• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention relates to a thickened aqueous detergent liquid comprising: (i) at least 5% by weight of a surfactant system comprising anionic surfactant, (ii) at least 0 .2% by weight of a thickener system comprising a linear copolymer formed by the addition polymerization of: (a) 0.1 to 5% by weight of a first monomer consisting of ethylenically unsaturated diacid of formula (i): hooc- cr1=cr2-cooh (i) or an unsaturated cyclic anhydride precursor of such an ethylenically unsaturated diacid, wherein the anhydride has the formula (ii), wherein r1 and r2 are individually selected from h, alkyl c1-c3, phenyl , chlorine and bromine; (b) 15 to 60% by weight of a second ethylenically unsaturated monoacid monomer consisting of (meth)acrylic acid; (c) 30 to 70% by weight of a third ethylenically unsaturated monomer consisting of C1-C8 alkyl ester of (meth)acrylic acid; (d) 1 to 25% by weight of a fourth ethylenically unsaturated monomer consisting of the surfmer of formula (iii).
    公开号:BR112015012322B1
    申请号:R112015012322-8
    申请日:2013-11-25
    公开日:2021-07-13
    发明作者:Philip Michael Ryan；Adam Peter Jarvis；Matthew Rhys Thomas；Adam John Limer
    申请人:Unilever Ip Holdings B.V.；
    IPC主号:
    专利说明:

    Field of Invention
    [0001] The present invention relates to detergent compositions comprising an alkaline polymer emulsion rheology modifier based on expandable acrylic with hydrophobic modification or HASE polymer. Background of the Invention
    [0002] A trend in detergent formulation is the reduction of surfactant concentration and the replacement of these petroleum-derived ingredients by highly efficient ingredients in weight, selected from cleaning and dirt release polymers, sequestrants and enzyme cocktails. Typically, some surfactant is retained in the composition and the linear alkylbenzene sulfonate (LAS) support surfactant is often a key part of the surfactant mixture. Polymer ethoxylated polyethylene imine can be used as one of the weight efficient ingredients. Suitable compositions are taught, for example, in WO 09153184.
    [0003] It has been found that consumers prefer the new type of concentrated liquid to be thickened in order to convey the impression of high contents when inside the bottle. On the other hand, it is desirable for the pouring viscosity to be low enough so that dosing can be carried out more easily and accurately. Thus, a shear thinning composition is desired.
    [0004] Hydrophobically modified alkaline swellable emulsion copolymers (HASE) are a type of synthetic associative thickener. This thickener typically has a backbone consisting of randomly distributed methacrylic acid (MAA) and ethyl acrylate (EA) monomers.
    [0005] A small proportion of hydrophobically modified groups, usually less than 3 mol%, are inserted into this backbone. The monomers to form these hydrophobic groups are sometimes referred to as surfmers or associative monomers. Due to its structure, the copolymer, when dissolved in an aqueous alkaline liquid, induces a series of interacting forces such as hydrophobic, hydrogen bonding, electrostatic etc. and this modifies the rheology of the liquid.
    [0006] The HASE copolymers are usually synthesized through the emulsion polymerization technique.
    [0007] US 5,015.711 (Coatex) describes a thickening terpolymer of the MAA/EA/surfmer type. US 5,015.711 makes the following description: "the first type of monomer, which is a carboxylic acid with an ethylenic unsaturation site, is a C3-C20, preferably C3-C12, compound that has an ethylenic bond and at least one group carboxylic acid or a carboxylic acid anhydride group. The carboxylated ethylenic monomer can be selected from monoacids such as acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, cinnamic acid, diacids such as itaconic acid, fumaric acid, maleic acid and citraconic acid, carboxylic acid anhydrides such as maleic anhydride and diacid semi-esters such as the C1-4 monoesters of maleic or itaconic acids. However, the ethylene carboxylic monomer is preferably selected from the group consisting of acrylic acid, methacrylic acid and itaconic acid.
