CN1078747A - The modified poly ester that is used for washing of cotton-containing fabrics - Google Patents
The modified poly ester that is used for washing of cotton-containing fabrics Download PDFInfo
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- CN1078747A CN1078747A CN 93105732 CN93105732A CN1078747A CN 1078747 A CN1078747 A CN 1078747A CN 93105732 CN93105732 CN 93105732 CN 93105732 A CN93105732 A CN 93105732A CN 1078747 A CN1078747 A CN 1078747A
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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
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
-
- 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
-
- 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
- C11D17/065—High-density particulate detergent compositions
-
- 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
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38645—Preparations containing enzymes, e.g. protease or amylase containing cellulase
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
- D06M15/03—Polysaccharides or derivatives thereof
- D06M15/05—Cellulose or derivatives thereof
- D06M15/07—Cellulose esters
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
- D06M15/15—Proteins or derivatives thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/507—Polyesters
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
- D06M16/003—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic with enzymes or microorganisms
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Textile Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Microbiology (AREA)
- Biochemistry (AREA)
- Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Molecular Biology (AREA)
- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
- Cleaning Implements For Floors, Carpets, Furniture, Walls, And The Like (AREA)
Abstract
The present invention relates to known modified poly ester with selection of decontamination is used as the purposes of the clean-out system of cotton-containing fabrics, therefore with compare with the several cycles of stain remover pattern work, the present invention can produce cleaning effect on this fabric only after disposable cycles of washing.
The present invention also comprises and contains described modified poly ester and a kind of cellulase, or a kind of detergent component that is divided into powder and/or the agent of a kind of anti-soil dirt redeposition.
Description
The present invention relates to adopt known polymer-modified clean-out system as cotton-containing fabrics with soil release characteristics; The invention still further relates to and contain described some polymer-modified detergent component.
The product that is used to do washing contains a large amount of compositions with some basic benefit.For example, cleaning product is formulated by the de-sludging surfactant system, so that remove the dirt in the clothing in washing process.These cleaning products can also comprise the composition with benefit (for example softening and static resistance) of adjusting fabric in washing process.
Except standard wash, beyond the softening and anlistatig benefit, washing composition can also produce other needed characteristic.A kind of is to make the fabric that is formed by weaving by trevira have decontamination.The hydrophobic property of polyester textile makes it be difficult to washing, when particularly relating to oily soil and oily stain.Preferred " infiltration " fabric of oily soil or stain, the result, oily soil or stain are difficult in the water washing process and are removed.
Find that some polyester is particularly suitable in detergent component as the decontamination compound.In washing process, these decontamination polyester are adsorbed on the fabric face that immerses in the washings.The polyester of absorption then after fabric is by taking-up and drying from washings, has formed one deck hydrophilic film on fabric face.This tunic is contained the decontamination polyester in ensuing fabric washing a kind of detergent component is changed.
This kind polyester is for example being done openly in the United States Patent (USP) 4,116,885 and 4,711,730.
Having made further effort aspect the improvement decontamination polyester, for example, this improved polyester has been described in EPA272033.Recently, EPA311372 has described the further improved stain remover that contains the end capped polyester of sulfo-aroyl.
Find at present pleasantly surprisedly, not only polyester textile is played the stain remover effect, but also can in the major cycle of a washing process, from cotton-containing fabrics, remove dirt and soil dispersion at some modified poly ester described in the EPA311342.
Find that also the modified poly ester here is with cellulase and the dirt redeposition agent of some anti-soil or be divided into that powder uses or use with a kind of nonionogenic tenside of selection, can in cotton-containing fabrics, produce beyond thought improved cleaning advantage.
The present invention is based on such discovery, promptly the modified poly ester in this selection can work in " tensio-active agent " mode at cotton-containing fabrics, so, several cycles when working according to the stain remover mode is compared, it can produce cleaning effect in this kind fabric only after the once washing circulation.
Modified poly ester
The modified poly ester here is the random copolymers of following material: dimethyl terephthalate (DMT), sulfo-dimethyl isophthalate, the pure and mild 1-2 propylene glycol of ethylene, end group at first contains the thiobenzoic acid ester and secondly contains ethylidene glycol and/or propylene glycol monoester.The target compound that goes for is the polymkeric substance that two ends are sealed by the thiobenzoic acid ester group, " at first ", and in this article, most of here described multipolymer is all end capped by the thiobenzoic acid ester.Therefore yet some multipolymer is not totally enclosed, and its end group can comprise the monoesters of the ethylidene glycol and/or the third 1-2 glycol, and its end group " secondly " is made of this class material.
Here selected polyester contains 46% terephthalic acid of about weight, 16% the third 1-2 glycol of about weight, 10% ethylidene glycol of about weight, 15% sulfo-m-phthalic acid of 13% dimethyl methyl yl benzoic acid of about weight and about weight, and have about 3.000 molecular weight.In EPA311342, describe polyester and preparation method thereof in detail.
In addition, find that modified poly ester of the present invention and cellulase and/or some are divided into powder and/or some nonionogenic tenside and combine to use and produced superior cleaning performance.
Cellulase
The cellulase that can combine use with the modified poly ester here can be any bacterium or fungal cellulase, and they have the best pH value between 5～9.5.
At GB-A-2075028; Suitable cellulase is disclosed among GB-A-2095275 and the DE-OS-2447832.
The example of the plain enzyme of this fibrid is (grey mutation thermoidea Humicola) for those by unusual Humicola (Humicola insolens).The cellulase that produces, be that cellulase and the 212-that DSM 1800 produces generates cellulase of the fungi that belongs to Aeromonas and the cellulase that extracts from the liver pancreas of extra large mollush (Dolabella Auricula Solander) particularly by Humicola.
