CN1213137C

CN1213137C - Laundry detergent compsns. with cellulosic polymers available for appearance and integrity of washing fabric

Info

Publication number: CN1213137C
Application number: CN97181945.9A
Authority: CN
Inventors: J·P·王; N·M·华盛顿; K·B·亨特; S·L·波耶尔
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1996-12-26
Filing date: 1997-12-23
Publication date: 2005-08-03
Anticipated expiration: 2017-12-23
Also published as: ES2203830T3; DE69723575D1; EP0948591B1; WO1998029528A2; ATE245184T1; DE69723575T2; CA2276188C; CN1247558A; JP2001507396A; EP0948591A2; CA2276188A1; WO1998029528A3; JP4267075B2; BR9714097A; AR010851A1

Abstract

The invention discloses detergent compositions and methods which utilize certain modified cellulose ethers as fabric treatment agents that can impart fabric appearance and integrity benefits to fabrics and textiles laundered in washing solutions which contain such agents. Such modified cellulose ether fabric treatment agents are those having selected types and amounts of anhydroglucose ring substituents in order to render them nonionic, cationic or anionic in nature.

Description

Contain laundry detergent composition to the outward appearance of the fabric that washed and whole favourable cellulosic polymer

Technical field

The present invention relates to liquid or granular heavy duty type laundry detergent composition, it contains the ether of cellulose material of the modification of some kinds, helps the fabric that washs in the washing soln of being made by said composition and the outward appearance and the whole structure of textiles.

Background of the present invention

As everyone knows, use and laundering of textile fabrics and textiles, for example the alternate cycles of Mo Sun clothing item inevitably to the fabric that uses and wash and textiles outward appearance and produce adverse influence on the whole.Fabric and textiles only will be damaged with use through after a while.Laundering of textile fabrics and textiles must be removed in daily use and assemble thereon and dirt wherein and stain.But washing operation itself can accelerate and promote the destruction to the integral body and the outward appearance of these fabrics and textiles through repeatedly circulating.

Fabric destruction whole and outward appearance itself can illustrate in several ways.The mechanical effect of washing can make staple fibre fall down from the fabric/textile structure with braiding of weaving.These fibers that fall down form fiber flock, fine hair or " balling-ups ", can fabric see them outwardly, and influence the new and old of appearance of fabrics.In addition, repeated washing fabric and textiles, particularly employing contain the laundry product of SYNTHETIC OPTICAL WHITNER, can remove the dyestuff on fabric and the textiles, reduced the density of color, the result cause fade, worn appearance, and be to cause in many cases by the color harmony light and shade that changes color.

As previously mentioned, obviously need find a kind of material, it be introduced in the detergent for washing clothes product, and they are had an effect with the fiber that adopts this class Betengent product laundering of textile fabrics and textiles, thereby reduces or reduce to be washed the ruined trend of outward appearance of fabric/textile.All these class Betengent product additive materials should be able to help the outward appearance and the globality of fabric certainly, and do not influence the ability that detergent for washing clothes is brought into play its clean fabric function.The objective of the invention is to contain the detergent composition of the fiber substance of some type, it is had an effect in a desired manner.

Summary of the present invention

Laundry detergent composition of the present invention contains the ether of cellulose fabric conditioner of modification of some kinds of the organic or inorganic detergent builder of the detergent surfactant of 1% to 80% weight of having an appointment, about 0.1% to 80% weight and about 0.1% to 8% weight.Detergent surfactant and detergent builder material can be any materials that can be used in the common detergent for washing clothes product.The molecular weight of the ether of cellulose material of modification is about 10000 to 2000000, and has the anhydroglucose unit that multiple replaces, and this unit has general structure I, II and the III in below " detailed description of the present invention " part.(in the listed hereinafter general structure, substituting group is on the specific position of glucose anhydro ring of the cellulose ether polymer that repeats to form replacement.Can think that this only is in order to illustrate, and this class substituting group can find on any carbon atom of glucose anhydro ring.)

The effective ether of cellulose of one class contains the nonionic of the hydrophobically modified that has the anhydroglucose naphthenic substituent, and its amount is 0.1% to 5% of an ether of cellulose.Have an appointment 1 to 20 mole amount alkoxyization of ring substituents.

The effective ether of cellulose of second class contains the cation cellulose ether material that has the anhydroglucose naphthenic substituent, and its amount is about 0.1% to 5% weight of ether of cellulose.The anhydroglucose ring substituents contains 1 to 20 mole oxyalkylated and about 0.005 to the 0.5 mole quaternary ammonium cation part of having an appointment.

The plain ether of the 3rd fibrid contains the anionic cellulose ether material that has the anhydroglucose naphthenic substituent, and its amount is about 0.1% to 5% weight of ether of cellulose.The substituent degree of carboxymethyl of the glucose anhydro ring on this anionoid material is 0.05 to 2.5.Also can engage and use nonionic, positively charged ion and anion-modified ether of cellulose.

With regard to its method, the present invention relates to washing or processing fabric or textiles in aqueous cleaning of making by the detergent composition of the present invention of significant quantity or make or treatment soln by the single component of this based composition.Laundering of textile fabrics and textiles in this class washing soln then carry out rinsing and drying, and be favourable to the appearance of fabrics of handled fabric and textile fabrics.Improve overall appearance, reduce balling-up/fine hair, prevent to fade, improve wear resistance and/or improve pliability so-called favourable comprising.

