CN1225122A - Detergent composition - Google Patents

Detergent composition Download PDF

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Publication number
CN1225122A
CN1225122A CN 97196381 CN97196381A CN1225122A CN 1225122 A CN1225122 A CN 1225122A CN 97196381 CN97196381 CN 97196381 CN 97196381 A CN97196381 A CN 97196381A CN 1225122 A CN1225122 A CN 1225122A
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China
Prior art keywords
composition
aqa
active agent
tensio
acid
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CN 97196381
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Inventor
K·阿什奥
J·J·沙伊贝尔
K·米那密卡洼
L·克龙
S·K·马诺哈
T·A·克里佩
J·D·库赖
K·L·克特
I·M·多德
R·T·哈特肖恩
P·R·福莱
R·卡特苏达
F·A·克维托克
M·H·-K·毛
M·A·J·莫斯
S·姆拉塔
K·W·维尔曼
R·K·帕南迪克
K·普拉莫德
K·M·K·萨奈克
C·A·J·K·托恩
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Procter and Gamble Co
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Procter and Gamble Co
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Priority to CN 97196381 priority Critical patent/CN1225122A/en
Publication of CN1225122A publication Critical patent/CN1225122A/en
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Abstract

Detergent composition comprising a photic-bleach activator, a non-AQA surfactant and an alkoxylated quaternary ammonium (AQA) cationic surfactant.

Description

Detergent composition
Invention field
It is (two-AQA) detergent composition of cats product to the present invention relates to comprise optical white, non--AQA tensio-active agent and two-alkoxy quaternary ammonium.
Background of invention
Owing to require composition now to remove various dirts and spot, thereby the preparation of detergent for washing clothes and other cleaning combination faces sizable challenge from various dirt-carrying bodies.Therefore, detergent for washing clothes, hard surface cleaner, shampoo and other personal wash composition, detergent for washing dishware with hand and the detergent composition that is applicable to the automatic dishwashing machine all need suitably to select and make up each component to reach effective function.Generally, this detergent composition contains the tensio-active agent of one or more types, and they are to be used for becoming flexible and removing dissimilar dirts and spot.As if the existing document of research illustrates that detergent manufacturers has the combination of many kinds of tensio-active agents and tensio-active agent available, but in fact many this components are special chemical, they are not suitable for for example low unit price consumer's goods of household laundry washing composition.Practical situation be most of this household product for example detergent for washing clothes still mainly comprise one or more conventional ethoxylated non-ionic types and/or sulfation or sulfonated aniorfic surfactant, this chances are for economy with needs preparations to various dirts and spot and all goodish composition of various fabric effect.
The various nitrogenous cats products of suggestion can be used in the various cleaning combinations in the existing document.This material generally is the compound of amino, amido or quaternary ammonium salt or tetrahydroglyoxaline form, and they are designed to special purposes usually.For example, advised various amino and quaternary surfactant are used for shampoo Compositions, the hairdressing effect has allegedly been arranged.Other nitrogen-containing surfactants is used to provide in some detergent for washing clothess soft fabric and antistatic property.But for most of, the commercial applications of these materials is owing to the difficulty of running in this compound of scale operation is restricted.Restriction in addition is that the anion active component and the cats product of detergent composition may produce precipitation because of their ionic interact.Above-mentioned nonionic and anion surfactant are still main surface active agent composition in current laundry composition.
For example human body dirt, fats/oils dirt and some food stains may be problematic to remove dissimilar dirts and spot fast and effectively.This dirt comprises the mixture of triglyceride level, lipoidis, complex polysaccharide, inorganic salt and proteic substance, and all these materials are formed by hydrophobic part to a certain extent, and therefore they are difficult to remove as everyone knows.After washing, usually keep the hydrophobic dirt and the residual spot of low amount at fabric face.
Except above-mentioned tensio-active agent, in detergent composition, use multiple SYNTHETIC OPTICAL WHITNER, for example peroxygen bleach, chlorine bleach and optical white usually.Stand intense light source at washed fabric and for example drying the general optical white that uses under the situation of direct sunlight of operation.Optical white is soft relatively SYNTHETIC OPTICAL WHITNER, and is effective especially to the color of the decolouring (for example particle form or fruit juice spot) of the pigment of the band look organic residue relevant with the human body dirt with removal.The whitening capacity of optical white produces owing to being exposed under the ultraviolet sunlight.It is believed that sunlight is converted into active bleaching thing with optical white, its oxidation is present in the band look spot on the fabric then.With any SYNTHETIC OPTICAL WHITNER of use, comprise that a relevant problem of optical white is to remove residual dirt and spot fully from fabric face.Constantly washing and dressing adds that the limited removal of dirt in the washing has caused the accumulation of residual soil and spot, and it is further held back dirty particle and causes the fabric yellowing.At last, fabric presents gloomy outward appearance, and the human consumer feels and should not dress and it be abandoned.
Found that (AQA) compound can be used in the various detergent composition to strengthen the scourability to the dirt of the common polytype dirt and the spot of being run into, particularly hydrophobic type some two-alkoxy quaternary ammonium.Independent a kind of product has better cleaning force and whiteness performance among both than only containing now to be surprised to find that the composition that contains two-AQA tensio-active agent and optical white.
Of the present invention pair-AQA tensio-active agent has brought very big benefit for the prescription teacher, known cats product before having surpassed.For example, the present invention use-the AQA tensio-active agent provides obvious improvement for cleaning the hydrophobic dirt of running into usually of " daily " fat/oiliness.In addition, for example alkyl-sulphate and alkylbenzene sulfonate are compatible for two-AQA tensio-active agent and the anion surfactant that usually uses in detergent composition; And use the factor of known cats product in the past with the incompatible normally restriction of anionic group in the detergent composition.Two-AQA the tensio-active agent of low amount (being low to moderate 3ppm in wash water solution) just can produce benefit as herein described.Two-AQA tensio-active agent can be prepared in the wide region of pH 5-12.Two-AQA tensio-active agent can be made into the pumpable solution of 30% (weight), therefore carries easily in production unit.Ethoxylation degree be higher than 5 two-the AQA tensio-active agent is to exist with liquid form sometimes, therefore can provide by 100% clean material.Except the favourable transportation performance of-AQA, two-AQA tensio-active agent can obtain by highly enriched solution, and this provides remarkable economic advantages aspect transportation cost.Two-AQA tensio-active agent and various perfume composition also are compatible, and these are different with cats products more commonly known in the art.
It is believed that therefore fat/oily dirt can be made optical white to cause the improvement of dirt decolouring near the chromoplastid in the dirt (pigment that for example is trapped) by two-AQA solubilising effectively.Therefore, the invention provides detergent composition, its-AQA tensio-active agent two by comprising and optical white not only provide the good cleaning force to hydrophobicity fat/greasy dirt dirt, but also the good cleaning force to wetting ability band look dirt is provided.
Background technology
A.Methreteab that authorize August 15 nineteen ninety-five and the US5441541 of F.J.Loprest relate to the mixture of negatively charged ion/cats product.The A.P.Murphy that on September 3rd, 1980 authorized, the UK2040990 of R.J.M.Smith and M.P.Brooks relates to the ethoxylation cats product in detergent for washing clothes.
Summary of the invention
The invention provides a kind of composition, it comprises following component or is mixed with by following component: the bis-alkoxy quaternary ammonium with following formula of optical white, non--AQA tensio-active agent and significant quantity (two-AQA) cats product:
Figure A9719638100061
R wherein 1Be the C of straight chain, side chain or replacement 8-C 18Alkyl, alkenyl, aryl, alkaryl, ether or sugar alcohol base ether moiety, R 2Be C 1-C 3Moieties, R 3And R 4Can change separately, and be selected from hydrogen, methyl, ethyl, X is a negatively charged ion, and A and A ' can change and each C naturally separately 1-C 4Alkoxyl group, p and q can change and be the integer of 1-30 separately.
The detailed Description Of The Invention optical white
The present composition comprises optical white as its essential characteristic.Be applicable to that optical white of the present invention comprises sulfonated Phthalocyanine Zinc and/or aluminium.US4033718 referring to the Holcombe that authorized on July 5th, 1977 etc.The phthalocyanine optical white for example can be buied or buy by phthalocyanine sulfonic acid zinc by trade(brand)name TINOLUX.
Generally, phthalocyanine can the middle described method preparation of reporting in " Englishize association will " (" Journalof the Chemical Society ") (the 1719th, 1936 year) by Linstead and co-worker thereof.As everyone knows, solubleness is extremely low usually in water for unsubstituted metal phthalocyanine, therefore is used as pigment.But for example sulfo group, carboxyl or other substituting group can improve water-soluble to add hydrophilic group by the oleum that uses heat in phthalocyanine structure.The sulfonated phthalocyanine is the dyestuff that is fit to, because they have avidity to the fiber of cotton or pulp form.
As mentioned above, phthalocyanine is by being sulfonated easily with the oleum heating.Therefore, can prepare single sulfonation, two sulfonation, three sulfonation and four sulfonated Phthalocyanine Zinc and aluminium.Three sulfonation and four sulfonated kinds preferably are used as optical white.Four sulfonated Phthalocyanine Zinc and three sulfonated Phthalocyanine Zinc are most preferred.
The detergent composition that the present invention uses contains this SYNTHETIC OPTICAL WHITNER of 0.025%-1.25% (weight).Two-oxyalkylated quaternary ammonium (two-AQA) cats product
Second kind of basal component of the present invention comprise the following formula of significant quantity two-the AQA tensio-active agent: R wherein 1Be to contain 8-18 carbon atom, preferred 8-16 carbon atom, the most preferably alkyl of the straight chain of 8-14 carbon atom, side chain or replacement, alkenyl, aryl, alkaryl, ether or sugar alcohol base ether moiety; R 2Be the alkyl that contains 1-3 carbon atom, preferable methyl; R 3And R 4Can change and be selected from hydrogen (preferably), methyl and ethyl separately, X-enough provides electroneutral negatively charged ion, for example chlorine, bromine, methylsulfate, sulfate radical.A and A ' can change and be selected from separately C separately 1-C 4Alkoxyl group, particularly oxyethyl group, propoxy-, butoxy and its mixture; P is 1-30, preferred 1-15, more preferably 1-8, most preferably 1-4; Q is 1-30, preferred 1-15, more preferably 1-8, most preferably 1-4.Most preferably p and q are 1.
