as measured using ASTM Method D2359.
Table 1.
UCAR 379G (Acrylic Vinyl Latex)
Load (% by weight), MFFT (”C)
Control 0 12.0 TPM 1% 6.0 TPM 2% 2.8 EtLPK 1% 4.4 EtLPK 2% 1.6 iPrLPK 1% 5.1 iPrLPK 2%2EH-LPK 1% 5.6 2EH-LPK 2% 2.2
UCAR 625 (Acrylic Latex)
Load (% by weight) MFFT ÇC)
Control 0 1 «fcr.afc» TPM 1% 52 ΊΡΜ 2% 2.3 EtLPK 1% 43 EtLPK 2% 0.9 iPrLPK 1% 4.1 iPrLPK 2% 0.9 2EH-LPK 1% 4.3 2EH-LPK 2% 13
Maincoatc 54D (Acrylic Latex) ________________
Load (% by weight) MFFT UC)
Control 0 > 33 TPM 3% 13.6 TPM 6% 2.8 EtLPK 3% 10.8 EtLPK 6% 0.0 iPrLPK 3% 11.0 iPrLPK 6% 12 2EH-LPK 3% 13.2 2EH-LPK 6% 2.4
Rhodoline 643 defoamer was added to each formulation in an amount of 0.2%, based on the weight of the latex formulation.
[0218] The data in Table 1 shows that 2EH-LPK decreases the
97/135 minimum film formation temperature compared to control. In addition, 2EH-LPK produces a minimum film-forming temperature that compares favorably with the TPM benchmark.
Example 3.
[0219] The relative contents of the volatile organic compound (VOC) of the coalescent solvents 2-ethylhexyl levulinate propylene glycol (2EH-LPK), 1-nonyl levulinate propylene glycol (1N-LPK) ketal, 3.5 ketal 5-trimethylhexyl levulinate propylene glycol (355TMH-LPK), propylene glycol ethyl levulinate kettle (EtLPK), isopropyl levulinate ketylene propylene glycol (iPrLPK) and 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (TPM) were determined by TPM emulation of the D2369 ASTM Method. Here, 15 milligrams (mg) of each coalescing solvent was maintained at 110 ° C for one hour with a nitrogen purge in a thermal gravimetric analyzer (thermo gravimetric analyzer - TGA). Table 2 shows the percentage of the remaining mass of each sample at various times.
Table 2.
í % of mass remaining I Component 0 min 5 min 10 min 15 min 20 min 30 min 60 min j EtLPK 100% 51% 7% 0% 0% 0% 0% ; iPrLPK 100% 60% 23% 0% 0% 0% 0% í TPM 100% 74% 49% 26% 4% 0% 0% ; 2EH-LPK 100% 97% 93% 90% 87% 80% 61% 1N-LPK 100% 99% 98% 97% 96% 93% 87% í 355TMH-LPK 100% 97% 95% 92% 90% 85% 71%
[0220] The results in Table 2 show that 2EH-LPK, 1N-LPK and 355TMH-LPK have low volatility compared to other coalescent solvents. Surprisingly, most 2EH-LPK, 1NLPK and 355TMH-LPK (80%, 93% and 85%, respectively) last after 30 minutes, whereas TPM, EtLPK and iPrLPK are completely volatile in less than 30 minutes (min) .
[0221] These data demonstrate that 2EH-LPK is a low VOC, efficient coalescing solvent.
Example 3.
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[0222] Hydrolytic stability of coalescent solvents at room temperature was determined by 2-ethylhexyl levulinate propylene glycol ketal (2EH-LPK), ethyl levulinate propylene glycol kettle (EtLPK) and isopropyl levulinate propylene glycol (iPrPK). The pH of latex formulations containing ether-functional coalescent solvents was monitored over time to assess the hydrolytic stability of the coalescent solvents. Not wanting to be limited by theory, ester hydrolysis can occur at a high alkaline pH (for example a pH greater than 9) during the storage of latex compositions. The products resulting from hydrolysis lower the pH of the latex composition and could decrease the coalescing efficiency of the coalescing solvent in relation to the initial amount of the coalescing solvent.
[0223] Latex formulations were prepared by adding 1.0 grams of each coalescing solvent to 10 grams of an acrylic latex (Rhoplex SG - 10M commercially available from Dow Chemical Company) and adjusting the pH of each sample to a pH of 9 using ammonia. A latex control formulation was prepared without adding a coalescing solvent. Table 3 shows the pH of each formulation measured weekly for four weeks, whereas latex formulations were stored at room temperature.
Table 3.
Coalescent initial pH 1 week 2 weeks 3 weeks 4 weeks Control (without coalescent) 9.02 8.98 9.00 9.06 9.05 EtLPK 9.00 8.69 8.53 8.41 8.24 iPrLPK 8.93 8.79 8.73 8.71 8.64 2EH-LPK 8.97 8.99 8.94 9.03 9.00
[0224] The data in Table 3 shows that 2EH-LPK maintains the pH at a value that is close to the initial pH, over at least four weeks. In addition, since the pH remains almost constant for 2EH-LPK, it is likely that the hydrolysis of the ester will not occur appreciably since carboxylic acids would form and subsequently decrease the
99/135 pH of the composition. The results for 2EH-LPK are quite similar to those for the control that have no coalescing solvent. Consequently, 2EH-LPK-containing latex formulations have hydrolytically stable storage properties under alkaline pH conditions.
Example 4.
[0225] Hydrolytic stability of coalescing solvents at elevated temperature (45 ° C) was determined by 1-nonyl levulinate propylene glycol ketal (1N-LPK), 3,5,5-trimethylhexyl ketal propylene glycol (355TMH-LPK) and cetal of ethyl levulinate propylene glycol (EtLPK). Latex formulations were prepared by adding 1.0 grams of each coalescing solvent to 10 grams of an acrylic latex (Rhoplex SG - 10M commercially available from Dow Chemical Company) and by adjusting the pH of each sample to a pH of 9 using ammonia. A latex control formulation was prepared without adding a coalescing solvent. Table 4 shows the pH of each formulation measured weekly for two weeks, while the latex formulations were stored at 45 ° C.
Table 4.
Coalescent initial pH 1 week 2 weeks Control (without coalescent) 8.94 9.01 8.87 EtLPK 8.95 8.06 7.53 1N-LPK 8.92 8.75 8.63 355TMH-LPK 8.92 8.78 8.64
[0226] The data in Table 4 shows that formulations containing 1N-LPK and 355TMH-LPK kept the pH close to the initial pH over two weeks at 45 ° C, suggesting that ester hydrolysis does not occur appreciably, since since carboxylic acids could form and subsequently decrease the composition's pH composition. The results for 1N-LPK and 355TMH-LPK are quite similar to those for control, which has no coalescing solvent. Per
100/135 therefore, 1N-LPK and 355TMH-LPK-containing latex formations have hydrolytically stable storage properties under alkaline pH conditions.
PROPHETIC EXAMPLES
[0227] The following examples are prophetic. As used throughout the examples, 2EH-LK refers to 2-ethylhexyl levulinate propylene glycol ketal, 1N-LPK refers to 1-nonyl levulinate propylene glycol ketal and 355TMH-LPK refers to 3, 5,5-trimethylhexyl levulonate propylene glycol.
Example 5.
[0228] This is a prophetic example that aims to demonstrate the composition of a temporary hair dye and a method of making a temporary hair dye. Temporary dye compositions are based on textile and hair dyes containing molecules that are too large to penetrate the fiber axis. After rinsing, the color comes off after a single wash with shampoo. Temporary inks are also called direct inks. Temporary dyes add color to the hair, but they cannot lighten the hair color. Table 5 below details temporary hair dye compositions. All weights in table 5 are given in grams.
Table 5.
101/135
ingredient Weight in gram Part A Deionized water 34.55 Carbopol Aqua SF-1 (acrylate copolymer, 30%) ¹ 10 Part B Deionized water 15 Disodium EDTA 0.05 Cetal · 5 Miraol Ultra-C37 (cocoanfoacetate (37%) / 15 Cocamidopropyl betaine (15%) 3 Polyquaternium-39 0.8 Part C Germaben II (propylene glycol (and urea diazolidinyl (e) methyl paraben (e) propylparaben) ³ 0.45 Sodium hydroxide (18%) 0.25, pH adjustment to 7 Part D Deionized water 8 Arianor Sienna Brown (basic brown 27 / CI12251) ’ 025 Arianor Steel Blue (basic blue 99 / CI 56059) ' 0.125 Arianor Madder Red (basic red 76 / CI12245) ' 0.1X5 Dow Corning 193 (PEG-12 dimethicone) ⁶ O.2 Part E decyl glucose (50%) 4 Deionized water 3 Timiron MP-149 Diamond Cluster (mica and titanium dioxide) ⁶ O.2
¹ commercially available from Lubrizol / Noveon Consumer Specialties; ² commercially available from Rhodia; ³ commercially available from ISP; ⁴ commercially available from Warner Jenkinson; ⁵ commercially available from Dow Corning; ⁶ commercially available from Rona;
* example A: ketal is 2EH-LPK; Example B: ketal is 1N-LPK. Example C: ketal is 355TMH-LPK.
[0229] The method for making the compositions in Table 5 is as follows:
[0230] Slowly add Carbopol in DI (deionized) water (part A). In a separate container, dissolve the EDTA in Dl water at about 50 ° C and then add the remaining Part B ingredients individually, and stirring. Part B is added slowly to Part A, stirring moderately. Add the ingredients of Part C individually to Parts A / B combined to form a main batch, which comprises Part A and Part B and Part C, adjusting the amount of sodium hydroxide so that the pH of the batch is 7. In one container separately, dissolve the inks in Dl water, keeping the temperature below
102/135 at 60 ° C and then add PEG-12 dimethicone. Add Part D to the main batch, which now comprises Part A, Part B, Part C and Part D. In a separate container, prepare Part E by spreading the pigments on the other ingredients in Part E. Add Part E to the main batch to form the temporary hair dye.
Example 6.
[0231] This is a prophetic example that aims to demonstrate the composition of a semi-permanent hair dye composition and the manufacture of a semi-permanent hair dye composition. As temporary dyes, these formulations depend on direct dyes. However, semi-permanent dyes comprise smaller molecules, based on nitro-phenylene diamine and due to their small size, direct inks in semi-permanent formulations can penetrate the fiber axis. As a result, semi-permanent hair dyes can last for about 6 to 8 shampoo applications. Table 6 below details temporary hair dye compositions. All weights in Table 6 are given in grams.
Table 6.
Ingredient Weight in gram Part A Deionized water 64 Carbomer 05 CROSULTAINE-C50 ¹ (cocamidopropril hydroxisultaine) 7 BRU 020 (Oleth-20> · 0.4 triethanolamine 04 Part BI (for light brown / medium) Deionized water 11.5 Blue HC # 2 CP ’ 13 HC Red # 1 ’ 06 Yellow HC 04 ' 03 Part B2 (for dark brown / black) Deionized water 10.6 Blue HC # 2 CP ' 23 HC Red # 1 ' 0.4
103/135
