CN1168812C - detergent composition - Google Patents

Abstract

A detergent composition comprising an enzyme, a non-alkoxylated quaternary ammonium surfactant and a bis-alkoxylated quaternary ammonium cationic surfactant.

Description

Detergent composition

Invention field

The present invention relates to a kind of detergent composition, it is (two-AQA) cats product that it comprises a kind of enzyme, a kind of non-alkoxy quaternary ammonium tensio-active agent and a kind of bis-alkoxy quaternary ammonium.

Background of invention

Because detergent composition now need be removed various types of dirts and spot on the multiple dirt-carrying body, therefore the prescription to detergent for washing clothes and other cleaning combination has proposed great challenge.Thereby for reaching effective effect, the dish washing detergent of detergent for washing clothes, hard surface cleaner, shampoo and other personal wash composition, hand washing and the detergent composition that is suitable for automatic dish washer all need to carry out the choose reasonable and the combination of composition.Above-mentioned various detergent composition are in order to become flexible and to remove dissimilar dirts and spot, and they generally contain the tensio-active agent of one or more types.As if but summary property document illustrates the combination of detergent manufacturers wide region option table surface-active agent and tensio-active agent, and in fact many compositions of washing composition are narrow spectrum chemical substances, are unsuitable for the article of low price, as the household laundry washing composition.In fact, most family expenses articles for washing, still close nonionic and/or the sulfation or the Sulfonated anion surfactant of one or more traditional ethoxylations as the household laundry washing composition, may and need preparation for economically consideration to various dirts and spot with to all goodish composition of various fabric effects.

Effectively and apace remove dissimilar dirts and spot,, be still a difficult problem to be solved as human body dirt, fats/oils dirt and some food stains.Contain triglyceride level, lipoidis, complex polysaccharide, inorganic salt and protein matter in this dirt, all these materials are made of hydrophobic part to a certain extent, remove very difficulty.After the washing, the surface of fabric is usually still residual a spot of hydrophobic dirt and spot.Wash and wear the limited removal that adds hydrophobic dirt continuously, in repeatedly washing, dirt and spot will be accumulated in a large number, its further adsorbent particles dust, cause the fabric yellowing, last, fabric presents the human consumer to be felt and can not wear and should the dim outward appearance of depleted.

Document shows that various nitrogenous cats products can use effectively in various cleaning combinations.These materials are amino, amido, quaternary ammonium or imidazolinium compounds form typically, and they are designed to special purposes usually.For example, various amino and quaternary ammonium surfactant are proposed to be used in the shampoo composite, and the hairdressing effect is allegedly arranged.Other nitrogenous tensio-active agent is used for some detergent for washing clothess, can make fabric sofetening and have anlistatig effect.Yet for most of, these materials use because of not being restricted by mass production at coml.Also be subjected to the anion active composition in the detergent composition in addition, and between the cats product because of they interionic interactions, may sedimentary restriction and form.Nowadays aforesaid nonionic and anion surfactant remain main surface active agent composition in the laundry detergent composition.

Find at present, some bis-alkoxy quaternary ammoniums (two-AQA) compound is used for various detergent composition, can strengthen the removing ability to all kinds dirt and spot, especially common hydrophobic type dirt.Now be surprised to find that, contain enzyme and the composition of bis-alkoxy quaternary ammonium surfactant and compare not only have good cleaning and whitening effect, also have the function of the nursing fabric of improvement simultaneously with only containing wherein a kind of composition of composition.

Bis-alkoxy quaternary ammonium surfactant of the present invention provides remarkable benefit for the prescription teacher than the cats product in the past.For example, the use of bis-alkoxy quaternary ammonium surfactant of the present invention is significantly improved to the cleaning performance of the hydrophobic dirt of fats/oils of " daily " that run into usually.In addition, anion surfactant such as alkyl-sulphate and alkylbenzene sulfonate can coexist mutually in bis-alkoxy quaternary ammonium surfactant and the commonly used detergent composition, and the anionic group in the detergent composition be just because of can not coexisting with cats product, and the use of cats product of today is restricted usually.The bis-alkoxy quaternary ammonium surfactant of low amount (only being 3ppm in wash water solution) just can produce benefit described herein.The bis-alkoxy quaternary ammonium surfactant can be prepared in the relative broad range between pH5-12, and two-AQA tensio-active agent can be formulated as the solution that concentration is 30% (wt.), and its available pump is carried, therefore easy handling in production unit.The bis-alkoxy quaternary ammonium surfactant that degree of ethoxylation surpasses more than 5 exists with liquid form sometimes, thereby pure material that can 100% provides.Except its easy handling properties, two-AQA tensio-active agent can obtain by highly enriched solution, and this has brought direct economic interests on the price of transportation.Different with cats products more commonly known in the art, the bis-alkoxy quaternary ammonium surfactant also can coexist mutually with various flavour ingredients.

The present invention provides a kind of method that strengthens the removal ability of fats/oils dirt by with bis-alkoxy quaternary ammonium surfactant and lipase combination.The fats/oils dirt is a kind of mixture that contains triglyceride level.Dirty clothing depositing in the process before washing, triglyceride level becomes lipid acid by the role transformation of bacterium in its dirt, and lipase can be transformed into lipid acid with any remaining triglyceride level in the process of washing.Lipid acid in the dirt and the hardness ions in the bath water are (as Mg ²⁺And Ca ²⁺) interact, form insoluble magnesium/calcium soap or calcium soap.Calcium soap precipitates from the aqueous solution, forms one deck calcium soap settling on fabric.Wash result will make the accumulation of calcium soap settling continuously, and adsorbent particles dust has influenced the removal of dirt, strengthen the dirt residue at the residual of washing on the fabric of back.In addition, also there is sheath degradation problem around the fiber of a Geju City/wearing and tearing cotton fabric or other fabric.The sheath degraded forms the cellulose gum of glue or indefinite form, also with adsorbent particles dust.In addition, this cellulose gum is the hydrophobic body dirt of fats/oils (as on neckline and pillowcase) deposition and residual desirable matrix.Wear frequently/wash, accumulated residual soil, calcium soap deposition and absorption dust, will cause the fabric flavescence, dirty until fabric, the user thinks and can't clean, and is dropped usually.

Have now found that, contain lipase and the detergent composition of bis-alkoxy quaternary ammonium surfactant and compare to have good cleaning and whitening effect with only containing wherein a kind of composition of composition.It is believed that this be because: (1) bis-alkoxy quaternary ammonium has reduced the generation of calcium soap, thereby makes lipase to contact with dirt; (2) from dirt, peel off lipid acid (by the bis-alkoxy quaternary ammonium) effectively, kept maximum lipase activity (high-load lipid acid has suppressed action of lipase in the dirt).

Find surprisingly that now the enzyme (as cellulase and/or interior living dextranase) that contains cellulose family and the detergent composition of bis-alkoxy quaternary ammonium surfactant are compared with only containing wherein a kind of composition of composition, have good cleaning and whitening effect.This is the result that the bis-alkoxy quaternary ammonium surfactant can infiltrate through hydrophobic body dirt effectively.Equally, this has also strengthened the amorphous cellulose glue (it stick to dirt fabric on) of cellulose family enzyme liberating around fiber.With cellulose gum dissolving, the dust of absorption will break away from fabric, just recover original fair and clear.The mixed system of the enzyme of cellulose family and bis-alkoxy quaternary ammonium cleans the benefit except having, also than this positively charged ion only or only softness and the nursing fabric effect during the enzyme Individual existence of cellulose family is better.

Now also find, contain amylase and the detergent composition of bis-alkoxy quaternary ammonium surfactant and compare, have and clean preferably and whitening effect with only containing wherein a kind of composition of composition.This is because the bis-alkoxy quaternary ammonium by effective solubilising dirt digestion, makes amylase be easy to enter in the responsive dirt, has improved fiber residual " glue " and degrading on every side.Along with the dissolving of glue, it is original fair and clear that fabric has recovered, and the dust of absorption breaks away from, and other detergent active composition is easy to bring into play bleaching action.

Background technology

U.S. Pat 5,441,541, authorize August 15 nineteen ninety-five, and A.Mehreteab and F.J.Loprest relate to negatively charged ion/cats product mixture.UK 2,040, and on September 3rd, 990,1980 authorized, A.P.murphy, and R.J.M.Smith and M.P.Brooks relate to ethoxylation cationic components in the detergent for washing clothes.

Summary of the invention

The present invention relates to a kind of detergent composition, it comprises following component or is mixed with by following component: the bis-alkoxy quaternary ammonium with following structural formula of a kind of enzyme, a kind of non-alkoxy quaternary ammonium tensio-active agent and significant quantity (two-AQA) cats product:

R in the formula ¹Be C straight chain, side chain or that replace ₈-C ₁₈Alkyl, alkenyl, aryl, alkaryl, ether or sugar alcohol ether (glycityl ether) part; R ²Be C ₁-C ₃Alkyl; R ³And R ⁴Can change and be selected from a kind of in hydrogen, methyl, the ethyl separately; X is a negatively charged ion; A and A ' can change and be selected from C separately ₁-C ₄Alkoxyl group; P and q can change separately and be the integer between the 1-30.

Detailed Description Of The Invention

Enzyme

Composition of the present invention comprises enzyme as essential composition.Enzyme in this detergent composition has multiple washing purpose, comprise remove protein-based, carbohydrate-based on the dirt-carrying body with the spot triglyceride level base, the transfer of the dyestuff that suppresses to come off in the fabric washing process and for the recovery of fabric.Suitable enzyme comprises proteolytic enzyme, amylase, lipase, cellulase, peroxidase and their mixture, and they are any suitable source such as plant, animal, bacterium, fungi and yeast source.Their selection is subjected to the decision of following factors: the stability of pH value activity and/or optimal stability point, thermostability, activated detergent and washing assistant etc.On bacterium aspect this or fungal enzyme is preferred, as bacterial amylase and proteolytic enzyme, and fungal cellulase.

" detergency enzymes " described here refers to have any enzyme of cleaning, decontamination or other beneficial effect in the detergent composition of laundry, hard surface cleaning or personal care.The preferred stain release enzyme is a lytic enzyme, as proteolytic enzyme, amylase and lipase.The preferred enzyme of purpose of being used to do washing includes but are not limited to proteolytic enzyme, cellulase, lipase and peroxidase.The most preferred enzyme that is suitable for the automatic dish washer washing is amylase and/or proteolytic enzyme.

Enzyme joins in washing composition or the laundry additive composition with the dosage of effective cleaning usually." effectively clean dosage " and refer to can produce cleaning, decontamination stain, decontamination dirt to washing substrate (as fabric, tableware), brighten, any dosage of deodorizing or raising freshness effect.With regard to present article of commerce, contain the organized enzyme composition in every gram detergent composition and be no more than 5mg, more general between 0.01-3mg.In other words, the content of the used commercial enzyme goods of composition of the present invention is generally 0.001%-5% (weight), is preferably 0.01%-1% (weight).The proteolytic enzyme effective level in article of commerce usually is 0.005-0.1 Anson unit (AU)/gram composition.For some washing composition (using) as automatic dish washer, in order to reduce the total amount of on-catalytic active substance greatly, improve knot spot/film thus or improve other final effect, can suitably increase the organized enzyme consumption in the article of commerce.In highly enriched detergent formulation, also need higher live vol.

Suitable examples of proteases is a subtilisin, and it is that specific bacterial strain by subtilis and Bacillus licheniformis produces.Another suitable proteolytic enzyme is produced by bacillus strain, and its activity in the pH8-12 scope is the highest, is to develop and press ESPERASE by Denmark Novo Industries A/S (hereinafter to be referred as " Novo ") ^_Sell.This enzyme or be described among the GB 1,243,783 of Novo with zymoid preparation.Other suitable proteolytic enzyme comprises the ALCALASE that Novo sells ^_And SAVINASE ^_, International Bio-synthetics, the MAXATASE that Inc. (Holland) sells ^_, protease A (referring to European patent application EP 130,756A, on January 9th, 1985 is open) and proteolytic enzyme B (referring to European patent application EP 303,761A, on April 28th, 1987 is open; European patent application EP 130,756A, on January 9th, 1985 is open).Comprise in addition: the high pH proteolytic enzyme that obtains among the bacillus NCIMB40338 that Novo describes in International Patent Application WO 9318140A, the enzyme-containing detergent that Novo describes in International Patent Application WO 9203529A wherein also comprises the enzyme and the reversible proteinase inhibitor of one or more other kinds; Other preferred proteolytic enzyme comprises Procter ﹠amp; Gamble company is at the proteolytic enzyme of describing in International Patent Application WO 9510591A; When needs, as Procter ﹠amp; Gamble company can obtain having the proteolytic enzyme that reduces absorption and strengthen hydrolytic action what describe in International Patent Application WO 9507791; Novo has described the proteolytic enzyme recombinant chou of the trypsin-like that is suitable for washing composition of the present invention in International Patent Application WO 9425583.

Particularly, particularly preferred proteolytic enzyme is called " proteolytic enzyme D ", and it has the carbonylic hydrolase varient of the undiscovered aminoacid sequence of nature.It is that in the following manner replacement obtains by carbonylic hydrolase is precursor-derived, this derive be according to coding in the bacillus amyloliquefaciens subtilisin with being equivalent in the described carbonylic hydrolase of different aminoacid replacement+a plurality of amino-acid residues of 76 positions, preferably also follow to be selected from+99, + 101 ,+103 ,+104, + 107 ,+123 ,+27, + 105 ,+109 ,+126, + 128, + 135 ,+156 ,+166, + 195, + 197 ,+204 ,+206, + 210, + 216 ,+217 ,+218, + 222, + 260 ,+265 and/or+replacement of one or more amino acid residue positions of 274, this is described in the U.S. patent application that is entitled as " cleaning combination that contains proteolytic enzyme " of A.Baeck etc., and (sequence number is 08/322,676) in, in the U.S. patent application that is entitled as " bleaching composition that contains proteolytic enzyme " (sequence number is 08/322,677) of C.Ghosh etc., both applyings date are on October 13rd, 1994.

The amylase that the present invention is fit to is particularly suitable for but is not limited only to the purpose that automatic dish washer is used, and comprising: british patent specification GB1,296, the α-Dian Fenmei of describing among 839 (Novo), by Intemational Bio-Synthetics, the RAPIDASE that Inc. sells ^_And the TERMAMYL of Novo company sale ^_, the FUNGAMYL that Novo company sells ^_It is particularly suitable.The enzyme engineering that improves enzyme stability (as oxidative stability) is known, reference example such as J.Biological Chem., Vol.260, No.11, in June, 1985,6518-6521 page or leaf.In some embodiment preferred of the present composition, the amylase that can improve at the washing composition type of dish (as be used for washing automatically) stability in use, particularly improved the amylase of oxidative stability, the reference point of this stability measurement is the TERMAMYL of commercial use in 1993 ^_Preferred these amylase of the present invention have the amylase feature of " stability strengthens ", under the situation of usage quantity minimum, be characterised in that at least following and have detectable improvement aspect one or more: oxidative stability, as in the buffered soln of pH9-10 to the oxidative stability of hydrogen peroxide/tetraacetyl ethylene diamine; Thermostability is as the stability under common wash temperature (as 60 ℃); Alkaline stability, as the stability under the pH8-11 condition, the measurement of these stability is in contrast to above definite reference amylase.The measurement of stability also can adopt the disclosed experimental technique of prior art to carry out, as disclosed reference among the patent documentation WO9402597.Stability enhanced amylase can be buied from Novo company or Genencor Intrenational.The preferred kind of starch enzyme of the present invention has general character, they are to utilize site-directed mutagenesis, deriving from one or more bacillus amylase, particularly bacillus α-Dian Fenmei obtains, and does not consider that whether a kind of, two or more amylase strains are direct precursors.Compare with above-mentioned reference amylase, have oxidative stability enhanced amylase and be optimized in the detergent composition of the present invention, especially in the bleach detergent compositions, more preferably be used for and other oxygen bleaching detergent composition of chlorine bleaching phase region.These preferred amylase comprise:

(a) amylase among the disclosed patent WO9402597 on February 3rd, 1994, explanation is that it is a kind of mutant in addition, wherein use L-Ala or Threonine (preferred Threonine) to replace the methionine residue that is positioned at 197 positions in the Bacillus licheniformis α-Dian Fenmei, promptly known TERMAMYL ^_, or for example same source position mutation of bacillus amyloliquefaciens, subtilis or bacstearothermophilus of similar homology amylase.

(b) by 207th the American Chemical Society whole nation meeting (Amercian Chemical Society National Meeting) of Genencor International at C.Mitchinson, the paper that deliver on the 13-17 in March, 1994, exercise question are the stable enhanced amylase of describing in " oxidation resistant α-Dian Fenmei ".Mention in the literary composition, with in the washing composition, SYNTHETIC OPTICAL WHITNER can make the α-Dian Fenmei inactivation, but has made oxidative stability enhanced amylase by Genencor from Bacillus licheniformis NCIB8061 at automatic dish washer.Methionine(Met) (Met) is confirmed as the residue that most probable is modified.Replace methionine(Met) one at a time in 8,15,197,256,304,366 and 438 positions, cause generating specific varient, particularly importantly M197L and M197T, wherein the M197T varient is the varient that the most stable quilt is expressed.Use CASCADE ^_And SUNLIGHT ^_Measured stability.

(c) the present invention particularly preferably be describe among the patent documentation WO9510613A directly in the parent other improved amylase variants being arranged, can buy from assignee Novo company, commodity are called DURAMYL ^_

Other particularly preferred oxidative stability enhanced amylase comprises the amylase of describing among patent documentation WO9418314 (Genencor International) and the WO9402597 (Novo).Also can use any other oxidative stability enhanced amylase, for example by carrying out the amylase that site-directed mutagenesis obtains from available known amylase chimeric, hybridization or simple mutant parent form.Also can carry out other preferred enzyme modification, referring to patent documentation WO9509909A (Novo).

Other amylase comprises the amylase of describing among the application PCT/DK96/00056 that do not wind up the case of WO95/26397 and Novo Nordisk.The specific amylase that uses in the detergent composition of the present invention comprises the α-Dian Fenmei with following characteristics: press Phadebas ^_The alpha-amylase activity check is measured, and at temperature 25-55 ℃, under the pH8-10 condition, its specific activity is at least than Termamyl ^_The big 25% (Phadebas of specific activity ^_WO95/26397 9-10 page or leaf is seen in the alpha-amylase activity check).Also comprise in addition with the amino acid sequence homology shown in the SEQ ID of the above-mentioned document table and surpass 80% α-Dian Fenmei.Described these enzymes join in the laundry detergent composition with pure enzyme form, and preferably its consumption is the 0.00018%-0.060% of composition total weight, more preferably the 0.00024%-0.048% of composition total weight.

The cellulase that can be used among the present invention comprises bacterium and mould cellulase, and their optimal ph is between 5-9.5.The U.S. Pat 4 of authorizing in people's such as Barbesgoard 6 days March in 1984,435, disclose in 307 and derived from Humicola insolens or rotten suitable mould cellulase of planting trichoderma strain DSM1800, perhaps belong to cellulase 212 that the mould of Aeromonas produces and the cellulase that in extra large mollush Dolabella Auricula Solander hepatopancreas, extracts.Suitable cellulase also is disclosed in GB-A-2, in 075,028, GB-A-2,095,275 and DE-OS-2,247,832.CAREZYME ^_And CELLUZYME ^_(Novo) also particularly suitable is with reference to WO9117243 (Novo).

The spendable suitable lipase of washing composition comprises: by the bacteriogenic lipase of Rhodopseudomonas, as the lipase of Situ Ci Shi aeruginosa atcc 19.154 (English Patent GB1,372,034 is open) generation; Lipase among the Japanese patent application 53-20487 of open special permission on February 24th, 1978 can be by Amano Pharmaceutical Co.Ltd.Nagoya, and Japan buys, commodity lipase P " Amano " by name or " Amano-P ".Other commercial lipase that is fit to comprises: Amano-CES, and from thickness look bacillus, for example thickness look bacillus is separated the lipase of fat mutation NRRLB 3673, and Toyo Jozo Co.Tagata Japan sells; Thickness look bacillus lipase, U.S.Biochemical Corp. (USA) and Disoynth Co. (Holland) sell; With lipase from the Chang of Tang pseudomonas.Bacterium is planted in corruption from fetal hair, and at the commercial LIPOLASE that sells by Novo (equally referring to EP341,947) ^_Enzyme is to be used for preferred fat enzyme of the present invention.Lipase and diastatic varient are seen description among the WO9414951A (Novo) at the stabilization of peroxidase, also can be referring to WO9205249 and RD94359044.

Although numerous disclosed lipase are arranged, so far only finding to derive from the fetal hair corruption plants the lipase of bacterium and aspergillus oryzae and extensively uses as the fabric detergent supplementary component for the lipase of host's generation, as above-mentioned, it can be buied by Novo Nordisk, and trade mark is Lipolase ^TMFor making Lipolase show best soil removability, Novo Nordisk has obtained a large amount of Lipolase varients.Described in WO92/05249, the varient D96L of the lipase of bacterium is planted in natural fetal hair corruption, compares with wild-type lipase, and the effect of lard greasiness removal has improved 4.4 times (are 0.075-2.5mg protein/liter comparison enzyme by consumption).Novo Nordisk described in ResearchDisclosure (numbering 35944) on March 10th, 1994: the amount that lipase varient (D96L) adds in every liter of washing soln is 0.001-100mg (5-500, a 000LU/ liter) lipase varient.Among the present invention, the detergent composition that contains the bis-alkoxy quaternary ammonium surfactant uses the D96L varient of low levels, and it is that 50-8500LU/ rises washing soln that the consumption of effect, especially D96L of the maintenance whiteness of improvement can be provided.

The at of describing among the patent application WO8809367A of Genencor is suitable in the present invention.

Peroxidase and oxygen source body, for example percarbonate, perborate, hydrogen peroxide etc. are used in combination, and they are used for " solution bleaching ", or are suppressed at the dyestuff that comes off in the washing process and pigment are transferred on other basic thing in the washing soln from basic thing.The peroxidase that oneself knows comprises, horseradish peroxidase, lignoenzyme and halo peroxidase (as chloro or bromoperoxidase).The detergent composition that contains peroxidase is disclosed in WO89099813A, and (open day on October 19th, 1989 is Novo) and among the WO8909813A (Novo).

Various enzyme material and they are mixed method in the synthetic detergent composition also at International Patent Application WO 9307263A and the WO9307260A of Genencor International, the International Patent Application WO 8908694A of Novo, U.S. Pat 3 with people such as McCarty, open in 553,139 (mandates on January 15th, 1971).Some enzymes also are disclosed in the U.S. Pat 4,507,219 (mandate on March 26th, 1985) of people's such as Place U.S. Pat 4,101,457 (mandate on July 18th, 1978) and Hughes.Useful enzyme material in the liquid detergent formula, and the method that they are incorporated in this prescription is disclosed in people's such as Hora the U.S. Pat 4,261,868 (mandate on April 14th, 1981).The enzyme that is used for washing composition can in all sorts of ways and make it stable.The enzyme stabilization technology is open and illustrate in the European patent EP 199,405, EP 200,586 (on October 29th, 1986 disclosed) of U.S. Pat 3,600,319 (mandates on August 17th, 1971) people such as Gedge and Venegas.The enzyme stabilization system also has document description, as U.S. Pat 3,519,570.Proteolytic enzyme, zytase and cellulase that suitable bacillus AC13 produces have been described among the International Patent Application WO 9401532A (Novo).