Detailed description of the present invention

Just as described, laundry detergent composition of the present invention mainly contains the ether of cellulose fabric conditioner of detergent surfactant, detergent builder and some modifications, by adopting detergent composition to come laundering of textile fabrics and textiles, can improve appearance of fabrics and globality.Put down in writing each of these main detergent composition components, the method that is used for the optional components of this based composition and is suitable for this based composition below: all percentage ratios given and ratio all are weight, unless other explanation is arranged.

A) Detergent surfactant

Detergent composition of the present invention mainly contains the detergent surfactant of 1% to 80% weight of having an appointment.Preferred this based composition contains this tensio-active agent of 5% to 50% weight of having an appointment.The detergent surfactant that is adopted can be the tensio-active agent of negatively charged ion, nonionic, zwitter-ion, both sexes or cation type, perhaps can contain the compatible mixture of this class type.Detergent surfactant of the present invention is documented in US3664961, Norris, on May 23rd, 1972, US3919678, Laughlin etc., on December 30th, 1975, US4222905, Cockrell, on September 16th, 1980 and US4239659, Murphy, on December 16th, 1980.All these patents all are incorporated herein by reference.In all these tensio-active agents, preferred anionic and nonionogenic tenside.

Effectively anion surfactant itself just has several classes.For example, the water-soluble salt of higher fatty acid, i.e. " soap ", it is the effective anion surfactant that can be used in the present composition.It comprises alkali metal soap, as contains and have an appointment 8 to about 24 carbon atoms, preferred about 12 salt to sodium, potassium, ammonium and the silane alcohol base ammonium of the higher fatty acid of about 18 carbon atoms.Soap can by direct saponification fat and oil or in and free fatty acids prepare.Special is the sodium salt and the sylvite of the mixture of the lipid acid made by Oleum Cocois and tallow, i.e. tallow and coconut sodium or potash soap effectively.

Other is applicable to that non-soap anionic surfactants of the present invention comprises water-soluble salt, preferably has to contain 10 an alkali metal salt and the ammonium salts to the organosulfur acid-respons product of the alkyl of about 20 carbon atoms and sulfonic acid or sulfate group of having an appointment in its molecular structure.(said " alkyl " is the moieties of acyl group.) example of these synthetic surfactants is a) sodium alkyl sulfate, potassium and ammonium, particularly by sulfation higher alcohols (C ₈-C ₁₈Individual carbon atom), the material that obtains as the alcohol of the glyceryl ester preparation by reduction tallow or Oleum Cocois; B) sodium sulfate of alkyl polyethoxylated, potassium and ammonium, particularly those wherein alkyl contain 10 to 22, preferred 12 to 18 carbon atoms, and wherein the chain of polyethoxylated contains 1 to 15, the material of preferred 1 to 6 oxyethyl group part; And c) sodium alkyl benzene sulfonate and potassium, wherein alkyl contains on straight chain or collateralization chain configuration and has an appointment 9 to about 15 carbon atoms, as is documented in those types in US2220099 and 2477383.Special is that wherein the average carbon atom number on alkyl is about 11 to 13 linear straight chain alkylbenzene sulfonate effectively, is abbreviated as C _11-13LAS.

Preferred nonionic has general formula R ¹(OC ₂H ₄) _nOH, wherein R ¹Be C ₁₀-C ₁₆Alkyl or C ₈-C ₁₂Alkyl phenyl, n are 3 to about 80.Particularly preferably be C ₁₂-C ₁₅Pure and every mol of alcohol about 5 is to the condensation product of about 20 moles oxyethane, as C ₁₂-C ₁₃The about 6.5 moles ethylene oxide condensation of pure and every mol of alcohol.

Another kind of suitable ionic surfactant pack is drawn together polyhydroxy fatty acid amide, and its general formula is:

Wherein R is C _9-17Alkyl or alkenyl, R ₁Be methyl, Z is the glycidyl (glycityl) that is produced by reducing sugar or its oxyalkylated derivative.Example is N-methyl N-1-deoxidation glycidyl coconut monoethanolamide and N-methyl N-1-deoxidation glycidyl oleylamide.The method that is used to prepare polyhydroxy fatty acid amide is known, and can be at Wilson, and US2965576 and Schwartz find among the US20703798, and it is disclosed in this in conjunction with as a reference.

B) Detergent builder

Detergent composition of the present invention also mainly contains the detergent builder of 0.1% to 80% weight of having an appointment.The composition of preferred this class I liquid I form contains the adjuvant component of 1% to 10% weight of having an appointment.Preferred this class granular composition contains the adjuvant component of 1% to 50% weight of having an appointment.Detergent builder are well known in the art, and contain for example phosphoric acid salt and various organic and inorganic phosphorus-free adjuvant.

Can be used for poly-acetate, carboxylate salt, polycarboxylate and polyhydroxy sulfonate that water miscible without phosphorus organic additive of the present invention comprises various basic metal, ammonium and replacement ammonium.The example of poly-acetate and PC auxiliary agent is the ammonium salt of sodium, potassium, lithium, ammonium and the replacement of ethylenediamine tetraacetic acid (EDTA), nitrilotriacetic acid(NTA), oxygen di-Succinic Acid, mellitic acid, benzene poly carboxylic acid and citric acid.Other can be used for suitable polycarboxylate of the present invention is poly-acetal carboxylate salt, and it is documented in US4144226, on March 13rd, 1979, and Crutchfield etc. and US4246495, on March 27th, 1979, Crutchfield etc., they are in this combination as a reference.Particularly preferred polycarboxylate auxiliary agent is oxygen di-succinate and ether carboxylate assistant composition, it contains the mixture of tartrate monobutane diacid salt and tartrate two succinates, is documented in US4663071, Bush etc., on May 5th, 1987, it is disclosed in this combination as a reference.