Hydrocarbyl substituent R wherein 1Be C 8-C 12 'C particularly 8-10-the long material of long-chain has improved laundry particulate dissolution rate to the AQA compound than having more, particularly under the cold water condition.Therefore, C 8-C 12Two-AQA tensio-active agent may be that some prescription teachers are preferred.The content that is used to prepare two-AQA tensio-active agent of finished product laundry detergent composition can be at 0.1%-5%, generally in 0.45%-2.5% (weight) scope.The weight ratio scope of two-AQA and percarbonate bleach is 1: 100-5: 1, preferred 1: 60-2: 1, and most preferably be 1: 20-1: 1.
The present invention uses the two-AQA tensio-active agent of " significant quantity " to contain the performance of the cleaning combination of other optional components with improvement.Here " significant quantity " of two-AQA tensio-active agent meaning is that this quantity is enough to directionally or significantly improve the removal performance of cleaning combination at least some target dirts and spot with 90% degree of confidence.Therefore, the target dirt at composition comprises under the situation of some food stains that the prescription teacher will use enough-AQA at least directionally to improve the cleaning performance to this spot in composition.Equally, the target dirt at composition comprises under the situation of great soil group dirt that the prescription teacher will use enough two-AQA at least directionally to improve the cleaning performance to this dirt in composition.
Two-AQA tensio-active agent can make up by a certain amount of detersive surfactant with other, and this amount can obtain improvement directed at least aspect cleaning performance effectively.In washing fabric composition, this " application quantity " can change, and it not only depends on the type and the seriousness of dirt and spot, and depends on the temperature of washing water, the volume of washing water and the type of washing machine.
For example using 45-83 premium on currency, cycles of washing in washing bath is in 10 ℃-50 ℃ the top feeding formula vertical shaft American version automatic washing machine as 10-14 minute and temperature of washing water, in wash water solution, preferably include 2ppm-50ppm, preferably two-AQA tensio-active agent of 5ppm-25ppm.For the heavy-filth liquid detergent for washing clothes, be that 50m1-150ml calculates by each washing load-carrying usage quantity, the concentration (weight) that two-AQA tensio-active agent converts in product is 0.1%-3.2%, preferred 0.3%-1.5%.For compact grain detergent for washing clothes (density is higher than 650g/l), be that 60g-95g calculates by each washing load-carrying usage quantity, the concentration (weight) that two-AQA tensio-active agent converts in product is 0.2%-5.0%, preferred 0.5%-2.5%.For spray-dired particle (i.e. " fluff type "; Density is lower than 650g/l), be that 80g-100g calculates by each load-carrying usage quantity, it is that about 0.1%-is about 3.5% that two-AQA tensio-active agent converts concentration (weight) in product to, preferably about 0.3%-1.5%.
For example, use the 8-15 premium on currency in the washing water-bath, cycles of washing is 10-60 minute, and the temperature of washing water is in 30 ℃-95 ℃ the European automatic washing machine of preceding charging type transverse axis, preferably in wash water solution, comprise 13ppm-900ppm, preferably 16ppm-390ppm pair-AQA tensio-active agent.For the heavy-filth liquid detergent for washing clothes, be that 45ml-270ml calculates by each washing load-carrying usage quantity, the concentration (weight) that two-AQA tensio-active agent is converted in product is 0.4%-2.64%, preferred 0.55%-1.1%.For compact grain detergent for washing clothes (density is higher than 650g/l), be that 40g-210g calculates by each washing load-carrying usage quantity, the concentration (weight) that two-AQA tensio-active agent is converted in product is 0.5%-3.5%, preferred 0.7%-1.5%.For spray-dired particle (that is, " fluff type "; Density is lower than 650g/l), be that 140g-400g calculates by each load-carrying usage quantity, the concentration (weight) that two-AQA tensio-active agent is converted in product is 0.13%-1.8%, preferred 0.18%-0.76%.
For example, use the 26-52 premium on currency in the washing water-bath, cycles of washing is 8-15 minute, and temperature of washing water is in 5 ℃-25 ℃ the Japanese automatic washing machine of top feeding formula vertical shaft, preferably in wash water solution, comprise 1.67ppm-66.67ppm, preferably 3ppm-6ppm pair-AQA tensio-active agent.For the heavy-filth liquid detergent for washing clothes, be that 20ml-30ml calculates by each washing load-carrying usage quantity, the concentration (weight) that two-AQA tensio-active agent is converted in product is 0.25%-10%, preferred 1.5%-2%.For compact grain detergent for washing clothes (density is higher than 650g/l), to calculate by each washing load-carrying usage quantity 18g-35g, the concentration (weight) that two-AQA tensio-active agent is converted in product is 0.25%-10%, preferred 0.5%-1.0%.For spray-dired particle (that is, " fluff type "; Density is lower than 650g/l), be that 30g-40g calculates by each washing load-carrying usage quantity, the concentration (weight) that two-AQA tensio-active agent is converted in product is 0.25%-10%, preferred 0.5%-1%.
By as can be seen above-mentioned, the consumption of the two-AQA tensio-active agent that uses in machine laundry can change, and this depends on the type etc. of user's custom and experience, washing machine.Yet in this respect, even the incognizant advantage of institute is them with the relatively low consumption use of other tensio-active agent (being generally negatively charged ion or anionic/nonionic mixture) in than final product composition having the time before two-AQA tensio-active agent a kind of, also can at least directionally improve cleaning performance to multiple dirt and spot.This is different from other composition of prior art, and the consumption of wherein various cats products and anion surfactant equals or near stoichiometric.Generally, in the invention process, the two-AQA in laundry composition: the weight ratio of anion surfactant is 1: 70-1: 2, preferred 1: 40-1: 6, more preferably 1: 30-1: 6, most preferably 1: 15-1: 8.In the laundry composition that comprises negatively charged ion and nonionogenic tenside, two-AQA: the weight ratio of blended anionic/nonionic tensio-active agent is 1: 80-1: 2, preferred 1: 50-1: 8.
Can also use two-AQA tensio-active agent preparation of significant quantity to comprise for example various other cleaning combinations of trimethyl-glycine, sultaine, amine oxide of anion surfactant, optional nonionogenic tenside and special-purpose tensio-active agent by mode of the present invention.This composition includes, but are not limited to manual dishwashing product (particularly liquid or gel), hard surface cleaner, shampoo, individual purge block agent, the agent of laundry piece etc.Because this composition user's custom and experience have faint difference, comprise in this composition that about 0.25%-is about 5%, preferably about 0.45%-is about, and 2% (weight) is two-and the AQA tensio-active agent is gratifying.In addition, the weight ratio of other tensio-active agent in a thing is low, and promptly the situation at anion surfactant is lower than stoichiometric quantity.Preferably, this cleaning combination comprises the two-AQA/ tensio-active agent of the above ratio of the laundry composition narration of using for machine just.
Opposite with other cats product commonly known in the art, the present invention is two-and oxyalkylated cats product has enough solvabilities, they can be used in combination with the blended surfactant system, and non-ionic surfactant concentration is very low and contain for example alkyl sulfate surfactant in this blended surfactant system.Be used for top feeding formula automatic washing machine for conventional design, especially for the washing machine type and the detergent composition under Japanese working conditions that use in the North America, this may be the importance that formulator will be considered.Generally, this composition comprises weight ratio about 25: about 1: 25 of 1-, preferred about 20: about 3: 1 interior anion surfactants of scope of 1-: nonionogenic tenside.This is opposite with European prescription, and European prescription generally comprises ratio about 10: about 1: 10 of 1-, preferred about 5: about 1: 1 interior negatively charged ion of scope of 1-: nonionogenic tenside.
The cats product of the preferred ethoxylation of the present invention can be buied from Akzo Nobel Chemicals company by trade(brand)name ETHOQUAD.In addition, this material can use synthetic (" EO " expression-CH wherein of following multiple different reaction scheme 2CH 2The O-unit): route 1
Figure A9719638100101
Figure A9719638100103
Route 2
Figure A9719638100104
Route 3
Figure A9719638100111
Figure A9719638100112
Route 4
Figure A9719638100113
Figure A9719638100114
Economic reaction scheme is as follows: route 5
Figure A9719638100115
Figure A9719638100116
Following parameter has been summarized the optional and preferred reaction conditions of route 5.The step 1 of this reaction is preferably carried out in water-bearing media.Temperature of reaction is generally 140-200 ℃ of scope.Reaction pressure is 50-1000 pound/inch 2Can use alkaline catalysts, preferred sodium hydroxide.The mol ratio of reactant amine and alkyl-sulphate is 2: 1-1: 1.The preferred C that uses of reaction 8-C 14Sodium alkyl sulfate carries out.Ethoxylation and quaternized step are to use normal condition and reactant to carry out.
In some cases, reaction scheme 5 produces the product that can be enough to be dissolved in the water-containing reacting medium and may form gel.Though can reclaim required product from gel, following two step of another kind synthetic route 6 may more cater to the need under some state of trade.First step in the route 6 is to be undertaken by route 5.Second step (ethoxylation) preferably use oxyethane and acid for example HCl carry out, obtain quaternised tensio-active agent.As shown below, chloro-hydrin(e), promptly chloroethanol also can obtain required dihydroxy ethyl derivative through reaction.
