WO2016005338A1 - Storage-stable compositions comprising soil release polymers - Google Patents
Storage-stable compositions comprising soil release polymers Download PDFInfo
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- WO2016005338A1 WO2016005338A1 PCT/EP2015/065389 EP2015065389W WO2016005338A1 WO 2016005338 A1 WO2016005338 A1 WO 2016005338A1 EP 2015065389 W EP2015065389 W EP 2015065389W WO 2016005338 A1 WO2016005338 A1 WO 2016005338A1
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- molar average
- polyesters
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- weight
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- 239000000203 mixture Substances 0.000 title claims abstract description 104
- 229920000642 polymer Polymers 0.000 title claims description 8
- 239000002689 soil Substances 0.000 title description 12
- 229920000728 polyester Polymers 0.000 claims abstract description 59
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 16
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000001298 alcohols Chemical class 0.000 claims abstract description 10
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims abstract description 8
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229940058015 1,3-butylene glycol Drugs 0.000 claims abstract description 4
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 235000019437 butane-1,3-diol Nutrition 0.000 claims abstract description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000654 additive Substances 0.000 claims description 16
- 229960004063 propylene glycol Drugs 0.000 claims description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 239000008139 complexing agent Substances 0.000 claims description 4
- 239000003352 sequestering agent Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003599 detergent Substances 0.000 abstract description 11
- 239000004744 fabric Substances 0.000 abstract description 11
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 abstract 1
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- -1 polyol compounds Chemical class 0.000 description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 229920002125 Sokalan® Polymers 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 239000007844 bleaching agent Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000005809 transesterification reaction Methods 0.000 description 4
- 239000013256 coordination polymer Substances 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000001632 sodium acetate Substances 0.000 description 3
- 235000017281 sodium acetate Nutrition 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 239000013011 aqueous formulation Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 229920002601 oligoester Polymers 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- FKKAGFLIPSSCHT-UHFFFAOYSA-N 1-dodecoxydodecane;sulfuric acid Chemical compound OS(O)(=O)=O.CCCCCCCCCCCCOCCCCCCCCCCCC FKKAGFLIPSSCHT-UHFFFAOYSA-N 0.000 description 1
- PQHYOGIRXOKOEJ-UHFFFAOYSA-N 2-(1,2-dicarboxyethylamino)butanedioic acid Chemical class OC(=O)CC(C(O)=O)NC(C(O)=O)CC(O)=O PQHYOGIRXOKOEJ-UHFFFAOYSA-N 0.000 description 1
- HOSGXJWQVBHGLT-UHFFFAOYSA-N 6-hydroxy-3,4-dihydro-1h-quinolin-2-one Chemical group N1C(=O)CCC2=CC(O)=CC=C21 HOSGXJWQVBHGLT-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000012753 anti-shrinkage agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 description 1
- 229940043264 dodecyl sulfate Drugs 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical class OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-K pentetate(3-) Chemical compound OC(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O QPCDCPDFJACHGM-UHFFFAOYSA-K 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
- C11D3/2041—Dihydric alcohols
- C11D3/2044—Dihydric alcohols linear
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2068—Ethers
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3715—Polyesters or polycarbonates
-
- C11D2111/12—
Definitions
- compositions comprising soil release polymers
- the invention relates to compositions comprising polyesters.
- the polyesters are e.g. useful as soil release agents and the inventive compositions may be used in laundry detergent and fabric care products.
- soil release agent is applied to materials that modify the fabric surface minimizing the subsequent soiling and making the cleaning of the fabric easier on further washing cycles.
- Laundry detergent compositions containing polyesters have been widely disclosed in the art.
- EP 0 964 015 A1 discloses soil release oligoesters that may be used as soil release polymers in detergents and that are prepared using polyols comprising 3 to 6 hydroxyl groups.
- EP 1 661 933 A1 is directed to at room temperature flowable, amphiphilic and nonionic oligoesters prepared by reacting dicarboxylic acid compounds, polyol compounds and water-soluble alkylene oxide adducts and their use as additive in washing and cleaning compositions.
- many of the polyesters described in the prior art are in need of improved stability in an alkaline environment. Especially in alkaline heavy duty washing liquids polyesters often show turbidity upon incorporation and by alkaline hydrolysis thereby also losing soil release power.
- polyesters described in WO 2013/019658 A1 fulfill these requirements and possess an advantageous, increased stability against hydrolysis and an excellent soil-release-effect, but they are solids that melt at approximately 50 °C and therefore, their handling is not easy in practice due to the necessity of hot storage and handling.
- compositions of these polyesters that can be handled easily in practice and that are liquid and storage-stable.
- compositions comprising
- R and R 2 independently of one another are X-(OC2H 4 )n-(OC 3 H 6 )m wherein X is
- Ci- 4 alkyl and preferably methyl, the -(OC 2 H 4 ) groups and the -(OC 3 H 6 ) groups are arranged blockwise and the block consisting of the -(OC 3 H 6 ) groups is bound to a COO group or are HO-(C 3 H 6 ), and preferably are independently of one another X-(OC2H 4 )n-(OC 3 H 6 )m, n is based on a molar average a number of from 12 to 120 and
- m is based on a molar average a number of from 1 to 10 and preferably of from 1 to 7, and
- a is based on a molar average a number of from 4 to 9 and B) of from 10 to 30 % by weight of one or more alcohols selected from the group consisting of ethylene glycol, 1 ,2-propylene glycol, 1 ,3-propylene glycol, 1 ,2-butylene glycol, 1 ,3-butylene glycol, 1 ,4-butylene glycol and butyl glycol and C) of from 24 to 42 % by weight of water, the amounts in each case being based on the total weight of the composition.
