CN1207764A - Detergent compositions contg. soil release polymers - Google Patents
Detergent compositions contg. soil release polymers Download PDFInfo
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- CN1207764A CN1207764A CN96199758A CN96199758A CN1207764A CN 1207764 A CN1207764 A CN 1207764A CN 96199758 A CN96199758 A CN 96199758A CN 96199758 A CN96199758 A CN 96199758A CN 1207764 A CN1207764 A CN 1207764A
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- Prior art keywords
- cleansing composition
- acid
- polyester
- soil release
- buider
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- 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/06—Phosphates, including polyphosphates
-
- 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
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- 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
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
A laundry detergent composition contains a surfactant, sodium tripolyphosphate builder in an amount of at least 5 wt.%, and a soil release polymer which is a defined water-soluble or water-dispersible sulphonated non-end-capped polyester, for example, of terephthalic acid, isophthalic acid, sulphoisophthalic acid and ethylene glycol.
Description
Technical field
The present invention relates to contain the washing cleansing composition of water-soluble or water-dispersible polyester, above-mentioned polyester shows the characteristic of the spot release that improves.
Background and prior art
Having the terephthalic acid of soil release performance or the polyester of other aromatic dicarboxylic acid is extensively disclosed in this field, especially so-called PET/POET (polyethylene terephthalate/polyoxyethylene terephthalate) and PET/PEG (polyethylene terephthalate/polyoxyethylene glycol) polyester, be disclosed in, for example, US 3557039 (ICI), GB 1467098 and EP1305A (Procter﹠amp; Gamble).The polyester of this type can derive from commerce, and for example, as Permalose, Aquaperle and Milease (trade mark) (ICI) and Repel-O-Tex (trade mark) SRP3 (Rh ne-Poulenc).Other patent announcement of open soil release polymers comprises EP 185427A, EP 241984A, EP241985A and EP 272033A (Procter﹠amp; Gamble), above-mentioned polymkeric substance is the condensation product of aromatic dicarboxylic acid and divalent alcohol.
EP 357280A (Procter﹠amp; Gamble) disclose with sulfonated end-blocked linear terephthalate oligomer, above-mentioned oligomer is a kind of low-molecular-weight glycol, and preferred propylene glycol or ethylene glycol are with the condensation product of terephthalic acid.
The present invention is based on the application of using one group of untight sulfonated polyester of end group that is obtained by dicarboxylic acid and polyvalent alcohol, above-mentioned polyester can provide very effective soil release, the spot on the polyester textile particularly also can effectively reduce the deposition again of spot in the washing process.
Definition of the present invention
The present invention aims to provide a kind of cleansing composition of laundering of textile fabrics, comprise: (a) a kind of organic surface active agent system of 2-50% (weight ratio), it comprises a kind of buider composition of one or more anionics, non-ionic type, cationic, both sexes or amphoteric ionic surfactant (b) 0-80% (weight ratio), comprise that one or more are inorganic or organically clean buider, comprise the tripoly phosphate sodium STPP of 5% (wt) (according to cleansing composition).(c) a kind of water-soluble or water-dispersible sulfonated polyester of soil release significant quantity, comprise following monomer unit: (i) a kind of non-sulfonated aromatic diacid monomer (A), (ii) a kind of sulfonated aromatic diacid monomer (SA), hydroxylated aromatics or the aliphatic diacid monomer of (iii) can choosing any one kind of them (HA), to replace (A) and/or (SA) up to the amount of 50% (mole), (iv) a kind of polyvalent alcohol (P) is selected from ethylene glycol, propylene glycol, Isopropanediol, glycerol, 1,2,4-butane three pure and mild 1,2,3-butane triol and its have the oligomer of 1-8 monomer unit.The sulphur content scope of above-mentioned polyester (d) can be chosen other clean-out system composition wantonly and add to 100% in 0.5-10% (weight ratio).
Detailed description of the present invention Polyester
The existing definition in polyester of the present invention front.Polyester and preparation thereof open and requirement in WO9532997A (Rh ne-Poulenc).
It is a kind of aromatic dicarboxylic acid or its acid anhydrides or rudimentary (C that preferred polyester has the Sulfonated diacid monomer of following characteristics :-non-(A)
1-C
4) alkyl diester, described monomer is selected from terephthalic acid, iso-phthalic acid, 2,6-naphthalene dicarboxylic acids and acid anhydrides thereof and rudimentary (C
1-C
4) alkyl diester;-Sulfonated diacid monomer (SA) is a kind of Sulfonated aromatic dicarboxylic acid, acid anhydrides or its rudimentary (C
1-C
4) alkyl diester;-(A): the molar ratio range of [(A)+(SA)] is 60: 100 to 95: 100, preferred 65: 100 to 93: 100;-(SA): the molar ratio range of [(A)+(SA)] is 5: 100 to 40: 100, preferred 7: 100 to 35: 100;-hydroxylation monomer (HA) (if existence) is a kind of hydroxylated aromatic dicarboxylic acid, or its acid anhydrides or its rudimentary (C
1-C
4) alkyl diester;-hydroxylation monomer (HA) (if exist) can not be replaced (A) that surpass 30% (mol ratio) and/or (SA);-(P) amount is a kind of like this ratio, and the ratio of OH functional group (P) and (A)+(SA)+any (HA) COOH functional group (or suitable functional group) was 1.05: 1 to 4: 1 scope, preferred 1.1: 1 to 3.5: 1, more preferably 18: 1 to 3: 1; The molecular-weight average of-polyester is lower than 20000, and the scope of-sulphur content is 1.2 to 8% (weight ratios);-carboxyl-content is at least 0.2 OH equivalent of every kilogram of polyester.
Non-sulfonated diacid monomer (A)
As previously mentioned, monomer (A) preferably contains and is selected from terephthalic acid, iso-phthalic acid and 2, at least a dicarboxylic acid or the acid anhydrides of 6-naphthalene dicarboxylic acids or acid anhydrides or its diester.
The amount of preferred monomers (A), according to the molar ratio range of (A)/[(A)+(SA)] at 95: 100 to 60: 100, preferred 93: 100 to 65: 100.
Not Sulfonated diacid monomer (A) preferably contains 50-100% (mol ratio), the more preferably terephthalic acid of 70-90% (mol ratio) or acid anhydrides or low alkyl group (methyl, ethyl, propyl group, sec.-propyl, butyl) diester and 0-50% (mol ratio), the more preferably iso-phthalic acid of 10-30% (mol ratio) or acid anhydrides and/or 2,6-naphthalene dicarboxylic acids or acid anhydrides or low alkyl group (methyl, ethyl, propyl group, sec.-propyl, butyl) diester; Preferred diester is the methyl diester.