Bis-alkoxy quaternary ammonium (bis-AQA) cats product

Second necessary component of the present composition comprises the bis-alkoxy quaternary ammonium surfactant of significant quantity, and its structural formula is as follows:

R in the formula ¹For containing 8-18 carbon atom, preferred 8-16 carbon atom, alkyl, alkenyl, aryl, alkaryl, ether or the sugar alcohol ether of most preferably the straight chain of 8-14 carbon atom, side chain or replacement; R ²For containing the alkyl of 1-3 carbon atom, preferable methyl; R ³And R ⁴Can change and be selected from hydrogen (preferably), methyl, ethyl separately; X ^-Be negatively charged ion, as chlorine, bromine, methylsulfate, sulfate radical, it can provide electric neutrality effectively; A and A ' can change and respectively be selected from C separately ₁-C ₄Alkoxyl group, particularly oxyethyl group, propoxy-, butoxy and their mixed type; P is 1-30, preferred 1-15, and more preferably 1-8 most preferably is 1-4, and q is 1-30, is preferably 1-15, and more preferably 1-8 is preferably 1-4 especially, and p and q most preferably are 1.

Bis-alkoxy quaternary ammonium (bis-AQA) compound, wherein hydrocarbyl substituent R ¹Be C ₈-C ₁₂, C especially ₈-C ₁₀, compare with the compound of the substituted hydrocarbon radical of long-chain, under the cold water condition, can increase detergent for washing clothes particulate dissolution rate especially.Therefore, this C ₈-C ₁₂The bis-alkoxy quaternary ammonium surfactant also can be the prescription Shi Youxuan.The consumption of bis-alkoxy quaternary ammonium surfactant is generally 0.1%-5% (wt.) in the finished product laundry detergent composition, is preferably 0.45%-2.5% (wt.).The part by weight of bis-alkoxy quaternary ammonium surfactant and percarbonate bleach is from 1: 100 to 5: 1, preferably from 1: 60 to 2: 1, most preferably from 1: 20 to 1: 1.

The present invention adopts the bis-alkoxy quaternary ammonium surfactant of " effective level ", contains the performance that other selects the cleaning combination of component with raising." effective level " of bis-alkoxy quaternary ammonium surfactant as herein described is meant when 90% confidence level, is enough to improve directionally or significantly the washing effect needed consumption of cleaning combination at least some target dirts and spot.Therefore, for the composition of some food target spots, the prescription teacher will use the bis-alkoxy quaternary ammonium of q.s, at least directionally to improve the cleaning performance to these spots.Equally, in the composition for great soil group target dirt, the prescription teacher will use the bis-alkoxy quaternary ammonium of q.s, at least directionally to improve the cleaning performance to this dirt.

The bis-alkoxy quaternary ammonium surfactant can be used in combination with other detergent surfactant, and its consumption is the significant quantity that obtains at least directionally to improve cleaning performance.With regard to fabric cleaning composition, its " consumption " can be different with light and heavy degree according to the type of dirt and spot, also can according to when washing water temperature, water consumption different with the washing machine type and change.

For example, top feeding formula vertical shaft U.S. (state) formula automatic washing machine, water 45-83 liter during washing, one cycles of washing 10-14 minute, during washing water temperature 10-50 ℃, the amount that preferably comprises the bis-alkoxy quaternary ammonium surfactant in washing liq is 2-50ppm, is preferably 5-25ppm.For heavy duty liquid detergent, wash the loading capacity usage quantity at every turn and calculate with 50-150ml, converting the concentration of bis-alkoxy quaternary ammonium surfactant in product to is 0.1%-3.2% (weight), is preferably 0.3%-1.5% (weight).For concentrating granular laundry detergent (density is more than 650g/l), each washing loading capacity usage quantity is calculated with 60-95g, converting the concentration of bis-alkoxy quaternary ammonium surfactant in product to is 0.2%-5.0% (weight), is preferably 0.5%-2.5% (weight).To spray-dired granulated detergent (i.e. " loose type ", density is lower than 650g/l), each washing loading capacity usage quantity is calculated with 80-100g, converting the concentration of bis-alkoxy quaternary ammonium surfactant in product to is 0.1%-3.5% (weight), is preferably 0.3%-1.5% (weight).

For example, preceding charging type transverse axis Europe (continent) formula automatic washing machine, water 8-15 liter during washing, one cycles of washing 10-60 minute, during washing water temperature 30-95 ℃, the amount that preferably comprises the bis-alkoxy quaternary ammonium surfactant in washing liq is 13-900ppm, is preferably 16-390ppm.For heavy duty liquid detergent, wash the loading capacity usage quantity at every turn and calculate with 45-270ml, converting the concentration of bis-alkoxy quaternary ammonium surfactant in product to is 0.4%-2.64% (weight), is preferably 0.55%-1.1% (weight).For concentrating granular laundry detergent (density is more than 650g/l), each washing loading capacity usage quantity is calculated with 40-210g, converting the concentration of bis-alkoxy quaternary ammonium surfactant in product to is 0.5%-3.5% (weight), is preferably 0.7%-1.5% (weight).To spray-dired granulated detergent (i.e. " loose type ", density is lower than 650g/l), each washing loading capacity usage quantity is calculated with 140-400g, converting the concentration of bis-alkoxy quaternary ammonium surfactant in product to is 0.13%-1.8% (weight), is preferably 0.18%-0.76% (weight).

For example, top feeding formula vertical shaft Japonica type automatic washing machine, water 26-52 liter during washing, one cycles of washing 8-15 minute, during washing water temperature 5-25 ℃, the amount that comprises the bis-alkoxy quaternary ammonium surfactant in the washing liq is 1.67-66.67ppm, is preferably 3-6ppm.For heavy duty liquid detergent, wash the loading capacity usage quantity at every turn and calculate with 20-30ml, converting the concentration of bis-alkoxy quaternary ammonium surfactant in product to is 0.25%-10% (weight), is preferably 1.5%-2% (weight).For concentrating granular laundry detergent (density is more than 650g/l), each washing loading capacity usage quantity is calculated with 18-35g, converting the concentration of bis-alkoxy quaternary ammonium surfactant in product to is 0.25%-10% (weight), is preferably 0.5%-1.0% (weight).To spray-dired granulated detergent (i.e. " loose type ", density is lower than 650g/l), each washing loading capacity usage quantity is calculated with 30-40g, and converting the concentration of bis-alkoxy quaternary ammonium surfactant in product to is 0.25%-10% (weight), is preferably 0.5%-1% (weight).

From above as seen, the amount of the bis-alkoxy quaternary ammonium that uses in machine washing can be according to user's custom and practical experience, and the type of washing machine and changing.Thereby, in this respect, before one of the bis-alkoxy quaternary ammonium surfactant incognizant advantage be: compare with other tensio-active agent (being generally negatively charged ion or anionic/nonionic mixture) in the existing washing composition, even under low relatively consumption, it has the directed at least ability that improves washing effect to various dirts and spot.This is different from other composition of prior art, and various cats products in the existing composition and anion surfactant are with stoichiometry or approach the stoichiometry use.Generally, in the enforcement of the present invention, bis-alkoxy quaternary ammonium surfactant and anion surfactant weight ratio are from 1: 70 to 1: 2 in the laundry detergent composition, are preferably from 1: 40 to 1: 6, more preferably from 1: 30 to 1: 6, more preferably from 1: 15 to 1: 8.Comprise in the laundry detergent composition of negatively charged ion and nonionogenic tenside the bis-alkoxy quaternary ammonium: the weight ratio of anionic/nonionic mixture is from 1: 80 to 1: 2, is preferably from 1: 50 to 1: 8.

Various other detergent composition that comprise a kind of anion surfactant, a kind of selectivity nonionogenic tenside and specific tensio-active agent (as trimethyl-glycine, sultaine, amine oxide) also can use the bis-alkoxy quaternary ammonium surfactant among the present invention of significant quantity to prepare.These compositions include but not limited to, the dish washing detergent that is suitable for hand-washing (particularly aqueous or gelatinous), hard surface cleaner, shampoo, personal wash composition, detergent for washing clothes etc.Because it is less that the user changes the use habit of these washing composition and practical experience, comprise in these compositions the bis-alkoxy quaternary ammonium surfactant amount from 0.25% to about 5% (weight) be suitable, be preferably 0.45% to about 2% (weight).In addition, with regard to granular and aqueous laundry cleaning composition, the part by weight of other tensio-active agent is lower in bis-alkoxy quaternary ammonium surfactant and these compositions, promptly compares with negatively charged ion to be lower than stoichiometry.Preferred this cleaning combination comprises the above laundry composition of using for the machine bis-alkoxy quaternary ammonium/tensio-active agent ratio of narration just.

Compare with known other cats product herein, the cats product of bis-alkoxyization of the present invention has enough solubleness, and it can be used in combination in very low and this system of the content of nonionogenic tenside in this mixed surfactant system with mixed surfactant system and contain as alkyl sulfate surfactant.The item that this considers emphatically for the prescription teacher of the detergent composition of following type: be used for the detergent composition of the traditional design of roof-mounted automatic washing machine, especially be designed for the type and the Japanese type that uses that use the North America.Generally, these compositions will comprise anion surfactant and nonionogenic tenside, and its ratio is from about 25: 1 to about 1: 25, is preferably about 20: 1 to about 3: 1.The prescription of Europe type is different therewith, and the ratio of its anion surfactant and nonionogenic tenside is generally from about 10: 1 to about 1: 10, is preferably about 5: 1 to about 1: 1.

The cats product of the preferred ethoxylation of the present invention can obtain from Akzo NobelChemicals Company, and commodity are called ETHOQUAD.In addition, it also can obtain (" EO " expression-CH wherein from following various reaction scheme is synthetic ₂CH ₂The O-unit):

Scheme 1

Scheme 2

Scheme 3

Scheme 4

The reaction scheme of an economy is as follows:

Scheme 5

Following parameter has been summed up the optional and preferred reaction conditions of scheme 5.The step 1 of reaction is preferably carried out at aqueous phase.Temperature of reaction is generally within 140-200 ℃ of scope.Reaction pressure is 50-1000 pound/inch ²Alkaline catalysts preferably uses sodium hydroxide.The mol ratio of reactant (amine: alkyl-sulphate) from 2: 1 to 1: 1.The preferred C that uses of reaction ₈-C ₁₄Sodium alkyl sulfate carries out.Alkylation and quaternized step adopt traditional condition and reactant to carry out.

Under some conditions, the sufficiently water-soluble reacting phase of the product of scheme 5 can form gel.Though can reclaim the purpose product from gel, commercial, two step synthetic another programs 6 described below will be more feasible.The first step reaction of scheme 6 is consistent with scheme 5, and the second step reaction (ethoxylation) preferably uses oxyethane and a kind of sour example hydrochloric acid to carry out, and will obtain quaternary surfactant.As following shown, chloroethanol also can react and obtain required double hydroxyethyl derivative.

With regard to reaction scheme 6, following parameter has been summed up the optional and preferred condition of its first step reaction.The first step reaction is preferably carried out at aqueous phase.Temperature of reaction is generally within 100-230 ℃ of scope.Reaction pressure is 50-1000 pound/inch ²The HSO that produces in preferred sodium hydroxide of alkali and the reaction ₄ ^-Reaction, excessive amine also can be used for and this acid-respons.The mol ratio of reactant (amine: alkyl-sulphate) generally from 10: 1 to 1: 1.5, preferred 5: 1 to 1: 1.1, further preferred 2: 1 to 1: 1.In the step that product reclaims, required replacement amine is soluble at aqueous phase, is different from water, is easy to separate.The reaction of second step adopts traditional reaction conditions to carry out.Further ethoxylation and quaternised being reflected under the standard reaction condition that produces the bis-alkoxy quaternary ammonium surfactant carried out.

Scheme 7 optionally adopts oxyethane to carry out under standard ethoxylation condition, does not need catalyzer, can obtain the monosubstituted ethoxy product.

Listed the reaction scheme of these increases below, wherein " EO " expression-CH ₂CH ₂The O-unit.In the reaction, the HSO that mineral alkali, organic bases or excessive amine are used to neutralize and produce ₄ ^-

Scheme 6

Scheme 7

Below increase in addition and introduce several above-mentioned reactions, only, do not limit it for prescription teacher reference.

Synthetic A:

N, the preparation of two (2-hydroxyethyl) n-Laurylamines of N-

In glass pressure still sleeve pipe, add 19.96g sodium lauryl sulphate (0.06921 mole), 14.55g diethanolamine (0.1384 mole), 7.6g sodium hydroxide 50% (weight) solution (0.095 mole), and 72g distilled water.Pack into after the glass bushing sealing in the stainless steel stirring-type autoclave pressure of 500ml, at 300-400 pound/inch ²Being heated to 160-180 ℃ under the nitrogen pressure kept 3-4 hour.Mixture is cooled to room temperature, and the liquid in the glass bushing is poured in the separating funnel of 250ml, adds the 80ml chloroform, vibration back several minutes, and mixture is promptly separable.Reclaim the chloroform of lower level, treat chloroform evaporated after, can obtain reaction product.

Synthetic B:

N, the preparation of two (2-hydroxyethyl) n-Laurylamines of N-

Under the condition that alkali exists, 1 mole of sodium lauryl sulphate is reacted with the method for synthesizing among the A with 1 molar ethanolamine.Reclaim reaction product 2-hydroxyethyl n-Laurylamine, again with 1-chloroethanol prepared in reaction N, two (2-hydroxyethyl) n-Laurylamines of N-.

Synthetic C:

N, the preparation of two (2-hydroxyethyl) n-Laurylamines of N-

In glass pressure still sleeve pipe, add 19.96g sodium lauryl sulphate (0.06921 mole), 21.37g thanomin (0.3460 mole), 7.6g sodium hydroxide 50% (weight) solution (0.095 mole), and 72g distilled water.Pack into after the glass bushing sealing in the stainless steel stirring-type autoclave pressure of 500ml, under 300-400 pound/in2 nitrogen pressure, be heated to 160-180 ℃ and kept 3-4 hour.Mixture is cooled to room temperature, and the liquid in the glass bushing is poured in the separating funnel of 250ml, adds the 80ml chloroform, vibration back several minutes, and mixture is promptly separable.Reclaim the lower level chloroform, treat chloroform evaporated after, can obtain reaction product.In the presence of no alkaline catalysts, under 120-130 ℃ condition, the reacting ethylene oxide of this reaction product and 1 molar equivalent can obtain required end product.

The bis substituted amine of preamble preparation can carry out ethoxylation by standard manner, and is quaternized according to a conventional method with alkyl halide again, can obtain bis-alkoxy quaternary ammonium surfactant of the present invention.

According to the description of front, for example the bis-alkoxy quaternary ammonium surfactant that uses among the present invention is described without limitation below.Be to be understood that, the alkyl degree of oxidation of the bis-alkoxy quaternary ammonium surfactant among the present invention is to report by mean value, below be the nonionogenic tenside common instance of common ethoxylation, this is because ethoxylation generally produces the mixture of different degree of ethoxylation.Thereby, write down total EO value with non-integer as " EO2.5 ", " EO3.5 " usually.

Title R ¹ R ² ApR ³ A ' qR ⁴

Bis-alkoxy quaternary ammonium-1 C ₁₂-C ₁₄CH ₃EO EO

(referring to coconut methyl EO2)

Bis-alkoxy quaternary ammonium-2 C ₁₂-C ₁₆CH ₃(EO) ₂EO

Bis-alkoxy quaternary ammonium-3 C ₁₂-C ₁₄CH ₃(EO) ₂(EO) ₂

(referring to coconut methyl EO4)

Bis-alkoxy quaternary ammonium-4 C ₁₂CH ₃EO EO

Bis-alkoxy quaternary ammonium-5 C ₁₂-C ₁₄CH ₃(EO) ₂(EO) ₃

Bis-alkoxy quaternary ammonium-6 C ₁₂-C ₁₄CH ₃(EO) ₂(EO) ₃

Bis-alkoxy quaternary ammonium-7 C ₈-C ₁₈CH ₃(EO) ₃(EO) ₂

Bis-alkoxy quaternary ammonium-8 C ₁₂-C ₁₄CH ₃(EO) ₄(EO) ₄

Bis-alkoxy quaternary ammonium-9 C ₁₂-C ₁₄C ₂H ₅(EO) ₃(EO) ₃

Bis-alkoxy quaternary ammonium-10 C ₁₂-C ₁₈C ₃H ₇(EO) ₃(EO) ₄

Bis-alkoxy quaternary ammonium-11 C ₁₂-C ₁₈CH ₃(propoxy-) (EO) ₃

Bis-alkoxy quaternary ammonium-12 C ₁₀-C ₁₈C ₂H ₅(isopropoxy) ₂(EO) ₃

Bis-alkoxy quaternary ammonium-13 C ₁₀-C ₁₈CH ₃(EO/ propoxy-) ₂(EO) ₃

Bis-alkoxy quaternary ammonium-14 C ₈-C ₁₈CH ₃(EO) ₁₅ ^*(EO) ₁₅ ^*

Bis-alkoxy quaternary ammonium-15 C ₁₀CH ₃EO EO

Bis-alkoxy quaternary ammonium-16 C ₈-C ₁₂CH ₃EO EO

Bis-alkoxy quaternary ammonium-17 C ₉-C ₁₁CH ₃-EO3.5 (on average)

Bis-alkoxy quaternary ammonium-18 C ₁₂CH ₃-EO3.5 (on average)

Bis-alkoxy quaternary ammonium-19 C ₈-C ₁₄CH ₃(EO) ₁₀(EO) ₁₀

Bis-alkoxy quaternary ammonium-20 C ₁₀C ₂H ₅(EO) ₂(EO) ₃

Bis-alkoxy quaternary ammonium-21 C ₁₂-C ₁₄C ₂H ₅(EO) ₅(EO) ₃

Bis-alkoxy quaternary ammonium-22 C ₁₂-C ₁₈C ₃H ₇Butoxy (EO) ₂

^*Oxyethyl group is optional with methyl or ethyl capping.

Particularly preferred bis-alkoxy quaternary ammonium compound structural formula is as follows:

R wherein ¹Be C ₈-C ₁₈Alkyl and mixed group thereof, preferred C ₈, C ₁₀, C ₁₂, C ₁₄Alkyl and mixed group thereof; X is for producing any conventional negatively charged ion of charge balance, preferred chlorion.With reference to bis-alkoxy quaternary ammonium formula mentioned above, because in preferred compound, R ¹Derived from coconut (C ₁₂-C ₁₄Alkyl) partial fatty acid, R ²Be methyl, and A _pR ³And A ' _qR ⁴Be respectively monosubstituted ethoxy, so this preferred compound is exactly to go up table listed " coconut MeEO2 " or " bis-alkoxy quaternary ammonium-1 ".

Be used for other bis-alkoxy quaternary ammonium surfactant of the present invention and comprise compound with following structural formula:

R wherein ¹Be C ₈-C ₁₈Alkyl, preferred C ₈-C ₁₄Alkyl, p and q are 1-3 respectively independently, R ²Be C ₁-C ₃Alkyl, preferable methyl, and X is negatively charged ion, especially chlorion or bromide anion.

Other compound of aforesaid kind comprises: oxyethyl group (CH wherein ₂CH ₂O) unit (EO) is by butoxy (Bu), isopropoxy [CH (CH ₃) CH ₂O] and [CH ₂CH (CH ₃) O] unit (i-Pr) or positive propoxy unit (Pr) or EO and/or Pr and/or displaced those compounds of the unitary mixed form of i-Pr.

The particularly preferred bis-alkoxy quaternary ammonium surfactant that is used for adding the washing assistant prescription has such structural formula: wherein p and/or q are the integer in the 10-15 scope.This compound is specially adapted to laundry hand washing detergent composition.

Non-alkoxy quaternary ammonium detergent surfactant

Except containing the bis-alkoxy quaternary ammonium surfactant, the present composition also preferably comprises non-alkoxy quaternary ammonium tensio-active agent.Non-alkoxy quaternary ammonium tensio-active agent comprises any negatively charged ion, nonionic or other cats product on substantially.

Anion surfactant

Usually the indefiniteness example that is used for anion surfactant of the present invention with content 1%-55% (weight) comprises: conventional C ₁₁-C ₁₈Alkylbenzene sulfonate (" LAS "); Uncle position (" AS "), side chain or random C ₁₀-C ₂₀Alkylsulfonate; Structural formula is CH ₃(CH ₂) _x(CHOSO ₃ ^-M ⁺) CH ₃And CH ₃(CH ₂) _y(CHOSO ₃ ^-M ⁺) CH ₂CH ₃C ₁₀-C ₁₈Secondary (2,3) alkylsulfonate, wherein x and (y+1) be to be at least 7 preferably be at least 9 integer, and M is water-soluble cationic (a particularly sodium); Unsaturated vitriol is as oleyl sulfate; C ₁₂-C ₁₈α-sulfonated fatty acid ester; C ₁₀-C ₁₈The sulfated polysaccharides glycosides; C ₁₀-C ₁₈Alkyl alkoxy sulfate (" AE _xS ", EO 1-7 ethoxy sulfate particularly), and C ₁₀-C ₁₈Alkyl alkoxy carboxylate salt (particularly EO 1-5 ethoxy carboxylate).C ₁₂-C ₁₈Trimethyl-glycine and sultaine, C ₁₀-C ₁₈Amine oxide can be included in the total composition, also can use conventional C ₁₀-C ₂₀The soap class.Foam enhancing can use side chain C if desired ₁₀-C ₁₆The soap class.In general textbook, listed other conventional surfactant.

Nonionogenic tenside

Usually the indefiniteness example that is used for nonionogenic tenside of the present invention with content 1%-55% (weight) comprises: alcohol alcoxylates (AE ' s), alkylphenol, polyhydroxy fatty acid amide (PFAA ' s), alkyl poly glucoside (APG ' s), C ₁₀-C ₁₈Glyceryl ether.