HC Yellow # 4 ' 06 Part B3 (for reddish-brown) Deionized water 12 1 Blue HC # 2 CP ' 0.3 HC Red # 1 ' 1.5 HC Yellow # 4 ' 0.2 Part C SD 40 alcohol 3 Cetal · 3 CROTHIX LIQUID ² (PET-150 pentaerythrityl tetra stearate (e) PEG-6 caprylic / capric glycerides (e) water 3 Crodasone W ² (PG-propyl silanethiol Hydrolyzed Wheat Protein 3 Germaben ll ^J (propylene glycol (and urea dlazolidinyl (e) methyl paraben (e) propylparaben) 1
¹ provided by Jos. H. Lowenstein and Sons; ² provided by Croda; ³ provided by ISP; * example A: ketal is 2EH-LPK; Example B: ketal is 1N-LPK. Example C: ketal is 355TMH-LPK.
[0232] The manufacturing process for the composition of Table 6 is ο following. The carbomer is placed in the water slowly while the solution is mixed quickly and the mixture is heated to 65 ° C. When evenly spread, add the remaining ingredients from Part A one at a time, while mixing at a moderate speed. Mix Part B ingredients (Part B1, Part B2 or Part B3) by mixing, while heating to a temperature of 65 ° C. Add Part B to Part A, mixing well. Continue mixing and cool to 40 ° C. Add Part C ingredients individually to the Part A and Part B mixture, mixing well after each addition.
Example 7.
[0233] This is a prophetic example that aims to demonstrate the composition for a semi permanent hair dye gel composition with a dark brown color. This example also details a method of making the composition in Table 7.
Table 7.
104/135
Ingredients Weight in grams Part A HC Blue # 2 solid 0.36 Lowadene Violet # 1 ’ 0.56 HC Yellow # 4 0.24 Blue Lowadene 61505 ’ 02 Blue Lowadene 62500 ’ 0.17 HC Yellow # 5 0.02 Cetal * 6 Deionized water 18.34 Part B Oleic acid 0.82 Ethanolamine 0.18 Part C Monamid SIO-ADY (linoleamide DEA) ² 2 Part D Structure 2001 polymer (acrylate / stearate-20 itaconate polymer) ’ 3.39 Deionized water 60.11 Part E
Ethanolamine] 2.5 Part F Citric acid (10%)1
¹ Jos. H. Lowenstein & Sons, Inc; ² Uniqema / Croda; ³ AkzoNobel; * example A: ketal is 2EH-LPK; Example B: ketal is 1N-LPK. Example C: ketal is 355TMH-LPK.
[0234] The composition is manufactured as follows. With moderate stirring, heat Part A to between 50 ° C and 60 ° C and mix the paints well. Cool to 40 ° C. Add Part B and Part C to Part A and mix well. Add Part D to the ink solution and mix well. Add Part E to the ink solution and mix well. Finally, add Part F to the ink solution and mix well.
Example 8.
[0235] This is a prophetic example that aims to demonstrate a composition used in the manufacture of a permanent hair dye composition. A method of making permanent hair dye is also described. Permanent hair dyes are based on oxidative dye chemistry and are formulated in two packages that are mixed at the time of sham. One package contains colored ink intermediates in an alkaline solution, while the other
105/135 package contains the peroxide activator that lightens the hair and converts the intermediate dye to its color format. Because permanent hair dye formulations can dye as well as a hair bleach, hair can be dyed a shade lighter than its natural color. Table 8 demonstrates the composition of a permanent hair dye.
Table 8.
Ingredients Weight in grams Phase A Deionized water 52 51 Sodium sulphite 0.30 ΕΓΙΓΛ 0.20 Erythorbic acid 0.30 p-Phenylenediamine 1.70 ' 4-amino-2-hydroxytoluene 0.06 RcsorcíiKtl 140 o-Aminophenol 1.40, Toluene-2,5-diamine sulfate 0.11 I 1-Naphthol 0.02 í Cetal * ........................... 3 .......! Incromide CA (Cocamide DEA) 3.50 Incromectant AMEA-100 (Acetamide MEA) 1.00 Phase B KeraTintz EZ ((Cetyl alcohol [e] stearyl alcohol (e) PPG-5 cetet-20 & Dicetyl Phosphate (e) cetet-10 phosphate [e] behentrimony methosulfate) 12 Cetal * 9 Phase C Crodasone W (hydrolyzed wheat protein PG-propyl silanetriol) 2.00 Crosilkquat (Cocamidopropyl hydroxypropyl silk amino acids) 0.50 Crosultaine C-50 (Cocamidopropyl hydroxisultaine) 1.00 Phase D Ammonia 10.00
'Example A: ketal is 2EH-LPK; Example B: ketal is 1N-LPK. Example C: ketal is 355TMH-LPK.
[0236] The method of manufacturing the composition in Table 8 is as shown below.
[0237] Combine the phase A ingredients in a main container and heat to 75 ° C. In a separate container, heat phase B to 75 ° C. Add phase B to phase A, mixing. Cool to 50 ° C and add phase C ingredients individually, mixing well after each addition. Cool to 40 ° C, add phase D and mix until smooth. This formulation must be mixed with a hydrogen peroxide developer before use.
106/135
Examples 9-47.
[0238] The following prophetic examples demonstrate soluble formulations that include an alkyl ketal ester and an essential oil.
[0239] Table 9 shows 39 different fragrance formulations that can be obtained by mixing an alkyl ketal ester and an essential oil. The ketal alkyl ester and the essential oil are mixed in a 1: 1 weight ratio at room temperature with gentle agitation. Solubility is determined visually immediately after mixing. Transparent solutions are described as miscible and solutions that are cloudy or show evidence of a second phase are labeled as immiscible.
Table 9
Ex. Solvent Pure Essential Oil Mixability 50/50 by weight 9 2EH-LPK Orange (Citrus sinensis) Miscible 10 2EH-LPK Patchouli (Pogostemon patchouli) Miscible 11 2EH-LPK llangue ilangue (Canaga odorata) Miscible 12 2EH-LPK Coriander seed (Coriandrum sativum) Miscible 13 2EH-LPK Birch seed (slow birch) Miscible 14 2EH-LPK Citronella (Cymbopogon nardus) Miscible 15 2EH-LPK Pine needle (Pinus sylvestris) Miscible 16 2EH-LPK Vetiver (vetivera zizanoides) Miscible 17 2EH-LPK Basil (Ocimum basilicum) Miscible 18 2EH-LPK Myrrh (Commiphora myrrh a) Miscible 19 2EHLPK Geranium (Pelargonium graveolens) Miscible 20 2EH-LPK Bergamot (Citrus bergamia) Miscible 21 2EH-LPK Lavender (Lavandula angustifolium) Miscible 22 1N-LPK Orange (Citrus sinensis) Miscible 23 1N-LPK Patchouli (Pogostemon patchouli) Miscible 24 1N-LPK llangue ilangue (Canaga odorata) Miscible 25 1N-LPK Coriander seed (Coriandrum sativum) Miscible 26 1N-LPK Birch seed (slow birch) Miscible 27 1N-LPK Citronella (Cymbopogon nardus) Miscible 28 1N-LPK Pine needle (Pinus sylvestris) Miscible 29 1N-LPK Vetiver (vetivera zizanoides) Miscible 30 1N-LPK Basil (Ocimum basilicum) Miscible 31 1N-LPK Myrrh (Commiphora myrrha) Miscible 32 1N-LPK Geranium (Pelargonium graveolens) Miscible 33 1N-LPK Bergamot (Citrus bergamia) Miscible 34 1N-LPK Lavender (Lavandula angustifolium) Miscible 35 355TMH-LPK Orange (Citrus sinensis) Miscible 36 355TMH-LPK Patchouli (Pogostemon patchouli) Miscible
107/135
37 355TMH-LPK llangue ilangue (Canaga odorata) Miscible 38 355TMH-LPK Coriander seed (Coriandrum sativum) Miscible 39 355TMH-LPK Birch seed (slow birch) Miscible 40 355TMH-LPK Citronella (Cymbopogon nardus) Miscible 41 355TMH-LPK Pine needle (Pinus sylvestris) Miscible 42 355TMH-LPK Vetiver (vetivera zizanoides) Miscible 43 355TMH-LPK Basil (Ocimum basilicum) Miscible 44 355TMH-LPK Myrrh (Commiphora myrrh a) Miscible 45 355TMH-LPK Geranium (Pelargonium graveolens) Miscible 46 355TMH-LPK Bergamot (Citrus bergamia) Miscible 47 355TMH-LPK Lavender (Lavandula angustifolium) Miscible Examples 4C I-63.
[240] The following examples demonstrate prophetic compatibility or incompatibility between various fragrance compositions and ketal alkyl esters. Table 10 demonstrates the solubility of 2EHLPK, 1N-LPK and 355 TMH-LPK with the listed oils.
Table 10
Example Oil % ketal alkyl ester Result 48 Castor oil 50 Miscible 49 C1215 alkyl benzoateMiscible 50 Isopropyl myristate 25 Miscible 51 Caprylic / capric acid triglycerides (Neobee M-5) 50 Miscible 52 Octyl palmitate 50 Miscible 53 Mineral oil 50 Miscible 54 Coconut oil 50 Miscible 55 Cylcomethicone 50 Miscible 56 Avocado oil 50 Miscible 57 Canola oil 50 Miscible 58 Grape seed oil 50 Miscible 59 Sesame oil 29 Miscible 60 Soy oil 49 Miscible 61 Squalane Pripure 3759 50 Miscible 62 Methicone Caprilyl 50 Miscible 63 Oleic alcohol 50 Miscible
[241] In Table 10 above, it can be seen that materials, including vegetable oils, animal fats and derivatives, are useful fragrance compounds and can be miscible with at least one of the ketal alkyl esters. Examples of useful aromatic compounds include, for example, açaí oil, almond oil, aloe vera oil, andiroba oil, annatto oil, avocado oil, babassu oil, borage oil, oil
108/135 Brazil nuts, buriti oil, camelina oil, coffee oil, copaiba oil, emu oil, passion fruit oil, almond oil, 'castor oil, coconut oil, grape seed oil, jojoba oil, macadamia oil, rosehip oil, ajwain oil, angelica root oil, anise oil, aragan oil, asafoetida, balm oil, basil oil, bay oil, bergamot oil, essential oil black pepper, buchu oil, birch oil, camphor oil, cannabis oil, caraway oil, cardamom seed oil, carrot seed oil, chamomile oil, calamus oil, cinnamon oil, oil citronella, sage, clove leaf oil, coffee, coriander, Balsamita major oil, cranberry seed oil, cubeba, cumin oil, cypress, cypriol, curry leaf, davana oil, dill oil, elecampane, oil eucalyptus, fennel seed oil, fenugreek oil, spruce, incense oil, galangal, geranium oil, ginger oil, solidago , grapefruit oil, grape seed oil, henna oil, helichrysum, horseradish oil, hyssop, tanachide, jasmine oil, juniper berries oil, lavender oil, lemon oil, lemon balm, marjoram, tea tree , lemon balm oil, mountain saturate, sagebrush oil, mustard oil, myrrh oil, myrtle, neem tree oil, neroli, nutmeg, orange oil, oregano oil, orris oil, paio santo , parsley oil, patchouli oil, perilla oil, penny oil, mint oil, petitgrain, pine oil, plum oil, ravensara, red cedar, Roman chamomile, rose oil, rosehip oil, rosemary, rosewood oil, sandalwood oil, sassafras oil, saturate oil, schisandra oil, pure lemongrass, pea, star anise oil, mandarin, tarragon oil, tea tree oil, thyme oil, oil tsuga, saffron, valerian, vetiver oil, western red cedar, wintergreen, yarrow oil, ilangue-ilangue, and zedoaria oil.
Examples 64-65.
[242] These examples demonstrate the manufacture of formulations of
109/135 perfumes containing akyl esters of ketal. Table 11 reflects Examples 64 and 65. The components are added at room temperature and gently stirred by stirring. Solubility is determined visually immediately after mixing. All formulations are transparent. The composition is given in weight percent (% by weight).