- compositions comprising
- R and R 2 independently of one another are X-(OC2H 4 )n-(OC 3 H 6 )m wherein X is
- the -(OC 2 H 4 ) groups and the -(OC 3 H 6 ) groups are arranged blockwise and the block consisting of the -(OC 3 H 6 ) groups is bound to a COO group or are HO-(C 3 H 6 ), and preferably are independently of one another X-(OC2H 4 )n-(OC 3 H 6 )m, n is based on a molar average a number of from 12 to 120 and
- m is based on a molar average a number of from 1 to 10 and preferably of from 1 to 7, and
- a is based on a molar average a number of from 4 to 9 and
- Butyl glycol has the following structure: Ch ⁇ ChysOCHsCHsOH.
- Aqueous or aqueous-alcoholic solutions of the polyesters often possess a relatively good stability when stored at 5 °C.
- non-inventive compositions of the polyesters at first show a turbidity during storage that later results in massive precipitations. These precipitations cannot be dissolved again at 80 °C, meaning that the respective products may not be regarded as being storage-stable, and their properties are changed irreversibly by storage at elevated temperature.
- the inventive compositions furthermore possess the advantage that they are sufficiently storage-stable, also at elevated temperatures.
- inventive compositions preferably are solutions at 25 °C.
- group "X" is Ci -4 alkyl and preferably is methyl.
- the one or more polyesters of component A) of the inventive compositions are according to the following formula (I)
- R and R 2 independently of one another are H3C-(OC2H 4 )n-(OC 3 H6)m wherein the -(OC 2 H 4 ) groups and the -(OC 3 H 6 ) groups are arranged blockwise and the block consisting of the -(OC 3 H 6 ) groups is bound to a COO group or are HO-(C 3 H 6 ), and preferably are independently of one another H 3 C-(OC 2 H 4 )n-(OC 3 H 6 )m,
- n is based on a molar average a number of from 40 to 50
- m is based on a molar average a number of from 1 to 7, and
- a is based on a molar average a number of from 4 to 9.
- variable "a" based on a molar average preferably is a number of from 5 to 8 and more preferably is a number of from 6 to 7.
- variable "m" based on a molar average preferably is a number of from 2 to 5.
- variable "n" based on a molar average preferably is a number of from 43 to 47, more preferably is a number of from 44 to 46 and even more preferably is 45.
- the one or more polyesters of component A) of the inventive compositions are according to the following formula (I)
- R and R 2 independently of one another are H3C-(OC2H 4 )n-(OC 3 H6)m wherein the -(OC 2 H 4 ) groups and the -(OC 3 H 6 ) groups are arranged blockwise and the block consisting of the -(OC 3 H 6 ) groups is bound to a COO group,
- n is based on a molar average a number of from 44 to 46
- n based on a molar average
- a is based on a molar average a number of from 5 to 8.
- R and R 2 independently of one another are H3C-(OC2H 4 )n-(OC 3 H6)m wherein the -(OC 2 H 4 ) groups and the -(OC 3 H 6 ) groups are arranged blockwise and the block consisting of the -(OC 3 H 6 ) groups is bound to a COO group,
- n based on a molar average
- the one or more polyesters of component A) of the inventive compositions are according to the following formula (I)
- R and R 2 independently of one another are H3C-(OC2H 4 )n-(OC 3 H6)m wherein the -(OC 2 H 4 ) groups and the -(OC 3 H 6 ) groups are arranged blockwise and the block consisting of the -(OC 3 H 6 ) groups is bound to a COO group,
- H 3 C-(OC 2 H 4 ) n -(OC 3 H 6 )m are of the formula -O-CH 2 -CH 2 -.
- the groups -0-C 3 H 6 - in the structural units indexed with "a”, in the structural units "X-(OC 2 H 4 )n-(OC 3 H6)m” or "H 3 C-(OC2H 4 )n-(OC 3 H 6 )m” and in the structural units HO-(C 3 H 6 ) are of the formula -0-CH(CH 3 )-CH 2 - or -0-CH 2 -CH(CH 3 )-, i.e. are of the formula
- the polyesters of component A) of the inventive compositions may advantageously be prepared by a process which comprises heating dimethyl terephthalate (DMT), 1 ,2-propylene glycol (PG), and X-(OC 2 H 4 )n-(OC 3 H6)m-OH, wherein X is Ci -4 alkyl and preferably methyl, the -(OC 2 H 4 ) groups and
- polyesters of component A) of the inventive compositions are e.g. described in WO 2013/019658 A1 .
- the one or more alcohols of component B) of the inventive compositions are e.g. described in WO 2013/019658 A1 .
- the one or more alcohols of component B) of the inventive compositions are e.g. described in WO 2013/019658 A1 .
- the inventive compositions preferably comprise one or more additives (component D)), and in this case the amount of water of component C) in the inventive compositions preferably is of from 24 to 39.95 % by weight, the amounts in each case being based on the total weight of the inventive compositions.
- the one or more additives of component D) of the inventive compositions are preferably selected from the group consisting of sequestering agents, complexing agents, polymers different from the one or more polyesters of component A) and surfactants.
- Suitable sequestering agents e.g. are polyacrylic acid or acrylic acid / maleic acid copolymers (e.g. Sokalan ® CP 12S, BASF).
- Suitable complexing agents e.g. are EDTA (ethylene diamine tetraactetate), diethylene triamine pentaacetate, nitrilotriacetic acid salts or iminodisuccinic acid salts.
- the viscosity of the inventive compositions is of from 500 to 2 000 m Pa- s.