For reaction scheme 6, following parameter has been summarized the optional and preferred reaction conditions for first step.First step preferably carries out in water-bearing media.Temperature of reaction is generally at 100-230 ℃.Reaction pressure is 50-1000 pound/inch 2Can use alkali, preferred sodium hydroxide and the HSO that in reaction process, produces 4Reaction or use excessive amine and this acid-respons.The molar ratio of amine and alkyl-sulphate generally is 10: 1-1: 1.5, preferred 5: 1-1: 1.1, more preferably 2: 1-1: 1.In the recycling step of product, make required replacement amine simply as different from its undissolved therein water-containing reacting medium, separating.Second step of this method is carried out under the popular response condition.Further ethoxylation and quaternized two to obtain-reaction of AQA tensio-active agent is to carry out under the standard reaction condition.
Route 7 can randomly use oxyethane to carry out under standard ethoxylation condition, but does not contain catalyzer, to realize monosubstituted ethoxyization.
The reaction scheme that these are other below has been described, wherein " EO " expression-CH 2CH 2The O-unit.In this reaction, use in mineral alkali, organic bases or the excessive amine reactant and the HSO that produces 4Route 6
Figure A9719638100121
Figure A9719638100122
Route 7
Figure A9719638100123
Several above reactions below also have been described, only are to be convenient to teacher of the prescription, rather than plan to limit them.Synthetic A prepares N, two (2-hydroxyethyl) lauryl amines of N-
The sodium hydroxide solution (0.095 mole) and the 72g distilled water that in autoclave glass bushing pipe, add 19.96g sodium lauryl sulphate (0.06921 mole), 14.55g diethanolamine (0.1384 mole), 7.6g 50% (weight).This glass bushing pipe is enclosed the 500ml stainless steel and is waved in the autoclave, and at 300-400 pound/inch 2Heated 3-4 hour at 160-180 ℃ under the nitrogen.This mixture is cooled to room temperature, and the liquid contents of this glass bushing pipe is poured in the 250ml separating funnel that is added with the 80ml chloroform.This funnel is fully shaken several minutes, makes demixing then.Discharge the chloroform of lower level, evaporate chloroform and obtain product.Synthetic B prepares N, two (2-hydroxyethyl) lauryl amines of N-
By the method for describing among the synthetic A, in the presence of alkali, 1 mole of sodium lauryl sulphate and 1 molar ethanolamine are reacted.The 2-hydroxyethyl lauryl amine that recovery obtains and with 1-chloroethanol prepared in reaction subject compound.Synthetic C prepares N, two (2-hydroxyethyl) lauryl amines of N-
The sodium hydroxide solution (0.095 mole) and the 72g distilled water that in the glass autoclave bushing pipe, add 19.96g sodium lauryl sulphate (0.06921 mole), 21.37g thanomin (0.3640 mole), 7.6g 50% (weight).This glass bushing pipe is enclosed the 500ml stainless steel and is waved in the autoclave, and at 300-400 pound/inch 2Heated 3-4 hour at 160-180 ℃ under the nitrogen.This mixture is cooled to room temperature, and the liquid contents of glass bushing pipe is poured in the 250ml separating funnel that is added with the 80ml chloroform.This funnel is fully shaken several minutes, makes demixing then.Discharge the chloroform of lower level, evaporate chloroform and obtain product.This product reacts under 120-130 ℃ in the presence of no alkaline catalysts with the oxyethane of 1 molar equivalent then, makes required the finished product.
The disubstituted amine of preparation can further be pressed standard manner by ethoxylation in above synthesizing.Use of the present invention pair-AQA tensio-active agent of the quaternized formation of alkyl halide as usual.
According to foregoing, below specify two-AQA tensio-active agent that the present invention uses without limitation.Should be appreciated that described herein two-degree of alkoxylation of AQA tensio-active agent is to report into mean value according to the common practice of conventional ethoxylated non-ionic surface active agent.This is because the general mixture with different ethoxylation degree materials that produces of ethoxylation.Therefore, total EO value of report and non-integral situation are much, for example " EO2.5 ", " EO3.5 ".Symbol R 1R 2ApR 3A ' qR 4Two-AQA-1 (and C 12-C 14CH 3EO EO is called coconut methyl EO2) two-AQA-2 C 12-C 16CH 3(EO) 2EO pair-AQA-3 (coconut palm C 12-C 14CH 3(EO) 2(EO) 2Sub-methyl EO4) two-AQA-4 C 12CH 3EO EO pair-AQA-5 C 12-C 14CH 3(EO) 2(EO) 3Two-AQA-6 C 12-C 14CH 3(EO) 2(EO) 3Two-AQA-7 C 8-C 18CH 3(EO) 3(EO) 2Two-AQA-8 C 12-C 14CH 3(EO) 4(EO) 4Two-AQA-9 C 12-C 14C 2H 5(EO) 3(EO) 3Two-AQA-10 C 12-C 18C 3H 7(EO) 3(EO) 4Two-AQA-11 C 12-C 18CH 3(propoxy-) (EO) 3Two-AQA-12 C 10-C 18C 2H 5(isopropoxy) 2(EO) 3Two-AQA-13 C 10-C 18CH 3(EO/PO) 2(EO) 3Two-AQA-14 C 8-C 18CH 3(EO) 15 *(EO) 15 *Two-AQA-15 C 10CH 3EO EO pair-AQA-16 C 8-C 12CH 3EO EO pair-AQA-17 C 9-C 11CH 3The average average EO3.5 of EO3.5 couple-AQA-18 C 12CH 3The average average EO3.5 of EO3.5 couple-AQA-19 C 8-C 14CH 3(EO) 10(EO) 10Two-AQA-20 C 10C 2H 5(EO) 2(EO) 3Two-AQA-21 C 12-C 14C 2H 5(EO) 5(EO) 3Two-AQA-22 C 12-C 18C 3H 7Bu (EO) 2
*Oxyethyl group is randomly with methyl or ethyl capping.
Be used for most preferred pair-AQA compound of the present invention and have following formula:
Figure A9719638100151
R wherein 1Be C 8-C 18Alkyl and its mixture, preferred C 8, C 10, C 12, C 14Alkyl and its mixture, X provides any negatively charged ion easily of charge balance, preferred chlorine.About above-mentioned two-AQA formula, because in preferred compound, R 1Be by coconut (C 12-C 14Alkyl) partial fatty acid obtains, R 2Be methyl, ApR 3And A ' qR 4All are monosubstituted ethoxies, therefore the compound of this preferred type is referred to herein as " two-AQA-1 " in " CocoMeEO2 " or the last table.
Other two-AQA tensio-active agent that is fit to of the present invention comprises the compound of following formula:
Figure A9719638100152
R wherein 1Be C 8-C 18Alkyl, preferred C 8-C 14Alkyl, p and q are 1-3 independently, R 2Be C 1-C 3Alkyl, preferable methyl, X is a negatively charged ion, particularly chlorine or bromine.
Other compound of the above-mentioned type comprises wherein oxyethyl group (CH 2CH 2O) unit (EO) is by butoxy (Bu), isopropoxy [CH (CH 3) CH 2O] and [CH 2CH (CH 3O] unit (i-Pr) or positive propoxy unit (Pr) or EO and/or Pr and/or the unitary mixture of i-Pr displaced those.
P and/or q are the integers of 10-15 scope in the formula of the most preferred two-AQA compound that uses in the low preparation of auxiliary agent content.This compound is specially adapted to Handwash laundry detergent compositions.Non-AQA detersive surfactant
Except two-AQA tensio-active agent, the present composition preferably also comprises non--AQA tensio-active agent.Non--AQA tensio-active agent can comprise any basically negatively charged ion, nonionic or other cats product.Anion surfactant
The unrestricted example that is suitable for general consumption of the present invention and is the anion surfactant of 1%-55% (weight) comprises: conventional C 11-C 18Alkylbenzene sulfonate (" LAS ") and uncle's type (" AS ") side chain and random C 10-C 20Alkyl-sulphate, formula 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) alkyl-sulphate, x and (y+1) be at least 7 integer wherein, preferably at least 9, M is a water-soluble cationic, sodium particularly, unsaturated vitriol is oleyl sulfate for example, C 12-C 18α-sulfonated fatty acid ester, C 10-C 18Sulfated alkyl polyglycoside, C 10-C 18Alkyl alkoxy sulfate (" AE xS "; EO 1-7 ethoxy sulfate particularly), C 10-C 18Alkyl alkoxy carboxylate salt (particularly EO1-5 ethoxy carboxylate).C 12-C 18Trimethyl-glycine and sultaine, C 10-C 18Amine oxide also can be included in the total composition.Also can use C 10-C 20Conventional soap.If wish many bubbles, can use side chain C 10-C 16Soap.Other conventional anion surfactant that is suitable for is listed in the standard textbook.Nonionogenic tenside
The general content that the present invention is suitable for is that the unrestricted example of the nonionogenic tenside of 1%-55% (weight) comprises alcohol alcoxylates (AE) and alkylphenol, polyhydroxy fatty acid amide (PFAA), alkyl polyglycoside (APG), C 10-C 18Glyceryl ether.
More particularly, the condensation product (AE) of primary and secondary Fatty Alcohol(C12-C14 and C12-C18) and 1-25 moles of ethylene oxide is suitable as nonionogenic tenside of the present invention.The alkyl chain of Fatty Alcohol(C12-C14 and C12-C18) can be straight or branched, uncle or secondary type, and generally contains 8 to 22 carbon atoms.Preferably have and contain 8 to 20 carbon atoms, the more preferably alcohol of the alkyl of 10 to 18 carbon atoms, by every mole of this alcohol, with 1 to 10 mole, preferred 2-7 mole, the condensation product of 2-5 moles of ethylene oxide most preferably.Commercial such ionic surfactant pack of buying is drawn together Tergitol TM15-S-9 (C 11-C 15The condensation product of straight chain alcohol and 9 moles of ethylene oxide), Tergitol TM24-L-6 NMW (C 12-C 14The condensation product of primary alconol and 6 moles of ethylene oxide has narrow molecular weight distribution), sell by Union Carbide Corporation for two kinds; 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), Neodol TM45-5 (C 14-C 15The condensation product of straight chain alcohol and 5 moles of ethylene oxide); Kyro TMEOB (C 13-C 15The condensation product of alcohol and 9 moles of ethylene oxide), by The Procter ﹠amp; Gamble Company sells; With the GenapolLA 030 or the 050 (C that sell by Hoechst 12-C 14The condensation product of alcohol and 3 or 5 moles of ethylene oxide).The preferred HLB scope of these AE nonionogenic tensides most preferably is 8-10 at 8-11.Can also use and the condenses of propylene oxide and butylene oxide ring.