Table 11
Example 64 Example 64 orange oil 1.4% 1.3% bergamot 1.9% 1.8% myrrh 1.2% 1.1% citronella 1.3% 1.2% cedar oil 0.6% 0.6% deionized water 8.2% 14.7% Cetal * 6.6% 6.1% ethanol 78.9% 73.2%
* example A: ketal is 2EH-LPK; Example B: ketal is 1N-LPK. Example C: ketal is 355TMH-LPK.
Example 66.
[243] This is a prophetic example that describes the manufacture of an air purifier. The formulation is listed in Table 12 below. To make the air purifier, the ingredients of part A and part B are first mixed individually and then added together with continuous mixing. The Part A ingredients are added in the order listed in Table 9 and then mixed for a minimum of 30 minutes. The water is heated to 100-130 ° F.
Table 12
Ingredient % by weight Part A Deionized water 65.7 Laponite RD 3.0 Aquaion CMC-9H4F 0.3 Part B Cetal * 15 Fragrance 15 Cola® Mulse Emultron PM 1
'Example A: ketal is 2EH-LPK; Example B: ketal is 1N-LPK. Example C: ketal is 355TMH-LPK.
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Waxes of Examples 67-72.
[244] The following examples are performed to demonstrate the use of a fragrance formulation in candles. The compatibility between various waxes and ketal alkyl esters is first determined as detailed below. Table 13 below details the fragrance formulations for different candles that contain the fragrance composition.
Beeswax
[245] Beeswax and 2EH-LPK are weighed in a 50/50 weight ratio container and heated to 80 ° C to form a uniform melted mixture. The mixture forms a single homogeneous wax layer after cooling to room temperature.
[246] Beeswax and 1N-LPK are weighed in a 50/50 weight ratio container and heated to 80 ° C to form a uniform melted mixture. The mixture forms a single homogeneous wax layer after cooling to room temperature.
[247] Beeswax and 355TMH-LPK are weighed in a 50/50 weight ratio container and heated to 80 ° C to form a uniform melted mixture. The mixture forms a single homogeneous wax layer after cooling to room temperature.
Paraffin
[248] The Gulf Wax brand of household paraffin wax for paraffin wax for canning and candle production (distributed by Royal Oak Enterprises) can be used in these experiments.
[249] Paraffin and 2EH-LPK are weighed in a 50/50 weight ratio container and heated to 80 ° C to form a uniform melted mixture. The mixture forms a single homogeneous wax layer after cooling to room temperature. Paraffin and 2EH-LPK are weighed in a 75/25 weight ratio container and heated to 80 ° C to form a uniform melted mixture. The mixture forms a single homogeneous wax layer after cooling to temperature
111/135 environment.
[250] Paraffin and 1N-LPK are weighed in a 50/50 weight ratio container and heated to 80 ° C to form a uniform melted mixture. The mixture forms a single homogeneous wax layer after cooling to room temperature. Paraffin and 1N-LPK are weighed in a 75/25 weight ratio container and heated to 80 ° C to form a uniform melted mixture. The mixture forms a single homogeneous wax layer after cooling to room temperature.
[251] Paraffin and 355TMH-LPK are weighed in a 50/50 weight ratio container and heated to 80 ° C to form a uniform melted mixture. The mixture forms a single homogeneous wax layer after cooling to room temperature. Paraffin and 355TMH-LPK are weighed in a 75/25 weight ratio container and heated to 80 ° C to form a uniform melted mixture. The mixture forms a single homogeneous wax layer after cooling to room temperature.
Carnauba wax
[252] Carnauba wax and 2EH-LPK are weighed in a 50/50 weight ratio container and heated to 120 ° C to form a uniform melted mixture. A single homogeneous wax layer is formed after cooling.
[253] Carnauba wax and 1N-LPK are weighed in a 50/50 weight ratio container and heated to 120 ° C to form a uniform melted mixture. A single homogeneous wax layer is formed after cooling.
[254] Carnauba wax and 355TMH-LPK are weighed in a 50/50 weight ratio container and heated to 120 ° C to form a uniform melted mixture. A single homogeneous wax layer is formed after cooling.
Stearic acid
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[255] Stearic acid and 2EH-LPK are weighed in a 50/50 weight ratio container and heated to 80 ° C to form a uniform melted mixture. The mixture forms a single homogeneous wax layer after cooling to room temperature.
[256] Stearic acid and 1N-LPK are weighed in a 50/50 weight ratio container and heated to 80 ° C to form a uniform melted mixture. The mixture forms a single homogeneous wax layer after cooling to room temperature.
[257] Stearic acid and 355TMH-LPK are weighed in a 50/50 weight ratio container and heated to 80 ° C to form a uniform melted mixture. The mixture forms a single homogeneous wax layer after cooling to room temperature.
[258] The following Table 13 details formulations for different candles containing the waxes detailed above and alkyl ester of cetai. The formulations are manufactured by combining three parts (Part A, Part B and Part C). Candle formulations 116-120 (Examples 116-120) are manufactured by weighing Part A ingredients in a container and heating at 80 ° C until the mixture is in liquid form. The container is removed from the heat and Part C is added to the container. While the mixture is still in liquid form, the mixture is poured into a container and a wick with a base metal guide is introduced into the center of the mixture. The completed candle is cooled to room temperature.
[259] Candle formulations 67-72 are manufactured by weighing Part A ingredients in a container and heating to 80 ° C until the mixture is in liquid form. Part B is added to Part A and mixed for 2 minutes. The container is removed from the heat and Part C is added to the container. While the mixture is still in liquid form, the candle is poured into a container and a wick with a base metal guide is introduced into the center of the mixture. The completed candle is cooled
113/135 at room temperature.
Table 13
Ingredient 67 68 69 70 71 72 Part A (weights of ingredients given as% by weight of the total formulation) Nature Wax P-1 10% 28% 28% 28% 0% 0% Nature Wax C-1 26% 6% 6% 6% 29.9% 29.9% Nature Wax C-3 26% 0% 0% 0% 29.9% 29.9% Beeswax 28% 56% 56% 56% 29.9% 29.9% Part B (weights of ingredients given as% by weight of the total formulation) Cinquasia Red B RT-195-D 0% 0% 0% 0% 0.30% 0.31% Part C (weights of the ingredients given as% by weight of the formulation to al) 355TMH-LPK 0% 5% 0% 0% 5% 0% 1N-LPK 5% 0% 0% 5% 0% 0% 2EH-LPK 0% 0% 5% 0% 0% 5% Essential oil of (Citrus bergamia)5% 5% 5% 0% 0% Grapefruit essential oil 4% 0% 0% 0% 0% 0% Lavender bergamot essential oil (Lavandula angustifolium) 1% 0% 0% 0% 0% 0% Lemon essential oil 0% 0% 0% 0% 5% 4.99%
[260] All formulations form candles.
Example 73.
[261] This example is performed to demonstrate the use of a fragrance composition comprising vanillin in a perfume formulation (a candle). The ingredients of the composition are shown in Table 14 below. The ingredients of the composition are divided into two parts - Part A and Part B, which are then processed as follows: The Part B ingredients are mixed at room temperature until the vanillin is completely dissolved. In a separate container, the Part A ingredients are heated to 80 ° C until they form a uniform melted mixture. Part B is then added to part A (when at 80 ° C) and mixed until uniform. The container containing Parts A and B is poured into a candle mold. A wick can be added to the candle.
Table 14
Ingredient % by weight Part A
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Paraffin 37.5% Beeswax 37.5% Part B Cetal * 22.5% vanillin 2.5%
'Example A: ketal is 2EH-LPK; Example B: ketal is 1N-LPK. Example C: ketal is 355TMH-LPK.
[262] A uniform solid candle is formed after cooling, with no signs of separation. Example 74 - Model solutions of ethanolic avobenzone sunscreen.
[263] Mixtures with three components of ketal, ethanol and avobenzone are prepared by mixing the materials in different proportions at room temperature in a flask and stirring. Avobenzone, alone, is immiscible in 5% ethanol by weight level. The acetals used are as follows: A: ketal is 2EH-LPK; Example B: ketal is 1N-LPK. Example C: Cetal is 355TMH-LPK.
[264] These data will show that avobenzone concentrations greater than 5% can be achieved in an ethanolic solution by adding ketal as a cosolvent. Thus, high concentrations of this UV agent can be provided in a formulation that is suitable for use in a spray sunscreen formulation.
Example 75 - Ethanolic and aqueous oxybenzone sunscreen solutions.
[265] Mixtures with three components of ketal, ethanol and oxybenzone are prepared by mixing the materials in different proportions at room temperature in a flask and stirring. The acetals used are as follows: A: ketal is 2EH-LPK; Example B: ketal is 1N-LPK. Example C: ketal is 355TMH-LPK. Transparent mixtures are considered miscible in this test, while cloudy mixtures or with separate phases are considered immiscible. Oxybenzone alone is immiscible in 10% ethanol by weight level.
[266] These data will show that oxybenzone concentrations
115/135 greater than 10% by weight can be achieved in an ethanolic solution by adding ketal as a cosolvent. Thus, high concentrations of this UV agent can be provided in a formulation that is suitable as a spray sunscreen formulation.
Example 76 - Spray solution of ethanolic sunscreen.
[267] A model formulation of spray sunscreen contains 64.4 parts of ethanol, 3 parts of an acrylate / octylacrylamide copolymer, 3 parts of octyldodecanol, 7.5 parts of octinoxate, 4 parts of oxybenzone, 5 parts of octysalate, 3 parts of avobenzone, 2.5 parts of POLYCRYLENE® (CAS No. 862993-96-2), 2.5 parts of octocrylene and 5.1 parts of water.
[268] Because the ethanol is drying, it is desirable to reduce the concentration of ethanol in the formulation. When 10 parts of ethanol are replaced by 10 parts of 2EH-LPK, 1N-LPK or 355TMH-LPK, a stable solution is obtained that dries out the skin less due to the decrease in the ethanol content.
