Poly-trisaryl-1,3,5-triazine carbamate ultraviolet light absorbers

专利摘要:
The present invention relates to novel carbamates containing trisaryl-1,3,5-triazines and their use as ultraviolet absorbers. In particular, the compounds claimed in the present invention are carbamate trees that are particularly useful in stabilizing polymeric films or shaped articles from degradation by actinic exposure, alone or in combination with other additives including other ultraviolet absorbers and stabilizers. Azine polymers.
公开号:KR20010053097A
申请号:KR1020007014580
申请日:1999-06-18
公开日:2001-06-25
发明作者:굽타램비；재키엘라데니스제이
申请人:에프. 아. 프라저, 에른스트 알테르 (에. 알테르), 한스 페터 비틀린 (하. 페. 비틀린), 피. 랍 보프, 브이. 스펜글러, 페. 아에글러；시바 스페셜티 케미칼스 홀딩 인크.；
IPC主号:

专利说明:

Poly-trisaryl-1,3,5-triazine carbamate ultraviolet light absorbers
Background of the Invention
Field of invention
The present invention generally relates to novel poly-trisaryl-1,3,5-triazine carbamates and their use for protection from actinic radiation.
Related fields of technology
Exposure to other light sources of sunlight and ultraviolet radiation is known to cause denaturation of various materials, in particular polymeric materials. For example, polymeric materials such as plastics are often discolored and / or brittle as a result of prolonged exposure to ultraviolet light. Therefore, the focus to be developed in the art relates to materials such as ultraviolet absorbers and stabilizers that can suppress such denaturation.
A class of materials known as ultraviolet absorbers is trisaryl-1,3,5-triazine, wherein at least one of the aryl rings has a hydroxyl group in the ortho position relative to the attachment site of the triazine ring. In general, this class of materials is well known in the art. Various techniques for such trisaryl-1,3,5-triazines can be found in the following publications, all of which are hereby incorporated by reference for all purposes: US Pat. Nos. 3,118,887, 3,242,175, 3244708, 3249608, 3268474, 3843371, 4619956, 4740542, 4775707, 4826978, 4962142, 5030731, 5071981, 5.08457 million, 5,106,891, 5,185,445, 5,189,084, 5,198,498, 5,288,778, 5,298,067, 5,322,868, 5,354,794, 5.36914 million, 5,412,008, 5,420,204, 5,461,151 and 5,478,935; Canadian patent documents CA A1-2162645 and CA 2,032,669; British Patent Documents GB 1033387 and GB-A-2293823; Swiss patent documents CH480091 and CH484695; And European Patent Documents EP-A-0434608, EP-A-0434619, EP-A-0444323, EP-A-0649841, EP-A-0654469, EP-A-0704437, EP-A-0706083 and PCT Patent Documents WO95 / 22959 and WO96 / 28431.
Typically, the above-mentioned aryl ring having a hydroxyl group in the ortho position with respect to the attachment site of the triazine ring is a resorcinol-based, and thus, such an aryl ring also has a second substituent (hydroxy) in the para position with respect to the site of the triazine ring. Hydroxyl groups or derivatives thereof). Such second substituents may be "non-reactive" as in the case of alkyloxy groups or "reactive" as in hydroxyalkyloxy (active hydrogen reactive sites) or (meth) acryloyl (ethylenically unsaturated reactive sites) groups. "Can be. The former is commonly referred to as "non-binding" trisaryl-1,3,5-triazine and the latter is referred to as "bonding" trisaryl-1,3,5-triazine.
Many polymer additives, such as UV stabilizers, have the disadvantage that they volatilize or transfer the polymer substrates they need to protect or are absorbed (chemically or physically) by one or more system components (e.g. pigments), thereby reducing their usefulness. May result.
Although the poly triazine carbamates claimed herein are not binding, their high molecular weights suggest that these triazines exhibit higher durability due to reduced volatility and reduced transition in the materials in which they are used. . In particular, it is believed that these triazines exhibit better thermal stability than other carbamate-containing triazines formed directly from phenolic systems, especially carbamate groups, directly bonded to aromatic rings.
EP 434,619 and CA 2,032,669 generally describe the incorporation of these compounds into various binding phenolic carbamoyl triazines and polymers by chemical bonding. In addition, US 5,354,794 generally describes triazines having one or more carbonyl and / or ester groups. However, we do not know any prior art describing the novel poly-trisaryl-1,3,5-triazine carbamate of the present invention.
Summary of the Invention
The present invention provides a new class of trisaryl-1,3,5-triazines comprising carbamate triazine polymers. More specifically, the novel poly-trisaryl-1,3,5-triazine carbamate of the present invention has formulas (I), (II) and (III).

In the above formula,
A is a polyvalent hydrocarbyl or heterocyclic ring,
Each X is independently selected from hydrogen, allyl, -COR ^a , -SO ₂ R ^b , -SiR ^c R ^d R ^e , -PR ^f R ^g and -POR ^f R ^g ,
Y and Z are the same as or different from each other, and independently Selected from the aryl ring of (IV),
Each R is independently selected from a hydrocarbyl group, a functional hydrocarbyl group and a hydroxy alkyl amide such as —CH ₂ CONC ₄ H ₉ (CH ₂ ) ₂ OH,
Each R ′ is independently selected from a group such as a hydrocarbyl group, a functional hydrocarbylene group, and —CH ₂ CONC ₄ H ₉ (CH ₂ ) ₂ —,
Each R ^a is independently C ₁ -C ₈ alkyl, halogen-substituted C ₁ -C ₈ alkyl, C ₅ -C ₁₂ cycloalkyl, C ₂ -C ₈ alkenyl, -CH ₂ -CO-CH ₃ , C ₇ -C ₁₂ aralkyl, C ₁ -C ₁₂ alkoxy or phenyl unsubstituted or substituted by C ₁ -C ₁₂ alkyl, C ₁ -C ₄ alkoxy, halogen and / or benzyl,
Each R ^b is independently selected from C ₁ -C ₁₂ alkyl, C ₆ -C ₁₀ aryl or C ₇ -C ₁₈ alkylaryl,
R ^c , R ^d and R ^e are each independently selected from C ₁ -C ₁₈ alkyl, cyclohexyl, phenyl or C ₁ -C ₁₈ alkoxy,
R ^f and R ^g are each independently selected from C ₁ -C ₁₂ alkoxy, phenoxy, C ₁ -C ₁₂ alkyl, C ₅ -C ₁₂ cycloalkyl, benzyl, tolyl or phenyl,
R ¹ , R ² and R ⁴ are each independently hydrogen, hydrocarbyl, functional hydrocarbyl, -O (hydrocarbyl), -O (functional hydrocarbyl), -SR, halogen, -SO ₃ R, -COOR , -COR, -OCOR, -NRR and cyano,
Each R ³ is independently selected from R, —OR, —SR, halogen, —SO ₃ R, —COOR, —COR, —NRR, and cyano,
n is 2 to about 50.
These poly-trisaryl-1,3,5-triazine carbamate polymers can generally be prepared by a number of methods described in the documents cited above, but preferably at least one aryl ring is each attached to the attachment site of the triazine ring. Having an hydroxyl group in the ortho position relative to the aryl ring further substituted by a hydroxyl functional —O (hydrocarbyl) group (and preferably a hydrocarbyl group in the para position relative to the attachment site of the triazine ring) Two or more trisaryl-1,3,5-triazine precursors may be reacted with a divalent hydrocarbyl binder such as diisocyanate or a trivalent hydrocarbyl binder such as triisocyanate to prepare compounds of Formulas (I)-(III). Further preferred methods are described below.
The novel poly-trisaryl-1,3,5-triazine carbamates of the present invention are, for example, organic compounds, oils, fats, waxes, cosmetics, dyes and biocides, and photographic materials, plastics, rubbers, UV absorbers for stabilizing a variety of materials, including various organic polymers (both crosslinked and noncrosslinked) used in applications such as paints and other coatings and in particular adhesives as described in many of the documents cited above. It is particularly useful as an additive. Accordingly, the present invention also relates to the incorporation of novel poly-trisaryl-1,3,5-triazine carbamate in such materials, for example in organic materials, in an amount effective to stabilize the materials against the effects of actinic radiation. And a material so stabilized.
The novel poly-trisaryl-1,3,5-triazine carbamate of the present invention is also a sunscreen agent in applications such as light blocking agents and other cosmetic agents, capstock layers for extruded polymers and laminated UV-blocking window films. Useful as Accordingly, the present invention also relates to a method of applying ultraviolet light from a substrate by applying a layer of a composition comprising the novel poly-trisaryl-1,3,5-triazine carbamate to the substrate and the substrate so blocked. .
These and other aspects and advantages of the present invention will be more readily understood by those skilled in the art upon reading the following detailed description.
Detailed Description of the Preferred Embodiments
Poly-trisaryl-1,3,5-triazine carbamate
As mentioned above, the trisaryl-1,3,5-triazines according to the invention are compounds of the formulas (I), (II) and (III).
As used herein, the term "poly-trisaryl-1,3,5-triazine carbamate" or "carbamate triazine" is broadly one of the compounds of formulas (I), (II) and (III).
Within the context of the present invention and in the above formula, the term "hydrocarbyl" is broadly a monovalent hydrocarbon group derived by the separation of hydrogen from a valence carbon atom. Hydrocarbyl includes, for example, groups of aliphatic (straight and branched), cycloaliphatic, aromatic and mixed properties (eg aralkyl, alkylaryl, alkynyl, cycloalkynyl). More specifically, hydrocarbyl preferably includes, but is not limited to, alkyl, cycloalkyl, aryl, aralkyl, alkylaryl, alkenyl and cycloalkenyl having up to 24 carbon atoms. Hydrocarbyl may optionally contain a carbonyl group or groups (including carbon atoms) and / or a hetero atom or hetero atoms (one or more oxygen, sulfur, nitrogen or silicon) in the chain or ring.
The term "polyhydric hydrocarbyl" is a hydrocarbyl as described above comprising a polyvalent hydrocarbon group derived by the separation of hydrogen from carbon atoms of different valences.
The term "functional hydrocarbyl" within the specification of the present invention and in the above formula is broadly a hydrocarbyl containing pendant and / or terminal "reactive" and / or "potentially reactive" functional groups and / or leaving groups. Reactive functional groups are functional groups that react with conventional monomer / polymer functional groups under conventional conditions well recognized by those of ordinary skill in the art. Examples of reactive functional groups include active hydrogen containing groups such as hydroxyl, amino, carboxyl, thio, amido and activated methylene, isocyanato, cyano, epoxy and ethylenically unsaturated groups such as allyl, Mention may be made of acryloyl and methacryloyl and maleate and maleimido. Potentially reactive functional groups are reactive functional groups that are blocked or masked to prevent premature reactions. Examples of latent reactive functional groups are ketimines and aldimines (amines blocked with ketones and aldehydes respectively), amine-carboxylate salts and blocked isocyanates such as alcohols (carbamate), oximes and caprolactam blocked Mention may be made of variants. A "leaving" group, apparently recognized by those skilled in the art and by those skilled in the art, is a substituent attached to a hydrocarbyl chain or ring that is replaced to generate valences on carbon atoms within the hydrocarbyl chain or ring during the reaction. Examples of leaving groups include halogen atoms such as chlorine, bromine and iodine, hydroxyl groups, quaternary ammonium salts (NT ₄ ⁺ ), sulfonium salts (ST ₃ ⁺ ), and sulfonates (-OSO ₃ T) (Wherein T is, for example, methyl or para-tolyl). Preferred functional groups are hydroxyl, -COOR ⁵ , -CR ⁶ = CH ₂ , -CO-CR ⁶ = CH ₂ , Cl, , Isocyanate group, blocked isocyanate group and -NHR ⁵ , wherein R ⁵ is selected from hydrogen and hydrocarbyl (preferably with up to 24 carbon atoms) and R ⁶ is selected from hydrogen and alkyl having 1 to 4 carbon atoms Include.
Within the context of the present invention the term "hydrocarbylene" is a divalent hydrocarbon group both of which are derived by the separation of hydrogen from a valent carbon atom. Included within the definition of hydrocarbylene are the same groups as mentioned in the above hydrocarbyl and functional hydrocarbyl having extra valences (eg, alkylene, alkenylene, arylene, alkylaryl, etc.).
The trisaryl-1,3,5-triazines according to the invention also relates to latent stabilizing compounds for actinic radiation of formulas (I), (II) and (III) in which at least one X is not hydrogen. Such latent stabilizing compounds liberate effective stabilizers by breaking down O-X bonds, for example, by heating or UV radiation exposure. Latent stabilizing compounds are preferred because they have many useful properties: good substrate compatibility, good coloration properties, high rate of decomposition of O-X bonds and long shelf life. The use of latent stabilizing compounds is further described in US 4,775,707, US 5,030731 and CA A1-2162645.
The latent stabilizing compounds comprising poly-trisaryl-1,3,5-triazine carbamate according to the present invention are those of Formulas I, II and III wherein at least one X is hydrogen as described in US 4,775,707 and US 5,030,731. It can be prepared by further reacting from the compound to form a latent stabilizing compound. For example, acylation can be carried out according to the method described in US 3,249,608, except that an excess of acylating agent is preferably used to provide a compound wherein X is -COR ^A.
Obtain a latent stabilizing compound of the invention of Formulas I, II and III wherein X is allyl, -COR ^a , -SO ₂ R ^b , -SiR ^c R ^d R ^e , -PR ^f R ^g or -POR ^f R ^g The reactions for reacting, for example, compounds of formulas (I), (II) and (III), wherein at least one of X is hydrogen, is a corresponding chloride, allyl chloride, Cl-COR ^a , Cl-SO ₂ R ^b , Cl-SiR ^c R ^d R ^e , Cl-PR ^f R ^g or Cl-POR ^f R ^g . Acylated compounds can also be obtained by reaction with anhydrides, ketenes or esters, such as lower alkyl esters, as is well known to those skilled in the art. The above described reagents may be used in approximately equimolar amounts or in excess, for example 2 to 20 mol, relative to the hydroxyl groups to be prepared potentially in the starting compounds of formula (I), (II) or (III).
Catalysts commonly used in acylation, sulfonylation, phosphorylation or silylation reactions can be used to form the latent stabilized poly-trisaryl-1,3,5-triazine carbamate of the present invention. For example, acylation and sulfonylation reaction catalysts such as tertiary or quaternary amines such as triethylamine, dimethylaminopyridine or tetrabutylammonium salts can be used to form these latent stabilizing compounds.
The reaction can be carried out in a solvent, for example a relatively inert organic material such as hydrocarbons such as toluene and xylene, chlorinated hydrocarbons such as carbon tetrachloride or chloroform or ethers such as tetrahydrofuran or di It may be carried out in the presence of a solvent such as butyl ether or in the absence of a solvent. Alternatively, the reagent (s) can be used as the solvent. The reaction temperature is usually from room temperature to about 150 ° C., for example below the boiling point of the solvent when a solvent is used.
In a preferred embodiment, each X is hydrogen.
In a preferred embodiment, the R group is selected from hydrocarbyl groups having 1 to 24 carbon atoms and functional hydrocarbyl groups having 1 to 24 carbon atoms. More preferably, these R groups are each independently optionally substituted by alkyl (one or more hydroxyl, carboxyl, carboalkoxy (ester), epoxy, amido and / or amino groups having 1 to 24 carbon atoms). Optionally substituted with one or more carbonyl groups, oxygen atoms and / or nitrogen atoms in the chain, alkenyl having 2 to 24 carbon atoms (hydroxyl, carboxyl, epoxy, amido and / or amino group (s) And / or optionally contain carbonyl, oxygen and / or nitrogen in the chain, cycloalkyl having 5 to 24 carbon atoms (hydroxyl, carboxyl and / or amino group (s)) and / or Or optionally substituted by carbonyl, oxygen atoms and / or nitrogen in the ring) and aralkyl (hydroxyl, carboxyl and / or amino group (s) having 7 to 24 carbon atoms) And / or contain carbonyl, oxygen and / or nitrogen in the ring).
More preferably, the R groups are each independently selected from alkyl having 1 to 24 carbon atoms which may optionally contain oxygen atoms in the chain or hydroxyalkyl having 1 to 24 carbon atoms which may optionally contain oxygen atoms in the chain.
In a preferred embodiment, the R 'group is selected from hydrocarbylene groups having 2 to 24 carbon atoms and functional hydrocarbylene groups having 2 to 24 carbon atoms. More preferably these R 'groups can each be optionally substituted independently by alkylene having 2 to 24 carbon atoms (one or more hydroxyl, carboxyl, carboalkoxy (ester), epoxy, amido and / or amino groups) Or contain one or more carbonyl groups, oxygen atoms and / or nitrogen atoms in the chain), alkenyl having 2 to 24 carbon atoms (hydroxyl, carboxyl, epoxy, amido and / or amino group (s) May be optionally substituted and / or may be optionally substituted by carbonyl, oxygen and / or nitrogen in the chain, cycloalkylene having 5 to 24 carbon atoms (hydroxyl, carboxyl and / or amino group (s)). And / or optionally contain carbonyl, oxygen atoms and / or nitrogen in the ring, and aralkylene (hydroxyl, carboxyl and / or amino group (s) having 7 to 24 carbon atoms. And / or contain carbonyl, oxygen and / or nitrogen in the ring).
More preferably, each R ′ group is independently selected from alkylene having 2 to 24 carbon atoms which may optionally contain oxygen atoms in the chain or hydroxyalkylene having 2 to 24 carbon atoms which may optionally contain oxygen atoms in the chain. do.
In a preferred embodiment, R ¹ and R ⁴ are each independently selected from hydrogen, acyl having 2 to 12 carbon atoms, acryloyl having 2 to 12 carbon atoms, and hydrocarbyl having 1 to 12 carbon atoms, preferably hydrogen and 1 carbon atom. It is selected from alkyl of 4 to 4, in particular hydrogen.
In a preferred embodiment, R ² is each independently selected from hydrogen, a hydrocarbyl group having 1 to 24 carbon atoms, a hadrocarbyloxy group having 1 to 24 carbon atoms, an acyloxy group having 1 to 24 carbon atoms, R and -OR. More preferably, each R ² independently represents hydrogen, alkyl having 1 to 24 carbon atoms optionally containing oxygen atoms in the chain, alkyloxy having 1 to 24 carbon atoms optionally containing oxygen atoms in the chain, and optionally an oxygen atom in the chain. Alkenyl containing 2 to 24 carbon atoms, alkenyloxy having 2 to 24 carbon atoms optionally containing an oxygen atom in the chain, and acyloxy group having 2 to 12 carbon atoms. Even more preferably, each R ² independently represents hydrogen, alkyl having 1 to 8 carbon atoms, alkyloxy having 1 to 8 carbon atoms optionally containing oxygen atoms in the chain, and having 1 to 8 carbon atoms optionally containing oxygen atoms in the chain. Hydroxyalkyl, hydroxyalkyloxy having 1 to 8 carbon atoms optionally containing an oxygen atom in the chain, and acyloxy group having 2 to 12 carbon atoms. Especially preferred are those in which R ² is each independently selected from hydrogen and alkyl having 1 to 4 carbon atoms, in particular hydrogen and methyl.
In a preferred embodiment, R ³ is each independently selected from hydrogen, a hydrocarbyl group having 1 to 24 carbon atoms, a functional hadrocarbyl group having 1 to 24 carbon atoms, R and -OR. More preferably, each R ³ group may be independently substituted by hydrogen, alkyl having 1 to 24 carbon atoms (hydroxyl, carboxyl and / or amino group (s)) and / or carbonyl, oxygen and / or nitrogen May be contained in the chain), alkenyl having 2 to 24 carbon atoms (hydroxyl, carboxyl and / or amino group (s) may be optionally substituted and / or contains carbonyl, oxygen and / or nitrogen in the chain Cycloalkyl having 5 to 12 carbon atoms (optionally substituted by hydroxyl, carboxyl and / or amino group (s) and / or containing carbonyl, oxygen and / or nitrogen in the ring) And -OR. Even more preferably, the R ³ groups are each independently from hydrogen, alkyl having 1 to 24 carbon atoms optionally containing oxygen atoms in the chain, hydroxyalkyl having 1 to 24 carbon atoms optionally containing oxygen atoms and -OR Is selected. Especially preferred are those in which the R ³ groups are each independently selected from hydrogen, alkyl of 1 to 4 carbon atoms and -OR, in particular hydrogen, methyl and -OR.
In a preferred embodiment, n is 2 or 3.
As mentioned above, A is a polyvalent hydrocarbyl or heterocyclic ring, for example 1,3,5-triazine, containing a polyvalent hydrocarbon group derived by the separation of hydrogen from carbon atoms of different valences. Such hydrocarbyls include, for example, groups of aliphatic (straight and branched), cycloaliphatic, aromatic and mixed properties such as aralkyl, alkylaryl, alkynyl, cycloalkynyl. More specifically, hydrocarbyl preferably includes, but is not limited to, alkyl, cycloalkyl, aryl, aralkyl, alkylaryl, alkenyl and cycloalkenyl having up to 24 carbon atoms. Hydrocarbyls may optionally contain carbonyl groups or groups (including in carbon atoms) and / or heteroatoms or heteroatoms (one or more oxygen, sulfur, nitrogen or silicon) in the chain or ring. A may also be a heterocyclic ring such as polyvalent 1,3,5-triazine. More preferably, the heterocyclic ring is divalent or trivalent 1,3,5-triazine.
A can also be derived from di- or triisocyanates. Suitable diisocyanates include hexamethylene diisocyanate, dimethyl hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, methaxylylene diisocyanate, paraxylylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, paratetramethylxylene di Isocyanates, meta-tetramethylxylene diisocyanates, xylene diisocyanates, para-phenylene diisocyanates and cyclohexyl diisocyanates. Suitable triisocyanates include, but are not limited to, isocyanurate trimers of toluene diisocyanate (abbreviated as TDI), hexamethylene diisocyanate, or isophorone diisocyanate (IPDE). Other conventional triisocyanates are tris- (4-isocyanopophenyl) methane and 1,3,5-tris- (6-isocyanatohexyl) biuret. In a preferred embodiment, A is