    [0008] US 4,384,096 describes a copolymer having 42% MAA, 6% IA, 42% EA and 10% surfmer (where IA is itaconic acid). The surfmer used was nonylphenoxypoly(ethyleneoxy)g ethyl methacrylate. US 4,384,096 contains a general description regarding the use of itaconic acid as follows: "acrylic, methacrylic acid or its mixtures with itaconic or fumaric acids are preferred, but crotonic and aconitic acids and their semi-esters and other polycarboxylic acids such as acid maleic acid with C1-C4 alkanols, particularly if used in lower concentration in combination with acrylic or methacrylic acid". The pH reaction of the polymer containing itaconic acid has not been tested.
    [0009] The manufacture of liquid detergent compositions containing LAS, for example, compositions intended for laundry applications or hard surface cleaning typically causes the neutralization of the corresponding alkylbenzene sulfonic acid with the base. During the manufacturing process, a composition with very high pH may be temporarily formed. We found that when some HASE polymers are exposed to pH above about 10, they can no longer function efficiently. The detergent formulator will appreciate being able to have the freedom to use manufacturing processes in which the pH may temporarily exceed 10. Thus, it is an object to find the thickening polymer that can be neutralized together with the surfactant and can function from efficiently even if it is temporarily exposed to a pH of more than 10 during processing. Invention Summary
    [0010] According to the present invention, there is provided a thickened aqueous detergent liquid comprising: (i) at least 5% by weight of a surfactant system comprising anionic surfactant; (ii) at least 0.2% by weight of a thickener system comprising a linear copolymer formed by addition polymerization of: (A) 0.1 to 5% by weight of a first monomer consisting of an ethylenically unsaturated diacid of formula (I):
    or an unsaturated cyclic anhydride precursor of such an ethylenically unsaturated diacid, wherein the anhydride has the formula (II):
    wherein R1 and R2 are individually selected from H, C1-C3 alkyl, phenyl, chlorine and bromine; (B) 15 to 60% by weight of a second ethylenically unsaturated monoacid monomer consisting of (meth)acrylic acid; ( C) 30 to 70% by weight of a third ethylenically unsaturated monomer consisting of C1-C8 alkyl ester of (meth)acrylic acid; and (D) 1 to 25% by weight of an ethylenically unsaturated fourth monomer, which consists of the formula (III) surfmer:
    wherein:- each of R3 and R4 is independently selected from H, methyl, -C(=O)OH or -C(=O)OR5;- R5 is C1-C30 alkyl;- T is -CH2C( =O)O-, -C(=O)O-, -O-, -CH2O-, -NHC(=O)NH-, -C(=O)NH-, -Ar- (CE2)z- NHC (=O)O-, -Ar-(CE2)z-NHC(=O)NH- or -CH2CH2NHC(=O)-;- Ar is divalent aryl;- E is H or methyl;- z is 0 or 1 ;- k is an integer in the range 0 to 30; m is 0 or 1; with the exception that when k is 0, m will be 0, and when k is in the range 1 to 30, m will be 1;- (R'O)n is polyoxyalkylene, which is a homopolymer, a random copolymer or a block copolymer of C2-C4 oxyalkylene units, wherein R6 is C2H4, C3H6, C4H8 or mixtures thereof and n is an integer in the range of 5 to 250; Y is -R6O-, -R6-, -C(=O)-, -C(=O)NH-, =R6NHC(=O)NH- or -C(=O)NHC(=O)-; and - R7 is substituted or unsubstituted alkyl selected from the group consisting of linear C8-C40 alkyl, branched C8-C40 alkyl, C8-C40 carbocyclic alkyl, substituted C2-C40 alkyl, phenyl, aryl substituted C8-C40 alkyl and C8-C80 ester complex; wherein the R7 alkyl group optionally comprises one or more substituents selected from the group consisting of hydroxy, alkoxy and halogen.
