CN1124496A

CN1124496A - Secondary (2,3) alkyl sulfate surfactants in stable enzyme-containing detergent compositions

Info

Publication number: CN1124496A
Application number: CN 94192199
Authority: CN
Inventors: B·P·默希; S·W·莫拉尔
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1993-04-08
Filing date: 1994-04-05
Publication date: 1996-06-12
Anticipated expiration: 2014-04-05
Also published as: AU6625694A; JPH08509012A; WO1994024240A1; PE10495A1; CA2160228C; CA2160228A1; EP0693111A1; CN1046954C

Abstract

当含有酶和钙离子或镁离子的洗涤剂组合物中常规使用的烷基苯磺酸盐或伯烷基硫酸盐表面活性剂被仲(2，3)烷基硫酸盐表面活性剂代替时，发现该洗涤剂组合物更稳定。因此，本发明提供了含有仲(2，3)烷基硫酸盐、钙离子或镁离子物源和一种或多种蛋白酶、纤维素酶、淀粉酶、脂肪酶或过氧化物酶洗涤剂酶的洗衣洗涤剂组合物。When conventionally used alkylbenzenesulfonate or primary alkyl sulfate surfactants in detergent compositions containing enzymes and calcium or magnesium ions are replaced by secondary (2,3) alkyl sulfate surfactants, The detergent composition was found to be more stable. Accordingly, the present invention provides detergent enzymes comprising a secondary (2,3) alkyl sulfate, a source of calcium ions or magnesium ions and one or more proteases, cellulases, amylases, lipases or peroxidases laundry detergent composition.

Description

The second month in a season in stable enzyme-containing detergent compositions (2,3) alkyl sulfate surfactant

The field of the invention

The present invention relates to use the detergency enzymes of secondary (2,3) alkyl sulfate surfactant, one or more types and provide calcium or the cleaning combination of the enzyme stabilizers of magnesium ion and method.

Background of invention

The most conventional detergent composition contains the mixture of various detersive surfactants, in order that from various dirts of surface removal and spot.For example various anion surfactants, especially alkylbenzene sulfonate is to be used to remove dirt particles, various nonionogenic tensides such as alkylethoxylate and alkyl phenol ethoxylate are to be used to remove the unctuousness dirt.

Simultaneously, investigated existing document and advised that as if the prescription teacher of washing composition can wide region option table surface-active agent, the fact then is that many this materials are individual chemical, is not suitable for being used in the product such as household laundry composition of low unit costs used in everyday.What practical situation still existed is that many household laundry washing composition still comprise one or more conventional alkylbenzene sulfonates or primary alkyl sulphates tensio-active agent.

Found that having a class tensio-active agent that is limited to use in the various compositions of emulsifying effect at needs comprises secondary alkyl sulfate.The random mixture of pasty state of the alkane of normally Sulfated straight chain of commercially available conventional secondary alkyl sulfate and/or part collateralization.This material can not be widely used in the detergent for washing clothes, because they can not provide than alkylbenzene sulfonate benefit more particularly.

Have now found that a class secondary alkyl sulfate of special subordinate, this paper refers to the second month in a season (2,3) alkyl-sulphate (" SAS "), considerable benefit is provided for the prescription teacher and the user of detergent composition.For example, secondary (2,3) alkyl-sulphate is equal to easier being dissolved in the water-bearing media of counterpart primary alkyl sulphates of chain length than them.Therefore, they can be configured to diffluent high surfactant (i.e. " high reactivity ") particle and are used for granular laundry detergent.Moreover they can be configured to the liquid washing agent of stable homogeneous.In addition, the solvability of secondary (2,3) alkyl-sulphate allows them to be configured to concentrated type, and what come into vogue now is granular and these two kinds of liquid laundry detergents.Because secondary (2,3) alkyl-sulphate can be made as solid, particle form, they can be granular detergent composition by dried blending together, and do not need to pass through spray-drying tower.

Secondary (2,3) alkyl-sulphate has now been measured their degradables all under aerobic or anaerobism except aforesaid known advantage, this helps their decomposition in environment.

Certainly, the security of being not only single component in this composition, property easy to control and performance that the manufacturers of the detergent composition that essence is joined is concerned about, and be concerned about their consistencies to each other.For example, all kinds detergency enzymes is normally used in the detergent for washing clothes to help removing albumen and lipid spot from fabric.The instability problem of enzyme is well-known, especially with tendency the detersive surfactant of enzyme denaturation, degeneration and passivation is contacted under the situation about using.There is this situation especially in lipase, but the enzyme of other important kind comprises that the unstable of proteolytic enzyme, amylase, cellulase and peroxidase also has been noted.When the preparation granulated detergent, become particulate technology or other coating technology by making enzyme, thereby this technology makes other component physical isolation in enzyme and the composition may protect this kind of enzyme.For liquid composition, this technology is of no use usually, obtains the rational Long-term Storage life-span so add various stablizers to help the composition for preparing.No matter use what technology, people are in the method for constantly studying with enzyme/surfactant system of seeking to provide more stable.

Compare with the anion sulfate acid tensio-active agent of routine, the present invention uses the second month in a season (2,3) alkyl sulfate surfactant that the stability of enzyme is enhanced.What now seem is that the comparable primary alkyl sulphates of secondary (2,3) alkyl-sulphate is slightly gentle to tissue.This means other living things system, comprise detergency enzymes, can show as inherent preferably consistency.Yet for the stability (with the performance of resulting improvement) of herein the improvement that (2,3) alkylsurfuric acid salt composition is had enzyme/second month in a season, this can not think main explanation.And would rather think that the existence in detergent composition of calcium ion seemingly, especially calcium or magnesium ion has strengthened the stability of detergency enzymes significantly.Do not accept keeping within bounds of opinion simultaneously, can conformational stability is provided for all enzymatic structures by imaginary this positively charged ion.No matter any reason for example makes the influence that the discharge meeting is born the stability generation of enzyme from enzyme system of this positively charged ion by chelating, precipitating action etc.Therefore, the various things source of calcium ion (or the magnesium ion that is of little use) is added in the washing composition that contains enzyme (especially liquid, stability problem wherein is more serious than solid phase prod usually) with enhanced stability.By the present invention, now measured the second month in a season (2,3) alkyl-sulphate and interacted not as conventional primary alkyl sulphates tends to this calcium or magnesium ion.As have now found that as if the discharge from enzyme has the tendency of reduction to secondary (2,3) alkyl-sulphate to this positively charged ion.No matter be what mechanism with molecular level, the long and is now to obtain having the more stable composition that enzyme is more comprehensively urged cleaning performance.

Background technology

The problem relevant with the enzyme unstable and the method for enhanced stability are described in the various patents in detergent composition.Referring to, for example: U.S.4,537,706, Severson, on August 27th, 1985; Also has U.S.4,261,868; 4,404,1J5,1 and 04,318,818; Japan J78028515, on August 15th, 1978 is open; Canadian Patent 947,213 and 1,092,036; Britain 2,079,305; Europe 80223, Boskamp, June 1 nineteen eighty-three is open; With German application 3,330,323.

The detergent composition that contains various " second month in a season " and branched-chain alkyl vitriol is disclosed in the various patents, referring to U.S.2,900,346, people such as Fowkes, Augusts 18 nineteen fifty-nine order; U.S.3,468,805, people such as Grifo, on September 23rd, 1969; U.S.3,480,556, people such as DeWitt, on November 25th, 1969; U.S.3,681,424, people such as Bloch, on August 1st, 1 972, U.S.4,052,342, people such as Fernley, on October 4th, 1977; U.S.4,079,020, people such as Mills, on March 14th, 1978; U.S.4,235,752, people such as Rossall, on November 25th, 1980; U.S.4,529,541, people such as Wilms, on July 16th, 1985; U.S.4,614,612, people such as Reilly, on September 30th, 1986; U.S.4,880,569, people such as Leng, on November 14th, 1989; U.S.5,075,041, Lutz, on December 24th, 1991; U.K.818,367, Bataafsche Petroleum, August 12 nineteen fifty-nine; U.K.1,585,030, Shell, on February 18th, 1981; GB 2,179,054A, people such as Leng, on February 25th, 1987 (referring to GB 2,155,031).February in 1966 Morris on the 8th United States Patent (USP) 3,234,258 relates to is the sulfation alpha-olefin, use be H ₂SO ₄, alkene reactant and lower boiling nonionic organic crystal medium.

The present invention's general introduction

The present invention relates to use secondary (2,3) alkyl sulfate surfactant so that cleanup action to be provided in detergent composition, this detergent composition also comprises: (a) detergency enzymes of one or more types; (b) calcium ion or magnesium ion or both thing sources.The present invention also comprises and uses secondary (2,3) alkyl sulfate surfactant to be provided at the cleanup action in the laundering of textile fabrics process, and described laundering of textile fabrics process is to use and contains calcium or magnesium ion, or its both and the laundry aqueous solution of one or more type detergency enzymes.In this application of the present invention and composition, the calcium of existence or magnesium ion or its both amount are " making the stable amount of enzyme ", and it is enough to sex change or degeneration that stabilization energy causes making the enzyme of any quite big loss of enzyme cleaning active at least.As mentioned below, both remove the grease performance to strengthen to mix the calcium ion of additional quantity or magnesium ion or its in composition.The consistency of secondary (2,3) alkyl-sulphate allows for this changes and improvements of the present composition.

The invention provides detergent composition, laundering of textile fabrics composition especially comprises:

(a) at least about 2%, preferred about 5% to secondary (2, the 3) alkyl sulfate surfactant of about 30% (weight);

(b) at least about the enzyme of 0.001% (weight), as soil release characteristics proteolytic enzyme, amylase, lipase, peroxidase, and cellulase and its mixture;

(c) make calcium ion or magnesium ion or its mixture of enzyme stable quantity;

(d) optionally additional enzyme stabilizers; With

(e) detergent additive optionally.This composition can be forms such as liquid, solid, stick, gel, particle, enriched material, slurry.

In the present composition, the water miscible second month in a season (2,3) alkyl-sulphate washing composition preferably to have chain length be about 10 alkyl and its mixtures to about 18 scopes.

The present composition and purposes be for the detergency enzymes of all kinds, and the enzyme that for example is selected from a group in proteolytic enzyme, amylase, lipase, cellulase peroxidase and its mixture is effective.

In one embodiment, the said composition selectivity comprises the non-calcium that makes the enzyme stable quantity, non-magnesium enzyme stabilizers, especially borate or boric acid enzyme stabilizers.

In another embodiment, composition selectivity of the present invention comprises additional surfactants, especially is non-alkyl benzene sulfonate surfactant.A preferred class additional surfactants comprises polyhydroxy fatty acid amide.

In another embodiment, composition of the present invention also comprises detergent builder compound.For liquid composition, this washing assistant is preferably the multi-carboxy acid salt washing agent, especially Citrate trianion.For granular or strip block composition, detergent builder compound is preferably selected from zeolite builders, layered silicate washing assistant, multi-carboxy acid salt washing agent and its mixture.Yet in strip block composition, the prescription teacher also can use phosphate builders, because in the presence of it, enzyme/calcium or enzyme/magnesium compound are quite stables, especially under the situation that alkyl benzene sulfonate surfactant exists.

The present invention also comprises clean surface, and especially the method for dirt fabric comprises said surface and the water-bearing media contact that contains the above disclosed composition of significant quantity (generally at least about 0.01%, preferably at least about 0.05%).Washing operation is included in automatic washing machine and the hand washing (preimpregnation and do not flood two kinds of situations) and uses the ordinary method that stirs.C ₁₀～C ₂₀Secondary (2,3) alkyl-sulphate can use in the present invention routinely.This C ₁₄～C ₁₈Compound is preferred in the laundry operations.

Except as otherwise noted, all herein percentage ratio, ratio and ratio all by weight.All documents that are cited are used as the reference of this paper.

Detailed description of the present invention

Main ingredient

Secondary (2,3) alkyl sulfate surfactant

Be convenient prescription teacher, the below difference between confirmation and the employed in this article sulfated surfactants of explanation and other conventional alkyl sulfate surfactant.

Conventional primary alkyl sulphates tensio-active agent has general formula:

ROSO ₃ ^-M ⁺Wherein R is generally straight chain C ₁₀～C ₂₀Alkyl, M are water-soluble cationic.Chain primary alkyl sulfate tensio-active agent (being side chain " PAS ") with 10～20 carbon atoms also is known; Referring to for example: the european patent application 439,316 of people's such as Smith application in 21 days January in 1991.