Examples of 77-78 - Sunscreen lotion.
[269] Model sunscreen lotions are made from the ingredients shown in Table 15.
Table 15.
Example 77 Example 78 Ingredients % by weight % by weight Part A Cetal ** 0 0 Cetyl alcohol 1 1 Stearic acid 2 2 Octyl palmitate 3 3 Cinnamateoctylmethoxy 7.5 7.5 Oxybenzone 3 3 PEG-40 stearate 1.5 1.5 Dimethyl stamina 2 2 Copolymer ofacrylates / octylacrylamide (Dermacryl 79) 2 2 Part B Deionized water To 100 To 100 Copolymer of 0.06 0.06
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cross-linked polyacrylate (Carbopol ETD 2050) * Triethanolamine 0.7 0.7
* The amount of thickener must be adjusted based on the efficiency of the carbopol class ** example A: ketal is 2EH-LPK; Example B: ketal is 1N-LPK. Example C: ketal is 355TMH-LPK.
[270] To prepare the sunscreen lotion formulations, Part B is first prepared by adding the carbomer slowly to the water with the mixture and heated to 80 ° C. Triethanolamine is added to complete Part B. In a separate container, the Part A ingredients are combined, except the acrylates / octylacrylamide copolymer. These components are heated to 80 ° C with mixing. The acrylates / octylacrylamide copolymer is then slowly sieved in Part A under constant stirring until dissolved. Part A is then added to Part B and mixed for 15 minutes at 80 ° C. The mixture is then slowly cooled to room temperature. Example 78 is less viscous and remains stable for at least four weeks. The modified product should feel less greasy and lighter.
Example 79. Active Medicinal or Personal Care Agents. Salicylic acid
[271] Salicylic acid (U.S.P. classification available from J.T. Baker) is dissolved in 1% solids in 2EH-LPK. After 24 hours at room temperature, there is no evidence of precipitation. The example is repeated with 1N-LPK and 355TMH-LPK replacing 2EH-LPK with similar results.
Retinoic Acid (all trans)
[272] Retinoic acid (Tretinoin, available from Tokyo Chemical Industry) is dissolved in 2EH-LPK in 0.1% solids. After 1 day at room temperature, there are no signs of precipitation. The example is repeated with 1N-LPK and 355TMH-LPK replacing 2EH-LPK with similar results.
Tea Tree Oil
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[273] Certified organic tea tree oil (Melaleuca alternifolia, a plant originating in Australia and extracted by steam distillation) can be purchased by Wyndmere Naturals. A 50/50 mixture of 2EHLPK, 1N-LPK or 355TMH-LPK and tea tree oil is miscible at room temperature.
Lactic acid
[274] Lactic acid (available from Alfa Chem, Ashland Distribution and Spectrum Chemical Mfg. Corp) forms a homogeneous solution in 2EH-LPK, 1N-LPK or 355TMH-LPK in the ratio of 5/95 between lactic acid and ketal.
Ubiquinone (Coenzyme Q10)
[275] Coenzyme Q10 is soluble in 2EH-LPK, 1N-LPK or 355TMHLPK in 0.1% or more and remains in solution at room temperature overnight.
Dimethylmethoxy chromanyl palmitate
[276] Dimethylmethoxy chrommanyl palmitate (available as Chromabright from Liopotec) forms a homogeneous solution in 2EH-LPK, 1N-LPK or 355TMH-LPK in 0.1% or more and remains in solution at room temperature overnight.
[277] The recommended dose level is 0.1%.
Tetrahydrodiferuloylmethane (Tetrahydrocurcuminoids)
[278] Tetrahydrocurcuminoids (available at lotioncrafter.com) are dissolved in 1% solids in 2EH-LPK at 50 ° C, to form a uniform clear solution. The mixture is still soluble after 24 hours of storage at room temperature. The example is repeated with 1NLPK and 355TMH-LPK replacing 2EH-LPK with similar results. The recommended usage rate is 0.1-1%.
Resveratrol
[279] Resveratrol (available from Enzo Life Sciences) is dissolved in 0.1% solids in 2EH-LPK, 1N-LPK or 355TMH-LPK at 50
118/135 ° C.The three mixtures are still soluble after 24 hours of storage at room temperature.
Tetrahydropiperine
[280] Tetrahydropiperine (available as Cosmoperine from lotioncrafter.com) is dissolved in 1% solids in 2EH-LPK, 1N-LPK and 355TMH-LPK at room temperature. The mixtures are still soluble after 24 hours of storage at room temperature. Tetrahydropiperine is a co-ingredient in anti-aging formulations and is considered to improve the bioavailability of active agents.
Dimethylmethoxy Cromanol
[281] Dimethylmethoxy Cromanol (available as Lipochroman-6 from lotioncrafter.com) is dissolved in 0.1% solids in 2EH-LPK, 1N-LPK and 355TMH-LPK at room temperature. The mixtures are still soluble after 24 hours of storage at room temperature. The recommended usage rate is 0.01-0.05%.
Example 80 - Antiperspirant.
A prophetic formulation for a roll-on antiperspirant follows.
Table 16 - Roll-on antiperspirant
Ingredient % by weight Part ASteareth-2 (VOLPOS S-2, Croda) 2.2 Steareth-20 (VOLPOS S-20, Croda) 0.6 PPG-10 cetyl ether 5 Ethanol 5 Cetal * 5 Part BDeionized water 37.2 Part CAluminum chloride, 32C Baum (Recheis Chemical Co.) 5 Hydrochloride, 50% (Recheis Chemical Co.) 40
* ketal examples: Ex: A, 2EH-LPK; Ex. B, 1N-LPK; Ex. C, 355TMH-LPK
[282] To make the roll-on antiperspirant, combine the Part A ingredients with the mixture and heat to 65-70 ° C. Heat Part B to 65-70 ° C. Add Part B to Part A with mixture and cool to 45 ° C. Add the
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Part C with mixture and cool to the desired filling temperature.
Example 81 - Lipstick.
[283] The following is a prophetic example of a lipstick formulation. Table 17 - Lipstick.
Ingredient % by weight Part A Caprylic / capric acid triglycerides 8.56 Stearoyl octyldodecyl stearate 13.37 Triisoestearyl citrate 4.05 Pentaerythrityl tetraisoestearate 5.60 Jojoba esters 1.72 Lanolin Oil 1.62 Bis-digliceril Polyacyladipate-2 1.02 Ricinus Communis seed oil (Castor) 20.50 Prunifera Copernicia Wax (Carnaúba) 2.30 Euphorbia Cerifera Wax (Candelilla) 5.24 Alba Wax (Beeswax) 2.09 Ozoquerita Wax 1.80 Microcrystalline Wax 1.13 Phenoxyethanol 1.00 Polyethylene 1.00 Octyl methoxycinnamate 0.60 Tocopheryl acetate 0.05 Part B Ricinus Communis seed oil (Castor) 10.00 Red No. 6 D&C with barium lacquer 6.25 Iron oxide 0.10 Cetal * 12
* ketal examples: Ex: A, 2EH-LPK; Ex. B, 1N-LPK; Ex. C,
355TMH-LPK
[284] To manufacture the sample formulations, weigh Part A and start heating to 80-85 ° C with mixing. Pre-crush Part B. When Part A is completely melted and transparent, add the crushed from Part B to the wax / oil mixture of Part A. When all the color is dispersed and the batch is uniform, pour into molds.
Example 82 - Solid lip gloss.
[285] The following is a prophetic example of a solid lip gloss formulation.
Table 18 - Solid lip gloss.
Ingredient % by weight Part A Castor oil 36.4
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Cetai * 10 Polyisobutene 250 30 Beeswax 10 Candelilla Wax 9 Mica pigment 3 Part B Vitamin E acetate 1 B HT 0.2 Food flavoring 0.4
* ketal examples: Ex: A, 2EH-LPK; Ex. B, 1N-LPK; Ex. C, 355TMH-LPK
[286] To manufacture the sample formulations, add part A in a container and heat to 75 ° C to melt the wax, mixing until uniform. Remove from heat and add Part B, stirring well. While still liquid, pour it into a cosmetic container.
Example 83 - Lip balm.
[287] The following is a prophetic example of a lip balm formulation.
Table 19 - Lip balm.
Ingredient % by weight Part A Fractionated coconut oil 13 Cetal 10 Castor oil 15 Triglyceride 23 Ori lard 12 Beeswax 17 Lecithin 1 Part B Titanium dioxide (optional: nano size) 2 Cetal * 4.8 Part C Pro-vitamin B5 1 Vitamin E acetate 0.1 Tocopherol Vitamin E 0.1 Allantoin 0.2 Parabeno-DU ** 0.5 Food flavoring 0.3
* ketal examples: Ex: A, 2EH-LPK; Ex. B, 1N-LPK; Ex. C, 355TMH-LPK ** Paraben-DU - wide spectrum pre-stirred preservative mixture (3% by weight propylparaben, 11% by weight ethylparaben, 30% by weight diazolidinyl urea, 56% by weight propylene glycol).
[288] To manufacture the sample formulations, grind or mix
121/135 'previously part C ingredients. Add Part A to the container and heat to 65 ° C until the wax and butter melt. Slowly add to Part C with mixing and mix until well dispersed. Remove from heat. Add the ingredients from Part C to Parts A / B one by one and make sure the formulation is well mixed. Fill molds while the formulation is still liquid. Let it cool.
Example 84 - Compact powder eyeshadow.
[289] The following is a prophetic example of a compact powder eyeshadow formulation.
Table 20 - Nude Glitter Compact Powder Eyeshadow
Ingredient % by weight Part A Cetai * 4 Cyclodimethicone 3 Polyglyceryl oleate 0.75 Vitamin E acetate 1 Part B Pearly white mica 31 Mica in spheres (based on powder) 20 Powdered talc (powder based) 20 Beige mica 5 Magnesium stearate 5 Bismuth oxychloride 5 Titanium dioxide 5
* cetai examples: Ex: A, 2EH-LPK; Ex: B, 1N-LPK; Ex: C, 355TMH-LPK
[290] To manufacture the exemplary formulations, combine titanium dioxide and pearly white mica in a mortar, shake well and thoroughly with the pestle until the color becomes uniform. Then add the other ingredients in Part B, one after the other, mixing well after each addition. Then add Part A to the mortar, starting with cetai, and mix well, for several minutes or until the ingredients are mixed and the color looks uniform. Fill an eye shadow container with the eye shadow and, using an appropriate tool, squeeze it into eye shadow containers.
Example 85 - Anhydrous eyelash mask.
[291] The following is a prophetic example of a mask formation
122/135 for anhydrous eyelashes.
Table 21 - Anhydrous eyelash mask
Ingredient % by weight Part A Cetal * 30.95 AC 6a polyethylene wax 11 Candelilla Wax 45 Hydroxylated lanolin 0.25 Part B Pentaerythrityl rosinate 2 Isoparaffin C9-11 2 Part C Methylparaben 0.2 Propylparaben 0.1 Part D Zinc stearate 1 Part E Silica Silylate 1 Part F Petroleum distillates, quaternium-18 hectorite, propylene carbonate 35 Part G Black iron oxide 12 * ketal examples: Ex. A, 2EH-LPK; Ex. B, 1N- LPK; Ex. C,
355TMH-LPK