Another kind ofly be applicable to that preferred nonionic surfactants of the present invention is the polyhydroxy fatty acid amide with following formula:
Figure A9719638100171
R wherein 1Be H, or C 1-4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or its mixture, R 2Be C 5-31Alkyl, Z are the polyhydroxy alkyls with the straight-chain alkyl chain that is connected directly to few 3 hydroxyls, or its oxyalkylated derivative.Preferred R 1Be methyl, R 2It is straight chain C 11-15Alkyl or C 15-17Alkyl or alkenyl be cocounut oil alkyl or its mixture for example, and Z is that for example glucose, fructose, maltose, lactose obtain in reductive amination process by reducing sugar.Typical example comprises C 12-C 18And C 12-C 14The N-methyl glucose amide.See US5,194,639 and US5298636.Can also use N-alkoxyl group polyhydroxy fatty acid amide; See US5489393.
What also be suitable as nonionogenic tenside of the present invention is alkyl polysaccharide, as the United States Patent (USP) 4 that is presented to Llenado on January 21st, 1986,565, those disclosed in 647, it has 6 to 30 carbon atoms, the hydrophobic grouping of preferred 10 to 16 carbon atoms and polysaccharide (for example polysaccharide glycosides) hydrophilic radical, and this hydrophilic radical contains 1.3 to 10, preferred 1.3 to 3,1.3 to 2.7 sugar units most preferably.Can use any reducing sugar that contains 5 or 6 carbon atoms, for example glucose, semi-lactosi, available galactosyl partly replaces glucosyl part (hydrophobic group randomly is connected on the positions such as 2-, 3-, 4-, thereby obtains glucose or the semi-lactosi different with glucoside or galactoside).Key can be for example between a position of 2-, 3-, 4-and/or 6-position and another sugar unit of previous sugar unit between sugar.
Preferred alkyl polyglycoside has following formula:
R 2O (C nH 2nO) t(glycosyl) xR wherein 2Be selected from alkyl, alkyl phenyl, hydroxyalkyl, hydroxyalkyl phenyl and its mixture, wherein alkyl contains 10 to 18 carbon atoms, preferred 12 to 14 carbon atoms; N is 2 or 3, preferred 2; T is 0 to 10, preferred 0; X is 1.3 to 10, and is preferred 1.3 to 3, most preferably 1.3 to 2.7.Glycosyl is preferably by the glucose deutero-.For preparing these compounds, at first make alcohol or alkyl polyethoxye alcohol, form glucoside (being connected) with glucose or source of glucose reaction then at 1.Other glycosyl unit can be connected with 2-, 3-, 4-and/or the 6-position of previous glycosyl unit at its 1 then, preferably mainly 2 connections.
The condensation product of the polyethylene oxide of alkylphenol, poly(propylene oxide) and polybutylene oxide also is suitable as the nonionogenic tenside in the surfactant system of the present invention, wherein polyethylene oxide condensation compound preferably.These compounds comprise having and contain 6 to 14 carbon atoms, preferred 8 to 14 carbon atoms and be the alkylphenol of alkyl of straight or branched configuration and the condensation product of oxyalkylene.In preferred embodiments, the amount of the oxyethane that exists in every mole of alkylphenol equals 2 to 25 moles, more preferably 3 to 15 moles.Commercial such ionic surfactant pack of buying is drawn together Igepal TMCO-630 is sold by GAF Corporation; And Triton TMX-45, X-114, X-100 and X-102, they all are by Rohm ﹠amp; Haas company sells.These tensio-active agents are commonly referred to alkyl phenolic alkoxy thing (for example alkylphenol ethoxylate).
Oxyethane also is suitable as additional nonionogenic tenside of the present invention with the condensation product of the hydrophobic group that forms by propylene oxide and propylene glycol condensation.The hydrophobic part of these compounds preferably has molecular weight 1500 to 1800, and performance water outlet insoluble.Addition polyethylene oxide part can increase the water-soluble of overall molecule on this hydrophobic part, and the fluid characteristics of product to be maintained to polyoxyethylated content be 50% of condensation product gross weight, this is equivalent to and as many as 40 moles of ethylene oxide condensations.The example of this type compound comprises some commercial Pluronic that buy TMTensio-active agent, it is sold by BASF.
Be suitable as the oxyethane in addition of the nonionogenic tenside in the nonionic surfactant system of the present invention and the condensation product of the product that obtains by propylene oxide and reacting ethylenediamine.The hydrophobic part of these products is made of the reaction product of quadrol and excessive propylene oxide, and generally has 2500 to 3000 molecular weight.This hydrophobic part and ethylene oxide condensation so far, promptly condensation product contains 40% to 80% weight polyoxyethylene, and has 5000 to 11000 molecular weight.The example of this type nonionogenic tenside comprises some commercial Tetronic that buy TMCompound is sold by BASF.Other cats product
The dispersible compound of water that the cats product that is fit to preferably has surfactant properties wherein comprises at least one ester bond (promptly-COO-) with the group of at least one positively charged.
Other cats product that is fit to comprises quaternary surfactant, is selected from single C 6-C 16, preferred C 6-C 10N-alkyl or alkenyl ammonium surfactant, wherein remaining N position is replaced by methyl, hydroxyethyl or hydroxypropyl.The cationic ester tensio-active agent that other is fit to comprises the cholinesterase tensio-active agent, for example is disclosed among the US4228042,4239660 and 4260529.Optional detergent component
Below explanation can be used for various other the optional components in the present composition, but does not mean that and limit them.Other SYNTHETIC OPTICAL WHITNER
Detergent composition of the present invention can randomly comprise other SYNTHETIC OPTICAL WHITNER.When existing, the content of this other SYNTHETIC OPTICAL WHITNER is generally detergent composition, especially for the 1%-30% of the detergent composition of laundering of textile fabrics, more generally is 5%-20%.
Being used for SYNTHETIC OPTICAL WHITNER of the present invention can be to be applicable to cleaning fabric, cleans crust, or other is known now or with any SYNTHETIC OPTICAL WHITNER in the detergent composition of known cleaning use.This comprises oxygen bleaching agent and other SYNTHETIC OPTICAL WHITNER.Can use perborate bleach herein, for example Sodium peroxoborate (for example its monohydrate or tetrahydrate).
Basic metal or alkaline-earth metal percarbonate, particularly SPC-D are the preferred percarbonate that is used for the present composition.SPC-D is that chemical formula is corresponding to 2Na 2CO 3.3H 2O 2Addition compound, obtain in commercial form that can crystalline solid, supplier comprises Solvay, FMC, Tokai Denka etc.
Preferred percarbonate bleach comprises having the dried particles of mean particle size in the 0.5mm-1mm scope, in the particle less than 10% weight that is no more than of 0.2mm, in the particle greater than 10% weight that is no more than of 1.250mm.
Percarbonate most preferably is incorporated in this composition with coated form, and coated form provides the stability in product.
Be provided at the mixing salt that the coating material that is fit to stable in the product comprises water-soluble alkali vitriol and carbonate.This coating agent and coating method are authorized existing explanation among the GB-1466799 of Interox on March 9th, 1977.The part by weight of mixing salt coating material and percarbonate is 1: 200-1: 4, more preferably 1: 99-1: 9, most preferably 1: 49-1: 19 scopes.Preferred this mixing salt is to have general formula Na 2SO 4.n.Na 2CO 3Sodium sulfate and yellow soda ash, wherein n is 0.1-3, preferred n is 0.3-1.0, most preferably n is 0.2-0.5.
It also is favourable using other coating material comprise silicate (independent or contain borate or boric acid or other inorganics), wax, oil, fatty acid soaps among the present invention.
Another kind of SYNTHETIC OPTICAL WHITNER that can unrestricted use comprises percarboxylic acids SYNTHETIC OPTICAL WHITNER and its salt.The suitable example of this class SYNTHETIC OPTICAL WHITNER comprises monoperphthalic acid magnesium hexahydrate, metachloroperbenzoic acid magnesium, 4-nonyl amino-4-oxo Perbutyric Acid magnesium and diperoxy dodecanedioic acid magnesium.These SYNTHETIC OPTICAL WHITNER are disclosed in the U.S. Pat 4483781 of the Hartman that authorized on November 20th, 1984, the people's such as Burns of application on June 3rd, 1985 U.S. Patent application 740446, February in 1985 people such as disclosed Banks on the 20th european patent application 0133354 and the people's such as Chung that authorize November 1 nineteen eighty-three U.S. Pat 4412934 in.Most preferred SYNTHETIC OPTICAL WHITNER also comprises 6-nonyl amino-6-oxo-mistake oxy hexanoic acid of describing as in the U.S. Pat 4634551 that licenses to people such as Burns on January 6th, 1987.
The present invention also can use peroxygen bleach.Suitable peroxy bleaching compound comprises the trisodium phosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide.Also can use perborate bleach, persulphate SYNTHETIC OPTICAL WHITNER (for example, OXONE is by the DuPont commercial production).
Can also use the mixture of SYNTHETIC OPTICAL WHITNER.Bleach-activating agent
Bleach-activating agent is the preferred ingredient that has the composition of peroxygen bleach.If present, the amount of bleach-activating agent be generally comprise SYNTHETIC OPTICAL WHITNER add bleach-activating agent bleaching composition 0.1%60%, more generally be 0.5%-40%.
The combination of peroxygen bleach and bleach-activating agent causes producing on the spot the peroxy acid corresponding to bleach activator in the aqueous solution (promptly at washing process).The various non-limiting examples of activator are disclosed in and license in people's such as Mao the U.S. Pat 4915854 and U.S. Pat 4412934 April 10 nineteen ninety.Nonanoly acyloxy benzene sulfonate (NOBS) and tetra acetyl ethylene diamine (TAED) activator are typical activators, also can use their mixture.Be fit to other typical SYNTHETIC OPTICAL WHITNER of the present invention and activator in addition referring to U.S. Pat 4634551.