The example of suitable without phosphorus inorganic assistant agent comprises silicate, aluminosilicate, borate and carbonate.Particularly preferably be carbonate, supercarbonate, sesquicarbonate, tetraboric acid decahydrate and silicate, the wherein SiO of sodium and potassium ₂With the weight ratio of alkalimetal oxide be about 0.5 to about 4.0, preferred 1.0 to about 2.4.It is further preferred that aluminosilicate, comprise zeolite.This class material and its purposes as detergent builder more fully are documented in Corkill etc., and among the US4605509, it is disclosed in this combination as a reference.The crystalline layered silicate for example is disclosed in Corkill etc., and (its be disclosed in this in conjunction with as a reference) is applicable to detergent composition of the present invention among the UD4605509.

C) The modified-cellulose polymkeric substance

The third main ingredient of detergent composition of the present invention contains one or several modified-cellulose polymkeric substance.The outward appearance that this class material is found fabric that washs in the washing soln of being made by the detergent composition of the cellulosic material that contains this class modification and textiles has many benefits.This class comprises the benefit of the outward appearance of fabric: for example the whole outward appearance of laundering of textile fabrics is improved, and reduces the formation of balling-up and fine hair, protect colour-fast, raising wear resistance etc.The modified-cellulose polymkeric substance that is used for the compositions and methods of the invention can help the outward appearance of fabric, and the while reduces fiddling or do not lose by the scourability that laundry detergent composition had that has wherein added this material.

Modified-cellulose polymkeric substance of the present invention can be nonionic, positively charged ion or anionic species, and perhaps the modified-cellulose polymeric constituent of composition of the present invention contains the mixture of these cellulose polymer compound kinds.The modified-cellulose polymeric constituent of the present composition is about 0.1% to 8% weight of said composition normally.More preferably the cellulosic material of this class modification is about 0.5% to 4% weight of said composition, most preferably from about 1% to 3%.

Can be used for the nonionic cellulose ether that a kind of suitable modified-cellulose polymkeric substance among the present invention contains hydrophobically modified, molecular weight is about 10000 to 2000000, preferred about 50000 to 1000000.Hydrophobic modified nonionic has the anhydroglucose unit that multiple replaces, and I is as follows for its formula formula:

General structure I

In general structure I, R is selected from H and C ₈-C ₂₄Alkyl, preferred C ₈-C ₁₆The alkyl substituent of alkyl on the glucose anhydro ring of polymkeric substance is about 0.1% to 5% weight of polymer material, more preferably from about 0.2% to 2% weight.R in structural formula I ¹Be H or methyl, x is about 1 to 20, preferred about 1 to 10.

The nonionic cellulose ether of the hydrophobically modified of general structure I comprises can industrial utilization, also comprise can industrial utilization material by the prepared material of conventional chemical modification.General structure I class can industrial utilization ether of cellulose comprise Polysurf 67, NatrosolPlus 430 and Natrosol Plus 330, provide by Hercules.Inc.

Can be used for another kind of suitable modified-cellulose polymkeric substance of the present invention and comprise cation cellulose ether, it can be or not be hydrophobically modified, and molecular weight is about 10000 to 2000000, more preferably from about 10000 to 1000000.These cationic substances have the anhydroglucose unit that multiple replaces, and it has following general structure II:

General structure II

In general structure II, R is H or C ₈To C ₂₄Alkyl, preferred C ₈-C ₁₆Alkyl.Alkyl substituent on the glucose anhydro ring of polymkeric substance is about 0.1% to 5% weight of polymer material, preferred about 0.2% to 2% weight.In general structure II, R ²Be CH ₂CHOHCH ₂Perhaps C ₈-C ₂₄Alkyl, preferred C ₈-C ₁₆Alkyl.R ³, R ⁴And R ⁵Be respectively methyl, ethyl or phenyl.R ⁶Be H or methyl.In general structure II, x is about 1 to 20, and is preferred about 1 to 10, and y is about 0.005 to 0.5, preferred 0.005 to 0.1, and Z is Cl ^-Perhaps Br ^-

The cation cellulose ether of general structure II comprises can industrial utilization, also comprise can industrial utilization by the conventional chemical modification the material for preparing of material.General structure II can industrial utilization ether of cellulose comprise JR 30M,, JR400, JR 125, LR 400 and LK 400 UCARE polymkeric substance, it is all provided by Union Carbide Corporation.

The suitable modified-cellulose polymkeric substance that can be used for the third type of the present invention comprises anionic cellulose ether, and it can be or not be hydrophobically modified, and molecular weight is about 10000 to 2000000, more preferably from about 50000 to 1000000.These anionic species have the anhydroglucose unit that multiple replaces, and it has following general structure III:

General structure III

In general structure III, R is selected from H and a) CH ₂COOA and b randomly) C ₂-C ₂₄, preferred C ₂-C ₁₆Alkyl (A is sodium or potassium).Alkyl substituent on the glucose anhydro ring of polymkeric substance is about 0.1% to 5% weight of polymer material, preferred about 0.2% to 2% weight.The carboxymethyl replacement degree of anionic cellulose ether is about 0.05 to 2.5, more preferably from about 0.1 to 1.0.