Conventional secondary alkyl sulfate surfactant is that those have along the material of the sulfate radical part of the irregular distribution of molecule alkyl " skeleton ".These materials can be used following structrual description:

CH ₃(CH ₂) _n(CHOSO ₃ ^-M ⁺) (CH ₂) _mCH ₃Wherein m and n are 2 or greater than 2 integer, and the summation of m+n is general about 9 to 17, and M is a water-soluble cationic.

With above contrast, the selected herein second month in a season, (2,3) alkyl sulfate surfactant comprised the material with formula A and B structure:

(A) CH ₃(CH ₂) _x(CHOSO ₃ ^-M ⁺) CH ₃With

(B) CH ₃(CH ₂) _y(CHOSO ₃ ^-M ⁺) CH ₂CH ₃They are respectively 2-vitriol and 3-vitriol.Can use the mixture of 2-vitriol and 3-vitriol herein.In formula A and B, x and (y+1) be respectively to be at least about 6 integer, and can be about 7 to about 20 scopes, preferred about 10 to about 16 scopes.M is a positively charged ion, as basic metal, ammonium, alkanol ammonium, alkaline-earth metal etc.M is generally sodium water miscible to prepare (2,3) alkyl-sulphate, but ethanol ammonium, di-alcohol ammonium, triethanol ammonium, potassium, ammonium etc. also can use.

The physical/chemical of having measured the alkyl sulfate surfactant of aforementioned type by the present invention has non-foresight difference each other aspect several, this prescription teacher for all kinds detergent composition is important.For example, primary alkyl sulphates unfavorable and metallic cation such as calcium and magnesium interaction, even can be precipitated by it.Therefore water hardness to the side effect comparison of primary alkyl sulphates herein the second month in a season (2,3) alkyl-sulphate the side effect degree big.In view of the above, have now found that the second month in a season (2,3) alkyl-sulphate is in the presence of calcium ion and under the high water hardness condition or to use down at alleged " low help wash " environment (environment that produces when using nonphosphate builders) be preferred.

Importantly, when preparation strengthen to be removed the concentrated liquid detergent of the calcic of greasy or lathering property or magnesium ion and provided according to enzyme stability of the present invention, have now found that primary alkyl sulphates owing to may have problems with this interaction of calcium or magnesium ion.In addition, the solubleness of primary alkyl sulphates is good not as the solvability of secondary (2,3) alkyl-sulphate.Therefore, have now found that with secondary (2,3) alkyl-sulphate than simpler and more effective with primary alkyl sulphates preparation high active surfactant particle and high concentration liquid washing composition.Therefore, secondary (2,3) alkyl-sulphate except have with enzyme compatibility, it is easy to be formulated as the heavy-filth liquid detergent for washing clothes especially, especially situation about being used in combination with the short chain additional surfactants.

About random secondary alkyl sulfate (being that sulfate groups is at for example locational secondary alkyl sulfate such as 4,5,6,7 secondary carbon(atom)s such as grade), it is the solid of viscosity that this material tends to, or more generally is paste.Therefore, this random alkyl-sulphate can not provide the technological advantage relevant with the solid second month in a season (2,3) alkyl-sulphate when preparation detergent particles, stick or flap.In addition, the second month in a season herein, (2,3) alkyl-sulphate had whipability preferably than this random mixture.This random secondary alkyl sulfate of preferably secondary (2,3) alkyl-sulphate essentially no (promptly contain and be lower than approximately 20%, more preferably be lower than approximately 10%, most preferably be lower than about 5%).

The second month in a season (2 herein, 3) alkyl sulfate surfactant is about under the fabric washing operational circumstances than another advantage of other position or " random " alkyl-sulphate isomer, by the said second month in a season (2,3) alkyl-sulphate for the benefit of improving that soil redeposition provided.Detergent for washing clothes disperses dirt and dirt is suspended in the laundry aqueous solution from the fabric that is washed, this person of being to use crowd knows.Yet the some parts dirt can deposit on the fabric again, and this is detergent formulation Shi Zhongzhi.Therefore some dirts may take place to distribute and deposits on the fabrics all in the loaded article that is washed.Certainly this is undesirable, and this can cause known fabric " change ash " phenomenon.(make the simple experiment of deposit properties with any laundry detergent formulations of giving, the fabric of the band dirt that clean white " spike " cloth can be washed mixes again.In the terminal of laundry operations, by the technology observer with photometric determination or with the naked eye estimate the degree that this white spike cloth departs from its initial whiteness.It is good more that the whiteness of spike cloth keeps, and soil redeposition does not take place more.)

As measuring, determined that now secondary (2,3) alkyl-sulphate has significant advantage at the soil redeposition aspect of performance than other position secondary alkyl sulfate isomer in detergent for washing clothes by above-described cloth tracing method.Therefore the choice of practice second month in a season (2, the 3) alkyl sulfate surfactant according to the present invention, the preferred secondary isomer of its essentially no other position, the method for not being familiar with institute before this unexpectedly helps to solve the soil redeposition problem.

Be noted that the second month in a season used herein, (2,3) alkyl-sulphate obviously was different from secondary alkene sulfonate (for example people's such as Klisch 12/20/77 United States Patent (USP) 4,064,076) aspect several critical natures; Secondary in view of the above sulfonate is not focus of the present invention.

Preparing the second month in a season used herein (2,3) alkyl-sulphate can be by with H ₂SO ₄Add in the alkene and carry out.In the United States Patent (USP) 5,075,041 of the Lutz that the United States Patent (USP) that uses alpha-olefin and the general building-up reactions of vitriolic to be disclosed in Morris was authorized on December 24th, 3,234,258 or 1991.This building-up reactions is carried out in solvent, obtains (2,3) the alkyl-sulphate second month in a season through cooling, and the product that obtains is removed unreacted matters, random sulfation material, not Sulfated by product such as C when making with extra care ₁₀Or more when high-grade alcohol, secondary alkene sulfonate etc., be generally the 2-sulfation of 90+% purity and the mixture of 3-sulfation material (generally having about 10% sodium sulfate), and be the inviscid transparent crystalline solid of white.Also can exist some 2,3-dithionate, but generally include the mixture of (2,3) alkyl monosulfate second month in a season of no more than 5%.This material can have been bought by " DAN " trade(brand)name, for example " DAN200 " that has been bought by Shell Oil company.

The solubleness of " crystallization " secondary (2,3) alkyl sulfate surfactant is enhanced if desired, and prescription Shi Keneng wishes to use this surfactant mixtures with mixinglength alkyl chain.Like this, has C ₁₂～C ₁₈The mixture of alkyl chain is to that is to say to be entirely C than alkyl chain aspect solvability ₁₆(2,3) the alkyl-sulphate second month in a season good.By to secondary (2,3) add other tensio-active agent such as alkylethoxylate or other nonionogenic tenside or in the alkyl-sulphate with reducing the second month in a season (2,3) any other material of alkyl-sulphate degree of crystallinity also can increase the solvability of (2,3) the alkyl-sulphate second month in a season.The material of this interference degree of crystallinity generally be this second month in a season (2,3) alkyl-sulphate 20% or be effective under the low levels more.

When the obtaining liq composition, during especially limpid liquid, preferred secondary (2,3) alkyl sulfate surfactant contains and is lower than about 3% sodium sulfate, preferably is lower than about 1% sodium sulfate.Sodium sulfate is in liquid composition and itself be innoxious substance.Yet sodium sulfate is dissolved in and adds " load " when having in the non-ionic water-bearing media, and this can make liquid composition be separated and gelatinous composition generation gel is destroyed.

Can make the sodium sulphate content in secondary (2, the 3) alkyl-sulphate of the reduction that ins all sorts of ways.For example, when in alkene, adding H ₂SO ₄After, before the second month in a season of sour form, (2,3) alkyl-sulphate was neutralized, remove unreacted H carefully ₂SO ₄Another kind method, (2,3) the alkyl-sulphate water second month in a season that will contain the sodium-salt form of sodium sulfate are near or below the second month in a season in temperature under the Krafft temperature of (2,3) sodium alkyl sulfate carries out rinsing.This will remove Na ₂SO ₄And required (2, the 3) sodium alkyl sulfate purified second month in a season of small loss only.Certainly these two kinds of steps all can be used, and first kind is step before the neutralization, and second kind is neutralization back step.

Term used herein " Krafft temperature " is a kind of technical term, and it is that worker in the tensio-active agent scientific domain is known.The Krafft temperature is described in " Principles of Solution and Solubility " article by K.Shinoda, with PaulBecher cooperation translation, publishes by Marcel Dekker Inc., and 1978, the 160-161 page or leaf.What explain the main points briefly is that tensio-active agent is rising to this point with temperature, and promptly before the Krafft temperature, its solubleness increase in water is quite slow, and under the Krafft temperature, solubility table reveals rapid fast rise.Under temperature was higher than about 4 ℃ of Krafft temperature, almost arbitrary composition solution all became homogeneous phase.General any tensio-active agent of giving type is as herein (2,3) the alkyl-sulphate second month in a season, and it contains anionic hydrophilic sulfate group and hydrophobic alkyl, and its Krafft temperature will be with the hydrocarbyl chain length variations.This be since the change of tensio-active agent solubleness in water along with the tensio-active agent hydrophobic part changes.

In the invention process, the prescription teacher can not be higher than in temperature and optionally washes (2, the 3) alkyl sulfate surfactant second month in a season that is polluted by sodium sulfate under the Krafft temperature with water, particularly for the second month in a season (2 that is washed, 3) sodium alkyl sulfate preferably carries out being lower than under the Krafft temperature.This makes sodium sulfate be washed water dissolution and is removed with washing water, keeps making the second month in a season (2,3) alkyl-sulphate to be lost to amount minimum in the washing water simultaneously.

The second month in a season of this paper (2,3) alkyl sulfate surfactant comprise under the situation of mixinglength alkyl chain, will recognize that the Krafft temperature is not a single point, but be represented as " Krafft scope ".This situation is that the technician in tensio-active agent/measured in solution sciemtifec and technical sphere is known.For this second month in a season (2,3) alkylsurfuric acid salt mixture, in any case, preferably optionally the removal of sodium sulfate component operates in and is lower than under the Krafft range temperature, preferably be lower than under the Krafft temperature of tensio-active agent of the short chain that exists in this mixture and carry out, because this is avoided secondary (2,3) alkyl-sulphate too to be lost in the washing soln.For example for C ₁₆Secondary alkyl (2,3) sodium sulfate tensio-active agent preferably being lower than about 30 ℃ of temperature, carries out washing operation under about 20 ℃.Be understood that cationic variation will change the preferred wash temperature of secondary (2,3) alkyl-sulphate, this is the reason owing to the Krafft temperature variation.

This washing process can be interrupted and carries out, promptly by will wet or the exsiccant second month in a season (2,3) alkyl-sulphate be suspended in the enough water to obtain 10～50% solids, generally be at least 10 minutes (for C in about 22 ℃ of following mixing times ₁₆Secondary (2,3) alkyl-sulphate), then pressure filtration.In preferred embodiments, slurries will contain a little less than about 35% solid, and this is because such slurries are runny and easy stirring in washing process.

Another advantage is the content that washing process has also reduced the organic pollutant that comprises above-mentioned random secondary alkyl sulfate.

Enzyme---for multiple laundering of textile fabrics purpose, comprise the spot of removing protein-based, carbohydrate-based or triglycerin ester group, and, in the prescription of this paper, can comprise enzyme for example for the dye migration that suppresses to come off with for the recovery of fabric.The enzyme that is impregnated in comprises proteolytic enzyme, amylase, lipase, cellulase and peroxidase, with and composition thereof.The enzyme that also can comprise other type.They can come from the source of any suitable, as plant, animal, bacterium, fungi and yeast source.Yet their selection determines by Several Factors, as pH-activity and/or optimal stability point, thermostability, to the stability of activated detergent, washing assistant or the like factor decision.On bacterium aspect this or fungal enzyme is preferred, as bacterial amylase and proteolytic enzyme and fungal cellulase.

Enzyme is impregnated in enough amounts usually so that maximum about 5mg (weight) in every gram composition to be provided, and is generally the organized enzyme of about 0.01mg to about 3mg.Be noted that in addition composition herein generally comprises about 0.001% to about 5%, preferred 0.01%～1%) (weight) commercial enzyme goods.The amount of proteolytic enzyme in this article of commerce is enough to usually guarantee that every gram composition has 0.005 to 0.1Anson unit (AV) activity.