    [0011] Preferably, surfmer D has formula (IV):
    wherein:- R8 and R9 are selected, independently of each other, from H and C1-3 alkyl;- R10 is C2-C4 and mixtures thereof, preferably C2;- m, the average number of alkoxy units R10O, is 6 to 40;- R11 is alkyl or alkylaryl, wherein the alkyl part is straight or branched; e- the total number of carbons is from 10 to 40.
    [0012] In this specification, the term (meth)acrylic acid includes acrylic acid and methacrylic acid and the term (meth)acrylate includes acrylate and methacrylate.
    [0013] The viscosity of the liquid at 20 s-1 and 25°C is preferably at least 0.3 Pa.s, more preferably at least 0.4 Pa.s.
    [0014] The compositions preferably comprise at least 1% by weight of copolymer (ii).
    [0015] Preferably, copolymer (ii) has a molecular weight of more than 250,000, more preferably above 500,000 Daltons.
    [0016] The copolymers (ii) are linear, non-crosslinked, alkaline hydrophobically modified acrylic copolymers (HASE) expandable. These polymers require alkaline conditions to expand and must be added to the composition in such a way that they are exposed to alkaline conditions at some point during the manufacture of the liquid detergent.
    [0017] To provide maximum charge density and improved expansion, it is preferred to use maleic acid as the diacid (A) in copolymer (ii). Conveniently, maleic anhydride is used as the first monomer A in the copolymerization.
    [0018] In addition, according to the present invention, a process for manufacturing a detergent composition is provided, in which the process comprises mixing the linear HASE copolymer formed from Monomers A, B, C and D as described above with an acid precursor of an anionic surfactant and then adding enough alkali to neutralize the surfactant acid and expand the copolymer. Detailed Description of the InventionFirst Monomer A
    [0019] The copolymer is formed using an A monomer that can open the ring to form a diacid unit in the polymer. Diacid moiety means that carboxylate groups are attached to adjacent carbon atoms in the carbon backbone of the copolymer. Conveniently, this unit is formed from an ethylenically unsaturated cyclic anhydride monomer of formula (II). It is preferred that monomer A is such an anhydride.
    wherein R1 and R2 are individually selected from H, C1-C3 alkyl, phenyl, chlorine and bromine. The use of a cyclic anhydride monomer with ethylenic unsaturation provides a cis diacid if the ring opens. This diacid has carboxylate groups arranged on the same side of the polymer - but on different carbon atoms.
    [0020] Preferably, R1 is hydrogen and R2 is selected from the group consisting of hydrogen, methyl, bromine and phenyl. Most preferably, R1 is hydrogen and R2 is selected from hydrogen and methyl. Even more preferably, R1 and R2 are hydrogen, so the anhydride is maleic anhydride. This is the precursor to maleic acid. It is believed that maleic acid production of carboxylate groups on adjacent carbon atoms in the polymer backbone increases the localized charge density and causes a difference in performance compared to copolymers that do not contain this diacid. Itaconic acid, which is outside the scope of the present invention, provides a polymer element in which one carbon has two carboxylate groups and the other has none. Fumaric acid is the trans isomer of maleic acid and cannot be formed from maleic anhydride monomer through hydrolysis during emulsion polymerization.
    [0021] Monomer A may vary in the range from 0.1 to 5% by weight, preferably from 0.2 to 4% by weight, more preferably from 0.3 to 1% by weight and ideally from 0.4 to 0.6% by weight of the total copolymer. Second monomer B
    [0022] The second B monomer is a monoacid vinyl monomer. Suitable monomers are acrylic acid, methacrylic acid, salts of the aforementioned acids and combinations thereof.
    [0023] In compositions, acid groups can be neutralized to form salts. Typical salt counterions for acidic groups are sodium, potassium, ammonium and triethanolammonium cations.
    [0024] Concentrations of vinyl monoacid monomer in the copolymers can range from 15 to 60% by weight, preferably from 20 to 55% by weight, more preferably from 25 to 50% by weight of the total copolymer. Third C monomer
    [0025] The third C monomer includes one or more C1-C8 esters of acrylic or methacrylic acid. Illustrative ester monomers are ethyl acrylate, methyl acrylate, ethyl methacrylate, methyl methacrylate, butyl acrylate, butyl methacrylate and mixtures thereof. Ethyl acrylate is top preferred.