The cellulase that adds in the component of the present invention can be a no dust powder form (for example " marumes " or " bead "), or be a kind of liquid form (therein, cellulase is to provide with the form that is suspended in for example a kind of nonionogenic tenside or be dissolved in the cellulase enriched material in a kind of water medium).
Preferred as used herein cellulase is characterised in that, according in the C14CMC-method described in the EPA350098, with 25 * 10 of washing test solution weight
-6The cellulase protein content of %, described cellulase can be removed at least 10% the radiolabeled carboxymethyl-Mierocrystalline cellulose of immobilization.
Most preferred cellulase is those cellulases of describing in international patent application Wo 91/17243.For example, a kind of preparation that can be used on the cellulase in the component of the present invention can consist essentially of a kind of uniform endo-dextranase composition, this composition can carry out immune response with a kind of antibody, this antibody is by unusual detritus mycin (Humicola insolens at a kind of, DSM 1800) the highly purified 43KD cellulase that obtains cultivates, perhaps mentioned component and described 43KD endo-dextranase allogeneic.
In general, the modified poly ester by will be here is included in the detergent component that contains other cleaning ingredients with 0.025%～10% content of composition weight, obtains polyester in the advantage aspect the cleaning of cotton-containing fabrics.
Perhaps, can adopt a kind of form of detergent additive to join the modified poly ester here in the cycles of washing respectively; Described additive may contain other decontamination active substance that chooses, as the redeposition agent of anti-soil dirt be divided into powder, and/or cellulase; Particularly, the modified poly ester here can be used to cotton-containing fabrics is carried out pre-treatment before the main cycles of washing of a washing process.
Detergent component
The detergent component here can be in a liquid state form or particulate state, and preferably directly put into rotating cylinder rather than indirect by the shell of washing machine.This requirement very easily reaches by following manner, is about to component and puts into a sack or container, and then along with stirring, temperature raises or is immersed in the washings in the rotating cylinder and discharges from sack or container component in the beginning of cycles of washing.This container can be with treating that laundering of textile fabrics is placed in the rotating cylinder.Perhaps can reequip washing machine itself and its permission is directly joined component in the rotating cylinder, for example establish divider at the entrance door place.
When component is in a liquid state form, can adopt rigid container (as described in the EPA151549), the detergent component here preferably is particulate state, and container will be for flexibility, as a sack or box.Sack can have fabric structure, scribbles the fluid-tight protecting materials of one deck on this structure so that inclusion is retained in the bag, as at EPA0, described in 018,678.Perhaps above-mentioned sack can be made of the water-insoluble synthesizing polymeric material of sealing of a kind of edge or sealing, and this material is designed to can break in water medium, as described in the EPAs0011500,0011501,0011502 and 0011968.In a kind of water easily the appropriate form of broken closure comprise a kind of water soluble adhesive of edge setting and the sealing along the box that constitutes by a kind of impermeable polymer film (as polyethylene or polypropylene).
In the distortion of a kind of sack or container products form, can adopt the synusia product, its center flexible layer is impregnated and/or covers with a kind of composition, adds that then one or more skins are to produce the aesthetic effect of fabric sample.Each layer is together salable maybe can separately to be contacted with water so that apply or the release of impregnation of matters so that in use keep to connect.
A kind of stratiform thing form of conversion comprises that a layer projection or distortion is to form a series of case type container, detergent component can be placed in one by exact dosage desired, and the second layer is placed on the first layer, and seals with the first layer on those zones of two-layer contact between the case type container.Before can adding in the entry with (particularly) pasty state or fusion placement and each layer of stratiform thing Ying Zaiqi, composition prevents that the inclusion in the case type container from flowing out.Each layer can separate maybe can connect together and contact with water, and unique requirement is exactly that this structure should allow the inclusion in the case type container to discharge in solution rapidly.The problem that the quantity of case type container per unit area Substrate is just selected, but generally between every square metre 500 and 25,000, do not wait.
Especially also comprise sponge, paper and yarn fabric or nonwoven fabric according to this suitable material that can be used as each layer of flexible layer thing on the one hand of the present invention.
Yet, implement preferred embodiment according to washing process of the present invention comprise adopt a reusable divider, this divider to have to allow liquid by but the outer wall of saturating solids component not.
This class device has been done open in EPAS 0343069 and 0344070.The a application in back discloses a device, and comprising a flexible sheets that is bag shape that extends out from a support ring that limits an opening, described opening is suitable for the goods that a cycles of washing that is enough in cycles of washing is used are packed in the bag.The part of washing medium flows in the bag by opening, the dissolving goods, and solution then outwards flows in the washing medium by opening.Support ring is furnished with a shading unit and flows out to prevent the undissolved goods of wetted, and this device generally comprises the wall that radially extends that extends out from a central protuberance that is the spoke wheel type, the helical similar structures of perhaps a kind of wall.
Contain a kind of tensio-active agent in the detergent ingredients here.
A large amount of tensio-active agents can be used in the detergent ingredients.Authorize on May 23rd, 1972 in the United States Patent (USP) 3,664,961 of Norris and provided a kind of typical arrangement, the kind of negatively charged ion, nonionic, both sexes and zwitterionic classes tensio-active agent and these tensio-active agents.
The mixture of anion surfactant is at this particularly suitable, particularly sulfonate and the sulfate surfactant mixture with 5: 1～1: 2 weight ratio, and preferred weight ratio is 3: 1～2: 3, is more preferably 3: 1～1: 1.Preferred sulfonate comprises having 9～15 carbon atoms in its alkyl group of such alkyl sulfate, and being in particular 11～13 carbon atoms and α-sulfonation fatty acid methyl ester lipid acid wherein is from C
12-C
18Fat source is preferably from C
16-C
18Obtain in the fat source.In each case, positively charged ion is a kind of basic metal, preferably sodium.Preferred sulfate surfactant is the alkyl-sulphate that 12～18 carbon atoms are arranged in the groups, preferably with in alkyl group, have 10～20, be preferably mixture 10～16 carbon atoms and that have the ethoxy sulfate of 1～6 average ethoxyquin degree.The example of the preferred alkyl vitriol here is (animal) fat alkyl-sulphate, cupraol alkyl-sulphate and C
14-15Alkyl-sulphate.Positively charged ion in every kind of example or alkali metal cation are preferably sodium.