Suitable examples of proteases is a Validase TSP Concentrate II, and it is that special bacterial strain by subtilis and Bacillus licheniformis obtains.Another kind of suitable proteolytic enzyme is obtained by bacillus strain, and it has maximum activity in pH8～12 scopes, and by Novo Industries A/S exploitation and sale, the commodity of registration are called ESPERASE.The preparation of this kind of enzyme and similar enzyme is described in the british patent specification 1,243,784 of Novo.The commercial commercially available proteolytic ferment that is suitable for removing protein-based spot comprises the proteolytic ferment of the commodity of being sold by Novo Industries A/S (Denmark) ALCALASE by name and SAVINASE, with by InternationalBio-Synthetics, the MAXATASE that Inc. (Holland) sells.Other proteolytic enzyme comprises that protease A is (referring to european patent application 130, on January 9th, 756,1985 is open) and proteolytic enzyme B (applied on April 28th, 87303761.8,1987 referring to the european patent application sequence number, disclosed european patent application 130,756 in 9 days January in 1985 with people such as Bott).

Amylase for example comprises in british patent specification 1,296, the α-Dian Fenmei of describing among 839 (Novo), RAPIDASE (International Bio-Synthetics, Inc. sells) and TERMAMYL (Novo Industries sale).

The cellulase that can be used among the present invention comprises bacterium and fungal cellulase.Preferably they have best pH scope 5～9.5.Suitable cellulase is disclosed in the United States Patent (USP) of authorizing in 6 days March in 1984 of people such as Barbesgoard 4,435, in 307, it discloses the mould cellulase that produced by Humicola insolens and humicola lanuginosa strain DSM 1800 or by the cellulase that extracts in the cellulase 212 of the mould preparation that belongs to Aeromonas and the hepatopancreas by extra large mollush (Dolabella Auricula Solander).Suitable cellulase also is disclosed in GB-A-2,075,028; GB-A-2 is in 095,275 and DE-OS-2,247,832.

The spendable suitable lipase of washing composition comprises by the microorganism in the Rhodopseudomonas family, and those lipase that produce as Situ Ci Shi aeruginosa atcc 19.154, as be disclosed in English Patent 1,372 are in 034.Also referring to the lipase on February 24th, 1978 disclosed Japanese patent application 53-20487.This lipase can be by AmanoPharmaceutical Co.Ltd., and Nagoya (Japan) has bought, and commodity are called lipase P " Amano ", hereinafter referred to as " Amano-P ".Other commercial lipase comprises Amano-CES, lipase ex Chromobacter viscosum, for example pigment bacillus (Chromobacter) viscosum var.1ipolyticum NRRLB 3673, commercial can be by Toyo Jozo company, Tagata, (Japan) has bought; With other Chromobacter viscosum lipase, bought and lipase ex gladiolus pseudomonas by U.S.Biochemical Corp. (U.S.) and Disoynth Co. (Holland).Plant Pseudomonas fetal hair bacterium and be the preferred enzyme that is used for herein from corruption at the commercial LIPOLASE enzyme that can buy by Novo (also referring to EPO341,947).

Peroxidase is and oxygen source that for example percarbonate, perborate, persulphate, hydrogen peroxide etc. are used in combination.They are used for " solution bleaching " and promptly are suppressed at dyestuff that washing operation comes off or pigment migration other basic thing to the washing soln from basic things.Peroxidase is being known in the art, comprises for example horseradish peroxidase, lignoenzyme and halo peroxidase such as chloro and bromoperoxidase.The detergent composition that contains peroxidase is disclosed in, and for example in the PCT International Application No. WO 89/099813, on October 19th, 1989 is open, by the O.Kirk invention, transfer Novo Industries A/S.

Far-ranging enzyme material and the method that they are mixed in the synthetic detergent particle also are disclosed in the United States Patent (USP) 3,553,139 that was presented to people such as McCarty on January 5th, 1971.Some enzymes are disclosed in the people's such as Place that authorized on July 18th, 1978 United States Patent (USP) 4,101,457 and the United States Patent (USP) of the Hughes that authorized on March 26th, 1,985 4,507,219 in the two.The method that useful enzyme material and they are incorporated in these prescriptions in the detergent formulation is disclosed in United States Patent (USP) 4,261, in 868, people's such as Hora, on April 14th, 1981 authorized.The enzyme that is used for washing composition can make its stabilization with various technology.The enzyme stabilization technology is open and exemplify people such as Horn is authorized in explanation on April 14th, 1981 United States Patent (USP) 4, authorized people's such as Gedge United States Patent (USP) 3 on August 17th, 261,868,1971,600,319 and European patent application publication No. 0,199,405, application number is open on October 29th, 86200586.5,1986, Venegas.The enzyme stabilization system for example also is described in the United States Patent (USP) 4,261,868,3,600,319 and 3,519,570.

Enzyme stabilizers---enzyme used herein can be by being stabilized (if only use one type positively charged ion in the presence of water dissolvable calcium in final composition and/or the magnesium ion source (it provides this ion to enzyme), calcium ion slightly is effective in magnesium ion usually, and is preferred herein).Stability in addition can obtain under existing at various other prior aries disclosed stablizer, especially borate family material (referring to Severson United States Patent (USP) 4,537,706 cited above).General washing composition, especially liquid washing agent comprise by every liter of final composition about 1 to about 30, preferred about 2 to about 20, more preferably about 5 to about 15, and 8 calcium ions most preferably from about to about 12 mmoles.It can change to some extent according to the amount of the enzyme that exists and the enzyme responsive to calcium or magnesium ion.Should select the amount of calcium or magnesium ion like this, promptly make its with composition in complexing such as auxiliary agent, lipid acid after, the minimum calcium or the magnesium ion that for enzyme, always can obtain existing.Water-soluble calcium or magnesium salts all can be used as calcium or magnesium ion source arbitrarily, comprise, but non-limiting in this, calcium chloride, calcium sulfate, calcium malate, calcium maleate, calcium hydroxide, calcium formiate and lime acetate and corresponding magnesium salts.Because the calcium ion that enzyme slurries and prescription contain in the water, make this small amount of calcium ion, general about 0.05 to about 0.4 mmole/liter, also often be present in the composition.The water-soluble calcium ion source that can comprise q.s in the solid detergent composition prescription is to be provided at required amount in the laundry aqueous solution.On the other hand, natural water hardness may be enough.

The amount that should be appreciated that aforementioned calcium and/or magnesium ion is enough to guarantee enzyme stability.More calcium and/or magnesium ion can be added in the composition so that the supplementary means that realizes that grease is removed to be provided.Therefore, be general purpose, the present composition generally comprises about 0.05% to about 2% (weight) water-soluble calcium or magnesium ion or the two thing source.Certainly this amount can change with the amount and the type of employed enzyme in the composition.

The present composition also optionally but preferably contains various other stablizer, especially stablizers of borate type.Generally, the consumption of this stablizer in composition is calculated as about 0.25% to 10% by the boric acid in the composition or other borate compound (is that base calculates by boric acid) that can form boric acid, preferred about 0.5% to about 5%, more preferably about 0.75% to about 3% (weight).Though other compound such as boron oxide, borax and other alkali metal borate (for example ortho-boric acid sodium, sodium metaborate and sodium pyroborate and penta borate) suit, preferably boric acid.The boric acid that replaces (for example, phenyl-boron dihydroxide, butane boric acid and to bromophenyl boric acid) also can replace boric acid to use.

Annexing ingredient

Except enzyme, present composition alternative include help or strengthen scourability, to the nursing of the basic thing that is washed or improve one or more other washing composition additional substances or other materials of the aesthetic feeling (for example spices, tinting material, dyestuff etc.) of detergent composition.It below is the example that exemplifies of these additional substancess.

Washing assistant---detergent builders optionally is included in the composition of the present invention to help the control hardness of minerals.Can use inorganic and organic washing-assisting detergent.Washing assistant generally is used for the fabric laundry composition to help removing dirt particles.

The amount of washing assistant can change in relative broad range according to end-use and its required physical form of composition.When it existed, composition generally contained at least about 1% washing assistant.Liquid formulations generally contains has an appointment 5% to about 50%, and more general about 5% to about 30% washing auxiliary detergent.The prescription of saccharoid generally comprises about 10% to about 80%, more general about 15% to about 50% (weight) detergent builders.Yet meaning that, this does not get rid of the washing assistant that uses lower or higher amount.

Inorganic detergent builders comprises, but be not restricted to this, basic metal, ammonium, the alkylammonium salt of polyphosphoric acid salt (exemplify and be tri-polyphosphate, pyrophosphate salt and glassy polymeric metaphosphate), phosphonate, phytinic acid, silicate, carbonate (comprising supercarbonate and sesquicarbonate), vitriol and silico-aluminate.Yet need use the washing assistant of nonphosphate in certain areas.Importantly the present composition in addition have so-called " weak " washing assistant (with phosphate ratio) also have beyond thought effect under as Citrate trianion or so-called " low helping washed " environment (zeolite or layered silicate washing assistant produce).In addition, in the presence of weak nonphosphate builders (not allowing to exist calcium ion), secondary (2,3) alkyl-sulphate adds that the enzyme component can bring into play optimal efficacy.Especially true for liquid composition.

The example of silicate-like builder is alkalimetal silicate, particularly SiO ₂: Na ₂O is than those silicate and layered silicate in 1.6: 1 to 3.2: 1 scopes, as is described in the lamina sodium silicate in the United States Patent (USP) 4,664,839 of authorizing H.P.Rieck on May 12nd, 1987.NaSKS-6 is the trade mark (being abbreviated as " SKS-6 " in this article usually) by the crystalline layered silicate of Hoechst sale.Do not resemble zeolite builders, the NaSKS-6 silicate-like builder does not contain aluminium.NaSKS-6 has δ-Na ₂SiO ₅The layered silicate of morphology configuration.It can by as be described in German DE-A-3, those methods preparations in 417,649 and DE-A-3,742,043.SKS-6 is the most preferred layered silicate that is used for herein, but other such layered silicate has general formula NaMSi as those _xO _2x+1YH ₂O, wherein M is that sodium or hydrogen, x are 1.9 to 4 numerical value, is preferably 2, y is 0 to 20 numerical value, is preferably 0 layered silicate and also can be used for herein.Various other layered silicates of buying from Hoechst comprise NaSKS-5, and NaSKS-7 and NaSKS-11 respectively are the structure of α, β and γ.As mentioned above, δ-Na ₂SiO ₅(NaSKS-6 type) most preferably uses herein.Other silicate also is useful, for example Magnesium Silicate q-agent, it can be used as in the saccharoid prescription crisp dose, the stablizer of oxygen bleaching agent and the component of control foam system.

The example of carbonate builders is for being disclosed in alkaline-earth metal and the alkaline carbonate in the disclosed German patent application 2,321,001 on November 15th, 1973.

The silico-aluminate washing assistant is useful among the present invention.The silico-aluminate washing assistant has great importance in the most frequently used commercially available heavy dirty granular detergent composition, and also is the important builder component in the liquid detergent formula, and the silico-aluminate washing assistant comprises those with following empirical formula:

M _z(zAlO ₂YSiO ₂) wherein M be the ammonium of sodium, potassium, ammonium or replacement.Z is about 0.5 to about 2; Y is 1; The magnesium ion exchange capacity that this material has is that the anhydrous silico-aluminate of every gram exchanges about 50 millinormal CaCO at least ₃Hardness.Preferred silico-aluminate is a zeolite builders, and it has following formula:

Na _z[(AlO ₂) _z(SiO ₂) _y] xH ₂O wherein z and y is at least 6 integer, and the mol ratio of z and y is 1.0 to about 0.5 scope, and x is about 15 to about 264 integer.

Useful silico-aluminate ion exchange material is commercial commercially available.These silico-aluminates can be crystallization or amorphous structure, and can naturally occurring silico-aluminate or synthetic obtaining.The method for preparing the silico-aluminate ion exchange material is disclosed in the United States Patent (USP) 3,985,669 of authorizing people such as Krummel on October 12nd, 1976.The preferred synthetic crystallization silico-aluminate ion exchange material that is used for this paper is buied by Zeolite A, ZeoliteP (B) and Zeolite X title.In particularly preferred embodiments, the crystal aluminosilicate ion exchange material has formula:

Na ₁₂[(AlO ₂) ₁₂(SiO ₂) ₁₂] xH ₂O wherein x is about 20 to about 30, especially about 27.This material is known to the public with Zeolite A.It is about 0.1～10 micron granularity that preferably aluminosilicate salt has diameter.