More particularly, the condensation product of primary aliphatic alcohols and secondary alcohol and 1-25 moles of ethylene oxide (AE) is suitable for use in the present invention as nonionogenic tenside.The alkyl chain of fatty alcohol can be a straight or branched, uncle position or secondary position, and generally comprise 8-22 carbon atom.Its alkyl group contains 8-20 carbon atom, alcohol (1 mole) that is preferably 10-18 carbon atom and 1-10 mole, and 2-7 mole more preferably, the condensation product that most preferably is the 2-5 moles of ethylene oxide is preferred.The example of commercial available this nonionogenic tenside comprises: Tergitol that is sold by Union CarbideCorporation all ^TM15-S-9 (C ₁₁-C ₁₅The condensation product of straight chain alcohol and 9 moles of ethylene oxide) and Tergitol ^TM24-L-6NMW (C ₁₂-C ₁₄The product with narrow molecular weight distributions of primary alconol and 6 moles of ethylene oxide condensations); Neodol by Shell Chemical Company sale ^TM45-9 (C ₁₄-C ₁₅The condensation product of straight chain alcohol and 9 moles of ethylene oxide), Neodol ^TM23-3 (C ₁₂-C ₁₃The condensation product of straight chain alcohol and 3 moles of ethylene oxide), Neodol ^TM45-7 (C ₁₄-C ₁₅The condensation product of straight chain alcohol and 7 moles of ethylene oxide) and Neodol ^TM45-5 (C ₁₄-C ₁₅The condensation product of straight chain alcohol and 5 moles of ethylene oxide); By Procter ﹠amp; The Kyro that Gamble Company sells ^TMEOB (C ₁₃-C ₁₅The condensation product of alcohol and 9 moles of ethylene oxide); And the Genapol LA O3O or the O5O (C that sell by Hoechest ₁₂-C ₁₄The condensation product of alcohol and 3 or 5 moles of ethylene oxide).In these AE non-ionic surface active systems, the preferable range of hydrophile-lipophile balance value (HLB) is 8-11, most preferably is 8-10.Also can use and the condenses of propylene oxide and butylene oxide ring.

The polyhydroxy fatty acid amide that to can be used for another kind of preferred nonionic of the present invention be following structural formula:

R wherein ¹Be H or C _1-4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or its mixed group; R ²Be C _5-31Alkyl; And Z is polyhydroxy alkyl or its alkoxylate deriveding group that at least directly is connected with 3 hydroxyls on the straight-chain alkyl chain.R ¹Be methyl, R ²It is straight chain C _11-15Alkyl, C _15-17Alkyl or alkenyl (as the coconut alkyl) or its mixed group, and Z is obtained in the reductive amination reaction as glucose, fructose, maltose, lactose by reducing sugar.Its typical example comprises C ₁₂-C ₁₈And C ₁₂-C ₁₄N-methyl glucoside acid amides is referring to U.S. Pat 5194639 and US 5298636.Also can use N-alkoxyl group polyhydroxy fatty acid amide, referring to U.S. Pat 5489393.

In the present invention, also can be used as having of nonionogenic tenside: the alkyl polysaccharide of tool hydrophobic grouping, open in the United States Patent (USP) 4565647 of the Llenado that authorizes on January 21st, 1986, its hydrophobic grouping contains 6-30 carbon atom, preferably 10-16 carbon atom; Polysaccharide contains 1.3-10 as its hydrophobic grouping, preferred 1.3-3, most preferably the glycan glycosides of 1.3-2.7 sugar unit.Can use any reducing sugar that contains 5 or 6 carbon atoms, as glucose, semi-lactosi, and the galactosyl part can be replaced to glucosyl group part (hydrophobic grouping optionally is connected on 2-, 3-, the 4-equipotential, can obtain like this and glucoside or sweet different glucose of semi-lactosi or semi-lactosi).Key can be positioned between sugar, as, between a position of other sugar unit and 2-, the 3-of previous sugar unit, 4-and/or the 6-position.

Preferred alkyl poly glucoside has following structural formula:

R ₂O (C _nH _2nO) _t(glycosyl) _x

Wherein: R ²Be selected from alkyl, alkane phenyl, hydroxyalkyl, hydroxyalkyl phenyl and mixed group thereof, wherein alkyl group contains 10-18, preferred 12-14 carbon atom; N is 2 or 3, preferred 2; T is 0-10, preferred 0; X is 1.3-10, preferred 1.3-3, more preferably 1.3-2.7.The preferred glucose-derivative of glycosyl.In order to prepare these compounds, at first prepare the many ethoxy alcohols of alcohol or alkyl, react with glucose or source of glucose then, form glucoside (being connected the 1-position).Then, the 1-position of other glycosyl units can be connected with previous glycosyl units 2-, 3-, 4-and/or 6-position (main preferred 2-position).

In surfactant system of the present invention, the polyethylene oxide of alkylphenol, propylene oxide and butylene oxide ring condenses also are suitable for and make nonionogenic tenside, and wherein polyethylene oxide condensation compound is preferred.These compounds comprise: alkyl group contains 6-14 carbon atom, and the alkylphenol of preferred 8-14 carbon atom is with the condensation product of straight or branched configuration and alkylene oxide.In a preferred embodiment, the amount of oxyethane is: every mole of alkylphenol 2-25 mole, preferred 3-15 moles of ethylene oxide.Can draw together from the commercial the type ionic surfactant pack that obtains: by the Igepal of GAFCorporation sale ^TMCO-630; And by Rohm ﹠amp; The Triton that Hass Company sells ^TMX-45, X-114, X-100 and X-102.The so-called alkyl phenolic alkoxy thing of these tensio-active agents (as the alkylphenol b-oxide).

The hydrophobic framework that condensation reaction by propylene oxide and propylene glycol obtains, again with ethylene oxide condensation, its product also is suitable for other nonionogenic tenside of doing among the present invention.The molecular weight of these compound hydrophobic parts is preferably 1500-1800, and water insoluble.By adding the polyoxyethylene part to this hydrophobic part, generally can improve the water-soluble of whole molecule, and be 50% o'clock of condensation product gross weight at polyoxyethylene content, still can keep the characteristics of liquids of this product.This is equivalent to and maximum 40 moles ethylene oxide condensation.The example of this compound comprises, by the part Pluronic of BASF sale ^TMTensio-active agent.

In nonionic surfactant system of the present invention, be suitable in addition and do having of nonionogenic tenside: the reaction product of propylene oxide and quadrol again with the condensation product of oxyethane.The hydrophobic part of these products is made up of the reaction product of quadrol and excessive propylene oxide, and its molecular weight is generally 2500-3000.This hydrophobic part and oxyethane carry out condensation, make condensation product contain 40-80% (weight) polyoxyethylene, and its molecular weight are 5000-11000.The example of this nonionogenic tenside comprises, by the part Tetronic of BASF sale ^TMCompound.

Other cats product

Suitable cationic surfactants preferably has the water-dispersion compound of surfactant properties, and it contains at least one ester bond (that is ,-COO-) with at least one positive electric group.

Other suitable cation tensio-active agent comprises: be selected from single C ₆-C ₁₆(preferred C ₆-C ₁₀) quaternary surfactant of N-alkyl or alkenyl ammonium surfactant, wherein remaining N position is replaced by methyl, hydroxyethyl or hydroxypropyl group.Other suitable cationic ester tensio-active agent (comprising the cholinesterase tensio-active agent), open in U.S. Patent No. 4228042,4239660 and 4260529.

Optional detergent ingredients

Other various compositions that optionally are used for the present composition are described below, but are not limited thereto.

The enzyme stabilising system

The present invention contains enzyme composition and also comprises 0.001%-10% (weight), is preferably 0.005%-8% (weight), most preferably is the enzyme stabilising system of 0.01%-6% (weight).The enzyme stabilising system can be any stabilising system compatible with detersive enzyme.This stabilising system can be provided by other active ingredient itself in the prescription, also can add separately, as by the prescription teacher or by the producer of washing composition alternation enzyme.This stabilising system can comprise for example calcium ion, boric acid, propylene glycol, short chain carboxy acid, boric acid and composition thereof etc., and can design according to detergent composition type and the different of physical form, can solve different stability problems.

A kind of approach that realizes stability is to use water miscible calcium and/or magnesium ion in final product composition having, so that these ions to be provided to enzyme.Calcium ion is more effective than magnesium ion usually, therefore, if only use a kind of cationic words, then preferred calcium ion.Common detergent composition, particularly liquid washing agent comprises 1-30 in every liter of final detergent composition, preferred 2-20, the calcium ion of 8-12 mmole more preferably, although may be according to the factor of the diversity that comprises enzyme, type, consumption different the variation.Preferred water miscible calcium and/or the magnesium salts of using comprises: for example calcium chloride, calcium hydroxide, calcium formiate, calcium malate, calcium maleate, calcium hydroxide and lime acetate; Generally also can use calcium sulfate or with the corresponding magnesium salts of listed calcium salt.Certainly, the consumption that further increases calcium and/or magnesium is useful, and that for example improves some kind tensio-active agent removes the grease function.

The another kind of approach that realizes stability is to use the borate family material in composition, referring to the United States Patent (USP) 4537706 of Severson.The borate stablizer when using, its content can up to composition 10% or more, although the boric acid in the general liquid washing agent or the content of other borate compound (as borax or ortho-borate) are that about 3% (weight) is suitable.Available substituted boracic acid such as phenyl-boron dihydroxide, fourth boric acid, right-bromophenyl boric acid or analogue substitute boric acid, and in addition, the use of this substituted boracic acid derivative can reduce in the detergent composition content of total boron.

The stabilising system of some detergent composition, the cleaning composition of using as automatic dish washer, can further comprise 0-10% (weight), the chlorine bleaching scavenging agent of preferred 0.01%-6% (weight), its adding can prevent to be present in material attack of chlorine bleaching class and the deactivating enzyme in many water sources, especially under alkaline condition.Although the cl content in the water is lower, general in the scope of 0.5ppm-1.75ppm,, for example in the washing process of tableware or fabric, the amount of the chlorine that can contact with enzyme in total water is sizable, and therefore, enzyme in use is in-problem to the stability of chlorine sometimes.Because percarbonate can react with the chlorine bleaching material, the use of other chlorine stablizer though can obtain the effect of improvement, in general, is unnecessary.The chlorine scavenger anionic species that is fit to all is known, and is easy to obtain.If you are using, it is the salt that comprises ammonium cation, as sulphite, hydrosulphite, thiosulfite, thiosulphate, iodide etc.Can also use antioxidant such as carbamate, xitix etc., organic amine such as ethylenediamine tetraacetic acid (EDTA) (EDTA) or its an alkali metal salt, monoethanolamine (MEA) and their mixture in addition.Equally, add special enzyme inhibition system, can make different enzymes have maximum consistency.If desired, can use other conventional scavenging agent, as hydrosulphite, nitrate, muriate, hydrogen peroxide cource body such as sodium perborate tetrahydrate, Sodium peroxoborate monohydrate and SPC-D and phosphoric acid salt, condensed phosphate, acetate, benzoate, Citrate trianion, formate, lactic acid salt, malate, tartrate, salicylate etc., and their mixture.In general, the scavenging agent effect of chlorine can assign to finish (as hydrogen peroxide cource class material) by the listed respectively several one-tenth with better generally acknowledged effect, therefore do not need to add separately again chlorine scavenger, unless the compound of finishing this function lacks to required degree in the present invention contains the embodiment of enzyme, even in this case, adding scavenging agent also only is in order to realize best effect.In addition, the prescription teacher will use the common skill of chemist to avoid using any enzyme scavenging agent or stablizer, and if you are using, they are most of incompatible with other component.About using ammonium salt, this salt can mix with detergent composition simply, but is easy to suction and/or discharges ammonia in depositing process.Therefore, this material needs protection in particle if present, for example describes in people's such as Baginski the United States Patent (USP) 4652392.

SYNTHETIC OPTICAL WHITNER

This detergent composition optionally comprises a kind of SYNTHETIC OPTICAL WHITNER.When having SYNTHETIC OPTICAL WHITNER, its content is generally the 1%-30% of detergent composition, more generally is 5%-20%, particularly for laundry detergent composition.

The used SYNTHETIC OPTICAL WHITNER of the present invention can be known or will known washing use at fabric washing, hard surface cleaning or other, any SYNTHETIC OPTICAL WHITNER that detergent composition is suitable for.These comprise oxygen bleaching agent and other SYNTHETIC OPTICAL WHITNER.Here can use perborate bleach such as Sodium peroxoborate (as Sodium peroxoborate one water or four hydrates).

The SYNTHETIC OPTICAL WHITNER that does not limit another kind of use comprises percarboxylic acids SYNTHETIC OPTICAL WHITNER and salt thereof.The suitable example of this SYNTHETIC OPTICAL WHITNER comprises six hydration monoperoxyphthalic acid magnesium, partially magnesium salts, 4-amino in the ninth of the ten Heavenly Stems-4-oxygen base peroxidation butyric acid and the diperoxy dodecanedioic acid of chlorine peroxybenzoic acid.November in 1984 disclosed Hartman on the 20th U.S. Pat 4483781, people such as Burns are in the U.S. Patent application 740446 of application on June 3rd, 1985, February in 1985 people such as disclosed Banks on the 20th european patent application 0133354, and November nineteen eighty-three people such as disclosed Chung on the 1st United States Patent (USP) 4412934 disclosed this class SYNTHETIC OPTICAL WHITNER.Preferred SYNTHETIC OPTICAL WHITNER also comprises 6-amino in the ninth of the ten Heavenly Stems-6-oxygen base peroxidation caproic acid, and this describes in the United States Patent (USP) 4634551 people such as Burns on January 6th, 1987.

Peroxygen bleach also can use.Suitable peroxy bleaching compound comprises yellow soda ash peroxyhydrate and corresponding " percarbonate " SYNTHETIC OPTICAL WHITNER, trisodium phosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide.Also can use persulphate SYNTHETIC OPTICAL WHITNER (for example OXONE, by the DuPont production and sales).

Preferred percarbonate bleach comprises the dried particles of mean particle size in 500 microns-1000 micrometer ranges, and wherein granularity is less than no more than 10% (weight) of 200 microns particle, and granularity is greater than no more than 10% (weight) of 1250 microns particle.Selectively wrap up percarbonate with silicate, borate or water soluble surfactant active.Percarbonate can be by various commercial sources such as FMC, Solvay and Tokai Denka acquisition.

Non-oxygen type SYNTHETIC OPTICAL WHITNER also is known in the art and can uses 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.United States Patent (USP) 4033718 referring to the people such as Holcombe that authorized on July 5th, 1977.If you are using, detergent composition generally comprises this SYNTHETIC OPTICAL WHITNER, particularly sulfonation phthalocyanine phthalocyanine zinc of 0.025%-1.25% (weight).

The SYNTHETIC OPTICAL WHITNER mixture also can use.

Bleach-activating agent

Bleach-activating agent is to use preferred ingredient in the detergent composition of oxygen bleaching agent.During use, its consumption is generally the composition 0.1-60% of (containing SYNTHETIC OPTICAL WHITNER and bleach-activating agent), more generally is 0.5-40%.

In the aqueous solution (promptly in washing process), peroxygen bleach such as perborate etc. mixes with bleach-activating agent, can generate on the spot and corresponding peroxy acid of bleach-activating agent or peracid.The people's such as Mao that authorize April 10 nineteen ninety United States Patent (USP) 4915854, and U.S. Pat 4412934 discloses the various indefiniteness examples of bleach-activating agent.Nonanoly acyloxy benzene sulfonate (NOBS) and tetraacetyl ethylene diamine (TAED) activator are used always, also can mix use.In addition, for can be used for other typical SYNTHETIC OPTICAL WHITNER and activator of the present invention, referring to U.S. Pat 4634551.

The bleach-activating agent of deriving of amido very preferably has following structural formula:

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

R wherein ¹For containing the alkyl of 6-12 carbon atom; R ²For containing the alkylidene group of 1-6 carbon atom; R ⁵For H or contain alkyl, aryl or the alkaryl of 1-10 carbon atom; L is arbitrary suitable leavings group.Leavings group is meant because of crossing the nucleophilic attack of hydrolysis negatively charged ion to bleach-activating agent, and any group that can cement out from bleach-activating agent.Preferred leavings group is a phenylbenzimidazole sulfonic acid salt.

Preferred example with bleach-activating agent of above structural formula comprises: (6-decoyl amino caproyl) the oxygen base benzene sulfonate described in the U.S. Pat 4634551, (the amino caproyl of 6-nonanoyl) oxygen base benzene sulfonate, (6-certain herbaceous plants with big flowers amido caproyl) oxygen base benzene sulfonate, and composition thereof, this patent is quoted for referencial use at this paper.

Another kind of bleach-activating agent comprises: disclosed benzoxazine type activator in the people's such as Hodge that authorize October 30 nineteen ninety the U.S. Pat 4966723.Benzoxazine type activator very preferably is:

Another kind of preferred bleach-activating agent comprises: the acyl lactam activator especially has the acyl caprolactam and the acyl group Valerolactim of following structural formula:

R wherein ⁶For H or contain alkyl, aryl, alkoxy aryl or the alkylaryl group of 1-12 carbon atom.Lactan activator very preferably comprises: benzoyl caprolactam, capryloyl hexanolactam, 3; 5; 5-trimethyl acetyl base hexanolactam, nonanoyl hexanolactam, certain herbaceous plants with big flowers acyl caprolactam, undecylene acyl caprolactam, benzoyl Valerolactim, capryloyl Valerolactim, certain herbaceous plants with big flowers acyl group Valerolactim, undecylene acyl group Valerolactim, nonanoyl Valerolactim, 3; 5,5-trimethyl acetyl base Valerolactim, and composition thereof.Referring to the U.S. Pat 4545784 of the Sanderson that authorized on October 8th, 1985, wherein disclose and comprised the acyl caprolactam that is absorbed into the benzoyl caprolactam in the Sodium peroxoborate.

Bleaching catalyst

Bleaching catalyst is the optional components in the present composition.If desired, can come the catalytically bleaching compound by manganic compound.This compound is well known in the art, and comprising: for example U.S. Pat 5,246,621, US 5,244,594, US 5,194,416, US 5,114,606 and publication number be 549,271A1,549272A1,544,440A2,544, disclosed manganese-based catalyst in the european patent application of 490A1.The preference of these catalyzer comprises: Mn ^IV ₂(u-O) ₃(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂(PF ₆) ₂, Mn ^III ₂(u-O) ₁(u-OAc) ₂(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂-(ClO ₄) ₂, Mn ^IV ₄(u-O) ₆(1,4, the 7-7-triazacyclononane) ₄(ClO ₄) ₄, Mn ^IIIMn ^IV ₄(u-O) ₁(u-OAc) ₂-(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂(ClO ₄) ₃, Mn ^IV(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂(OCH ₃) ₃(PF ₆), and composition thereof.Other metal matrix bleaching catalyst comprises: U.S. Pat 4,430,243 and US 5,114,611 in disclosed catalyzer.In following United States Patent (USP), also reported the application of various complex compound parts on the enhancing bleaching effect of manganese: 4,728,455,5,284,944,5,246,612,5,256,779,5,280,117,5,274,147,5,153,161 and 5,227,084.

In fact, and indefiniteness ground, the compositions and methods of the invention can be conditioned, and the active bleaching catalyst material of 0.1ppm approximately at least can be provided in containing water lotion, and 0.1-700ppm, the more preferably catalyst substance of 1-500ppm preferably are provided in washing lotion.

It is known can be used for cobalt bleaching catalyst of the present invention, and for example, M.L.Tobe exists Adv. Inog.Bionorg.Mech., (1983), 2, the 1-94 page or leaf is described it in the alkaline hydrolysis of transition metal complex (" Base Hydrolysis of Transition-Metal the Complex ") literary composition.Can be used for most preferred cobalt catalyst of the present invention is: have structural formula [Co (NH ₃) ₅OAc] the five nitrilo acetic acid cobalts (wherein " OAc " expression acetate part, " Ty " is negatively charged ion), particularly cobalt chloride five nitrilo acetic acids, [Co (NH of Ty ₃) ₅OAc] Cl ₂, and [Co (NH ₃) ₅OAc] (OAc) ₂, [Co (NH ₃) ₅OAc] (PF ₆) ₂, [Co (NH ₃) ₅OAc] (SO ₄), [Co (NH ₃) ₅OAc] (BF ₄) ₂, and [Co (NH ₃) ₅OAc] (NO ₃) ₂(" PAC " of the present invention).

These cobalt catalyst can prepare with the currently known methods described in the following document: the article of Tobe and the reference of being quoted thereof, March in 1989 people such as disclosed Diakun on the 7th U.S. Pat 4,810,410, J.Chem.Ed.(1989), 66, (12), 1043-45, TheSynthesis and Characterization of Inorganic Compounds, W.L.Jolly (Prentice Hall, (1970), pp.461-3, Inorg.Chem., 18,1497-1502 (1979), Inorg.Chem., 21,2881-2885 (1982), Inorg.Chem., 18,2023-2025 (1979), Inorg.Synthesis, 173-176 (1960) and Journal of Physical Chemistry, 56,22-25 (1952).

In fact, and indefiniteness ground, adjust automatic dish washer of the present invention detergent composition and purging method, approximately at least the active bleaching catalyst material of 0.01ppm can be provided in containing water lotion, and preferably in washing lotion, provide 0.01-25ppm, more preferably 0.05-10ppm, most preferably the bleaching catalyst material of 0.1-5ppm.In order to obtain this content in the washing lotion of washing dish automatically, the typical automatic dish washer detergent composition of the present invention comprises the 0.0005-0.2% that accounts for detergent composition weight, bleaching catalyst, especially manganese or the cobalt catalyst of preferred 0.004-0.08%.

Washing assistant

For example for be beneficial to control in the washing water mineral substance, especially Ca2+ and/or the hardness of Mg2+, perhaps be beneficial to and remove lip-deep particulate fouling, the present composition optionally and preferably comprises the detergent use washing assistant.Washing assistant plays a role by various mechanism, comprises by ion-exchange forming solubility or insoluble complex with hardness ions, and more helps the sedimentary surface of hardness ions by forming one than the article surface that will clean.The consumption of washing assistant can change according to the physical form difference of end-use and composition.The washing composition that adds washing assistant comprises at least 1% washing assistant usually.Liquid formulations generally comprises 5%-50%, the washing assistant of preferred 5%-35%.The particulate state prescription generally comprises the 10%-80% that accounts for detergent composition weight, the washing assistant of preferred 15%-50%.Do not get rid of the lower of washing assistant or high-content more.For example, some detergent additives or high surface agent prescription can not add washing assistant.

Suitable washing assistant can be selected from: phosphoric acid salt and poly-phosphate, especially sodium salt; Silicate, comprising water-soluble and moisture solid-state, and comprise have chain-, layer-or those silicate and the amorphous solid or the non-structured liquid of three-dimensional structure; Carbonate, supercarbonate; Sesquicarbonate except that yellow soda ash or concentrated crystal soda and carbonate minerals; Silico-aluminate; Organic list-, two-, three-and tetracarboxylic acid hydrochlorate, the water-soluble nonsurfactant carboxylate salt of especially sour sodium, potassium or alkanol ammonium salt form, and the oligopolymer or the water-soluble low molecular weight polymeric carboxylates that comprise aliphatic series and aromatics type; Can use borate (for example for pH value buffered purpose) or use vitriol with these materials of phytinic acid, especially sodium sulfate and any other filler or carrier replenish, and these fillers or carrier may be important to producing the stable detergent composition that contains tensio-active agent and/or contain washing assistant.