[292] To manufacture exemplary formulations, prepare Part B in advance by stirring in a sealed container until it dissolves. In a separate closed container, combine the ingredients from Part A and the one up to 90-95 ° C without stirring. When Part A is still and well mixed, add Part B and Part C, stirring well until dissolved. Add parts D to F in sequential order, mixing well with high shear after each addition.
Example 86 - Colored pencils.
[293] The following is a prophetic example of a colored pencil formulation.
Table 22 - Colored Pencils.
Ingredient % by weight Part A Ethyl cellulose 1.5 Isostearyl alcohol 5.9 Stearyl alcohol 5.9 Part B Hydrogenated vegetable oil 6.7 Paraffin 6.7 Part C Coloring 33.3 Cetal * 5 Part D Cyclomethicone 35
* ketal examples: Ex: A, 2EH-LPK; Ex. B, 1N-LPK; Ex. C,
355TMH-LPK
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[294] To manufacture the exemplary formulations, mix Part A and heat to 65-90 ° C, with stirring, until everything dissolves. Maintain Part A temperature. In a separate container, mix Part B and melt. Add the melted part B to the heated part A. Mix Part C and add Parts A / B. Homogenize the mixture and then mix in Part D. Transfer the mixture to a cooling mold. Remove the pencil from the mold when solidified and cooled.
Example 87 - Oil-in-Water Base
[295] The following is a prophetic example of an oil-in-water formulation.
Table 23 - Oil in Water Base
Ingredient % by weight Occupation Part A Deionized water 50.92 Thinners Tromethamine 0.8 Alkali (soap) PEG-12 Dimethicone 0.1 Wetting agent 80% TiO2 / talc extender 8 Pigment 80% yellow iron oxide / talc extender 0.95 Pigment 80% red iron oxide / talc extender 0.75 Pigment 80% black iron oxide / talc extender 0.07 Pigment Talc, average of 4 microns 4.23 Fill Part B Butylene glycol 4 Humectants Aluminum and magnesium silicate 1 Thickener Part C Butylene glycol 2 Humectants Cellulose gum 0.15 Thickener Part D Sucrose cocato 1 Emulsifier Methyl paraben 0.2 Preservative Disodium EDTA 0.05 Preservative additive Part E Stearic acid 1.5 Acid portion of soap Isostearic acid 0.5 Soap Dicaprilila maléate 10 Emollient Cetal * 6 Emollient Sorbitol monolaurate 3 Emulsifier Cetyl alcohol 0.5 Stabilizer Propyl Paraben 1 Preservative Part F Cyclomethicone 2 Volatile emollient Part G Deionized water 2 Thinners DMDM Hydantoin 0.1 Preservative
* ketal examples: Ex: A, 2EH-LPK; Ex. B, 1N-LPK; Ex. C,
355TMH-LPK
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[296] To manufacture the exemplary formulations, combine the Part A ingredients in order during homogenization. Combine and add Part B. Heat to 85-90 ° C for 15 minutes and then cool to 75 ° C. Combine and add Part C. Add the Part D ingredients in order. Combine the ingredients from part E and the one at 75-80 ° C with stirring. Just before emulsification, add Part F and readjust the temperature to 75-80 ° C. Add the oil phase (parts E and F combined) to the water phase (part A-D combined) during homogenization. Maintain temperature and agitation for at least 15 minutes. Cool to 55 ° C and check for water loss. Cool to 45 ° C with a foot shaker. Combine the ingredients of part G and add to the formulation. Cool to 30 ° C and remove from heat.
Example 88 - Base.
[297] The following is a prophetic example of a basic formulation.
Table 24 - Base
Ingredient % by weight Part A Deionized water 54.33 Potassium hydroxide (10% aqueous solution) 1.3 Polysorbate 80 0.1
Part B Titanium dioxide 7 Baby powder 3.76 Yellow iron oxide 0.8 Red iron oxide 0.36 Black iron oxide 0.09 Part C Propylene glycol 2 Aluminum and magnesium silicate 1 Part D Propylene glycol 4 Cellulose gum 0.12 Part E Di-ppg-3 myristyl ether adipate 12 Alkyl ester of ketal * 4 Cetearyl alcohol, ceteth-20 phosphate, dicetyl phosphate 3 Steareth-10 2 Cetyl alcohol 0.62 Steareth-2 0.50 Part F Parabeno-DU ** 1
* ketal examples: Ex: A, 2EH-LPK; Ex. B, 1N-LPK; Ex. C,
355TMH-LPK
125/135 ** Paraben-DU - wide spectrum pre-stirred preservative mixture (3% by weight propylparaben, 11% by weight ethyl paraben, 30% by weight urea of diazolidinyl, 56% by weight propylene glycol).
[298] To manufacture the exemplary formulations, combine Part A and start mixing. Pre-grind Part B until the pigments are well mixed. Add Part B to Part A and mix until the pigments are evenly spread. Start A / B heating. Prepare a slurry from part C, add to parts A / B and heat to 85 ° C, keeping the temperature in the range between 85-90 ° C for 10 minutes. Remove from heat and prepare a second slurry from the ingredients in Part D. Add the Part D paste to A / B / C at 77 ° C. Homogenize until uniform and smooth. Check weight and add water to compensate for any loss, plus another 20g / kg of the formulation. Continue mixing and increasing the temperature to 77 ° C. Combine the Part E ingredients separately and heat to 77 ° C. Add to the main mixture and keep the temperature at 77-80 ° C for 10 minutes. Remove from heat. Add Part F when the mixture has cooled to 50 ° C. Check for water loss and adjust the formulation accordingly. If necessary, adjust the pH to 7.5. Homogenize until the temperature reaches 35 ° C.
Example 89 - Stick concealer.
[299] The following is a prophetic example of a formulation for stick concealer.
Table 25 - Stick Correction.
Ingredient % by weight Part A Titanium dioxide (A-8112) 20 Red iron oxide (A-1301) 1.4 Red iron oxide (A-1226) 0.65 Black iron oxide (A-7133) 0.1 Cetal * 15.85 Di-PPG-3 myristyl ether adipate 4.25 Sorbitan isostearate 4.25 Part B Sericita AS 10 Baby powder 5 Di-PPG-3 myristyl ether adipate 2.5
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Kaolin 4 Part C Squalene 3.5 Candelilla wax 5 Ozoquerite wax 2.5 Propyl Paraben 0.1 Methyl paraben 0.2 Carnauba wax 1.75 C18-36 glycol acid ester 2.25 C18-36 acid triglyceride 1.1 Di-PPG-3 myristyl ether adipate 14.6 DERMAXYL (from Croda) 1
* ketal examples: Ex: A, 2EH-LPK; Ex. B, 1N-LPK; Ex. C, 355TMH-LPK
[300] To manufacture the exemplary formulations, grind the ingredients in Part A and mix for at least 15 minutes. Add the ingredients from Part B to Part A and mix for at least 10 minutes. Combine all the ingredients in Part C in a separate container and start heating during mixing. Continue heating until the batch is clear. Start cooling during mixing and add Parts A / B to the batch. Preheat the stick molds and transfer the batch contents to the molds while the batch contents are still transferable. Allow the mold to cool.
Example 90 - Diaper Rash Cream
[301] The following is a prophetic example of a cream formulation for diaper rashes.
Table 26 - Soft Diaper Rash Cream for Babies
Ingredient % by weight Part A Squalene 30 Cetal * 5 Zinc oxide 12CRODAFOS CES (cetearyl alcohol, dicetyl phosphate and ceteth-10 phosphate) 6 Part B Deionized water 44.10 Methylparaben, butylparaben, ethylparaben and propylparaben 0.3 Part C Dimethicone 0.6 * ketal examples: Ex: A, 2EH-LPK; Ex. B, 1 N-LPK; Ex.
355TMH-LPK
[302] To manufacture the exemplary formulations, disperse oxide
127/135 zinc in the ketal and then add the other ingredients of Part A individually with stirring. Heat to 70-75 ° C. In a separate receptacle, combine Part B and heat to 70-75 ° C. Add Part B to Part B and mix well. Start cooling and add Part C with agitation when the temperature reaches 50 ° C. Continue to mix and cool until desired temperature.
Example 91 - Removers.
[303] The following tables show prospective examples of formulations for a variety of uses, as indicated. The quantities are in percentage by weight (% by weight), based on the total weight of the formulations. The term ketal is intended to encompass 2EH-LPK, 1N-LPKor 355TMH-LPK.
Removal Formulation for General Purpose Component Quantity (% by weight) CetalDimethyl sulfoxide (DMSO) Dipropylene glycol methyl ether Ethyl-3-ethoxypropionate (EEP) ThickenerSurfactant 352925515 Component Graphite Removal Formulation Quantity (% by weight) DMSOSolvesso ™ 150 ND * CetalEEPSurfactantThickener 35 25-3025 841-5
‘ExxonMobil Corporation
Component Paint Removing Formulation Quantity (% by weight) NMPCetalPropylene glycol methyl ester acetateTriton ™ X-100 **Klucel-H *** 4040170-21
** The Dow Chemical Company *** Ashland, Inc.
Gel Formulation for Hand Cleaning
Quantity (% by weight)
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Component
Cetal 75% by weight BIO-SOFT N1-7fViscos ABIT NATURALff Fragrance 1510q.s.
fStephan Company ffReact-NTI.LLC
Aerosol Formulation for Asphalt / Tar RemovalComponent Quantity (% by weight) Aromatic 100CetalCola®COR 600f Surfactant Isobutane Propellant ^ Colonial Chemical, Inc. 2950120 Formulation for washing component parts Quantity (% by weight) Methyl soate Cetal d-limonene BIO-SOFT N1-7f 5035510
fStephan Company
Degreasing Formulation for Component EngineSoy methyl ester Quantity (% by weight) 50.00 CetalNonylphenol ethoxylated surfactant DefoamerMineral oil 15.005.003.00 27.00 Formulation for Mastic Removal from Component Floor Quantity (% by weight) CetalBIO-SOFT N25-9f 7525
fStephan Company
Formulation for Oil Stain Removal from ConcreteComponent Quantity (% by weight) CetalBIO-SOFT N25-9f 7525
fStephan Company Example 92 - Cleaner Formulation.
[304] An exemplary cleaner formulation can be prepared
129/135 by combining the following components in a 20 ml scintillation vial: 4 parts of ketal (Example 92A - 2EH-LPK, and Example 92B - 1NLPK, example 92C - 355TMH-LPK); 4.5 parts of nonionic surfactant (Biosoft N91-6, Stepan Co., Northfield, Illinois); 0.5 parts of sodium citrate dihydrate (Fisher Scientific, a division of Thermo Fisher Scientific; Waltham, Massachusetts), with water being the balance of the formulation.
Example 93 - Method for forming a pigmented dispersion.
[305] Using an overhead stirrer with a Cowles paddle, Ti-pure titanium dioxide R960 (DuPonto) is slowly added to the solvent, as shown in Table 27, mixing between additions until the viscosity is uniform. After adding mixture for the reported period of time, the quality of the dispersion is measured on a Hegman meter. Additional solvent (unspecified quantity) is added to achieve a transferable viscosity, and the dispersion viscosity is measured on a Brookfield viscometer.