    [0026] The concentration of acrylate ester monomers in the copolymer can range from 30 to 70% by weight, preferably from 25 to 60% by weight and even more preferably from 40 to 65% by weight of the total copolymer. fourth monomer D
    [0027] The fourth ethylenically unsaturated monomer consists of a formula (III) surfmer:
    wherein:- R3 and R4 are independently selected from H, methyl, -C(=O)OH or -C(=O)OR5; and R5 is C1-C30 alkyl;- T is -CH2C(=O)O-, -C(=O)O-, -O-. -CH2O-, -NHC(=O)NH-, -C(=O)NH-, -Ar-(CE2)z- NHC(=O)O-, -Ar-(CE2)z-NHC(=O )NH- or -CH2CH2NHC(=O)-;- Ar is divalent aryl;- E is H or methyl;- z is 0 or 1;- k is an integer in the range 0 to 30 and m is 0 or 1; with the exception that when k is 0, m will be 0, and when k is in the range 1 to 30, m will be 1.- (RθO)n is polyoxyalkylene, which is a homopolymer, random copolymer, or block copolymer of C2-C4 oxyalkylene units, wherein R' is C2H4, C3H6, C4H8 or mixtures thereof and n is an integer in the range of 5 to 250; Y is -R6O-, -Rθ-, -C(=O)-, -C(=O)NH-, =RθNHC(=O)NH- or -C(=O)NHC(=O)-; and- R7 is substituted or unsubstituted alkyl selected from the group consisting of linear C8-C40 alkyl, branched C8-C40 alkyl, C8-C40 carbocyclic alkyl, substituted C2-C40 alkyl, phenyl, aryl substituted C8-C40 alkyl and C8-C80 ester complex; wherein the R7 group optionally comprises one or more substituents selected from the group consisting of hydroxy, alkoxy and halogen.
    [0028] Preferably, surfmer D has formula (IV):
    wherein:- R8 and R9 are selected, independently of each other, from H and C1-3 alkyl;- R10 is C2-C4 and mixtures thereof, preferably C2;- m, the average number of alkoxy units R10O, is 6 to 40;- R11 is alkyl or alkylaryl wherein the alkyl part is straight or branched; e- the total number of carbons is from 10 to 40.
    [0029] The fourth monomer D is most preferably a surfmer of formula (V):
    wherein:- each R8 and R9 is independently selected from H and C1 to C3 alkyl; preferably, R8 is a methyl group and R9 is H; e- n varies in the range from 6 to 40 and varies in the range from 6 to 40; preferably, n ranges from 10 to 30 and ranges from 15 to 35; more preferably, n ranges from 12 to 22 and ranges from 20 to 30. It is preferred that m is greater than or equal to n.
    [0030] The concentration of surfmer D in the copolymer can range from 1 to 25% by weight, preferably from 3 to 20% by weight and more preferably from 2 to 12% by weight of the total copolymer.
    [0031] Preferably, the level of copolymer in the thickener system is from 0.2 to 3% by weight of the total composition; more preferably, from 0.4 to 2% by weight, to 0.5 to 2% by weight.
    [0032] Copolymers can be used with other thickeners to compose the thickener system. Preferred co-thickeners are other thickening polymers and thickening clays.
    [0033] Preferably, the surfactant system comprises at least 3% by weight of anionic surfactant; more preferably, the anionic surfactant comprises linear alkylbenzenesulfonate.
    [0034] Conveniently, the composition comprises one or more additional polymers that are included in the composition for purposes other than rheology modification. These additional polymers can reduce the viscosity of the compositions and this reduction can be compensated for by the inclusion of the thickening polymer. Additional preferred polymers are ethoxylated polyethyleneimine and/or polyester dirt release polymer. These two polymers were found to thin detergent compositions. Preferably, the detergent liquid further comprises at least 1% by weight of ethoxylated polyethyleneimine polymer. More preferably, it further comprises at least 0.5% by weight of polyester soil release polymers. More preferably still, the composition comprises at least 3% by weight of ethoxylated polyethyleneimine.