to be.
Particularly preferred embodiments of the trisaryl-1,3,5-triazines of formula (I) are illustrated by formulas (V), (VI) and (VII).

Particularly preferred embodiments of trisaryl-1,3,5-triazines of formula (II) are illustrated by formulas (VIII), (IX) and (X).

In the above formula,
n is 2 or 3.
Particularly preferred embodiments of the trisaryl-1,3,5-triazines of formula III are illustrated by formula XI.
In the above formula,
n is 2 or 3.
Manufacturing method
The poly-trisaryl-1,3,5-triazine carbamate of the present invention contains a hydroxyl group in which the aryl ring is in the ortho position relative to the attachment site of the triazine ring and is added by a hydroxyl functional containing hydrocarbyl group Two or more trisaryl 1,3,5-triazines substituted with a carba of formula (I) to (III) by reaction using conventional methods involving reaction with polyisocyanates or transcarbamoylated with other polycarbamate It can be prepared by a method of obtaining a mate triazine polymer.
The selection of triazines suitable for use in the triazine carbamate synthesis of the present invention is such that the triazines are parahydryls further substituted by hydroxyl groups and hydroxyl functional hydrocarbyl groups at the ortho position relative to the attachment site of the triazine ring. It is only limited by the conditions which must contain a siloxane group. Suitable triazines include, but are not limited to:
In the above formula,
R 'is a group containing hydroxyl functional groups,
to be.
Preferred hydroxyl-containing R 'groups are-(CH ₂ ) _N OH, where N is 2 to 6, -CH ₂ CH (OH) CH ₂ O (CH ₂ ) _m CH ₃ , where m is 3 To 13), -OCH ₂ CONn-Bu (CH ₂ ) ₂ OH.
Preferably, the divalent hydrocarbyl binder is diisocyanate. Suitable diisocyanates include hexamethylene diisocyanate, dimethyl hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, methaxylylene diisocyanate, paraxylylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, para-α, α , α ', α'-tetramethylxylylene diisocyanate, meta-α, α, α', α'-tetramethylxylene diisocyanate (commercially available under the trade name m-TMXDI aliphatic isocyanate, Cytec Industries, Inc., West Paterson, NJ), xylene diisocyanate, para-phenylene diisocyanate and cyclohexyl diisocyanate.
Specific examples of suitable diisocyanates include 1-chloro-2,4-phenylene diisocyanate, 2,4-toluene diisocyanate, mixtures of 2,4-toluene and 2,6-toluene diisocyanate, tetramethylphenylene diisocyanate, Diphenylmethane-4,4'-diisocyanate, metaphenylene diisocyanate, paraphenylene diisocyanate, 1,5-naphthalene diisocyanate, biphenyl-4,4'-diisocyanate, 4,4'-isopropyl Lidene diphenylisocyanate, benzophenone-4,4'-diisocyanate, diphenylether- and diphenylsulfide diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate, 3,3'-di Methoxydiphenyl-4, diisocyanate, 3,3'-dichlorodiphenyl-4,4'-diisocyanate, benzofuran-2,7-diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3 '-Dimethyl-4,4'-biphenylene diisocyanate, 4,4'-dicyclo One chamber contains the diisocyanate and 1,4-cyclohexane diisocyanate, it is not limited thereto. Further suitable diisocyanates include hexane 1,6-diisocyanate, 2,2,4-trimethyl-hexane-1,6-diisocyanate, bis- (4-isocyanatocyclohexenyl) methane, ethylene diisocyanate, 1 , 2-diisocyanatopropane, 3-diisocyanatopropane, 1,2-diisocyanato-cyclohexane, 1,3-diisocyanatocyclohexane, 1,4-diisocyanatobenzene, bis (4-iso Cyanatosaaclohexyl) methane, bis (4-isocyanatophenyl) methane, 3,3-dichloro-4,4'-diisocyanatobiphenyl, 1,5-diisocyanatonaphthalene, hydrogenated toluene diisocyanate, 2,2'-diisocyanatodiethyl fumarate, 1,5-diisocyanato-1-carboxypentane, 1,2-, 1,3-, 1,6-, 1,7-, 1,8- , 2,7- and 2,3-diisocyanato-naphthalene, 2,4- and 2,7-diisocyanato-1-methylnaphthalene, 4,4'-diisocyanatobiphenyl, 4,4'- Diisocyanato-3,3'-diisocyanato-6 (7) -methyl Naphthalene, 4,4'-diisocyanato-2,2'-dimethylbiphenyl, bis- (4-isocyanatophenyl) ethane and bis (4-isocyanatophenyl) ether.
Preferred diisocyanates are meta-α, α, α ', α'-tetramethylxylylene diisocyanate (m-TMXDI ^R ), hexane 1,6-diisocyanate (also known as hexamethylene diisocyanate, abbreviated as HDI) Bis- (4-isocyanatocyclohexyl) methane and 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl cyclohexane (isophorone diisocyanate, abbreviated as IPDI) Include.
In addition to carbamate dimers derived from diisocyanates, the present invention includes carbamate trimers derived from triisocyanates. Typical triisocyanates are isocyanurate trimers of toluene diisocyanate (abbreviated as TDI), hexamethylene diisocyanate, or isophorone diisocyanate (IPDI). These trimers are characterized by 1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione rings. Other common triisocyanates are tris- (4-isocyanatophenyl) methane and 1,3,5-tris- (6-isocyanatohexyl) biuret. Examples of heterocyclic triisocyanates are 2,4,6-triisocyanato-1,3,5-triazine.
The present invention also relates to reaction products of hydroxyl functional triazines with diisocyanates and polyols such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, pentaerythritol and the like and oligomeric and polymeric polyols Carbamate triazine obtained by reaction with. Preferred examples are diisocyanate / trimethylolpropane adducts. Particularly preferred examples are commercially available under the trade name 3: 1 meta-α, α, α ', α'-tetramethylxylylene diisocyanate (m-TMXDI ^R ) / trimethylolpropane adduct (Cythane ^R 3160 aliphatic polyisocyanate), Cytec Industries, Inc.) and 3: 1 IPDI / trimethylolpropane adduct (Reichhold Chemicals, Research Triangle Park, North Carolina) under the trade name Sppenlite ^R P25-A4-60 aliphatic urethane prepolymer.
In addition to carbamate dimers derived from diisocyanates and carbamate trimers derived from triisocyanates. There are a number of other modified polyisocyanate precursors. Examples of modified polyisocyanate precursors are as follows:
(a) polymethylene polyphenylene ester (polymethylene polyphenylene polyisocyanate) of isocyanic acid,
(b) meta-isopropenyl-α, α'-dimethylbenzyl isocyanate (commercially available under the trade name m-TMI ^R , Cytec Industries, Inc.) and vinyl monomers such as ethyl acrylate, butyl acrylate, methyl methacryl Copolymers of late styrene and α-methyl styrene,
(c) reaction products of diphenylmethane diisocyanate (abbreviated as MDI) and low molecular weight polyether diols such as Luprante ^R MP 102, BASF Wyandotte Corp.,
(d) reaction products of diphenylmethane diisocyanate (abbreviated as MDI) and low molecular weight polyester diols (e.g. Baytec ^R MS-242, Mobay Corp.),
(e) reaction products of IPDI dimers and polyols such as IPDI-BF 1540, Nuodes ^R ,
(f) reaction products of toluene diisocyanate (abbreviated as TDI) trimer and phenol (Desmodur ^R CT Stabil, Mobay Corp.),
(g) Uretonimine from Lupranate ^R MM 103, BASF Wyandotte Corp.
Preferred examples of carbamate used in the transcarbamoylation reaction are 2,4,6-trialkoxy carbamoylamino 1,3,5-triazine, 2,4,6-trisphenoxy carbamoylamino-1, 3,5-triazine and triazine isocyanate.
Use of poly-trisaryl-1,3,5-triazine carbamate
As mentioned above, the novel poly-trisaryl-1,3,5-triazine carbamate of the present invention is, for example, suitable for various polymers (both crosslinked and thermoplastic), photographic materials and fibrous materials. It is particularly useful as a sunscreen agent (eg, a sunscreen agent) as well as a UV absorber for stabilizing various substances, including dye solutions. The novel poly-trisaryl-1,3,5-triazine carbamates of the present invention include many conventional methods, including, for example, physical mixing or blending, optionally using chemical bonding to a material (typically a polymer). By means of a component in a light stabilizing composition, such as a coating or solution, or as a component in a UV blocking composition, such as a sunscreen composition.
In one aspect of the invention, the poly-trisaryl-1,3,5-triazine carbamate of the invention is a substance which is modified by ultraviolet irradiation by chemically or physically incorporating the compound claimed herein into the polymeric material. It can be used to stabilize. Non-limiting examples of such stabilizing polymeric materials include polyolefins, polyesters, polyethers, polyketones, polyamides, natural and synthetic rubbers, polyurethanes, polystyrenes, high impact polystyrenes, polyacrylates, polymethacrylates , Polyacetal, polyacrylonitrile, polybutadiene, polystyrene, ABS, SAN (styrene acrylonitrile), ASA (acrylate styrene acrylonitrile), cellulosic acetate butyrate, cellulosic polymer, polyimide, polyamideimide, Polyetherimide, polyphenylsulfide, PPO, polysulfonate, polyethersulfonate, polyvinylchloride, polycarbonate, polyketone, aliphatic polyketone, thermoplastic TPU's, amino resin crosslinked polyacrylate and polyester, polyisocyanate Cross-linked polyester and polyacrylic Latex, phenol / formaldehyde, urea / formaldehyde and melamine / formaldehyde resin, dry and undry alkyd resin, alkyd resin, polyester resin, melamine resin, urea resin, isocyanate, isocyanurate, carbamate, and epoxy Crosslinked epoxy resins, polysiloxanes, Michael addition polymers, amines, activated unsaturateds crosslinked with acrylate resins, anhydrides or amines crosslinked with resins and derived from aliphatic, cycloaliphatic, heterocyclic, and aromatic glycidyl compounds And blocking amines with methylene compounds, ketimines with activated unsaturated and methylene compounds, polyketimines mixed with unsaturated acrylic polyacetoacetate resins, polyketimines mixed with unsaturated acrylic resins, radiation curable compositions, epoxymelamine resins, organic Dye, cosmetics, cellulose , A mixture of a photographic film paper, ink, and mixtures thereof.
Further non-limiting examples of specific polymers that can be stabilized include:
1. Monoolefins and diolefins and cyclopentenes including but not limited to ethylene, propylene, isobutylene, butene, methylpentene, hexene, heptene, octene, isoprene, butadiene, hexadiene, dicyclopentadiene, ethylidene And homopolymers, copolymers and terpolymers of cycloolefins such as norbornene, for example polyethylene (which may be optionally crosslinked), for example high density polyethylene (HDPE), high density and high molecular weight polyethylene ( HDPE-HMW), high density and ultra high molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), branched low density polyethylene (BLDPE), polypropylene, syndiotactic Polypropylene, isotactic polypropylene, ethylene-propylene (EP), eth-prop-dicyclopentadiene and (EPDM) terpolymers. Further examples are copolymers and tertiary copolymers with the abovementioned polymers, blends thereof and other unsaturated monomers, in which metallocene catalysts are used in the preparation.
2. Other vinyl monomers, acrylates and methacrylates, acrylamides, acrylonitrile, styrene, vinyl acetates, including one or more monoolefins and / or diolefins and carbon monoxide and / or limited acrylic and methacrylic acids Ethylene / vinyl acetate copolymers), vinyl halides, vinylidene halides, maleic anhydride and allyl monomers such as allyl alcohol, allyl amine alkyl glycidyl ethers and derivatives thereof.
3. Hydrocarbon resins (eg C ₅ -C ₉ ) and mixtures of polyalkylenes and starches, including hydrogenated modifications thereof.
4. Homopolymers and copolymers of styrene, for example styrene, p-methylstyrene and α-methylstyrene.
5. one or more styrene and other vinyl monomers, for example olefins and diolefins (such as ethylene, isoprene and / or butadiene), acrylic acid and methacrylic acid, acrylates and methacrylates, acrylamides, acrylonitrile, Vinyl acetates such as ethylene / vinyl acetate copolymers, vinyl halides, vinylidene halides, maleic anhydride and allyl compounds such as allyl alcohols, copolymers with allyl amine allyl glycidyl ethers and derivatives thereof.
6. Graft copolymers on polybutadiene, polybutadiene / styrene copolymers and polybutadiene / acrylonitrile copolymers of styrene, styrene (or α-methylstyrene) and acrylonitrile (or methacrylonitrile) on polybutadiene, Styrene and maleic anhydride on polybutadiene, styrene on polybutadiene, acrylonitrile and maleic anhydride or maleimide, styrene on ethylene / propylene / diene copolymer and styrene on acrylonitrile, polyalkyl acrylate or methacrylate and Acrylonitrile, and styrene and acrylonitrile on acrylate / butadiene copolymers.
7. Halogen-containing polymers such as polychloroprene, chlorinated rubber, chlorinated and brominated isobutylene / isoprene copolymers, chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin polymers and copolymers And polymers and copolymers of halogen-containing vinyl compounds such as vinyl chloride, vinylidene chloride, vinyl fluoride and / or vinylidene fluoride and other vinyl monomers.
8. Homopolymers and copolymers derived from α, β-unsaturated acids and derivatives thereof such as acrylic acid, methacrylic acid, acrylates, methacrylates, acrylamides and acrylonitrile.
9. Monomers mentioned in (8) and other unsaturated monomers, for example olefins and diolefins such as butadiene, styrene, vinyl halides, maleic anhydride and allyl monomers such as allyl alcohol, allyl amine, Copolymers with allyl glycidyl ethers and derivatives thereof.
10. Unsaturated alcohols and amines or acyl derivatives or acetals thereof, such as vinyl alcohol, vinyl acetate, vinyl stearate, vinyl benzoate, vinyl maleate, vinyl butyral, allyl alcohol, allyl amine, allyl glycidyl ether , Homopolymers and copolymers derived from allyl phthalate and allyl melamine, and copolymers of these monomers with the other ethylenically unsaturated monomers mentioned above.
In the polymer group of (1) to (10), the present invention further includes these polymers as prepared by metallocene catalysts.
11. Homopolymers and copolymers of cyclic ethers such as alkylene glycols and alkylene oxides, and copolymers with bisglycidyl ethers.
12. Polyacetals such as polyoxymethylene and these polyoxymethylenes comprising ethylene oxide as comonomer, and polyoxymethylene modified with thermoplastic polyurethanes, acrylates and / or MBS.
13. Polyphenylene oxides and sulfides.
14. Polyethanes derived from hydroxy-functional components such as polyhydric alcohols, polyethers, polyesters, polyacryl and / or polybutadienes and aliphatic and / or aromatic isocyanates, and precursors thereof.
15. Polyamides and copolyamides or corresponding lactams derived from diamines, dicarboxylic acids and / or aminocarboxylic acids, for example polyamide 4, polyamide 6, polyamide 6/6, polyamide 6/10, poly Aromatic polyamides starting from amide 6/9, polyamide 6/12, polyamide 4/6, polyamide 12/12, polyamide 11 and polyamide 12, m-xylene diamine and adipic acid, elastomers as modifiers Polyamides prepared from hexamethylene diamine and isophthalic acid and / or terephthalic acid in the presence or absence of, for example, poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; Polyamides and polyolefins mentioned, olefin copolymers, ionomers, chemically bonded or grafted elastomers or polyethers, for example polyethylene glycol, pro Block copolymers with ethylene glycol or polytetramethylene glycol, and polyamides condensed during processing (RIM polyamide systems).
16. Polyurea, polyimide, polyamide-imide, polyetherimide, polyesterimide, polyhydantoin and polybenzimidazole.
17. Polyesters or corresponding lactones derived from dicarboxylic acids, diols and / or hydroxycarboxylic acids such as polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylcyclohexane terephthalate and polyhydric Block copolyether esters derived from hydroxybenzoates as well as hydroxyl-terminated ethers, PETG, PEN, PTT, and polyesters modified with polycarbonates or MBS.
18. Polycarbonates and polyester carbonates.
19. Polysulfonates, polyether sulfonates and polyether ketones.
20. Crosslinked polymers derived from aldehyde condensation resins such as phenol / formaldehyde resins, urea / formaldehyde resins and melamine / formaldehyde resins.
21. Dry and undry alkyd resins.
22. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinkers and also halogen-containing modifiers thereof.
23. Crosslinkable acrylic resins derived from substituted acrylates such as epoxy acrylate, hydroxy acrylate, isocyanato acrylate, urethane acrylate or polyester acrylate.
24. Alkyd resins, polyester resins and acrylate resins crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, carbamates or epoxy resins.
25. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic and / or aromatic glycidyl compounds, for example bisphenol A and bisphenol F crosslinked with curing agents such as anhydrides or amines.