In not Sulfonated dicarboxylic acid monomer (A), may there be some a spot of aromatic diacids (non-front is mentioned) in addition, for example phthalic acid, anthracene, 1,8-naphthalene, 1,4-naphthalene and diphenyl dicarboxylic acid or fat diacid such as hexanodioic acid, pentanedioic acid, Succinic Acid, trimethyladipic acid, pimelic acid, nonane diacid, sebacic acid, suberic acid, methylene-succinic acid, maleic acid etc. are with the form existence of acid, acid anhydrides or rudimentary (methyl, ethyl, propyl group, sec.-propyl, butyl) diester.
Sulfonated dicarboxylic acid monomer (SA)
Preferred sulfonated dicarboxylic acid monomer (SA) contains at least a sulfonated aromatics or sulfonated aliphaticdicarboxylic acid or acid anhydride acid anhydride or rudimentary (C
1-C
4) alkyl diester, preferred aromatic dicarboxylic acid and derivative thereof.
The amount that preferred monomers (SA) exists, according to the ratio of the mol ratio of (SA)/[(A)+(SA)] in 5: 100 to 40: 100 scope, more preferably 7: 100 to 35: 100.
Sulfonated diacid monomer (SA) contains at least one sulfonic acid group, preferably with the form of azochlorosulfonate acid alkali metal (preferred sodium) salt, with two acidic functionalities or suitable acidic functionality (that is to say a kind of anhydride functional group or two ester functional groups), when aromatic dicarboxylic acid or acid anhydrides or their ester exist, above-mentioned functional group is connected on one or several aromatic ring, or when aliphaticdicarboxylic acid or acid anhydrides or their ester existed, above-mentioned functional group was connected on the aliphatic chain.
The aromatic sulfonic acid diacid monomer that is fit to comprises sulfo group iso-phthalic acid, sulfo group terephthalic acid, sulfo group-neighbour-phthalic acid or its acid anhydride, 4-sulfo group-2,7-naphthalene dicarboxylic acids or acid anhydride, sulfo group 4,4 '-two (hydroxycarbonyl group) sulfobenzide, diphenylsulfone base dicarboxyl acid or anhydride, sulfo group 4,4 '-two (hydroxycarbonyl group) ditan, sulfo group-5-phenoxy group iso-phthalic acid or acid anhydride or their rudimentary (methyl, ethyl, propyl group, sec.-propyl, butyl) diester.
The aliphatic sulfonic diacid monomer (SA) that is fit to comprises sulfo-succinic acid or acid anhydride or their low alkyl group (methyl, ethyl, propyl group, sec.-propyl, butyl) diester.
Most preferred sulfonated diacid monomer is that sulfo group iso-phthalic acid, particularly 5-sodium with acid, acid anhydride or diester (preferred dimethyl esters) form is for oxygen base alkylsulfonyl iso-phthalic acid dimethyl ester.
Hydroxylated diacid monomer (HA)
Hydroxylated diacid monomer (HA) (can choose existence wantonly, and replaceable 50% (mole) that reach, (A) of preferred 30% (mole) and/or (SA)) contains at least a hydroxylated aromatics or aliphatic dicarboxylic acid or acid anhydrides or its rudimentary (C
1-C
4) alkyl diester.
Hydroxylation diacid monomer (HA) contains at least one oh group, and when being an aromatic monomer, above-mentioned hydroxyl is connected on one or more aromatic rings; When being an aliphatic monomer, above-mentioned hydroxyl then is connected on the aliphatic chain.Preferred aromatic monomer.
The hydroxylation diacid monomer (HA) that is fit to comprises 5-hydroxyl iso-phthalic acid, 4-hydroxyl iso-phthalic acid, 4-hydroxybenzene dioctyl phthalate, 2-hydroxymethyl Succinic Acid, meglutol and the hydroxyl pentanedioic acid with acid, acid anhydride or low alkyl group diester form.
Polyvalent alcohol (P)
Polyvalent alcohol (P) can be one by the oligomer of forming up to 8 monomer unit (preferred 6, more preferably 4 monomer unit, most preferably a monomer).Polyvalent alcohol can be selected from ethylene glycol, propylene glycol, glycerol, 1,2,4-trihydroxybutane, 1,2, rudimentary (2 to 8, preferred 2 to 6, more preferably 2-4) oligomer of the composition of 3-trihydroxybutane and they and they.
Preferred polyol (P) exists with following amount, this amount is decided according to the ratio of the COOH functional group of the OH functional group number of polyvalent alcohol (P) and total diacid monomer (A)+(SA)+(HA) or suitable functional group's number, the aforementioned proportion scope was at 1.05: 1 to 4: 1, preferred 1.1: 1 to 3.5: 1, more preferably 1.8: 1 to 3: 1.
Preferred polyol (P) is ethylene glycol and glycerol, preferred especially ethylene glycol.
When polyvalent alcohol (except that dibasic alcohol) does not contain any polyvalent alcohol maybe when not having hydroxylated diacid monomer (HA) when existing, preferred sulfonated diacid monomer (SA) contains mixture and the sulfonated fatty acid or anhydride or their diester of at least a sulfonated aromatic dicarboxylic acid or acid anhydride or a kind of sulfonated aromatics acid or anhydride.
Molecular weight
The polyester molecular-weight average that uses among preferred the present invention is no more than 20000, and preferably is no more than 15000.
Molecular weight may be well below these limits, and the polyester that molecular weight is lower than 1000 (as 500-1000) is proved to be very effective.
The digital average molecular weight can be measured by gel permeation chromatography, for example, is containing 10
-2In the N,N-DIMETHYLACETAMIDE of N LiBr (25 ℃ time) or in tetrahydrofuran (THF).The result represents with the polystyrene equivalent.
The hydroxyl-functional mass contg
Preferably, the content of hydroxy functional group (representing with OH equivalent in every kilogram of polyester) is no less than 0.2 in the polyester.The hydroxyl-functional mass contg can be calculated from proton N MR, is determined in the dimethyl sulfoxide (DMSO) and carries out.
Think (A), (SA) or (HA) fundamental unit of monomeric mole definition be COOH functional group in the diacid or the suitable COOH functional group in acid anhydrides or the diester.