A kind of useful especially in the present invention nonionogenic tenside is a kind of condenses that has the ethylene oxide of hydrophobic parts, a kind ofly have 5～17 to produce, be preferably 6～14, more preferably the tensio-active agent of 7～12 average hydrophilic-lipophilic balances (HLB).Hydrophobicity (lipophilicity) part in fact can be aliphatic series or aromatics, and the length with the polyoxyethylene group of any specific hydrophobic group condensation can be regulated easily so that obtain a kind of water-soluble cpds, and this compound has needed quality of balance between wetting ability and hydrophobicity element.
Particularly preferred this class nonionogenic tenside is C
9～C
15The primary aliphatic alcohols ethoxylate contains 3～8 mole ethylene oxides in wherein every mol of alcohol, contains the C of 6～8 mole ethylene oxides in particularly every mol of alcohol
14～C
15Primary alconol contains the C of 3～5 mole ethylene oxides in every mol of alcohol
12-C
15Primary alconol and composition thereof.
Another kind of suitable ionic surfactant pack is drawn together has overall texture formula RO(CnH
2NO) the alkyl polyglucoside compound of tZx, wherein Z is a part taking from glucose; R is a saturated hydrophobic alkyl group, wherein contains 12～18 carbon atoms; T is 0～10, and n is 2 or 3; X is 1.3～4, and this compound comprises unreacted Fatty Alcohol(C12-C14 and C12-C18) that is less than 10% and the short-chain alkyl polyglucoside that is less than 50%.The application that in EP-B0070077,0075996 and 0094118, discloses this compounds and be in the suds.
Be suitable for make nonionogenic tenside have structural formula in addition
Poly-hydroxy fatty acid amine tensio-active agent, R wherein
1Be H, or R
1Be C
1-4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or its mixture, R
2Be C
5-21Alkyl, and Z is poly-hydroxy alkylene (it has a straight-chain alkyl, and has at least three hydroxyls that directly are connected with this chain) or a kind of its alkoxy derivative.Preferably, R
1Be methyl, R
2Be straight chain C
11-15Alkyl or alkenyl, as coconut alkyl or its mixture, and Z obtains from a kind of reducing sugar (as glucose, fructose, maltose, lactose) in a kind of reduction amination.
Also having a kind of tensio-active agent is the semi-polarity tensio-active agent, as amine oxide.Suitable amine oxide is selected from single C
8-C
20, be preferably C
10-C
14N-alkyl or alkenyl amine oxide and propylene-1, the 3-diamines, wherein Sheng Xia N position is replaced by methyl, hydroxyethyl or hydroxypropyl group.
Another kind of tensio-active agent is an amphoterics, as the polyamine class.
Cats product also can be used in the detergent component here, and suitable quaternary ammonium surfactant is selected from single C
8-C
16, preferably be selected from C
10-C
18N-alkyl or alkenyl ammonium surfactant, wherein Sheng Xia N position is replaced by methyl, hydroxyethyl or hydroxypropyl group.
Surfactant-based mixture is preferred, more particularly negatively charged ion-nonionic and negatively charged ion-nonionic-cation mixt in addition.Particularly preferred mixture discloses in English Patent 2040987 and EPA0087914.Detergent component can contain the tensio-active agent of weight 1%～70%, but usually tensio-active agent is with 1%～30% of weight, and 10～25% the content that is more preferably weight is present in the component here.
The detergent component here also contains a kind of washing assistant.
Builder material generally will exist with 5%～80% content of detergent component here.The component here do not contain or do not contain substantially comprise phosphatic washing assistant (being substantially free of of being limited here be meant be less than total decontamination lotion promoter system 1%), and the builder system here comprises water soluble detergency promoter, water-insoluble washing assistant or its mixture.
The water-insoluble washing assistant can be a kind of mineral ion cross-linked material, is generally a kind of synthetic zeolite of inorganic hydrated aluminosilicate material, particularly a kind of hydration, as hydrated zeolite A, X, B or HS.
Preferred silico-aluminate ion exchange material has crystalline network formula MZ ((ALO
2) Z(SiO
2) y) xH
2O wherein M is that a kind of calcium is changed positively charged ion, and z and y are at least 6; The mol ratio of z and y is 1.0～0.5, and x is at least 5, is preferably 7.5～276, more preferably 10～264.The silico-aluminate material is hydrated form, and is preferably crystalline, wherein contains 10%～28%, more preferably 18%～22% water.
The feature of above-mentioned silico-aluminate ion exchange material is that also its particle diameter size is 0.1～10 micron, is preferably 0.2～4 micron.Utilize routine analysis means (carrying out microscopic measurement) when measuring in this used term " particle diameter size " expression, the average particulate diameter size of given ion exchange material as utilizing scanning electronic microscope.The feature of silico-aluminate ion exchange material is that also its calcium ion exchange capacity (by anhydrous algorithm) is at least the CaCO of 200 milligrams of silico-aluminates
2Water hardness equivalent is generally in 300～352 milligramequivalent scopes.The feature of the silico-aluminate ion exchange material here also is its calcium ion-exchanged rate of describing in detail in GB-1429143.