Suitable organic detergent washing assistant of the present invention comprises, but is not restricted to this, multiple multi-carboxylate's compound." multi-carboxylate " used herein refers to the compound that has a plurality of carboxylate groups, preferably has 3 carboxylate groups at least.The multi-carboxy acid salt washing agent adds in the composition with the form of acid usually, but form that also can neutralized salt adds.When using the form of salt, basic metal is preferred as sodium, potassium and lithium or alkanol ammonium salt.

In the multi-carboxy acid salt washing agent, comprise polytype useful matter.An important class multi-carboxy acid salt washing agent comprises the ether multi-carboxylate, comprises the oxidation disuccinate, as is disclosed in Berg. United States Patent (USP) 3,128, authorized on April 7th, 287,1964 and people's such as Lamberti United States Patent (USP) 3, on January 18th, 635,830,1972 authorized.Also see also " TMS/TDS " washing assistant in the people's such as Bush that authorized on May 5th, 1987 the United States Patent (USP) 4,663,071.Suitable ether multi-carboxylate also comprises ring compound, particularly alicyclic compound, as in US 3,923,679; 3,835,163; 4,158,635; Those that describe in 4,120,874 and 4,102,903.

Other useful detergent builder compound comprises the multipolymer, 1 of ether hydroxypolycarboxylic acid salt, maleic anhydride and ethene or vinyl methyl ether, 3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxy methoxy-succinic acid, various polyacetic acid, as basic metal, ammonium and the substituted ammonium salt of ethylenediamine tetraacetic acid (EDTA) and nitrilotriacetic acid(NTA) and multi-carboxylate such as mellitic acid, succsinic acid, oxidation disuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxy methoxy-succinic acid and its water-soluble salt.

The Citrate trianion washing assistant, for example citric acid and its soluble salt (particularly sodium salt) are the multi-carboxy acid salt washing agents of particularly important in the dirt-cleaning agent prescription, reason is that they can be obtained and their biological degradability by renewable resources.Citrate trianion also can be used in the granular composition, especially is used in combination with zeolite and/or layered silicate washing assistant.The oxidation disuccinate also is useful especially in these compositions and mixture.

Also have that suitable in detergent composition of the present invention that use is the U.S.4 that authorizes people such as Bush on January 28th, 1986, disclosed 3 in 566,984,3-dicarboxyl-4-oxa--1,6-adipate and relevant compound.Useful succsinic acid washing assistant comprises C5～C20 alkyl and alkenyl succinic and its salt.Particularly preferred compound is the dodecenyl succinic succsinic acid in this type.The object lesson of succinate washing assistant comprises: lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinic succinate (preferably), 2-15 carbene base succinates etc.The lauryl succinate is a preferred washing assistant in such, and is described in the disclosed european patent application 86200690.5/0,200,263 on November 5th, 1986.

Other suitable multi-carboxylate is disclosed in the people's such as Crutchfield that issued on March 13rd, 1979 the United States Patent (USP) 4,144,226 and in the people's such as Diehl that issued on March 7th, 1967 the United States Patent (USP) 3,308,067.Also see also people's such as Diehl United States Patent (USP) 3,723,322.

Lipid acid, for example C ₁₂～C ₁₈Monocarboxylic acid also can mix in the composition separately, or mixes in the composition so that additional washing assistant activity to be provided with aforesaid washing assistant, especially Citrate trianion and/or the combination of succinate washing assistant.Use lipid acid generally to cause whipability to reduce, this prescription teacher should consider.

Using under the phosphorated washing assistant situation, especially in the used stick prescription of hand washing operation, can use various alkali metal phosphates, as everyone knows tripoly phosphate sodium STPP, trisodium phosphate and sodium orthophosphate.Phosphate builders such as ethane-1-hydroxyl-1,1-diphosphate and other known phosphate (referring to, U.S.3 for example, 159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137) also can be used.

Bleaching compounds one SYNTHETIC OPTICAL WHITNER and bleach-activating agent---detergent composition of the present invention optionally contains SYNTHETIC OPTICAL WHITNER or contains SYNTHETIC OPTICAL WHITNER and the bleaching composition of one or more bleach-activating agents.When having SYNTHETIC OPTICAL WHITNER, its amount is generally detergent composition, in particular for the detergent composition of laundering of textile fabrics about 1% to about 30%, be more generally about 5% to about 20%.If there is bleach-activating agent, its amount be generally the bleaching composition that contains SYNTHETIC OPTICAL WHITNER and bleach-activating agent about 0.1% to about 60%, be more generally about 0.5% to about 40%.

SYNTHETIC OPTICAL WHITNER used herein is in any SYNTHETIC OPTICAL WHITNER that fabric cleaning, hard surface cleaning or other are now known maybe to be used in will be for the cleaning purpose known to the public to detergent composition.Comprising oxygen bleaching agent and other SYNTHETIC OPTICAL WHITNER.Can use perborate bleach herein, for example Sodium peroxoborate (for example monohydrate or tetrahydrate).

The class SYNTHETIC OPTICAL WHITNER that can use without limits comprises percarboxylic acids SYNTHETIC OPTICAL WHITNER and its salt.The suitable example of this class SYNTHETIC OPTICAL WHITNER comprises monoperphthalic acid magnesium hexahydrate, metachloroperbenzoic acid magnesium, 4-amino 4-oxo Perbutyric Acid magnesium in the ninth of the ten Heavenly Stems and diperoxy dodecanedioic acid magnesium.These SYNTHETIC OPTICAL WHITNER are disclosed in the United States Patent (USP) 4 of the Hartman that issued on November 20th, 1984,483,781, the people's such as Burns of application on June 3rd, 1985 U.S. Patent application 740,446, February in 1985 people such as disclosed Banks on the 20th european patent application 0,133,354 and the people's such as Chung that issue November 1 nineteen eighty-three United States Patent (USP) 4, in 412,934.Most preferred SYNTHETIC OPTICAL WHITNER also comprises 6-amino in the ninth of the ten Heavenly Stems-6-oxo-mistake oxy hexanoic acid of describing as in the United States Patent (USP) 4,634,551 that is presented to people such as Burns on January 6th, 1987.

Also can use peroxygen bleach.Suitable peroxy bleaching compound comprises yellow soda ash peroxyhydrate (" percarbonate " SYNTHETIC OPTICAL WHITNER), trisodium phosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide.Also can use persulphate SYNTHETIC OPTICAL WHITNER (for example, OXONE is made by Du Pont commercial).

Also can use the mixture of SYNTHETIC OPTICAL WHITNER.

Peroxygen bleach, perborate, percarbonate etc. preferably are used in combination with bleach-activating agent, and this causes producing on the spot the peroxy acid corresponding to bleach-activating agent in the aqueous solution (promptly at washing process).The various non-limiting examples of activator are disclosed in the United States Patent (USP) 4,915,854 and United States Patent (USP) 4,412,934 that is presented to people such as Mao April 10 nineteen ninety.Nonanoly acyloxy benzene sulfonate (NOBS) and Tetrahydroxyethyl ethylenediamine (TAED) activator are normally used, also can use their mixture.Representative SYNTHETIC OPTICAL WHITNER of useful herein other and activator be referring to U.S.4, and 634,551.

Those SYNTHETIC OPTICAL WHITNER of non-oxygen type SYNTHETIC OPTICAL WHITNER also are known in the art and can use in the present invention.The non-oxygen type of class SYNTHETIC OPTICAL WHITNER with specific benefits comprises the SYNTHETIC OPTICAL WHITNER of photoactivation, as sulfonation phthalocyanine phthalocyanine zinc and/or aluminium.Referring to July 5 in 1977 order be presented to people's such as Holcombe U.S.4,033,718.If generally containing, use SYNTHETIC OPTICAL WHITNER, detergent composition have an appointment 0.025% to about 1.25% (weight) this SYNTHETIC OPTICAL WHITNER, especially sulfonation phthalocyanine phthalocyanine zinc.

The polymerization dirt release agent

Well known to a person skilled in the art that any polymerization dirt release agent alternative is used for the compositions and methods of the invention.The polymerization dirt release agent is characterised in that and contains hydrophilic segment simultaneously that this part makes hydrophobic fiber, as the surface hydrophilic of polyester and nylon; With the hydrophobic part, this part anchors at the surface of hydrophobic fiber and anchors at all the time on the fiber surface in whole washing, rinse cycle process, thus hydrophilic segment is played fixed action.This makes after dirt release agent is handled, and is easier in the spot of the Chan Shenging washing process afterwards afterwards remove.

The polymerization dirt release agent that the present invention uses especially comprises those dirt release agents with following composition: (a) mainly by (i), (ii) or one or more nonionic hydrophilic components of (iii) forming, wherein (i) is that the polymerization degree is at least 2 polyoxyethylene part, (ii) be that the propylene oxide or the polymerization degree are at least 2～10 polyoxypropylene part, hydrophilic segment does not wherein comprise any propylene oxide unit, unless this unit is attached at the two ends of adjacent part by ehter bond; (iii) be to contain ethylene oxide and 1 the unitary mixture of oxidation alkene to about 30 propylene oxide units, wherein said mixture contains abundant ethylene oxide unit, thereby makes the wetting ability of hydrophilic component big to the wetting ability that can increase normal polyester synthon surface (dirt release agent anchors on this surface).Described hydrophilic segment preferably contains the ethylene oxide unit at least about 25%, contains 20～30 propylene oxide units and be particularly preferred at least about the composition of 50% ethylene oxide unit of having an appointment; Or (b) by (i), (ii), (iii) or (iv) one or more hydrophobic compositions of forming, wherein (i) is C ₃Oxidation alkene terephthalate part, if wherein described hydrophobic composition also comprises the ethylene oxide terephthalate, then ethylene oxide terephthalate and C ₃The ratio of oxidation alkene terephthalate units is about 2: 1 or is lower, (ii) is C ₄～C ₆Alkene or oxidation C ₄～C ₆Alkene part, or their mixture (iii) are poly-(vinyl ester) parts, and preferred degree of polymerization is at least 2 poly-(vinyl-acetic ester), (iv) is C ₁～C ₄Alkyl oxide or C ₄Hydroxyalkyl ether substituting group, or their mixture, substituting group wherein is with C ₁～C ₄Alkyl oxide or C ₄Hydroxyalkyl ether derivatived cellulose or its form of mixtures exist, and this derivatived cellulose is an amphipathic, makes them have competent C thus ₁-C ₄Alkyl oxide and/or C ₄The hydroxyalkyl ether unit anchors on the conventional polyethylene terephthalate surface, and keeps the hydroxyl of q.s, in case be adsorbed on these conventional synthon when surperficial when it, wetting ability that can the increased fiber surface; Or (a) and (b) make up.

Generally speaking, (a) polymerization degree of the polyoxyethylene in (i) part be 2～about 200, although also can use the higher polymerization degree, preferred 3～about 150; 6～about 100 is more preferred.Suitable oxidation C ₄～C ₆The alkene hydrophobic comprises that partly (but be not limited to this) is as MO ₃S (CH ₂) _nOCH ₂CH ₂The polymerization dirt release agent end-blocking part of O-, M is a sodium in the formula, n is 4～6 integer, and is as Gosselink, disclosed in the United States Patent (USP) 4,721,580 that on January 26th, 1988 authorized.

The polymerization dirt release agent that uses among the present invention also comprises derivatived cellulose, hydroxy ethers cellulose polymer compound for example, the copolymerization block thing of glycol terephthalate or propylene glycol terephthalate and polyoxyethylene terephthalate or polyoxypropylene terephthalate etc.These reagent all have commercially available, comprising the cellulosic hydroxy ethers as METHOCEL (Dow).The Mierocrystalline cellulose dirt release agent that the present invention uses also comprises C ₁～C ₄Alkyl and C ₄Hydroxy alkyl cellulose; United States Patent (USP) 4,000,093 referring to the people such as Nicol of 28 order mandates December in 1976.