Particularly preferred polyesterA kind of particularly preferred polyester can obtain from following monomer :-with the terephthalic acid (A1) of low alkyl group (preferable methyl) diester form;-with the optional iso-phthalic acid (A2) of acid or anhydride form;-with optional a kind of hydroxylation phthalic acid of acid or anhydride form or iso-phthalic acid (HA) (A1): [(A1)+(A2)] or (A1): [(A1)+(HA)] or (A1): the molar ratio of [(A1)+(A2)+(HA)] should be in 50: 100 to 100: 100 scope, preferred 70: 100 to 90: 100;-sulfo group iso-phthalic acid (SA), preferred low alkyl group (preferable methyl) diester form; With-monoethylene glycol and/or glycerol (P)
Can be described as having the skeleton unit of following formula according to the preferred polyester that the present invention is based on phthalic acid, iso-phthalic acid, sulfo group terephthalic acid and monoethylene glycol:
Wherein Ar=terephthaldehyde base, different xylylene or the different xylylene of sulfo group and n represent 1,2,3 or 4.To different n values, general molar percentage is as follows:
n＝1 58.7
n＝2 30.5
n＝3 8.8
N=4 1.9 only exists n greater than 4 in (if any) polyethylene oxide unit of trace.
Most of end groups as shown in the formula:
-Ar-COO-(CH
2-CH
2-O-)
nWherein n is 1,2,3 or 4, minority as shown in the formula:
-Ar-COOH or-Ar-COOR wherein R be a kind of low-grade alkyl group, preferable methyl.
These polyester are unlike disclosed in many past technology, not with alkyl or the sealing of sulfonated blocking groups end.
The preparation of polyester
Polyester can be prepared by common esterification and/or transesterification and polycondensation process, the for example esterification and/or the transesterification of polyvalent alcohol P in the presence of catalyzer and various diacid monomer (with acid, acid anhydride or diester form), the polycondensation of multi-hydroxy ester when polycondensation catalyst exists under decompression state.
Open and the requirement in WO 9532997 A (Rh ne-Poulenc) of a kind of preferred polyester preparation process.
Cleansing composition
The amount that polyester is fit in the cleansing composition is from 0.01-10% (wt), preferred 0.1-5% (wt), more preferably 0.25-3% (wt).
Cleansing composition of the present invention also contains one or more cleaning-active compounds (tensio-active agent) as basal component, also can contain one or more and clean buider; They also can be chosen wantonly and contain bleaching composition and other active ingredient to strengthen the property and feature.
Surfactant system
The optional negatively charged ion of cleaning active compound (tensio-active agent), nonionic, positively charged ion, both sexes or amphoteric ion type cleaning active compound and composition thereof from soap kind or non-soap kind.Many cleaning active compounds are obtainable, and in paper, described in detail, as " tensio-active agent and clean-out system " I volume and the II volume of Schwartz, Perry and Berch, operable preferred cleaning active compound has the negatively charged ion and the nonionic compound of soap kind and the non-soap kind of synthetic.
Total weight range of tensio-active agent is 2-50% (wt), preferable range 5-40% (wt).
For those those skilled in the art's anion surfactants is well-known.Example comprises alkylbenzene sulfonate, and particularly alkyl chain length is C
8-C
15Linear alkyl benzene sulfonate; Primary and secondary alkyl-sulphate, particularly C
8-C
15Primary alkyl sulphates; Sulfated alkyl ether; Alkene sulfonate; Alkylxylene sulfonate; The sulfonic group succinic acid dialkyl ester; And fatty sulfonate.General particular certain cancers.
The polyester of the present invention that is suitable for especially using in the composition contains anionic sulphonate and sulfated surfactant, for example, and primary alkyl sulfonate, alkylether sulfonate, alkylbenzene sulfonate and composition thereof.
According to an embodiment preferred of the present invention, composition of the present invention contains a kind of surfactant system, and this system only contains anion surfactant or contains negatively charged ion and the nonionic surface active agent that weight ratio is at least 0.9: 1 (preferably at least 1: 1).The preferred amount of tensio-active agent is 5-45% (wt), more preferably 10-40% (wt).
Operable ionic surfactant pack is drawn together primary and secondary base fatty alcohol ethoxylate, particularly has the C of average every mol of alcohol 1 to 20 moles of ethylene oxide
8-C
20Fatty alcohol ethoxylate, the C of more preferably average every mol of alcohol 1 to 10 moles of ethylene oxide
10-C
15Primary and secondary base fatty alcohol ethoxylate, the ionic surfactant pack of non-ethoxylated thing is drawn together alkylpolyglycosides, monoglyceride and polyhydroxyamide (glucamide).
The nonionogenic tenside of preferred especially ethoxylation, alkylpolyglycosides and composition thereof.
As top listed on-soap tensio-active agent, cleaning combination of the present invention also can contain fatty acid soaps valuably.
Clean the buider system
Cleansing composition of the present invention also contains the cleaning buider.The suitable scope of total amount of cleaning buider in the composition is 5 to 80% (wt), preferred 10 to 60% (wt).
The sanitising agent system contains the tripoly phosphate sodium STPP (STP) as the amount of a kind of at least 5% (wt) of fundamental component, preferred at least 1% (wt), and above-mentioned amount is decided based on whole composition.
STP may be the unique buider that exists, and the amount that it preferably exists in this scheme is at least 15% (wt) and preferred at least 20% (wt), and suitable amount is 20-50% (wt).
STP can choose wantonly with may be inorganic or organically one or more other buiders be used in combination.
Other inorganic buider that may exist comprises other phosphoric acid salt buider, for example, and sodium orthophosphate and/or trisodium phosphate; Yellow soda ash (combining with the lime carbonate crystal seed if desired) has been disclosed in GB 1437950 (Unilever); Crystal type and amorphous aluminosilicate, for example, zeolite has been disclosed in GB 1473201 (Henkel), and amorphous aluminosilicate has been disclosed in GB 1473202 (Henkel) and blended crystallization/amorphous aluminosilicate as being disclosed in BG 1470250 (Procter﹠amp; Gamble); With stratified silicate as being disclosed in EP 164514B (Hoechst).
Preferred especially STP and other phosphoric acid salt, with yellow soda ash and with the combining of sodium aluminium silicate (zeolite).Particularly preferred buider system contains at least 5% STP and at least 10% zeolite A.
Zeolite can obtain in commerce, and zeolite 4A extensively is used in washing with in the clean-out system powder now.Other spendable zeolite comprises X zeolite and Y.Other zeolite buider is peaked zeolite aluminium P (zeolite MAP), as the open and requirement at EP 384070B (Unilever).
Zeolite MAP is defined as a kind of manosil AS an alkali metal salt of zeolite P type, and the ratio of its silicon and aluminium is no more than 1.33.The ratio of preferred especially silicon and aluminium is no more than 1.07, is more preferably 1.00 zeolite MAP.