The silico-aluminate ion exchange material that can be used in the present invention practice is commercial available, and can be naturally occurring material, but preferably synthetic obtains.At United States Patent (USP) 3,985, a kind of method for preparing the silico-aluminate ion exchange material is disclosed in 669.Can be used on here preferred synthetic crystalline silico-aluminate ion exchange material can by specify zeolite A, zeolite B, X zeolite, zeolite HS with and composition thereof obtain.In a particularly preferred embodiment, crystalline silico-aluminate ion exchange material is zeolite A and has structural formula
Wherein x is 20～30, particularly 27.Has structural formula
X zeolite, and have structural formula
Na
6((ALO
2)
6(SiO
2)
6) 7.5H
2O) zeolite HS also suits.
Another kind of suitable water-fast inorganic builders material is lamellated silicate, for example SKS-6(Hoechst).SKS-6 is a kind of water glass (Na that contains
2Si
2O
5) the crystal layered silicate.Ca
++/ Mg
++High binding ability mainly be cationic exchange mechanism.In hot water, the easier dissolving that becomes of this material.
Water-soluble additive can be the carboxy acid salt chelator of monomeric or oligomer.
The suitable carboxylate salt that contains a carboxylic group comprises lactic acid, and the derivative of oxyacetic acid and ether thereof is as disclosed in belgian patent 831368,821369 and 821370.The polycarboxylate that contains two carboxylic groups comprises the water-soluble salt of following acid: succsinic acid, propanedioic acid, (ethylenedioxy), diacetic acid, toxilic acid, diethyl alkyd, tartrate, tartronic acid and fumaric acid, and in German Patent 2446686 and 2446687 and United States Patent (USP) 3, sulfinyl carboxylate salt described in ether carboxylate salt of describing in 935,257 and the belgian patent 840623.The polycarboxylate that contains three carboxyls is particularly including water-soluble citrate, aconitate and Citrate trianion, and succinate derivative, as in English Patent 1,379, the carboxymethyl oxysuccinic acid described in 241, at the newborn oxygen base succinate described in the Netherlands patent applications 7205873 with at the material of oxidation polycarboxylate described in the English Patent 1387447, as 2-Evil-1,1,3-tricarballylic acid salt.
The polycarboxylate that contains four carboxyls is included in disclosed oxidation disuccinate in the English Patent 1261829,1,1,2,2-ethane tetracarboxylic acid salt, 1,1,3,3-propane tetracarboxylic acid salt and 1,1,2,3-propane tetracarboxylic acid salt.Contain the substituent polycarboxylate of sulfo group be included in English Patent 1398421 and 1398422 and in United States Patent (USP) 3936448 disclosed thio succinate derivative and the sulfonation pyrolytic Citrate trianion in English Patent 1082179, described, contain the substituent polycarboxylate of phosphine and in English Patent 1439000, disclose.
Alicyclic ring and heterocycle adoption carboxylate salt comprise ring-pentaene-cis, cis, suitable-the tetracarboxylic acid hydrochlorate, cyclopentadiene pentacarboxylic acid salt, 2,3,4,5-tetrahydrofuran (THF)-cis, cis, suitable-tetracarboxylic acid hydrochlorate, 2,5-tetrahydrofuran (THF)-suitable-dicarboxylate, 2,2,5,5-tetrahydrofuran (THF)-tetracarboxylic acid hydrochlorate, 1,2,3,4, the carboxymethyl derivant of 5-hexane-hexacarboxylic acid salt and polyvalent alcohol (as sorbyl alcohol, mannitol and Xylitol).The aromatics polycarboxylate comprises mellitic acid, 1,2,4,5-pyromellitic acid and phthalic acid derivative, and these have all done open in English Patent 1425343.
In all above-mentioned substances, most preferred polycarboxylate is the hydroxycarboxylate that each molecule contains 3 following carboxyls, particularly Citrate trianion.
The preferred builder system that is used for the preferred granular detergent component here comprises the mixture of a kind of water-insoluble silico-aluminate washing assistant (as zeolite A) and a kind of water-soluble carboxylate sequestrant (as citric acid).
Other builder material that can constitute a builder system part of the present invention comprises inorganics (as alkaline carbonate, supercarbonate, silicate) and organism (as organic phosphonate, polyalkylene phosphonic acids ammonia and poly carboxylic acid ammonia).
In a preferred embodiment of the invention, the detergent component here will contain a kind of cellulase, and as mentioned above, content is 0.025%～10% of component.
In another preferred embodiment of the present invention, detergent component here or detergent additive will contain anti-soil dirt redeposition agent or the soil-suspending agent that modified poly ester a kind of and combines here.
Comprise derivatived cellulose at this anti-redeposition agent and soil-suspending agent that is suitable for, as methylcellulose gum, carboxymethyl cellulose and Natvosol, the poly carboxylic acid of homopolymerization or copolymerization or their salt and polyamino acid compound.This base polymer is included in detailed disclosed polyacrylate and maleic anhydride-acrylic acid multipolymer among the EPA137669.And the multipolymer of maleic anhydride and ethene, methylvinylether or methacrylic acid, maleic anhydride accounts for 20% of multipolymer mole number at least.Those polyamino acid compounds that obtain from aspartic acid are for example disclosed in UK Patent Application 9226942.2.
These materials are used with 0.025%～5% the content that accounts for composition weight here usually.
Detergent component of the present invention preferably is particulate state, more preferably is " compacting " shape, promptly has certain density, and this density is higher than the density of conventional detergent component.The component preferred density is here measured down at 20 ℃, in 550～950 grams per liter scopes, preferably, in 650～850 grams per liter scopes.
The dosage of inorganic filling salt can reflect (with regard to component) " compacting " state in this most preferred composition of the present invention; Inorganic filling salt is for the conventional composition that is in pulverous detergent component, in conventional detergent component, fills salt and exists with basic content (be generally total composition weight 17～35%).