- the polyester synthesis is carried out by the reaction of dimethyl terephthalate (DMT), 1 ,2-propylene glycol (PG), and methyl polyalkyleneglycol using sodium acetate (NaOAc) and tetraisopropyl orthotitanate (IPT) as the catalyst system.
- the synthesis is a two-step procedure. The first step is a transesterification and the second step is a polycondensation. Transesterification
- the mixture is heated up to 170 °C for 1 h and then up to 210 °C for a further 1 h sparged by a nitrogen stream.
- the mixture is heated up to 230 °C. At 230 °C the pressure is reduced to 1 mbar over 160 min. Once the polycondenzation reaction has started, 1 ,2-propylene glycol is distilled out of the system. The mixture is stirred for 4 h at 230 °C and a pressure of 1 mbar. The reaction mixture is cooled down to 140 - 150 °C. Vacuum is released with nitrogen and the molten polymer is transferred into a glass bottle.
- n is based on a molar average 45
- m is based on a molar average 5
- R and R 2 are H 3 C-(OC 2 H 4 )n-(OC 3 H 6 )m wherein the -(OC 2 H 4 ) groups and
- a is based on a molar average a number of from 6 to 7. Stability tests
- Sokalan ® CP 12S (acrylic acid / maleic acid copolymer, BASF) has been used as the additive. From the table it can be seen that solutions of the soil release polyesters in water (Examples 1 - 4) become turbid at 45°C already after two weeks of storage.
- compositions comprising 1 ,2-propylene glycol or butyl glycol are still clear after 4 weeks of storage at 45°C.
Abstract
Compositions are described comprising A) of from 45 to 55 % by weight of one or more polyesters according to the following formula (I) wherein R1 and R2 independently of one another are X-(OC2H4)n-(OC3H6)m wherein X is C1-4 alkyl, the -(OC2H4) groups and the -(OC3H6) groups are arranged blockwise and the block consisting of the -(OC3H6) groups is bound to a COO group or are HO-(C3H6), n is based on a molar average a number of from 12 to 120, m is based on a molar average a number of from 1 to 10, and a is based on a molar average a number of from 4 to 9 and B) of from 10 to 30 % by weight of one or more alcohols selected from the group consisting of ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol and butyl glycol and C) of from 24 to 42 % by weight of water, the amounts in each case being based on the total weight of the composition. The compositions may advantageously be used in laundry detergent and fabric care products.
Description
Storage-stable compositions comprising soil release polymers
The invention relates to compositions comprising polyesters. The polyesters are e.g. useful as soil release agents and the inventive compositions may be used in laundry detergent and fabric care products.
The term "soil release agent" is applied to materials that modify the fabric surface minimizing the subsequent soiling and making the cleaning of the fabric easier on further washing cycles.
Laundry detergent compositions containing polyesters have been widely disclosed in the art.
DE 10 2007 013 217 A1 and WO 2007/079850 A1 disclose anionic polyesters that may be used as soil release components in washing and cleaning compositions.
DE 10 2007 005 532 A1 describes aqueous formulations of soil release oligo- and polyesters with a low viscosity. The aqueous formulations may e.g. be used in washing and cleaning compositions.
EP 0 964 015 A1 discloses soil release oligoesters that may be used as soil release polymers in detergents and that are prepared using polyols comprising 3 to 6 hydroxyl groups. EP 1 661 933 A1 is directed to at room temperature flowable, amphiphilic and nonionic oligoesters prepared by reacting dicarboxylic acid compounds, polyol compounds and water-soluble alkylene oxide adducts and their use as additive in washing and cleaning compositions. However, many of the polyesters described in the prior art are in need of improved stability in an alkaline environment. Especially in alkaline heavy duty washing liquids polyesters often show turbidity upon incorporation and by alkaline hydrolysis thereby also losing soil release power.
The polyesters described in WO 2013/019658 A1 fulfill these requirements and possess an advantageous, increased stability against hydrolysis and an excellent soil-release-effect, but they are solids that melt at approximately 50 °C and therefore, their handling is not easy in practice due to the necessity of hot storage and handling.
Therefore, it was the object of the present invention to provide compositions of these polyesters that can be handled easily in practice and that are liquid and storage-stable.
Surprisingly this object is solved by compositions comprising
A) of from 45 to 55 % by weight of one or more polyesters according to the following formula (I)
O O O O II
R— O -C -C3H6 -O - c- C -O -R (I)
wherein
R and R2 independently of one another are X-(OC2H4)n-(OC3H6)m wherein X is
Ci-4 alkyl and preferably methyl, the -(OC2H4) groups and the -(OC3H6) groups are arranged blockwise and the block consisting of the -(OC3H6) groups is bound to a COO group or are HO-(C3H6), and preferably are independently of one another X-(OC2H4)n-(OC3H6)m, n is based on a molar average a number of from 12 to 120 and
preferably of from 40 to 50,
m is based on a molar average a number of from 1 to 10 and preferably of from 1 to 7, and
a is based on a molar average a number of from 4 to 9 and
B) of from 10 to 30 % by weight of one or more alcohols selected from the group consisting of ethylene glycol, 1 ,2-propylene glycol, 1 ,3-propylene glycol, 1 ,2-butylene glycol, 1 ,3-butylene glycol, 1 ,4-butylene glycol and butyl glycol and C) of from 24 to 42 % by weight of water, the amounts in each case being based on the total weight of the composition.