The anionic cellulose ether of general structure III comprises can industrial utilization, also comprise by conventional chemical improve can industrial utilization the material for preparing of material.General structure III can industrial utilization ether of cellulose comprise CMC 7H, CMC 99-7M and CMC 99-7L, all by Hercules, Inc. provides and CMC D72, CMC D65 and CMC DHT, is all provided by Penn Carbose.

Can be used for ether of cellulose material that can industrial utilization of the present invention is that itself is produced by suitable natural cellulose ether raw material.These raw materials comprise for example velveteen or other plant tissue.Being used for modified cellulose ethers of the present invention generally all is water miscible material.If desired, the aqueous solution form that they can the plain polymkeric substance of this fibrid is used for the production of detergent composition.

D) Optional detergent component

Except the ether of cellulose of main tensio-active agent, auxiliary agent and modification of front record, detergent composition of the present invention can also comprise many other optional components.They comprise conventional detergent composition component, for example SYNTHETIC OPTICAL WHITNER and SYNTHETIC OPTICAL WHITNER promoting agent, enzyme and enzyme stabilizers, profoamer or froth suppressor, anti-tarnishing agent and sanitas, soil-suspending agent, stain remover, sterilant, pH regulator agent, non-auxiliary agent basic materials, sequestrant.Organic and inorganic assistant agent, solvent, hydrotropic agent, white dyes, pigment and spices.

A kind of preferred optional component that can join in the detergent composition of the present invention comprises SYNTHETIC OPTICAL WHITNER, as peroxygen bleach.This class peroxygen bleach can be organic or the inorganics state.The inorganic peroxy SYNTHETIC OPTICAL WHITNER is used in combination with bleach activator usually.

Effectively the organic peroxy SYNTHETIC OPTICAL WHITNER comprises percarboxylic acids SYNTHETIC OPTICAL WHITNER and its salt.The suitable example of this class reagent comprises monoperphthalic acid magnesium hexahydrate, metachloroperbenzoic acid magnesium salts, 4-nonyl amino-4-oxo Perbutyric Acid and diperoxy dodecandioic acid.These SYNTHETIC OPTICAL WHITNER are disclosed in US4483781, Hartman, on November 20th, 1984; EP-A-133354, Banks etc., on February 20th, 1985; US4412934, Chung etc., November 1 nineteen eighty-three.SYNTHETIC OPTICAL WHITNER very preferably comprises that also 6-nonyl amino-6-oxo crosses oxy hexanoic acid (NAPAA), as at US4634551, and Burns etc., record in 6 days January in 1987.

In detergent composition of the present invention, also can adopt normally granular inorganic peroxy SYNTHETIC OPTICAL WHITNER.It is preferred that inorganic SYNTHETIC OPTICAL WHITNER is actually.This class inorganic peroxy compounds comprises alkali metal perborate and percarbonate material.For example can adopt Sodium peroxoborate (as one or tetrahydrate).Suitable inorganic SYNTHETIC OPTICAL WHITNER can also comprise " percarbonate " SYNTHETIC OPTICAL WHITNER, trisodium phosphate peroxyhydrate, urea peroxyhydrate and the sodium peroxide of yellow soda ash or salt of wormwood peroxyhydrate and equivalence.Also can adopt persulphate SYNTHETIC OPTICAL WHITNER (as OXONE, by the DuPont industrial production).Usually adopt the inorganic peroxy SYNTHETIC OPTICAL WHITNER of silicate, borate, vitriol or water soluble surfactant active's coating.For example the percarbonate particles of Tu Fuing is provided by various industrial raw material, FMC for example, Solvay Interox, Tokai Denka and Degussa.

The inorganic peroxy SYNTHETIC OPTICAL WHITNER, preferably can be used in combination as perborate, percarbonate etc. with bleach activator, it can be in the aqueous solution on the spot (as in the process that composition of the present invention is used for fabric washing/bleaching) preparation corresponding to the peroxy acid of bleach activator.The non-limiting example of each of promoting agent is disclosed in US4915854, in April 10 nineteen ninety, and Mao etc. and US4412934, November 1 nineteen eighty-three, Chung etc.Nonanoyl oxygen benzene sulfonate (NOBS) and tetra acetyl ethylene diamine (TAED) promoting agent are representational and are preferred.Also can adopt their mixture.The US4634551 that other type SYNTHETIC OPTICAL WHITNER and promoting agent are quoted referring to preamble.

The general formula of other effective acid amides deutero-bleach activator is:

R ¹N (R ⁵) C (O) R ²C (O) L or R ¹C (O) N (R ⁵) R ²C (O) L

R wherein ¹Be the alkyl that contains 6 to 12 carbon atoms of having an appointment, R ²Be to contain 1 the alkylidene group of having an appointment, R to about 6 carbon atoms ⁵Be hydrogen or contain 1 alkyl, aryl or the alkaryl to about 10 carbon atoms of having an appointment, L is any spendable leavings group.Leavings group be since cross the hydrolysis negatively charged ion to bleach activator produce nucleation the result and from bleach activator by any group of metathetical.Preferred leavings group is the Phenylsulfonic acid root.

Preferred embodiment with bleach activator of above-mentioned general formula comprises (6-decoylamide-caproyl) oxygen benzene sulfonate, (6-pelargonamide caproyl) oxygen benzene sulfonate, (6-decanoyl-caproyl) oxygen benzene sulfonate and their mixture, and they are documented at this in conjunction with among the US4634551 as a reference.