Organic buider of augmenting that may exist comprises the polycarboxylate of polycarboxylic acid ester polymer such as polyacrylic ester, vinylformic acid/maleic acid and phospho acid propylene ester; Monomeric polycarboxylate such as citrate, gluconate, hydroxyl two succinates, glycerine one, two, three succinates, carboxymethyl oxysuccinic acid ester, carboxymethyl oxomalonic acid ester, dipicolinates, hydroxyethylamino-diacetic acid salt, alkyl-and alkenyl malonic ester and succinate; With Sulfonated soap.Do not pardon and describe in detail one by one.
The present invention's cleansing composition also can suitably contain a kind of SYNTHETIC OPTICAL WHITNER system, and said system contains the peroxide bleaching compound, for example inorganic persalt or organically peroxidation acid, and it can produce hydrogen peroxide in the aqueous solution.Suitable peroxide bleaching compound comprises organo-peroxide, for example urea peroxide and inorganic persalt such as alkali metal perborate, percarbonate, superphosphate, persilicate and persulphate.Preferred inorganic persalt is Sodium peroxoborate monohydrate and tetrahydrate and SPC-D.The suitable amount of peroxide bleaching compound is 5 to 35% (wt), preferred 10 to 25% (wt).
The peroxide bleaching compound can use so that strengthen bleaching action under low wash temperature with bleach-activating agent (bleach precursor).The suitable amount of bleaching precursor is 1-8% (wt), preferred 2-5% (wt).
Also can there be a kind of bleaching stibilizer (heavy metal sequestering agent).Suitable bleaching stibilizer comprises edetate (EDTA) and poly phosphate such as phosphoric acid ethylenediamine tetramethylene ester (EDTMP) and salt and p diethylaminobenzoic acid diamines pentamethylene ester (DETPMP) and salt thereof.
The present invention also has the special composition that does not contain SYNTHETIC OPTICAL WHITNER that is applied to wash soft and fine fabric.This composition can be if any following one or more features :-in softening water, the pH of 1% (wt) aqueous solution is no more than 10.5, preferably is no more than 10.-do not contain or extremely low-level fluorescent agent;-contain a kind of polycarboxylate polymer, for example, a kind of vinylformic acid/maleic acid such as Sokalan (trade mark) CP5 ex BASF;-contain a kind of polymkeric substance that prevents that effectively color from shifting, as polyvinylpyrrolidone;-contain a heavy metal species sequestering agent, as methylene amido phosphoric acid and salt such as EDTMP and DETPMP, carried in the content of bleaching stibilizer in front.
The present composition also can contain one or more enzymes.The suitable enzyme that uses in the cleansing composition comprises proteolytic enzyme, amylase, cellulase and lipase.
The preferred normally protein matter of solid, catalytic activity of Proteolytic enzyme (proteolytic enzyme) that promotes, when above-mentioned substance when the textile stains hydrolysis reaction exists, they can degrade or change the protein type of spot.They can be any suitable sources, as vegetables, animal, bacterium or yeast source.
Various character, source and keep active proteoclastic enzyme or proteolytic enzyme to obtain and can use in the present invention in different pH scopes (4-12).The example of suitable proteolytic ferment is the subtilysin that is obtained by special Pseudomonas B.subtilis and B.licheniformis, for example can derive from commercial subtilysin Maxatase (trade mark), by Gist-Brocades N.V, Delft, Holland supply, and Alcalase (trade mark) are by Novo Industri A/S, Copenhagen, the Denmark supply.
Derived from commerce that is obtained by the Bacillus Pseudomonas, the proteolytic enzyme that has maximum activity at pH scope 8-12 also suits, and for example, can derive from Novo Industri A/S, registers with trade(brand)name Esperase (trade mark) and Savinale (trade mark).The preparation narration in GB 1243785 of the above and similar enzyme.Other commercial existing proteolytic enzyme is that Kazusase (trade mark) (derive from Japan Showa-Denko), Optimase (trade mark) (derive from the Miles Kali-Chemie of West Germany, Hannover) and Superase (trade mark) (deriving from the Pfizer of the U.S.).
Iso-electric point is lower than 10 proteolytic enzyme and comprises Alcalase, Maxatase, Optimase and Primase (all being trade mark).Be equal to or greater than 10 proteolytic enzyme Deng some electricity and comprise Savinase, Maxacal, Purafect, Opticlean and Esperase (all being trade mark).
The cleaning enzyme uses with particle form usually, and its consumption is 0.01-5.0% (wt).
Other material that can exist in the cleansing composition of the present invention comprises inorganic salt such as yellow soda ash, sodium sulfate or water glass; Anti redeposition agent such as cellulosic polymer; Fluorescent agent; Inorganic salt such as sodium sulfate; Foam Control or profoamer are as being fit to; Pigment; Painted spot; Perfume compound; Foam Control and fabric softening immunomodulator compounds.Do not enumerate one by one for this reason.
Cleansing composition of the present invention can be any proper physical form, as powder or particle, liquid, colloid and solid bar piece.
The preparation method that it is suitable that cleansing composition of the present invention can any suitable method prepares the particulate state cleansing composition is that the suspension with compatible hot insensitive composition carries out spraying drying, and then spraying or irradiation those be not suitable for composition via the suspension process.Skilled cleaning agent formula person can determine without difficulty which kind of composition is included in the suspension, and which kind of composition is not therein.
The volume density of particulate state cleansing composition of the present invention should be preferably 400g/l at least, more preferably 500g/l at least.The volume density that special preferred composition has is at least 650g/l, more preferably 700g/l at least.
Such powder can perhaps pass through non-tower (non-tower) method such as dry mixed and the preparation of granulating completely by with (post-tower) compacting preparation behind the spray-dired powder drying tower; In above two kinds of methods, can use high-speed mixer/nodulizer valuably.Use the method for high-speed mixer/nodulizer open, for example in EP 340013A, EP 367339A, EP 390251A and EP 420317A (Unilever).
Embodiment
The present invention further illustrates by following indefiniteness embodiment, and wherein part and per-cent unless otherwise indicated all refer to weight.Among the whole embodiment
*Represent trade mark.
Polymkeric substance
The used polymkeric substance (polymkeric substance 1) of the present invention is the water-soluble sulfonated polyester of a kind of terephthalic acid, iso-phthalic acid, sulfo group iso-phthalic acid or propylene glycol, has following about composition :-the diacid monomer be made up of the sulfo group iso-phthalic acid of the iso-phthalic acid, 18.2% (mole) of the terephthalic acid, 3.7% (mole) of about 77% (mole);-OH group (from (ex) ethylene glycol) is approximately 1.22 with the ratio of COOH group (from diacid monomer); In-25 ℃ the tetrahydrofuran (THF) be that the GPC that standard substance is checked and approved measures with the polystyrene, the digital average molecular weight is 534; Weight average molecular weight is 1667;-sulphur content is 2.4% (wt).-oh group content is the about 1.4-1.5 of per kilogram polymkeric substance.