Can use sometimes the washing assistant mixture that is called " builder system ", it comprises two or more conventional washing assistants usually, optionally replenish with sequestrant, pH value buffer reagent or filler, although when describing amount of substance of the present invention, these materials of back generally calculate individually.The relative quantity in washing composition of the present invention about tensio-active agent and washing assistant, preferred builder system is normally with tensio-active agent: washing assistant (weight ratio) is 60: 1-1: 80 prepare.In some preferred detergent for washing clothes, above-mentioned proportional range is 0.90: 1.0-4.0: 1.0, preferred 0.95: 1.0-3.0: 1.0.

As long as rules allow, the phosphorus-containing detergent washing assistant is normally preferred, includes, but are not limited to: the basic metal of poly-phosphate, ammonium and alkanol ammonium salt, for example tri-polyphosphate, pyrophosphate salt, vitreous state polymer metaphosphate and phosphonate.

Suitable silicate-like builder comprises: alkalimetal silicate, particularly SiO ₂: Na ₂The O ratio is 1.6: 1-3.2: those liquid and solid alkali metal silicates in 1 scope, comprise, and especially in order to wash the purpose of dish automatically, be 2 silicate by the solid-state moisture ratio of PQ Corp supply, commodity are called BRITESIL ^_, as BRITESIL H ₂O; Layered silicate is seen the description in the U.S. Pat 4664839 of the H.P.Rieck that authorized on May 12nd, 1987; NaSKS-6 abbreviates " SKS-6 " sometimes as, is a kind of crystalline layered no aluminium δ-Na that is sold by Hoechst company ₂SiO ₅Attitude silicate, it is preferred especially in the granulated detergent of laundry usefulness, referring to DE-A-3, the preparation method in 417,649 and DE-A-3,742,043.As has a general formula NaMSi _xO _2x+1.yH ₂Other layered silicate of O also can be used for or selectivity is used for the present invention, and wherein: M is sodium or hydrogen, and n is 1.9-4, and is preferred 2, and y is 0-20, is preferably 0.The layered silicate of Hoechst company comprises: be respectively α-, β-and NaSKS-5, NaSKS-7 and the NaSKS-11 of gamma lay shape silicate attitude.Also can use other silicate, Magnesium Silicate q-agent for example, it can be used as crisp dose in particle, as the stablizer of SYNTHETIC OPTICAL WHITNER with as the component in the foam control system.

Be applicable to that washing assistant of the present invention also has: have synthesizing crystalline ion exchange material or its hydrate of chain structure, and by following general formula with forming that the form of acid anhydride is represented: xM ₂OySiO ₂ZM ' O, wherein M is Na and/or K, and M ' is Ca and/or Mg, and y/x is 0.5-2.0, and z/x is 0.005-1.0, authorizes the description of people's such as Sakaguchi US 5427711 as nineteen ninety-five.

Suitable carbonate builders comprises: be disclosed in alkaline earth and alkaline carbonate described in the German patent application № 2321001 in November 15 in 1973.Sodium bicarbonate, yellow soda ash, concentrated crystal soda and other carbonate mine material as any common double salt of urao or yellow soda ash and lime carbonate, have composition 2Na when anhydrous ₂CO ₃Ca ₂CO ₃Double salt, even comprise the lime carbonate of calcite, aragonite and vaterite, Zhi Mi calcite has the form of large surface area especially relatively, also can use, as crystal seed or be used for synthetic bar.

The silico-aluminate washing assistant is preferred especially in detergent granules, and also can add in liquid, paste or the gel.Those silico-aluminates that are applicable to this purpose have the experiment structural formula: [Mz (AlO ₂) z (SiO ₂) v] xH ₂O, wherein z and v are at least 6 integer, and the mol ratio of z and v is in the 1.0-0.5 scope, and x is the integer of 15-264.Silico-aluminate can be crystalline or undefined structure, and can be naturally occurring or synthetic.The method for preparing silico-aluminate is disclosed in the people's such as Krummel that authorized on October 12nd, 1976 the U.S. Pat 3985669.The preferred synthetic crystal aluminosilicate ion exchange material that is used for this paper is to buy by Zeolite A, Zeolite P (B) and Zeolite X title, in any case this and Zeolite P, promptly so-called Zeolite MAP difference.The silico-aluminate of natural form comprises clinoptilolite, also can use.The structural formula of Zeolite A is: Na ₁₂[(AlO ₂) ₁₂(SiO ₂) ₁₂] xH ₂O, wherein x is 20-30, preferred 27.Dehydration zeolite (x=0-10) also can use.The diameter of preferred silico-aluminate is between the 0.1-10 micron.

Suitable organic detergent washing assistant comprises: the multi-carboxylate's compound that comprises water miscible nonsurfactant dicarboxylate and tricarboxylate.Preferred multi-carboxy acid salt washing agent has a plurality of carboxylate group, preferably at least 3 carboxylate group.The carboxylate salt washing assistant generally can be mixed with acidity, part neutral, neutrality or parlkaline form.When using with the form of salt, the salt of basic metal such as sodium, potassium and lithium, or the alkanol ammonium salt is preferred.The multi-carboxy acid salt washing agent comprises the ether multi-carboxylate, as oxygen di-succinate, referring to the United States Patent (USP) 3128287 of the Berg that authorizes April in 1964 7 and the people's such as Lamberti that authorized January 18 in 1972 United States Patent (USP) 3635830, in addition referring to " TMS/TDS " washing assistant in the people's such as Bush that authorized May 5 in 1987 the United States Patent (USP) 4633071.Other suitable ether carboxylate comprises ring-type and aliphatic cyclic compound, describes in United States Patent (USP) 3922679,3835163,4158635,4120874 and 4102903.

Other washing assistant that is fit to comprises ether hydroxyl multi-carboxylate, the multipolymer of maleic anhydride and ethene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4, the 6-trisulfonic acid, the carboxymethyl oxosuccinic acid, various polyacetic acids are as basic metal, ammonium and the substituted ammonium salt of ethylenediamine tetraacetic acid (EDTA) and nitrilotriacetic acid(NTA), and mellitic acid, succsinic acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid, carboxymethyl oxosuccinic acid, and water-soluble salt.

The Citrate trianion washing assistant, as citric acid and water-soluble salt thereof, because of can being obtained and biodegradable by renewable resource, they are carboxylate salt washing assistants of particularly important, as are used for liquid heavy duty type detergent for washing clothes.Citrate trianion also can be used in the granular composition, particularly mixes use with zeolite and/or layered silicate washing assistant.Oxygen di-succinate also is useful especially in this composition and mixture.

In the occasion that can use phosphorus base washing assistant, and, can use various alkali metal phosphates, as tripoly phosphate sodium STPP, trisodium phosphate and sodium orthophosphate particularly in the preparation of the bar that is used for hand-washing.Also can use the phosphonate washing assistant, as ethane-1-hydroxyl-1,1-diphosphonate and other known phosphonate (referring to United States Patent (USP) 3159581,3213030,3422021,3400148 and 3422137) also can play the effect of scale removal.

Some detergent surfactants or their short chain analogue also help washes function.For the prescription that offers some clarification on, when component has the effect of tensio-active agent, these materials generally are classified as detergent surfactant.Have and help the tensio-active agent preference of washing function to be: 3,3-dicarboxyl-4-oxa--1,6-adipic acid ester, and related compound, disclosed in the United States Patent (USP) 4566984 of the Bush that authorizes in January in 1986 28.The succsinic acid washing assistant comprises C ₅-C ₂₀Alkyl and alkenyl succinic and salt thereof.The succinate washing assistant also comprises: month basic amber salt of extension, tetradecyl amber salt, hexadecyl amber salt, 2-dodecenyl succinic amber salt (preferably), 2-15 carbene base amber salt.Lauryl amber salt was described in the disclosed european patent application 86200690.5/0200263 on November 5th, 1986.Lipid acid such as C ₁₂-C ₁₈Monocarboxylic acid also can be individually, or mix with aforementioned washing assistant, particularly Citrate trianion and/or succinate washing assistant and to add in the composition as the surfactivity detergent builders, can produce additional washing assistant activity.March in 1979 people such as disclosed Crutchfield on the 13rd United States Patent (USP) 4144226 and March in 1967 disclosed Diehl on the 7th United States Patent (USP) 3308067, other suitable multi-carboxylate has been described.In addition referring to the United States Patent (USP) 3723322 of Diehl.

The inorganic builders material of spendable other type has structural formula: (M _x) _iCa _y(CO ₃) _z, wherein x and i are the integer between the 1-15, and y is the integer between the 1-10, and z is the integer between the 2-25, M _iBe positively charged ion, wherein at least one is water miscible, satisfies the equation ∑ simultaneously _i=1-15 (x _i* M _iValency)+2y=2z, this structural formula has the electric charge of a neutral or " balance " like this.Washing assistant described here refers to " mineral washing assistant ".Combination water or the negatively charged ion except that carbonate can add, with the balance that keeps total charge or be electric neutrality.The right that these anionic electric charges or valency should add aforesaid equation to.Preferred water-soluble cationic is selected from hydrogen, water-soluble metal, boron, ammonium, silicon and their mixture, further preferred sodium, potassium, hydrogen, lithium, ammonium and their mixture, most preferably sodium and potassium.The anionic non-limitative example of noncarbonate comprises: muriate, sulfate radical, fluorochemical, oxygen, oxyhydroxide, silicon-dioxide, chromate, nitrate radical, borate and their mixture.The simplest the type washing assistant of form is preferably from Na ₂Ca (CO ₃) ₂, K ₂Ca (CO ₃) ₂, Na ₂Ca ₂(CO ₃) ₃, NaKCa (CO ₃) ₂, NaKCa ₂(CO ₃) ₃, K ₂Ca ₂(CO ₃) ₃And their mixture.Most preferred builder material described herein is the Na with its arbitrary crystallization mode ₂Ca (CO ₃) ₂Suitable washing assistant type defined above also can comprise, any in the material of following natural form or synthesized form or combination: Ah's cancrinite, andersonite, ashcroftine Y, beyerite, the carbon kurchatovite, yellow carbon strontium sodium stone, aqueous carbonate potassium calcium stone, cancrinite, stone cerium sodium stone, the carbon canasite, davyne, carbon yttrium strontium city Y, carbon potassium calcium stone, Fetrrisurite, the sulphur davyne, carbon boron manganese calcium stone, gaylussite, Girvasite, ilmenite, sulphur carbon calcium manganese stone, Kamphaugite Y, kettnerite, Khanneshite, LepersonniteGd, liottite, carbon barium yttrium ore deposit Y, microsommite, the carbon carlfriesite, Buddhist nun's charcoal sodium calcium stone, Buddhist nun's shortite, Remondite Ce, the Sa davyne, the plate carburane, shortite, the plumbous stone of carbon sial, carbon sodium mayenite, sulphur silico-calcium potassium stone, tyrolite, vishnevite and Zemkorite.The preferred mineral form comprises Buddhist nun's shortite, carbon potassium calcium stone and shortite.

The polymerization dirt release agent

Known polymkeric substance stain remover hereinafter claims " SRA " or " SRA ' s ", can optionally use in detergent composition of the present invention.If use, generally account for total composition weight 0.01%-10.0%, preferred 0.1%-5%, most preferably SRA ' s of 0.2%-3.0%.

General and the hydrophobic fiber of the hydrophilic segment of preferred SRA, surperficial affine as polyester or nylon, and hydrophobic part is deposited on the hydrophobic fiber and keeps adsorbing with it until washing or the end of cleaning process, thereby grappling hydrophilic segment.This can be so that the spot of handling with SRA that produces subsequently be easy to remove in ensuing washing process.

SRA can comprise, various electric charges, as negatively charged ion or even monomeric unit and its structure of positively charged ion (referring to U.S. Pat 4956447) and non-electric charge can be straight chain, side chain or even star.They comprise can control molecular weight especially effectively or change physical property or the end-blocking part of change surface active properties.Can adjustment structure with charge distribution to be applicable to different fibers or fabric type and different washing composition or detergent additives products.

Preferred SRA ' s comprises oligomeric terephthalate, and generally by containing the process preparation of at least one transesterification reaction/oligomerizing, this process common metal catalyzer is as titanium alkoxide (IV) catalysis.Such ester by using 1-, 2-, 3-, 4-or more multipoint additional monomer preparation that can join ester structure, does not form a tight crosslinked overall texture certainly.

Suitable SRA comprises: the sulfonated products of linear oligoester basically comprises the oligomer ester skeleton of terephthaloyl and oxyalkylene oxygen repeating unit and covalency and joins allyl group deutero-sulfonated terminal portions on this skeleton to.This is as the description in the U.S. Pat 4968451 of J.J.Scheibel that authorizes November 6 nineteen ninety and E.P.Gosselink: this oligomer ester can make by following steps: (a) ethoxylation allyl alcohol, (b) by two steps of transesterification reaction/oligomerization, product and dimethyl terephthalate (DMT) (" DMT ") and 1 with (a), 2-propylene glycol (" PG ") reacts, and (c) product and the sodium metabisulfite with (b) reacts in water; The people's such as Gosselink that on December 8th, 1987 authorized U.S. Pat 4,711, negatively charged ion end-blocking terephthalic acid 1 in 730,2-propylidene polyester/terephthalic acid polyoxyethylene polyester is as generating by the transesterification reaction/oligomerization of poly-(ethylene glycol) methyl ether, DMT, PG and polyoxyethylene glycol (" PEG "); Part and whole negatively charged ion end-blocking oligomer ester in the U.S. Pat 4,721,580 of the Gosselink that on January 26th, 1988 authorized, as ethylene glycol (" EG "), PG, DMT and 3, the oligopolymer of the hot sodium sulfonate of 6-two oxa-s-8-hydroxyl; The U.S. Pat 4 of the Gosselink that on October 27th, 1987 authorized, 702, nonionic end-blocking block polyester oligopolymer in 857, as by the end capped PEG of DMT, Me and EG and/or PG, perhaps the mixture by DMT, EG and/or the end capped PEG of PG, Me and dimethyl-5-sulfoisophthalic acid sodium generates; And the Maldonado of mandate on October 31st, 1989, the end capped terephthalate of the negatively charged ion in people's such as Gosselink the U.S. Pat 4,877,896 (particularly sulphur aroyl).The latter is typical SRA, can be used for detergent for washing clothes and fabric-conditioning product, for example: by-single sodium salt, PG and the DMT of sulfosalicylic acid, preferably but preferably comprise institute and add the ester composition that PEG (for example, PEG 3400) makes.

SRA also comprises: the simple segmented copolymer of ethylene glycol terephthalate or propylene glycol ester terephthalate and polyethylene oxide or poly(propylene oxide) terephthalate, U.S. Pat 3 referring to the Hays that authorized on May 25th, 1976,959, the U.S. Pat 3 of the Basadur that on July 8th, 230 and 1975 authorized, 893,929; Derivatived cellulose is as the hydroxy ethers cellulose polymer compound METHOCEL that obtains from Dow; C ₁-C ₄Alkylcellulose and C ₄Hydroxy alkyl cellulose is referring to the people's such as Nicol that authorized on December 28th, 1976 U.S. Pat 4,000,093.Suitable SRA with poly-(vinyl ester) hydrophobic part feature comprises: be grafted to poly-(vinyl ester) on the polyoxyalkylene skeleton, as poly-(C ₁-C ₆Vinyl ester), the graft copolymer of preferred poly-(vinyl-acetic ester).Referring to disclosed european patent application 0,219,048 in people such as Kud on April 22nd, 1987.The example of commercial acquisition comprises: SOKALAN SRA ' s, and as the SOKALAN HP-22 of German BASF AG.Other SRA is: derived from molecular-weight average is the polyester that the repeating unit of the polyoxyethylene glycol of 300-5000 contains 10-15% (weight) ethylene glycol terephthalate and poly-(oxygen ethene) ester of 80-90% (weight) terephthalic acid.The example of commercial acquisition comprises: the ZELCON5126 of DuPont company and the MILEASET of ICI.

Another kind of preferred SRA is: have experiment structural formula (CAP) ₂(EG/PG) ₅(T) ₅(SIP) ₁Oligopolymer; wherein comprise terephthaloyl (T), sulfo group isophthaloyl base (SIP), oxygen inferior ethoxyl and Oxy-1; 2-propenyl (EG/PG) unit; and preferentially select capping group (CAP) for use; preferred modified hydroxyl esilate carries out end-blocking; for example in an oligopolymer; wherein comprise a sulfo group isophthaloyl base, 5 terephthaloyl, give certainty ratio and (be preferably about 0.5: 1-10: 1) oxygen inferior ethoxyl and Oxy-1, the inferior propoxy-unit of 2-and derived from two end-blocking unit of 2-(2-hydroxyl-oxethyl)-ethyl sulfonic acid sodium.Described SRA also preferably comprises: what account for oligopolymer weight 0.5%-20% reduces the crystalline stablizer, for example: anion surfactant such as linear alkyl benzene sulphonate or be selected from dimethylbenzene-, isopropyl benzene-and toluene-sulfonate or its mixture, wherein these stablizers or properties-correcting agent all are the Gosselink that authorizes according to May 16 nineteen ninety-five, Pan, the U.S. Pat 5 of Kellett and Hall, described mode in 415,807 adds in the synthesis reactor.The monomer that is applicable to above-mentioned SRA comprises: 2-(2-hydroxyl-oxethyl)-ethyl sulfonic acid sodium, DMT, dimethyl-5-sulfoisophthalate sodium, EG and PG.

Another kind of preferred SRA is an oligomer ester, comprising: (1) skeleton, at least one is selected from dihydroxyl sulphonate or poly-hydroxy sulphonate to comprise (a), thus a unit with at least three functional groups' formation ester bonds with generation band branched oligomers skeleton, and mixed cell; (b) at least one terephthaloyl unit; (c) at least one is 1, the unsulfonated unit of 2-oxyalkylene oxygen base; (2) be selected from one or more end-blockings unit of nonionic end-blocking unit, negatively charged ion end-blocking unit (alkoxylate for example, preferred ethoxylation isethionate, alkoxylate propanesulfonic acid salt, alkoxylate third stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate, alkoxylate phenolsulfonate, sulphur aromatic acyl derivative, and composition thereof).This ester preferably has the experiment structural formula:

{ (CAP) _x(EG/PG) _{Y '}(DEG) _{Y "}(PEG) _{Y_}(T) _z(SIP) _{Z '}(SEG) _q(B) _mWherein CAP, EG/PG, PEG, T and SIP (DEG) represent two (oxyalkylene) oxygen base unit as defined above; (SEG) expression is derived from the unit and the relevant portion unit of the sulfo group ethyl ether of glycerine; (B) expression has three functional group's branching units at least, thereby it forms ester bond to produce the branched oligomers skeleton; X is about 1-12; Y ' is about 0.5-25; Y " is about 0-12; Y_ is about 0-10 '; " ten y_ amount to and are about 0.5-25 y '+y; Z is about 1.5-25; Z ' is about 0-12; Z+z ' total is about 1.5-25; Q is about 0.05-12; M is about 0.01-10; And x, y ', y ", y_, z, z ', q and m represent the average mol of the corresponding units of every mole of described ester, the molecular weight of described ester is about 500-5000.

The preferred SEG and the CAP monomer of above-mentioned ester comprise: 2-(2,3-dihydroxyl propoxy-) ethyl sulfonic acid sodium (" SEG "), 2-{ (2-(2-hydroxyl-oxethyl) oxyethyl group } ethyl sulfonic acid sodium (" SE3 ") and homologue thereof, and composition thereof and the ethoxylation and the sulfonated products of allyl alcohol.Preferred this class SRA ester comprises: in the presence of suitable Ti (IV) catalyzer, 2-{ (2-(2-hydroxyl-oxethyl) oxyethyl group } and ethyl sulfonic acid sodium and/or 2-[2-{ (2-(2-hydroxyl-oxethyl) oxyethyl group } oxyethyl group] ethyl sulfonic acid sodium, DMT, 2-(2,3-dihydroxyl propoxy-) product that obtains by transesterification reaction and oligomerization of ethyl sulfonic acid sodium, EG and PG, it may be defined as (CAP) ₂(T) ₅(EG/PG) _1.4(SEG) _2.5(B) _0.13, wherein: CAP is (Na ^+-O ₃S[CH ₂-CH ₂O] _3.5)-, and B are a glyceryl unit, and the EG/PG mol ratio that records with conventional gas-chromatography after the complete hydrolysis is about 1.7: 1.

Another kind of SRA comprises: (I) use the vulcabond coupler to connect the nonionic terephthalate of polymer esters structure, referring to people's such as people's such as Violland U.S. Pat 4,201,824 and Lagasse U.S. Pat 4,240,918; (II) have the SRA of carboxylicesters end group, it is by trimellitic acid 1,2-anhydride being added on the known SRA, changing terminal hydroxyl group into trimellitate and obtain.By selecting correct catalyzer, the ester that trimellitic acid 1,2-anhydride can be by an isolated carboxylic acid of trimellitic acid 1,2-anhydride rather than by opening on the end group that anhydride bond is keyed to polymkeric substance.Nonionic or negatively charged ion SRA can be used as starting raw material, as long as contain can esterified hydroxyl terminal groups for they.U.S. Pat 4,525,524 referring to people such as Tung.In addition, SRA also comprises: (III) SRA based on the negatively charged ion terephthalate of urethanum-keyed jointing type, referring to people's such as Violland U.S. Pat 4,201,824; (IV) poly-(caprolactam) and have monomer such as the corresponding copolymers of vinyl pyrrolidone and/or methacrylic acid (dimethylaminoethyl) ester, comprising nonionic and cationic polymers, U.S. Pat 4,579,681 referring to people such as Ruppert; (V) except the SOKALAN type of BASF AG, by acrylic monomer being grafted to the graft copolymer that obtains on the sulfonated polyester; These SRA have decontamination the dirt active and antiredeposition activity similar to the plain ether of known fiber certainly, referring to Rhone-Poulenc Chemie. company European patent application EP in 1988 279,134A; (VI) grafts of vinyl monomer is grafted to grafts on the protein (for example casein) as vinylformic acid and vinyl-acetic ester, referring to the European patent application EP 457 of BASF AG, and 205A (1991); (VII) the polyester-polyamide SRA that makes by condensation hexanodioic acid, hexanolactam and polyoxyethylene glycol, it is specially adapted to handle tynex, referring to people's such as the Unilever N.V. Bevan of company DE2,335,044 (1974 years).US 4,240, and 918,4,787,989,4,525,524 and 4,877,896 have described other useful SRA.

Remove native dirt/anti redeposition agent

The present composition also can randomly comprise the water-soluble ethoxylated amine with native dirt/antiredeposition performance.The particulate state cleaning composition that comprises this compounds comprises the water-soluble ethoxylated amine of 0.01%-10.0% (weight) usually; Liquid detergent compositions then comprises 0.01%-5% (weight) usually.