The bleach activator of other kind is included in the promoting agent of disclosed benzo oxazinyl in October 30 nineteen ninety disclosed US4966723 such as Hodge, its at this in conjunction with as a reference.Benzo oxazinyl promoting agent very preferably is:

Another kind of preferred bleach activator comprises the acyl lactam promoting agent, particularly has the acyl caprolactam and the acyl group Valerolactim of following general formula:

R wherein ⁶Be hydrogen or contain 1 to alkyl, aryl, alkoxy aryl or the alkaryl of about 12 carbon atoms.Lactan promoting agent very preferably comprises benzoyl caprolactam, capryloyl hexanolactam, 3; 5; 5-trimethyl acetyl base hexanolactam, nonanoyl hexanolactam, decanoyl hexanolactam, undecylene acyl caprolactam, benzoyl Valerolactim, capryloyl Valerolactim, nonanoyl Valerolactim, decanoyl Valerolactim, undecylene acyl group Valerolactim, 3; 5,5-trimethyl acetyl base Valerolactim and their mixture.Also can be referring to US4545784,198 5 on October 8,, Sanderson, in conjunction with as a reference, it discloses the acyl caprolactam that is absorbed in the Sodium peroxoborate, comprises benzoyl caprolactam at this for it.

If adopt, peroxygen bleach is about 2% to 30% weight of detergent composition of the present invention.More preferably be that peroxygen bleach is about 2% to 20% weight of said composition.More preferably be that peroxygen bleach is about 3% to 15% weight of the present composition.If adopt, bleach activator is about 2% to 10% weight of detergent composition of the present invention.Usually, be about 1: 1 to 10: 1 with the ratio of SYNTHETIC OPTICAL WHITNER and promoting agent, more preferably from about 1.5: 1 to 5: 1 ratio adopts promoting agent.

Another kind in the detergent composition of the present invention optional components very preferably is the detersive enzyme component.Enzyme can be included in the detergent composition of the present invention, to realize various various objectives, comprises the spot of removing protein-based, carbohydrate-based or triglyceride level base from base material, preventing dye transfer in laundry processes, and is used for fabric and restores.Suitable enzyme comprises any raw material useful proteases, amylase, lipase, cellulase, peroxidase and their mixture, for example plant, animal, bacterium, fungi and yeast source.Preferred select to be subjected to some factors, for example pH is active and/or stability, thermostability and to the influence of the stability of activated detergent, auxiliary agent etc.From this respect, preferred bacterium or fungal enzyme, for example bacterial amylase and proteolytic enzyme, and fungal cellulase.

Here " detersive enzyme " of Cai Yonging is meant all enzymes that have cleaning, decontamination or other beneficial effect in laundry detergent composition.The preferred enzyme that is used to wash purpose includes, but are not limited to proteolytic enzyme, cellulase, lipase and peroxidase.

Enzyme is generally to be enough to the providing amount of " washing significant quantity " to join in the detergent composition.Said " washing significant quantity " is meant can be to matrix, and for example fabric produces cleaning, decontamination, de-sludging, brightens, any amount of deodorizing or bright-coloured improvement effect.In fact for present industrial production, general amount is the about at the most 5 milligrams of weight of every gram detergent composition, more generally is 0.01 to 3 milligram organized enzyme.Be noted that also composition of the present invention generally contains 0.001% to 5%, the industrial enzyme preparation of preferred 0.01% to 1% weight.Proteolytic enzyme exists to be enough to making every gram composition have 0.005 activity to 0.1Anson unit (AU) in these industrial preparations usually.Higher activity level also is that the high concentration detergent preparation is needed.

The example that proteolytic enzyme is suitable for is a subtilysin, and it is by the specified genus preparation of Bacillus subtillis and lichenoid form bacillus.A kind of useful proteases be by the PH scope of maximum activity in 8～12 Bacillaceae preparation, this Bacillaceae by the Novo Industries A/S (this paper is " Novo ") of Denmark with ESPERASE ^Exploitation and sale.The preparation of this kind of enzyme and similar enzyme is documented among the GB1243784 of Novo.The ALCALASE that is provided by Novo is provided other enzyme that is suitable for ^And SAVINASE ^With the International Bio-Synthetics by Holland, the MAXATASE that Inc. provides ^And be disclosed in EP130756A, the protease A on January 9th, 1985 and be disclosed in EP303761A, on April 28th, 1987 and EP130756A, the proteolytic enzyme B on January 9th, 1985.Also can be referring to the high pH proteolytic enzyme of the WO9318140A that is documented in Novo from bacillus NCIMB 40338.The enzyme washing composition that contains proteolytic enzyme, one or more other enzymes and reversible proteinase inhibitor is documented among the WO9203529A of Novo.Other preferred proteolytic enzyme comprises Procter ﹠amp; Those of the WO9510591 record of Gamble.When needs, can adopt Procter ﹠amp; The reduction absorption of putting down in writing among the WO9507791 of Gamble and the proteolytic enzyme of raising hydrolysis.The proteolytic enzyme that is used for the recombinant chou Trypsin enzyme of washing composition of the present invention is documented in the WO9425583 of Novo.