The dirt release agent that is characterised in that poly-(vinyl ester) hydrophobic part comprises that poly-(vinyl ester) is as, C ₁～C ₆The graft copolymer of vinyl ester preferably grafts on poly-(vinyl-acetic ester) on polyoxygenated alkene skeleton such as the polyoxyethylene skeleton.Be illustrated in people's such as disclosed Kud on the 4th and 22 in 1987 european patent application 0,219,048.This commercially available class dirt release agent comprises SOKALAN type material, SOKALAN HP-22 for example, and BASF (West Germany) produces.

The preferred dirt release agent of one class is the multipolymer with glycol terephthalate and the random block of polyoxyethylene (PEO) terephthalate.The molecular weight of this polymerization dirt release agent is about 25,000～about 55,000.Be issued to the United States Patent (USP) 3,893,929 of Basadur on July 8th, 3,959,230 and 1975 referring to 1976 5 about United States Patent (USP)s that were issued to Hays on the 25th.

Another kind of preferred polymerization dirt release agent is the polyester that has ethylene glycol terephthalic acid groups ester repeating unit, wherein contain the polyoxyethylene terephthalate unit of the glycol terephthalate unit and 90%～80% (wt) of 10～15% (wt), it comes from the polyoxygenated ethylidene glycol of molecular-weight average 300～5000.The example of this polymkeric substance comprises commercially available ZELCON5126 (Dupont product) and MILEASE T (ICI product).Be issued to the United States Patent (USP) 4,702,857 of Gosselink referring on October 27th, 1987.

Also having a kind of preferred polymerization dirt release agent is to be the sulfonated products of the ester oligomer of straight chain substantially, and this oligopolymer contains terephthaloyl and the multiple unitary oligomer ester skeleton of oxyalkylene oxygen basic weight, and the terminal portions that links to each other with this skeleton covalency.Authorize November 6 nineteen ninety in the United States Patent (USP) 4,968,451 of J.J.Scheibel and E.P.Gosselink these dirt release agents are had complete description.

Other suitable polymerization dirt release agent comprises the United States Patent (USP) 4 of authorizing people such as Gosselink on December 8th, 1987,711, terephthalate polyester in 730, authorized the United States Patent (USP) 4 of Gosselink on January 26th, 1988,721, the oligomer ester of negatively charged ion end in 580 envelope and authorized block polyester oligopolymer in the United States Patent (USP) 4,702,857 of Gosselink on October 27th, 1987.

Preferred polymerization dirt release agent also comprises the dirt release agent in the United States Patent (USP) 4,877,896 of authorizing people such as Maldonado on October 31st, 1989, this patent disclosure negatively charged ion, the particularly end capped terephthalate of sulfo group aroyl.

If the use dirt release agent, then its consumption for detergent composition weight of the present invention about 0.01%～about 10.0%, be generally about 0.1%～about 5%, preferred about 0.2%～about 3.0%.

Sequestrant

Detergent composition of the present invention can also selectivity contains the sequestrant of one or more iron and/or manganese.This class sequestrant can be selected from aminocarboxylate, phosphoro-amidate, and fragrant chelating agent of multifunctional replacement and composition thereof, whole definition is all hereinafter.Do not accept keeping within bounds of opinion, it is believed that the benefit of these materials is that partly they are by forming soluble inner complex removes demanganize and iron from washing soln outstanding performance.

Aminocarboxylate as selectivity chelator comprises edetate, N-hydroxyethyl-ethylenediamine triacetate, nitrilotriacetic acid(NTA) salt, ethylenediamine tetrapropionic acid(EDTP) salt, triethylenetetraaminehexaacetic acid salt, diethylentriamine pentacetate and ethanol Diglycocol, they are an alkali metal salt, ammonium salt and substituted ammonium salt, and composition thereof.

When allowing at least in detergent composition, to exist total content to be a spot of phosphorus, amino phosphonates do also is fit to be used as sequestrant of the present invention, comprising: ethylenediamine tetraacetic (methylene phosphonic acid salt), nitrilo three (methylene phosphonic acid salt) and diethylenetriamine five (methylene phosphonic acid salt) are (DEQUEST).Preferably these amino phosphonates do do not contain the alkyl or alkenyl above six carbon atom.

In the present composition, also can use the aromatic chelating agent of multifunctional replacement.Authorize people's such as Connor United States Patent (USP) 3,812,044 referring on May 21st, 1974.The compound of preferred this class acid form is the dihydroxyl disulfobenzene, for example: 1,2-dihydroxyl-3,5-disulfobenzene.

The preferred in the present invention biodegradable cheating agent of using was ethylenediamine disuccinate (" EDDS "), authorized the United States Patent (USP) 4,704,233 of Hartman and Perkins referring on November 3rd, 1987.

If the use sequestrant, then its consumption is about 0.1%～about 10% of detergent composition weight of the present invention.Preferred amount of chelant is about 0.1%～about 3.0% of a said composition weight.

Remove clay soil/anti redeposition agent

Composition of the present invention also can contain the water-soluble ethoxylated amine with removal clay soil and antiredeposition performance.The granular detergent composition that contains these compounds generally contains the 0.01% water-soluble ethoxylated amine to about 10.0% (wt) of having an appointment; Liquid detergent composition generally contains has an appointment 0.01% to about 5%.

Most preferred removal dirt and anti redeposition agent are the tetrens of ethoxylation.The example of ethoxylated amine is invested on July 1st, 1986 in the United States Patent (USP) 4,597,898 of VanderMeer description.Another kind of preferred removal clay soil/anti redeposition agent be on June 27th, 1984 disclosed Oh and the european patent application 111,965 of Gosselink in the cation compound of report.Other removal clay soil/anti redeposition agent that can use in the present invention comprises the ethoxylated amine polymer of reporting in the european patent application 111,984 of disclosed Gosselink on the 27th June in 1984; July in 1984 disclosed Gosselink on the 4th european patent application 112,592 in the report amphiphilic polymers; With October 22 in 1985 order authorize the amine oxide of the United States Patent (USP) 4,548,744 of Connor.As known in the art other removes clay soil and/or anti redeposition agent also can be used in the composition of the present invention.Another kind of preferred anti redeposition agent comprises carboxymethyl cellulose (CMC).This class material is well known in the art.Polymeric dispersant

Consumption is that about polymeric dispersant of 0.1%～about 7% (wt) of the present composition is favourable, and is especially more favourable when having zeolite and/or layered silicate washing assistant to exist.Suitable polymeric dispersant comprises polymeric multi-carboxylate and polyoxyethylene glycol, and the known polymeric dispersant of other of this area also can use.Do not limited by theoretical although do not wish, but can be sure of when polymeric dispersant with other washing assistant (comprising low-molecular-weight multi-carboxylate) when using, generate restraining effect by crystal, especially free the peptization and the anti-redeposition of dirt, can improve the performance of all detergent builder compounds.

By making suitable unsaturated monomer, the polymerization of unsaturated monomers of especially sour form or copolymerization multi-carboxylate polymer.Can comprise through the unsaturated monomer acid that polymerization prepares suitable multi-carboxylate polymer: vinylformic acid, toxilic acid (or maleic anhydride), fumaric acid, methylene-succinic acid, equisetic acid, methylfumaric acid, citraconic acid and methylene radical propanedioic acid.In multi-carboxylate polymer of the present invention, do not have the monomer segment of hydroxy-acid group, as vinyl methyl ether, vinylbenzene, ethene, as long as its content is no more than about 40% (wt) and suits.

Can be particularly suitable by the multi-carboxylate polymer that vinylformic acid obtains.Such that uses among the present invention is that the polymkeric substance of base is the water-soluble salt of polymeric acrylic acid with vinylformic acid.The molecular-weight average preferably about 2,000～10,000,4,000～7,000 of this base polymer of acid form is more preferred, and 4,000～5,000 is the most preferred.The example of the water-soluble salt of such acrylate copolymer comprises the ammonium salt of an alkali metal salt, ammonium salt and replacement.Such polymer soluble is known.Authorize on March 7th, 1967 in the United States Patent (USP) 3,308,067 of Diehl and disclose this application of class polymerization acrylate in detergent composition.

With vinylformic acid/toxilic acid is that the multipolymer of base also can be as the preferred ingredient of dispersion/anti redeposition agent.This class material comprises the water-soluble salt of vinylformic acid and maleic acid.The molecular-weight average of this analog copolymer of acid form is preferably about 2,000～100,000; The 5,000～75, the 000th, preferred, 7,000～65,000 is the most preferred.The ratio of acrylate moiety and toxilic acid part was generally about 30: 1～about 1: 1 in this analog copolymer, and is about 10: 1～2: 1st, comparatively preferred.The water-soluble salt of this class vinylformic acid/maleic acid for example can comprise: the ammonium salt of an alkali metal salt, ammonium salt and replacement.Vinylformic acid/the maleic acid of such solubility is the known substance described in the disclosed european patent application 66915 on December 15 nineteen eighty-two.

Included another kind of polymeric material is polyoxyethylene glycol (PEG).PEG is except can be as removing the performance that also has dispersion agent clay soil/anti redeposition agent.That the molecular weight that is used for this purpose polyoxyethylene glycol is generally is about 500～about 100,000, about 1,000～about 50,000th, preferred, about 1,500～about 10,000 is more preferred.

Also can use polyaspartic acid salts and polyglutamate, especially together use with zeolite builders.Whitening agent

Can in detergent composition of the present invention, mix well known in the prior art any white dyes or other whitening agent of general about 0.05%～about 1.2% (wt).Can be used for commercially available white dyes of the present invention and can be divided into following group, comprise, but be not limited: Stilbene, pyrazoline, tonka bean camphor, carboxylic acid, methyne cyanines, dibenzothiophen-5,5-dioxide, pyrroles, 5-and 6-unit heterocyclic derivative, and other variegated dose.The example of these whitening agent is disclosed in " The Production and Application of Fluorescent BrighteningAgent ", M.Zahradnik, John Wiley﹠amp; Sons publishes, among the New York (1982).

The specific examples of the white dyes that in the present composition, uses be same as in the United States Patent (USP) 4,790,856 that was issued to Wixon on December 13rd, 1988 disclosed those.These whitening agent comprise the PHORWHITE whitening agent series that Verona produces.Disclosed other whitening agent comprises in this reference: the TinopalUNPA that Ciba-Geigy produces, Tinopal CBS and Tinopal 5BM; (place of production Italy) Arctic White CC and Artic White CWD that Hilton-Davis produces; 2-(4-styryl phenyl)-2H-naphthalene alcohol [1,2-d] triazole; 4,4 '-two (1,2,3-triazoles-2-yl) Stilbene; 4,4 '-bis-styrylbiphenyl and aminocoumarin.The object lesson of these whitening agent has: 4-methyl-7-diethyl amino coumarin; 1, the two (ethene of benzimidazolyl-2 radicals-yl) of 2-; 1, the 3-diphenylpyrazoline; 2, the two (benzoxazoles of 5--2-yl) thiophene; 2-styryl-naphthalene-[1,2-d] oxazole and 2-(stilbene-4-yl)-2H-naphtho--[1,2-d] triazole.Also can authorize the United States Patent (USP) 3,646,015 of Hamilton referring on February 29th, 1972.

Suds suppressor

Can in the present composition, mix and to reduce or to suppress the compound that foam forms.Foamy is suppressed at and uses in the preceding material filling type washing machine of European plan, or at United States Patent (USP) 4,489, in 455 and 4,489,574 the thickening and washing method, or under the condition in detergent composition of the present invention, particularly important when selectivity contains height bubble cosurfactant.

Can use multiple material as suds suppressor, suds suppressor is known in those skilled in the art.Referring to, as: Kirk Othmer Encyclopedia of Chemical Technology, the third edition, 7 volumes, 430～447 pages of (John Wiley﹠amp; Sons, Inc., 1979).The suds suppressor of one class particularly important comprises mono carboxylic lipid acid and its soluble salt.Authorize the United States Patent (USP) 2,954,347 of Wayne St.John referring to September 27 nineteen sixty.Be used as the mono carboxylic lipid acid of suds suppressor and salt thereof and generally have and contain 10～about 24 carbon atoms, preferably contain the hydrocarbyl chain of 12～18 carbon atoms.Suitable salt comprises an alkali metal salt, for example sodium salt, sylvite and lithium salts; Ammonium salt and alkanol ammonium salts.