26. Natural polymers such as cellulose, rubber, gelatin, and chemically modified cognate derivatives thereof such as cellulose acetate, cellulose propionate and cellulose butyrate or cellulose ethers such as methyl cellulose, as well As well as rosin and derivatives thereof.
27. Polysiloxanes.
28. Michael addition polymers of amines or blocked amines such as ketamine with activated unsaturated and / or methylene compounds such as acrylates and methacrylates, maleates and acetoacetates.
29. Mixtures or blends of any of the above, such as PP / EPDM, polyamide / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PBTP / ABS, PC / ASA, PC / PBT, PVC / CPE, PVC / acrylate, POM / thermoplastic PUR, PC / thermoplastic polyurethane, POM / acrylate, POM / MBS, PPO / HIPS, PPO / PA 6.6 and copolymers, PATENT / HDPE, PP / HDPE, PP / LDPE, LDPE / HDPE, LDPE / EVA, LDPE / EAA, PATENT / PP, PATENT / PPO, PBT / PC / ABS, PBT / PET / PC etc.
30. Polyketimines in combination with unsaturated acrylic polyacetoacetate resins or unsaturated acrylic resins such as urethane acrylates, polyether acrylates, vinyl or acrylic copolymers having pendant unsaturated groups and acrylated melamine.
31. A radiation curable composition containing an ethylenically unsaturated monomer or oligomer and a polyunsaturated aliphatic oligomer.
32. Photo-stable epoxy resins crosslinked by epoxy melamine resins, for example, epoxy functional coetherated highly solid melamine resins.
Other materials that can be stabilized include:
33. Mixtures and also any ratios of compounds comprising oils, fats or waxes based on mineral oils, animal and vegetable fats, oils and waxes, or synthetic esters such as phthalates, adipates, phosphates, or trimellitates. Natural or synthetic organic materials which may be mixtures of synthetic esters with mineral oils.
34. Aqueous emulsions of natural or synthetic rubber, such as natural latex or lattice of carboxylated styrene / butadiene copolymers.
35. Organic dyes such as azo dyes (diazo, triazo and polyazo), atlaquinone, benzodifuranone, polycyclic carbonyl dyes, indigoid dyes, polymethines, styryl dyes, di And triaryl carbonium dyes, phthalocyanines, quinacridones, carbazoles and perylene tetracarboxylic acid diimides.
36. Synthetic materials such as antioxidants, preservatives, lipids, solvents, surfactants, colorants, antiperspirants, skin conditioners, humectants and the like and natural materials such as collagen, proteins, mink oils, olive oils, coconuts Cosmetics including oils, carnauba wax, beeswax, lanolin, cocoa butter, xanthan gum, aloe and the like, for example, skin lotions, collagen creams, sunscreens, facial makeup and the like.
37. For example, newspapers, cardboard, posters, packaging, labels, stationary, book and magazine paper, combined typing paper, multipurpose and office paper, computer paper, electrophotographic paper, laser and ink-jet printer paper, offset paper Cellulose-based paper for use as a diffuser,
38. Photographic film making.
39. Ink.
Aliphatic polyamide
The novel poly-trisaryl-1,3,5-triazine carbamate of the present invention may also be used with aliphatic polyamide polymers. An "aliphatic polyamide" is a polyamide characterized by the presence of repeating carbonamide groups as an integral part of the polymer chain separated from each other by two or more aliphatic carbon atoms. Examples of these polyamides are repeating monomeric units of the formula -NHC (O) RC (O) NHR ¹ -or -NH-RC (O)-, wherein R and R ¹ are the same or different and are alkyl having at least about 2 carbon atoms Ene groups, preferably alkylene having from about 2 to about 12 carbon atoms) or combinations thereof. Examples of suitable polyamides are polyamides formed by the reaction of diamines and transitions, for example poly (tetramethylene adipamide) (nylon 4,6), poly (hexamethylene adipamide) (nylon 6,6) , Poly (hexamethylene azelamide) (nylon 6,9), poly (hexamethylene sebacamide) (nylon 6,10), poly (heptamethylene pimelamide) (nylon 8,8), poly (nonmethylene azel Amide) (nylon 9,9), poly (decamethylene azelamide) (nylon 10,9), and the like. Examples of useful aliphatic polyamides are those formed by polymerization of amino acids and derivatives thereof such as lactams. Examples of these useful polyamides are poly (4-aminobutyric acid) (nylon 4), poly (6-aminohexanoic acid) (nylon 6), poly (7-aminoheptanoic acid) (nylon 7), poly (8-amino Octanoic acid (nylon 8), poly (9aminononanoic acid) (nylon 9), poly (10-aminodecanoic acid) (nylon 10), poly (11-aminoundecanoic acid) (nylon 11), poly (12- Aminododecanoic acid) (nylon 12) and the like. Blends of two or more aliphatic polyamides can also be used.
Copolymers formed from combinations of repeat units of the abovementioned aliphatic polyamides can be used. As non-limiting examples, such aliphatic polyamide copolymers include caprolactam / hexamethylene adipamide copolymer (nylon 6 / 6,6), hexamethylene adipamide / caprolactam copolymer (nylon 6,6 / 6) using aliphatic / aromatic polyamide repeating units which can be used from hexamethylene adipamide / hexamethylene-azelamide copolymers (nylon 6,6 / 6,9) and repeating units of the aforementioned aliphatic polyamides It includes a copolymer formed by. Examples of such copolyamides are nylon 6 / 6T, nylon 6,6 / 6, T, nylon 6 / 10T, nylon 6 / 12T, nylon 6, 10 / 6T and the like.
Preferred aliphatic polyamides for use in the practice of the present invention are poly (caprolactam), poly (7-aminoheptanoic acid), poly (tetramethylene adipamide), poly (hexamethylene adipamide) and mixtures thereof . Particularly preferred aliphatic polyamides are poly (caprolactam), poly (hexamethylene adipamide), poly (tetramethylene adipamide) and mixtures thereof.
Aliphatic polyamides useful in the practice of the present invention can be obtained from commercial sources or prepared according to known manufacturing techniques. For example, polycaprolactam can be obtained from Allied Signal Inc. and poly (hexamethylene adipamide) can be obtained from DuPont Co.
The number average molecular weight of the aliphatic polyamide can be wide. Typically, aliphatic polyamides are one of the films that are high enough to form a glass top film and that form a molecular weight low enough for melt processing of the blend into the film. Such number average molecular weights are well known to those skilled in the film art and are typically at least about 5,000 as measured by the formic acid viscosity method. In this method, a solution of 9.2 wt concentration of aliphatic polyamide in 90% formic acid at 25 ° C. is used. In a preferred embodiment of the invention, the number average molecular weight of the aliphatic polyamide is from about 5,000 to about 1,000,000, and in particularly preferred embodiments, from about 10,000 to about 100,000. In a particularly preferred embodiment, it is most preferred that the molecular weight of the aliphatic polyamide is from about 20,000 to about 40,000.
Polyurethane
Polyurethane (PUR) elastomeric products (“spandex”) can be combined with UV absorbers and hindered amine light stabilizers according to the invention to stabilize against discoloration and loss of elasticity during UV-ray exposure. Spandex fibers are PUR elastomeric products that require very characteristic UV absorber and hindered amine light stabilizer properties to obtain optimal performance. The triazine class UV absorbers of the present invention can be combined with polymeric hindered amine light stabilizers (HALS) to provide excellent performance in obtaining the desired properties for the spandex fiber field.
The triazine UV absorbers of the present invention, used alone or in combination with HALS, provide the following properties in the field of spandex fibers: (1) low color contribution at typical levels of use ranging from 0.5 to 2.0%, (2) fibers Sufficient MW for processing and thermal exposure conditions, (3) high compatibility and durability, (4) prevention of discoloration and loss of elasticity during exposure to UV-ray energy, (5) water and dry cleaning solvents Low extraction by (6) low color development during exposure to air pollutants, NO _X , SO _X , hydrocarbons, etc., (7) low interaction with seawater and low water chemicals, (8) thermal stabilization of spandex fibers Low interactivity and color development with conventional phenolic antioxidants used in and (9) low interactions with copper based antioxidant systems used in nylon fibers for nylon / spandex fabrics.
Triazine UV absorbers with or without polymeric HALS are excellent in minimizing side effects on incidental performance properties such as low color development during NO _s exposure and low interreactivity with copper-based antioxidant systems used in nylon fibers. Provide stabilization.
As mentioned above, the triazine compounds described herein can impart one or more of the properties described above to spandex fibers when applied to the spandex fibers in a stabilizing effective amount.
Preferably, these triazine compounds are added with the polymeric HALS. The polymeric HALS is preferably poly [(6-morpholino-s-triazine-2,4-diyl) [2,2,6,6-tetramethyl-4-piperidyl) imino] -hexa Methylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]]. Most preferably, the polymeric HALS is a methylated (M) derivative of the HALS sold by Cytec Industries, Inc. as a CYASORB ^R UV-3529 light stabilizer. Other polymeric HALS described in US Pat. No. 4,331,586 are also suitable.
Spandex fibers are formed from polyurethane (PUR) prepolymers made from diisocyanates and glycols. These are the four basic processes used to convert PUR prepolymers to fiber products. These processes are solution anhydrous spinning, solution wet spinning, melt extrusion, and reaction spinning. The UV stabilizers, used alone or in combination with HALS, are suitable for use in any or all of these four procedures.
Spandex fibers can be processed antioxidants. In addition, pigments such as TiO ₂ are commonly used in fiber products.
Triazine UV absorbers, alone or in combination with M-HALS, can be dissolved in DMF or DMAC and added to the PUR prepolymer solution prior to the solution fiber spinning process. The blend can also be extrusion blended into the PUR compound used in the melt spinning process.
Polycarbonate
Among the polymeric compounds, preferred are polycarbonates, polyesters, polyamides, polyacetals, polyphenylene oxides and polyphenylene sulfides, in particular polycarbonates. These compounds in particular have structural repeat units Is understood as a polymer corresponding to wherein A is a divalent phenolic radical. Examples of A are described in particular in US Pat. No. 4,960,863 and DE-A-3 922,496. A is in broad terms hydroquinone, resorcinol, dihydroxybiphenylene or bisphenol, for example bis (hydroxyphenyl) alkane, cycloalkane, sulfide, ether, ketone, sulfone, sulfoxide, α, α '-Bis (hydroxyphenyl) -diisopropylbenzene, for example compound 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl ) -Propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane or derived from
It can be derived from the compound of.
In one embodiment, preferred resins are dihydric alcoholic polycarbonates such as 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2,4-bis (4-hydroxyphenyl) -2 -Methylbutane, 1,1-bis- (4-hydroxyphenyl) -cyclohexane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 4,4'-sulfonyldiphenol and 1, 1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane.
Also preferred is a polycarbonate copolymer comprising two or more phenols, a branched polycarbonate in which a polyfunctional aromatic compound is reacted with a dihydric phenol (s) and a carbonate precursor and a polymer blend comprising a portion of the blend that is significant .
Most preferred resins for these layers are bisphenol A based polycarbonates.
U.S. Patent 5,288,788 also discloses polycarbonates and polyester carbonates, especially aromatic polycarbonates such as 2,2-bis (4-hydroxyphenyl) propane or 1,1-bis (4-hydroxyphenyl) cyclohexane Describe the basics.
British Patent 2,290,745 describes a number of methods developed by concentrating UV absorbers near or on the surface of polymeric materials. These include surface impregnation (eg US Pat. Nos. 3,309,220, 3,043,709, 4,481,664 and 4,937,026) and coating plastic products with solutions containing thermoplastic resins and UV absorbers (eg US 4,668,588 and 4,353,965). Both of these techniques offer the disadvantages of requiring additional processing steps (ie, application, drying or curing), and there are difficulties associated with handling large workpieces. A further disadvantage, in particular associated with the production of polycarbonate sheets, is the deleterious effect such post-treatment is provided on the surface of the polymeric substrate.
As described in US Pat. No. 5,445,872, application of the surface layer via coextrusion is carried out in a manner known by known coextrusion equipment as taught in US Pat. Nos. 3,487,505 and 3,557,265. Coextrusion is a widely recognized method of making laminated thermoplastics by co-extrusion of multiple layers forming the only composite material. U.S. Patent 4,540,623 describes more than 40 layers of coextrusion materials. Another method produces as few as two or three different layers.
In one aspect, the present invention also provides a thermoplastic layer of 0.1 to 10 mils (0.00254 mm to 0.254 mm), preferably 0.1 to 5 mils (0.00254 mm to 0.127 mm) thick, wherein the layer is a poly-trisaryl- And 0.1 to 20% by weight of 1,3,5-triazine carbonate). 2 to 15% by weight is the preferred concentration, and 5 to 10% by weight is the most preferred concentration.
The poly-trisaryl-1,3,5-triazine carbamate of the present invention may be incorporated into the thermoplastic of the surface layer by standard methods such as anhydrous mixing of the additive with the granular resin prior to extrusion.
The poly-trisaryl-1,3,5-triazine carbamate containing layer may be applied to one or both sides of the thermoplastic article.
Laminated thermoplastic articles containing additional layers, such as water resistant layers, as described in US Pat. No. 4,992,322 are also part of the present invention.
The core layer and the cladding layer are combined with the same thermoplastic resin or with different thermoplastic polyesters, polyester carbonates, polyphenylene oxides, polyvinyl chlorides, polypropylenes, polypropylenes, polyethylenes, polyacrylates, polymethacrylates and maleic anhydrides. Copolymers and blends such as styrene and acrylonitrile on polybutadiene and styrene.
Mixtures of such polymers (polyblends) with one another or with other polymers, such as polyolefins, polyacrylates, polydienes or other elastomers, are in the form of impact strength modifiers.
The poly-trisaryl-1,3,5-triazine carbamate of the present invention can also be chemically bonded to a substrate, such as a polymer, so that the transition of such UV absorbers, for example, out of the substrate or out of the substrate surface. Can be greatly reduced. The binding mechanism of the triazines of the present invention is a combination of functional groups attached to amido or carbamate groups, for example by pendant vinyl or hydroxyl groups, and bonds between "host" substrates, such as polymers (chemical and And / or covalent).
The incorporation of the poly-trisaryl-1,3,5-triazine carbamate of the invention can be carried out by copolymerization, by addition of a covalent condensation, by reaction with a polymer containing a suitable functional group, or by grafting. It may be carried out by a method as described in US Pat. Nos. 3,423,360 and 5,189,084, which are incorporated by reference in their entirety herein.
The binding of the poly-trisaryl-1,3,5-triazine carbamate of the present invention can be carried out by polymerization or copolymerization. In the case of the novel triazines of the invention comprising pendant vinyl groups, one or more vinyl monomers, for example (meth) acrylic acid, esters of (meth) acrylic acid, such as methyl acrylate, (meth) acrylic acid The polymerization or copolymerization with amides, hydroxyethyl acrylates, olefins, vinyl chlorides, styrene, butadiene, isoprene and acrylonitrile in can be carried out to form homopolymers or copolymers in which vinyl groups are incorporated into the backbone of the polymer. have. The polymerization or copolymerization is well known in the field of polymerization by free radicals in the form of initiators, for example anions and cations, or by gamma irradiation from actinic radiation, for example UV, electron beams, x-rays and Co ⁶⁰ sources. It may be initiated as described. The polymerization or copolymerization can be carried out as well known in the field of polymerization in solution, emulsifying, dispersing, melting or solid state.