The adoptable cellulase of the present invention comprises bacterium class and Mycophyta, and preferred ideal pH is between 5 and 10.Barbesgoard etc. disclose by Humicola insolens or rotten fungal cellulase of planting mould genus DSM1800 preparation or cellulase 212-by fungi preparation that belongs to Aeromonas and the cellulase Dolabella Auricula Solander that extracted by the hepatopancreas of shipworm at the US4435307 on March 6th, 1984.Suitable cellulase also is disclosed among GB-A-2075028, GB-A-2095275 and the DE-OS-2247832.CAREZYME ^(Novo) and CELLUZYME ^(Novo) be effective especially.WO9117243 referring to Novo.

The suitable lipase that is used to wash purposes comprises those by Rhodopseudomonas, and for example microorganism of Pseudomonas stutzeri ATCC19.154 preparation is disclosed as GB1372034.Lipase also can be referring at disclosed Japanese patent application 5320487 on February 24th, 1978.This lipase is by Amano Pharmaceutical Co.Lth., Nagoya, and Japan provides with trade name Lipase P " Amano " or " Amano-P ".Other suitable industrial lipase comprises Amano-CES, the lipase that is produced by Chromobacter viscosum, the Chromobacter viscosumvar.lipolyticumNRRLB 3673 that provides as the Toyo Jozo Co.Tagata by Japan; The Chromobacter viscosum lipase that provides by the Disoynth Co. of the U.S.Biochemical Corp. of the U.S. and Holland, and by the lipase of gladiolus pseudomonas preparation.By Humicola lanuginosa deutero-and by the LIPOLASE of Novo industrial preparation ^*Enzyme referring to EP341947, here is preferred lipase.

The enzyme composition that contains of the present invention can randomly contain and has an appointment 0.001% to about 10%, and preferred about 0.005% to about 8%, most preferably from about the enzyme stabilising system of 0.01% to 6% weight.This kind of enzyme stabilising system can be any stabilising system compatible with detersive enzyme.Such system can be that the active substance by other preparation provides or added respectively by formulator or the manufacturers that is washed agent finished product enzyme and provides originally.This class stabilising system can for example contain calcium ion, boric acid, propylene glycol, short chain carboxy acid, boric acid and their mixture, and designs at different stable problems with physical condition according to the type of detergent composition.

E) The preparation of detergent composition

Detergent composition of the present invention can be liquid, mashed prod or particle form.This based composition can by with main ingredient and optional components with required concentration, with any suitable order and adopt any conventional equipment to prepare.

The preparation example of particulate composition as be by basic granules component (as tensio-active agent, auxiliary agent, water etc.) is mixed and made into slurry, and the slurry that jet drying generated prepares for (5-12%) to drop to residual moisture.Residual dried ingredients can be mixed in mixing rotary drum with the particle of jet drying with the form of particle powder, and liquid ingredient (as the organic solution of main cellulose polymer compound, enzyme, caking agent and spices) can be ejected on the particle of generation, makes the finished product detergent composition.Particulate composition of the present invention also can be " concentrated type ", and promptly they have the density higher than conventional granulates washing composition, promptly 550 arrives 950g/l.In this case, granular detergent composition of the present invention can contain compare with the conventional granulates washing composition a spot of " mineral filler salt "; Representational filling salt is the vitriol and the muriate of alkaline-earth metal, generally is sodium sulfate; " concentrated type " washing composition generally contains and is no more than 10% filling salt.

Liquid detergent composition can be by mixing main and optional components with required order, makes the composition that contains component with desired concn and prepare.Liquid composition of the present invention also can be " concentrated type ", and in this case, liquid detergent composition of the present invention contains a spot of water of comparing with the conventional liq washing composition.

Adding the ether of cellulose component in the liquid detergent composition of the present invention can finish by mix required ether of cellulose simply in the liquid washing agent aqueous solution.Ether of cellulose can change viscosity or other rheological property of detergent product.Therefore must compensate variation by changing the hydrotropic agent that adopted and/or solvent types and amount by the rheology that adds the caused detergent product of ether of cellulose.

F) Fabric cleaning process

The present invention also provides a kind of method of laundering of textile fabrics, and by this method, cellulose polymer compound of the present invention produces useful effect to the outward appearance of fabric.This method is that this kind fabric is contacted with the aqueous cleaning solution of being made by the previously described detergent composition of significant quantity or made by the single component of said composition.It generally is to carry out under stirring condition that fabric contacts with washing soln, although also can adopt composition of the present invention to make to be used for the immersion aqueous solution that need not stir of clean fabric and processing.

Preferably in washing machine, stir to clean well.Preferably dry in the normal laundry drying machine after the washing.The liquid of the significant quantity in the aqueous cleaning solution in washing machine or granular detergent composition preferably about 500 to about 7000ppm more preferably from about 1000 arrive about 3000ppm.

G) Textile finishing

The ether of cellulose of previously described modification as laundry detergent composition of the present invention also can be used for handling and regulating fabric and textiles under the situation of tensio-active agent that lacks detergent composition embodiment of the present invention and adjuvant component.Therefore, the fabric regulating composition that for example only contains modified cellulose ethers itself or contain the aqueous solution of modified cellulose ethers can add in the rinse cycle process of conventional home laundry operation, is beneficial to required appearance of fabrics and overall performance that the front is put down in writing.

Embodiment

The following examples explanation the compositions and methods of the invention still are not any qualification to scope of the present invention.