In the most preferred component here, fill salt, preferably be no more than 10%, most preferably be no more than 5% content existence to be no more than 15% of total composition weight.
Inorganic filling salt (as represented in component of the present invention) is selected from the vitriol and the muriate of basic metal and alkaline-earth metal.
A kind of preferred filling salt is sodium sulfate.
Component of the present invention generally comprises the selectable composition of a part that constitutes detergent component of the present invention.The example of this selectable composition is: enzyme, and white dyes, SYNTHETIC OPTICAL WHITNER, bleach-activating agent, inhibitor, anti-caking agent, dyestuff and pigment, these compositions can add with different dosage on demand.
Enzyme (as proteolytic enzyme, lipase or amylase) is the composition that needs especially in the component here.
Preferred white dyes is corresponding negatively charged ion, and its example is: 4,4
1-two-(2-ethylene glycol amine-4-anilino-S-triazine-6-amino) stilbene-2: 2
1Disulfonic acid disodium, 4-4
1-two-(amino stilbene-2: 2 of 2-morpholino-4-anilino-S-triazine-6-
1-disulfonic acid disodium, 4,4
1-two-(2,4-dianiline base-S-triazine-6-amino) stilbene-2: 2
1-disulfonic acid disodium, 4
1, 4
11-two-(2,4-dianiline base-S-triazine-6-amino) stilbene-2-sulfonic acid one sodium, 4,4
1-two-(2-anilino-4-(N-methyl-N-2-hydroxyethyl ammonia)-S-triazine-6-amino) stilbene-2,2
1-disulfonic acid disodium, 4,4
1-two-(4-phenyl-2,1,3-triazole-2-yl)-stilbene-2,2
1Disulfonic acid disodium, 4,4 '-two-(2-anilino-4-(1-methyl-2-hydroxyethyl ammonia)-S-triazine-6-amino) stilbene-2,2
1Disulfonic acid disodium, and 2(stilbene radicals-4
11-naphtho--1
1, 2
1: 4,5)-1,2,3-triazoles-2
11-sodium sulfonate.
Can adopt any particulate inorganic ortizon SYNTHETIC OPTICAL WHITNER, its content is 3%～40% of composition weight, is more preferably 8%～25%, and most preferred be 12%～20% of composition weight.The example of preferred this SYNTHETIC OPTICAL WHITNER is the monohydrate and the tetrahydrate of Sodium peroxoborate, percarbonate and composition thereof.
Another kind preferably respectively the blended composition be percarboxylic acids SYNTHETIC OPTICAL WHITNER precursor, be commonly referred to bleach-activating agent, this composition is preferably with in the spherical or block adding granulated detergent.In English Patent 1586769 and 2143231, disclose the suitable example of this compounds, and in european patent application 0062523, described and a kind of they are formed globular method.The preferred embodiment of this compound is tetra-acetylated ethylene diamine and 3,5,5 trimethyl acetyl phenolsulfonic acid sodium.
Usually 0.5%～10% content with composition weight uses bleach-activating agent, and more frequent is 1%～8%, and preferably composition weight 2%～6%.
Another kind of selectable composition is a suds suppressor, for example: siloxanes and silica one mixture of siloxanes.Siloxanes generally can be represented with the alkylation polysiloxane, and silica uses with form in small, broken bits usually, for example silica aerogel and xerogel and all kinds of hydrophobicity silica.These materials can be used as that particle is involved enters, and wherein suds suppressor preferably is included in water-soluble or water is diffusible does not see through in the carrier of on-surface-active detergent basically releasedly.Perhaps, suds suppressor is dissolved in or is spread in a kind of liquid carrier and by spraying and is applied on one or more other compositions.
As mentioned above, the silicone suds suppressor of Shi Yonging can comprise a kind of previously described all kinds of alkylation siloxanes and the mixture of solid silica.This mixture prepares by siloxanes being made an addition to the solid silica surface.A kind of preferred silicone suds suppressor is by the representative of a kind of hydrophobic silaneization (preferably trimethylammonium-silanization) silica, it has from the granular size of 10 millimicrons～20 millimicrons of scopes, with the particular table area more than 50 meters squared per gram, it is mixing about 1: 1～1: 2 weight ratio of silanization silica with siloxanes with the dimethyl siloxane with about 500～200,000 molecular weight at the beginning.
A kind of preferred silicone suds suppressor is disclosed in people's such as Bartollota United States Patent (USP) 3933672.Other useful especially suds suppressor is at the self-emulsifying silicone suds suppressor described in the German patent application DOTS 2646126 of publication on April 28th, 1977.An example of this compound is the DC-544 that can buy from Dow Corning, and this is a kind of siloxanes/glycol copolymer.
Usually with 0.001%～2% of composition weight, be preferably 0.01%～1% content and use above-mentioned suds suppressor.Preferably add foaming regulator with isolating particle form, and do like this and comprise other suds suppressor at this allowing, as C20-C24 lipid acid, the high molecular of Microcrystalline Wax and ethylene oxide and propylene oxide (MW) multipolymer, otherwise can influence the diffusibility of matrix on the contrary.This foam adjusting particulate method that constitutes is disclosed in people's such as the Bartolotta that mentions in the above the United States Patent (USP) 3,933,672.
In detergent component according to the present invention, also can add fabric softener.These preparations can be inorganic or organic on kind, disclose several inorganic tenderizers in GB-A-1400898, for example green clay.
The organic fabric tenderizer comprises water-soluble tertiary amine, as described in the GB-A-1400898.The organic fabric tenderizer also is included in disclosed water-insoluble tertiary amine among GB-A-1514276 and the EP-B-0011340 and the combining and disclosed long-chain diamino in EP-B-0242919 of disclosed above-mentioned tertiary amine and single C12-C14 quaternary ammonium salt in EP-B-0026527 and EP-B-0026528.Other useful organic composition of fabric-softening system comprises the high-molecular weight oxidic polyethylene, as disclosed in EP-A-0299575 and 0313146.