Most preferred amido deutero-bleach-activating agent has formula:
R 1N (R 5) C (O) R 2C (O) L or R 1C (O) N (R 5) R 2C (O) L
R wherein 1Be the alkyl that contains 6 to 12 carbon atoms, R 2Be the alkylidene group that contains 1 to 6 carbon atom, R 5Be H or alkyl, aryl or the alkylaryl that contains 1 to 10 carbon atom, L is any suitable leavings group.Leavings group is because any group under the hydrolysis negatively charged ion replaces at nucleophilic attack on the bleach activator and from bleach-activating agent excessively.Preferred leavings group is the phenylbenzimidazole sulfonic acid root.
The preferred embodiment of following formula bleach-activating agent comprises (the amino caproyl of 6-decoyl) the oxygen base benzene sulfonate as describing in U.S. Pat 4634551 (document is quoted as a reference by this paper); (the amino caproyl of 6-nonanoyl) oxygen base benzene sulfonate; (the amino caproyl of 6-caprinoyl) oxygen base benzene sulfonate and their mixture.
Another kind of bleach activator is included in (this patent is quoted as a reference by this paper) disclosed benzo oxazinyl activator in the people's such as Hodge that authorize October 30 nineteen ninety the U.S. Pat 4966723.The most preferred activator of benzo oxazinyl is:
Another kind of preferred bleach-activating agent comprises the acyl lactam activator, especially the acyl caprolactam of following formula and acyl group Valerolactim:
Figure A9719638100212
Figure A9719638100213
R wherein 6Be H or alkyl with 1 to 12 carbon atom, aryl, alkoxy aryl, or alkylaryl.Most preferred lactan activator comprises benzoyl caprolactam, capryloyl hexanolactam, 3; 5,5-trimethyl acetyl base hexanolactam, nonanoyl hexanolactam; the decanoyl hexanolactam, undecylene acyl caprolactam, benzoyl Valerolactim; the capryloyl Valerolactim, decanoyl Valerolactim, undecylene acyl group Valerolactim; the nonanoyl Valerolactim; 3,5,5-trimethyl acetyl base Valerolactim and their mixture.Also referring to the U.S. Pat 4545784 of the Sanderson that authorized on October 8th, 1985, this patent is quoted as a reference by this paper, wherein discloses the acyl caprolactam that is adsorbed onto in the Sodium peroxoborate, comprises benzoyl caprolactam.Bleaching catalyst
Bleaching catalyst is except comprising optical white, also comprises the preferred ingredient of the present composition of the SYNTHETIC OPTICAL WHITNER that discharges oxygen.Bleaching catalyst is well known in the art, comprises, for example, and in U.S. Pat 5246621, US5244594, US5194416, US5114606 and European patent EP 549271A1, EP549272A1, disclosed manganese-based catalyst among EP544440A2 and the EP544490A1; The preferred embodiment of such 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-triazacyclononanes) 2(ClO 4) 3, Mn IV(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) (OCH 3) 3(PF 6) and their mixture.Other metal matrix bleaching catalysts are included in those disclosed among U.S. Pat 4430243 and the US5114611.In following United States Patent (USP), also reported and used the manganese that has various complex ligands to improve bleaching power: US4728455, US5284944, US5246612, US5256779, US5280117, US5274147, US5153161, US5227084.
(but not being restriction) in actual applications, can regulate the present composition and method so that in wash water solution, provide at least about per active bleaching catalyst of 1/10000000th, preferably in the laundry aqueous solution, provide 0.1ppm to 700ppm, more preferably such catalyzer of 1ppm to 500ppm.
It is known being used for cobalt bleaching catalyst of the present invention, at for example M.L.Tobe, " alkaline hydrolysis of transition metal complex ", Adv.Inorg.Bioinorg.Mech., (1983), and 2, in the 1-94 page or leaf explanation is arranged.Being suitable for most preferred cobalt catalyst of the present invention is to have formula [Co (NH 3) 5OAc] T YAcetate moiety five ammino cobalt salts, wherein OAc represents the acetate moiety part, " Ty " is negatively charged ion, particularly chlorination acetate moiety five cobaltammines [Co (NH 3) 5OAc] Cl 2And [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[Co (NH 3) 5OAc] (NO 3) 2(this paper " PAC ").
These cobalt catalyst are easily with known method preparation, for example tell about in the Tobe article neutralizes the reference wherein quoted and following document: the United States Patent (USP) 4,810,410 of authorizing Diakun etc. on March 7th, 1989; Chemical education (1989), 66 (12), 1043-1045; Synthetic and the feature of mineral compound, W.L.Jolly (Prentice-Hall; 1970), 461-463 page or leaf; Inorganic chemistry, 18,1497-1502 (1979); Inorganic chemistry, 21,2881-2885 (1982); Inorganic chemistry, 18,2023-2025 (1979); Inorganic synthetic, 173-176 (1960); With the physical chemistry magazine, 56,22-25 (1952).
(but not being restriction) in actual applications, can regulate automatic dishwashing composition of the present invention and purging method so that active bleaching catalyst at least about 0.01ppm is provided in the washing water medium, 0.01ppm to 25ppm preferably is provided in washing soln, more preferably 0.05ppm to 10ppm, the most preferably bleaching catalyst of 0.1ppm to 5ppm.In order in the wash water solution of automatic dishwashing process, to reach this amount, by cleaning combination weight, typical automatic dishwashing composition of the present invention will comprise 0.0005%-0.2%, more preferably the bleaching catalyst of 0.004%-0.08%, particularly manganese or cobalt catalyst.Washing assistant
Detergent builders can be randomly but is preferably incorporated in the present composition, for example helps to be controlled at the mineral substance in the washing water, particularly Ca and/or Mg hardness, or helps to remove particulate fouling from the surface.Washing assistant can work by multiple mechanism, comprises by ion-exchange with by providing than the article surface that is washed being more suitable in the sedimentary surface of hardness ions, forms solubility or insoluble inner complex with hardness ions.Washing assistant content can be with the end-use of composition and physical form and is changed in very wide scope.The washing composition that adds washing assistant generally comprises at least 1% washing assistant.Flowing product generally comprises 5%-50%, is more typically the 5%-35% washing assistant.Particle product by detergent composition weight, generally comprises 10%-80%, is more typically the 15%-50% washing assistant.The content of not getting rid of washing assistant is lower or higher.For example, some detergent additives or high surfactant goods can not contain washing assistant.
The washing assistant that the present invention is fit to can be selected from phosphoric acid salt and poly-phosphate, particularly sodium salt; Silicate comprises water miscible and hydration solid type, and comprise have chain, those and amorphous solid or non-structured kind of liquid of stratiform or three-dimensional structure; The carbonate mine material of carbonate, supercarbonate, sesquicarbonate and non-yellow soda ash or concentrated crystal soda; Silico-aluminate; Organic single, two, three and the water miscible nonsurfactant carboxylate salt of tetracarboxylic acid hydrochlorate, particularly acid, sodium salt, sylvite or alkanol ammonium salts form, and oligomeric or water-soluble low molecular weight polymerization of carboxylic acid salt comprises aliphatic series and aromatics type; And phytinic acid.Can replenish and for example be used for pH-buffering purpose borate, or vitriol, particularly sodium sulfate and be important any other filler or carrier to producing the stable detergent composition that contains tensio-active agent and/or washing assistant.
Can use the washing assistant mixture, be sometimes referred to as " builder system ", it generally comprises two or more conventional washing assistants, can randomly replenish to add sequestrant, pH regulator agent or filler, but when describing the content of material herein, these materials of back are calculated respectively usually.About tensio-active agent and washing assistant relative consumption in washing composition of the present invention, preferred builder system is 60 by the weight ratio of tensio-active agent and washing assistant generally: 1-1: 80 preparations.The aforementioned proportion of some preferred detergent for washing clothes is 0.90: 1-4.0: 1.0 scopes, and more preferably 0.95: 1.0-3.0: 1.0 scopes.
When rules allowed, it was normally preferred to contain the P detergent builders, included, but not limited to basic metal, ammonium and the alkanol ammonium salt of polyphosphoric acid, and the example comprises tri-polyphosphate, pyrophosphate salt, glassy polymeric metaphosphate and phosphonate.
The silicate-like builder that is fit to comprises alkalimetal silicate, particularly SiO 2: Na 2O is than 1.6: 1-3.2: 1 those liquid and solid silicate, comprise, and be 2 metaborate monohydrate silicate especially for the ratio of automatic dishwashing, it is sold by Pq Corp., and commodity are called BRIESIL R, BRIESIL H for example 2O; And layered silicate, for example those that in the US4664839 that authorizes 12 days Mays in 1987 of H.P.Rieck, describe.NaSKS-6 is abbreviated as " SKS-6 " sometimes, is the crystalline layered no aluminium δ-Na that is sold by Hoechst 2SiO 5The silicate of form especially preferably is used in the granular laundry composition.See the preparation method in DE-A-3417649 and DE-A-3742043.Other layered silicate, for example those have general formula NaMSi xO 2x+1YH 2The layered silicate of O, wherein M is sodium or hydrogen, and x is 1.9 to 4 numerical value, is preferably 2, and y is 0 to 20 numerical value, is preferably 0, also can be used for the present invention.The layered silicate of buying from Hoechst also comprises NaSKS-5, NaSKS-7, and NaSKS-11, and they are layered silicates of α, β and γ form.Other silicate also is useful, Magnesium Silicate q-agent for example, and it can be used as the stiffener of particle product, as the stablizer of SYNTHETIC OPTICAL WHITNER and the component of control foam system.