It is most preferred that to remove native dirt/anti redeposition agent be the tetren of ethoxylation.Further described the example of ethoxylated amine in the United States Patent (USP) 4597898 of the VanderMeer that on July 1st, 1986 authorized.It is cation compound that another kind is preferably removed native dirt/anti redeposition agent, describes in the european patent application 111965 of on June 27th, 1984 disclosed Oh and Gosselink.Spendable other goes native dirt/anti redeposition agent to comprise: ethoxylated amine polymer, in the european patent application 111984 of disclosed Gosselink on the 27th June in 1984, describe; Amphoteric ion polymer is described in the european patent application 112592 of disclosed Gosselink on the 4th July in 1984; Amine oxide is described in the United States Patent (USP) 4548744 of the Connor that authorizes on October 22nd, 1985.Other the native dirt/anti redeposition agent that goes known in the art also can be used for this composition.Referring to the United States Patent (USP) 4891160 of the VanderMeer that authorizes January 2 nineteen ninety, and November 30 nineteen ninety-five disclosed international monopoly 95/32272.Another kind of preferred anti redeposition agent comprises carboxymethyl cellulose (CMC) material.These materials are known in the art.

Polymeric dispersant

In this composition, particularly when wherein containing zeolite and/or multi-layer type silicate-like builder, the polymeric dispersant that adds 0.1%-7% (weight) is good.Although other known dispersion agents of this area also can use, the polymeric dispersant that is fit to comprises polymeric multi-carboxylate and polyoxyethylene glycol.Although accepting opinion institute limits everybody and believes, polymeric dispersant and other washing assistants (comprising the lower molecular weight polycarboxylate) are when combining, by crystal growth restraining effect, the peptization of freeing particulate fouling and anti-redeposition, and increased the effect of whole detergent builders.

The polymeric multi-carboxylate can be by suitable unsaturated monomer, and preferably sour form makes by polymerization or copolyreaction.The unsaturated monomer acid that the energy polymerization forms suitable polymeric multi-carboxylate comprises vinylformic acid, toxilic acid (or maleic anhydride), fumaric acid, methylene-succinic acid, aconic acid, methylfumaric acid, citraconic acid and methylene radical propanedioic acid.Here containing non-carboxylate groups in polymeric multi-carboxylate or the monomer fragment, is to be fit to as vinyl methyl ether, vinylbenzene, ethene etc., and condition is 40% (weight) that these fragments are no more than composition.

The multi-carboxylate polymer of particularly suitable is by vinylformic acid, and useful herein acrylic acid based polymer is polyacrylic water-soluble salt.Molecular-weight average when these polymkeric substance exist with sour form suits 2000～10000, and preferable range is 4000～7000, and preferably 4000～5000.The water-soluble salt of these acrylate copolymer comprises, as an alkali metal salt, ammonium salt and substituted ammonium salt.Such water-soluble polymers is known, and for example Diehl has announced in the United States Patent (USP) U.S 3308067 that published on March 7th, 1967 and use this type polyacrylate in detergent composition.

The multipolymer of vinylformic acid/maleic also can be used as a kind of preferred component in dispersion agent/anti redeposition agent.Such material comprises the water-soluble salt of vinylformic acid and maleic acid, and the molecular-weight average when these multipolymers exist with sour form suits 2,000～100,000,5,000～75, and 000 is better, is preferably in 7,000～65,000.Acrylate fragment and the segmental ratio of maleate be normally from 30: 1 to 1: 1 in the multipolymer, preferably 10: 1 to 2: 1.The water-soluble salt of these vinylformic acid/maleic acids comprises, as an alkali metal salt, ammonium salt and substituted ammonium salt.This class water-soluble acrylic/maleic acid also is known, it is described in the application number that is published in November 15 nineteen eighty-two is among the EP193360 that publishes in EP66915 and on September 3rd, 1986, wherein also discloses this multipolymer of being made up of the hydroxypropyl acrylate.Other available dispersion agents also comprise the terpolymer of toxilic acid/vinylformic acid/vinyl alcohol.These materials also have been disclosed in the European patent EP 193360, comprise for example terpolymer of vinylformic acid/toxilic acid of 45/45/10/vinyl alcohol.

The another kind of polymkeric substance that is suitable for is polyoxyethylene glycol (PEG), and PEG can show the performance of dispersion agent, simultaneously can be as the removal-anti redeposition agent of clay soil.The molecular weight ranges that is used for such use is usually 500～100, and 000, preferable range is 1,000～50,000, preferably 1,500～10,000.

Polyaspartic acid salts and polyglutamic acid dipersant also can use, and particularly are used in combination with zeolite builders.The molecular-weight average of dispersion agent such as polyaspartic acid salts preferably 10,000.

Whitening agent

Any white dyes known in the art or other whitening agent can mix in this detergent composition, weight content normally 0.01%～1.2%.Can be used for commercial white dyes of the present invention and can be divided into several groups, include, but is not limited to stilbene, pyrazoline, tonka bean camphor, carboxylic acid, methyne cyanine, dibenzothiophen-5,5-dioxide, pyrroles, five yuan and the derivative of hexa-member heterocycle and other miscellaneous dose.The example of above-mentioned whitening agent is open in " production of white dyes and use " (TheProduction and Application of Fluorescent Brightening Agents), and author M.Zahradnik is by John Wiley ﹠amp; Sons.New York (1982) publishes.

The special case of useful white dyes and applicant are Wixon in the present composition, and disclosed among the US4790856 that open day is on November 13rd, 1988 is consistent.These whitening agent comprise the PHORWHITE series whitening agent that originates from Verona.Disclosed other whitening agent also have in this patent: Tinopal UNPA, and Tinopal CBS and Tinopal 5BM can be buied by Ciba-Geigy; Artic White CC and Artic White CWD, 2-(4-styryl phenyl)-2H-naphthols [1,2d] triazole; 4,4 '-two (1,2,3-triazoles-2-yl)-stilbenes; 4,4 '-two (styryl) biphenyl; And aminocoumarin.The specific example of these whitening agent comprises: 4-methyl-7-diethyl-aminocoumarin; 1, two (benzopyrazoles-2-yl) ethene of 2-; 1, the 3-diphenylpyrazoline; 2, the two (benzoxazoles of 5--2-yl) thiophene; 2-styryl-naphthols [1,2d] oxazole; And 2-(1,2-stilbene-4-yl)-2H-naphthols [1,2d] triazole.Also be found in Hamilton in the US3646015 that delivered on February 29th, 1972.

Dye transfer inhibitor

Can also comprise one or more dye transfer inhibitors in the present composition, be used for suppressing the transfer of dyestuff between fabric at washing process.Usually, such inhibitor comprises the mixture of multipolymer, manganese phthalocyanine, peroxidase and the above-mentioned substance of polyvinyl pyrrolidone polymers, polyamine N-oxide pllymers, N-vinyl pyrrolidone and N-vinyl imidazole.These inhibitor account for 0.01%～10% of composition weight usually during use, and preferable range is 0.01%～5%, is preferably 0.05%～2%.

More particularly, the polyamine N-oxide pllymers that preferably uses of the present invention contains the unit of following structural formula: R-Ax-P; Wherein P is polymerisable unit, and the N-O group can be connected with this unit, or the N-O group can become this unitary part or the N-O group can be connected with two polymerizable units; A is one of following structure :-NC (O)-and ,-C (O) O-,-S-,-O-,-N=; X is 0 or 1; R is any combination of aliphatic series, the aliphatic aromatic series of ethoxylation, heterocycle or alicyclic group or above-mentioned group, the N that they can be incorporated into the N-O group go up or N-O basic be the part of these groups.R is heterocyclic group such as pyridine, pyrroles, imidazoles, tetramethyleneimine, piperidines and their derivative in the preferred polyamine N-oxide compound.

The N-O group can be represented with following general formula:

R wherein ₁, R ₂, R ₃Be aliphatic series, aromatic series, heterocycle or alicyclic group or the combination between them; X, y, z are 0 or 1; N in the N-O group can be connected or become the part of above-mentioned group with any above-mentioned group; The unitary pKa of the amine oxide of polyamine N-oxide＜10, better when pKa＜7, pKa＜6 preferably.

As long as formed amine-oxide polymer is water miscible and has the dye transfer inhibition that the skeleton of any polymkeric substance all can use.The suitable polymers skeleton is for example: polyethylene, polyalkylene, polyester, polyethers, polymeric amide, polyimide, polyacrylic ester and their mixture.These polymkeric substance comprise random copolymers or segmented copolymer, and wherein, a kind of monomer is an amine n-oxide, and another kind of monomer is the N-oxide compound.The ratio of amine and amine n-oxide is generally 10: 1 to 1: 1 in the amine n-oxide polymkeric substance, and 000,000.Yet the number of amine oxide group can be along with suitable interpolymerization or suitable N-degree of oxidation and is changed in the polyamine oxide polymer.Almost can obtain the polyamine oxide compound under any polymerization degree, usually, its molecular-weight average is 500～1,000,000, and preferable range is 1,000～500,000, preferably 5,000～100,000.The preferred material of this class is called " PVNO ".

In this cleaning composition, the most suitable polyamine N-oxide is poly-(4-vinylpyridine-N-oxide compound), and molecular-weight average is 50,000, and the ratio of amine and amine n-oxide is 1: 4.

The multipolymer of N-vinyl pyrrolidone and N-vinyl imidazole polymkeric substance also is preferred (being classified as the PVPVI class) of using.Usually the molecular-weight average of PVPVI is 5,000～1,000,000, preferable range is 5,000～200,000, preferably 10,000～20,000 (scope of molecular-weight average is by light scattering determining, as people such as Barth (ChemicalAnalysis) at " chemical analysis ", describe among the Vol.113, " modernism of polymer property " (Modern Methods ofPolymer Characterization), its disclosure is quoted for referencial use at this paper.In PVPVI, the mol ratio of N-vinyl imidazole and N-vinyl pyrrolidone is usually from 1: 1 to 0.2: 1, and preferable range is from 0.8: 1 to 0.3: 1, and optimized scope is from 0.6: 1 to 0.4: 1, and these multipolymers can be straight or brancheds.

The present composition also can contain polyvinylpyrrolidine (PVP), and its molecular-weight average is 5,000～400,000, and preferable range is 5,000～200, and 000, optimum is 5,000～50,000.PVP is well-known to the technician of detergent applications.For example, see EP-A-262897 and EP-A-256696 (seeing this paper reference).The composition that contains PVP also can contain polyoxyethylene glycol (PEG), and the molecular-weight average of PEG is from 500～100, and 000, preferably 1,000～10,000.What add in washings is generally 2: 1 to 50: 1 in the PEG of ppm and the ratio of PVP, is preferably 3: 1 to 10: 1.

This detergent composition also can randomly add the hydrophilic white dyes of some type of 0.005%～5% (weight), and these whitening agent also need to suppress the transfer of dyestuff.In use, preferably account for 0.01%～1% (weight) that composition weight is formed.

The spendable hydrophilic white dyes of the present invention has following structural formula:

R wherein ₁Be selected from anilino, N-2-pair-hydroxyethyl and NH-2-hydroxyethyl; R ₂Be selected from N-2-pair-hydroxyethyl, N-2-hydroxyethyl-N-methylamino-, morpholino, chlorine, amino; M is the salifiable positively charged ion of shape, as Na ⁺Or K ⁺

Work as R ₁Be anilino, R ₂Be N-2-pair-hydroxyethyl, M is positively charged ion such as Na ⁺, then whitening agent be 4,4 '-two [(4-anilino-6-(N-2-two-hydroxyethyl)-1,3,5-triazines-2-yl) amino]-2,2 '-stilbene disulfonic acid and disodium salt.This whitening agent is sold by Ciba-Geigy company, and commodity are called Tinapol-UNPA-GX.Tinapol-UNPA-GX is the hydrophilic preferably white dyes that is applicable to this cleaning composition.

Work as R ₁Be anilino, R ₂Be N-2-hydroxyethyl-N-2-methylamino-, M is positively charged ion such as Na ⁺, then whitening agent be 4,4 '-two [(4-anilino-6-(N-2-hydroxyethyl-N-methylamino-)-1,3,5-triazines-2-yl) amino] 2,2 '-the stilbene disulfonic acid disodium salt, this whitening agent also is to be sold by Ciba-Geigy company, commodity are called Tinapol 5BM-GX.

Work as R ₁Be anilino, R ₂Be morpholino, M is positively charged ion such as Na ⁺, then whitening agent be 4,4 '-two [(4-anilino-6-morpholino-1,3,5-triazines-2-yl) amino] 2,2 '-the stilbene disulfonic acid disodium salt, this whitening agent also is to be sold by Ciba-Geigy company, commodity are called Tinapol AMX-GX.

The special white dyes that the present invention selects for use when being used in combination with the polymeric dye transfer inhibitor of selecting for use as mentioned before, can produce the effect of very effective inhibition dye transfer.The polymkeric substance of selecting (as PVNO and/or PVPVI) and the white dyes (as Tinapol-UNPA-GX, Tinapol 5BM-GX and Tinapol AMX-GX) selected for use in the water washings be used in combination than any independent use wherein the time can bring into play better dye transfer restraining effect.Do not accept opinion and keep within bounds, this mode of action that can believe such whitening agent is because they have high-affinity to fabric in washings, therefore can be attached to relatively apace on these fabrics.The degree that whitening agent is attached in washings on the fabric can be determined with " consumption coefficient ".Consumption coefficient normally a) is attached to whitening agent on the fabric to b) ratio of the original concentration of whitening agent in the washings.Whitening agent with relative high flow rate coefficient is best suited for the transfer that suppresses dyestuff in the present invention.

Certainly, will be appreciated that also can choose the habitual optical brightener compounds of other kinds wantonly is used for the present composition, produce common fabric and " brighten " effect, rather than real dye transfer restraining effect.This usage in detergent formulation be habitually practise with known.

Sequestrant

This washing composition also can randomly contain one or more iron and/or manganese sequestrant.These sequestrants can be selected from organize down: the fragrant chelating agent of aminocarboxylate, amino phosphonates do, multi-functional replacement and their mixture, all these will be explained in the back in detail.The advantage part that it is believed that these materials has by forming the soluble chelating thing owing to them, and the special ability that iron and mn ion are removed from washings, and this is a bound by theory not.

Aminocarboxylate as optional sequestrant comprises edetate, N-hydroxyethyl-ethylenediamine triacetate, nitrilotriacetic acid(NTA) salt, ethylenediamine tetrapropionic acid(EDTP) salt, triethylenetetraaminehexaacetic acid salt, diethylentriamine pentacetate and ethanol Diglycocol, their basic metal, ammonium and substituted ammonium salt and mixture.

When allowing at least low-level total phosphorus content in the cleaning composition, amino phosphonates do also can be used as the sequestrant that the present composition is suitable for, and comprises ethylenediamine tetraacetic (methene phosphonate ester), such as DEQUEST.These amino phosphonates do preferably do not contain alkyl or the alkenyl group that surpasses 6 carbon atoms.

Multi-functional substituted aroma sequestrant also is useful in the composition of this patent, sees the U.S.3 that deliver on Mays 21st, 1974 such as Connor, 812,044.This class is preferably the dihydroxyl disulfobenzene with the compound of sour form, such as 1, and 2-dihydroxyl-3,5-disulfobenzene.

Using a kind of sequestrant of biological degradation preferably herein is ethylenediamine disuccinate (" EDDS "), the especially U.S.4 that delivers on December 3rd, 1987 at Hartman and Perkin etc., [S, the S] isomer described in 704,233.

Also can contain in the composition of this patent water-soluble methylglycine oxalic acid (MGDA) the salt form of acid (or with) as sequestrant or with other insoluble auxiliary washing assistant, for example zeolite, multi-layer type silicate share.

If use these sequestrants, these sequestrants generally account for weight composition 0.1% to 15% in this cleaning composition, and it is better to account for 0.1% to 3.0% of weight.

Froth suppressor

In the present composition, can add and reduce or suppress the compound that foam forms, in U.S. Pat 4,489,455 and US 4,489,574 in the what is called " high density cleaning " described and before to suppress foam in the European washing machine of charging be weight extremely.

Many kinds of materials can be used as froth suppressor, and froth suppressor also is well-known to those skilled in the art.For example, see the Kirk Othmer chemical encyclopedia third edition, the 7th volume, 430-447 page or leaf (John Wiley ﹠amp; Son company, 1979).A very important class A foam A inhibitor comprises mono carboxylic lipid acid and its soluble salt.See the United States Patent (USP) 2,954,347 that Wayne St.John announces on September nineteen sixty 27.As mono carboxylic lipid acid and its salt of froth suppressor, contain the hydrocarbon chain of 10 to 24 carbon atoms usually, preferably 12 to 18 carbon atoms.The salt that is fit to comprises an alkali metal salt, such as sodium salt, sylvite, lithium salts and ammonium salt and alkanol ammonium salt.

Also can contain the nonsurfactant froth suppressor in this cleaning composition.Comprise, for example: high-molecular-weight hydrocarbons such as the fatty acid ester of paraffinic hydrocarbon, fatty acid ester (for example fatty acid triglyceride), monovalent alcohol, contain the aliphatic ketone (for example sterone) of 18-40 carbon atom etc.Other froth suppressor comprises N-alkylation aminotriazine, arrive the tetraalkyl diammonium chloride for triazine such as three to six alkyl melamines or two, they are to contain the primary amine of 1 to 24 carbon atom or secondary amine, propylene oxide and single stearyl phosphoric acid ester by cyanuric chloride and 2 or 3 moles to generate such as single stearyl alcohol phosphoric acid ester and single stearyl two-basic metal (for example K, Na and Li) phosphoric acid salt and phosphoric acid ester.Hydrocarbon, such as paraffinic hydrocarbon and halo paraffinic hydrocarbon, can be with the liquid form utilization.Liquid hydrocarbon is a liquid under room temperature and normal atmosphere, and solidification point is-40 ℃～50 ℃ scopes, and minimum boiling point is not less than 110 ℃ (normal atmosphere).Utilize waxy hydrocarbon also known, its fusing point is preferably lower than 100 ℃.Hydrocarbon has been formed a class preferred foam inhibitor in the cleaning composition.The hydrocarbon froth suppressor is existing to be described, for example the U.S. Pat 4,265,779 on May 5th, 1981 announced such as Gandolfo.And hydro carbons comprises the aliphatic series that contains 12 to 70 carbon atoms, alicyclic, aromatic series and heterocycle is saturated or unsaturated hydrocarbons.In the discussion of froth suppressor, with " paraffin wax hydrocarbon " speech, the meaning is to comprise the real paraffin wax hydrocarbon and the mixture of cyclic hydrocarbon.

Another kind of preferred nonsurfactant froth suppressor comprises the polysiloxane froth suppressor.This class A foam A inhibitor comprises that the use organopolysiloxane is such as polydimethylsiloxane, the organopolysiloxane that the suspension liquid of organopolysiloxane oil or resin or emulsion, organopolysiloxane chemisorption or consolidation form to the silicon-dioxide and the mixture of silica dioxide granule.The polysiloxane froth suppressor is well-known in this area, for example sees that application number that U.S. Pat 4,265,779 that Gandolfo1981 delivered at May 5 and Starch M.S.1990 delivered at February 7 is 89307851.9 European patent.

Other polysiloxane froth suppressor is published in United States Patent (USP) 3,455,839, and this piece patent is about adding a small amount of polydimethylsiloxane fluid so that the composition of aqueous solution froth breaking and method in the aqueous solution.

The silica mixture of polysiloxane and silanization also has description, for example, sees German patent application DOS 2,124,526.The United States Patent (USP) U.S.4 that polysiloxane defoamers in the particulate state cleaning composition and Foam Control are delivered on March 24th, 1987 at the United States Patent (USP) 3,933,672 of Bartolotta etc. and Baginski etc. has announcement in 652,392.

The typical polysiloxane froth suppressor of Shi Yonging is the Foam Control that a class suppresses the foam consumption herein, and essentially consist is:

(i) 25 ℃ the time viscosity from 20cs to 1, the polydimethylsiloxane fluid of 500cs

(ii) according to weight per 100 parts (i), about 5 to about 50 parts polyorganosiloxane resin, by (CH ₃) ₃SiO _1/2Unit and SiO ₂The unit is formed, (CH ₃) ₃SiO _1/2Unit and SiO ₂Unitary ratio was from about 0.6: 1 to 1.2: 1; And

(iii), contain 1 to 20 part solid silicone approximately according to weight per 100 parts (i).

In this paper preferred foam inhibitor, the solvent of external phase is made up of certain polyoxyethylene glycol or polyethylene glycol-propylene glycol copolymers or their mixture (preferably) or polypropylene glycol.Main polysiloxane froth suppressor is a side chain/crosslinked, preferred non-straight chain.

For further setting forth this viewpoint, typically in the laundry liquid agent of energy control foam, can randomly contain above-mentioned polysiloxane suds suppressor, weight percent is about 0.001% to about 1%, preferable range is preferably in 0.05% to about 0.5% about 0.01% to about 0.7%.These polysiloxane comprise the nonaqueous emulsion of (1) main defoamer, this defoamer is following (a) and (b), (c) and mixture (d): (a) organopolysiloxane, (b) arborescens siloxanes or produce the polysiloxane compound of polyorganosiloxane resin, (c) the finely disintegrated weighting material and (d) promote (a) (b) and (c) mixture reaction generate the catalyzer of silane alkoxide; (2) at least a nonionic silicones tensio-active agent and (3) polyoxyethylene glycol or polyethylene glycol-propylene glycol copolymers, its at room temperature the solubleness in the water approximately be 2%, and do not have polypropylene glycol.In granular composition gel etc., can use similar content, the United States Patent (USP) 4,978 that also visible Starch announces on December nineteen ninety 18,471 and the United States Patent (USP) 4 announced on January 8th, 1991 of Starch, 983,316, Huber etc. are at the U.S.5 on February 22nd, 1994,288,431 and Aizawa etc. at United States Patent (USP) 4,639,489 and 4,749,740 the 1st are listed as the 46th row is listed as the 35th row to the 4th.

The polysiloxane froth suppressor of this paper preferably comprises polyoxyethylene glycol and polyethylene/polypropylene glycol multipolymer, and it is about 1,000 that their molecular-weight average all is lower than, and is better between 100 to 800.Herein polyoxyethylene glycol and polyethylene/polypropylene glycol multipolymer at room temperature the solubleness in the water greater than about 2% weight, more preferably greater than about 5% weight.

This paper preferred solvent is a polyoxyethylene glycol, and it is about 1,000 that its molecular-weight average is lower than, and preferable range is about 100-800, and is best between 200 to 400; With the multipolymer of polyethylene/polypropylene glycol, preferably PPG 200/PEG 300.Polyoxyethylene glycol was advisable preferably 1: 3 to 1: 6 with the ratio of polyethylene/polypropylene glycol multipolymer weight with about 1: 1 to 1: 10.

The preferred herein polysiloxane froth suppressor that uses does not contain polypropylene glycol, especially the polypropylene glycol of molecular weight 4,000.The segmented copolymer that does not preferably also contain oxyethane and propylene oxide is as PLURONIC L101.

Other useful froth suppressor that the present invention uses comprise secondary alcohol (mixture of 2-alkyl chain triacontanol and these alcohol and polysiloxane oil for example, such as United States Patent (USP) 4,798,679 and 4,075,118 and EP 150,872 disclosed polysiloxane.Secondary alcohol comprises having C ₁-C ₁₆The C of chain ₆-C ₁₆Alkanol.Preferably 2-butyl octanol can be buied from Condea, and trade mark is ISOFOL 12.Can buy the secondary alcohol mixture from Enichem, trade mark is ISALCHEM 123.Foam inhibition agent composition contains 1: 5 to 5: 1 pure and mild polysiloxane of weight ratio usually.