In this preferred detergent granules component, the content of green clay is usually in 5%～20% of weight, and is preferred in 8%～15% scope, and material to be added is then as the dry mixed composition of remainder in the component.The organic fabric tenderizer, as water-insoluble tertiary amine or long-chain diamino, with weight 0.5～5% and generally add with 1%～3% content, and with weight 0.1%～2% and generally add high-molecular weight oxidic polyethylene and water-soluble cationic material with 0.15%～1.5% content.These materials generally are added in the spraying drying part of component, although add with the dry mixed particle in some cases, or as a kind of melt liquid it are sprayed on that add on the another kind of solids component in the component may be more more convenient.
Also can comprise dye transfer inhibitor in the component here, as having a polyvinylpyrrolidone of 5000～2200 molecular weight, it is present in the preferred detergent granules component here with the content of for example putting into the described polyvinylpyrrolidone of 5～500 mg/litre in washing soln usually.
Embodiment
The following example is used for illustrating the present invention and is convenient to understand the present invention.
Abbreviation to each composition has following meanings:
LAS: linear alkyl benzene sulphonate
The AS:C14-C15 alkyl sodium sulfonate
The TAS:(animal) lipidol sodium sulfate
FA45E7: with the Fatty Alcohol(C12-C14 and C12-C18) (C14-C15) of about 7 mole ethylene oxide ethoxylations
FA25E3: with the Fatty Alcohol(C12-C14 and C12-C18) (C12-C15) of about 3 mole ethylene oxide ethoxylations
The CAT:C12 alkyl trimethyl ammonium chloride
Clay: green clay
Zeolite A4: sodium salt with zeolite 4A of 1～10 micron particle size
SKS-6: crystalline layered silicate (Hoechst)
CopolymerAA/MA: the multipolymer of vinylformic acid and toxilic acid
PAA: polyacrylate polymkeric substance
CMC: carboxymethyl cellulose
Phosphonate: sodium ethylenediamine tetramethylenephosphonate
EDTA: sodium ethylene diamine tetracetate
PB
1：NaBO
2·H
2O
2
TAED: tetra-acetylated ethylene diamine
PVP: polyvinylpyrrolidone
Silicate（R＝n）：SiO
2/Na20＝n
Callulase: according to above-described 43KD class
Amylase：Termamyl：60T（Novo-Nordisk）
Lipase：Lipolase 100T（Novo-Nordisk）
Protease：Savinase 4T（Novo-Nordisk）
SSS: press down foam system (silica/mixture of siloxanes)
The modified poly ester that uses in the following example is corresponding to the kind described in the claim 2 here.
The preparation method is as follows:
Here the preparation process of selected polyester is included in all monomers of mixing in the round-bottomed flask, stirs down at 180 ℃, until obtaining a kind of purified solution, and continues to stir 24 hours.Then the solution in the round-bottomed flask is poured in the round-bottomed flask (being generally 1 liter) of a further single-ended necking down, heated 45 minutes down for 200 ℃, from flask, take out and cooling in vacuum.Obtain one glass of purified solid, this solid is pulverized gently with standby.
Embodiment 1:
Prepare following detergent component.
Test procedure:
Washing a bundle pollutent in the washing composition of the compacting of prescription shown in having, this fabric contain the fabric that speckles with a series of dirts (as particulate state dirt, greasy dirt, the dirty and changeable colour dirt of enzyme) on cotton fabric and polyester/cotton fabric.Detergent component washing shown in half of each bundle fabric used, and second half uses the not same composition washing of cellulase.25 ° of H(Deutschland hardnesss at 40 ℃) test in the water.All tests repeat 4 times.
Under the same conditions, with respect to each washed in advance reference stain assessment soil removability.The prescription that is used for washing the reference fabric does not contain modified poly ester or cellulase.
The Schefe number scale assessment detersive power of the following stick unit of keeping the score that determines by two umpires that employing is known:
I think 1=and have difference in two kinds of stains.
Between two stains of 2=difference is arranged certainly.
Between two stains of 3=very big difference is arranged.
There is the black and white difference between two stains of 4=.
Calculate and reference fabric average data relatively.Relevant smeary result on the polyester/cotton fabric material is as follows
*Statistics is effective
Embodiment 2:
Have the stain remover that is similar at prescription described in the embodiment 1 and be used to wash a bundle by a series of particulate, greasy, enzymatic and the fabric that dirt the polluted changeable colour type.In every bundle half washed in embodiment 1 described prescription, and second half does not contain having same recipe in the stain remover of modified poly ester and washs.The condition that is used for washing these fabrics is 40 ℃, the water of 25H.Each test repeats 4 times.According to soil removal efficiency % with sample classification.Adopt 1 traditional a b system, utilize McBeth(color dispersing meter) calculate.Employing account for detergent component weight 0.025%～10% between the different content repeated test of modified poly ester.
Detail record is as follows:
Be considered to typical greasy dirt and comprise dirty machine oil, shoe polish and makeup.
Cited numeral is the increase for the average soil removal efficiency % of reference goods.
Embodiment 3:
Increase the degreasing rate by adding modified poly ester and carboxymethyl cellulose.
With the washing prescription that contains carboxymethyl cellulose (CMC) repeatedly to poly-cotton sample pre-treatment.The purpose of doing like this is to make fabric have a CMC to be deposited on process on the cotton of polyester/cotton fabric.Then the polyester/cotton fabric drying is also made dirty it with dirty machine oil (DMO).Washing is with as reference in being similar to the described washing prescription of embodiment 1 for half stain, and second half stain washs in the same recipe that only contains the modified poly ester here.