Be suitable for also have synthetic crystallization ion-exchange material or its hydrate of the present invention, it has chain structure and the forming of the anhydrous form represented by following general formula: xM 2O.ySiO 2.zM ' O, wherein M is Na and/or K, M is Ca and/or Mg; Y/x is 0.5-2.0, and z/x is 0.005-1.0, described in the US5427711 that authorizes in the June 27 nineteen ninety-five of Sakaguchi etc.
The carbonate builders that is fit to comprises as disclosed basic metal and alkaline earth metal carbonate on November 15th, 1973 disclosed German patent application 2321001, but also can use for example urao of sodium bicarbonate, yellow soda ash, concentrated crystal soda and other carbonate mine material, or any suitable composite salt of yellow soda ash and lime carbonate, for example anhydrous form consists of 2Na 2CO 3.CaCO 3Those, even comprise calcite, graupel aragonite and vaterite, particularly have those of high surface area forms, for example as crystal seed or be used for the agent of synthetic detergent piece with respect to the calcite of densification.
The silico-aluminate washing assistant is specially adapted in the granulated detergent, but also can mix liquid, in cream or the gel product.What be applicable to the object of the invention is to have those of following empirical formula: [M (AlO 2) z(SiO 2) v] .xH 2O, wherein z and v are at least 6 integers, and the mol ratio of z and v is in 1.0 to 0.5 scopes, and x is 15 to 264 integer.Silico-aluminate can be crystallization or unbodied, naturally occurring or synthetic obtaining.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.Preferred synthetic crystallization aluminosilicate ion exchange material can have been bought by Zeolite A, Zeolite P (B), Zeolite X and so-called Zeolite MAP (being different from Zeolite P to a certain extent).Natural type comprises clinoptilolite, also can use.Zeolite A has formula:
Na 12[(AlO 2) 12(SiO 2) 12] xH 2O, wherein x is 20 to 30, especially 27.Dehydration zeolite (x=0-10) also can use.Silico-aluminate preferably has the granularity of diameter 0.1-10 micron.
The organic detergent washing assistant that is fit to comprises multi-carboxylate's compound, comprises the dicarboxylate and the tricarboxylate of water miscible nonsurfactant.More generally, the washing assistant multi-carboxylate has a plurality of carboxylate group, preferably at least 3 carboxylate group.The carboxylate salt washing assistant can be formulated into acid, part neutral, neutral or overbasic form.When being the form of salt, basic metal for example sodium, potassium and lithium or alkanol ammonium salt is preferred.The multi-carboxy acid salt washing agent comprises the ether multi-carboxylate, and oxygen disuccinate is for example seen the U.S. Pat 3635830 of authorizing in 8 days January in 1972 of people such as the U.S. Pat 3128287 of authorizing in 7 days April in 1964 of Berg and Lamberti; " TMS/TDS " in the people's such as Bush that authorized on May 5th, 1987 the U.S. Pat 4663071 and other ether carboxylate comprise ring-type and alicyclic compound, as in U.S. Pat 3923679; US3835163; US4158635; Described in US4120874 and the US4102903 those.
Other washing assistants that are fit to are ether hydroxypolycarboxylic acid salt, the multipolymer of maleic anhydride and ethene or vinyl methyl ether; 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid; Carboxymethyl oxygen base succsinic acid; Polyacetic acid, as various 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 oxygen base succsinic acid and their water-soluble salt.
Citrate trianion, for example citric acid and its water-soluble salt are for example to be used for the important carboxylate salt washing assistant of heavy duty liquid laundry detergent, reason is that they can be obtained and their biodegradability by renewable resource.Citrate trianion also can be used for particulate composition, especially is used in combination with zeolite and/or layered silicate.The oxygen disuccinate also is useful especially in these compositions and mixture.
Under situation about allowing, particularly, can use alkali metal phosphate, for example tripoly phosphate sodium STPP, trisodium phosphate and sodium orthophosphate at the stick goods that are used for hand-washing operation.Also can use the phosphonate washing assistant, ethane-1-hydroxyl-1 for example, 1-diphosphonate and other known phosphonate, for example U.S. Pat 3159581; 3213030; 3422021; Those disclosed in 3400148 and 3422137, they have required antiscale character.
Some detersive surfactant or their short chain homologues also have the washing assistant effect.For formula calculation is clear and definite, when they had the tensio-active agent ability, these materials were summed up as detersive surfactant.Illustrative examples with preferred type of washing assistant function is: 3, and 3-dicarboxyl-4-oxa--1,6-adipate and corresponding compounds are disclosed in Bush, among the US4566984 on January 28th, 1986.The succsinic acid washing assistant comprises C 5-C 20Alkyl and alkenyl succinic and its salt.The succinate washing composition also comprises lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinic succinate (preferably), 2-15 carbene base succinates.In the european patent application 86200690.5/0,200,263 of promulgation on November 5th, 1986, the lauryl succinate has been described.Lipid acid, for example C 12-C 18Monocarboxylic acid also can mix in the present composition so that additional washing assistant activity to be provided as tensio-active agent/builder material or with above-mentioned washing assistant, particularly Citrate trianion and/or the combination of succinate washing assistant separately.Other multi-carboxylate who is fit to be disclosed in the people's such as Crutchfield that authorized on March 13rd, 1979 U.S. Pat 4144226 and the U.S. Pat 3308067 of the Diehl that authorized on March 7th, 1967 in.Also referring to U.S. Pat 3723322.
The inorganic builders material of spendable other type has formula: (M x) iCa y(CO 3) 2, wherein x and i are the integers of 1-15, and y is the integer of 1-10, and z is the integer of 2-25, M iBe positively charged ion, wherein at least a is water miscible, and satisfies the equation ∑ i=1-15 (x iTake advantage of M iValence state)+2y=2z so that this formula has neutrality or " balance " electric charge.These washing assistants are called as " mineral substance washing assistant " here.The water of hydration or the negatively charged ion of noncarbonate can add, and condition is that total charge is equilibrated or neutrality.The influence of this anionic charge or valence state should be added to the right of above equation.Preferably there is water miscible positively charged ion, is selected from hydrogen, water-soluble metal, boron, aluminium, silicon and its mixture, more preferably sodium, potassium, hydrogen, lithium, ammonium and its mixture, sodium and potassium are most preferred.The non-limiting example of non-carbonate anion comprises and is selected from following those: chlorine, sulfate radical, fluorine, oxygen, hydroxide radical, silicon-dioxide, chromate, nitrate radical, borate and its mixture.The preferred washing assistant of the simple form of this class is selected 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) 3With its mixture.Particularly preferred material as washing assistant of the present invention is the Na of any crystal modification 2Ca (CO 3) 2The suitable washing assistant of above define styles further specifies as follows, comprises the natural or synthesized form of any or its combination of following mineral substance: Ah's cancrinite, andersonite, ashcroftine Y, beyerite, the carbon kurchatovite, yellow carbon strontium sodium stone, aqueous carbonate potassium calcium stone, cancrinite, carbon cerium sodium stone, the carbon canasite, davyne, carbon yttrium strontium city Y, carbon potassium calcium stone, Ferrisurite, the sulphur davyne, carbon boron manganese calcium stone, gaylussite, Girvasite, ilmenite, sulphur carbon calcium manganese stone, Kamphaugite Y, kettnerite, Khanneshite, Lepersonnite Gd, liottite, carbon barium yttrium ore deposit Y, microsommite, the carbon carlfriesite, Buddhist nun's shortite, Ni Leier stone, 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 Ni Leier stone, carbon potassium calcium stone and shortite.
Enzyme
Detergent composition of the present invention can comprise enzyme to reach various washing purposes, comprise the spot of removing protein-based, carbohydrate-based or triglyceride level base from the dirt-carrying body, and for fear of the dye migration that in the fabric washing process, comes off with for the recovery of fabric.Suitable enzyme comprises proteolytic enzyme, amylase, lipase, cellulase, peroxidase, and their mixture, and they can derive from any suitable source, for example plant, animal, bacterium, mould and yeast source.Preferred select to be subjected to some factor affecting, as pH-activity and/or optimal stability value, thermostability with to the stability of activated detergent and washing assistant etc.In this respect, bacterium or fungous enzyme are preferred, as bacterial amylase and proteolytic enzyme and mould cellulase.
" detergency enzymes " used herein refers to have washing in laundry, hard surface cleaning or personal care detergent composition, decontamination is steeped or any enzyme of other beneficial effect.Preferred detergency enzymes is lytic enzyme such as proteolytic enzyme, amylase and lipase.The enzyme of purposes of preferably being used to do washing includes, but are not limited to proteolytic enzyme, cellulase, lipase and peroxidase.The most preferably amylase and/or the proteolytic enzyme that are used for automatic dishwashing.
Usually the enzyme that mixes q.s in washing composition or laundry additive composition is to provide " effectively flushing dose ".Term " effectively flushing dose " refers to and can cleanings is provided, remove spot, decontamination dirt dirt-carrying body such as fabric, tableware, brightens deodorizing or increase the refreshing any amount that acts on.In the practical situation of present commercial formulation, the quantity of organized enzyme generally is to be up to about 5 milligrams of weight in every gram detergent composition, and more typical is 0.01 milligram to 3 milligrams.Except as otherwise noted, composition herein generally comprises 0.001% to 5%, preferred 0.01%-1% (weight) commercial enzyme goods.Proteolytic enzyme is usually to be enough to providing 0.005 active quantities to 0.1Anson unit (AU) to be present in the commodity preparation in every gram composition.For some washing composition, for example the washing composition that uses in the automatic dishwashing may need to increase the organized enzyme content of this article of commerce, does not have the total amount of catalytic active substance minimum so that make, and improves thus and removes spot/conjunctiva or other net result.In highly enriched detergent body, also need higher live vol.