For the cleaning composition of being useful on automatic washing machine or dishwasher, foamy forms and should not surpass certain scope, thereby overflows washing machine or to the washing mechanism generation negative interaction of dishwasher.When froth suppressor uses, preferably exist with " suppressing the foamy amount "." suppress the foamy amount " and mean that composition ingredients teacher selects a certain amount of this froth suppressor, fully control foam.And obtain can be used for the low foam laundry or the dishwasher detergent of automatic washing machine or dishwasher.

Usually contain 0% to 10% froth suppressor in this composition.When using as froth suppressor, the consumption of mono carboxylic lipid acid and salt thereof mostly is 5% of cleaning composition weight usually most, preferably uses 0.5% to 3% fatty monocarboxylate froth suppressor.The common consumption of polysiloxane froth suppressor mostly is 2.0% of cleaning composition weight most, although also can use greater concn.Because will consider that at first carrying cost is minimum and keep the low dosage high-level efficiency to bubble with effective control, in fact, this upper limit will be decided according to practical situation.Using the preferable amount of polysiloxane froth suppressor is 0.01% to 1%, preferably 0.25% to 0.5%.Just as used herein, these weight percent values comprise that all can be used for the silicon-dioxide that makes up with organopolysiloxane, and any material that can select for use.Single stearyl phosphoric acid ester froth suppressor, general usage quantity is the 0.1%-2% of composition weight.Though the hydrocarbon froth suppressor also can use greater concn, its common usage quantity is 0.01%-5%.The alcohol froth suppressor accounts for 0.2% to 3% weight of final product composition having usually.

The alkoxylate polycarboxylate

The alkoxylate polycarboxylate, those that come such as preparing by polyacrylate, very useful in the present invention, extra degrease ability can be provided.These materials have description at pages or leaves such as the page 4 of WO 91/08281 and PCT90/01815 and back, quote for referencial use at this paper.

On chemical structure, these materials comprise the polyacrylate that every 7-8 acrylic ester unit has an oxyethyl group side chain.The molecular formula of side chain is-(CH ₂CH ₂O) _m(CH ₂) _nCH ₃, m equals 2-3, and n equals 6-12.Side chain is connected on the polyacrylate skeleton by ester bond, produces " comb " formula polymer architecture.Molecular weight can change, but usually 2,000-50 is between 000.Can contain weight in this composition and form 0.05% to 10% this alkoxylate polycarboxylate.

Fabric softener

The fabric softener of various experience washing whole processes, especially the United States Patent (USP) U.S.4 that delivers on December 13rd, 1977 of Storm and Nirsclal, 062,647 trickle montmorillonitic clay, and other softening agent clay known in the art, can select arbitrarily to use, in the present composition, generally from 0.5% to 10% (weight) level just can play the effect of fabric softener, simultaneously can also clean textile.The clay softening agent can use with amine and cationic softener, and these amine and cationic softener are existing open, such as, the United States Patent (USP) U.S.4 that Crisp etc. delivered in March 1 nineteen eighty-three, 375,416 and the U.S.4 that announces on September 22nd, 1981 such as Harris, 291,071.

Spices

Spices and aroma constituent very useful in this composition and technology comprise a large amount of natural and synthetic chemistry compositions, include but not limited to: aldehyde, ketone, ester.Also comprise various natural extracts and essence, it is the complex mixture that contains many compositions, such as, mandarin oil, lemon oil, rose juice extracts, lavender, Moschus, Wrinkled Gianthyssop Herb, the celestial China of phoenix essence, santal oil, pine-tree oil and arborvitae.Finished product spices generally is to account for 0.01% to 2% of this cleaning composition weight, and each component of band fragrance can account for 0.0001% to 90% of finished product flavor compositions.

Many useful fragrance component herein includes, but is not limited to: 7-ethanoyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl-naphthalene; Methylionone, cetone gamma, vertofix coeur, methyl dihydrojasmonate, methyl 1,6,10-trimethylammonium-2,5,9-cyclododecatriene-1-base ketone; 7-ethanoyl-1,1,3,4,4,6-hexamethyl tetraline; 4-ethanoyl-6-the tertiary butyl-1,1-dimethyl indane; Right-hydroxyl-phenyl-butanone; Benzophenone; Methyl-β-naphthalenone; 6-ethanoyl-1,1,2,3,3,5-hexamethyl indane; 5-ethanoyl-3-sec.-propyl-1,1,2,6-tetramethyl-indane; The 1-dodecanal; 4-(4-hydroxyl-4-first amyl group)-3-tetrahydrobenzene-1-formaldehyde; 7-hydroxyl-3,7-dimethyl octanal; 10-undecene-1-aldehyde; Dissident's thiazolinyl hexahydrobenzaldehyde; The formyl tristane; The condenses of fragrant lance aldehyde of hydroxyl and methyl anthranilic acid ester, the condenses of fragrant lance aldehyde of hydroxyl and indoles, the condenses of phenylacetic aldehyde and indoles; 2-methyl-3-(right-tert-butyl-phenyl)-propionic aldehyde; Vanillal; Piperonylaldehyde; Hexyl cinnamic aldehyde; Amyl cinnamic aldehyde; 2-methyl-2-(right-isopropyl phenyl)-propionic aldehyde; Tonka bean camphor; γ-decalactone; Ring Pentadecane alcohol acid anhydride; 16-hydroxyl-9-hexadecanoic acid lactone; 1,3,4,6,7,8-hexahydro--4,6,6,7,8,8-hexamethyl pentamethylene-γ-2-chromene; β-Nai Jiami; Ambroxane; Ten dihydros-3a, 6,6,9a-tetramethyl-naphtho-[1,2d] furans; Cypress camphor; 5-(2,2,3-front three basic ring penta-3-thiazolinyl)-3-methylpent-2-alcohol; 2-ethyl-4-(2,2,3-trimethylammonium-3-cyclopentenes-1-yl)-2-butylene-1-alcohol; Caryophyllenol; The tricyclic decenyl propionic ester; The tricyclo decene yl acetate; Benzyl salicylate; Cedryl acetate; With right-(tertiary butyl) hexalin acetate.

Only spices should be able to farthest improve the smell of the final product composition having of cellulase, and these spices include, but is not limited to: hexyl cinnamic aldehyde; 2-methyl-3-(right-tert-butyl-phenyl)-propionic aldehyde; 7-ethanoyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl-naphthalene; Benzyl salicylate; 7-ethanoyl-1,1,3,4,4,6-hexamethyl tetraline; Right-the tert.-butylacetic acid cyclohexyl; Methyl dihydrojasmonate; β-Nai Jiami; Methyl-β-naphthalenone; 2-methyl-2-(right-isopropyl phenyl)-propionic aldehyde; 1,3,4,6,7,8-six hydrogen-4,6,6,7,8,8-hexamethyl-pentamethylene-γ-2-chromene; Ten dihydros-3a, 6,6,9a-tetramethyl-naphtho-[1,2d] furans; Aubepine; Tonka bean camphor; Cypress camphor; Vanillin; The Cyclopentadecanol acid anhydride; Tricyclo decene yl acetate and tricyclic decenyl propionic ester.

Other spices comprises perfume oil, the resin in resinoid and various sources.Comprising (but being not limited to): Surinam balsam, olibanum resinoid, st-yrax, ladanum resin, Semen Myristicae, Oleum Cinnamomi, styrax resinoid, Fructus Coriandri oil and hybrid lavandula angustifolia.Also have some other flavor compounds to comprise styroyl alcohol, Terpineol 350, phantol, the bitter camphor tree ester of acetate, Geraniol, vernol, 2-(1,1-diformazan ethyl)-adnoral acetate, jasmal and oxymethoxyallylbenzene.In the finished product flavor compositions, also can add carrier, as diethyl phthalate.

Other compositions

Various other compositions useful in cleaning composition all can be included in this composition, comprise other activeconstituents, carrier, and hydrotropic agent, processing aid, dyestuff or pigment are used for the solvent of liquid formulations, solid filler that bar compositions is required or the like.If need high bubble, mix 1% to 10% suds booster in the composition usually, such as the alkylolamide that contains 10-16 carbon atom.The monoethanolamine of 10-14 carbon atom and diglycollic amide are exactly a typical class in these suds boosters, and these suds boosters and can play high foaming option list surface-active agent such as aforesaid amine oxide, trimethyl-glycine and sultaine use together, also are very useful.If need, also can add water soluble magnesium and/or calcium salt, such as MgCl ₂, MgSO ₄, CaCl ₂, CaSO ₄, the content that adds is 0.1%～2% usually, to produce more foams and to strengthen the greasy ability of removing.

The various cleaning ingredients of selecting arbitrarily in this composition to add can be adsorbed onto in the porous hydrophobic material, are made it further stable with the hydrophobic coating bag by above-mentioned hydrophobic substance then.Cleaning ingredients mixes with tensio-active agent before being preferably in and being adsorbed onto porous matrix.During use, detergent ingredients is discharged into from matrix in the water lotion, carries out washing function.

For describing this technology in detail, the protein enzyme solution of the ethoxylated alcohol that contains 3%-5%13-15 carbon atom (EO7) non-ionic surfactant and porous hydrophobic silicon-dioxide (trade mark SIPERNAT D10, DeGussa) mixing.Usually, the solution weight of enzyme/tensio-active agent is 2.5 times of silica gel.The powder of gained by dispersed with stirring (viscosity is 500～12, and 500 various silicone oil all can use) in silicone oil.The silicone oil dispersion agent that obtains is emulsified, or it is added in the final washing composition matrix.By this method, above-mentioned enzyme, SYNTHETIC OPTICAL WHITNER, bleach-activating agent; bleaching catalyst, light activating agent, dyestuff; white dyes, fabric conditioner and hydrolyzable tensio-active agent just can obtain " protection " and use in order to comprising in the laundry liquid agent at washing composition.

Liquid detergent compositions can contain water and other liquid solvents as carrier.Low molecular weight primary or secondary alcohol, for example methyl alcohol, ethanol, propyl alcohol and Virahol all are well suited for.The agent alive of the most handy monohydroxy-alcohol dissolving table, but also can use polyvalent alcohol, such as those content that contain these carriers of polyvalent alcohol (for example 1, ammediol, ethylene glycol, glycerine and 1,2-propylene glycol) of 2 to 6 carbon atoms and 2-6 hydroxyl can from 5% to 90%, general content is 10% to 50%.

This cleaning composition preferably can be mixed with the pH of bath water when using 6.5 to 11 in the washing operation, better between 7.5 to 10.5, the liquid dishwasher detergent is filled a prescription best pH 6.8 to 9.0.Scouring agent is usually at pH9-11.Control pH value comprises the use buffer reagent in the method for recommended value, alkali, and acid etc., this is well-known to those skilled in the art.

Particulate is produced

Two-alkoxylate positively charged ion among the present invention is added to and mixes in the machine mixture, use conventional spraying drying subsequently, to help removing all residual stink short chain amine pollutents that may exist.In this case, ingredients Shi Xiang makes a kind of composite grain that contains this alkoxylate cats product and is used for for example high density granular detergent, and preferably particulate composition is not a strong basicity.In U.S. Pat 5,366, describe high-density (greater than 650g/L) granule preparing process in detail in 652.These particles that form can effectively be avoided the stink of impure amine below pH9 or 9.Add a small amount of acidic substance such as boric acid, citric acid and so on or suitable pH buffer reagent just can reach this purpose in particle.In another approach, the perfume composition that also can use as described herein is covered the issuable problem of amine stink.

Embodiment

In the example below, writing a Chinese character in simplified form of used various compositions has following connotation in the composition.

The alkyl benzene sulphonate (ABS) salt anionic surfactant of average 11.5 the carbon atom chain lengths of LAS

Promoting agent, preferably sodium salt

The primary alkyl sulphates negatively charged ion of the average 14-15 of an AS carbon atom chain length

Tensio-active agent, preferably sodium salt

The ethoxyquin that contains 12-15 carbon atom of the average EO9 ethoxyquin of NI degree

Alcohol (nonionogenic tenside)

SKS-6 multi-layer type silicate is as Hoechst

The sodium salt of the multipolymer of multipolymer vinylformic acid and toxilic acid

The zeolite A of zeolite 1-10 μ m

The PEG4000 polyoxyethylene glycol; Molecular-weight average is 4000

NOBS nonanoly acyloxy benzene sulfonate bleach-activating agent

PB-1 Sodium peroxoborate monohydrate

The aforesaid protelytic detersive enzyme of proteolytic enzyme; Comprise BIOSAM3.0

The detersive enzyme of amylorrhexis starch

The SRA-1 dirt release agent; Methylcellulose gum; Molecular weight is about 13000, gets

For degree 1.8-1.9

Dirt release agent among the SRA-2 US 5415807

Whitening agent X Tinopal CBS_X; Toluylene biphenyl disulfonic acid salt;

Ciba-Geigy

Whitening agent Y Tinopal UNPA-GX; Cynauric chlorine/diaminostilbene class;

Ciba-Geigy

Foam Control silicon-dioxide/polysiloxane froth suppressor

Following Example is to explanation of the present invention, rather than to the qualification or the definition of its scope.All umbers, per-cent and ratio all represents with weight percent, unless otherwise specified.

Detergent granules such as following examples A and Embodiment B.

Embodiment A

Weight percentages of components (%) ppm

Tensio-active agent

LAS 21.47 143.20

AS 6.55 43.69

NI 3.30 22.01

CocoMeEO2 ^* 0.47 3.13

The alkaline auxiliary lotion

SKS-6 3.29 21.94

Multipolymer 7.10 47.36

Zeolite 8.40 56.03

PEG4000 0.19 1.27

Yellow soda ash 17.84 118.99

Silicate (2.0R) 11.40 76.04

Whitening agent

NOBS 4.05 27.01

PB-1 3.92 26.15

Enzyme

Proteinase-10 .85 5.67

Amylase 1.20 8.00

Other

SRA-1 0.26 1.73

SRA-2 0.26 1.73

Whitening agent X 0.21 1.40

Whitening agent Y 0.10 0.67

Water drain silica 0.30 2.00

Froth suppressor 0.17 1.13

Sodium sulfate 5.14 34.28

Spices 0.25 1.67

Moisture and miscellaneous 3.28 21.88

Total amount 100 667.00

Dosage-20g/30L

^*Any or other AQA tensio-active agent of this paper substitutes among the AQA-2-AQA-22 of the available equivalent of the surfactant A QA-1 among the embodiment (CocoMeEO2).

Embodiment B

Weight percentages of components (%) ppm

Tensio-active agent

LAS 21.47 143.20

AS 6.55 43.69

NI 3.30 22.01

CocoMeEO2 ^* 0.47 3.13

The alkaline auxiliary lotion

SKS-6 3.29 21.94

Multipolymer 7.10 47.36

Zeolite 8.40 56.03

PEG4000 0.19 1.27

Yellow soda ash 19.04 127.00

Silicate (2.0R) 11.40 76.04

Whitening agent

NOBS 4.05 27.01

PB-1 3.92 26.15

Enzyme

Proteinase-10 .85 5.67

Other

SRA-1 0.26 1.73

SRA-2 0.26 1.73

Whitening agent X 0.21 1.40

Whitening agent Y 0.10 0.67

Water drain silica 0.30 2.00

Froth suppressor 0.17 1.13

Sodium sulfate 5.14 34.28

Spices 0.25 1.67

Moisture and miscellaneous 3.28 21.88

Total amount 100 667.00

^*Two-AQA-1 (CoCoMeEO2) tensio-active agent can substitute to one of two-AQA-22 or other pair-AQA tensio-active agent with the two-AQA-2 of equivalent among this embodiment.

Illustrate below and use the interior composition of the scope of the invention, will find out from data that the cleaning force to miscellaneous dirt and spot has all improved on various fabrics various dirts and filthy laboratory operation and detected result of carrying out.

The process of performance test

The preparation of sample

The preparation of sample consists essentially of following steps:

1. the preparation of premix LAS+AS.

2. the preparation of premix LAS+AS+ cats product.

3. the preparation of a large amount of nonionic (AE) tensio-active agents.

4. the preparation of washing assistant solution

5. the preparation of particulate matter.

Tensio-active agent:

Tensio-active agent Weight ^* Gms Active % Wash concentration (ppm)

LAS 78.85 44.50 143.20

AS 34.55 31.00 43.70

Cats product 01.90 40.00 3.10

AE 19.44 100.00 22.00

^*Actual weight is different with active per-cent

The preparation process that is used for the product of Performance Detection:

Step I:

Weighing according to the following steps of each tensio-active agent and mixing

1. claim 78.85gm LAS.

2. claim again that 34.55gm AS is added in the same beaker.

3. add 498.10ml distilled water in the mixed solution of LAS and AS.

4. premix LAS and AS heat about 30 minutes until dissolving fully until dissolving fully at 40 ℃.

Step II:

1. claim that 01.90gm cats product of the present invention is added in the same beaker that contains LAS and AS liquid of premix.

2. at this moment the cumulative volume of solution is 500ml.

This 500ml surfactant mixture can effectively wash 5 times, and this batch of 100ml solution is used in each washing.When in this 100ml solution, adding 49 liters of tap water, be exactly each tensio-active agent corresponding washing concentration.

Step II I:

1. claim 19.44gm AE separately.

2. in AE, add 900ml distilled water.

3. this 900ml solution can effectively wash 18 times.

4. each washing this solution of 50ml.

Step IV:

Silicate: contain 148.32gm in every 900ml distilled water; This solution of 50ml is used in each washing.

Multipolymer: contain 92.88gm in every 900ml distilled water; This solution of 50ml is used in each washing.

Particulate matter: weigh up every kind of grain fraction and put into same beaker respectively.

The order of in washing machine, adding:

Component is under agitation added in the following order:

1. silicate (2.0R).

2. multipolymer (as mentioned above).

3. particulate matter.

Stop to stir (to avoid when adding tensio-active agent, producing foam) herein.

4.LAS+AS+ cats product solution.

5.AE solution.

Stirred 15 seconds.

Hardness: under tap water hardness, there is not extra hardness of adding.

Loading: use the following washing loading of forming of 2.4Kg usually.

Cotton uniform shirt (1)

Old T-shirt (from appraising house through discussion) (3)

Big T-shirt (11)

DKPE T-shirt (1)

P/C pants (2)

Cotton pants (1)

DKPE is a polyester crosspointer fabric.

DMO is dirty motor oil.

Detected result I is as follows, and what show is the composition properties that coconut MeEO2 used according to the invention adds LAS, AS mixture.What detected result II showed is to make comparisons with coconut MeEO2/LAS, uses coconut MeEO10 to add the performance of LAS/AS.Performance is to be the health dirt at various dirts in test, and the responsive dirt of washing assistant, the responsive dirt of SYNTHETIC OPTICAL WHITNER, the responsive dirt of tensio-active agent and socks are measured.The term here " two ", " EO10 " show two polyethylene oxide chains, and 10 ethylene oxide units of overall average are arranged in molecule, and (but being not limited to) every approximately chain is 5 usually.

Detected result I

With LAS and AS (total negatively charged ion system) with

Coconut MeO2 cats product is pre-mixed

Dirt Detect I Detect II On average

Duds neck-0.02-0.27-0.15

Edge neck 0.77S 0.73S 0.75

Cuff-0.17 0.33 0.08

Filthy-0.1 0.17S 0.04

Health filth (on average) 0.12 0.24 0.18

Clay C/D 1.03S 0.7S 0.87

Clay DKPE 0.7S-0.02 0.34

To the washing assistant sensitivity

Dirt (on average) 0.87 0.34 0.61

Spinach 0.33 0.56 0.45

Coffee 0.21 0.42S 0.32

To the SYNTHETIC OPTICAL WHITNER sensitivity

Dirt (on average) 0.27 0.49 0.38

Meat pulp 0.84S 1.08S 0.96

Curry 1.14S 1.11S 1.13

Bacon oil 0.1 0.16 0.13

DMO 0.44 -0.34 0.05

Quick to tensio-active agent

The dirt (on average) 0.63 0.5 0.57 of sense

On average (comprise socks) 0.39 0.38 0.39

Socks (preceding) 0.32 0.35A 0.34

Socks (back) 0.08 0.64A 0.36

Socks (δ)-0.24 0.28 0.02

Test result I

In advance coconut MeEO2 cats product and LAS are mixed separately

Dirt Detect I Detect II On average

Duds neck 0.27-0.73-0.23

Edge neck-0.04 0.15 0.06

Cuff-0.35-0.25-0.30

Filthy 0.13 0.51S 0.32

Health filth (on average) 0.00-0.08-0.04

Clay C/D 0.59 0.79S 0.69

Clay DKPE 0.04 0.66 0.35

To the washing assistant sensitivity

Dirt (on average) 0.32 0.73 0.53

Spinach 0.07 0.58 0.33

Coffee 0.24 0.24 0.24

To the SYNTHETIC OPTICAL WHITNER sensitivity

Dirt (on average) 0.16 0.41 0.29

Meat pulp-0.1-0.08-0.09

Curry 0.1 0.54 0.32

Bacon oil-0.53-0.02-0.28

DMO -0.22 0.05 -0.09

Quick to tensio-active agent

The dirt (on average)-0.19 0.12-0.04 of sense

On average (comprise socks) 0.04 0.19 0.12

Socks (preceding) 0.33-0.07 0.13

Socks (back) 0.7S-0.05 0.33

Socks (δ) 0.36 0.02 0.19

Test result II

In advance coconut MeEO2 cats product is mixed with LAS+AS

Dirt Detect I Detect II On average

Duds neck 0.48-0.02 0.23

Edge neck 0.02 0.06 0.04

Cuff 0.33 0.25 0.29

Filthy-0.28 0.11-0.09

Health dirt (on average) 0.14 0.10 0.12

Clay C/D 0.75S 0.44 0.60

Clay DKPE 0.27-0.47-0.10

To the washing assistant sensitivity

Dirt (on average) 0.51-0.02 0.25

Spinach 0.00 0.33 0.17

Coffee 0.38 0.82S 0.60

To the SYNTHETIC OPTICAL WHITNER sensitivity

Dirt (on average) 0.19 0.58 0.39

Meat pulp 0.05 0.96S 0.51

Curry 0.42 0.91S 0.67

Bacon oil 0.23-0.07 0.08

DMO 0.31 -0.13 0.09

Quick to tensio-active agent

The dirt (on average) 0.25 0.42 0.34 of sense

On average (comprise socks) 0.2 0.26 0.23

Socks (preceding) 0.14 0.23 0.19

Socks (back)-0.19 0.48S 0.15

Socks (δ)-0.32 0.25-0.04

Test result II

Coconut MeE10 cats product and the independent premix of LAS

Dirt

Duds neck 0.17

Edge neck-0.52

Sleeve 0.19

Filthy-0.17

Person dirt (on average)-0.08

Clay C/D-0.34

Clay DKPE 0.09

Dirt (on average)-0.13 to the washing assistant sensitivity

Spinach 0.06

Coffee 0.08

Dirt (on average) 0.07 to the SYNTHETIC OPTICAL WHITNER sensitivity

Meat pulp-0.20

Curry-0.38

Bacon oil-0.33

DMO -0.33

Dirt (on average)-0.31 to the tensio-active agent sensitivity

On average (comprise socks)-0.11

Socks (preceding) 0.42S

Socks (back) 0.64S

Socks (δ) 0.22

Following Example is illustrated this patent, but does not mean that this just limits or stipulated its scope.All umbers used herein, per-cent and ratio all represent with weight percent, unless otherwise specified.