Adopt the Hunter color laboratory system, the soil removal efficiency % by calculating each tracer is with the cloth specimen classification.All data can also with comparing of adopting the washing prescription that only do not contain CMC with the processed cloth specimen of above-mentioned definitely identical mode with soil release polymer.Outcome record is as follows.
The water of 40 ℃/25 ° of H of experiment condition-repetition 4 times.
Embodiment 4:
The preprocessing solution component that contains the modified poly ester here is by preparation as follows
Fill a prescription 123456
Modified poly ester 0.5 1.0 3.0 5.0 6.0 6.0
LAS 40 50 75 75 - -
FA45E7 13 17 17 - 30 22
Toxilic acid/third 46.5 32 5.0 20 64 72
The olefin(e) acid multipolymer
All solution all are used to carry out pre-treatment for the polyester/cotton fabric that is polluted by a series of fatty soils (as dirty machine oil, sun-proof paint makeup and lipstick) before washing.
All fabrics of handling with any described component are with untreated in advance dirt relatively the time in advance, show be significantly increased aspect the polyester/cotton fabric decontamination.
The detergent component that also can prepare following compacting:
Claims (11)
1, a kind of detergent component or additive, it is characterized in that: it comprises the modified poly ester of a kind of tensio-active agent, a kind of washing assistant and a kind of 0.025%～10%, this polyester is the random copolymers of dimethyl terephthalate (DMT), the pure and mild 1-2 propylene glycol of sulfo-dimethyl isophthalate ethylene, and end group at first comprises the thiobenzoic acid ester and secondly comprises the monoesters of ethylidene glycol and/or propylene glycol.
2, detergent component according to claim 1 or additive, it is characterized in that: described polyester contain 46% dimethyl terephthalic acid of about weight, about weight 16% the third-1,15% sulfo-iso-phthalic acid of 13% sulfosalicylic acid of 10% ethylidene glycol of 2 glycol, about weight, about weight and about weight, and have 2,500～3, the molecular weight between 500.
3, detergent granules component according to claim 1 and 2 or additive is characterized in that: comprise 15% the inorganic filling salt that is no more than weight, and have the density of fraction of 550～950 grams per liters.
4, detergent component according to claim 1 or additive is characterized in that: also comprise a kind of anti-soil dirt redeposition agent or soil-suspending agent that is selected from carboxymethyl cellulose polycarboxylate, polypeptide compound and composition thereof.
5, according to claim 1,2,3 or 4 described detergent component or additives is characterized in that: also comprise a kind of cellulase.
6, a kind of purposes of modified poly ester, described polyester is a kind of random copolymers of dimethyl terephthalate (DMT), the pure and mild 1-2 propylene glycol of sulfo-dimethyl isophthalate ethylene, end group at first comprises the thiobenzoic acid ester and secondly comprises the monoesters of ethylidene glycol and/or propylene glycol, described modified poly ester is as the clean-out system of cotton-containing fabrics, and described fabric contacts with a kind of aqueous washing composition liquid that contains described compound and experiences a cycles of washing.
7, purposes according to claim 6, it is characterized in that: described polyester contains 46% dimethyl terephthalic acid of about weight, about weight 16% the third-1,2 glycol, 10% ethylidene glycol of about weight, 15% sulfo-m-phthalic acid of 13% sulfosalicylic acid of about weight and about weight, and have 2,500～3, the molecular weight between 500.
8, according to claim 6 or 7 described purposes, it is characterized in that: described polyester combines with a kind of cellulase.
9, according to the described purposes of any one claim of claim 6 to 8, it is characterized in that: described polyester joins in a kind of detergent component that comprises other cleaning ingredients with 0.025～10% compounds content of composition weight.
10, according to the described purposes of any one claim in the claim 6 to 8, it is characterized in that: described polyester is added in a kind of detergent additive component to be used for the pre-wash to cotton-containing fabrics.
11, according to claim 9 or 10 described purposes, it is characterized in that: described detergent component or binder component are placed in the container that component can be discharged at the beginning in cycles of washing or pre-wash round-robin, and described container washs and/or treats that the fabric of pre-wash is placed in the rotating cylinder of washing machine with waiting.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP92870060 | 1992-04-13 | ||
| EP92870060.8 | 1992-04-13 | ||
| EP92202383.3 | 1992-07-31 | ||
| EP92202383 | 1992-07-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1078747A true CN1078747A (en) | 1993-11-24 |
Family
ID=26131602
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 93105732 Pending CN1078747A (en) | 1992-04-13 | 1993-04-13 | The modified poly ester that is used for washing of cotton-containing fabrics |
Country Status (14)
| Country | Link |
|---|---|
| EP (1) | EP0641378A4 (en) |
| JP (1) | JPH07505670A (en) |
| KR (1) | KR950700976A (en) |
| CN (1) | CN1078747A (en) |
| AU (1) | AU4279393A (en) |