Suitable examples of proteases is a subtilisin, and it is that special bacterial strain by subtilis and bacillus licheniformis obtains.A kind of suitable proteolytic enzyme is to be obtained by Bacillus strain, and it has maximum activity in the pH8-12 scope, by the Novo IndustriesA/S company exploitation of Denmark, with ESPERASE Title is sold, and hereinafter is called " Novo ".The preparation of this kind of enzyme and similar enzyme is described among the british patent specification GB1243784 of Novo company.Other proteolytic enzyme that are fit to comprise the ALCALASE from Novo And SAVINASE With from the International Bio-Synthetics of Holland, the MAXATASE of Inc. And be described in the protease A among the european patent application 130756A on January 9th, 1985 and be described in the european patent application 303761A on April 28th, 1987 and the proteolytic enzyme B in the european patent application 130756 on January 9th, 1985.Simultaneously referring to the high pH proteolytic enzyme among the WO 9318140A that is described in Novo from genus bacillus NCIMB40338.In the WO of Novo 9203529A, described and contained proteolytic enzyme, the enzyme-containing detergent of one or more other enzymes and reversible protease inhibitors.Other preferred proteolytic enzyme comprise P﹠amp; Those proteolytic enzyme among the WO9510591A of G company.When needs, as at P﹠amp; Describe among the WO 9507791 of G company, can obtain adsorbing the proteolytic enzyme of reduction and hydrolysis increase.A kind of recombinant trypsin proteinoid enzyme that is applicable to washing composition of the present invention has been described in the WO 9425583 of Novo.
Particularly, the particularly preferred proteolytic enzyme that is called as " proteolytic enzyme D " is to have the carbonylic hydrolase mutation that does not have the aminoacid sequence of discovery at occurring in nature, and it obtains from carbonylic hydrolase is precursor-derived, this deriving is coding according to the bacillus amyloliquefaciens subtilisin, in described carbonylic hydrolase, be equivalent to+76 position, preferably also be equivalent 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+one or more amino acid residue positions place of 274, finish with a plurality of amino-acid residues of the different said positions of aminoacid replacement, as at the U.S. Patent application 08/322676 of exercise question for the people such as A.Baeck of " cleaning composition that contains proteolytic enzyme ", with exercise question for what describe in the people's such as C.Ghosh of " bleaching composition that contains proteolytic enzyme " the U.S. Patent application 08/322677, above-mentioned two pieces of patent applications all are to submit on October 13rd, 1994.
Be suitable for the present invention, especially for but the amylase that is not limited to automatic dishwashing comprises the α-Dian Fenmei of describing for example in the british patent specification GB-1296839 of Novo; International Bio-Synthetics, the RAPIDASE of Inc. TERMAMYL with Novo FUNGAMYL from Novo Particularly useful.It is known improving the stable for example enzyme engineering of oxidative stability.Referring to, for example " journal of biological chemistry ", the 260th volume, o. 11th, in June, 1985,6518-6521 page or leaf.Some embodiment preferred of the present composition can be utilized at the washing composition amylase of improved stability in the washing composition of automatic dishwashing type for example, especially with the TERMAMYL of listing in 1993 The amylase of the oxidative stability of measuring as benchmark with improvement.These preferred amylase all have the diastatic feature of " stability improves " among the present invention, the benchmark amylase of determining above the contrast is measured, at least show detectable improvement in following one side or several respects: oxidative stability, for example, in the buffered soln of pH9-10 to the stability of hydrogen peroxide/tetra acetyl ethylene diamine; Thermostability, for example, under the common wash temperature as under 60 ℃ the temperature; Or alkaline stability, for example under pH8-11.Stability can be used disclosed any experimental technique mensuration in the prior art.Referring to, disclosed reference in WO 9402597 for example.Stability-enhanced amylase can obtain from Novo or from Genencor International.Class amylase very preferably has a general character among the present invention, promptly use site-directed mutagenesis method from one or more bacillus amylases, especially the genus bacillus α-Dian Fenmei is derived and is obtained, no matter and whether have a kind ofly, two or more amylase strains are direct precursors.The amylase that the oxidative stability of comparing with top definite benchmark amylase improves is preferably used, and in particular for bleach detergent, is more preferably and is used for the oxygen bleaching detergent composition different with the chlorine bleaching washing composition.This preferred amylase comprises the amylase among the WO9402597 on 3 days February in 1994 of the Novo that (a) above quotes, it can further specify by a kind of mutant, use L-Ala or Threonine (preferred Threonine) to replace the methionine residue of 197 positions that are positioned at bacillus licheniformis alpha-amylase (being called TERMAMYL ) in this mutant, or similar parent amylase, as bacillus amyloliquefaciens, subtilis, or the same source position variation of bacstearothermophilus; (b) the stable enhanced amylase of being described by GenencorInternational, this amylase is announced for the article of " oxidation resistant α-Dian Fenmei " with exercise question in the 207th American Chemical Society's whole nation meeting holding 13-17 day in March, 1994 by C.Mitchinson.The SYNTHETIC OPTICAL WHITNER that this article middle finger goes out in the automatic dishwashing detergent makes the α-Dian Fenmei inactivation, but the amylase that oxidative stability improves is obtained from bacillus licheniformis NCIB8061 by Genencor.Methionine(Met) (Met) is confirmed as the residue that most probable is modified.8,15,197,256,304,366 and 438 replace Met one at a time, obtain special mutant, particularly importantly M197L and M197T, and wherein the M197T mutation is the mutation that the most stable quilt is expressed.Stability is at CASCADE And SUNLIGHT Middle mensuration; (c) particularly preferred amylase comprises the amylase mutation of carrying out other modifications in direct parent as describing among the present invention in WO 9510603A, and they can be from transferee Novo as DURAMYL Bought.The amylase that other particularly preferred oxidative stabilities improve is included in those amylase of describing among the WO 9402597 of the WO 9418314 of Genencor International and Novo.The amylase that can use any other oxidative stability to improve, for example, from commercially available diastatic known chimeric, mutant strain parent form hybridization or simple is derived and is obtained by site-directed mutagenesis.Other preferred enzyme modifications can be realized.WO 9509909A referring to Novo.
Other amylase is included in those that describe among the application PCT/DK 96/00056 that do not wind up the case of WO95/25397 and Novo Nordisk.The specific amylase that is used for detergent composition of the present invention comprises α-Dian Fenmei, it is characterized in that carrying out Phadebas (this Phadebas is measured in the alpha-amylase activity check Alpha-amylase activity check is described in the 9-10 page or leaf of WO95/26397) time, under the 8-10 scope, its specific activity compares Termamyl at 25 ℃-55 ℃ and pH Exceed at least 25%.The present invention also comprises the aminoacid sequence at least 80% homologous α-Dian Fenmei shown in arranging with SED ID in this reference.These enzymes, by the weight of total composition, preferably with the pure enzyme of 0.00018%-0.060%, more preferably the pure enzyme amount of 0.00024%-0.048% is mixed in the laundry detergent composition.
Can be used for the cellulase that cellulase among the present invention comprises bacterium and mould type, preferably they have the best pH scope of 5-9.5.The U.S. Pat 4435307 of authorizing in 6 days March in 1984 of people such as Barbesgoard disclose derive from unusual rotten plant mould or humicola lanuginosa strain DSM 1800 or belong to the suitable mould cellulase of mould of generation cellulase 212 of Aeromonas and the hepatopancreas by extra large mollush Dolabella Auricula Solander in the cellulase that extracts.Suitable cellulase also is disclosed in GB-A-2075028; Among GB-A-2095275 and the DE-OS-2247832.CAREZYME And CELLUZYME (Novo) be useful especially.Also referring to the WO 9117243 of Novo.
The spendable suitable lipase of washing composition comprises by the microorganism in the Rhodopseudomonas family, those lipase that produce as Pseudomonas stutzeri ATCC 19.154, as be disclosed among the English Patent GB-1372034 those.Also referring to the lipase of speciallyying permit on February 24th, 1978 among the disclosed Japanese patent application 53-20487.This lipase can be from Amano Pharmacetical Co.Ltd.Nagoya, and Japan has bought, commodity lipase P " Amano " by name or " Amano-P ".Other suitable commercial lipase comprise Amano-CES, and they are that (Jagata Japan) by thickness look bacillus, separates the lipase that fat mutation NRRLB 3673 obtains as thickness look bacillus to Toyo JozoCo.; Thickness look bacillus lipase, from U.S.Biochemical Corp., U.S.A. and the Disoynth Co. of Holland and the lipase that obtains by gladiolus pseudomonas (Pseudomonasgladioli).Plant the LIPOLASE that mould (Humicola lanuginosa) derives and obtain and can have been bought by Novo (equally referring to EP341947) by the fetal hair corruption Enzyme is the preferred herein lipase that uses.Among the WO 9414951A that the stable lipase of peroxidase and amylase mutation are described in Novo.Also referring to WO 9205249 and RD 94359044.
Although lot of documents discloses lipase, only plant mould (Humicola1anuginosa) deutero-and be widely used as the additive of fabric washing product so far at the lipase that aspergillus oryzae produces in as the host by the fetal hair corruption.As mentioned above, they can be by Novo Nordisk by trade(brand)name Lipolase TMBuy.Best for the decontamination stain performance that makes Lipolase, Novo Nordisk has made many varients.As describing in WO92/05249, the D96L varient that mould lipase is planted in natural fetal hair corruption has improved the effectiveness of removing lard, and its effectiveness is 4.4 times (enzyme is to compare in every liter of 0.075-2.5mg protein content scope) of wild-type lipase.Disclosing lipase varient (D96L) by Novo Nordisk in the Research Disclosure No.35944 that announced on March 10th, 1994 can be corresponding to every liter of washing soln 0.001-100mg (5-500, the 000LU/l) quantity of lipase varient adding.Press this paper publicity pattern, the present invention uses the D96L varient of low amount in the detergent composition that contains two-AQA tensio-active agent, the benefit that provides retention of whiteness to improve to fabric is particularly as D96L during with every liter of washing soln 50LU-8500LU amount use.
Be applicable to that at enzyme of the present invention is described among the WO 88809367A of Genencor.