Example I

The preparation of liquid washing agent subject composition

Prepare several heavy duty liquid detergent compositions that contain various modified-cellulose polymkeric substance.This class I liquid I detergent composition all has following basic recipe:

Table A

Component % weight

C ₁₂-C ₁₅Alkyl oxide (2.5) vitriol 38

C ₁₂Glucamide 6.86

Citric acid 4.75

C _12-14Lipid acid 2.00

Enzyme 1.02

MEA 1.0

Propylene glycol 0.36

Borax 6.58

Dispersion agent 1.48

Toluenesulfonic acid sodium salt 6.25

Modified-cellulose polymkeric substance (if containing) 2.0

Dyestuff, spices, whitening agent, sanitas, Balance

Froth suppressor, other minor component, water

100％

Example II

The preparation of granulated detergent subject composition

Prepare several heavy duty type granular detergent compositions that contain various modified-cellulose polymkeric substance.This class granular detergent composition all has following basic recipe:

Table B

Component % weight

C ₁₂Linear alkyl benzene sulfonate 9.31

C _14-15Alkyl oxide (0.35EO) vitriol 12.74

Zeolite builder 27.79

Yellow soda ash 27.31

PEG?4000 1.60

Dispersion agent 2.26

C _12-13Alcohol b-oxide (9EO) 1.5

Sodium peroxoborate 1.03

Soil release polymer 0.41

Enzyme 0.59

Modified-cellulose polymkeric substance (if containing) 2.5

Spices, whitening agent, froth suppressor, Balance

Other minor component, water, vitriol

100％

EXAMPLE III

Be used in the cellulose polymer compound in the subject composition

The representational modified-cellulose polymkeric substance that is used in liquid described in example I and the II and the granular detergent composition is characterised in that table C.Listed various substituting groups are among foregoing general structure I, II and the III.

Table C

Be used in the cellulose polymer compound in the test detergent composition

Polymkeric substance ID

The description of polymkeric substance A B C D

Trade(brand)name Polysurf67 LK-400 CMC (D72) the modification LK-400 of polymkeric substance

Polymer producers Hercules Union Carbide Penn Carbose Union Carbide

Polymer type non-ionic cation negatively charged ion positively charged ion

Molecular weight 700-750M～400M～300M～400M

Structural formula numbering I II III II

R hexadecyl (C ₁₆) H CH ₂COOA H

The amount 0.4%-0.6% 000 of alkyl substituent on the ring

The degree--0.5 that carboxymethyl replaces on the ring-

R ¹ H - - -

R ² - -CH ₂CH(OH)CH ₂-?- -CH ₂CH(OH)CH ₂-

R ³ - -CH ₃ - -CH ₃

R ⁴ - -CH ₃ - -CH ₃

R ⁵ - -CH ₃ - -CH ₃

R ⁶ - H - H

x 1-3 1-3 - 1-3

y - -0.1 - ～0.006

Z - Cl ^- - Cl ^-

A - - Na -

Record as example I and II prepares subject composition, when adopting the sample of described subject composition laundering of textile fabrics or clothes under same condition, estimates the useful effect of the various cellulose polymer compounds of EXAMPLE III.Do not contain the control sample of polymkeric substance and the composition of the test polymkeric substance that a kind of employing will be estimated compares with a kind of.The careful test conditions that detects.The condition of controlling for example comprises: washing time, the gentle hardness of washing water; The time and the temperature of the stirring of washing machine, rinsing time, rinsing temperature and hardness, drying machine; The content of wash load fiber and weight.

EXAMPLE IV

Overall appearance

In the overall appearance test, adopt and do not contain cellulose polymer compound or contain a kind of enforcement

The various subject composition of example III cellulose polymer compound are come laundering of textile fabrics.Then the overall appearance of the fabric of the washing after ten circulations being estimated institute's laundering of textile fabrics by three evaluation personnel is come classification.As for the project that will estimate, be to decide by the evaluation personnel, estimate an attribute unless provide, as the concrete direction of color, balling-up, fine hair etc.

In the overall appearance test, adopt the Scheff grade to represent the personnel's that estimate vision selection.

That is: 0=does not have difference.

I think this better (not be sure oing) 1=.

I know that this is a little better 2=.

I know that this is better 3=.

I know that this is best 4=.

For the overall appearance test, wash conditions is as follows:

Washing machine type: Kenmore (17 gallons)

Washing time: 12 minutes

Wash temperature: 90 (32.2 ℃)

Washing water hardness: per gallon 6 grams

Washing machine stirs: general

The rinsing time: 2 minutes

Rinsing temperature: 60 (15.6 ℃)

Rinsing water hardness: per gallon 6 grams

Wash load fabric capacity: various colored and white clothes and fabric

5.5 pounds of wash load weight (2.5 kilograms)

The test-results of average overall appearance is listed in table D and E.

Table D

The overall appearance test-results

Liquid pilot composition I D The polymkeric substance of test The overall appearance grade

Contrast does not have 0

A Polysurf?67 1.5

B LK-400 1.8

C CMC(D72) 1.0

The LK-400 1.2 of D modification

Table E

The test-results of overall appearance

Particle subject composition ID The polymkeric substance of test The overall appearance grade

Contrast does not have 0

A Polysurf?67 1.4

B LK-400 1.0

C CMC(D72) 1.0

The LK-400 1.1 of D modification

EXAMPLE V

Reduce balling-up

In reducing pilling testing, adopt the various subject composition that do not contain cellulose polymer compound or contain a kind of cellulose polymer compound of EXAMPLE III to come laundering of textile fabrics.Fabric that then will washing adopts the computer-auxiliary balling-up model analysis system of utilization model analysis to be determined at the quantity of balling-up on the clothing of test and the fabric, with to reducing the pilling testing classification.What balling-up reduced is calculated as follows:

The minimizing of balling-up (%)={ [# balling-up (contrast)-# balling-up (polymkeric substance)]/# balling-up (contrast) } * 100%.