Therefore, a subject matter of the present invention are compositions comprising
A) of from 45 to 55 % by weight of one or more polyesters according to the following formula (I)
O O O O
R1— o-c™ -C-O-C3H6 -O-C— < y— C-O-R (I)
wherein
R and R2 independently of one another are X-(OC2H4)n-(OC3H6)m wherein X is
C-i -4 alkyl and preferably methyl, the -(OC2H4) groups and the -(OC3H6) groups are arranged blockwise and the block consisting of the -(OC3H6) groups is bound to a COO group or are HO-(C3H6), and preferably are independently of one another X-(OC2H4)n-(OC3H6)m, n is based on a molar average a number of from 12 to 120 and
preferably of from 40 to 50,
m is based on a molar average a number of from 1 to 10 and preferably of from 1 to 7, and
a is based on a molar average a number of from 4 to 9 and
B) of from 10 to 30 % by weight of one or more alcohols selected from the group consisting of ethylene glycol, 1 ,2-propylene glycol, 1 ,3-propylene glycol, 1 ,2-butylene glycol, 1 ,3-butylene glycol, 1 ,4-butylene glycol and butyl glycol and
C) of from 24 to 42 % by weight of water, the amounts in each case being based on the total weight of the composition.
Butyl glycol has the following structure: Ch^ChysOCHsCHsOH.
It is an advantage of the inventive compositions that they are based on water and on solvents that are not easily flammable.
Aqueous or aqueous-alcoholic solutions of the polyesters often possess a relatively good stability when stored at 5 °C. However, when stored at 25 °C for a longer period of time and even faster at elevated temperatures of from 30 to 50 °C, that may occur during transport or storage, non-inventive compositions of the polyesters at first show a turbidity during storage that later results in massive precipitations. These precipitations cannot be dissolved again at 80 °C, meaning that the respective products may not be regarded as being storage-stable, and their properties are changed irreversibly by storage at elevated temperature. The inventive compositions furthermore possess the advantage that they are sufficiently storage-stable, also at elevated temperatures.
The inventive compositions preferably are solutions at 25 °C. In the polyesters of component A) of the inventive compositions according to formula (I) group "X" is Ci-4 alkyl and preferably is methyl.
In a preferred embodiment of the invention the one or more polyesters of component A) of the inventive compositions are according to the following formula (I)
wherein
R and R2 independently of one another are H3C-(OC2H4)n-(OC3H6)m wherein the -(OC2H4) groups and the -(OC3H6) groups are arranged blockwise and the block consisting of the -(OC3H6) groups is bound to a COO group or are HO-(C3H6), and preferably are independently of one another H3C-(OC2H4)n-(OC3H6)m,
n is based on a molar average a number of from 40 to 50,
m is based on a molar average a number of from 1 to 7, and
a is based on a molar average a number of from 4 to 9.
In the one or more polyesters of component A) of the inventive compositions according to formula (I) variable "a" based on a molar average preferably is a number of from 5 to 8 and more preferably is a number of from 6 to 7.
In the one or more polyesters of component A) of the inventive compositions according to formula (I) variable "m" based on a molar average preferably is a number of from 2 to 5.
In the one or more polyesters of component A) of the inventive compositions according to formula (I) variable "n" based on a molar average preferably is a number of from 43 to 47, more preferably is a number of from 44 to 46 and even more preferably is 45.
In one particularly preferred embodiment of the invention the one or more polyesters of component A) of the inventive compositions are according to the following formula (I)
wherein
R and R2 independently of one another are H3C-(OC2H4)n-(OC3H6)m wherein the -(OC2H4) groups and the -(OC3H6) groups are arranged blockwise and the block consisting of the -(OC3H6) groups is bound to a COO group,
n is based on a molar average a number of from 44 to 46,
m is based on a molar average 2, and
a is based on a molar average a number of from 5 to 8.
Among these one or more polyesters the polyesters according to formula (I)
wherein
R and R2 independently of one another are H3C-(OC2H4)n-(OC3H6)m wherein the -(OC2H4) groups and the -(OC3H6) groups are arranged blockwise and the block consisting of the -(OC3H6) groups is bound to a COO group,
n is based on a molar average 45,
m is based on a molar average 2, and
a is based on a molar average a number of from 6 to 7
are especially preferred.
In another particularly preferred embodiment of the invention the one or more polyesters of component A) of the inventive compositions are according to the following formula (I)
wherein
R and R2 independently of one another are H3C-(OC2H4)n-(OC3H6)m wherein the -(OC2H4) groups and the -(OC3H6) groups are arranged blockwise and the block consisting of the -(OC3H6) groups is bound to a COO group,
n is based on a molar average a number of from 44 to 46,
m is based on a molar average 5, and
a is based on a molar average a number of from 5 to 8.
Among these one or more polyesters the polyesters according to formula (I)
wherein
R and R2 independently of one another are H3C-(OC2H4)n-(OC3H6)m wherein the -(OC2H4) groups and the -(OC3H6) groups are arranged blockwise and the block consisting of the -(OC3H6) groups is bound to a COO group,
n is based on a molar average 45,
m is based on a molar average 5, and
a is based on a molar average a number of from 6 to 7
are especially preferred.
The groups -O-C2H4- in the structural units "X-(OC2H4)n-(OC3H6)m" or
"H3C-(OC2H4)n-(OC3H6)m" are of the formula -O-CH2-CH2-.