Table 27
Ex. Solvent Pigment(g) Solvent(g) Mixing Speed (rpm) Mixing Time (min) Quality ofDispersal 6A DPM acetate 200 300 800 3 7.5 6B Cetal * 200 300 800 3 7.5
* ketal examples: Ex: A, 2EH-LPK; Ex. B, 1N-LPK; Ex. C,
355TMH-LPK
Example 94 - Coating formulations.
[306] Coating formulations are performed using a Cowles paddle and an overhead stirrer as shown in the Tables below. The formulas below are made by adding the ingredients in order. The crushing paste portion is made and sheared until the proper 7 + Hegman dispersion is achieved. Then, the remaining ingredients are added to complete the formulation. The ingredients are loaded into a receptacle and a Dupont Ti-pure Titanium Dioxide R960 is loaded into the mixture slowly, until the viscosity is uniform and the mixing solution
130/135 form a thread when mixing. After mixing for a period of time, an amount of the mixture is deposited on a Hegman meter and a measure of the dispersion is read. All systems must have Hegman readings of 7.5 or better. Then, the remaining ingredients are added to complete the formulation.
Table 28 - Formula 94-1A-C Polyester Melamine
Comparative Example Ingredient Formula94-1A * Formula94-1B 94-1C Saturated polyester resin Polymac 575789 45.73 45.73 45.73 Melamine resin Cymel 300 7.53 7.53 7.53 Titanium dioxide Ti-pure R960 28.79 28.79 28.79 crushing paste82.05 82.05Solvent DPM acetate 3.91 3.91 0 Solvent DBE 3.91 0 0Cetal ** 0 3.91 7.82 Hydrocarbon solvent BAS 1150 7.73 7.73 7.73 Catalyst Nacure 1051 0.40 0.40 0.40 Solvent Optifilm 300 2.00 2.00 2.00 Total100.00 100.00 100.00
‘Comparative examples ** examples of ketal:
Ex. A, 2EH-LPK Ex. B, 1N-LPK Ex. C, 355TMH-LPK
Table 29 Polyester Urethane Formula 94-2A-B - 1K
Comparative Example Ingredient Formula94-1 A * Formula94-1B Saturated polyester resin Polymac HS575789 43.72 43.72 Rheological additive Aerosil 200 0.29 0.29 Titanium dioxide Ti-pure R960 19.28 19.28 crushing paste63.29 63.29 Blocked isocyanate Desmodur BL3175 1.95 1.95 tin catalyst Dabco T12 1.08 1.08 epoxy resin Epon 828 1.31 1.31 Solvent BAS 150 10.76 10.76 Solvent DBE 8.37 0 Solvent Cetal ** 0 8.37 Solvent Diacetone alcohol 4.78 4.78 Total91.54 91.54
* Comparative ** examples of ketal: Ex: A, 2EH-LPK; Ex. B, 1N-LPK; Ex. C,
355TMH-LPK
131/135
Table 30. Formula 94-3A-B - 2K Polyester Urethane
Comparative Example Ingredient 94-3A * Formula 94-3BB * Formula PART AAcrylic Resin Joncryl 500 200.00 200.00 Leveling Agent BYK 320 2.00 2.00 Solvent MAK 40.00 0 Solvent Pigment CETAL ** Ti-Pure R-960 0 329.00 40.00 329.00 Grind Paste Acrylic Resin Joncryl 500 199.60 199.60 Solvent MAK 116.10 116.10 Tin catalyst Dabco T12 0.23 0.23 Subtotal886.93 886.93 PART B3B 3B Aliphatic isocyanate Desmodur N3300 152.60 152.60 Solvent MAK 29.20 29.20 Total1068.73 1068.73
Comparative ** examples of ketal: Ex: A, 2EH-LPK; Ex. B, 1N-LPK; Ex. C,
355TMH-LPK
[307] After allowing formulations to define over night, observations are made about material stability. All formulas must exhibit minimal separation that is easy to mix to uniformity. Using a lifting bar on steel Q-panels, film thicknesses of 1 and 3 mils are achieved using each of the formulations. The panels are placed in a 200 ° C oven for 60 minutes. The final film is evaluated for its appearance, cross-hatch adhesion, and double rubbing of Methyl Ethyl Ketone. Cross-hatch adhesion is performed according to ASTM D3359 and double MEC rubs are performed according to the ASTM D5402-06 method. Double rubbing is performed using a cloth that is moistened with MEC, and then the number of double rubbing is counted to see the effects on the coating. If the coating wears down to the substrate, testing is stopped and the number is reported.
Examples 95-98.
[308] Examples 95-98 evaluated the use of 2EH-LPK.1N-LPK and 355TMH-LPK as a coalescing agent for a polymer binder
132/135 alkyd which is neutralized. Therefore, in the following examples, triethylamine (TEA) is added in sufficient quantity to stoichiometrically neutralize 100% of the acid groups in the alkyd polymer binder. The components of each example in Table 31 are weighed in a bottle and mixed by hand stirring at room temperature (approximately 73 ° F) with the indicated amount of deionized water (Dl).
Table 31
Example Solvent Solvent (g) Duramac® WR216-3610 (g) Water Dl (g) TEA (g) 95 none 0 5 5 0.765 96 Cetal * 0.75 4.25 5 0.65 97 none 0 2.5 7.5 0.3825 98 Cetal * 0.375 2,125 7.5 0.325 * examples of ketal: Ex: A, 2EH-LPK; Ex. B, 1N-L PK; Ex.
355TMH-LPK
Examples 99-102.
[309] Examples 99-102 evaluate the use of 2EH-LPK, 1N-LPK and 355TMH-LPK as a coalescing agent for a one-part polyurethane dispersion, Hauthaway's HauthaneTM HD 4669, which is an aliphatic polyurethane dispersion free from co-solvent at 38% solids (± 1%) that provides hard coating, and is designed for last coat applications on a wide range of substrates, including concrete, metal, plastic and wood.
[310] Compositions with Hauthane® HD-4675 are mixed by hand according to the examples in table 32. Films are adhered to polished steel panels (Q-Panel® from Q-Lab) with a lifting bar with a thickness of 5 thousand (127 micrometer). The panels are left on the bench to dry at room temperature.
Table 32
Example Solvent % by weight of solvent % by weight of Hauthane® ¹ HD-4675 99 none 0 100 100 2EH-LPK 0.5 99.5
133/135
101 1N-LPK 0.5 99.5 102 355TMH-LPK 0.5 99.5 Examples 10 3-105.
[311] Examples 103-105 evaluate the use of 2EH-LPK.1N-LPK and 355TMH-LPK as a cohesive agent for dispersion of single-part polyurethane, Hauthane ® HD-4669 (from Hauthaway), an aqueous polyurethane dispersion , aliphatic and co-solvent free at 40% solids (± 1%) which forms a hard coating where heat curing is recommended, and is designed for last coat applications on a wide variety of substrates, including concrete, metal, plastic and wood, or as an individual vehicle or mixed with mixed acrylic emulsions.
[312] In Example 103, Hauthane® HD-4669 (95% by weight) is manually mixed with 2EH-LPK (5% by weight). A film is adhered to polished steel panels (Q-Panel® from Q-Lab) with a lifting bar with a thickness of 5 mil (127 micrometers). The panel is cured in an oven at 200 ° C for 60 minutes. After oven curing, the compositions form a hard, smooth film.
[313] In Example 104, Hauthane® HD-4669 (95% by weight) is manually mixed with 1N-LPK (5% by weight). A film is adhered to polished steel panels (Q-Panel® from Q-Lab) with a lifting bar with a thickness of 5 mil (127 micrometers). The panel is cured in an oven at 200 ° C for 60 minutes. After oven curing, the compositions form a hard, smooth film.
[314] In Example 105, Hauthane® HD-4669 (95% by weight) is manually mixed with 355TMH-LPK (5% by weight). A film is adhered to polished steel panels (Q-Panel® from Q-Lab) with a lifting bar with a thickness of 5 mil (127 micrometers). The panel is cured in an oven at 200 ° C for 60 minutes. After oven curing, the compositions form a hard, smooth film.
[315] The terminology used in this document is intended to
134/135 describe particular embodiments only and is not intended to limit the invention. As used in this document, singular forms one, one and (a) are intended to also include plural forms, unless the context clearly indicates otherwise. Or means and / or. The endpoints of all scales directed at the same component or property are inclusive of the endpoint and independently combinable.
[316] Unless otherwise defined, all terms (including technical and scientific terms) used in this document have the same meaning as commonly understood by a person moderately versed in the technique to which this invention belongs. The term paint encompasses any protective outer coating that is also known as, for example, varnish, electro-paint, shellac, last coat of paint, base coat, coloring coat and the like.
[317] The compounds made according to the methods described above have, in some embodiments, one or more isomers. Where an isomer may exist, it should be understood that the invention encompasses methods that form any isomer thereof, including any stereoisomer, any conformational isomer, and any cis or trans isomer; isomers isolated from it; and mixtures thereof.
[318] Compounds are described using standard nomenclature. For example, any position that is not replaced by any indicated group is understood to have its valence filled by a bond as indicated, or a hydrogen atom. A dash (-) that is not between two letters or symbols is used to indicate a fixation point for a substituent. For example, -CHO is bonded through carbon of the carbonyl group. Unless otherwise specified, alkyl groups may be directly bonded or branched. Throughout the specification, reference is made to several divalent groups. Such groups are the same as the monovalent groups that are named after
135/135 similarly, and are typically indicated with a * 'ena suffix. For example, a C7 to C18 alkylene group is a bivariate linking group with the same structure as a C7 to C18 group.
[319] All patents, patent applications, and other references cited are incorporated into this document in its entirety for reference only.
[320] The various modalities described above are provided by way of illustration only and should not be construed as limiting the claims attached to this document. The present invention may suitably comprise, consist of, or be composed essentially of, any of the elements disclosed or cited. Therefore, the invention illustratively disclosed in this document can be properly practiced in the absence of any element that is not specifically disclosed in this document. Several modifications and changes will be recognized that can be made without following the exemplary modalities and applications illustrated and described in this document, and without departing from the true spirit and scope of the following claims.