In addition, the binding of the claimed poly-trisacyl-1,3,5-triazine carbamate compounds of the invention can be carried out by aerial addition or by cocondensation. Such incorporation can be effected by condensation during the synthesis of addition polymers or copolymers or during the synthesis of addition polymers or copolymers by methods known to those skilled in the art. For example, compounds of formulas I to V containing suitable functional groups include polyesters, polyamides, polyurethanes, epoxy resins, melamine resins, alkyd resins, phenolic resins, polyurethanes, polycarbonates, polysiloxanes, polyacetals And many can be incorporated into polyanhydrides.
In addition, the compounds of formulas (I) to (V) are bonded to the monomeric component and then incorporated into the polymer or copolymer, for example, by the free radical initiated addition or co-condensation methods described above. Similar methods of incorporation of benzotriazole and benzophenone stabilizers into diol precursors followed by condensation polymerization into polyurethanes and polyesters to impart UV stabilizing properties to the polymers are described, for example, in US Pat. Which is hereby incorporated by reference in its entirety).
Alternatively, the poly-trisaryl-1,3,5-triazine carbamate of the present invention may be bound by reaction with oligomers and / or polymers containing functional groups suitable for the polymer. For example, one or more triazine compounds comprising a vinyl pendant group are added to an unsaturated polyester resin, unsaturated polybutadiene oligomer or unsaturated rubber, optionally with one or more other vinyl monomers or compounds comprising a vinyl group, and then actinic or It can be cured by a free radical catalyst. Alternatively, one or more triazine compounds comprising terminal functional groups such as hydroxyl or amido may be prepared by polymers and / or oligomers such as polyesters, polyurethanes and polydiols having reactive terminal groups, in part The hydrolyzed polyvinylacetate, epoxy resin, polysiloxane and polymers comprising maleic anhydride in the main chain or side chain can be reacted in a manner similar to those well known to those skilled in the art.
Grafting is another method of binding the poly-trisaryl-1,3,5-triazine carbamate claimed herein to polymers and / or oligomers. Grafting can be carried out using initiators or actinic radiation of the type described in the above polymerizations when using the novel triazines of the invention which include, for example, pendant vinyl groups in solution, molten, or solid state. Such poly-trisaryl-1,3,5-triazine carbamate can be used to form saturated polymers such as polyolefins and copolymers thereof such as polyethylene, polypropylene and poly (ethylene-vinyl acetate) or unsaturated moieties. It can be grafted to a polymer comprising, for example, polybutadiene, polyisoprene, ethylene-propylene- (diene monomer) terpolymer and polystyrene and copolymers thereof.
The poly-trisaryl-1,3,5-triazine carbamate of the present invention can be used in a wide variety of amounts for applications and specific applications depending on the material to be stabilized. However, when used as stabilizing additives for materials such as organic polymers, the poly-trisaryl-1,3,5-triazine carbamate of the present invention is typically about 0.01 based on the weight of the material to be stabilized. To about 20 weight percent, preferably about 0.1 to about 10 weight percent. Most preferably in an amount of about 0.1 to about 5% by weight. In blocking applications such as in sunscreen compositions, triazine is used in the same relative amounts, but based on the total amount of the blocking agent.
The novel stabilizers of the present invention are non-binding and can be used for stabilizing thermoplastic polymers, for example as described in the many references cited above. Examples of preferred thermoplastic polymers are polyolefins and polymers comprising hetero atoms in the main chain. Preferred polymers are also thermoplastic polymers comprising nitrogen, oxygen and / or sulfur, in particular nitrogen or oxygen in the main chain. It is interesting that the polymer is a polyolefin such as polyethylene or polypropylene.
Incorporation into the thermoplastic polymer can be carried out by the addition of novel poly-trisaryl-1,3,5-triazine carbamate compounds and any additional additives in a manner customary in the art. The incorporation is conveniently carried out before or during shaping, for example by mixing powdery ingredients or by adding a stabilizer to the melt or solution of the polymer or by applying the dissolved or dispersed compound to the polymer with or without subsequent evaporation of the solvent. Can be done. Elastomers may be stabilized as latices.
The new mixture can be added in the form of a masterbatch to the polymer to be stabilized, wherein these compounds are included at a concentration of about 2.5 to about 25%, preferably about 5 to about 20%, by weight of the polymer.
The novel mixtures are conveniently used, for example, a) as emulsions or dispersions (e.g. in latices or emulsified polymers), b) as anhydrous mixtures during mixing of additional components or polymer mixtures, and c) processing equipment (e.g. Extruder, internal mixer, etc.), or d) as a solution or melt, can be incorporated into the polymeric material by a number of methods commonly used in the art.
Stabilized polymer compositions obtained in this way can be molded into a number of conventional methods such as fibers, films, tapes, sheets, sandwich boards, containers, pipes and other forms, for example hot pressing, spinning, extrusion, roto It can be switched by molding or injection molding. The present invention therefore further relates to the use of the polymer composition according to the invention for the production of shaped articles.
According to their ultimate end use, the poly-trisaryl-1,3,5-triazine carbamate of the present invention can be combined with various additives commonly used in the field of UV stabilization. Examples of such additives include, but are not limited to:
a. Antioxidant
(i) alkylated monophenols such as 2,6-di-tert-butyl-4-methylphenol, 2-3-butyl-4,6-dimethylphenol, 2,6-di-tert- Butyl-4-ethylphenol, 2,6-di-tert-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4- Methylphenol, 2- (α-methylcyclohexyl) -4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di- Tert-butyl-4-methoxymethylphenol, nonylphenol linear or branched, for example 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6- (11-methyl Undec-1-yl) phenol, 2,4-dimethyl-6- (1-methylheptadec-1-yl) phenol, 2,4-dimethyl-6- (1-methyltridec-1-yl) phenol , And mixtures thereof.
(ii) alkylthiomethylphenols such as 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthio Methyl-6-ethylphenol and 2,6-didodecylthiomethyl-4-nonylphenol.
(iii) hydroquinones and alkylated hydroquinones such as 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di- Tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyani Sol, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate and bis (3,5-di-tert- Butyl-4-hydroxyphenyl) adipate.
(iv) tocophenols such as α-tocophenol, β-tocophenol, γ-tocophenol, δ-tocophenol and mixtures thereof (vitamin E).
(v) hydroxylated thiodiphenyl ethers such as 2,2'-thiobis (6-tert-butyl-4-methylphenol), 2,2'-thiobis (4-octylphenol), 4,4'-thiobis (6-tert-butyl-3-methylphenol), 4,4'-thiobis (6-tert-butyl-2-methylphenol), 4,4'-thiobis ( 3,6-di-tert-amylphenol) and 4,4'-bis (2,6-dimethyl-4-hydroxyphenyl) disulfide.
(vi) alkylidenebisphenols such as 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethyl Phenol), 2,2'-methylenebis [4-methyl-6- (α-methylcyclohexyl) phenol], 2,2'-methylenesis (4-methyl-6-cyclohexylphenol), 2,2 ' Methylenebis (6-nonyl-4-methylphenol), 2,2'-methylenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (4,6-di- Tert-butylphenol), 2,2'-ethylidenebis (6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis [6- (α-methylbenzyl) -4-nonyl Phenol], 2,2'-methylenebis [6- (α, α-dimethylbenzyl) -4-nonylphenol], 4,4'-methylenebis (2,6-di-tert-butylphenol), 4 , 4'-methylenebis (6-tert-butyl-2-methylphenol), 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis ( Tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1 , 1-bis (5-tert-butyl-4-hydroxy-2-methylbutyl) -3-n-dodecylmer Tobutane, ethylene glycol bis [3,3-bis (3'-tert-butyl-4'-hydroxyphenyl) butyrate], bis (tert-butyl-4-hydroxy-5-methylphenyl) di Cyclopentadiene, bis [2- (3'-tert-butyl-2'-hydroxy-5'-methylbenzyl) -6-tert-butyl-4-methylphenyl] terephthalate, 1,1-bis ( 3,5-dimethyl-2-hydroxyphenyl) butane, 2,2-bis (3,5-di-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (5-tert- Butyl-4-hydroxy-2-methylphenyl) -4-n-dodecylmercaptobutane and 1,1,5,5-tetra (5-tert-butyl-4-hydroxy-2-methylphenyl) pentane.
(vii) O-, N- and S-benzyl compounds, such as 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl- 4-hydroxy-3,5-dimethylbenzyl mercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert-butylbenzyl mercaptoacetate, tris (3,5-di-tert- Butyl-4-hydroxybenzyl) amine, bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, bis (3,5-di-tert-butyl-4 -Hydroxybenzyl) sulfide, and isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.
(viii) hydroxybenzylate malonates such as dioctadecyl-2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonate, dioctadecyl-2- (3-tert-Butyl-4-hydroxy-5-methylbenzyl) malonate, dididosylmercaptoethyl-2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) Malonate and bis [4- (1,1,3,3-tetramethylbutyl) phenyl] -2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate.
(ix) aromatic hydroxybenzyl compounds, for example 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1, 4-bis (3,5-di-tert-butyl--4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, and 2,4,6-tris (3,5-di- Tert-butyl-4-hydroxybenzyl) phenol.
(x) triazine compounds, for example 2,4-bis (octylmercapto-6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-tri Azine, 2-octylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4, 6-bis (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,3,5-triazine, 2,4,6-tris (3,5-di-tert-butyl 4-hydroxyphenoxy) -1,3,5-triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1, 3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris (3,5-di-tert-butyl-4 -Hydroxyphenylethyl) -1,3,5-triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -hexahydro-1,3 , 5-triazine and 1,3,5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.
(xi) benzylphosphonates, for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4- Hydroxybenzylphosphonate, Dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, Dioctadecyl-5-tert-butyl-4-hydroxy-3-methyl Calcium salts of benzylphosphonates and monoethyl esters of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.
(xii) acylaminophenols such as 4-hydroxylauranilide, 4-hydroxystearanilide, and octyl N- (3,5-di-tert-butyl-4-hydroxyphenyl) Carbamate.
(xiii) β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid and monohydric or polyhydric alcohols such as methanol, ethanol, n-octanol, i-octanol, octadecane Ol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris Oxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaoundaneol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane and 4-hydroxymethyl-1 Esters with phospha-2,6,7-trioxabicyclo [2.2.2] octane.
(xiv) β- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid and monohydric or polyhydric alcohols such as methanol, ethanol, n-octanol, i-octanol, octadecanol , 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxy Ethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaoundaneol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane and 4-hydroxymethyl-1- Esters with phospha-2,6,7-trioxabicyclo [2.2.2] octane.
(xv) β- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid and mono or polyhydric alcohols, such as methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1 , 9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaoundaneol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane and 4-hydroxymethyl-1-phospha-2,6,7- Esters with trioxabicyclo [2.2.2] octane.
(xvi) 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid and mono or polyhydric alcohols such as methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1, 9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N '-Bis (hydroxyethyl) oxamide, 3-thiaoundaneol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane and 4-hydroxymethyl-1-phospha-2,6,7-tri Ester with oxabicyclo [2.2.2] octane.
(xvii) Amides of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, for example N, N'-bis (3,5-di-tert-butyl-4 -Hydroxyphenylpropionyl) hexamethylenediamine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylenediamine and N, N'-bis (3, 5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine.
(xviii) ascorbic acid (vitamin C).
(xix) amine antioxidants such as N, N'-diisopropyl-p-phenylenediamine, N, N'-di-tert-butyl-p-phenylenediamine, N, N'- Bis (1,4-dimethylphenyl) -p-phenylenediamine, N, N'-bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N, N'-bis (1-methylheptyl ) -p-phenylenediamine, N, N'-dicyclohexyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N'-bis (2-naphthyl)- p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N- (1-methyl Heptyl) -N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4- (p-toluenesulfonamoyl) diphenylamine, N, N'-dimethyl -N, N'-di-tert-butyl-p-phenylenediamine, diphenylamine, allyldiphenylamine, 4-isopropoxydiphenylamine, -phenyl-1-naphthylamine, N- (4 -Tert-octylphenyl) -1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, for example p, p'-di-tert-octyldi Nylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, bis (4-methoxyphenyl) Amine, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4'-diaminophenylmethane, 4,4'-diaminodiphenylmethane, N, N, N ', N' -Tetramethyl-4,4'-diaminodiphenylmethane, 1,2-bis [(2-methylphenyl) amino] ethane, 1,2-bis (phenylamino) propane, (o-tolyl) biguanide, Bis [4- (1 ', 3'-dimethylbutyl) phenyl] amine, tert-octylated N-phenyl-1-naphthylamine, monoalkylated and dialkylated tert-butyl tert-octyldiphenyl Mixtures of amines, mixtures of monoalkylated and dialkylated nonyldiphenylamines, mixtures of monoalkylated and dialkylated dodecyldiphenylamines, mixtures of monoalkylated and dialkylated isopropyl / isohexyldiphenylamines, monoalkylated and dialkylated 3 Mixture of tert-butyldiphenylamine, 2,3-dihydro -3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, monoalkylated and dialkylated tert-butyl / 3 tert-octylphenothiazine, monoalkylated and dialkylated tert-jade Mixtures of tilphenothiazine, N-allylphenothiazine, N, N, N ', N'-tetraphenyl-1,4-diaminobut-2-ene, N, N-bis (2,2,6, 6-tetramethylpiperid-4-yl) hexamethylenediamine, bis (2,2,6,6-tetramethylpiperid-4-yl) sebacate, 2,2,6,6-tetramethylpiperidine -4-one and 2,2,6,6-tetramethylpiperidin-4-ol.
b. UV absorbers and light stabilizers
(i) 2- (2'-hydroxyphenyl) benzotriazole, for example 2- (2'-hydroxy-5'-methylphenyl) -benzotriazole, 2- (3 ', 5'-di -Tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5 ' -(1,1,3,3-tetramethylbutyl) phenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) -5-chlorobenzotriazole , 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-5'-tert-butyl- 2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-4'-octoxyphenyl) benzotriazole, 2- (3 ', 5'-di-tert-amyl-2'- Hydroxyphenyl) benzotriazole, 2- (3 ', 5'-bis (α, α-dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole; 2- (3'-tert-butyl-2'-hydroxy-5 '-(2-octyloxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl- 5 '-[2- (2-ethylhexyloxy) -carbonylethyl] -2'-hydroxyphenyl) -chloro-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy -5 '-(2-methoxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonyl Ethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '-(2-octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3'-3 Tert-butyl-5 '-[2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5 Mixture of '-methylphenyl) benzotriazole and 2- (3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl) phenylbenzotriazole; 2,2-di Methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-ylphenol], 2- [3'-tert-butyl-5 '-(2-methoxy Carbonylethyl) -2'-hydroxyphenyl] bene Triazole and a transesterification product of a polyethylene glycol _{300, [R-CH 2 CH} -COO (CH 2) 3] 2 B ( wherein, R represents 3'-tert-butyl-4'-hydroxy-5'- 2H-benzotriazol-2-ylphenyl).
(ii) 2-hydroxybenzophenones such as 4-hydroxy, 4-methoxy, 4-octoxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ' , 4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives.
(iii) esters of saturated and unsaturated benzoic acids, for example 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis (4-tert- Butylbenzoyl) resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-3 Tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate and 2-methyl-4,6-di-tert-butylphenyl 3,5- Di-tert-butyl-4-hydroxybenzoate.