Be the purpose of contrast, use the following polymkeric substance that obtains by commerce: polymer A: Sokalan (trade mark) HP 22 ex BASF, the graft copolymer of polyoxyethylene glycol and Vinyl Acetate Copolymer.Polymer B: Repel-O-Tex (trade mark) ex Rh ne-Poulenc, a kind of PET/OPET polymkeric substance uses with the form of particle (50%wt polymkeric substance, 50%wt sodium sulfate).Polymkeric substance C:Aquaperle (trade mark) 3991 ex ICI, a kind of PET/POET polymkeric substance.
Embodiment 1
Use spraying drying and irradiation technique, press the particulate state cleansing composition of the phosphorous hydrochlorate combination of following general formulation:
Linear alkyl benzene sulfonate 5.60
Nonionic surface active agent 7EO 4.20
Nonionic surface active agent 3EO 3.30
Soap kind 0.25
Pristerine
*4916 (lipid acid) 0.28
Alkaline sodium silicate 5.60
Tripoly phosphate sodium STPP 22.00
Yellow soda ash 9.00
Xylo-Mucine 0.30
Vinylformic acid/maleic acid (Sokalan
*CP5) 0.97
EDTA (4Na salt) 0.12
Fluorescent agent 0.16
Sodium sulfate 27.00
Sodium peroxoborate 13.00
TAED
Soil release polymers (face as follows) 0 or 0.40
Anti-foam beads, enzyme
Yellow soda ash, perfume compound, water adds to 100.00
The use radiation (
3H) triolein of mark is measured the removing and the washing of spot as dirt.Washing procedure is as follows: 40 ℃ of temperature, in the water of 24 H of hardness (only in calcium), with the product dosage of regulation, washed the polyester clothing 20 minutes with experimental formula (having or do not have the soil release polymers of 0.4%wt) in Tergotometers.Single wash: have the clothing of spot to wash as stated above.Prewashing: the same with single wash, just do not have spot and exist; After pre-wash, in 20 ℃ with water in bucket the rinsing of fabric with 1 liter, dried overnight then.Main washing: the same with single wash, but use through pretreated fabric.Wash result:
Product dosage: 7.8g/l
Polymkeric substance cleans %
(0.4wt％)
Single wash prewashing+master washes
Do not have 79.1 53.6
Polymkeric substance 1 100.0 100.0
Polymer A 86.3 87.1
Polymer B 92.6 100.0
Polymkeric substance C 79.1 53.6
Embodiment 2
Use spraying drying and irradiation technique, press the phosphatic particulate state cleansing composition of following general formulation:
LINER ALKYL BENZENE SULPHONIC ACID SOFT 96 sodium 25.00
Zeolite 1.17
Tripoly phosphate sodium STPP 21.68
Water glass 5.00
Lime carbonate 10.00
Sodium sulfate 21.24
Xylo-Mucine 0.70
Fluorescent agent 0.01
Vinylformic acid/maleic acid (Sokalan
*CP5) 1.80
Perfume compound 0.25
Proteolytic enzyme (Savinase
*6T) 0.20
Lipase (Lipolasa
*100T) 0.05
Amylase (Termamyl
*60T) 0.08
Antifoams (silicone oil/silicon-dioxide) 0.01
Soil release polymers is face as follows
Moisture content and other are to 100.00
The volume density of this prescription is 420-440g/l, and 25 ℃ the time, the aqueous solution pH of its 1% (weight) is 9.7-9.8 in softening water.
Pollute the polyester experiment clothing of braiding with Oilsol Blue dyestuff/sweet oil, by two kinds of different product dosage, estimate the removing and the washing of spot in Tergotometer, washing procedure is as follows:
3.8g/l 1.3g/l
25: 3 Ca of the water hardness: 15: 3 Ca of Mg: Mg
pH 8.45 8.22
28 ℃ of temperature
Immersion/washing time was soaked washing in/10 minutes in 30 minutes
Prewashing 5
Repeat 2
Estimate cleaning performance by the reflectance that uses Micromatch (trade mark) Instrument measuring washing front and back.Difference (Δ R580
*) see the following form:
Polymkeric substance% 3.8g/l 1.3g/l
Do not have 0 32.68 22.94
Polymkeric substance 1 0.5 57.29 63.02
Polymer A 1.0 50.63 27.96
Polymer B 0.5 52.05 50.41
Soil release is evaluated by range estimation by five people's experience groups.Result's (grade is explained to 10 (removing fully) by 1 (serious spot, initial spot)) sees the following form:
Polymkeric substance% 3.8g/l 1.3g/l
Initial-1 1
Do not have 033
Polymkeric substance 1 0.5 10 10
Polymer A 1.0 64
Polymer B 0.5 88
Implement 3
Adopt spraying drying and irradiation technique, press the particulate state cleansing composition of the other phosphorous hydrochlorate combination of following general formulation:
LINER ALKYL BENZENE SULPHONIC ACID SOFT 96 sodium 25.00
Tripoly phosphate sodium STPP 22.50
Water glass 5.00
Sodium sulfate 28.90
Xylo-Mucine 0.70
Vinylformic acid/maleic acid (Sokalan
*CP5) 2.00
Yellow soda ash 2.00
Fluorescent agent spot 1.00
Citric acid (anhydrous) 3.00
Proteolytic enzyme (Opticlean
*M375) 0.784
Lipase (Lipolase
*100T) 0.253
Antifoams (silicone oil/silicon-dioxide) 0.04
Perfume compound 0.33
Soil release polymers is face as follows
Moisture content and other are to 100.00
The volume density of this prescription is 370-430g/l, and in 25 ℃, softening water, the aqueous solution pH of its 1% (wt) is 9.7-9.8.