Detergent composition of the present invention also can contain the nonsurfactant suds suppressor.The example of this class suds suppressor has: high-molecular-weight hydrocarbons, for example paraffin, fatty acid ester (as fatty acid triglyceride), the fatty acid ester of MHA, aliphatic C ₁₈～C ₄₀Ketone (as stearone) etc.Other suds suppressor comprises the alkylating aminotriazine of N-, for example three-to six-alkyl melamine or two-to four-alkyl diamine chloro triazine, this compound is cyanuryl chloride and 2 or 3 moles of uncle or secondary amine, propylene oxide and single stearic alkyl phosphate salts that contain 1～24 carbon atom, as the product of single stearic alkanol phosphoric acid ester and single stearic alkylphosphonic acid carboxylic acid two basic metal (as K, Na and Li) salt and phosphoric acid ester.Can use by liquid form as paraffin and halowax hydrocarbon.It is liquid that this liquid hydrocarbon should be under room temperature and normal atmosphere, and should have-40 ℃～about 5 ℃ pour point approximately, and minimum boiling point is not less than about 110 ℃ (normal atmosphere).Known use waxy hydrocarbon, preferably this hydrocarbon has and is lower than about 100 ℃ fusing point.This class hydrocarbon is the preferred suds suppressor of a class of detergent composition.For example authorize in people's such as Gandolfo the United States Patent (USP) 4,265,779 and described the hydrocarbon suds suppressor on May 5th, 1981.This hydrocarbon comprises the aliphatic series that contains 12～about 70 carbon atoms of having an appointment, alicyclic, aromatics and heterocycle is saturated or unsaturated hydrocarbons.The term that uses in the discussion about such suds suppressor " paraffin " meaning is to comprise the real paraffin and the mixture of cyclic hydrocarbon.

Another kind of preferred nonsurfactant suds suppressor comprises the polysiloxane suds suppressor.Comprising using organopolysiloxane oil, the for example dispersion agent of polydimethylsiloxane, organopolysiloxane or resin or emulsifying agent, and the mixture of organopolysiloxane and silica dioxide granule, organopolysiloxane wherein condenses on silicon-dioxide through chemisorption.The polysiloxane suds suppressor is known in the art, for example is disclosed in the United States Patent (USP) 4,265,779 and the Starch that authorized people such as Gandolfo on May 5th, 1981, M.S. in February 7 nineteen ninety disclosed european patent application 89307851.9.

Other polysiloxane suds suppressor is disclosed in United States Patent (USP) 3,455, and in 839, this patent relates to by mixing a small amount of polydimethylsiloxane fluid to eliminate aqueous solution foamy composition and method in composition.

The mixture of polysiloxane and silanized silica is as German patent application DOS2, describes to some extent in 124,526.Polysiloxane defoamers in the granulated detergent and froth suppressor are disclosed in U.S. Patent application 3,933, and in 672 people such as () Bartolotta and the United States Patent (USP) 4,652,392 people such as () Baginski, on March 24th, 1987 authorized.

What use in the present invention is that the example of the suds suppressor of base is the froth suppressor that presses down the bubble amount that mainly has following composition with the polysiloxane:

(i) polydimethylsiloxane fluid of the 25 ℃ of about 20cs of following viscosity～about 1500cs;

(ii) about 5～about 50 parts of (wt) polyorganosiloxane resins/100 parts (wt) (i), this resin

By (CH ₃) ₃SiO _1/2Unit and SiO ₂The unit, with about 0.6: 1～about 1.2: 1

Ratio is formed; With

(iii) about 1～about 20 parts of solid silicones (wt)/100 part (i) (wt);

In the present invention in the preferred polysiloxane suds suppressor of Shi Yonging, the solvent that is used for external phase is made up of some polyoxyethylene glycol or polyethylene glycol-propylene glycol copolymers or its mixture (preferably) (but not comprising polypropylene glycol).Based on the suds suppressor of polysiloxane is side chain/crosslinked and nonlinear.

Be exemplified below in order to further specify this viewpoint, cloth-washing detergent with the effect of control bubble generally can contain 0.001%～about 1% (wt) that have an appointment, preferred about 0.01%～0.7% (wt), the described polysiloxane suds suppressor of 0.05%～about 0.5% (wt) most preferably from about, this suds suppressor contains: (1) is the nonaqueous emulsion of main suds suppressor, this suds suppressor is following (a), (b), (c) and mixture (d), (a) organopolysiloxane, (b) arborescens polysiloxane or can produce the polysiloxane compound of polyorganosiloxane resin, (c) pulverizing filler and (d) promote component (a), (b) and (c) mixture reaction is to generate the catalyzer of silane alkoxide; (2) at least a nonionic silicones tensio-active agent; (3) solubleness in water surpasses the polyoxyethylene glycol of 2% (wt) or the multipolymer of polyethylene glycol-propylene glycol under the room temperature; Wherein do not contain polypropylene glycol.In granular composition, gel, can use similar quantity.Authorize the United States Patent (USP) 4,978,471 of Starch referring to December 18 nineteen ninety; Authorized United States Patent (USP) 4,983,316 and the United States Patent (USP) 4,639,489 and 4,749,740 of Starch on January 8th, 1991, people such as Aizawa, 46 row～the 4 hurdle, the 1st hurdle, 35 row.

Preferred polysiloxane suds suppressor comprises among the present invention: the multipolymer of polyoxyethylene glycol and polyethylene/polypropylene glycol, their molecular-weight average should be lower than about 1,000, preferably between about 100～800.Polyoxyethylene glycol of the present invention and polyethylene/polypropylene glycol multipolymer solubleness in the water of room temperature should be higher than 2% (wt), preferably is higher than about 5% (wt).

The preferred solvent of the present invention is a molecular-weight average less than about 1,000, more preferably is about 100～800, most preferably is 200～400 polyoxyethylene glycol and polyethylene/polypropylene glycol multipolymer, preferred PPG 200/PEG 300.Preferred 1: 1～1: 10 of the weight ratio of polyoxyethylene glycol and polyethylene glycol-propylene glycol copolymers; 1: 3～1: 6 the most preferred.

The polysiloxane suds suppressor that the present invention preferably uses does not contain polypropylene glycol, does not especially contain the polypropylene glycol of molecular weight 4,000.The preferred segmented copolymer that does not also contain oxyethane and propylene oxide, for example PLURONIC L101.

Other suds suppressor that the present invention uses comprises the mixture of secondary alcohol (as the 2-alkyl chain triacontanol) and these alcohol and polysiloxane oil, and this polysiloxane oil is as U.S.4, disclosed polysiloxane in 798,679,4,075,118 and EP150,872.Secondary alcohol comprises and has C ₁～C ₁₆The C of chain ₆～C ₁₆Alkyl alcohol.Preferred alcohol is 2-butyl octanol, and the trade mark that this alcohol can ISOFOL 12 is buied from Condea.The secondary alcohol mixture can be buied from Enichem with the trade mark of ISALCHEM 123.Mix suds suppressor and generally contain the mixture that weight ratio is 1: 5～5: 1 a pure and mild polysiloxane.

For any detergent composition that is used for automatic washing machine, the foam of formation all should not overflow washing machine.Preferred its exists with " foam inhibition amount " when using suds suppressor.The implication of " foam inhibition amount " is the consumption of suds suppressor of the prescription Shi Xuanding of composition, this amount fully control foam to obtain can be used for the low foam laundry washing composition of automatic washing machine.

Composition of the present invention contains 0%～about 5% suds suppressor usually.When using mono carboxylic lipid acid and its salt as suds suppressor, its consumption is the highest 5% of the detergent composition weight that is about usually.Preferred about 0.5%～about 3% the fatty monocarboxylate suds suppressor that uses.Although also can adopt higher consumption, the consumption of polysiloxane suds suppressor the highest general about 2.0% of the detergent composition weight that is about.Because at first will consider to make cost to keep the efficient of the low consumption of minimum and effective control foam, this upper limit is practical from its character.About 0.01%～about 1% the polysiloxane suds suppressor of preferred use, about 0.25%～about 0.5% is more preferred.In the present invention, comprise the whole silicon-dioxide and the operable any additives material that can use with organopolysiloxane in these weight percent numerical value.The consumption of single stearic alkylphosphonic suds suppressor is generally about 0.1～about 2% of composition weight.Although can use the hydrocarbon suds suppressor of higher consumption, its consumption is generally about 0.01%～about 5.0%.The consumption of alcohol suds suppressor is generally 0.2%～3% of final product composition having weight.

Except that said components, composition of the present invention can also bring multiple other binder component of other benefit to be used in combination with giving the various compositions in the scope of the invention.Enumerate the example of multiple such binder component below, but be not limited only to this.Fabric softener

The also alternative fabric softener that uses various experience washing whole processes in the present composition, particularly authorized the United States Patent (USP) 4 of Storm and Nirschl on December 13rd, 1977,062, disclosed microgranular montmorillonitic clay and other softening agent well known in the prior art in 647, thereby make the effect that obtains soft fabric in clean textile, the consumption of softening agent is generally about 0.5%～10% (wt).Also can authorize people's such as Crisp United States Patent (USP) 4,375,416 as March 1 nineteen eighty-three and authorize people's such as Harris United States Patent (USP) 4,291,071 on September 22nd, 1981 disclosed like that, clay softening agent and amine and cationic softener are together used.

Additional surfactants---present composition alternative contains tensio-active agents such as various negatively charged ion, nonionic, positively charged ion, zwitter-ion.If use these additional surfactants, its amount is about 5% to about 35% of composition.Yet, it should be understood that mixing additional anion surfactant among the present invention is optionally fully.Because the cleaning performance of secondary (2,3) alkyl-sulphate is fabulous, therefore in the detergent composition of preparation comprehensively, can use this class material to replace fully as this class tensio-active agent of alkylbenzene sulfonate.

The unrestricted example of selective meter's surface-active agent used herein comprises conventional C ₁₁～C ₁₈Alkylbenzene sulfonate, uncle and random alkyl-sulphate (should consider above-mentioned enzyme stability problem), C ₁₀～C ₁₈Alkyl alkoxy sulfate (especially EO1～5 ethoxy sulfates), C ₁₀～C ₁₈Alkyl alkoxy carboxylate salt (especially EO1～5 ethoxy carboxylates), C ₁₀～C ₁₈The poly-glycosides of alkylpolyglycosides and its corresponding sulfation, C ₁₂～C ₁₈α-sulfonated fatty acid ester, C ₁₂～C ₁₈Alkyl and alkylphenol based alkoxylation thing (especially ethoxylate and blended oxyethyl group/propoxylated glycerine), C ₁₂～C ₁₈Trimethyl-glycine and sultaine (" sultaines "), C ₁₀～C ₁₈Amine oxide or the like.Other conventional useful tensio-active agent is listed in the general document.

Especially in the present invention the special additional ionic surfactant pack of a useful class is drawn together the polyhydroxy fatty acid amide of following formula:

R wherein ¹Be H, C ₁～C ₈Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or its mixture, preferred C ₁～C ₄Alkyl, C more preferably ₁Or C ₂Alkyl, C most preferably ₁Alkyl (being methyl); R ²Be C ₅～C ₃₂Hydrocarbyl portion, preferred straight chain C ₇～C ₁₉Alkyl or alkenyl, straight chain C more preferably ₉～C ₁₇Alkyl or alkenyl, most preferably straight chain C ₁₁～C ₁₉Alkyl or alkenyl or its mixture; Z directly is connected in polyhydroxy alkyl part on the straight-chain alkyl chain or its alkoxylate (preferred ethoxylation or propoxylation) derivative for having at least 2 hydroxyls (in the situation of Glycerose) or at least 3 hydroxyls (in the situation of other reducing sugar).Z is preferably derived from the reducing sugar in the reductive amination reaction; More preferably Z is a glycosyl part.Suitable reducing sugar comprises glucose, fructose, maltose, lactose, semi-lactosi, seminose and wood sugar and Glycerose.High glucose maize treacle, high-fructose corn syrup and high malt sugar maize treacle and above listed single sugar can be used, the mixture of sugared composition Z can be obtained by these maize treacle as raw material.Will be appreciated that the meaning of not getting rid of other suitable raw material.Z be preferably selected from

-CH ₂-(CHOH) _n-CH ₂OH、

-CH(CH ₂OH)-(CHCH) _n-1CH ₂OH、

-CH ₂(CHOH) ₂(CHOR ') (CHOH)-CH ₂OH, wherein n is 1 to 5 integer, comprises that 1 and 5 is own, R ' is the single or many saccharidess of H or cyclic and its alkoxy derivative.Glycosyl most preferably, wherein n is 4, particularly-CH ₂-(CHOH) ₄-CH ₂OH.