The groups -0-C3H6- in the structural units indexed with "a", in the structural units "X-(OC2H4)n-(OC3H6)m" or "H3C-(OC2H4)n-(OC3H6)m" and in the structural units HO-(C3H6) are of the formula -0-CH(CH3)-CH2- or -0-CH2-CH(CH3)-, i.e. are of the formula
CH3 CH3 — O— CH CH2 or — O— CH2 CH
The inventive compositions may advantageously be used in laundry detergent and fabric care products and in particular in liquid laundry detergent and fabric care products. Besides the inventive compositions these laundry detergent and fabric care products may comprise one or more optional ingredients, e.g. they may comprise conventional ingredients commonly used in laundry detergent and fabric care products. Examples of optional ingredients include, but are not limited to builders, surfactants, bleaching agents, bleach active compounds, bleach activators, bleach catalysts, photobleaches, dye transfer inhibitors, color protection agents, anti-redeposition agents, dispersing agents, fabric softening and antistatic agents, fluorescent whitening agents, enzymes, enzyme stabilizing agents, foam regulators, defoamers, malodour reducers, preservatives, disinfecting agents, hydrotopes, fibre lubricants, anti-shrinkage agents, buffers, fragrances, processing aids, colorants, dyes, pigments, anti-corrosion agents, fillers, stabilizers and other conventional ingredients for laundry detergent and fabric care products.
The inventive compositions have an advantageous stability in alkaline
environment, possess a beneficial solubility and advantageously are clearly soluble in alkaline compositions such as heavy duty washing liquids and also possess advantageous soil release properties. In laundry detergent or fabric care products they result in a beneficial washing performance, in particular also after storage. Furthermore, they are storage stable at elevated temperature, i.e. they are clear solutions at elevated temperature also after a prolonged time of storage.
The polyesters of component A) of the inventive compositions may advantageously be prepared by a process which comprises heating dimethyl terephthalate (DMT), 1 ,2-propylene glycol (PG), and X-(OC2H4)n-(OC3H6)m-OH, wherein X is Ci-4 alkyl and preferably methyl, the -(OC2H4) groups and
the -(OC3H6) groups are arranged blockwise and the block consisting of the -(OC3H6) groups is bound to the hydroxyl group -OH and n and m are as defined for the polyesters of component A) of the inventive compositions, with the addition of a catalyst, to temperatures of from 1 60 to 220 °C, firstly at atmospheric pressure, and then continuing the reaction under reduced pressure at
temperatures of from 160 to 240 °C.
Reduced pressure preferably means a pressure of from 0.1 to 900 mbar and more preferably a pressure of from 0.5 to 500 mbar.
Preferably, the process for the preparation of the polyesters of component A) of the inventive compositions is characterized in that
a) dimethyl therephthalate, 1 ,2-propylene glycol, X-(OC2H4)n-(OC3H6)m-OH, wherein X is Ci-4 alkyl and preferably methyl, and a catalyst are added to a reaction vessel, heated under inert gas, preferably nitrogen, to a
temperature of from 1 60 °C to 220 °C to remove methanol and then pressure is reduced to below atmospheric pressure, preferably to a pressure of from 200 to 900 mbar and more preferably to a pressure of from 400 to 600 mbar for completion of the transesterification, and
b) in a second step the reaction is continued at a temperature of from 210 °C to 240 °C and at a pressure of from 0.1 to 10 mbar and preferably of from 0.5 to 5 mbar to form the polyester.
Sodium acetate (NaOAc) and tetraisopropyl orthotitanate (IPT) is preferably used as the catalyst system in the preparation of the polyesters of component A) of the inventive compositions.
The preparation of the polyesters of component A) of the inventive compositions is e.g. described in WO 2013/019658 A1 .
Preferably, the one or more alcohols of component B) of the inventive
compositions are selected from the group consisting of 1 ,2-propylene glycol, 1 ,3-propylene glycol and butyl glycol.
More preferably, the alcohol of component B) of the inventive compositions is 1 ,2-propylene glycol.
The inventive compositions preferably comprise
- of from 45 to 55 % by weight of the one or more polyesters of
component A),
of from 15 to 25 % by weight of the one or more alcohols of component B), and
of from 24 to 40 % by weight of water of component C),
the amounts in each case being based on the total weight of the inventive composition.
The inventive compositions may preferably comprise of from 0 to 10 % by weight, and more preferably of from 0 to 5 % by weight, of one or more additives, that may generally be used in detergent applications. Additives that may be used are e.g. sequestering agents, complexing agents, polymers different from the one or more polyesters of component A) of the inventive compositions, and surfactants.
In a preferred embodiment of the invention the inventive compositions preferably comprise one or more additives (component D)), and in this case the amount of water of component C) in the inventive compositions preferably is of from 24 to 39.95 % by weight, the amounts in each case being based on the total weight of the inventive compositions. The one or more additives of component D) of the inventive compositions are preferably selected from the group consisting of sequestering agents, complexing agents, polymers different from the one or more polyesters of component A) and surfactants.
Suitable sequestering agents e.g. are polyacrylic acid or acrylic acid / maleic acid copolymers (e.g. Sokalan® CP 12S, BASF). Suitable complexing agents e.g. are EDTA (ethylene diamine tetraactetate), diethylene triamine pentaacetate, nitrilotriacetic acid salts or iminodisuccinic acid salts.
Suitable polymers different from the one or more polyesters of component A) of the inventive compositions e.g. are dye transfer inhibitors such as e.g. vinyl pyrrolidone.
Suitable surfactants may be anionic surfactants such as lauryl sulfate, lauryl ether sulfate, alkane sulfonates, linear alkylbenzene sulfonates, methylester sulfonates, amine oxides or betaine surfactants.
Preferably, the one or more additives of component D) are present in the inventive compositions in an amount of up to 10 % by weight, and in this case the amount of water of component C) in the inventive compositions preferably is of from 24 to 39.95 % by weight, the amounts in each case being based on the total weight of the inventive compositions.