In the example below, writing a Chinese character in simplified form of used various compositions has following connotation in the composition.

The LAS straight chain C ₁₂Sodium alkyl benzene sulfonate

TAS tallow alkyl sodium sulfate

C45AS C _14-15Straight-chain alkyl sulfate

CxyEzS C _1x-C _1yThe sodium alkyl sulfate of side chain and the condensation of z moles of ethylene oxide

C45E7 C _14-15Mainly be the primary alconol and average 7 moles of ethylene oxide of straight chain

Condensation

C25E3 C _12-15The primary alconol of side chain and average 3 moles of ethylene oxide condensations

C25E5 C _12-15The primary alconol of side chain and average 5 moles of ethylene oxide condensations

Coconut EO2 R ₁N ⁺(CH ₃) (C ₂H ₄OH) ₂R wherein ₁Be C _12-14

Soap from 80/20 the butter coconut oil blend and the straight chained alkyl carboxylic that comes

Acid sodium

TFAA C _16-18Alkyl N-methyl glucose amide

TPKFA C _12-14Cut the lipid acid tops entirely

The STPP anhydrous sodium tripolyphosphate

Zeolite A hydrated sodium aluminosilicate molecular formula Na ₁₂(AlO ₂SiO ₂) ₁₂27H ₂O,

The size of basic granules is 0.1-10 μ m

NaSKS-6 crystalline layered silicate δ-Na ₂Si ₂O ₅

The anhydrous citric acid citric acid

The carbonate anhydrous sodium carbonate, granular size 200-900 μ m

The supercarbonate anhydrous sodium bicarbonate, granular size 400-1200 μ m

Silicate amorphous sodium silicate (SiO ₂: Na ₂O=2.0)

The sodium sulfate anhydrous sodium sulphate

Citrate trianion two hydration trisodium citrates, activity 86.4%, size distribution

425-850μm

1: 4 toxilic acid/acrylic acid multipolymer of MA/AA, molecular-weight average 70,000

The CMC Xylo-Mucine

The protease protein lytic enzyme, activity 4KNPU/g, trade(brand)name Savinase,

NOVO Industries A/S sells

The Alcalase proteolytic ferment, activity 3AU/g, NOVO Industries A/S

Sell

The cellulase hydrolysis cellulase, activity 1000CEVU/g,

Trade(brand)name Carezyme, NOVO Indusrties A/S sells

Amylorrhexis amylase, activity 60KNU/g, trade(brand)name Termamy

160T, NOVO Industries A/S sells

Lipase hydrolysis fat enzyme, activity 100KLU/g, trade(brand)name Lipolase,

NOVO Industries A/S sells

Glucose enzyme in the endoenzyme, activity 3000EVU/g, NOVO Industries

A/S sells

PB4 four hydrated sodium perborates, general formula NaBO ₂.3H ₂O.H ₂O ₂

PB1 anhydrous sodium perborate SYNTHETIC OPTICAL WHITNER, general formula NaBO ₂.H ₂O ₂

The percarbonate SPC-D, general formula 2NaCO ₃.3H ₂O ₂

NOBS nonanoyl Oxybenzene sodium sulfonate

The TAED tetraacetyl ethylene diamine

NACA-OBS (the amino hexanoyl of 6 nonanoyls) Oxybenzene sulfonate

DTPMP diethylenetriamine five (methylene phosphonic acid salt)

Cobalt catalyst five amine cobaltous acetate (III) salt

Mn catalyst Mn ^IV ₂(m-o) ₃(1,4,7-trimethylammonium-1,4,7-three nitrogen heterocyclics

Nonane) ₂-(PF ₆) ₂As U.S. Pat 5246621 and 5244594

Described

Photosensitization thing sulfonation zinc phthalocyanine phthalocyanine is enclosed bleaching dextrin soluble polymer

Whitening agent 14,4 '-two (2-sulfo group styryl) biphenyl disodium

Whitening agent 24,4 '-two (4-anilino-6-morpholino-1,3,5-

Triazine-2-yl) amino) 1,2-stilbene-2,2 '-disulfonic acid two

Sodium

HEDP 1,1 hydroxyethanediphosphonic acid

The PVNO polyvinyl pyridine N-oxide

The multipolymer of PVPVI polyvinylpyrrolidone and vinyl imidazole

SRA1 sulfo group benzoyl is end capped to have the oxygen ethyleneoxy group and to benzene

The ester of diacyl skeleton

The short embedding of SRA2 diethoxyization poly-(terephthalic acid 1,2-propylene glycol ester)

The section polymkeric substance

Polysiloxane defoamers polydimethylsiloxane Foam Control and as the silicon of dispersion agent

Oxygen alkane-oxyalkylene copolymers, the ratio of Foam Control and dispersion agent

It is 10: 1 to 100: 1

In the following embodiments, all content are represented with the weight percent (%) of composition

Embodiment 1

Following detergent formulation produced according to the present invention, wherein A and C are phosphorous cleaning composition, B contains the zeolite cleaning composition.

A B C

The powder of blowing

STPP 24.0 - 24.0

Zeolite A-24.0-

C45AS 8.0 5.0 11.0

MA/AA 2.0 4.0 2.0

LAS 6.0 8.0 11.0

TAS 1.5 - -

Coconut MeEO2 ^*1.5 1.0 2.0

Silicate 7.0 3.0 3.0

CMC 1.0 1.0 0.5

Whitening agent 2 0.2 0.2 0.2

Soap 1.0 1.0 1.0

DTPMP 0.4 0.4 0.2

Spray on it

C45E7 2.5 2.5 2.0

C25E3 2.5 2.5 2.0

Polysiloxane defoamers 0.3 0.3 0.3

Spices 0.3 0.3 0.3

Dried additive

Carbonate 6.0 13.0 15.0

PB4 18.0 18.0 10.0

PB1 4.0 4.0 0

TAED 3.0 3.0 1.0

Photosensitization SYNTHETIC OPTICAL WHITNER 0.02 0.02 0.02

Proteolytic enzyme 1.0 1.0 1.0

Lipase 0.4 0.4 0.4

Amylase 0.25 0.30 0.15

Dry mixed sodium sulfate 3.0 3.0 5.0

Balance (Shui Fen ﹠amp; Miscellaneous) 100.0 100.0 100.0

Concentration (g/L) 630 670 670

^*Among the two AQA-22 of two AQA-2-of the available equivalent of the surfactant A QA-1 among this embodiment (coconut MeEO2) any or herein other pair AQA tensio-active agent substitute.

Example II

The following cleaning composition that does not contain SYNTHETIC OPTICAL WHITNER is to be used in particular for washing colored clothing

D E F

The powder of blowing

Zeolite A 15.0 15.0 2.5

Sodium sulfate 0.0 5.0 1.0

LAS 2.0 2.0 -

Coconut MeEO2 ^*1.0 1.0 1.5

DTPMP 0.4 0.5 -

CMC 0.4 0.4 -

MA/AA 4.0 4.0 -

Agglomerate

C45AS - - 9.0

LAS 6.0 5.0 2.0

TAS 3.0 2.0 -

Silicate 4.0 4.0-

Zeolite A 10.0 15.0 13.0

CMC - - 0.5

MA/AA - - 2.0

Carbonate 9.0 7.0 7.0

Spray on it

Spices 0.3 0.3 0.5

C45E7 4.0 4.0 4.0

C25E3 2.0 2.0 2.0

Dried additive

MA/AA - - 3.0

NaSKS-6 - - 12.0

Citrate trianion 10.0-8.0

Supercarbonate 7.0 3.0 5.0

Carbonate 8.0 5.0 7.0

PVPVI/PVNO 0.5 0.5 0.5

Alcalase 0.5 0.3 0.9

Lipase 0.4 0.4 0.4

Amylase 0.6 0.6 0.6

Cellulase 0.6 0.6 0.6

Polysiloxane defoamers 5.0 5.0 5.0

Dried additive

Sodium sulfate 0.0 9.0 0.0

Balance (Shui Fen ﹠amp; Miscellaneous) 100.0 100.0 100.0

Concentration (g/L) 700 700 850

^*Any or other pair AQA tensio-active agent is alternative herein among the two AQA-22 of two AQA-2-of the two available equivalent of AQA-1 (coconut MeEO2) of the tensio-active agent among this embodiment.

EXAMPLE III

Be detergent formulation prepared in accordance with the present invention below.

G H I

The powder of blowing

Zeolite A 30.0 22.0 6.0

Sodium sulfate 19.0 5.0 7.0

MA/AA 3.0 3.0 6.0

LAS 13.0 11.0 21.0

C45AS 8.0 7.0 7.0

Coconut MeEO2 ^*1.0 1.0 1.0

Silicate-1.0 5.0

Soap--2.0

Whitening agent 1 0.2 0.2 0.2

Carbonate 8.0 16.0 20.0

DTPMP - 0.4 0.4

Spray on it

C45E7 1.0 1.0 1.0

Dried additive

PVPVI/PVNO 0.5 0.5 0.5

Proteolytic enzyme 1.0 1.0 1.0

Lipase 0.4 0.4 0.4

Amylase 0.1 0.1 0.1

Cellulase 0.1 0.1 0.1

NOBS - 6.1 4.5

PB1 1.0 5.0 6.0

Sodium sulfate-6.0-

Balance (Shui Fen ﹠amp; Miscellaneous) 100.0 100.0 100.0

^*Any or other pair AQA tensio-active agent is alternative herein among the two AQA-22 of two AQA-2-of the two available equivalent of AQA-1 (coconut MeEO2) of the tensio-active agent among this embodiment.

EXAMPLE IV

Be high-density and the detergent formulation that contains SYNTHETIC OPTICAL WHITNER below according to this patent preparation

J K L

The powder of blowing

Zeolite A 15.0 15.0 15.0

Sodium sulfate 0.0 5.0 0.0

LAS 3.0 3.0 3.0

Coconut MeEO2 ^*1.0 1.5 1.5

DTPMP 0.4 0.4 0.4

CMC 0.4 0.4 0.4

MA/AA 4.0 2.0 2.0

Agglomerate

LAS 5.0 5.0 5.0

TAS 2.0 2.0 1.0

Silicate 3.0 3.0 4.0

Zeolite A 8.0 8.0 8.0

Carbonate 8.0 8.0 4.0

Spray on it

Spices 0.3 0.3 0.3

C45E7 2.0 2.0 2.0

C25E3 2.0 - -

Dried additive

Citrate trianion 5.0-2.0

Supercarbonate-3.0-

Carbonate 8.0 15.0 10.0

TAED 6.0 2.0 5.0

PB1 13.0 7.0 10.0

Molecular weight 5,000,000

Polyethylene oxide--0.2

Bentonite clay--10.0

Proteolytic enzyme 1.0 1.0 1.0

Lipase 0.4 0.4 0.4

Amylase 0.6 0.6 0.6

Cellulase 0.6 0.6 0.6

Polysiloxane defoamers 5.0 5.0 5.0

Dried additive

Sodium sulfate 0.0 3.0 0.0

Balance (Shui Fen ﹠amp; Miscellaneous) to 100.0 100.0 100.0

Concentration (g/L) 850 850 850

^*Any or other pair AQA tensio-active agent is alternative herein among the two AQA-22 of two AQA-2-of the two available equivalent of AQA-1 (coconut MeEO2) of the tensio-active agent among this embodiment.

EXAMPLE V

Below be high density detergent composition prepared in accordance with the present invention:

M N

The powder of blowing

Zeolite A 2.5 2.5

Sodium sulfate 1.0 1.0

Coconut MeEO2 ^*1.5 1.5

Agglomerate

C45AS 11.0 14.0

Zeolite A 15.0 6.0

Carbonate 4.0 8.0

MA/AA 4.0 2.0

CMC 0.5 0.5

DTPMP 0.4 0.4

Spray on it

C25E3 5.0 5.0

Spices 0.5 0.5

Dried additive

HEDP 0.5 0.3

SKS-6 13.0 10.0

Citrate trianion 3.0 1.0

TAED 5.0 7.0

Percarbonate 15.0 15.0

SRA1 0.3 0.3

Proteolytic enzyme 1.4 1.4

Lipase 0.4 0.4

Cellulase 0.6 0.6

Amylase 0.6 0.6

Polysiloxane defoamers 5.0 5.0

Whitening agent 1 0.2 0.2

Whitening agent 2 0.2-

Balance (Shui Fen ﹠amp; Miscellaneous) to 100.0 100.0

Concentration (g/L) 850 850

^*Any or other pair AQA tensio-active agent is alternative herein among the two AQA-22 of two AQA-2-of the two available equivalent of AQA-1 (coconut MeEO2) of the tensio-active agent among this embodiment.

Example VI

It below is liquid detergent composition prepared in accordance with the present invention

O P O R S

LAS 10.0 13.0 9.0 2.0 15.0

C25AS 4.0 10.0 2.0 8.0 10.0

C25E3S 1.0 - - 3.0 -

C25E7 5.5 7.0 11.0 2.0 -

TFAA - - - 3.5 -

Coconut MeEO2 ^*0.5 1.0 2.0 1.5 3.0

TPKFA 2.0 - 13.0 2.0 -

Vegetable seed lipid acid---5.0-

Citric acid 2.0 3.0 1.0 1.5 1.0

Dodecylene/tetradecene succsinic acid 12.0 10.0--15.0

Oleic acid 4.0 2.0 1.0-1.0

Ethanol 4.0 4.0 7.0 2.0 7.0

1,2-propylene glycol 4.0 4.0 2.0 7.0 6.0

Monoethanolamine---5.0-

Trolamine--8--

It is 8.0 8.0 7.6 7.7 8.0 that NaOH is transferred to pH

Ethoxylation tetren 0.5-0.5 0.2-

DTPMP 1.0 1.0 0.5 1.0 2.0

SRA2 0.3 - 0.2 0.1 -

PVNO - - 0.1 - -

Proteinase-10 .5 0.5 0.4 0.25-

Alcalase - - - - 15

Lipase-0.10-0.01-

Amylase 0.25 0.25 0.6 0.5 0.25

Cellulase---0.05-

Endoenzyme---0.10-

Boric acid 0.1 0.2-2.0 1.0

Sodium formiate--1.0--

Calcium chloride-0.015-0.01-

Bentonite clay----4.0

Suspended clay SD3----0.6

Balance (Shui Fen ﹠amp; Miscellaneous) to 100 100 100 100 100

^*Any or other pair AQA tensio-active agent is alternative herein among the two AQA-22 of two AQA-2-of the two available equivalent of AQA-1 (coconut MeEO2) of the tensio-active agent among this embodiment.

Any granular detergent composition provided herein all can be pressed into detergent tablet by known tabletting method.

Heavy duty liquid detergent compositions comprises nonaqueous carrier matrix especially for the heavy duty liquid detergent of washing clothes.Their mode of production will be described in detail below.This water-free composition also can prepare according to the another kind of mode of following patent disclosure: US4753570; 4767558; 4772413; 4889652; 4892673; GB-A-2158838; GB-A-2195125; GB-A-2195649; US4988462; US5266233; EP-A-225654 (6/16/87); EP-A-510762 (10/28/92); EP-A-540089 (5/5/93); EP-A-540090 (5/5/93); US4615820; EP-A-565017 (10/13/93); EP-A-030096 (6/10/81), above-mentioned patent is listed reference in.Such composition can contain the various particulate state cleaning ingredients (as: aforesaid whitening agent) that can stably be suspended in wherein, and therefore, this non-aqueous composition just comprises liquid phase, and solid phase is not essential, but preferably has.All these are also at the document of quoting with hereinafter have a detailed description.For the clothes washing composition of producing other, the AQA tensio-active agent adds in the composition by above-mentioned content and adding mode.

Liquid phase

Liquid phase accounts for the 35%-99% of this detergent composition weight usually, and content is preferable range at 50-95%, is best when content accounts for 45-75%.The liquid phase of this detergent composition contains certain anion surfactant of relative high density basically, and this anion surfactant combines with certain on-aqueous liquid thinner.

(A) Necessary anion surfactant

The main anion surfactant that is used as the neccessary composition of non-water liquid phase is selected from an alkali metal salt of alkyl benzene sulphonate (ABS), wherein alkyl contains 10-16 carbon atom, and there be (see U.S. Pat 2220099 and US2477383, listed reference in) with the configuration of straight or branched.Particularly preferred anion surfactant is linear alkylbenzene sulphonic acid or sylvite (LAS), and wherein alkyl on average contains 11-14 carbon atom.The LAS sodium salt that contains 11-14 carbon atom is best.

The on-aqueous liquid thinner forms second kind of neccessary composition in the nonaqueous phase, and the alkyl benzene sulphonate (ABS) salt anionic surfactant can be dissolved in wherein.In order to form the structure liquid phase, to satisfy suitable stable mutually and qualified rheol requirement, the weight content of alkyl benzene sulphonate (ABS) salt anionic surfactant in liquid phase is generally 30%-65%, and more preferably the alkyl benzene sulphonate (ABS) salt anionic surfactant accounts for the 35%-50% weight of the non-water liquid phase of the present invention.The anionic surfactant concentration that uses anion surfactant to be equivalent in total composition with these concentration is the 15%-60% of composition weight, and preferable range is 20%-40%.

(B) The on-aqueous liquid thinner

In order to form the liquid phase of cleaning composition, above-mentioned alkyl benzene sulphonate (ABS) salt anionic surfactant combines with the on-aqueous liquid thinner.This thinner contains two kinds of neccessary compositions, and a kind of is the liquid alcohol alcoxylates, and another kind is the low polar organic solvent of non-water.

I) alcohol alcoxylates

Alkoxy fatty alcohols is to be used to form a kind of essential composition in the liquid diluent of this composition, and this material itself also is a nonionogenic tenside, corresponding to following general formula:

R ¹(C _mH _2mO) _nOH

R wherein ¹Be C ₈-C ₁₆Alkyl; M is 2-4; N is 2-12.R ¹Be preferably primary alkyl or secondary alkyl, contain 9-15 carbon atom, preferably 10-14 carbon atom; Alkoxy fatty alcohols is ethoxylate preferably, and per molecule contains 2-12 ethylene oxide unit, and preferably per molecule contains 3-10 ethylene oxide unit.

Alkoxy fatty alcohols component in the liquid diluent, having hydrophilic-hydrophobic balance (HLB) scope usually is 3-17, and wherein 6-15 is better, and 8-15 is best.

Comprise alcohol alkoxy fatty alcohols that make and that contain 7 moles of epoxy group(ing) ethane as the example of the alkoxy fatty alcohols of one of main ingredient of the on-aqueous liquid thinner of the useful present composition by 12-15 carbon atom, this class material is sold by Shell company, commodity Neodol25-7 by name and Neodol 23-6.5.Other useful Neodols comprise Neodol 1-5, and it is on average to contain the alkyl chain of 11 carbon atoms and the ethoxylized fatty alcohol of 5 moles of ethylene oxide; Neodol 23-9, it is the ethoxylation primary alconol that contains 9 moles of ethylene oxide and 12-13 carbon atom; Neodol 91-10, it is the ethoxylation primary alconol that contains 10 moles of ethylene oxide and 9-11 carbon atom, and such ethoxylated alcohol is also sold by Shell chemical company, and commodity are called Dobanol.Dobanol 91-5 is a kind of ethoxylized fatty alcohol that contains average 5 moles of ethylene oxide and 9-11 carbon atom; Dobanol 25-7 is the ethoxylized fatty alcohol that a kind of per molecule contains average 7 moles oxyethane and 12-15 carbon atom.

The example of the ethoxylated alcohol that other are suitable also comprises Tergitol 15-S-7 and Tergitol115-S-9, and these two kinds all is straight chain ethoxylation secondary alcohol, is sold by Union Carbide company.The former is by the straight chain ethoxylation secondary alcohol of 11-15 carbon atom and the blended ethoxylated product of 7 moles of ethylene oxide, and the latter and the former are similar, and different is to have 9 moles of ethylene oxide to participate in reaction.

The ethoxylated alcohol that is applicable to the other types of this composition is the high-molecular weight nonionogenic tenside, as Neodol 45-11, this is a kind of similarly oxyethane polycondensate of more senior Fatty Alcohol(C12-C14 and C12-C18), this high fatty alcohol contains 14-15 carbon atom, every mole contains the 11mol ethylene oxide group, and this product is also sold by Shell chemical company.

In this non-aqueous composition, as the alcohol alcoxylates of the essential composition of liquid diluent, account for the 1%-60% of liquid phase component usually, wherein 5%-40% is a preferable range, 5-30% is best.It is 1%-60% that alcohol alcoxylates these concentration in liquid phase are equivalent to its weight concentration scope in total composition, and wherein 2%-40% is a preferable range, and 5%-25% is best.

Ii) Non-water hangs down polar organic solvent

As in the liquid diluent of the integral part of cleaning composition liquid phase second kind must form by non-water, low polar organic solvent by composition." solvent " herein comprises the thinner part in on-surface-active carrier or the liquid phase.Though in fact some necessity in the composition and/or optional member are dissolved in the liquid phase that contains " solvent ", other component can be scattered in the liquid phase that contains " solvent " with the form of particulate matter.Therefore, " solvent " and do not mean that the component that requires solvent in fact can dissolve adding all cleaning composition wherein.

The non-water organism that uses as solvent is meant that tool hangs down polar liquid herein.To achieve the object of the present invention, " low polarity " liquid is meant that one of preferred particulates material that uses in this composition is not almost had solvency power, even have also very low.So-called preferred particulates material refers to the peroxide whitening agent exactly, Sodium peroxoborate or SPC-D.Therefore, just can not use polar solvent such as ethanol are arranged relatively.The suitable low polar solvent that uses in the on-aqueous liquid cleaning composition comprises the non-aklylene glycol that connects 4-8 carbon atom, and aklylene glycol hangs down alkyl oxide, low molecular poly, lower molecular weight methyl esters and acid amides.

A kind of preferred type that is used for the non-water low polar solvent of composition is made up of 4-8 the carbon atom side chain or the straight-chain alkyl-sub-glycol of non-company.This class material comprises hexylene glycol (4-methyl-2,4-pentanediol), 1,6-hexylene glycol, 1,3 butylene glycol and 1,4-butyleneglycol.Hexylene glycol is only.

The non-water low polar solvent that is used for another kind of preferred type of the present invention comprises list, and is two, three, or four-C _2-3Alkylene glycol mono C _2-6Alkyl oxide.Object lesson has the Diethylene Glycol monobutyl ether, TEG monobutyl ether, dipropylene glycol one ether and dipropylene glycol monobutyl ether.Wherein Diethylene Glycol monobutyl ether and dipropylene glycol monobutyl ether are particularly suitable.This compounds is on sale, and commodity are called Dowanol, Carbitol and Cellosolve.