(iv) acrylates such as ethyl α-cyano-β, β-diphenylacrylate, isooctyl α-cyano-β, β-diphenylacrylate, methyl α-carbomethoxycinnamate, Methyl α-cyano-β-methyl-p-methoxycinnamate, butyl α-cyano-β-methyl-p-methoxycinnamate, methyl α-carbomethoxy-p-methoxycinnamate and N- (β-carbomethoxy-β-cyanovinyl) -2-methylindolin.
(v) 2 comprising 1: 1 or 1: 2 complexes in the presence or absence of nickel compounds, such as additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine Nickel complex of, 2'-thio-bis- [4- (1,1,3,3-tetramethylbutyl) phenol], nickel dibutyldithiocarbamate, 4-hydroxy-3,5-di-3 Nickel salts of monoalkyl esters including methyl or ethyl esters of tert-butylbenzylphosphonic acid, nickel complexes of ketoxime including 2-hydroxy-4-methylphenyl undecyl ketoxime, and 1 with or without additional ligands Nickel complex of -phenyl-4-lauroyl-5-hydroxypyrazole.
(vi) sterically hindered amines as well as their N derivatives (eg N-alkyl, N-hydroxy, N-alkoxy and N-acyl), for example bis (2,2,6,6-tetramethylpyrepidine 4-yl) sebacate, bis (2,2,6,6-tetramethylpiperidin-4-yl) succinate, bis (1,2,2,6,6-pentamethylpiperidine-4 -Yl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (1,2,2,6,6-pentamethylpiperi Din-4-yl) -n-butyl 3,5-di-tert-butyl-4-hydroxybenzylmalonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl- Condensates of 4-hydroxypiperidine and succinic acid, N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) hexamethylenediamine and 4-tert-octylamino Condensate of -2,6-dichloro-1,3,5-triazine, tris (2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate, tetrakis (2,2, 6,6-tetramethylpiperidin-4-yl) -1,2,3,4-butanetetracarboxylate, 1,1 '-(1,2- Tandiyl) bis (3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6, 6-tetramethylpiperidine, bis (1,2,2,6,6-pentamethylpiperidyl) -2-n-butyl-2- (2-hydroxy-3,5-di-tert- Butylbenzyl) malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4,5] decane-2,4-dione, bis (1-octyl) Oxy-2,2,6,6-tetramethylpiperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate, N, N'-bis ( Condensate of 2,2,6,6-tetramethylpiperidin-4-yl) hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, 2-chloro- 4,6-bis (4-n-butylamino-2,2,6,6-tetramethylpiperidyl) -1,3,5-triazine and 1,2-bis (3-aminopropylamino) ethane Condensates of 2-chloro-4,6-bis (4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl) -1,3,5-triazine and 1,2 Condensates of bis (3-aminopropylamino) ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, 3-dodecyl-1- (2, 2,6,6-tetramethylpiperidin-4-yl) pyrrolidine-2,5-dione, 3-dodecyl-1- (1-ethanol-2,2,6,6-tetramethylpiperi Din-4-yl) pyrrolidine-2,5-dione, 3-dodecyl-1- (1,2,2,6,6-pentamethylpiperidin-4-yl) pyrrolidine-2, A mixture of 5-dione, 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, N, N'-bis (2,2,6,6-tetra Condensate of methylpiperidin-4-yl) hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, 1,2-bis (3-aminopropylamino) ethane , Condensates of 2,4,6-trichloro-1,3,5-triazine and 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS reg. No. [136504-96-6 ]), 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospyro [4.5] decane, oxo-piperazinyl-triazine or so-called PIP -T HALS, e.g. GOODRITE ^R 3034, 315 0 and 3159 and similar materials described in US 5071981, such as the photocoupling HALS, eg, SANDUVOR ^R PR-31 and PR-32 (Clariant Corp.) and similar materials described in GB-A-2269819, and 7, Reaction product of 7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospyro [4.5] decane and epichlorohydrin. See generally US4619956, US5106891, GB-A-2269819, EP-A-0309400, EP-A-0309401, EP-A-0309402 and EP-A-0434608.
(vii) oxamides such as 4,4'-dioctyloxyoxanide, 2,2'-diethoxyoxanide, 2,2'-dioctyloxy-5,5'-di-3 Tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butyloxanide, 2-ethoxy-2'-ethyloxanide, N, N'-bis (3-dimethylaminopropyl) oxanide, 2-ethoxy-5-tert-butyl-2'-ethyloxanide, and 2-ethoxy-2'-ethyl-5,4-di-3 thereof Mixtures with tert-butoxanilides, and mixtures of o- and p-methoxy disubstituted oxides and mixtures of o- and p-ethoxy disubstituted oxides.
(viii) 2- (2-hydroxyphenyl) -1,3,5-triazines described in the above references, for example 2,4,6-tris (2-hydroxy-4-octyloxyphenyl ) -1,3,5-triazine, 2- (2-hydroxy-4-n-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine , 2- (2-hydroxy-4- (mixed iso-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4 -Dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5- Triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy- 4-tridecyloxywanyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butyl Oxypropyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-ha Hydroxy-4- (2-hydroxy-3-octyloxypropyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4-dode Siloxy / tridecyloxy-2-hydroxypropoxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2 -Hydroxy-4- (2-hydroxy-3-dodecyloxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2 -Hydroxy-4-hexyloxy) phenyl-4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl- 1,3,5-triazine, 2,4,6-tris [2-hydroxy-4- (3-butoxy-2-hydroxypropoxy) phenyl] -1,3,5-triazine and 2 -(2-hydroxyphenyl) -4- (4-methoxyphenyl) -6-phenyl-1,3,5-triazine.
(c) metal deactivators such as N, N'-diphenyloxamide, N-salicyl-N'-salicylyl hydrazine, N, N'-bis (salicyl) hydrazine, N, N '-Bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis (benzylidene) oxalyl dihi Drazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N, N'-diacetyladifoyl dihydrazide, N, N'-bis (salicyl oil) oxalyl Dihydrazide, and N, N'-bis (salicyloyl) thiopropionyl dihydrazide.
(d) phosphites and phosphonites such as triphenyl phosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite , Distearyl pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) Pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (isodecyloxy) pentaerythritol diphosphite, bis (2,4-di- Tert-butyl-6-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tris (tert-butyl) phenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2 , 4-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10- Tra-tert-butyl-12H-dibenzo [d, g] -1,3,2-dioxaphosphosine, 6-fluoro-2,4,8,10-tetra-tert-butyl-12- Methyl-dibenzo [d, g] -1,3,2-dioxaphosphosine, bis (2,4-di-tert-butyl-6-methylphenyl) methylphosphite, and bis (2,4-di Tert-butyl-6-methylphenyl) ethylphosphite.
(e) hydroxylamines such as N, N-dibenzylhydroxylamine, N, N-diethylhydroxylamine, N, N-dioctylhydroxylamine, N, N-dilaurylhydroxylamine , N, N-ditetradecylhydroxylamine, N, N-dihexadecylhydroxylamine, N, N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecyl-hydroxylamine, N- Heptadecyl-N-octadecylhydroxylamine, and N, N-dialkylhydroxylamine derived from hydrogenated resin fatty acid amine.
(f) nitrons such as N-benzyl-alpha-phenyl nitron, N-ethyl-alpha-methyl nitron, N-octyl-alpha-heptyl nitron, N-lauryl-alpha-undecyl knit Lone, N-tetradecyl-alpha-tridecyl nitron, N-hexadecyl-alpha-pentadecyl nitron, N-octadecyl-alpha-heptadecyl nitron, N-hexadecyl-alpha-heptadecyl nitron, N, N-dialkylhydrides prepared from N-octadecyl-alpha-pentadedecyl nitron, N-heptadecyl-alpha-heptadecyl nitron, N-octadecyl-alpha-hexadecyl nitron and hydrogenated resin fatty acid amines Roxylamine.
(g) thiosynergists such as dilauryl thiodipropionate and distearyl thiodipropionate.
(h) peroxide scavengers such as esters of β-thiodipropionic acid, such as lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazoles or 2-mercaptobenziimi Zinc salt of dozol, zinc dibutyldithiocarbamate, dioctadecyl disulfide, and pentaerythritol tetrakis (β-dodecylmercupto) propionate.
(i) polyamide stabilizers such as copper salts and divalent manganese salts in combination with iodides and / or phosphorus compounds.
(j) basic co-stabilizers such as melamine, polyvinylpyrrolidone, dicyanidiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts of higher fatty acids and Alkaline earth metal salts such as calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate and tin pyrocatecholate.
(k) nucleating agents, for example inorganic materials such as talc and metal oxides (such as titanium oxide or magnesium oxide) and preferably phosphates, carbonates and sulfates of alkaline earth metals, organic compounds such as , Mono- or polycarboxylic acids and salts thereof such as 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate and sodium benzoate and polymeric compounds such as ionic copolymers (E.g. ionomers).
(l) fillers and reinforcing agents, for example powders from calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour, and other natural products, or Fibers and synthetic fibers.
(m) Other additives such as plasticizers, lubricants, emulsifiers, pigments, rheological additives, catalysts, leveling aids, optical brighteners, flame retardants, antistatic agents and blowing agents.
(n) described in US 4,325,863, US 4,338,244, US 5,175,312, US 5,216,052, US 5,252,643, DE-A-4316611, DE-A-4316622, DE-A-4316876, EP-A-0589839 and EP-A-0591102 Benzofuranone and indolinone, 3- [4- (2-acetoxyethoxy) phenyl] -5,7-di-tert-butylbenzofuran-2-one, 5,7-di-tertiary as -Butyl-3- [4- (2-stearoyloxyethoxy) phenyl] benzofuran-2-one, 3,3'-bis [5,7-di-tert-butyl-3- (4- [2-hydroxyethoxy) phenyl] benzofuran-2-one, 5,7-di-tert-butyl-3- (4-ethoxy) phenyl] benzofuran-2-one, 3- (4- Acetoxy-3,5-dimethylphenyl) -5,7-di-tert-butyl-benzofuran-2-one, 3- (3,5-dimethyl-4-pivaloyloxyphenyl) -5,7 Di-tert-butylbenzofuran-2-one and 5,7-di-tert-butyl-3- (3,4-dimethylphenyl) -3H-benzofuran-2-one.
The novel poly-trisaryl-1,3,5-triazine carbamate of the present invention can be used in multilayer systems. In such a system, from about 0.1 to about 20% by weight, preferably a relatively high concentration of the novel stabilizer, for example from about 5 to 15% by weight of the polymer composition is thin film (e.g. from about 5 to 500 μm thick, preferably Preferably from about 10 to 100 μm thick) to molded articles made from polymers containing almost no UV stabilizer. Such compositions may be applied simultaneously with shaping the base structure by coextrusion in a manner similar to that described in, for example, US Pat. No. 4,948,666, which is incorporated herein by reference in its entirety. Alternatively, the application can be carried out on a basic structure which is ready for shaping, for example by lamination with a film or coating with a solution. The outer layer or layers of the finished product have the function of a UV filter that protects the interior of the product from ultraviolet light. The outer layer is preferably about 0.1 to about 20 weight percent of the outer layer composition, preferably about 1 to about 15 weight percent, and most preferably about 2 to about 10 weight percent of the poly-trisaryl-1 of the present invention. , 3,5-triazine carbamate compound.
Polymers stabilized in this way are remarkable for high weathering resistance, in particular high resistance to ultraviolet radiation. This retains their mechanical properties and their colored surface properties, such as gloss and clarity, for a long time even when used externally. Moreover, due to the binding properties of the triazine compounds claimed herein, the transition of these UV absorbers between layers of the multilayer coating can be minimized under appropriate circumstances.
In another aspect of the invention, the novel mixtures comprising the compounds of the formulas I to V can be used as coatings, for example as stabilizers for paints as described in various literature (see US 4,619,956, US 4,740,542). , US 4,826,978, US 4,962,142, US 5,106,891, US 5,198,498, US 5,298,067, US 5,322,868, US 5,354,794, US 5,369,140, US 5,420,204, US 5,461,151, US 5,476,937, EP-0434608 and EP-A-0444323. Of particular interest are automotive coatings and paints. The invention also relates to these compositions which are film-forming binders for coatings.
Such novel coating compositions comprise about 0.01% to about 20%, preferably about 0.01% to about 10%, most preferably about 0.02% to about 5% by weight of the binder of the coating composition of the claimed poly-trisaryl of the present invention. -1,3,5-triazine carbamate.
At least one layer, and typically a relatively high concentration of novel stabilizer in the outer layer, such as a clearcoat, for example from about 0.01 to about 20 weight percent of the binder, preferably from about 0.01 to about 10 weight percent, More preferably from about 0.02 to about 5% by weight, multilayer systems are also possible (e.g. electrocoat / basecoat / clearcoat systems).
The use of new stabilizers in coatings is achieved by the further advantage of preventing deamination, for example peeling of the coating from the substrate. This advantage is particularly important in the case of metallic substrates, including multilayer systems on metallic substrates, in particular epoxy coated metallic substrates.
The binder may in principle be a binder conventional to the industry. Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A 18, pp. 368-426, VCH, Weinheim 1991, incorporated herein by reference]. In general, these are thermoplastic or curable resins, notably curable resin based film-forming binders. Examples of thermoplastic binders include acrylics, polyesters, polyurethanes and PVC plastisols. Examples of curable binders include functional alkyds, acrylics, polyesters, phenols, melamines, epoxy and polyurethane resins, and mixtures thereof.
Such curable binders may be ambient curable or thermoset binders. In addition, in some systems, it may be beneficial to add a curing catalyst to such a system. Suitable catalysts for promoting curing of binders are described in Ullmann's Encyclopedia of Industrial Chemistry, Vol. A 18, p. 469, VCH, Verlagsgesellschaft, Weinheim 1991]. Preferred binders are those comprising functional acrylate resins and crosslinkers.
Several types of binders can be used in such coating systems. Examples of suitable coating compositions containing specific binders include, but are not limited to:
1. Optionally, based curable or thermosetting alkyd, acrylate, polyester, epoxy or melamine resins or mixtures of such resins in the presence of a curing catalyst.
2. hydroxyl-containing acrylate, polyester or polyether resins and aliphatic or aromatic isocyanates, isocyanurates or polyisocyanate-based two-component polyurethane paints.
3. Blocked isocyanates, isocyanurates or polyisocyanate based one-component polyurethane paints blocked during baking.
4. (poly) ketimines and aliphatic or aromatic isocyanates, isocyanurates or polyisocyanate based two-component paints.
5. Two-component paints based on (poly) ketimines and unsaturated acrylate resins or polyacetoacetate resins or metatrilamidoglycolate methyl esters.
6. Carboxyl- or amino-containing polyacrylates and polyepoxide-based two-component paints.
7. Anhydride group containing acrylate resins and polyhydroxy or polyamino component two-component paints.
8. (Poly) oxazoline and anhydride group-containing acrylate resins or unsaturated acrylate resins, or aliphatic or aromatic isocyanates, isocyanurates or polyisocyanate-based two-component paints.
9. Unsaturated polyacrylate and polymalonate-based two-component paints.
10. External crosslinked acrylate resin based thermoplastic polyacrylate paint blended with thermoplastic acrylate resin or etherified melamine resin.
11. Silox-modified or fluorine-modified acrylate resin based pate systems.
In addition to the binder and the novel poly-trisaryl-1,3,5-triazine carbamate of the invention, the coating composition according to the invention preferably further comprises, but is not limited to, those specifically listed in (b) above. One or more additional ultraviolet absorbents are not limited. Additional UV absorbers are, for example, other tris-aryl-1,3,5-triazines, 2-hydroxyphenyl-2H-benzotriazole, 2-hydroxybenzophenone, esters of unsaturated benzoic acids, acrylates, oxa Mead (oxanide) or a combination thereof. Preferably, the additional UV absorber is 2-hydroxyphenyl-2H-benzotriazole and the weight ratio of benzotriazole to amido or carbamate triazine is from 4: 1 to 1: 4. More preferably, the weight ratio of benzotriazole to amido or carbamate triazine is from 2: 1 to 1: 2.
In order to obtain maximum light stability, it is particularly important to add the hindered amine mentioned in b (vi) above. The present invention relates to a coating composition comprising a light stabilizer in the form of a hindered amine in addition to a binder, a novel poly-trisaryl-1,3,5-triazine carbamate and optionally an additional UV absorber. The hindered amine is used in an amount of about 0.01 to about 5% by weight, preferably about 0.02 to 2% by weight, based on the weight of the solid binder.