More preferably, the one or more additives of component D) are present in the inventive compositions in an amount of from 0.1 to 10 % by weight, and in this case the amount of water of component C) in the inventive compositions preferably is of from 24 to 39.9 % by weight, the amounts in each case being based on the total weight of the inventive compositions.
Even more preferably, the one or more additives of component D) are present in the inventive compositions in an amount of from 0.5 to 5 % by weight, and in this case the amount of water of component C) in the inventive compositions preferably is of from 24 to 39.5 % by weight, the amounts in each case being based on the total weight of the inventive compositions.
In a further preferred embodiment of the invention the inventive compositions consist of the one or more polyesters of component A), the one or more alcohols of component B), and water of component C).
Preferably, the viscosity of the inventive compositions, measured at 25 °C, is of from 200 to 5 000 mPa-s.
More preferably, the viscosity of the inventive compositions, measured at 25 °C, is of from 500 to 2 000 m Pa- s.
The viscosities are measured on the inventive compositions themselves using a Brookfield-viscosimeter, model DV II and the spindles of the set of spindles RV at 20 revolutions per minute and 25 °C. Spindle No. 1 is used for viscosities of up to 500 mPa-s, spindle No. 2 for viscosities of up to 1 000 mPa-s, spindle No. 3 for viscosities of up to 5 000 mPa-s, spindle No. 4 for viscosities of up to
10 000 mPa-s, spindle No. 5 for viscosities of up to 20 000 mPa-s, spindle No. 6 for viscosities of up to 50 000 mPa-s and spindle No. 7 for viscosities of up to 200 000 mPa-s.
The examples below are intended to illustrate the invention in detail without, however, limiting it thereto. Unless explicitly stated otherwise, all percentages given are percentages by weight (% by wt. or wt.-%). General procedure for the preparation of the polyesters of the Examples
The polyester synthesis is carried out by the reaction of dimethyl terephthalate (DMT), 1 ,2-propylene glycol (PG), and methyl polyalkyleneglycol using sodium acetate (NaOAc) and tetraisopropyl orthotitanate (IPT) as the catalyst system. The synthesis is a two-step procedure. The first step is a transesterification and the second step is a polycondensation.
Transesterification
Dimethyl terephthalate (DMT), 1 ,2-propylene glycol (PG), methyl
polyalkyleneglycol, sodium acetate (anhydrous) (NaOAc) and tetraisopropyl orthotitanate (IPT) are weighed into a reaction vessel at room temperature.
For the melting process and homogenization, the mixture is heated up to 170 °C for 1 h and then up to 210 °C for a further 1 h sparged by a nitrogen stream.
During the transesterification methanol is released from the reaction and is distilled out of the system (distillation temperature < 55 °C). After 2 h at 210 °C nitrogen is switched off and the pressure is reduced to 400 mbar over 3 h.
Polycondenzation
The mixture is heated up to 230 °C. At 230 °C the pressure is reduced to 1 mbar over 160 min. Once the polycondenzation reaction has started, 1 ,2-propylene glycol is distilled out of the system. The mixture is stirred for 4 h at 230 °C and a pressure of 1 mbar. The reaction mixture is cooled down to 140 - 150 °C. Vacuum is released with nitrogen and the molten polymer is transferred into a glass bottle.
Example I :
Amount Amount Raw Material
[g] [mol] [Abbreviation]
101 .95 0.53 DMT
84.0 1 .104 PG
343.5 0.15 H3C-(OC2H4)45-(OC3H6)5-OH
0.5 0.0061 NaOAc
0.2 0.0007 IPT
A polyester according to formula (I) is obtained wherein
R and R2 are H3C-(OC2H4)n-(OC3H6)m wherein the -(OC2H4) groups and
the -(OC3H6) groups are arranged blockwise and the block consisting of the -(OC3H6) groups is bound to a COO group,
n is based on a molar average 45,
m is based on a molar average 5, and
a is based on a molar average a number of from 6 to 7.
Example II :
A polyester according to formula (I) is obtained wherein
R and R2 are H3C-(OC2H4)n-(OC3H6)m wherein the -(OC2H4) groups and
the -(OC3H6) groups are arranged blockwise and the block consisting of the -(OC3H6) groups is bound to a COO group,
n is based on a molar average 45,
m is based on a molar average 2, and
a is based on a molar average a number of from 6 to 7.
Stability tests
Solutions according to the compositions of the following table have been prepared by dissolving the polyester in the respective mixture of water and alcoholic solvent. The additive Sokalan® CP 12S was dissolved in the final mixture. The mixtures were investigated with respect to their stability in a storage cabinet (+ = clear solution, o = turbidity, - = pronounced turbidity / precipitation). Freshly prepared samples are clear solutions. The polyester of Example I (Ex. I) has been used for the stability tests.
Sokalan® CP 12S (acrylic acid / maleic acid copolymer, BASF) has been used as the additive. From the table it can be seen that solutions of the soil release polyesters in water (Examples 1 - 4) become turbid at 45°C already after two weeks of storage.
Inventive compositions comprising 1 ,2-propylene glycol or butyl glycol are still clear after 4 weeks of storage at 45°C.