As embodiment 2, use Micromatch (trade mark) device to measure washing front and back reflectance and evaluate cleansing power.Difference (Δ R580
*) see the following form:
Polymkeric substance% 3.8g/l 1.3g/l
Do not have 0 30.34 38.56
Polymkeric substance 1 0.25 57.84 60.67
Polymer A 1.0 53.23 59.48
Polymer B 0.25 53.71 61.77
Polymkeric substance C 0.35 54.50 58.53
When product dosage is 1.3g/l, evaluate the removing performance of spot by measuring reflectance behind the washing back and washing for the second time for the first time, the washing procedure in Tergotometer is as follows:
The polyester of experiment clothing braiding
Spot Oilsol Violet/ sweet oil
21: 6 Ca of the water hardness: Mg
28 ℃ of temperature
Prewashing does not have
Immersion/washing time is soaked 30 minutes/washing 10 minutes
2 * 2 minutes rinsing time result:
Polymkeric substance% R 580
*
Washing 1 washing 2 differences do not have 0 42.30 44.49 2.19) 2.70
43.34 46.55 3.21 )1 1.0 46.75 58.31 11.56 ) 12.99
56.05 70.47 14.42 )B 1.0 50.45 60.52 10.07 ) 10.12
45.58 55.75 10.17)
Embodiment 4, comparative examples D and E
In these embodiments, the effect of polymkeric substance 1 and B in the prescription that relatively constitutes by STP and zeolite.Used zeolite is zeolite 4A (Wessalith
*P de Degussa) and have Si: the ratio of Al is less than 1.33 zeolite P (zeolite MAP) (Doucil
*A24 ex CrosfieldChemicals).
Each composition according to dosage places tergotometers to constitute following prescription respectively:
Weight ratio
D E 4Linear alkyl benzene sulfonate 20.00 20.00 20.00 sodium carbonate 25.00 25.00 25.00 sodium chloride 20.00 20.00 20.00 zeolite MAPs 22.00--Wessalith CS-22.00-sodium phosphate trimer--22.00 soil release polymers--------0 or 1.00-------
As embodiment 1, adopt the described single wash program of embodiment 1 (20 minutes, 25 ℃, the water of 24 H (only in calcium)), measure for pollution have radioactivity (
3H) soil release and the cleaning performance on the polyester clothing of the triolein of mark, the dosage of " product " is 1.5g/l.The results are shown in nextpage.
In three kinds of all compositions, polymkeric substance 1 obviously increases cleaning performance.In two kinds of zeolite prescriptions, it is less that polymer B increases cleaning performance, but the existence of polymer B makes cleaning performance that substantial reduction be arranged in the STP prescription, and the existence of polymkeric substance 1 raises cleaning performance relatively.
The difference of two kinds of polymkeric substance effects is highly significant in the STP prescription.
Comparative examples D: zeolite MAP
Cleaning polymkeric substance usefulness does not have polymkeric substance 29.6 polymkeric substance 1 56.7 27.1 polymer B 37.2 7.6
Polymkeric substance 1 and polymer B inefficiency=19.5
Comparative examples E: zeolite 4A
Cleaning polymkeric substance usefulness does not have polymkeric substance 50.0 polymkeric substance 1 73.8 23.8 polymer B 62.0 12.0
Polymkeric substance 1 and polymer B inefficiency=11.8
Embodiment 4: tripoly phosphate sodium STPP
Cleaning polymkeric substance usefulness does not have polymkeric substance 63.1 polymkeric substance 1 75.3 12.2 polymer B 50.8-12.3
Polymkeric substance 1 and polymer B inefficiency=24.5
Embodiment 5-7
It is of the present invention that to contain soil release polymers, phosphoric acid salt combination, as not have bleaching particulate state cleansing composition property, high volume density embodiment as follows:
5 6 7Na LAS
128.66 24.70 15.00Na PAS
22.88 4.19-non-ionic surface active agent 9EO--2.51 zeolites, 18.84 21.31 6.24 sodium phosphate trimers, 29.69 6.78 39.25 sodium carbonate-16.43,23.52 sodium acid carbonate 6.26-, 2.97 sodium metasilicate--2.37SCMC 0.78 0.78 0.57 fluorescer 0.01 0.56 0.30 copolymer (Sokalan*CP5) 1.93 1.99 1.18 proteolytic enzyme (Savinase
*6T) 0.32 0.40 0.70 lipase (Lipolase
*100T) 0.08 0.10 0.26 amylase (Termamyl
*60T) 0.14--soil release polymers 0.50 0.50 0.50 perfume compound, 0.40 0.40 0.60 moisture content and other-----add to 100.00----volume density (g/l) 780-820 ca.800 ca.800
1LINER ALKYL BENZENE SULPHONIC ACID SOFT 96 sodium
2Primary alconol sodium sulfate
The composition of embodiment 5 has low pH value of solution (9.7-9.8), is suitable for washing soft and fine fabric especially.
Embodiment 8
The additional embodiments of the powder of the phosphorous hydrochlorate combination of the nothing bleaching property of the high volume density of the low pH value of solution of the soft and fine fabric of suitable washing is as follows according to the present invention:
Na?LAS 6.50
Nonionogenic tenside 6/7EO 4.00
Soap 4.30
Tripoly phosphate sodium STPP 29.17
Water glass 10.00
SCMC 0.43
Polyvinylpyrrolidone 0.95
Sodium sulfate 17.00
Yellow soda ash (heavy) 6.00
Ammonium sulfate 2.00
Citric acid 2.25
Starso 2.00
Amorphous aluminosilicate 1.12
Proteolytic enzyme (Savinase
*6T) 0.20
Lipase (Lipolase
*100T) 0.05
Amylase (Termamyl
*60T) 0.25
Cellulase (Celluzyme
*0.7T) 0.40
Soil release polymers 0.55
Perfume compound 0.40
Moisture content and other add to 100.00
The volume density of this prescription is 700g/l, and in softening water, the pH of its 1% (wt) aqueous solution is 9.7-9.8.