One specific example of such sterically hindered amines is one or more of 2,2,6,6-tetramethyl piperazinone containing a group of wherein J is for example hydrogen, hydroxyl, alkyl (eg methyl), alkoxy (eg methoxy) or acyl to be.
More preferably, the stabilizer is at least one formula 2,2,6,6-tetraalkylpiperidine containing a group of wherein J is for example hydrogen, hydroxyl, alkyl (eg methyl), alkoxy (eg methoxy) or acyl Derivatives.
Examples of tetraalkyl piperidine derivatives that can be used in combination with the trisaryl-1,3,5-triazine compounds of the present invention are described in US Pat. Nos. 4,314,933, 4,344,876, 4,426,471, 4,426,472, 4,619,956, 5,004,770, 5,006,577, 5,064,883, 5,112,890, 5,124,378, 5,106,891, 5,204,473 and 5,461,151, which are incorporated herein by reference in their entirety. It is particularly convenient to use the following tetraalkylpiperidine derivatives and their N-alkyl, N-acyl, N-hydroxyl and N-alkoxy derivatives (if not already included in the following list): bis (2 , 2,6,6-tetramethylpiperid-4-yl) succinate, bis (2,2,6,6-tetramethylpiperid-4-yl) sebacate, bis (1,2,2,6 , 6-pentamethylpiperid-4-yl) sebacate, di (1,2,2,6,6-pentamethylpiperid-4-yl) butyl- (3,5-di-tert-butyl- 4-hydroxybenzyl) malonate, bis (1-octyloxy-2,2,6,6-tetramethylpiperid-4-yl) sebacate, tetra (2,2,6,6-tetramethylpiperid 4-yl) butane-1,2,3,4-tetracarboxylate, tetra (1,2,2,6,6-pentamethylpiperid-4-yl) butane-1,2,3,4- Tetracarboxylate, 2,2,4,4, -tetramethyl-7-oxa-3,20-diaza-21-oxo-disspiro [5.1.11.2] henicoic acid, and 8-acetyl-3-dode Cil-1,3,8-tria-7,7,9,9-tetramethylspiro [4.5] decane- 2,4-dione. Commercial examples of these and other tetraalkylpiperidine derivatives include SANDUVOR ^R 3050, 3052, 3055, 3056, 3058, PR-31 and PR-32 (Clariant Corp.), TINUVIN ^R 079L, 123, 144, 292, 440L and 622LD (Ciba Specialty Chemicals), CHIMASORB ^R 119 and 944 (Ciba Specialty Chemicals), and CYASORB ^R UV-3346, UV 3529, UV-3853, UV-500 and UV-516 (Cytec Industries Inc.).
In addition to the binder, poly-trisaryl-1,3,5-triazine carbamate and, if used, additional ultraviolet absorbers or stabilizers, the coating composition further comprises components such as solvents, pigments, dyes, plasticizers, stabilizers, Thixotropic agents, drying catalysts and / or leveling agents. Examples of possible ingredients are described in a number of references and literatures incorporated above by Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A 18, pp. 429-471, VCH, Weinheim 1991, and Calbo, Leonard J., ed., Handbook of Coatings Additives, New York: Marcel Dekker (1987).
Possible drying catalysts or curing catalysts are, for example, organometallic compounds, amines, acids, amino-containing resins and / or phosphines.
Examples of acid catalysts include inorganic acids, aliphatic and aromatic sulfonic acids (eg p-toluene sulfonic acid, dinonylnaphthalene, disulfonic acid, dodecylbenzene sulfonic acid), oxalic acid, maleic acid, hexane acid, phosphoric acid, alkyl phosphate esters , Phthalic acid and acrylic acid copolymers.
Examples of organometallic compounds are metal carboxylates, in particular carboxylates or metal chelates of metals Pb, Mn, Co, Zn, Zr or Cu, in particular chelates of metals Al, It or Zr or organometallic compounds, for example organotin Compound. Examples of metal carboxylates are stearates of Pb, Mn, or Zn, octoates of Co, Zn or Cu, naphthenates of Mn and Co or the corresponding linoleates, resinates or thalates. Examples of metal chelates are aluminum, titanium or zirconium chelates of acetylacetone, ethyl acetylacetate, salicyaldehyde, salicylicoxime, o-hydroxyacetophenone, or ethyl trifluoroacetyl acetate and alkoxides of these metals. Examples of organotin compounds are dibutyltin oxide, dibutyltin dilaurate or dibutyltin dioctoate.
Examples of amine drying or curing catalysts are in particular tertiary amines, for example tributylamine, triethanolamine, N-methyldiethanolamine, N-dimylethanolamine, N-ethylmorpholine, N-methylmorpholine or diadia Zabicyclooctane (triethylenediamine) and salts thereof. Further examples are quaternary ammonium salts such as trimethylbenzylammonium chloride. The amino-containing resin is simultaneously a binder and a curing catalyst. Examples thereof are amino-containing acrylate copolymers.
The curing catalyst used may also be a phosphine, for example triphenylphosphine.
Another type of curing catalyst is peroxide, which can be used, for example, to cure gel coatings for fiber glass products.
The novel coating composition may also be a radiation-curable coating composition. In this case, the binder essentially comprises monomeric or oligomeric compounds containing ethylenically unsaturated bonds and is cured by actinic radiation after application. That is, converted to a crosslinked high molecular weight form. If the system is UV-curable, it usually also contains a photoinitiator. Corresponding systems are described in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A 18, pp. 451-453. In radiation-curable coating compositions, novel stabilizers can also be used without addition of sterically hindered amines.
The novel coating composition according to the invention can be applied to the desired substrate, for example metal, wood, plastic, fiber glass or ceramic material. The coating composition may be an automotive finish in the form of a colored mono-coat or a multilayer (primer / basecoat / clearcoat) system. In the latter case, the novel coating composition can be used for either the base coat or the clear coat, or both layers. If the topcoat of the automotive finish comprises two layers, where the bottom layer is colored and the top layer is not colored, the novel coating composition is applied to both the top or bottom layer or layers, preferably the top topcoat. Used for layers.
The novel coating composition can be applied to the substrate by conventional methods such as brushing, spraying, pouring, dipping or electrophoresis. Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A 18, pp. 491-500.
Depending on the binder system, the coating can be cured at room temperature or by heating. The thermosetting coating is preferably cured at 50 to 150 ° C., and even higher temperatures in the case of powder coatings.
The coatings obtained according to the invention have excellent resistance to damage by light, oxygen and heating, and the excellent light stability and weathering resistance of the coatings thus obtained, for example paints, are of particular note.
The present invention therefore relates to coatings, in particular paints, which are stabilized against damage to light, oxygen and heating by the content of compounds of formulas I to V according to the invention. The paint may be a colored mono-coat comprising a film-forming binder and an organic pigment or dye, an inorganic pigment, a metallic pigment or a mixture thereof. Paints also adhere to film-based primers, colored basecoats that adhere to the primer, adhere to the primers, and form film-forming binders and organic pigments or dyes, inorganic pigments, metallic pigments, or mixtures thereof, and It may be a composition comprising a clear coat comprising a forming binder and optionally a clear pigment. Particularly preferred is a paint which is a clear topcoat for automotive raw material manufacturing (OEM) and / or refinishing.
The present invention also includes mixing a coating composition with a mixture comprising a poly-trisaryl-1,3,5-triazine carbonate compound to stabilize the polymeric coating against damage by light, oxygen, and / or heating. A method and the use of a mixture comprising a poly-trisaryl-1,3,5-triazine carbamate compound in a coating composition as a stabilizer against damage by light, oxygen and / or heating.
The coating composition may comprise an organic solvent or solvent mixture in which the binder is soluble. The coating composition may be an aqueous solution or a dispersion. The vehicle can also be a mixture of organic solvent and water. The coating composition may be a high solid paint or solvent-glass (eg powder coating material).
The pigment may be an inorganic, organic or metallic pigment. The novel coating composition preferably contains no pigment and is used as a clearcoat.
The use of coating compositions as topcoats, in particular as colored or uncolored topcoats of paint finishes, is also preferred for the automotive industry. Moreover, the use as a base coat is also possible.
The poly-trisaryl-1,3,5-triazine carbamate of the present invention is characterized by the presence of poly-trisaryl-1,3,5-triazine carbamate and inert carriers such as solvents, petroleum jelly, water Compositions comprising heavy oil silicone emulsions or automotive paint waxes such as carnauba wax may be poured and applied locally. These topical treatment compositions can be used to stabilize coating films, textiles, leather, vinyl and other plastics, and wood.
Preference is given to the use of the novel poly-trisaryl-1,3,5-triazine carbamate compounds in photographic materials as stabilizers against damage by light, in particular ultraviolet light. The invention also relates to a photographic material comprising a poly-trisaryl-1,3,5-triazine carbamate compound.
The compounds according to the invention can be used for all kinds of photosensitive materials. For example, they can be used for colored paper, reverse colored paper, direct-positive colored materials, negative colored films, positive colored films, reverse colored films and other materials. These are especially used for photosensitive colored materials which comprise a reverse substrate or form a positive.
The novel compounds also contain other UV absorbers, in particular absorbents which are dispersible in aqueous gelatin, for example hydroxyphenylbenzotriazole (see US Pat. Nos. 4,853,471, 4,973,702, 4,921,966 and 4,973,701), benzophenones, oxanilides, sia Noacrylate, salicylate, or acrylonitrile or thiazolin. In this case, it is advantageous to use these additional oil-dissolving UV absorbers in the photographic material in layers other than the layer comprising the novel UV absorbers.
The present invention includes compositions containing one or more binders. In particular, the binder may include alkyd, acrylic, polyester, phenolic, melamine, epoxy or polyurethane resins or blends thereof. Examples of such binders include, but are not limited to:
(a) cold- or heat-crosslinkable alkyd, acrylate, polyester, epoxy or melamine resins or mixtures of such resins.
(b) a two-component polyurethane system comprising hydroxyl-containing acrylate, polyester or polyether resins and aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates.
(c) A one-component polyurethane system comprising blocked isocyanates, isocyanurates or polyisocyanates which are deblocked during baking.
(d) two-component systems comprising (poly) ketimines and aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates.
(e) Two-component systems containing (poly) ketimines and unsaturated acrylate resins or polyacetoacetate resins or methacrylamidoglycolate methyl esters.
(f) Two-component systems comprising carboxyl- or amino-containing polyacrylates and polyepoxides.
(g) Two-component systems comprising an anhydride group containing acrylate resin and on a polyhydroxy or polyamino component.
(h) Two-component systems comprising (poly) oxazolines and anhydride group containing acrylate resins, or unsaturated acrylate resins or aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates.
(i) two-component systems comprising unsaturated polyacrylates and polymalonates.
(j) A thermoplastic polyacrylate system comprising a terminal crosslinked acrylate resin in combination with a thermoplastic acrylate resin or an etherified melamine resin.
(k) A system comprising a siloxane-modified or fluorine-modified acrylate resin.
Such binder-containing compositions may further comprise a curing catalyst, or organic solvent, and may be radiation-curable. In particular, such a composition may be provided as a coating composition.
In particular, photographic materials similar to those described in US Pat. No. 4,518,686 can be successfully stabilized.
The present invention thus comprises a blue-sensitive, green-sensitive and / or red-sensitive silver-halide emulsion layer and optionally a protective layer on a support, wherein the layer comprising the UV absorber is on top of the upper silver-halide emulsion layer. And a UV absorber is a poly-trisaryl-1,3,5-triazine carbamate compound.
It is further desirable to provide a photographic material wherein the layer comprising the compounds of formulas I to V is on the upper silver-halide emulsion layer and / or between the green- and red-sensitive silver-halide emulsion layers.
It may also be beneficial for some or all of the layers that may include a UV absorber to have a UV absorber mixture and / or additional UV absorbers that are dispersible in aqueous gelatin, wherein the compounds of Formulas I-V are at least one layer. Must exist in
The new material preferably has a gelatin interlayer between the silver-halide emulsion layers.
Preference is given to photographic materials wherein the silver halide in the blue-sensitive, green-sensitive and / or red-sensitive layer is silver chloride bromide comprising at least 90 mol% silver chloride.
The compounds of the formulas (I) to (V) used according to the invention can be incorporated into the color photographic material either alone or together with color couplers and additional additives when used, by dissolving the compound in advance in a high boiling organic solvent. Preference is given to using solvents which boil at temperatures higher than 160 ° C. Typical examples of such solvents are phthalic acid, phosphoric acid, citric acid, benzoic acid or esters of fatty acids or alkylamides and phenols.
Preferred color couplers used in the compositions of the invention, examples of such compounds, further additives, such as color inhibitors, DIR couplers, and further light stabilizers such as UV absorbers, phenols, phosphorus (III) ) Detailed descriptions of the structures of the compounds, organometallic complexes, hydroquinones and hydroquinone ethers and various more precise photographic materials can be found in, for example, EP-A-0531258 and EP-A-0520938 and the documents cited above.
The invention also encompasses the incorporation of sterically hindered amines and oxides of zinc, aluminum, calcium and magnesium and metal oxides of hydroxides selected from hydroxides of zinc, aluminum and calcium into polyolefins or polyolefin copolymers, for agricultural, in particular greenhouse polyolefins. Or to a method of stabilizing a polyolefin copolymer film, wherein the polyolefin or polyolefin copolymer film has improved light stability and pesticide resistance. Another subject of the invention is a novel poly-trisacyl-1,3,5-triazine carbamate compound and sterically hindered amines and zinc, aluminum, which are covered with polyolefins or polyolefin copolymers having improved light stability and insecticide resistance , Greenhouses stabilized with metal oxides or hydroxides selected from oxides of calcium and magnesium and hydroxides of zinc, aluminum and calcium, and novel poly-trisaryl-1,3,5-triazine carbamate compounds and sterically hindered amines and zinc , Pesticides and harmful effects of light, oxygen and / or heating, including incorporating metal oxides or hydroxides selected from oxides of aluminum, calcium and magnesium and hydroxides of zinc, aluminum and calcium into polyolefin or polyolefin copolymer greenhouse films It is a method for stabilizing such a greenhouse film.
Another subject of the invention is a novel poly-trisacyl-1,3,5-triazine carbamate compound and hindered amines and zinc, aluminum, calcium and magnesium for use in agriculture, in particular in greenhouses, which require pesticides. Of polyolefin copolymer films stabilized with metal oxides or hydroxides selected from oxides of oxides and hydroxides of zinc, aluminum and calcium and zinc, aluminum for stabilizing polyolefin or polyolefin copolymer films in contact with pesticides against photolysis and damage by pesticides And the use of novel poly-trisacyl-1,3,5-triazine carbamate compounds and sterically hindered amines in combination with oxides of calcium and magnesium and metal oxides or hydroxides selected from hydroxides of zinc, aluminum and calcium.
To form a film, an amount of the molten composition is added to a film die, such as a flat film die or a circular foam film die, from which a film is formed. If the composition is used to form a film therefrom, the film may be unoriented or provide a degree of orientation in a conventional operation on the film. Such films may be oriented in one direction, for example in the machine direction such as "machine direction" and / or "cross direction" or in both directions or "biaxial" orientation.