Example Polyester Water 1 ,2-Propy- Butyl Glycerol Additive clarity clarity Viscosity of Ex. I lene glycol glycol at 45 °C at 45 °C at 25 °C
[wt.-%] [wt.-%] [wt.-%] [wt.-%] [wt.-%] [wt.-%] after after [mPa-s]
2 weeks 4 weeks
1 35 65 - - 250
2 35 64 1 - - 260
3 40 60 - - 850
4 50 50 - - 3300
5 45 44 10 - -
1
6 45 39 15 1 + +
7 45 34 20 1 + +
8 45 24 30 1 + +
9 45 44 10 - -
1
10 45 39 15 1 + +
1 1 45 34 20 1 + +
12 50 40 10 + +
13 50 40 10 + +
14 50 39 10 1 + +
15 50 39 10 1 + +
1 6 55 34 10 + 0
17 55 34 10 + +
18 50 30 20 + + 1 170
19 50 35 15 + + 1260
20 50 29 20 1 + + 1 170
21 50 25 25 + + 870
22 50 30 20 + 0 285
23 40 50 10 - -
24 45 45 10 - -
25 40 49 10 1 - -
26 45 44 10 1 - -
27 50 30 20 - -
28 50 30 20 - -
Claims
1 . Composition comprising A) of from 45 to 55 % by weight of one or more polyesters according to the following formula (I)
O O O O
R— O-C C-0-C3H6 -0-C C-O-R (I)
wherein
R and R2 independently of one another are X-(OC2H4)n-(OC3H6)m wherein X is
C-i -4 alkyl and preferably methyl, the -(OC2H4) groups and the -(OC3H6) groups are arranged blockwise and the block consisting of the -(OC3H6) groups is bound to a COO group or are HO-(C3H6), and preferably are independently of one another X-(OC2H4)n-(OC3H6)m, n is based on a molar average a number of from 12 to 120 and
preferably of from 40 to 50,
m is based on a molar average a number of from 1 to 10 and preferably of from 1 to 7, and
a is based on a molar average a number of from 4 to 9 and
B) of from 10 to 30 % by weight of one or more alcohols selected from the group consisting of ethylene glycol, 1 ,2-propylene glycol, 1 ,3-propylene glycol, 1 ,2-butylene glycol, 1 ,3-butylene glycol, 1 ,4-butylene glycol and butyl glycol and
C) of from 24 to 42 % by weight of water, the amounts in each case being based on the total weight of the composition.
2. Composition according to claim 1 , characterized in that in the one or more polyesters of component A) according to formula (I)
R and R2 independently of one another are H3C-(OC2H4)n-(OC3H6)m wherein the -(OC2H4) groups and the -(OC3H6) groups are arranged blockwise and the block consisting of the -(OC3H6) groups is bound to a COO group or are HO-(C3H6), and preferably are independently of one another H3C-(OC2H4)n-(OC3H6)m,
n is based on a molar average a number of from 40 to 50,
m is based on a molar average a number of from 1 to 7, and
a is based on a molar average a number of from 4 to 9.
3. Composition according to claim 1 or 2, characterized in that in the one or more polyesters of component A) according to formula (I) a based on a molar average is a number of from 5 to 8.
4. Composition according to claim 3, characterized in that in the one or more polyesters of component A) according to formula (I) a based on a molar average is a number of from 6 to 7.
5. Composition according to one or more of claims 1 to 4, characterized in that in the one or more polyesters of component A) according to formula (I) m based on a molar average is a number of from 2 to 5.
6. Composition according to one or more of claims 1 to 5, characterized in that in the one or more polyesters of component A) according to formula (I) n based on a molar average is a number of from 43 to 47.
7. Composition according to claim 6, characterized in that in the one or more polyesters of component A) according to formula (I) n based on a molar average is a number of from 44 to 46.
8. Composition according to claim 7, characterized in that in the one or more polyesters of component A) according to formula (I) n based on a molar average is 45.
9. Composition according to one or more of claims 1 to 3 and 5 to 7, characterized in that in the one or more polyesters of component A) according to formula (I)
R and R2 independently of one another are H3C-(OC2H4)n-(OC3H6)m wherein the -(OC2H4) groups and the -(OC3H6) groups are arranged blockwise and the block consisting of the -(OC3H6) groups is bound to a COO group,
n is based on a molar average a number of from 44 to 46,
m is based on a molar average 2, and
a is based on a molar average a number of from 5 to 8.
10. Composition according to claim 9, characterized in that in the one or more polyesters of component A) according to formula (I) n based on a molar average is 45, and a based on a molar average is a number of from 6 to 7.
1 1 . Composition according to one or more of claims 1 to 3 and 5 to 7, characterized in that in the one or more polyesters of component A) according to formula (I)
R and R2 independently of one another are H3C-(OC2H4)n-(OC3H6)m wherein the -(OC2H4) groups and the -(OC3H6) groups are arranged blockwise and the block consisting of the -(OC3H6) groups is bound to a COO group,
n is based on a molar average a number of from 44 to 46,
m is based on a molar average 5, and
a is based on a molar average a number of from 5 to 8.
12. Composition according to claim 1 1 , characterized in that in the one or more polyesters of component A) according to formula (I) n based on a molar average is 45, and a based on a molar average is a number of from 6 to 7.
13. Composition according to one or more of claims 1 to 12, characterized in that the one or more alcohols of component B) are selected from the group consisting of 1 ,2-propylene glycol, 1 ,3-propylene glycol and butyl glycol.
14. Composition according to claim 13, characterized in that the alcohol of component B) is 1 ,2-propylene glycol.
15. Composition according to one or more of claims 1 to 14, characterized in that it comprises
of from 45 to 55 % by weight of the one or more polyesters of
component A),
of from 15 to 25 % by weight of the one or more alcohols of component B), and
of from 24 to 40 % by weight of water of component C),
the amounts in each case being based on the total weight of the composition.