Reduce test for balling-up, it is identical that wash conditions and the overall appearance described in being used for EXAMPLE IV are in front tested.

Average % balling-up reduces test-results and lists in table F and G.

Table F

Test-results-liquid that balling-up reduces

Liquid pilot composition I D The polymkeric substance of test The minimizing of balling-up/fine hair(%)

Contrast does not have 0

A Polysurf?67 21.5

B LK-400 42.4

C CMC(D72) 26.8

The LK-400 25.9 of D modification

Table G

Test-results-particle that balling-up reduces

Particle subject composition ID The polymkeric substance of test The minimizing of balling-up/fine hair(%)

Contrast does not have

A Polysurf?67 33.3

B LK-400 51.6

C CMC(D72) 7.6

The LK-400 16.6 of D modification

Example VI

The color protection

In the color protection test, adopt the various subject composition do not contain cellulose polymer compound or to contain a kind of cellulose polymer compound of EXAMPLE III to come laundering of textile fabrics.Fabric that then will washing adopts the Hunter color meter to test successively, determines that each is tested the DeltaE of fabric ^*Value.Delta E ^*Aberration between fabric that is defined as washing and the unwashed fabric (reflection strength, tone migration etc.).

For the color protection test, wash conditions is identical with the test of overall appearance described in the EXAMPLE IV that is used in front.

The degree of the color that provided protection is based on washing sample not and compares Delta E ^*The percentage ratio of difference.Being calculated as follows of color protection:

% color protection={ [dE ^*(contrast)-dE ^*(polymkeric substance)]/dE ^*(contrast) } * 100%.

The test-results of average color protection is listed in table H and I.

Table H

Test-results-the liquid of color protection

Liquid pilot composition I D The polymkeric substance of test Color protection (%)

Contrast does not have 0

A Polysurf?67 24.2

B LK-400 36.5

C CMC(D72) 26.6

The LK-400 27.2 of D modification

Table I

Test-results-the particle of color protection

Particle subject composition ID The polymkeric substance of test Color protection (%)

Contrast does not have 0

A Polysurf?67 33.9

B LK-400 39.2

C CMC(D72) 15.5

The LK-400 24.7 of D modification

Claims

1. the compound highly effective laundry detergent composition of a particle form, it can make the fabric and the textiles that wash in the wash water solution of being made by it have the appearance of fabrics advantage that is selected from minimizing balling-up/fine hair, prevents to fade, improve wear resistance and/or improve pliability, and said composition contains:

A) detergent surfactant of 1% to 80% weight;

B) the organic or inorganic detergent builder of 1% to 80% weight;

C) the modified cellulose ethers fabric conditioner of 0.1% to 8% weight, it is selected from:

Hydrophobically modified, nonionic cellulose ether, its molecular weight is 10000 to 2000000, and has the anhydroglucose unit of multiple, replacement, the corresponding structure formula is as follows:

Wherein:

R is H or C ₈-C ₂₄Alkyl, the alkyl substituent on the glucose anhydro ring are 0.1% to 5% weight of ether of cellulose material;

R ¹Be H or methyl; With

X is 1 to 20.

2. the composition of claim 1, wherein

A) content of detergent surfactant is 5% to 50% weight, and is selected from negatively charged ion and nonionogenic tenside material;

B) washing auxiliary detergent is characterised in that content is 10% to 50% weight, and is selected from carboxylate salt, silicate, carbonate, borate and their combination; With

C) content of the ether of cellulose fabric conditioner of modification is 0.5% to 4% weight, and molecular weight is 10000 to 1000000.

3. the composition of claim 2, wherein washing auxiliary detergent is selected from aluminosilicate, oxygen two succinates and Citrate trianion.

4. claim 2 or 3 composition, wherein the ether of cellulose fabric conditioner of modification is the nonionic of hydrophobically modified, corresponding to structural formula (I), wherein

A) R is H or C ₈-C ₁₆Alkyl;

B) alkyl substituent on the glucose anhydro ring is 0.2% to 2% weight of ether of cellulose;

C) R ¹Be H; With

D) x is 1 to 10.

5. claim 2 or 3 composition are particulate state, it is characterized in that:

A) 5% to 50% weight detergent surfactant is selected from:

I) vitriol of the poly-ethoxyquin of the alkyl of sodium and potassium, wherein alkyl contains 10 to 22 carbon atoms, and the chain of polyethoxylated contains 1 to 15 inferior ethoxyl part;

The ii) C of sodium and potassium ₉To C ₁₅Alkylbenzene sulfonate;

The iii) C of sodium and potassium ₈To C ₁₈Alkyl-sulphate;

Iv) polyhydroxy fatty acid amide, general formula is

Wherein R is C ₉-C ₁₇Alkyl or alkenyl, Z are the glycidyls that is produced by reducing sugar or its oxyalkylated derivative;

The v) combination of these tensio-active agents; With

B) detergent builder of 1% to 50% weight are selected from yellow soda ash, silicate, oxygen two succinates and Citrate trianion.

6. the composition of claim 5, wherein washing auxiliary detergent is selected from crystalline layered silicate, aluminosilicate.