In formula (I), R ¹Can be for example N-methyl, N-ethyl, N-propyl group, N-sec.-propyl, N-butyl, N-isobutyl-, N-2-hydroxyethyl or N-2-hydroxypropyl.For obtaining best whipability, R ¹Be preferably methyl or hydroxyalkyl.Low if desired whipability, R ¹Be preferably C ₂～C ₈Alkyl, especially n-propyl, sec.-propyl, normal-butyl, isobutyl-, amyl group, hexyl and 2-ethylhexyl.

R ²-CO-N＜can be is coconut monoethanolamide, stearylamide, oleylamide, laurylamide, myristic amide, decyl amide, palmitic amide, butter acid amides etc. for example.

Simultaneously polyhydroxy fatty acid amide can use Schuartz, United States Patent (USP) 2,703, and the method preparation in 798 might exist the by product that has cyclisation and the pollution problem of other coloring matter.As comprehensive method, at WO-9, the preparation method who describes in 206,154 and WO-9,206,984 will obtain the high quality polyhydroxy fatty acid amide.This method comprises the use alkoxide catalysis, under about 85 ℃ of temperature with N-alkylamino polyvalent alcohol with, the preferred fatty acid methyl esters reacts in solvent and obtains high yield (90%～98%) polyhydroxy fatty acid amide, it contains the degradable cyclisation by product of suboptimum of required low levels (generally being lower than about 1.0%), and have the colourity of improvement and a colour stability of improvement, for example Gardner Colors be lower than about 4, preferably in 0 to 2 scope.(for as butyl, isobutyl-and n-hexyl compound, the methyl alcohol of introducing or generating in reaction by catalyzer provides enough rheomorphisms, can optionally use other reaction solvent in addition).If desired, be retained in the product unreacted N-alkylamino polyvalent alcohol arbitrarily and can use acid anhydrides, for example acidylate such as diacetyl oxide, maleic anhydride is to reduce the total amount of this residual amine in product.The residual source of classical lipid acid, it can suppress foam, can be by being consumed with for example trolamine reaction.

The meaning of " by product of cyclisation " is a unwanted byproduct of reaction in the main reaction herein, and a plurality of hydroxyls in main reaction in the obvious polyhydroxy fatty acid amide can form ring structure, and it generally speaking is not easy to biological degradation.The technician of chemical field will recognize use two-and more high-grade saccharides such as maltose preparation polyhydroxy fatty acid amide herein will cause generating wherein linear substituting group Z (it contains the multi-hydroxy substituting group) by the polyhydroxy fatty acid amide of poly-hydroxy ring structure nature " sealing ".This class material is not the cyclisation by product that defines herein.

Aforesaid polyhydroxy fatty acid amide also can be by sulfation, for example by with SO ₃The reaction of/pyridine is obtained the sulfation material that uses into the additional anion surfactant of the present invention by sulfation.

In addition, because with the second month in a season among the present invention (2,3) mixture of alkyl-sulphate (SAS) and polyhydroxy fatty acid amide surfactant (PFAS), alkyl ethoxylated tensio-active agent (AE) and primary alkyl sulphates tensio-active agent (AS) mix with agglomeration to make blended SAS/PFAS/AE/AS particle, the present invention has as a result improved the solvability in cold water fully and significantly.Do not accept keeping within bounds of opinion simultaneously, seeming deliquescent increase is because the crystalline destruction of SAS.No matter what reason, the solvability of improvement has great benefit under cold water condition (for example, 5 ℃ to about 30 ℃ of temperature) (wherein the dissolution rate of detergent particles in wash water solution may be a problem).Certainly, may be debatable concentrate now or during closely knit detergent particles, the solvability of the improvement that is obtained among the present invention also has great benefit when the preparation solvability.Other component

In the present composition, can also contain other useful in multiple detergent composition component, solvent of using comprising other active ingredient, carrier, processing aid, dyestuff or pigment, liquid formulations etc.High if desired bubble then can mix as C in said composition ₁₀～C ₁₆The suds booster of alkanolamide, its consumption is generally 1%～10%.C ₁₀～C ₁₄Monoethanolamine and diglycollic amide are the representative instances of such suds booster.It also is favourable that this class suds booster is used as above-mentioned amine oxide, trimethyl-glycine, sultaine with height bubble cosurfactant.If desired, also can add as MgCl ₂, MgSO ₄The solubility magnesium salts obtain more foam, the consumption of this magnesium salts is generally 0.1%～2%.

The various decontamination components of using in the present composition can also be by being adsorbed on these components on the porous hydrophobic matrix, and then wrap up in application with hydrophobic and this matrix is wrapped up in to apply further make its stabilization.Preferably before adsorbing, this decontamination component is mixed with tensio-active agent with porous matrix.In use, this decontamination component is discharged into the wash water solution from matrix, and finishes the washing functions of its expection in this washings.

Following Example is understood this technology in more detail: with the porous hydrophobic silicon dioxide (trade mark SIPERNAT D10, DeGussa) with contain 3%～5%C _13～15The proteolysis enzyme solution of the nonionogenic tenside of ethoxylated alcohol EO (7) mixes.The amount of this enzyme/surfactant soln generally is 2.5 times of silica weight.The gained powder (can use viscosity 500～12,500 various polysiloxane oils) through dispersed with stirring in polysiloxane oil.Add in the last washing composition matrix with the polysiloxane oil dispersion thing emulsification of gained or with it.By this method; enzyme, SYNTHETIC OPTICAL WHITNER, bleach-activating agent, bleaching catalyst, photosensitizers, dyestuff, white dyes, fabric regulator and hydrolyzable tensio-active agent can " protected form " be used in washing composition as the aforementioned, comprise in the liquid laundry detergent compositions.

Liquid detergent composition can contain water and other solvent as carrier.Lower molecular weight uncle or secondary alcohol, for example methyl alcohol, ethanol, propyl alcohol and Virahol suit.For the solubilization tensio-active agent, monohydroxy-alcohol is preferred, also can use to about 6 carbon atoms and 2 those polyvalent alcohols to about 6 hydroxyls (for example: 1, ammediol, ethylene glycol, glycerine and 1,2-propylene glycol) but contain 2.Said composition can contain 5%～90%, general 10%～50% such carrier.

Detergent composition of the present invention preferably be formulated into the pH that is adapted at washing water about 6.5～about 11, use in preferred about 7.5～about 10.5 aqueous cleaning operation.The preferred pH of the formula for a product of liquid wash up is about 6.8～9.0, and laundry product is generally 9～11.The method that the pH value is controlled at the use value of requirement comprises use buffer reagent, alkali, acid etc., and all methods known in those skilled in the art.

Hereinafter be illustrate detergent composition of the present invention and the second month in a season of the present invention (2,3) alkyl-sulphate purposes typical, but the example of indefiniteness.For most of purposes, the not phosphorous hydrochlorate of preferred compositions.

With components dissolved shown below or to be dispersed in the aqueous carrier and to regulate pH be 9.0～10.5, with the liquid laundry detergent of preparation embodiment 1.

Example I

The liquid laundry detergent compositions of the present invention that comprises following component:

Secondary (2, the 3) alkyl-sulphate of component % (weight) ^*15.0C ₁₄N-methyl glucose amide 5.0 Trisodium Citrate 3.0C ₁₀Alcohol ethoxylate (3) 13.0 monoethanolamine 2.5MAXATASE (enzyme) 0.5LIPOLASE (enzyme) 0.5CaCl ₂0.9 water/propylene glycol/ethanol (100: 1: 1) surplus

^*C ₁₂～C ₁₆Mean chain length; Sodium-salt form; Be lower than 1%Na ₂SO ₄

In general, the particle of (2,3) the alkyl sulfate surfactant second month in a season that comprises used herein can prepare with various known methods.For example can form particle by agglomeration, wherein solid (comprising (2,3) the alkyl-sulphate second month in a season) pushes/piles up and stick together with binding agent by mechanically mixing.The suitable equipment of nodulizing comprises dry powder blend device, thermopnore and turbilizers, can be from as Lodige, and Eric, Bepex and Aeromatic manufacturers have bought.

In another embodiment, particle can be by extruding formation.In the method, solid passes through with relatively high pressure and high-energy charging as secondary (2,3) alkyl-sulphate, and the powder of this damping of pumping is pressed together by the aperture on the template.This method has obtained bar-shaped particle, and it can be ground into required granularity arbitrarily.Equipment comprises axially or the radial extrusion machine, as can be from Fuji, and those that Bepex and Teledyne/Readco have bought.

In another embodiment, particle can form by granulation.In the method, the liquid mixture that contains required component (being that a kind of in them is secondary (2,3) alkyl sulfate particles) under high pressure is pumped and is sprayed in the freezing air.When drop cooled off, they became more firm, have so just formed particle.This solidification be owing to hot-melt adhesive transfers the solid phase transformation to or free-water is converted into the reason of the phase transformation that crystal water produces by some hydratable materials in the primary liquid mixture.

In another embodiment, particle can form by compacting.This method is similar to the compressing tablet manufacturing process, by powder is forced together solid (promptly secondary (2,3) alkyl sulfate particles) being pressed into mould/moulded product on the roller or on the flat board.

In another embodiment, particle can form by fusion/solidification.In the method, by with the second month in a season (2,3) alkyl-sulphate with arbitrarily required annexing ingredient fusion, and make this melt cooling, for example in a mould or, and form particle with the form cooling of drop.

The alternative tackiness agent that uses is to increase particulate integrity and intensity in above method.Independent water, it is a kind of operability tackiness agent of secondary (2,3) alkyl-sulphate, because it will dissolve some second month in a season (2,3) alkyl-sulphates so that adhesive effect to be provided.Other tackiness agent comprises, for example starch, polyacrylic ester, carboxymethyl cellulose or the like.Tackiness agent is known in granulation process.If you are using, the general usage quantity of tackiness agent is a final particulate 0.1%～5% (weight).

If desired, additive, but as hydration and salt non-hydrated, crystalline and vitreous solid, various decontamination component such as zeolite, or the like can be incorporated in the particle.If desired, this additive generally accounts for about 20% (weight) of particulate at the most.

According to prescription teacher's needs, the particle for preparing by preceding method can then be dried or cool off to regulate its intensity, physicals and final moisture content.

The whole manufacturing of particulate product of the present invention preferably includes three independent step: (1) forms common base-material with the component agglomeration, then; (2) agglomerate (as percarbonate bleach, bleach-activating agent etc.) that step (1) is formed mixes with various components; Can also comprise in addition, but also be simultaneously that preferred (3) spray into the material as spices in final mixture.

Base-material is agglomerant rather than spray-dired, is in order to prevent the tensio-active agent degraded of some thermo-sensitivity.The product of gained is that (the free flowing detergent mixture of 600g/l～800g/l), it can substitute existing spraying drying cloth-washing detergent and use high-density.

For the agglomeration (above-mentioned steps 1) of base-material, this process comprises following 4 steps: (A) use as Readco Standard Sigma Mixer, the mixing machine of T-series prepares the tensio-active agent paste; (B) use as Eirich Mixer, the mixing machine of R-series makes tensio-active agent paste and powdery components agglomeration; (C) as intermittent type Aeromatic fluidized-bed continous way is fixed or vibrated fluidized bed (NIRO, Bepex or Carrier Companics) in dry this agglomerate and (D) use as Eirich Mixer, R-series mixing machine is wrapped up in deposited this agglomerate.

Specifically describe agglomeration step below.

Steps A: the preparation of tensio-active agent paste

The purpose of this step be with the tensio-active agent in the composition and liquid mixing make dissolving that blend is beneficial to tensio-active agent turn into and nodulizing.In this step, with the tensio-active agent in the composition and other liquid ingredient together in Sigma Mixer in 140F (60 ℃), mixing about l5 minute～about 30 minutes under about 40rpm～about 75rpm, make the paste that viscosity is 20,000～40,000 centipoise.After thoroughly mixing, when storage is extremely prepared to carry out the nodulizing of step (B) under 140F (60 ℃) with this mashed prod.The component of using in this step comprises tensio-active agent, vinylformic acid/toxilic acid polymkeric substance (m.w.70,000) and polyoxyethylene glycol " PEG " 4000～8000.