16. Composition according to one or more of claims 1 to 15, characterized in that it comprises one or more additives (component D)), and in this case the amount of water of component C) in the composition preferably is of from 24 to 39.95 % by weight, the amounts in each case being based on the total weight of the composition.
17. Composition according to claim 1 6, characterized in that the one or more additives of component D) are selected from the group consisting of sequestering agents, complexing agents, polymers different from the one or more polyesters of component A) and surfactants.
18. Composition according to claim 1 6 or 17, characterized in that the one or more additives of component D) are present in the composition in an amount of up to 10 % by weight, and in this case the amount of water of component C) in the composition preferably is of from 24 to 39.95 % by weight, the amounts in each case being based on the total weight of the composition.
19. Composition according to one or more of claims 1 6 to 18, characterized in that the one or more additives of component D) are present in the composition in an amount of from 0.1 to 10 % by weight, and in this case the amount of water of
component C) in the composition preferably is of from 24 to 39.9 % by weight, the amounts in each case being based on the total weight of the composition.
20. Composition according to one or more of claims 1 6 to 19, characterized in that the one or more additives of component D) are present in the composition in an amount of from 0.5 to 5 % by weight, and in this case the amount of water of component C) in the composition preferably is of from 24 to 39.5 % by weight, the amounts in each case being based on the total weight of the composition.
21 . Composition according to one or more of claims 1 to 15, characterized in that it consists of the one or more polyesters of component A), the one or more alcohols of component B), and water of component C).
22. Composition according to one or more of claims 1 to 21 , characterized in that its viscosity, measured at 25 °C, is of from 200 to 5 000 mPa-s.
23. Composition according to claim 22, characterized in that its viscosity, measured at 25 °C, is of from 500 to 2 000 mPa-s.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BR112016030988-0A BR112016030988B1 (en) | 2014-07-09 | 2015-07-06 | STABLE COMPOSITIONS FOR STORAGE INCLUDING POLYMERS FOR DIRT RELEASE |
| JP2017500390A JP6505205B2 (en) | 2014-07-09 | 2015-07-06 | Storage-stable composition comprising soil release polymer |
| CN201580036878.3A CN106536699B (en) | 2014-07-09 | 2015-07-06 | The composition of stable storing including soil release polymer |
| ES15734373.2T ES2682984T3 (en) | 2014-07-09 | 2015-07-06 | Stable storage compositions comprising soil release polymers |
| PL15734373T PL3167032T3 (en) | 2014-07-09 | 2015-07-06 | Storage-stable compositions comprising soil release polymers |
| MX2017000323A MX2017000323A (en) | 2014-07-09 | 2015-07-06 | Storage-stable compositions comprising soil release polymers. |
| EP15734373.2A EP3167032B1 (en) | 2014-07-09 | 2015-07-06 | Storage-stable compositions comprising soil release polymers |
| US15/324,143 US10087400B2 (en) | 2014-07-09 | 2015-07-06 | Storage-stable compositions comprising soil release polymers |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP14002349.0 | 2014-07-09 | ||
| EP14002349.0A EP2966160A1 (en) | 2014-07-09 | 2014-07-09 | Storage-stable compositions comprising soil release polymers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2016005338A1 true WO2016005338A1 (en) | 2016-01-14 |
Family
ID=51167559
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2015/065389 WO2016005338A1 (en) | 2014-07-09 | 2015-07-06 | Storage-stable compositions comprising soil release polymers |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US10087400B2 (en) |
| EP (2) | EP2966160A1 (en) |
| JP (1) | JP6505205B2 (en) |
| CN (1) | CN106536699B (en) |
| BR (1) | BR112016030988B1 (en) |
| ES (1) | ES2682984T3 (en) |
| MX (1) | MX2017000323A (en) |
| PL (1) | PL3167032T3 (en) |
| WO (1) | WO2016005338A1 (en) |
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| WO2020058024A1 (en) | 2018-09-17 | 2020-03-26 | Unilever Plc | Detergent composition |
| WO2020104157A1 (en) | 2018-11-20 | 2020-05-28 | Unilever Plc | Detergent composition |
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| WO2020259949A1 (en) | 2019-06-28 | 2020-12-30 | Unilever Plc | Detergent composition |
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| WO2020260006A1 (en) | 2019-06-28 | 2020-12-30 | Unilever Plc | Detergent compositions |
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| EP3975984A1 (en) * | 2019-05-28 | 2022-04-06 | Unilever IP Holdings B.V. | An oral care composition for anti-staining benefits |
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| WO2017202923A1 (en) | 2016-05-27 | 2017-11-30 | Unilever Plc | Laundry composition |
| WO2019105675A1 (en) | 2017-11-30 | 2019-06-06 | Unilever Plc | Detergent composition comprising protease |
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| WO2020058024A1 (en) | 2018-09-17 | 2020-03-26 | Unilever Plc | Detergent composition |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2017523279A (en) | 2017-08-17 |
| BR112016030988A2 (en) | 2017-08-22 |
| BR112016030988B1 (en) | 2022-05-03 |
| PL3167032T3 (en) | 2018-11-30 |
| JP6505205B2 (en) | 2019-04-24 |
| CN106536699A (en) | 2017-03-22 |
| EP3167032A1 (en) | 2017-05-17 |
| EP3167032B1 (en) | 2018-06-27 |
| US20170145348A1 (en) | 2017-05-25 |
| EP2966160A1 (en) | 2016-01-13 |
| MX2017000323A (en) | 2017-04-27 |
| US10087400B2 (en) | 2018-10-02 |
| CN106536699B (en) | 2019-04-23 |
| ES2682984T3 (en) | 2018-09-24 |
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