The non-water low polar solvent that is used for another kind of preferred type of the present invention comprises low molecular poly (PEGs), and the molecular weight of this material is at least 150, preferably 200-600.

Also have the nonpolar preferably non-aqueous solvent of another kind to comprise the lower molecular weight methyl esters, its general formula is R ¹-C (O)-OCH ₃, R wherein ¹Be from 1-18.The example of suitable lower molecular weight methyl esters has methyl acetate,, methyl propionate, methyl caprylate and methyl laurate.

Certainly, the low polar organic solvent of the non-water of employing should be and other component compatibility and not interreaction, as be used for the SYNTHETIC OPTICAL WHITNER and/or the activator of liquid detergent composition.The common amount ranges of a kind of like this solvent composition is the 1%-70% that accounts for liquid phase weight, and preferable range is 10%-60%, and 20%-50% is best.These concentration that organic solvent uses in liquid phase are equivalent to its concentration in total composition and are 1%-50%, and wherein 5%-40% is a preferable range, preferably from 10%-30%.

Iii) The ratio of alcohol alcoxylates and solvent

The weight ratio of alcohol alcoxylates and organic solvent can be used for changing the rheological properties of the cleaning composition of final formation in the liquid diluent.Usually, the scope of this ratio is from 50: 1 to 1: 50, preferably from 3: 1 to 1: 3.

Iv) The liquid diluting agent concentration

About the concentration of alkylbenzene sulfonate anionic surfactant mixture, the liquid diluent total amount in the non-water liquid phase of the present invention is by kind and the quantity and the required composition character decision of other component of composition.Usually, liquid diluent accounts for the 35%-70% of the non-water liquid phase of composition, and preferable range is 50%-65%, and this is equivalent to the concentration of non-water liquid diluent in total composition is 15%-70%, and preferable range is 20%-50%.

Solid phase

Also need comprise in the non-water washing composition accounting for the solid phase particles thing that weight is formed 1%-65%, preferably its content is at 5%-50%, and this material disperses and is suspended in the liquid phase.Usually the size of such particulate matter is between 0.1-1500 μ m, preferably at 5-200 μ m.

Here used particulate matter mass-energy contains one or more granular detergent ingredients, and these compositions are insoluble basically in the non-water liquid phase of cleaning composition, and the particulate matter type that can be utilized has a detailed description below:

The preparation of cleaning composition and use

The preparation of nonaqueous phase liquid cleaning composition can mix necessity and optional ingredients by any order easily among the present invention, and prepares by mixing for example to stir.Make component in conjunction with forming the phase stable composition.In a kind of typical preparation technology of this composition, be to mix necessary and some preferred optional component under certain condition by particular order.

In this typical preparation technology's the first step,, form composition down at 30 ℃ to 100 ℃ by two kinds of neccessary composition Hybrid Heating of alkyl benzene sulphonate (ABS) salt anionic surfactant and non-diluent water.

In second step, above-mentioned formed heated mixt kept 2 minutes to 20 hours at 40 ℃ to 100 ℃ under certain shear agitation.At this moment also can select mixture is used vacuum tightness.Second step was for anion surfactant is dissolved in the non-water liquid phase fully.

In the 3rd step, liquid phase mixture is cooled to 0 ℃-35 ℃, this cooling step be for form one structurized, contain the liquid base material of tensio-active agent, so that the particulate matter in this cleaning composition can add and disperse wherein.

In the 4th step, keep liquid base material under the shear agitation condition, to add particulate matter, particulate matter is mixed with liquid base material.When adding more than a kind of particulate matter, preferably follow certain interpolation order.For example, when keeping shear agitation, all basically sizes all can add at 0.2 to 1000 micron option list surface-active agent solid particulate.After adding all optional surfactant granules, all organic washing-assisting detergent particles Citrate trianion and/or lipid acid and/or alkali source yellow soda ash for example for example substantially, all can keep mixture to be under the shear agitation in continuation adds, at this moment, can in mixture, add other solid phase optional member.Continue to stir the mixture, if necessary, can strengthen and stir so that insoluble solid phase particles forms homogeneous dispersion in liquid phase.

After some or all solid matters join in the stirred mixture in front, also keep mixture to be under the whipped state, can be added to highly preferred peroxygen bleach particle in the composition.In the end or after all or other composition of great majority, especially the alkali source particle after, add peroxygen bleach, just can obtain the stability of peroxygen bleach of needs.If add the enzyme grain, preferably join at last in the non-water liquid matrix.

Step in the end, after adding all particulate matters, the sufficiently long time of continuing to stir the mixture is to form the required viscosity of tool and the composition of stabilising characteristic mutually.Usually this comprises 1 to 30 fen clock time of stirring.

A kind of variation as the above-mentioned composition preparation process, one or more solid ingredients can be pre-mixed with a small amount of one or more liquid ingredients, form with mixed pulp is added in the composition that stirred, thereby a small amount of alcohol alcoxylates and/or non-water low polar solvent and organic washing-assisting detergent material and/or inorganic alkaline particle and/or bleach activator particles can be pre-formed mixture separately, is added in the stirred mixture with the form of starching.These addings that are pre-mixed slurry will be before adding peroxygen bleach and/or enzyme granulate, and peroxygen bleach and enzyme granulate self can constitute the part of a kind of mixed pulp that forms in a similar fashion.

Zhi Bei the present composition as mentioned above can be used for forming rinsing solution, is used for washing or bleached woven fabric.General, Xiang Shuizhong adds this composition of significant quantity, preferably adds in the automatic washing machine of conventional cleaning fabric, forms this aqueous-based cleaning/liquid lime chloride.Washing/the sodium hypochlorite solution of Xing Chenging preferably under agitation contacts with the fabric of preparing to clean or bleach like this.

The significant quantity that is added to the liquid washing agent that forms aqueous-based cleaning/sodium hypochlorite solution in the water contains to be enough to form from 500 to 7 in the aqueous solution, the quantity of the composition of 000ppm.Add the cleaning composition preferably from 800 to 3 in the washing/sodium hypochlorite solution, 000ppm.

Example VII A

Prepare a kind of on-aqueous liquid scouring agent that contains SYNTHETIC OPTICAL WHITNER, it has listed composition in the Table I, is not limited thereto example certainly.

Table 1

Component Weight percent (%) Weight percentage ranges (%)

Liquid phase

C ₁₂Linear alkylbenzene sulphonic acid (LAS) 25.3 18-35

C _12-14, 5 ethylene oxide unit 13.6 10-20

Ethoxylated alcohol

Hexylene glycol 27.3 20-30

Spices 0.4 0-1.0

Two-AQA-1 ^*2.0 1-3.0

Solid phase

Proteinase-10 .4 0-1.0

Anhydrous sodium citrate 4.3 3-6

Sodium peroxoborate 3.4 2-7

Nonanoyl Oxybenzene sodium sulfonate (NOBS) 8.0 2-12

Yellow soda ash 13.9 5-20

Diethyl pentetic acid (DTPA) 0.9 0-1.5

Whitening agent 0.4 0-0.6

Froth suppressor 0.1 0-0.3

The accessory constituent balance---

^*Coconut MeEO2. couple-AQA-1 can be substituted by two-AQA tensio-active agent 2-22 or other pair-AQA tensio-active agent.

This preparation of compositions is at first to mix two-AQA and LAS, adds hexylene glycol and ethoxylated alcohol then, keeps 1/2 hour down at 54 ℃ (130 °F) together.This mixture is cooled to 29 ℃ (85 °F), adds other composition this moment.The composition that obtains stirs at 29 ℃ (85 °F) and kept 1/2 hour.

The composition that obtains is a kind of stable anhydrous heavy duty type laundry liquid agent, uses to produce very high soil removability in common laundry operations.

The following examples A and B further illustrate the present invention about a kind of strip washing soap.

Example VII A I

CompositionWeight content (%) scope (%)

A B

C ₁₂-C ₁₈Vitriol 15.75 13.50 0-25

LAS 6.75 - 0-25

Na ₂CO ₃ 15.00 3.00 1-20

DTPP ¹ 0.70 0.70 0.2-1.0

Bentonite clay-10.0 0-20

Sokolan CP-5 ² 0.40 1.00 0-2.5

Two-AQA-1 ³2.0 0.5 0.15-3.0

TSPP 5.00 0 0-10

STPP 5.00 15.00 0-25

Zeolite 1.25 1.25 0-15

Sodium laurate-9.00 0-15

SRA-1 0.30 0.30 0-1.0

Proteolytic enzyme-0.12 0-0.6

Amylase 0.12-0-0.6

Lipase-0.10 0-0.6

Cellulase-0.15 0-0.3

----balance ⁴----

1. diethylenetriamine five (phosphonic acids) sodium

2.Sokolan CP-5 is a maleic acid-acrylic acid copolymer

3. two-AQA-1 can substitute to two-AQA-22 or other pair-AQA tensio-active agent by-AQA-2 two by the two-AQA class tensio-active agent of equivalent.

4. equipoise comprises water (2%-8% comprises combination water), sodium sulfate, lime carbonate and other accessory constituent.

Example I X

Preparation is according to the hand washing detergent composition below of the present invention, according to the weight percentage of following listed each composition each component mixed to prepare.

A B C D

LAS 15.0 12.0 15.0 12.0

TFAA 1.0 2.0 1.0 2.0

C25E5 4.0 2.0 4.0 2.0

AQA-9 ^* 2.0 3.0 3.0 2.0

STPP 25.0 25.0 15.0 15.0

MA/AA 3.0 3.0 3.0 3.0

CMC 0.4 0.4 0.4 0.4

DTPMP 1.0 1.6 1.6 1.6

Carbonate 2.0 2.0 5.0 5.0

Supercarbonate--2.0 2.0

Silicate 7.0 7.0 7.0 7.0

Proteolytic enzyme 1.0-1.0 1.0

Amylase 0.4 0.4 0.4-

Lipase 0.12 0.12-0.12

Photosensitization SYNTHETIC OPTICAL WHITNER 0.3 0.3 0.3 0.3

Vitriol 2.2 2.2 2.2 2.2

PB1 4.0 5.4 4.0 2.3

NOBS 2.6 3.1 2.5 1.7

SRA1 0.3 0.3 0.7 0.3

Whitening agent 1 0.15 0.15 0.15 0.15

Equipoise is miscellaneous/water to 100 100.0 100.0 100.0 100.0

AQA-9 ^*: can replace by any AQA tensio-active agent described herein.Preferred AQA tensio-active agent is the AQA that contains 10-15 oxyethyl group in this example; AQA-10 for example, AQA-16.

Above embodiment composition about laundering of textile fabrics is described among the present invention.And following Example will illustrate the cleaning composition according to other types of the present invention, but the present invention is not limited in these examples.

The modern hand washing efficiently contained some compositions with dishwasher detergent and can be made product have specific use attribute, as the degrease ability, and high whipability, gentleness and good hand touch.This with two-composition that the AQA tensio-active agent uses, comprise, as amine oxide surfactant, trimethyl-glycine and/or sultaine tensio-active agent, alkyl-sulphate and alkyl ethoxy sulfate surfactant, liquid carrier, particularly water and water/propylene glycol mixture, natural oil is as lemon oil.In addition, good hand washing may also contain Ca with liquid state and/or gel dishwashing agent ²⁺, Mg ²⁺, or Ca ²⁺/ Mg ²⁺Mixture can produce stronger detersive power, particularly with contain and amine oxide, alkyl-sulphate and alkyl ethoxy sulfate bonded be two-when the purging compound of AQA tensio-active agent uses together.Ca ²⁺, or Mg ²⁺Or mixed C a ²⁺/ Mg ²The source accounts for the 0.01%-4% that this composition weight is formed usually, preferably accounts for 0.02%-2%.Various water soluble ions source comprises for example vitriol, muriate and acetate.And these compositions also can contain nonionogenic tenside, particularly polyhydroxy fatty acid amide and alkyl polyglucoside class, and the member who contains 12-14 carbon atom (coconut alkyl) in this class is preferable.A kind of particularly preferred nonionogenic tenside that is used to wash with dishwashing liquid is C _12-14The N-methyl glucose amide, preferable amine oxide comprises C _12-14Dimethyl oxidation amine, alkyl-sulphate and alkyl ethoxy sulfate are as mentioned above, the consumption of this tensio-active agent in dishwashing liquid is generally the 3-50% of finished product.The prescription of dishwashing composition has obtained describing in detail in various patent publications, comprises United States Patent (USP) U.S.5378409, U.S.5576310 and U.S.5417893, and above document is listed reference in.

Modern automatization dishwasher detergent can contain SYNTHETIC OPTICAL WHITNER such as hypochlorous acid source; Perborate, percarbonate or persulphate SYNTHETIC OPTICAL WHITNER; Enzyme, as proteolytic enzyme, lipase and amylase or their mixture; Rinse aids, particularly nonionogenic tenside; Washing assistant comprises zeolite and phosphate builder; The condenses of low bubble detergent surfactant, particularly ethylene oxide/propylene oxide, this composition exists with particle or gel form usually.If when using, can adopt known various jelling agents in the document with gel form.

Following Example further specifies the present invention about the hand washing dishwashing liquid.

Embodiment X

Composition weight content (%) scope (%)

Two-AQA-1 ^*2.0 0.15-3

C _12-13Alkylsurfuric acid ammonium 7.0 2-35

C _12-14Ethoxylation (1) vitriol 20.5 5-35

Coconut amine oxide 2.6 2-5

Trimethyl-glycine/Tetronic 704 ^_0.87-0.10 0-2 (mix)

Ethoxylated alcohol C ₈E ₁₁5.0 2-10

Ammonium xylene sulfonate 4.0 1-6

Ethanol 4.0 0-7

Ammonium citrate 0.06 0-1.0

Magnesium chloride 3.3 0-4.0

Calcium chloride 2.5 0-4.0

Ammonium sulfate 0.08 0-4.0

Hydrogen peroxide 200ppm 0-300ppm

Spices 0.18 0-0.5

Maxatase ^_Proteinase-10 .50 0-1.0

Water and accessory constituent----balance----

^*Can be replaced to two-AQA-22 or other pair-AQA tensio-active agent by two-AQA-2

^*The coconut alkyl betaine

The following examples A and Embodiment B further illustrate among the present invention about the agent of a kind of phosphatic particulate state automatic bowl.

Embodiment XI

% is according to the weight of active substance

Composition A B

STPP (anhydrous) ¹31 26

Yellow soda ash 22 32

Silicate (%SiO ₂) 97

Tensio-active agent (nonionic) 3 1.5

The NaDCC SYNTHETIC OPTICAL WHITNER ²2-

Two-AQA-1 ^*0.5 1.0

Sodium peroxoborate-5

TAED - 1.5

Savinase(Au/g) 0.1 0.04

Termamyl(Amu/g) 0.5 0.5

Vitriol 25 25

Spices/accessory constituent to 100% is to 100%

1 tripoly phosphate sodium STPP

2 dichloro cyanogen ureas acid sodium

^*Two-AQA-1 can be replaced to two-AQA-22 by two-AQA-2

Embodiment XII

The following examples further specify the present invention about a kind of liquid-gel automatic bowl agent or other washing composition with high detersive power.

% is according to the weight of active substance

Composition A B C D E F G

Citric acid 16.5 16.5 16.5 16.5 16.5 10 10

Yellow soda ash/salt of wormwood--25 25 25 15 15

Two-AQA-1 ^*0.5 0.7 0.5 0.5 0.4 0.6 0.7

Dispersion agent (480N) 4444444

HEDP/SS-EDDS 2 2 0-2 2 2 1.5 1.5

Benzoyl peroxide 88888 1.5 1.5

Butylated hydroxytoluene 0.05 0.05 0.05 0.05 0.05 0.05 0.05

(BHT)

Tensio-active agent 2.5 2.5 1.5 1.5 1.5 1.5 1.5

Boric acid-4 44444

Sorbyl alcohol-6 66666

Savinase 24L - - 0.2 0.53 - 0.53 -

The Savinase 16L----0.53-0.53 that suspends

Maxamyl/Termamy 0.54 - 0.31 1.0 1.0 - -

The Termamyl-0.54---0.31 0.31 that suspends

Water----balance----

^*Two-AQA-1 (coconut MeEO2) can be substituted to two-AQA-22 or other pair-AQA tensio-active agent by the two-AQA-2 of equivalent.

According to prescription teacher's requirement, various jelling agents such as CMC and clay can be used in the composition so that various viscosity and hardness to be provided.

Embodiment XIII

Illustrate below two-AQA institute that can replace listing in any above-mentioned example pair-the AQA surfactant mixtures.As mentioned above, use this mixture can reach various useful performances and/or the cleaning composition that is applicable to various working conditionss is provided.Preferably two-AQA tensio-active agent differs 1.5 at least in this mixture, preferably differs 2.5-20 ethylene oxide unit, and weight ratio was from 10: 1 to 1: 10, and it is described that the example is not limited to following table.

Component Ratio (weight)

Two-AQA-1+ couple-AQA-5 1: 1

Two-AQA-1+ couple-AQA-10 1: 1

Two-AQA-1+ couple-AQA-15 1: 2

Two-AQA-1+ pair-AQA-5

+ two-AQA-20 1: 1: 1

Two-AQA-2+ couple-AQA-5 3: 1

Two-AQA-5+ couple-AQA-15 1.5: 1

Two-AQA-1+ couple-AQA-20 1: 3

Also can use two-AQA tensio-active agent and the mixture that only contains the cats product of an ethoxylation chain accordingly here.Therefore, for example, molecular formula is R ¹N ⁺CH ₃[EO] _X[EO] _YX ^-And R ¹N ⁺(CH ₃) ₂[EO] _zX ^-Ethoxylation cats product mixture can be used for the present invention, R wherein ¹With X as mentioned above, (x+y) of a cats product or z can be 1-5,1-2 preferably, another (x+y) or z are from 3-100, are preferably from 10-20, the best is 14-16.Such composition can be than using cats product of the present invention to produce higher detersive power (particularly under the situation at laundering of textile fabrics) separately under the water hardness condition an of wider scope.Have been found that short oxyethane cats product (as EO2) can improve the scourability of anion surfactant in soft water, and long oxyethane cats product (as EO15) can improve the tolerance level of anion surfactant to hardness, thereby improves the scourability of anion surfactant in hard water.The general knowledge in washing field shows that washing assistant can make performance " the window " optimizing of anion surfactant.Yet, up to now, enlarge that the water hardness that this " window " make it to comprise basically various conditions still can not reach.

Embodiment XIV

Following examples have illustrated flavoring formulation prepared in accordance with the present invention (A-C), and they are impregnated in above-mentioned any detergent composition example that contains two-AQA.Each component and content are listed in the following table.

(% weight)

Perfume composition A B C

Hexyl cinnamic aldehyde 10.0-5.0

2-methyl-3-(right-the tert-butyl phenyl)-propionic aldehyde 5.0 5.0-

7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-

Tetramethyl-naphthalene 5.0 10.0 10.0

Benzyl salicylate 5.0--

7-ethanoyl-1,1,3,4,4,6-hexamethyl tetraline 10.0 5.0 10.0

Right-(tert-butyl) cyclohexyl acetic acid ester 5.0 5.0-

Methyl dihydrojasmonate-5.0-

β-Nai Jiami-0.5-

Methyl-β-naphthalenone-0.5-

2-methyl-2-(right-different-the propyl group phenyl)-propionic aldehyde-2.0-

1,3,4,6,7,8-six hydrogen-4,6,6,7,8,8-hexamethyl

-ring penta-γ-2-chromene-9.5-

Ten dihydros-3a, 6,6, the 9a-tetramethyl

Naphtho-[1,2d] furans--0.1

Aubepine--0.5

Tonka bean camphor--5.0

Cypress camphor--0.5

Vanillin--5.0

Encircle penta decalactone 3.0-10.0

Tricyclo decene acetic ester--2.0

Labdanum resin--2.0

Tricyclo decene propionic ester--2.0

Phenylethyl alcohol 20.0 10.0 27.9

Terpineol 350 10.0 5.0-

Phantol 10.0 10.0 5.0

Linalyl acetate 5.0-5.0

Geraniol 5.0--

Vernol-5.0-

2-(1,1-diformazan ethyl)-adnoral acetate 5.0--

Orange oil, cold compaction-5.0-

Jasmal 2.0 2.0-

Orange terpenes-10.0-

Oxymethoxyallylbenzene-1.0-

Diethyl phthalate-9.5-

Lemon oil, cold compaction --10.0

Total amount 100.0 100.0 100.0

Above-mentioned flavor compositions (normal contents be at most total detergent composition weight about 2%) is blending or is sprayed in various washing (the comprising bleaching) composition that contains two-AQA tensio-active agent disclosed herein, thereby guarantees that spices or its single component are in the lip-deep deposition that will clean (bleaching) and/or reservation raising.

Claims (15)

1. A granular detergent composition comprising the following components: 0.001%-5% of enzymes, 1%-55% of anionic surfactants and 0.1%-5% of a dialkoxy group of the following structural formula Quaternary Ammonium Cationic Surfactants:

In the formula, R ¹ is linear, branched, or substituted C ₈ -C ₁₂ alkyl, alkenyl, aryl, alkaryl, ether with glycosyl ether moiety; R ² is C ₁ -C ₃ alkyl; R ³ and R ⁴ vary independently and are selected from hydrogen, methyl and ethyl; X is an anion; A and A' vary independently and are each C ₁ -C ₄ alkoxy; p and q can be Varies independently and is an integer between 1-30. 2. The composition according to claim 1, wherein the enzyme is lipase. 3. The composition of claim 1, wherein the enzyme is a protease. 4. The composition of claim 1, wherein the enzyme is a cellulase. 5. The composition of claim 1, wherein the enzyme is endoglucanase. 6. The composition of claim 1, wherein the enzyme is amylase. 7. The composition of claim 1, wherein the enzyme is peroxidase. 8. The composition of claim 1, further comprising an enzyme stabilizer. 9. The composition according to claim 1, wherein the ratio of dialkoxyquaternary ammonium cationic surfactant to anionic surfactant is from 1:15 to 1:8. 10. composition according to claim 1, wherein the ^R of dialkoxy quaternary ammonium cationic surfactant is methyl, A and A ' are ethoxy or propoxy, p and q are 1- Integer between 8. 11. composition according to claim 1, wherein the ^R of bis-alkoxy quaternary ammonium cationic surfactant is methyl, A and A ' are ethoxyl group or propoxyl group, p and q are 1-4 Integer between. 12. The composition according to claim 1, wherein p and/or q in the structural formula of the dialkoxy quaternary ammonium cationic surfactant is an integer between 10-15. 13. A composition according to claim 1 comprising two or more bis-alkoxy quaternary ammonium cationic surfactants, or a bis-alkoxy quaternary ammonium cationic surfactant and a monoethoxy A mixture of alkylated cationic surfactants. 14. The composition of claim 1 comprising a mixture of two or more anionic surfactants and two or more bisalkoxyquaternary ammonium cationic surfactants. 15. The composition of claim 1 which is free of bleach.