The invention is also suitable for use in sheets.
Poly-trisaryl-1,3,5-triazine carbamate compounds of formulas I to V include, for example, silk, leather, wool, polyamide or polyurethane and especially all kinds of cellulose-containing fiber materials It is suitable for photochemical stabilization of undyed, dyed or printed fibrous materials. Examples of such fibrous materials are natural cellulose fibers such as cotton, linen, jute and hemp and also viscose artificial fibers and regenerated cellulose. Preferred fiber materials are cotton. The triazine and pyrimidine compounds of the present invention are also suitable for photochemically stabilizing hydroxyl-containing fibers in blend fabrics, such as blends of cotton and polyester fibers or polyamide fibers. A further preferred area of the present invention is that the UV radiation passing through the fiber material finished with the new compound is blocked or reduced (UV cut) and provides enhanced sun protection to human skin.
For this end use, one or several different compounds of the formulas (I) to (V) are advantageously added to the fiber material by one of the usual dyeing methods, preferably from 0.01 to 5% by weight, preferably based on the weight of the fiber material. Application in amounts of 0.1 to 3% by weight, in particular 0.25 to 2% by weight.
Poly-trisaryl-1,3,5-triazine carbamate compounds are applied to the fiber material in various ways and fixed to the fibers, in particular in the form of aqueous dispersions or printing pastes.
Fibrous materials finished with the novel compounds of formulas I to V provide improved protection against photochemical breakdown and yellowing of the fibers and enhanced (high temperature) light fastness in the case of dyed fibrous materials. The photoprotective effect of the treated fibrous material is greatly enhanced, especially the protection effect against short wavelength UV-B rays. This is evidenced by the fact that fiber materials finished with poly-trisaryl-1,3,5-triazine carbamate compounds have a significantly increased sun protection factor (SPF) compared to untreated fabrics.
Sun protection factor is defined as the index of UV radiation damaging the protected skin to UV radiation damaging unprotected skin. Thus, the sun protection factor is also a measure of the degree of UV radiation permeability of fibrous and untreated fibrous materials treated with the novel compounds of Formulas I-V. Measurement of the sun protection factor of fiber materials is described, for example, in WO94 / 04515 or J. Soc. Cosmet. Chem. 40, 127-133 (1989) and can perform similarly.
Another use of the UV absorbers according to the invention is the stabilization of intraocular or contact lenses.
The UV absorbers of the present invention are suitable as photoprotective agents of cosmetic preparations. Further, the present invention relates to cosmetic preparations comprising at least one poly-trisaryl-1,3,5-triazine carbamate compound and a cosmetically acceptable carrier or adjuvant.
The novel perfume compositions are 0.1 to 15% by weight, preferably 0.5 to 10% by weight, based on the total weight of the composition, poly-trisaryl-1,3,5-triazine carbamate UV absorbers and cosmetically acceptable Containing adjuvant.
The fragrance composition can be prepared by the novel UV absorber by adjuvant and conventional methods, for example by physically mixing the two materials together simply by stirring.
The cosmetic preparations according to the invention can be formulated as water-in-oil or water-in-oil emulsions, oil-in-water alcohol lotions, vesicle dispersions of ionic or nonionic amphiphilic lipids, gels, solid sticks or aerosol formulations.
As a water-in-oil or oil-in-water emulsion, the cosmetically acceptable adjuvant preferably contains 5 to 50% in oil phase, 5 to 20% in emulsifier and 30 to 90% in water. The oily phase may comprise oils suitable for cosmetic formulations, for example one or more hydrocarbon oils, waxes, natural oils, silicone oils, fatty acid esters or fatty alcohols. Preferred mono- or polyols are ethanol, isopropanol, propylene glycol, hexylene glycol, glycerol and sorbitol.
In these cosmetic formulations, commonly used emulsifiers such as ethoxylated esters of one or more natural derivatives, ie polyethoxylated esters of hydrogenated castor oil, or silicone oil emulsifiers such as silicone polyols, unmodified or Ethoxylated fatty acid soaps, ethoxylated fatty alcohols, unmodified or ethoxylated sorbitan esters, ethoxylated fatty acids or ethoxylated glycerides can be used.
Cosmetic formulations may contain additional ingredients such as emollients, emulsion stabilizers, skin moisturizers, tanning accelerators, thickening agents, such as xanthan, water retention agents such as glycerol, preservatives or fragrances. And colorants.
The new cosmetic formulations provide good tanning to the skin while providing good protection of human skin against sun damage.
The invention will be illustrated by the following examples. The examples are not intended to limit the scope of the invention. In combination with the above general and detailed description, the examples facilitate further understanding of the present invention.
Example 1: Compounds of Formula XIII
(2,4-bis (2,4-dimethylphenyl) -6- [2-hydroxy-4- (2-hydroxyethoxy) phenyl] -1,3,5-triazine) 8.82 g, m- 2.43 g of TMXDI ^R (Cytec Industries, Inc., West Paterson, NJ), and 120 mg of 1,3-diacetoxy-1,1,3,3, -tetrabutyldistannoic acid ("TK-1") catalyst The mixture is heated in 50 ml of xylene at about 120 ° C. for 4 hours. TLC in this step indicates the absence of starting material and formation of the main product. The heating is stopped and the mixture is cooled to room temperature. Concentration under reduced pressure afforded 11.5 g of crude XIII. Analytical samples are prepared by purifying the crude product on silica gel using column chromatography. The structure of the product is found to be XIII in NMR and mass spectra.
Example 2: Compounds of Formula XV
M-TMXDI according to Example 1 in the presence of TK-1 as catalyst in xylene in 2- (2-hydroxy-4- (N- (n-butyl) -N- (2-hydroxyethyl) -methanami Compound XV is prepared by reaction with dooxy) phenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine (Compound XIV).
Example 3: Compounds of Formula XVI
2,4,6-triisocyanato-1,3,5-triazine (melamine triisocyanate) 2.04 g, 2,4-bis (2,4-dimethylphenyl) -6- {2-hydroxy-4 A mixture of 14.9 g of-(2-hydroxyhexyloxy) phenyl} -1,3,5-triazine and 200 mg of TK-1 is heated in 100 ml of xylene at 120 ° C. for 4 hours. The reaction mixture can be cooled to room temperature and the solvent removed under reduced pressure to afford compound XVI, which can be purified on silica gel by column chromatography.
Example 4: Compounds of Formulas XVI, XVII, and XVIII
2,4,6-trisphenylcarbamoyl-1,3,5-triazine 0.972 g, 2,4-bis (2,4-dimethylphenyl) -6- {2-hydroxy-4- (2-hydroxy A mixture of 2.98 g of oxyhexyloxy) phenyl} -1,3,5-triazine and 100 mg of TK-1 is heated in xylene at 120 ° C. for 6 hours. The reaction mixture is analyzed for the disappearance of 2,4,6-trisphenylcarbamoyl-1,3,5-triazine. Formation of new products XVI, XVII and XVIII is confirmed by TLC (Thin Layer Chromatography).
Example 5: Isothermal Magnetic Temperature Analysis of Compounds of Formula XIII
Two samples, Compound XIII and Tinuvin 1577, are heated from 20 ° C. to 320 ° C. at 40 ° C./min in a Perkin-Elmer 7 series thermobalance and held isothermally at 320 ° C. for 60 minutes. Air is used as the purge gas (flow rate about 25 ml / min). The temperature of 320 ° C. is one of those used during the injection molding of any given planned thermoplastic, eg polycarbonate. As shown in Table I, XIII is significantly less volatile at 320 ° C. than the triazine stabilizer Tinuvin 1577 in the current field.
Cumulative weight loss percentage of stabilizer at 320 ° CMinutes at 320 ℃ Stabilizera304560gun Compound of formula (XIII)0.441.549.553.354.1 Tinuvin 15770.150.773.385.386.1 a)% loss during heating from 20 ° C to 320 ° C
Example 6: Initial Colors of Stabilized Polycarbonate Compositions
Polycarbonate platelets are prepared as follows. GE Lexan 105 beerfoot natural flake polycarbonate resin (melting temperature 310-333 ° C.) is dry blended with 0.35% stabilizer with 0.10 wt.% Mark ^R 2112 phosphite. The blended composition is melt mixed and extruded in a Haake torque rheometer equipped with a 0.75 inch 25: 1 single mixed screw extruder. Zone temperatures are 246, 265, 295 and 304 ° C. The extruded polycarbonate is withdrawn through a water bath, dried and pelletized and re-dried at 120 ° C. in a forced air oven for 4 to 48 hours. The pellets are injection molded at 305-310 ° C. using an Arburg “Allrounder” hydraulic injection molding machine to form 2 × 2.5 × 0.100 inch platelets. The mold temperature is 100 ° C. Yellow index and delta E data are obtained using a Macbeth Color Eye colorimeter with illumination C, 2 ° observer, remove speculum component, and include UV component. As shown in Table 2, XIII is Compound A (2- (2-hydroxy-4-ethoxycarbonylmethoxyphenyl-4,6-bis (2,4-dimethylphenyl) -1, which is a UV stabilizer in the current field , 3,5-triazine) and Compound B (2- (2-hydroxy-4- (2-ethylhexanoyl))-4,6-bis (2,4-dimethylphenyl) -1,3,5 -Triazine) and lower initial color.
Yellowness Index of Polycarbonate Compositions StabilizerYellowing index ^aXIII14.7 A18.0 B18.2 a) mean from two platelets
Example 7 Xenon Arc Weathering of Polycarbonate Compositions Containing XIII
Stabilized polycarbonate platelets are prepared as described in Example 5. 400 hours xenon arc weathering test according to ASTM G-26 using Test Method B with alternating exposure of platelets to contrast and water spray intermittent exposure maintaining an ambient temperature of 63 ± 3 ° C. and a relative humidity of 30 ± 5%. (Miami, Fla. Conditions). The irradiation is 0.35 W / m ² at 340 nm. The results are summarized in Table 3.
Xenon arc weathering of stabilized polycarbonate composition (400 hours) StabilizerYellowing index none5.3 XIII2.8 A3.8 B3.7
Example 8: OUV Weathering of Clear Coating Compositions Containing Carbamate Triazine Dimer XIII
Appropriate UV absorbers and / or Sanduvor 3055 (1% based on total resin solids) are pre-dissolved in the solvent mixture (5-10% solids) and added to the clear acrylic urethane formulations described in Table 4. Compounds I and II are mixed just before use. 4 "x12" frozen roll steel panels pre-coated with ED5050A E-coat and # 542AB839 white basecode from ACT Laboratories, Inc. (Hillsdale, Michigan) are used. The clear coat composition is applied to a panel previously coated using a consuming technique using WC-60 Wire-Cators ^™ (Leneta Co., Ho-Ho-Kus, NJ). The clear coat is poured at ambient temperature for 10 minutes and cured at 135 ° C. for 30 minutes.
Acrylic Urethane Clear Coat Composition Raw materialsupplyamount Component I Joncryl ^R CDX-588 Acrylic Resin (70% Solids)S.C.Johnson & Son, Inc., Racine, Wisconsin100 copies T-12 (2% solids in catalyst solution) Part 5 Solvent mixture Part 45 UV absorbers Part 2 ^aSanduvor ^R S-3055Clariant Corporation, Charlotte, N.C.Part 1 ^bComponent II Desmodur ^R N-3390 (90% solids)Miles Inc., Pittsburgh, PennsylvaniaPart 33 Solvent mixture Part 17 Catalyst solution T-12 (dibutyltin dilaurate)Air Productschapter 1 Acetic acid Part 4 PM acetate Part 45 Solvent mixture xylene chapter 1 PM acetate chapter 1 MAK chapter 1 a) 2% based on total resin solids b) 1% based on total resin solids
Accelerated weathering is performed on the coating using a QUV facility equipped with a UVB-313 fluorescent bulb. Speculum properties (gloss and clarity, or DOK) and yellowing (delta b) are measured as a function of weathering time. The effects of carbamate triazine dimer XIII alone and in combination with S-3055 on weathering ability are shown in Tables 5-7. Compositions containing XIII have a longer time to break than unstabilized controls. The effect of XIII alone on yellowing under QUV exposure is shown in Table 5. The yellowing of the stabilized composition is less than the unstabilized control and less than the composition containing Compound C, a triazine UV absorber of the prior art. The data also showed that the XIII / S-3055 blend had a synergistic effect on yellowing and break time.
QUV weathering (UVB-313 bulb), yellowing effect (delta b) of 2k acrylic urethane clear coat composition containing XIIIQUV exposure time Stabilizer24993003350449785500 none8.059.14.8.86 ^a -- 2% XIII5.705.175.845.695.74 2% C5.455.636.466.505.96 1% XIII, 1% S-30553.003.333.893.944.21 2% S-30554.575.917.828.46 ^a - a) cloth failure b) C is 2- [4-((2-hydroxy-3-dodecyloxypropyl) -oxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine and 2- [4-((2-hydroxy-3-tridecyloxypropyl) oxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl)- It is a mixture of 1,3,5-triazine.
The effects of carbamate triazine dimer XIII on gloss retention and DOI retention under QUV exposure are shown in Tables 6 and 7. Compositions containing XIII show improved gloss and DOI retention over compositions containing XIV, which is a triazine UV absorber of the control and prior art. The data also shows that the XIII / S-3055 formulation has a synergistic effect on gloss and DOI retention.
Effect of 2k acrylic urethane clear coat composition containing XIII on QUV weathering (UVB-313 bulb), gloss retention (%)QUV exposure time Stabilizer2499300335043988448449785500 none57.010.2a---- 2% XIII100.785.270.151.744.539.344.7 2% C99.080.864.346.528.127.114.3 1% XIII, 1% S-3055103.691.595.183.266.865.850.1 2% S-3055105.298.597.291.259.7a- a) cloth failure b) C is 2- [4-((2-hydroxy-3-dodecyloxypropyl) -oxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine and 2- [4-((2-hydroxy-3-tridecyloxypropyl) oxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl)- It is a mixture of 1,3,5-triazine.
Effect of 2k acrylic urethane clear coat composition containing XIII on QUV weathering (UVB-313 bulb), DOI retention (%)QUV exposure time Stabilizer2499300335043988448449785500 none44.00.90.0 ^a ---- 2% XIII98.380.274.847.654.246.645.2 2% C98.181.568.336.529.829.8a 1% XIII, 1% S-3055101.1101.2100.584.057.571.255.4 2% S-3055100.5101.596.876.823.2a- a) cloth failure b) C is 2- [4-9 (2-hydroxy-3-dodecyloxypropyl) -oxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine and 2- [4-((2-hydroxy-3-tridecyloxypropyl) oxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl)- It is a mixture of 1,3,5-triazine.
Example 9 Xenon Arc Weathering of Clear Coating Compositions Containing Carbamate Triazine Dimer XIII
Accelerated weathering is performed on the clear coat composition of Example 7 according to SAE J1960 external test protocol using an Altas Ci65 WeatherOmeter equipped with a xenon arc lamp. Speculum properties (gloss and clarity, or DOK) and yellowing (delta b) are measured as a function of weathering time. The effect of carbamate triazine dimer XIII on weathering capacity is shown in Tables 8-10. Compositions containing XIII have a longer time to break than unstabilized controls (more than 9000 hours versus 8000 hours). The effect of XIII on yellowing under xenon is shown in Table 8. The yellowing of the stabilized composition is less than that of the unstabilized control, especially at 8000 hours.
Xenon arc weathering (SAE J1960 automotive exterior), yellowing effect (delta b) of 2k acrylic urethane clear coat composition containing XIIIXenon exposure time Stabilizer30024014550060006500750080009000 none2.042.332.932.993.243.338.13 ^a - 2% XIII1.781.801.962.112.382.322.212.64 a) cloth failure
The effects of carbamate triazine dimer XIII on gloss retention and DOI retention under xenon are shown in Tables 9 and 10. The gloss and DOI loss of the composition containing XIII is much lower than the unstabilized coating which fails at 8000 hours. In this case DOI proved to be a more sensitive measure of degradation. Compositions containing XIII began to differentiate themselves within 3000 hours from the control and these data were given.
Effect of 2k acrylic urethane clear coat composition containing XIII on xenon arc weathering (SAE J1960 automotive exterior), gloss retention (%)Xenon exposure time Stabilizer550060006500750080009000 none80.968.760.839.06.8 ^a - 2% XIII90.181.185.574.741.834.8 a) cloth failure
Effect of 2k polyurethane acrylic coating composition containing XIII on xenon arc weathering (SAE J1960 automotive exterior), DOI retention (%)Xenon exposure time Stabilizer30024014550060006500750080009000 none92.583.273.758.152.437.10.8 ^a - 2% XIII106.6103.8103.698.297.996.152.235.8 a) cloth failure