    [0035] Conveniently, the detergent composition comprises effective concentration of at least one enzyme selected from the group comprising pectate lyase, protease, amylase, cellulase, lipase, mannanase. More conveniently, it comprises at least 2 of that group of enzymes, even more conveniently at least 3 and, more conveniently, at least 4 of the enzymes in that group. Brief Description of Figures
    [0036] The present invention will now be further described with reference to the following non-limiting examples and the figures which are briefly described as follows:
    [0037] Figure 1 is a graph showing changes in viscosity with pH for Carbopol 980 (prior art ASE copolymer);
    [0038] Figure 2 is a graph showing changes in viscosity with pH for Acusol 820 (prior art HASE copolymer);
    [0039] Figure 3 is a graph showing viscosity changes with pH for a linear HASE copolymer produced using a maleic anhydride monomer; and
    [0040] Figure 4 is a graph showing viscosity changes with pH for an additional linear HASE copolymer produced using a maleic anhydride monomer. EXAMPLES
    [0041] Surfmer synthesis:
    n = 12m = 23
    Brij® 35P (150 g) from Sigma Aldrich was dissolved in 500 ml of anhydrous dichloromethane under nitrogen atmosphere and cooled in an ice bath to 5°C. Triethylamine (18.6 g) was added via syringe before the addition of methacryloyl chloride (20.9 g) dropwise over a period of 30 minutes. After the addition was complete, the solution was allowed to warm to room temperature and the reaction was stirred for 4 weeks. The solution was then filtered to remove the resulting precipitate and washed once with saturated sodium hydrogen carbonate solution (200 ml) and once with saturated brine (200 ml). The solution was then passed through a column containing basic alumina before drying the product with anhydrous magnesium sulfate, filtered and the solvent removed in vacuo. In subsequent examples, the product is called surfmer A. HASE Copolymer Synthesis
    [0043] A domed-bottom flask was charged with ethyl acrylate (EA) (66.8 g), methacrylic acid (MAA) (37.7 g), maleic anhydride (MA) (0.515 g) and surfmer A (10 .0 g). The mixture was sealed and purged with nitrogen for 60 minutes before adding sodium dodecyl sulfonate (1.03 g) and deoxygenated water (26.5 g) and stirring, forming a pre-emulsion. A multi-necked, convex-bottomed flask was equipped with a nitrogen sparger and overhead stirrer. Deoxygenated water (181 g) and sodium dodecyl sulfonate (0.298 g) were added, stirred at 250 rpm and heated to 90°C. Ammonium persulfate (0.073 g) in water (1 ml) was added via syringe. The pre-emulsion was supplied to the surfactant solution by means of a peristaltic pump for 150 minutes. After the addition was complete, ammonium persulfate (0.033 g) in water (1 ml) was added and the reaction was stirred for an additional 240 minutes. The resulting product is hereinafter referred to as Copolymer 1. Additional Copolymers 2 and 3 were synthesized using appropriate adaptations of this process. All Copolymers are detailed in Table 1.
    pH test
    [0044] Figures 1 and 2 demonstrate how, for several known associative thickener polymers, viscosity drops again under high pH.
    [0045] Figure 1 is Carbopol 980, a hydrophobically modified crosslinked MMA (containing surfmer) copolymer. The Copolymer was added to water by 2.9% by weight and then neutralized with NaOH. Allow time for expansion to occur each time before testing the viscosity of a sample of the thickened liquid using an Anton Paar viscometer. Additional acid aggregation reduces pH as the diluting effect initiated at high pH does not increase viscosity.
    [0046] Figure 2 shows another very similar viscosity drop for a hydrophobically modified linear acrylate copolymer marketed by Dow as Acusol 820. The copolymer was added to water at 0.8% by weight, neutralized with NaOH and tested in the same way than Carbopol.