Embodiment 9 and 10
The bleaching particulate state cleansing composition embodiment of the phosphorous hydrochlorate combination of high volume density is as follows according to the present invention:
9 10
Na?LAS 6.50 9.00
Nonionogenic tenside 6/7EO 4.00 4.00
Soap 4.30-
Tripoly phosphate sodium STPP 28.40 30.00
Water glass 10.00 10.00
SCMC 0.36 0.36
Fluorescent agent 0.20 0.20
EDTA 0.06 0.06
Yellow soda ash (heavy) 18.50 18.72
Citric acid 2.25 2.25
Sodium peroxoborate 4H
2O 8.55 8.55
TAED 2.08 2.08
Amorphous aluminosilicate 0.86 0.97
Proteolytic enzyme (Savinase
*4.8T)) 0.65 1.00
Lipase (Lipolase
*100T))
Soil release polymers 0.55 0.55
Perfume compound 0.40 0.40
Moisture content and other----add to 100.00-----
Volume density (g/l) 700 700
Embodiment 11 and 12
The embodiment of spray-dired nothing bleaching property particulate state cleansing composition of phosphorous hydrochlorate combination that contains high concentration anionic surfactant according to the present invention is as follows:
11 12Na LAS 26.00 26.00 sodium phosphate trimers 26.00 26.00 alkali formula sodium metasilicate 9.00 9.16 sodium sulphate, (in matrix) 14.57 9.71SCMC 1.00 1.00 fluorescence agent 0.25 0.25 sodium carbonate 10.00 10.00 sodium sulphate, (radiation)-6.41 enzyme, (Maxacal*600000) 0.14 0.20 soil release polymers, 0.50 0.50EDTA, tinting material, nonionogenic tenside water, perfume compound-----add to 100.00-----volume density (g/l) 365-435 365-435
Embodiment 13 and 14
It is as follows that the high volume density that contains the phosphorous hydrochlorate combination of high concentration anionic surfactant according to the present invention does not have the embodiment of particulate state cleansing composition of bleaching property:
13 14Na LAS 26.00 26.00 sodium phosphate trimers 26.00 26.00 alkali formula sodium metasilicate 9.53 9.53 sodium sulphate, (matrix) 12.52 12.52SCMC 1.04 1.04 fluorescence agent 0.26 0.26 sodium carbonate 8.47 8.53 Wessalith CSs, (hydration) 3.00 3.00 enzyme: Savinase*/ Lipolase
*0.50 0.50 soil release agent, 0.50 0.50 perfume compound, 0.25 0.30EDTA, tinting material, water etc.-----add to 100.00----volume density (g/l) 720-800 720-800
Embodiment 15
The embodiment of bleaching graininess cleansing composition of phosphate-containing combination of high volume density that contains high concentration anionic surfactant according to the present invention is as follows: NaLAS 26.355 sodium phosphate trimers 24.478 alkali formula sodium metasilicate 8.931 sodium sulphate, (matrix) 8.215SCMC 0.938 fluorescer 0.149 sodium carbonate 5.365 Wessalith CSs, (hydration) 3.576 sodium perborate, (hydrate) 7.294TAED green particles 2.824EDTMP, (Dequest*2047) 0.471 enzyme: Savinase
*/ Lipolase
*0.224
Kazusase
*0.224 soil release agent 0.500 perfume compound 0.300EDTA, tinting material, water etc. add to 100.00 volume density 720-800g/l
Embodiment 16 and 17
The additional embodiments that a kind of nothing spray-dired and the highdensity phosphorous hydrochlorate combination of another volume is bleached property and particulate state cleansing composition according to the present invention is as follows:
16 17Na LAS 6.50 11.25 sodium phosphate trimers 28.00 39.25 alkali formula sodium metasilicate 9.00 4.13 sodium sulphate (matrix) 24.30 5.42EDTA 0.01 0.004SCMC 1.00 1.00 fluorescers 0.38 0.38 non-ionic surface active agent 7EO 3.00 5.00 soap 5.00-anti-foam particle-2.00 sodium carbonate 12.00 22.68 enzyme: Savinase*/ Lipolase
*0.22 0.70 soil release polymers, 0.50 0.50 perfume compound: 0.15 0.30EDTA, tinting material, water etc.-----add to 100.00-----volume density (g/l) 375-425 760-840
Embodiment 18
The embodiment that contains a kind of phosphorous hydrochlorate of high concentration anionic surfactant, a kind of bleaching system and a kind of optical white (photobleach) and the spray-dried granules shape cleansing composition that carbonate makes up according to the present invention is as follows:
Na?LAS 22.00
Yellow soda ash (heavy) 15.00
Tripoly phosphate sodium STPP 13.30
Alkali formula water glass 7.30
Sodium sulfate 22.30
Sodium peroxoborate 8.00
TAED 2.40
SCMC 0.35
EDTMP 0.40
Proteolytic enzyme (Savinase
*6T) 0.65
Lipase (Lipolase
*100T) 0.13
Fluorescent agent 0.20
CuPc 0.011
Soil release polymers 0.50
Perfume compound 0.25
Moisture content and other add to 100.00
Volume density 460g/l
Embodiment 19 and 20
The embodiment of particulate state cleansing composition of nothing bleaching property of high volume density that contains blended zeolite, phosphoric acid salt and carbonate buider according to the present invention is as follows:
21 22Na LAS 18.00 22.00 nonionic 7EO 1.60 2.00 soap sodium (stearate)-2.00 sodium phosphate trimer 22.50 28.00 Wessalith CSs (no hydrate) 8.00 12.00 sodium carbonate 25.00 27.00 fluorescers 0.12 0.12SCMC 0.55 0.55 sodium sulphate 19.50 0.49Savinase*6.0T/Lipolase
*100T 0.75 0.75 soil release polymers 0.50 0.50 perfume compound 0.35 0.35 moisture content and a small amount of other----add to 100.00----volume density (g/l) 850 840
Claims (10)
1. one kind is used for the cleansing composition of laundering of textile fabrics, comprising:
(a) a kind of organic surface active agent system that contains one or more anionics, non-ionic type, cationic, both sexes or amphoteric ionic surfactant of 2-50% (wt),
(b) 10-80% (wt) contain one or more a kind of buider components inorganic or the organic washing buider,
(c) a kind of soil release polymers of water-soluble or water dispersible of soil release significant quantity,
(d) can choose other cleaning composition wantonly and add to 100% (wt), it is characterized by the cleaning buider component (b) of the tripoly phosphate sodium STPP that contains at least 5% (wt) (according to cleansing composition), and soil release polymers (c) is a kind of water-soluble or sulfonated polyester of water dispersible, and it is as follows to contain monomer unit:
(i) a kind of not Sulfonated aromatic diacid monomer (A),
(ii) a kind of Sulfonated aromatic diacid monomer (SA),
(iii) optional a kind of hydroxylation fragrance or fat diacid monomer (HA), its amount can replace (A) of 50% (mole) nearly and/or (SA),
(iv) a kind of polyvalent alcohol (P) is selected from ethylene glycol, propylene glycol, Isopropanediol, glycerol, 1,2,4-trihydroxybutane and 1,2, and 3-trihydroxybutane and oligomer thereof with 1-8 monomer unit, the sulphur content of polyester should be in the scope of 0.5-10% (wt).
2. as the cleansing composition in the claim 1, it is characterized by the polyester (C) that it contains 0.01-10% (wt).
3. as the cleansing composition in the claim 2, it is characterized by the polyester (C) that it contains 0.1-5% (wt).
4. as each cleansing composition in the claim of any front, it is characterized by the tripoly phosphate sodium STPP that it contains 5-50% (wt).
5. each cleansing composition as in any aforementioned claim is characterized by the tripoly phosphate sodium STPP that it contains at least 10% (wt).
6. as the cleansing composition in the claim 5, it is characterized by the tripoly phosphate sodium STPP that it contains 20-50% (wt).