| BR (1) | BR9306245A (en) |
| CA (1) | CA2117997A1 (en) |
| CZ (1) | CZ248694A3 (en) |
| EG (1) | EG20531A (en) |
| HU (1) | HUT69329A (en) |
| IE (1) | IE930280A1 (en) |
| MA (1) | MA22870A1 (en) |
| MX (1) | MX9302143A (en) |
| WO (1) | WO1993021294A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104704103A (en) * | 2012-08-18 | 2015-06-10 | 科莱恩金融(Bvi)有限公司 | Use of polyesters in washing and cleaning agents |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69324084T2 (en) * | 1992-07-31 | 1999-10-28 | Procter & Gamble | Use of modified polyesters to remove fat from textiles |
| DE4433027A1 (en) * | 1994-09-16 | 1996-03-21 | Henkel Kgaa | Powdery, enzyme-containing bleach and detergent |
| DE19543196A1 (en) * | 1995-11-20 | 1997-05-22 | Henkel Kgaa | Dirt-repellent polymer-containing enzyme preparation |
| GB9524488D0 (en) * | 1995-11-30 | 1996-01-31 | Unilever Plc | Detergent compositions containing soil release polymers |
| GB9524491D0 (en) * | 1995-11-30 | 1996-01-31 | Unilever Plc | Detergent compositions containing soil release polymers |
| GB9524494D0 (en) * | 1995-11-30 | 1996-01-31 | Unilever Plc | Detergent compositions containing soil release polymers |
| US5919697A (en) * | 1996-10-18 | 1999-07-06 | Novo Nordisk A/S | Color clarification methods |
| US7285523B1 (en) * | 1999-01-19 | 2007-10-23 | Seydel Companies, Inc. | Enzyme-containing granule and detergent composition |
| DE19906367A1 (en) | 1999-02-16 | 2000-08-17 | Clariant Gmbh | Soil release polymer, useful in laundry detergent, aid or conditioner or detergent for hard surface, is comb oligoester obtained by condensing polycarboxylic acid or polyol, polyol or polyglycol and monofunctional compound |
| GB0704933D0 (en) | 2007-03-15 | 2007-04-25 | Reckitt Benckiser Nv | Detergent composition |
| JP7138554B2 (en) * | 2018-12-17 | 2022-09-16 | ライオン株式会社 | Liquid detergent composition for textiles |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4116885A (en) * | 1977-09-23 | 1978-09-26 | The Procter & Gamble Company | Anionic surfactant-containing detergent compositions having soil-release properties |
| DK187280A (en) * | 1980-04-30 | 1981-10-31 | Novo Industri As | RUIT REDUCING AGENT FOR A COMPLETE LAUNDRY |
| GB2095275B (en) * | 1981-03-05 | 1985-08-07 | Kao Corp | Enzyme detergent composition |
| US4711730A (en) * | 1986-04-15 | 1987-12-08 | The Procter & Gamble Company | Capped 1,2-propylene terephthalate-polyoxyethylene terephthalate polyesters useful as soil release agents |
| US4818569A (en) * | 1987-10-05 | 1989-04-04 | The Procter & Gamble Company | Articles and methods for treating fabrics in clothes dryer |
| US4976879A (en) * | 1987-10-05 | 1990-12-11 | The Procter & Gamble Company | Sulfoaroyl end-capped ester oligomers suitable as soil-release agents in detergent compositions and fabric-conditioner articles |
| 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 |
| US4908150A (en) * | 1989-02-02 | 1990-03-13 | Lever Brothers Company | Stabilized lipolytic enzyme-containing liquid detergent composition |
| CA2027995C (en) * | 1989-10-31 | 1996-05-14 | Stephen William Morrall | Sulfobenzoyl end-capped ester in oligomers useful as soil release agents in granular detergent compositions |
| DE69107455T3 (en) * | 1990-05-09 | 2004-09-23 | Novozymes A/S | A CELLULASE PREPARATION CONTAINING AN ENDOGLUCANASE ENZYME. |
| JP3357049B2 (en) * | 1990-09-07 | 2002-12-16 | ザ、プロクター、エンド、ギャンブル、カンパニー | An improved soil release agent for granular laundry detergents |
| EP0495258A1 (en) * | 1991-01-16 | 1992-07-22 | The Procter & Gamble Company | Detergent compositions with high activity cellulase and softening clays |
-
1993
- 1993-04-07 CA CA002117997A patent/CA2117997A1/en not_active Abandoned
- 1993-04-07 HU HU9402940A patent/HUT69329A/en unknown
- 1993-04-07 CZ CZ942486A patent/CZ248694A3/en unknown
- 1993-04-07 EP EP93912134A patent/EP0641378A4/en not_active Ceased
- 1993-04-07 BR BR9306245A patent/BR9306245A/en not_active Application Discontinuation
- 1993-04-07 WO PCT/US1993/003245 patent/WO1993021294A1/en not_active Application Discontinuation
- 1993-04-07 JP JP5518439A patent/JPH07505670A/en active Pending
- 1993-04-07 AU AU42793/93A patent/AU4279393A/en not_active Abandoned
- 1993-04-08 IE IE028093A patent/IE930280A1/en not_active Application Discontinuation
- 1993-04-09 MA MA23161A patent/MA22870A1/en unknown
- 1993-04-12 EG EG22093A patent/EG20531A/en active
- 1993-04-13 MX MX9302143A patent/MX9302143A/en unknown
- 1993-04-13 CN CN 93105732 patent/CN1078747A/en active Pending
-
1994
- 1994-10-13 KR KR1019940703635A patent/KR950700976A/en not_active Application Discontinuation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104704103A (en) * | 2012-08-18 | 2015-06-10 | 科莱恩金融(Bvi)有限公司 | Use of polyesters in washing and cleaning agents |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0641378A1 (en) | 1995-03-08 |
| CA2117997A1 (en) | 1993-10-28 |
| MA22870A1 (en) | 1993-12-31 |
| HUT69329A (en) | 1995-09-28 |
| EP0641378A4 (en) | 1995-08-09 |
| IE930280A1 (en) | 1993-10-20 |
| HU9402940D0 (en) | 1995-03-28 |
| EG20531A (en) | 1999-07-31 |
| CZ248694A3 (en) | 1995-05-17 |
| BR9306245A (en) | 1998-06-23 |
| JPH07505670A (en) | 1995-06-22 |
| WO1993021294A1 (en) | 1993-10-28 |
| KR950700976A (en) | 1995-02-20 |
| AU4279393A (en) | 1993-11-18 |
| MX9302143A (en) | 1994-05-31 |
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