权利要求:
Claims (18)
[1]
1. Compound of formula (1), characterized by the fact that:

[2]
2. The compound of claim 1, characterized in that R ¹ is a 2-ethylhexyl, 1-nonyl or 3,5,5-trimethylhexyl group, R ² is methyl, each R ³ , R ⁴ , R ⁵ and R ⁶ is hydrogen or an alkyl CI_ _3, R ⁷ is hydrogen, a is 2-3 and b is 0-1; or wherein R ¹ is a 2-ethylhexyl group, 1-nonyl or 3,5,5-trimethylhexyl, R ² is methyl, each R ^3, R ⁴ and R ⁵ is hydrogen, ^R6 is hydrogen or an alkyl CI_ ₃ , R ⁷ is hydrogen, a is 2 and b is 0-1; or that R ¹ is a 2-ethylhexyl, 1-nonyl or 3,5,5-trimethylhexyl group, R ² is methyl, R ³ is hydrogen, R ⁶ is hydrogen, methyl or ethyl, R ⁷ is hydrogen, a is 2e b is 0.
[3]
3. The compound of claim 1, characterized by the fact that the compound is a compound of formula (1a) o

[4]
A compound of claim 1, characterized by the fact that R ¹ is a 2-ethylhexyl group.
[5]
5. The compound of claim 3, characterized by the fact that R ¹ is
Petition 870200012851, of 01/27/2020, p. 13/30
2/4 a 2-ethylhexyl group
[6]
6. Coating composition characterized by the fact that it comprises water;
a polymer binder; and the compound of any claim from 1 to 6; and further wherein the coating composition comprises less than or equal to about 250 g / l of VOC as determined using the ASTM D396 Method.
[7]
The coating composition of claim 6, characterized by the fact that the compound is of formula (1a)
O 'OR ¹
CH3 (1a); and
R ¹ is a 2-ethylhexyl, 1-nonyl or 3,5,5-trimethylhexyl group.
[8]
The coating composition of claim 6 or 7, characterized in that R ¹ is a 2-ethylhexyl group.
[9]
Coating composition of any one of claims 6 to 8, characterized in that the polymer binder is a latex polymer binder
[10]
Coating composition according to any one of claims 6 to 8, characterized in that the polymer binder is a water-reducible polymer binder.
[11]
11. Cleaning and personal hygiene composition, characterized by the fact that it comprises a cleaning or personal hygiene component; and the compound of any of claims 1 to 5.
[12]
12. Composition of claim 11, characterized by the fact that the compound is a compound of formula (1a)
Petition 870200012851, of 01/27/2020, p. 14/30
3/4