权利要求:
Claims (17)
[1" claim-type="Currently amended] A compound selected from the group consisting of compounds of formula (I), (II) or (III).
Formula I

Formula II

Formula III

In the above formula,
(a) A is a polyvalent hydrocarbyl or heterocyclic ring,
(b) X is each independently selected from hydrogen, allyl, -COR ^a , -SO ₂ R ^b , -SiR ^c R ^d R ^e , -PR ^f R ^g and -POR ^f R ^g ,
(c) Y and Z are each independently formula Heterocyclic compounds containing an aryl ring of (IV) or oxygen, nitrogen, sulfur or phosphorus, wherein the heterocyclic compound is optionally a heterocarbyl group, a functional hydrocarbyl group, hydrogen, halogen, cyano or isocyano Further substituted with
(d) each R is independently selected from a hydrocarbyl group and a functional hydrocarbyl group and is different from each other,
(e) R ^a is each independently C ₁ -C ₈ alkyl, halogen-substituted C ₁ -C ₈ alkyl, C ₅ -C ₁₂ cycloalkyl, C ₂ -C ₈ alkenyl, -CH ₂ -CO-CH ₃ , C ₇ -C ₁₂ aralkyl, C ₁ -C ₁₂ alkoxy or phenyl unsubstituted or substituted by C ₁ -C ₁₂ alkyl, C ₁ -C ₄ alkoxy, halogen and / or benzyl,
(f) R ^b are each independently selected from C ₁ -C ₁₂ alkyl, C ₆ -C ₁₀ aryl or C ₇ -C ₁₈ alkylaryl,
(g) R ^c , R ^d and R ^e are each independently selected from C ₁ -C ₁₈ alkyl, cyclohexyl, phenyl or C ₁ -C ₁₈ alkoxy,
(h) R ^f and R ^g are each independently selected from C ₁ -C ₁₂ alkoxy, phenoxy, C ₁ -C ₁₂ alkyl, C ₅ -C ₁₂ cycloalkyl, benzyl, tolyl or phenyl,
(i) R ¹ , R ² and R ⁴ are each independently hydrogen, hydrocarbyl, functional hydrocarbyl, -O (hydrocarbyl), -O (functional hydrocarbyl), -SR, halogen, -SO ₃ R , -COOR, -COR, -OCOR, -NRR and cyano,
(j) R ³ are each independently selected from R, —OR, —SR, halogen, —SO ₃ R, —COOR, —COR, —NRR, and cyano,
(k) n is an integer from 2 to about 50.
[2" claim-type="Currently amended] The compound of claim 1 selected from the group consisting of compounds of formula V, VI or VII.
Formula V

Formula VI

Formula VII

In the above formula,
(a) A is a polyvalent hydrocarbyl or heterocyclic ring,
(b) each R is independently selected from a hydrocarbyl group and a functional hydrocarbyl group and is different from each other,
(c) each R ² is independently selected from hydrogen, a hydrocarbyl group having 1 to 24 carbon atoms, a hydrocarbyloxy group having 1 to 24 carbon atoms and an acyloxy group having 1 to 24 carbon atoms,
(d) each R ³ is independently selected from hydrogen, a hydrocarbyl group having 1 to 24 carbon atoms, a functional hydrocarbyl group having 1 to 24 carbon atoms, and -OR;
(e) n is 2 or 3.
[3" claim-type="Currently amended] The compound of claim 1 selected from the group consisting of compounds of formula (VIII), (IX) or (X).
Formula VIII

Formula IX

Formula X

In the above formula,
(a) A is a polyvalent hydrocarbyl or heterocyclic ring,
(b) each R is independently selected from a hydrocarbyl group and a functional hydrocarbyl group and is different from each other,
(c) each R ² is independently selected from hydrogen, a hydrocarbyl group having 1 to 24 carbon atoms, a hydrocarbyloxy group having 1 to 24 carbon atoms and an acyloxy group having 1 to 24 carbon atoms,
(d) each R ³ is independently selected from hydrogen, a hydrocarbyl group having 1 to 24 carbon atoms, a functional hydrocarbyl group having 1 to 24 carbon atoms, and -OR;
(e) n is 2 or 3.
[4" claim-type="Currently amended] The R ² is each independently hydrogen, alkyl having 1 to 8 carbon atoms, alkyloxy having 1 to 8 carbon atoms optionally containing oxygen atoms in the chain, and carbon atoms optionally containing oxygen atoms in the chain. A compound selected from the group consisting of hydroxyalkyl having 1 to 8, hydroxyalkyloxy having 1 to 8 carbon atoms optionally containing an oxygen atom in the chain, and acyloxy having 2 to 12 carbon atoms, and A is selected from the group consisting of:



[5" claim-type="Currently amended] A composition comprising at least one compound of claim 1.
[6" claim-type="Currently amended] The compound of claim 4, wherein R ² is each independently selected from hydrogen, R, —OR, and alkyl having 1 to 4 carbon atoms, and A each has a hydroxyl group in a para position relative to the attachment site to the triazine ring Of two or more trisaryl-1,3,5-triazine compounds having at least one aryl ring and further substituted by hydroxyl functional hydrocarbyl groups with polyhydric hydrocarbyl compounds such as diisocyanates, triisocyanates or polyisocyanates A compound selected from the group consisting of polyisocyanate moieties formed by the reaction.
[7" claim-type="Currently amended] 7. One or more aryls according to claim 6, wherein R ² is each independently selected from hydrogen, C ₁ -C ₄ alkoxy and methyl, and A each has a hydroxyl group in the para position with respect to the attachment site to the triazine ring By reaction of two or more trisaryl-1,3,5-triazine compounds having a ring and further substituted by hydroxyl functional hydrocarbyl groups with polyhydric hydrocarbyl compounds such as diisocyanates, triisocyanates or polyisocyanates A compound selected from the group consisting of polyisocyanate residues formed.
[8" claim-type="Currently amended] The alkyl group according to claim 2 or 3, wherein each R ³ independently represents hydrogen, alkyl having 1 to 24 carbon atoms optionally containing oxygen atoms in the chain, hydroxyalkyl having 1 to 24 carbon atoms optionally containing oxygen atoms in the chain, Compound selected from R and -OR.
[9" claim-type="Currently amended] The compound of claim 8, wherein R ³ is each independently selected from hydrogen, alkyl having 1 to 4 carbon atoms, and —OR.
[10" claim-type="Currently amended] The compound of claim 9, wherein R ³ is each independently selected from hydrogen, methyl, C ₁ -C ₄ alkoxy and tertiary butyl.
[11" claim-type="Currently amended] A method of stabilizing said material, comprising adding an effective amount of at least one compound selected from the group consisting of compounds of formula (I), (II) or (III) to a substance decomposed by actinic radiation.
Formula I

Formula II

Formula III

In the above formula,
(a) A is a polyvalent hydrocarbyl or heterocyclic ring,
(b) X is each independently selected from hydrogen, allyl, -COR ^a , -SO ₂ R ^b , -SiR ^c R ^d R ^e , -PR ^f R ^g and -POR ^f R ^g ,
(c) Y and Z are each independently formula Selected from the aryl ring of (IV),
(d) each R is independently selected from a hydrocarbyl group and a functional hydrocarbyl group and is different from each other,
(e) R ^a is each independently C ₁ -C ₈ alkyl, halogen-substituted C ₁ -C ₈ alkyl, C ₅ -C ₁₂ cycloalkyl, C ₂ -C ₈ alkenyl, -CH ₂ -CO-CH ₃ , C ₇ -C ₁₂ aralkyl, C ₁ -C ₁₂ alkoxy or phenyl unsubstituted or substituted by C ₁ -C ₁₂ alkyl, C ₁ -C ₄ alkoxy, halogen and / or benzyl,
(f) R ^b are each independently selected from C ₁ -C ₁₂ alkyl, C ₆ -C ₁₀ aryl or C ₇ -C ₁₈ alkylaryl,
(g) R ^c , R ^d and R ^e are each independently selected from C ₁ -C ₁₈ alkyl, cyclohexyl, phenyl or C ₁ -C ₁₈ alkoxy,
(h) R ^f and R ^g are each independently selected from C ₁ -C ₁₂ alkoxy, phenoxy, C ₁ -C ₁₂ alkyl, C ₅ -C ₁₂ cycloalkyl, benzyl, tolyl or phenyl,
(i) R ¹ , R ² and R ⁴ are each independently hydrogen, hydrocarbyl, functional hydrocarbyl, -O (hydrocarbyl), -O (functional hydrocarbyl), -SR, halogen, -SO ₃ R , -COOR, -COR, -OCOR, -NRR and cyano,
(j) R ³ are each independently selected from R, —OR, —SR, halogen, —SO ₃ R, —COOR, —COR, —NRR, and cyano,
(k) n is an integer from 2 to about 50.
[12" claim-type="Currently amended] The method of claim 11, wherein the compound of Formula I, II, or III is added in an amount of about 0.01 to about 20 weight percent based on the weight of the material to be stabilized.
[13" claim-type="Currently amended] The method of claim 11, wherein the compound of Formula I, II, or III is added in an amount of about 0.1 to about 10 weight percent based on the weight of the material to be stabilized.
[14" claim-type="Currently amended] The method of claim 13, wherein the material to be stabilized is a polymer.
[15" claim-type="Currently amended] The method of claim 14, wherein the polymer is a thermoplastic polymer.
[16" claim-type="Currently amended] The method of claim 15, wherein the thermoplastic polymer is polycarbonate.
[17" claim-type="Currently amended] The method of claim 15, wherein the thermoplastic polymer is polyketone.

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US5844026A|1998-12-01|N,N',N''-tris{2,4-bis Hydrocarbyloxy-2,2,6,6-tetra-methylpiperidin-4-yl)alkylamino!-s-triazin-6-yl}-3,3'-ethylenediiminodipropylamines, their isomers and bridged derivatives and polymer compositions stabilized therewith

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ES2227138T3|2005-04-01|Synergic stabilizing compositions for thermoplastic polymers in contact prolonged with water.

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JP4114177B2|2008-07-09|Synergistic stabilizer mixture

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RU2273634C2|2006-04-10|Method for synthesis of aminoxyl ethers from secondary amine oxides

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AU698297B2|1998-10-29|2-Hydroxyphenyltriazines

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US7332105B2|2008-02-19|Synergistic UV absorber combination

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US6420462B1|2002-07-16|Preparation of sterically hindered amine ethers

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ES2264681T3|2007-01-16|Mixtures of inorganic phenols and materials with antimicrobial activity.

---

ES2297438T3|2008-05-01|Highly compatible and non-migration polymer uv uv absorber.

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US6846929B2|2005-01-25|Benzotriazole/hals molecular combinations and compositions stabilized therewith

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US5648488A|1997-07-15|Compositions stabilized with red-shifted tris-aryl-s-triazines

同族专利:

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公开号 | 公开日

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EP1089986B1|2005-03-30|

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AU4695699A|2000-01-10|

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DE69924490T2|2006-01-19|

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BR9911416A|2001-03-20|

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ES2238839T3|2005-09-01|

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DE69924490D1|2005-05-04|

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US6306939B1|2001-10-23|

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CA2333286A1|1999-12-29|

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TW522149B|2003-03-01|

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EP1089986A1|2001-04-11|

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JP2002518489A|2002-06-25|

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WO1999067227A1|1999-12-29|

引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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法律状态:
1998-06-22|Priority to US9024998P

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1998-06-22|Priority to US60/090,249

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1999-06-18|Application filed by 에프. 아. 프라저, 에른스트 알테르 (에. 알테르), 한스 페터 비틀린 (하. 페. 비틀린), 피. 랍 보프, 브이. 스펜글러, 페. 아에글러, 시바 스페셜티 케미칼스 홀딩 인크.

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1999-06-18|Priority to PCT/US1999/013826

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2001-06-25|Publication of KR20010053097A

优先权:

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申请号 | 申请日 | 专利标题

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US9024998P| true| 1998-06-22|1998-06-22|

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US60/090,249|1998-06-22|

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PCT/US1999/013826|WO1999067227A1|1998-06-22|1999-06-18|Poly-trisaryl-1,3,5-triazine carbamate ultraviolet light absorbers|