Step B: the nodulizing of powder and tensio-active agent paste

The purpose of this step is the flowed detergent particles that base ingredient is gone to the about 300 μ m of median size～about 600 μ m.In this step, powder (is comprised as zeolite, Citrate trianion, citric acid washing assistant, layered silicate washing assistant (as SKS-6), yellow soda ash, ethylenediamine disuccinate, sal epsom and white dyes) feed intake in EinichMixer (R-series), and under about 1500rpm～about 3000rpm, carry out of short duration stirring (about 5～10 seconds), make various dry powder thorough mixing.Tensio-active agent paste with steps A feeds intake in mixing machine then, and mixes about 1 minute～about 10 minutes preferred 1～3 minute under about 1500rpm～about 3000rpm and room temperature continuously.When forming thick agglomerate (median size 800～1600 μ m), stop mixing.

Step C:

The purpose of this step be by remove/dry moisture content reduces the viscosity of agglomerate, and helps particle diameter is reduced to target grain size (measuring its median size with sieve analysis is about 300～about 600 μ m).In this step, it is dry in the fluidized-bed of about 41 ℃ of airflow temperature～about 60 ℃ that wet agglomerate is fed intake, to the final water content of this particulate be about 4%～about 10%.

Step D: wrap up in and apply agglomerate and add free-flow agent

The purpose of this step is to obtain the ultimate aim particle diameter of about 300 μ m～about 600 μ m, mixes wrapping up in the material that applies agglomerate, reduces particulate caking trend and helps to keep acceptable flowability.In this step, the dry agglomerates that obtains among the step C is fed intake in Eirich Mixer (R-series), under about 1500～about 3000rpm speed, mix, in mixing, add 2～6% zeolite A (median size 2～5 μ m) simultaneously.Be mixed to continuously and obtain about 1200 required about 400 μ m median sizes (generally being about 5 seconds～about 45 seconds).Add about 0.1%～about 1.5% (wt) precipitated silica (median size 1～3 μ m) this moment, stop mixing as flow promotor.

Illustrate cloth-washing detergent below by the preceding method preparation.

Example II

Agglomerate

% (weight) % (wt)

In final product in agglomerate C _14～15Sodium alkyl sulfate 5.8 6.8C ₁₆Secondary (2,3) sodium alkyl sulfate 17.3 20.4C ₁₂～C ₁₃The alcohol of ethoxylation (EO3) 4.7 5.5C _12～14N-methyl glucose amide 4.7 5.5 acrylate/maleate copolymer 6.2 7.3 polyoxyethylene glycol, 1.4 1.7 silico-aluminates (zeolite) 8.8 10.3 Trisodium Citrates 1.9 2.2 citric acids/SKS-6 ¹11.5 3.5 yellow soda ash, 12.2 14.4EDDS ²0.4 0.5 sal epsom, 0.4 0.5 white dyess, 0.1 0.1 moisture, 7.6 8.9 silicon-dioxide ³0.4 0.5 balance material (unreacted and Na ₂SO ₄) 1.6 1.9

Agglomerate amounts to 85.0 100.0

Dried yellow soda ash (400-600 micron) 7.8NOBS that sneaks out ⁴5.9 siloxanes/PEG defoamer 0.3Lipolase 0.3Savinase 0.3

Spray spices 0.4

The finished product amount to 100.0

¹The blended particles of citric acid and layered silicate (2.0 ratio)

²Ethylenediamine disuccinate

³Hydrophobicity deposition of silica (trade(brand)name SIPERNATD-11)

⁴The ninth of the ten Heavenly Stems acyloxy benzene sulfonic acid sodium salt

EXAMPLE III

Spissated heavy dirty low bulb liquid detergent for washing clothes is as follows:

Secondary (2,3) the sodium alkyl sulfate 17.0C of component % (weight) ₁₄N-butyl glucamide 7.0 Trisodium Citrates 3.0 calcium formiate 1.5C ₁₀Alcohol ethoxylate (EO3) 6.0 boric acid 0.1 siloxanes ^*0.7MAXATASE (enzyme) 0.5LIPOLASE (enzyme) 0.5 monoethanolamine is to pH8.5 water/propylene glycol/ethanol (100: 1: 1) surplus ^*Defoamer

EXAMPLE IV

Be applicable to the laundry stick of hand-washing the dirt fabric by conventional extrusion process preparation, comprise following component:

Component % (weight) C ₁₆Secondary (2,3) sodium alkyl sulfate 30C _12～13Alkylbenzene sulfonate 7C _12～14N-methyl glucose amide 5 tripoly phosphate sodium STPPs 7 trisodium phosphate 7 yellow soda ash, 25 zeolite A (0.1～10 μ) 5 coconut single ethanol amide 2 carboxymethyl celluloses, 0.2 polyacrylates (m.w.1400) 0.2 whitening agent, spices 0.2 proteinase-10 .3CaSO ₄1MgSO ₄1 water, 4 additives ^*Surplus

^*Can be selected from conventional substances, as CaCO ₃, talcum powder, clay, silicate etc.

EXAMPLE V

By being prepared as follows gelatinous composition:

0.8 gram sal epsom in being dissolved in 25 gram water, 0.8 gram calcium formiate and 6.7 gram coconut acyl group CAB (30% activity; Albright-Wilson; Britain) add 8 gram C91-8T Dobanol (100% activity, Shell in; USA), 1.00 gram boric acid and 20 gram urea (99% activity; Fisher Scientific; USA), and at 71～74 ℃ mix down.Be uniformly mixed after the thing, add 8 gram 97.6% active coconut N-methyl glucose amides and 28 gram C ₁₆Secondary (2,3) sodium alkyl sulfate, and continue to stir.(when fluid temperature reaches about 35～40 ℃, adding) as the detergency enzymes component.Final product liquid forms gel through cooling.

Another embodiment does not add urea and makes gel.Under agitation, be dissolved in 62 ℃ the water of 42 grams and add 0.25 gram MgSO in the solution that forms to 0.002 gram blue dyes ₄, 0.25 the gram CaCl ₂, 0.50 gram spices and 35% heavy 50% (activity) coconut alkyl C ₁₂～C ₁₄N-methyl glucose amide paste.After all materials are dissolved, add 21 gram 80%C _12～14Secondary (2,3) sodium alkyl sulfate paste.77 ℃ of following restir 30 minutes.At about 40 ℃, restrain commercially available decontamination protease composition to wherein adding 0.5, and continue to stir.After stirring stopped, after the cooling, this viscous liquid was solidified into gel rapidly.

Example VI

The granulated detergent of the present invention that comprises following component.

Secondary (2, the 3) alkyl-sulphate of component % (weight) ^*10.0 zeolite A (1～10 micron) 26.0C _12～14Primary alkyl sodium sulfate salt 5.0 Trisodium Citrates 5.0 yellow soda ash 20.0 white dyess 0.1 detergency enzymes ^*1.0 sodium sulfate 15.0MgSO ₄1.0CaSO ₄1.0 water and minor component surplus

^*C ₁₄～C ₁₈Mean chain length; Sodium salt

^*1: 1 mixture LIPOLASE/ESPERASE

Example VII A

The composition that adds 0.5% commercially available amylase goods (TERMAMYL) improvement example I and II.

Example VII A I

Be specially adapted to, as follows as the other example of detergent for washing clothes particulate that contains mixed surfactant of those preceding filler washing machines of generally using in Europe:

Surfactant A B C

% (weight) % (weight) % (weight) C ₁₆Secondary (2,3) sodium alkyl sulfate 6.92 9.00 7.60C _16/18Primary alkyl sulphates 2.05 3.00 1.30C ₁₂～C ₁₅Alkyl ethoxy (1-3) sulfuric acid 0.17 0.40 0.10 salt C ₁₄～C ₁₅Alkylethoxylate (EO7) 4.02 5.00 1.30C ₁₆～C ₁₈AE11 alkylethoxylate 1.10 1.40 1.10 (EO11) C ₁₆～C ₁₈AE25 alkylethoxylate 0.85--0.66 (EO25) dimethyl monosubstituted ethoxy C _12～14Alkylammonium----1.40 muriates

Washing assistant Citrate trianion 5.20 10.00 5.00 zeolite 4A 20.50 37.20 17.90 carbonate (Na) 15.00 5.50 12.10 amorphous silicates 2.0 3.00 2.00 3.10SOKALAN CP5 ¹4.00 4.90 3.20 carboxymethyl celluloses 0.31 0.39 0.20

SYNTHETIC OPTICAL WHITNER perborate-hydrate 8.77--5.80 perborate tetrahydrate 11.64--7.40CO ₃/ SO ₄Percarbonate--12.0--TAED that coats ²--5.00 3.40 Phthalocyanine Zinc 20ppm--20ppmDEQUEST 2060 (Monsanto) 0.36 0.60 0.38MgSO ₄0.40 0.40 0.40LIPOLASE (100,000LU/g) 0.36 0.25 0.15Savinase (4.0 KNPU), 1.40 1.60 1.40 cellulases (1000CEVU/g), 0.13 0.13 0.26 dirt release agent polymkeric substance ³0.20 0.20 0.15 anionic optical brighteners 0.19--0.15 Polyvinylpyrolidone (PVP)--0.15--wilkinite----, 12.50 polyoxyethylene glycol ⁴----0.30 glycerine----, 0.62 spices, 0.43 0.43 0.43 siloxanes+dispersion agent (defoamer), 0.49 0.60 0.49 water, minor component----surplus----

¹Vinylformic acid/maleic acid; Molecular weight 70,000; Sodium salt

²Tetraacetyl ethylene diamine

³Sulfosalicylic acid, terephthalic acid, 1, the negatively charged ion pet reaction product of 2-propylene glycol, ethylene glycol and sulfoisophthalic acid, by Maldonado, ibid buys.

⁴Molecular weight 4,000,000 scope.

Previous embodiment has illustrated enforcement of the present invention, but the present invention is not limited.Preferred Ca or Mg ion approach chemical approximately calculated amount value with the weight ratio of secondary (2,3) alkyl-sulphate, by about 1: 16 to about 1: 30, also can use higher or lower ratio.Can be appreciated that higher rate may have negative influence to liquid or gel, but can accept in some cases.The low ratio that is 1: 300 scope still provides benefit in all formula for a product.

Simultaneously previous embodiment illustrated contain the second month in a season (2,3) alkyl sulfate surfactant and other be mainly the enforcement of the present composition of anionic additional surfactants.Said composition also optionally contains the mixture of various additional cats products and positively charged ion and nonionic additional surfactants.Spendable cats product comprises C ₁₀～C ₁₈Alkyl trimethyl ammonium halogenide, C ₁₀～C ₁₈Alkyl dimethyl (C ₁～C ₆) hydroxyalkyl ammonium halogenide, C ₁₀～C ₁₈Cholinesterase etc.If the use cats product, its-as be 1%～15% of present composition weight.

Claims

1. secondary (2,3) alkyl sulfate surfactant provides the purposes of cleanup action in detergent composition, described detergent composition comprises in addition:

(a) enzyme of one or more types; With

(b) the thing source of calcium ion, magnesium ion or its mixture.

2. secondary (2,3) alkyl sulfate surfactant provides the purposes of cleanup action in the laundering of textile fabrics process, described laundering of textile fabrics process is to use the laundry aqueous solution that contains calcium ion, magnesium ion or its mixture and one or more type enzymes.

3. detergent composition comprises:

(a) secondary (2,3) alkyl sulfate surfactant of at least 2% (weight);

(b) enzyme;

(c) make calcium ion or magnesium ion or its mixture of enzyme stable quantity;

(d) optionally additional enzyme stabilizers; With

(e) detergent additive optionally.

4. according to the composition of claim 1～3 in each, it is alkyl and its mixture in 10 to 18 scopes that wherein secondary (2,3) alkyl-sulphate washing composition has chain length.

5. according to the composition of claim 1～4 in each, wherein enzyme is selected from proteolytic enzyme, amylase, lipase, cellulase, peroxidase and its mixture.

6. according to the composition of claim 1～5 in each, it comprises borate or boric acid enzyme stabilizers in addition.

7. according to the composition of claim 1～6 in each, it comprises additional surfactants in addition.

8. according to the composition of claim 7, wherein additional surfactants is non-alkyl benzene sulfonate surfactant or polyhydroxy fatty acid amide.

9. according to the composition of claim 1～8 in each, it comprises detergent builder compound in addition.

10. according to the composition of claim 9, wherein detergent builder compound is selected from zeolite builders, layered silicate washing assistant, multi-carboxy acid salt washing agent and its mixture.

11. according to the composition of claim 9, wherein washing assistant is a phosphate builders.