[13]
The coating composition of claim 11 or 12, characterized in that R ¹ is a 2-ethylhexyl group.
[14]
14. The composition of claim 11, characterized in that the composition is a cleaning composition and the cleaning component is a cosolvent, a plurality of abrasive particles, an organic amine, an antioxidant, a biocide, a dye, an anti-corrosion, a antifoaming agent, tincture, enzyme, light stabilizer, odor inhibiting agent, plasticizer, preservative, rust inhibitor, surfactant, thickener, soil suspending agent, builder, chelating agent , bleach, a bleach activator, a bleach stabilizer, a pH control agent, a hydrotrope, a softener or a combination comprising at least one of the above components.
[15]
15. The composition of claim 11, characterized in that the composition is a personal hygiene composition and the personal hygiene component is an active agent, a cosmetic dye, a surfactant or a combination comprising at least one of the aforementioned compositions.
[16]
16. Scented composition characterized by the fact that it comprises: at least one scented composition; and the compound of any of claims 1 to 5.
[17]
17. The fragrant composition of claim 16, characterized by the fact that the compound is a compound of formula (1a)
Petition 870200012851, of 01/27/2020, p. 15/30
4/4 ο

[18]
18. Composition of claim 16 or 17, characterized in that R ¹ is a 2-ethylhexyl group.

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EP2925738A1|2015-10-07|

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JP2016506383A|2016-03-03|

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US20140147395A1|2014-05-29|

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CN104918929A|2015-09-16|

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AU2013352172A1|2015-06-11|

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法律状态:
2018-01-23| B11A| Dismissal acc. art.33 of ipl - examination not requested within 36 months of filing|

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2018-05-15| B04C| Request for examination: reinstatement - article 33, solely paragraph, of industrial property law|

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2018-05-22| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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2019-10-29| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|

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2020-03-10| B09A| Decision: intention to grant|

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2020-05-19| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 27/11/2013, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US201261731194P| true| 2012-11-29|2012-11-29|

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PCT/US2013/072268|WO2014085609A1|2012-11-29|2013-11-27|Carboxy ester ketals, methods of manufacture, and uses thereof|

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