    [0047] Figure 3 shows the same test performed with linear copolymer 1 used at 2.8% by weight and neutralized with NaOH. Figure 4 shows the same test performed with 1% by weight of copolymer 3. Viscosity reduction when exceeding the pH limit is not observed for these copolymers made with maleic anhydride. Liquid compositions using copolymers
    [0048] The alkalinity resistant copolymers provide flexibility to the detergent formulator to use manufacturing processes that can expose the copolymers to high pH without fear of loss of rheology as a consequence. Thus, they are especially useful for compositions containing anionic surfactants that are normally neutralized during the manufacture of the liquid detergent; thus allowing the heat emitted to be used to aid the incorporation of other ingredients into the compositions, especially non-ionic surfactants.
    [0049] To test the resilience of the polymer to be added before neutralizing the acidic surfactant, the aqueous detergent liquid provided in Table 2 was prepared. In this example, the polymer is mixed with some alkali and the acid is added to this mixture before the addition of the remainder of the alkali. The order of addition of key ingredients is displayed and the remaining ingredients are added once the key ingredients have been mixed and neutralized.

    [0050] After 8 weeks of storage, the thickened detergent liquid produced in this way is still homogeneous and has the viscosity profile at room temperature shown below in Table 3.


    [0051] Some additional suitable liquid detergent formulations are provided in Table 4 below. Table 4. Examples of detergent compositions
    LAS is linear alkylbenzenesulfonic acid.SLES is lauryl ether sulfate 3EO.EPEI is ethoxylated polyethyleneimine PEI(600) 20EO.MPG is monopropylene glycol.
    权利要求:
    Claims (11)
    [0001]
    1. A thickened aqueous detergent liquid, characterized in that it comprises:- i) at least 5% by weight of a surfactant system comprising an anionic surfactant;- ii) at least 0.2% by weight of a thickener system comprising a linear copolymer formed by addition polymerization of: (A) 0.1 to 5% by weight of a first monomer consisting of ethylenically unsaturated diacid of formula (I):
    [0002]
    2. Composition according to claim 1, characterized in that the fourth monomer D is a surfmer of formula (IV):
    [0003]
    3. Composition, according to any one of the preceding claims, characterized in that the fourth monomer D is a surfmer of the formula (V):
    [0004]
    4. Composition according to any one of the preceding claims, characterized in that the viscosity of the liquid at 20 s’1 and 25°C is at least 0.3 Pa s, preferably at least 0.4 Pa s.
    [0005]
    Composition according to any one of the preceding claims, characterized in that it comprises at least 0.4% by weight of the copolymer (ii).
    [0006]
    6. Composition according to any one of the preceding claims, characterized in that the anionic surfactant is selected from the group consisting of alkylbenzenesulfonate and alkyl sulfate.
    [0007]
    7. Composition according to any one of the preceding claims, characterized in that the anionic surfactant comprises sodium salt of linear alkylbenzenesulfonate.
    [0008]
    8. Composition according to any one of the preceding claims, characterized in that the composition additionally includes a viscosity reducing polymer selected from ethoxylated polyethylene imine and polyester dirt release polymer.
    [0009]
    9. Composition, according to any one of the preceding claims, characterized in that the copolymer (ii) has a molecular weight of at least 500 000 Daltons.
    [0010]
    10. Composition according to any one of the preceding claims, characterized in that the first monomer (A) in copolymer (ii) is maleic anhydride.
    [0011]
    11. Detergent composition manufacturing process, characterized in that the process comprises mixing a linear HASE copolymer formed from Monomers A, B, C and D as defined in claim 1 with an acidic anionic surfactant precursor and addition in followed by enough alkali to neutralize the surface-active acid and expand the copolymer.