7. as the cleansing composition of claim 1-5 in any one, it is characterized by cleaning buider system and further contain one or more other inorganic buiders, described inorganic buider is selected from sodium orthophosphate, trisodium phosphate, yellow soda ash, zeolite A and zeolite MAP.
8. as one cleansing composition in any aforementioned claim, it is characterized by the organic surface active agent system and contain a kind of aniorfic surfactant of choosing wantonly with a kind of nonionic surface active agent bonded vitriol or Sulfonates.
9. as the cleansing composition in the claim 8, it is characterized by anion surfactant and comprise primary alkyl sulfuric ester and/or alkyl ether sulphate and/or phenylbenzimidazole sulfonic acid salt.
10. one cleansing composition as in any aforementioned claim, to it is characterized by it be granular and have the volume density that is at least 650g/l.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9524493.5 | 1995-11-30 | ||
| GBGB9524493.5A GB9524493D0 (en) | 1995-11-30 | 1995-11-30 | Detergent compositions containing soil release polymers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1207764A true CN1207764A (en) | 1999-02-10 |
| CN1113087C CN1113087C (en) | 2003-07-02 |
Family
ID=10784701
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96199758A Expired - Fee Related CN1113087C (en) | 1995-11-30 | 1996-11-11 | Detergent compositions contg. soil release polymers |
Country Status (15)
| Country | Link |
|---|---|
| EP (1) | EP0977827A1 (en) |
| CN (1) | CN1113087C (en) |
| AR (1) | AR004811A1 (en) |
| AU (1) | AU698202B2 (en) |
| BR (1) | BR9611677A (en) |
| CA (1) | CA2238479A1 (en) |
| CZ (1) | CZ166898A3 (en) |
| GB (1) | GB9524493D0 (en) |
| HU (1) | HUP9903487A3 (en) |
| IN (1) | IN187473B (en) |
| PL (1) | PL184578B1 (en) |
| SK (1) | SK71498A3 (en) |
| TR (1) | TR199800963T2 (en) |
| WO (1) | WO1997020021A1 (en) |
| ZA (1) | ZA969727B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024032573A1 (en) * | 2022-08-08 | 2024-02-15 | Specialty Operations France | Biodegradable soil release polyester polymer and cleaning composition comprising same |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19837604A1 (en) † | 1998-08-19 | 2000-02-24 | Henkel Kgaa | Use of soil-releasing polymers in fixing perfumes to various surfaces and use of perfumes in improving the detergent effect of these polymers in textile washing agents or shampoos |
| GB0229146D0 (en) | 2002-12-13 | 2003-01-15 | Unilever Plc | Polymers and laundry detergent compositions containing them |
| GB0229147D0 (en) | 2002-12-13 | 2003-01-15 | Unilever Plc | Polymers and laundry detergent compositions containing them |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57143400A (en) * | 1981-02-27 | 1982-09-04 | Nippon Synthetic Chem Ind | Detergent composition |
| AU581417B2 (en) * | 1984-11-16 | 1989-02-23 | Ciba Specialty Chemicals Water Treatments Limited | Water soluble polymers and dispersions containing them |
| US4877896A (en) * | 1987-10-05 | 1989-10-31 | The Procter & Gamble Company | Sulfoaroyl end-capped ester of oligomers suitable as soil-release agents in detergent compositions and fabric-conditioner articles |
| SG76454A1 (en) * | 1988-08-26 | 2000-11-21 | Procter & Gamble | Soil release agents having allyl-derived sulfonated end caps |
| JPH0321698A (en) * | 1989-06-20 | 1991-01-30 | Sanyo Chem Ind Ltd | Polyelectrolyte builder and detergent composition |
| EP0707626B1 (en) * | 1993-07-08 | 1997-05-02 | The Procter & Gamble Company | Detergent compositions comprising soil release agents |
| FR2720400B1 (en) * | 1994-05-30 | 1996-06-28 | Rhone Poulenc Chimie | New sulfonated polyesters and their use as an anti-fouling agent in detergent, rinsing, softening and textile treatment compositions. |
-
1995
- 1995-11-30 GB GBGB9524493.5A patent/GB9524493D0/en active Pending
-
1996
- 1996-11-11 AU AU75714/96A patent/AU698202B2/en not_active Ceased
- 1996-11-11 TR TR1998/00963T patent/TR199800963T2/en unknown
- 1996-11-11 CZ CZ981668A patent/CZ166898A3/en unknown
- 1996-11-11 BR BR9611677A patent/BR9611677A/en not_active IP Right Cessation
- 1996-11-11 PL PL96327008A patent/PL184578B1/en unknown
- 1996-11-11 EP EP96938202A patent/EP0977827A1/en not_active Withdrawn
- 1996-11-11 HU HU9903487A patent/HUP9903487A3/en unknown
- 1996-11-11 SK SK714-98A patent/SK71498A3/en unknown
- 1996-11-11 CA CA002238479A patent/CA2238479A1/en not_active Abandoned
- 1996-11-11 WO PCT/EP1996/004994 patent/WO1997020021A1/en not_active Application Discontinuation
- 1996-11-11 CN CN96199758A patent/CN1113087C/en not_active Expired - Fee Related
- 1996-11-19 IN IN550BO1996 patent/IN187473B/en unknown
- 1996-11-20 ZA ZA9609727A patent/ZA969727B/en unknown
- 1996-11-29 AR ARP960105419A patent/AR004811A1/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024032573A1 (en) * | 2022-08-08 | 2024-02-15 | Specialty Operations France | Biodegradable soil release polyester polymer and cleaning composition comprising same |
Also Published As
| Publication number | Publication date |
|---|---|
| BR9611677A (en) | 1999-03-02 |
| PL327008A1 (en) | 1998-11-09 |
| GB9524493D0 (en) | 1996-01-31 |
| TR199800963T2 (en) | 1998-12-21 |
| HUP9903487A2 (en) | 2000-03-28 |
| IN187473B (en) | 2002-05-04 |
| AR004811A1 (en) | 1999-03-10 |
| CN1113087C (en) | 2003-07-02 |
| AU7571496A (en) | 1997-06-19 |
| SK71498A3 (en) | 1998-12-02 |
| CZ166898A3 (en) | 1998-10-14 |
| EP0977827A1 (en) | 2000-02-09 |
| PL184578B1 (en) | 2002-11-29 |
| CA2238479A1 (en) | 1997-06-05 |
| ZA969727B (en) | 1998-05-20 |
| WO1997020021A1 (en) | 1997-06-05 |
| HUP9903487A3 (en) | 2002-04-29 |
| AU698202B2 (en) | 1998-10-29 |
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