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US4384096A|1979-08-27|1983-05-17|The Dow Chemical Company|Liquid emulsion polymers useful as pH responsive thickeners for aqueous systems|
    US4529773A|1982-03-17|1985-07-16|David Witiak|Alkali-soluble emulsion polymers in acidic surfactant compositions|
    US4892916A|1984-08-15|1990-01-09|Allied Colloids Limited|Polymeric thickeners and their production|
    GB8613408D0|1986-06-03|1986-07-09|Crown Decorative Prod Ltd|Thickeners|
    FR2633930B1|1988-07-07|1991-04-19|Coatex Sa|THICKENING AGENT FOR MODIFYING THE RHEOLOGICAL CHARACTERISTICS OF AQUEOUS LOADED AND / OR PIGMENTED, WHITE OR COLORED COMPOSITIONS|
    US5057241A|1988-11-16|1991-10-15|S. C. Johnson & Son, Inc.|Dual polymer self-sealing detergent compositions and methods|
    MX200986B|1997-07-29|2001-03-07|Rohm & Haas|Solubilized hydrophobically-modified alkali-soluble emulsion polymers|
    KR20040012487A|2002-07-31|2004-02-11|롬 앤드 하스 캄파니|Triggered response compositions|
    ES2308331T5|2005-05-11|2012-03-05|Cognis Ip Management Gmbh|INFLATABLE HYDROPHOBE EMULSIONS IN THE ALCALINE MEDIUM .|
    WO2008017620A1|2006-08-10|2008-02-14|Basf Se|Cleaning formulation for a dish washer|
    EP2300586B1|2008-06-16|2015-04-08|Unilever PLC|Improvements relating to fabric cleaning|
    GB201116660D0|2011-09-28|2011-11-09|Unilever Plc|Thickening vinyl copolymers|CN104968771B|2012-11-29|2019-03-01|荷兰联合利华有限公司|The aqueous detergent composition of polymer architecture|
    US10316273B2|2015-01-29|2019-06-11|Conopco, Inc.|Thickened aqueous detergent liquid|
    JP2019500455A|2015-12-14|2019-01-10|ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ|Concentrated liquid detergent containing anti-redeposition polymer|
    EP3440172B1|2016-04-08|2019-08-21|Unilever PLC|Laundry detergent composition|
    CN110023469A|2016-12-15|2019-07-16|荷兰联合利华有限公司|Laundry detergent composition|
    EP3622047B1|2017-05-10|2020-12-16|Unilever PLC, a company registered in England and Wales under company no. 41424 of|Liquid laundry detergent composition|
    CN110621769A|2017-05-10|2019-12-27|荷兰联合利华有限公司|Laundry detergent compositions|
    WO2018210524A1|2017-05-15|2018-11-22|Unilever Plc|Composition|
    WO2018210522A1|2017-05-15|2018-11-22|Unilever Plc|Composition|
    WO2018210523A1|2017-05-15|2018-11-22|Unilever Plc|Composition|
    EP3625320A1|2017-05-15|2020-03-25|Unilever PLC|Composition|
    EP3833730B1|2018-08-10|2022-02-16|Unilever Global Ip Limited|Detergent|
    WO2021247339A1|2020-06-02|2021-12-09|Dow Global Technologies Llc|Aqueous liquid laundry formulation|
    WO2021247340A1|2020-06-02|2021-12-09|Dow Global Technologies Llc|Method of making and using an aqueous cotton renewing composition|
    法律状态:
    2018-01-23| B11A| Dismissal acc. art.33 of ipl - examination not requested within 36 months of filing|
    2018-03-20| B11N| Dismissal: publication cancelled|Free format text: ANULADA A PUBLICACAO CODIGO 11.1 NA RPI NO 2455 DE 23/01/2018 POR TER SIDO INDEVIDA. |
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-10-01| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-02-09| B25A| Requested transfer of rights approved|Owner name: UNILEVER IP HOLDINGS B.V. (PB) |
    2021-06-01| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-07-13| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 25/11/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    CNPCT/CN2012/085567|2012-11-29|
    CN2012085567|2012-11-29|
    PCT/EP2013/074596|WO2014082955A1|2012-11-29|2013-11-25|Thickened aqueous detergent liquid|
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