Peroxidase can with oxygen source, for example, percarbonate, perborate, hydrogen peroxide etc. are used in combination, other dirt-carrying body that they are used for " solution bleaching " or avoid existing to the washing soln in dyestuff that washing process comes off from the dirt-carrying body or pigment migration.Known peroxidase comprises horseradish peroxidase, lignoenzyme and halo peroxidase such as chloro and bromoperoxidase.The detergent composition that contains peroxidase be disclosed in Novo on October in 1989 19 disclosed WO 89099813A and the WO 8909813 of Novo in.
Various enzyme material and their methods in the synthetic detergent composition of mixing also are disclosed in WO 9307262A and the WO 9307260A of Genencor International, in the people's such as McCarty that the WO8908694A of Novo and on January 5th, 1971 authorize the U.S. Pat 3553139.Various enzymes are also disclosed in the U.S. Pat 4507219 of the people's such as Place that authorize on July 18th, 1978 U.S. Pat 4101457 and the Hughes that authorized on March 26th, 1985.Enzyme material and their the mixing in this class preparation that is used for liquid detergent preparation disclosed in the people's such as Hora that authorize on April 14th, 1981 the U.S. Pat 4261868.The enzyme that is used for washing composition can make its stabilization with various technology.The enzyme stabilization technology is open and illustrate the people's such as Gedge that authorize on August 17th, 1971 U.S. Pat 3600319, EP199405 and October in 1986 disclosed Venegas on the 29th European patent EP 200586 in.For example in the U.S. Pat 3519570 the enzyme stabilising system is being described also.A kind of useful genus bacillus AC13 that produces proteolytic enzyme, zytase and cellulase has been described in the WO9401532A of Novo.
The enzyme stabilising system
The present invention contains enzyme composition can also randomly contain 0.001% to 10%, preferred 0.005% to 8%, more preferably the enzyme stabilising system of 0.01% to 6% (weight).The enzyme stabilising system can be any stabilising system with the detergency enzymes compatibility.This system can itself be provided by other preparation activess, and perhaps the manufacturer by for example teacher of prescription or washing composition alternation enzyme adds separately.This stabilising system can contain, calcium ion for example, and boric acid, propylene glycol, the short chain carboxy acid, borinic acid and their mixture, and design to be used to solve various stabilization problem according to the type and the physical form of detergent composition.
A kind of stabilising method are water-soluble calcium and/or the magnesium ion thing sources of using in final product composition having, and it provides these ions to enzyme.Calcium ion is more effective than magnesium ion usually, if only use one type positively charged ion, the present invention preferably uses calcium ion.Typical detergent composition, especially liquid washing agent contain in every liter of finished product detergent composition and have an appointment 1 to about 30, preferred about 2 to about 20,8 calcium ions to about 12 mmoles more preferably from about can be according to the kind diversity of the enzyme that is impregnated in, factors vary such as type and content.Preferred water-soluble calcium or the magnesium salts of using comprises for example calcium chloride, calcium hydroxide, calcium formiate, calcium malate, calcium maleate and lime acetate, more generally be can use calcium sulfate and corresponding to the magnesium salts of the calcium salt of exemplifying explanation.The content that further increases calcium and/or magnesium comes in handy certainly, has for example promoted the delipidation of the tensio-active agent of some type.
Another stabilising method are to use borate.U.S. Pat 4537706 referring to Severson.When using, the content of borate stablizer can be up to composition 10% or more, but for being used for liquid washing agent, more generally be boric acid or other borate compounds such as borax or the ortho-borate that is up to about 3% (weight) content.The boric acid such as the phenyl-boron dihydroxide that replace, butyl boron dihydroxide, right-bromophenyl boric acid etc. can be used to replace boric acid, by using the boron derivative of this replacement, might reduce the total boron content in the detergent composition.
Some cleaning combination, for example the stabilising system of automatic dishwashing composition can also comprise 0 to 10%, the chlorine bleach scavenging agent of preferred 0.01% to 6% (weight), with the chlorine bleach material avoiding existing in many water sources to the destruction of enzyme with make enzyme deactivation, especially under alkaline condition.The content of the chlorine in water may be very little, generally is in 0.5ppm to 1.75ppm scope, and the chlorine that exists in the cumulative volume of the water that contacts with enzyme when for example wash up or laundering of textile fabrics may be relative a large amount of; Therefore, in actual use sometimes enzyme can go wrong to the stability of chlorine.Because percarbonate has the ability with chlorine bleach reaction, therefore needn't use other anti-chlorine stablizer usually, although use them can improved result.The chlorine scavenger negatively charged ion thing that is fit to is known and obtains easily that if you are using, they can be the sulphite that contains ammonium cation, hydrosulphite, thiosulfite, thiosulphate, iodide etc.Also can use polyphenoils such as carbaminate, ascorbate salt etc., organic amine such as ethylenediamine tetraacetic acid (EDTA) (EDTA) or its an alkali metal salt, monoethanolamine (MEA) and their mixture.Equally, can mix special enzyme inhibition system so that different enzymes has maximum consistency.If necessary, can use other conventional scavenging agent such as hydrosulfates, nitrate, muriate, hydrogen peroxide cource 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.Usually, since in addition be listed under the function name of more knowing other component (for example, hydrogen peroxide cource) can play the effect of chlorine scavenger, therefore not necessarily leave no choice but add chlorine scavenger in addition, lack compound with this effect that reaches required degree unless the present invention contains in the embodiment of enzyme; However, adding chlorine scavenger also only is in order to obtain optimal results.In addition, if use chlorine scavenger, the prescription teacher also can avoid using and inconsistent basically any enzyme scavenging agent of other active ingredients or stablizer when preparation according to chemist's common sense.Relate to when using ammonium salt, this salt can mix with detergent composition simply, but they tend to planar water and/or emit ammonia in storage process.Therefore, if there is this class material, they preferably are protected in the particle, as what describe in people's such as Baginski U.S. Pat 4652392.
The polymkeric substance degreaser
Can randomly use known polymkeric substance degreaser in the detergent composition of the present invention, hereinafter referred is " SRA ".If you are using, SRA generally accounts for 0.01% to 10.0% of composition weight, is typically 0.1% to 5%, and preferred 0.2% to 3.0%.
Preferred SRA has the hydrophilic segment that makes hydrophobic fiber such as polyester and nylon surface hydrophilic usually, with the hydrophobic part that is deposited on the hydrophobic fiber and keeps being attached thereto in whole washing and rinse cycle, therefore this hydrophobic part plays a part the fixture of hydrophilic segment.This can use SRA to handle spot easier being cleaned in washing process afterwards that the back produces.
SRA can comprise various charged, as negatively charged ion or or even positively charged ion (referring to US4956447) monomeric unit and uncharged monomeric unit, their structure can be straight chain, side chain or or even star.They can comprise the end-blocking part, and this part is effective especially to controlling molecular weight or change physics or surfactivity.Can adjustment structure with charge distribution to be applicable to different fibers or fabric type and various washing composition or detergent additive product.
Preferred SRA comprises oligomeric terephthalate, and it generally by relating to the method preparation of at least a transesterify/oligomerization, carries out under metal catalyst such as titanium alkoxide (IV) usually.This ester can use can by one, two, three, four or more position add other monomers preparations of ester structure, certainly, do not form fine and close full crosslinking structure.
The SRA that is fit to comprises the sulfonated products of the ester oligomer that is straight chain basically, wherein contain multiple unitary oligomer ester skeleton of terephthaloyl and oxyalkylene oxygen basic weight and the allyl group deutero-sulfonation end-blocking part covalently bound with skeleton, for example described in the U.S. Pat 4968451 of J.J.Scheibel that authorizes in November 6 nineteen ninety and E.P.Gosselink, this ester oligomer can prepare through the following steps: (a) ethoxylation allyl alcohol; (b) product that will (a) in two step transesterify/oligomerization process and terephthalic acid dimethyl ester (" DMT ") and 1,2 propylene glycol (" PG ") react; (c) in water with the product of (b) and sodium metabisulfite reaction; Nonionic end capped 1 in the people's such as Gosselink that on December 8th, 1987 authorized the U.S. Pat 4711730,2-propylidene/polyoxyethylene terephthalic acid polyester, for example by gathering (ethylene glycol) methyl ether, DMT, the product of the transesterify of PG and poly-(ethylene glycol) (" PEG ")/low dimerization preparation; Part in the United States Patent (USP) 4721580 of the Gosselink that on January 26th, 1988 authorized and whole end capped oligomer ester of negatively charged ion, as derive from ethylene glycol (" EG "), PG, DMT and 3, the oligopolymer of 6-two oxa-s-8-hydroxyl perfluorooctane sulfonate; Nonionic end-blocking block polyester oligomeric compound in the United States Patent (USP) 4702857 of the Gosselink that on October 27th, 1987 authorized, for example by DMT, (Me)-end capped PEG and EG and/or PG preparation, perhaps by DMT, EG and/or PG, the product of the mixture preparation of end capped PEG of Me-and 5-sulfoisophthalic acid dioctyl phthalate sodium salt; With the Maldonado that authorized on October 31st, 1989; the end capped terephthalate of negatively charged ion in people's such as Gosselink the U.S. Pat 4877896 (especially sulfo group aroyl); the latter is typical useful SRA in laundry and fabric-conditioning product; one example is by a sulfosalicylic acid list sodium salt; the ester composition of PG and DMT preparation; but the PEG that randomly preferably also contains adding, for example, PEG3400.
SRA also comprises: the simple copolymerization block thing of ethylene terephthalate or terephthalic acid propylene glycol ester and polyethylene oxide or poly(propylene oxide) terephthalate, referring to the U.S. Pat 3959230 on May 25th, 1976 and the U.S. Pat 3893929 of the Basadur on July 8th, 1975; Derivatived cellulose such as the hydroxy ethers cellulose polymer compound bought from Dow by METHOCEL; C 1-C 4Alkylcellulose and C 4Hydroxy alkyl cellulose is referring to the people's such as Nicol on December 28th, 1976 U.S. Pat 4000093.The SRA that is fit to that is characterised in that poly-(vinyl ester) hydrophobic part comprises poly-(vinyl ester), for example, and C 1-C 6Vinyl ester, preferred poly-(vinyl-acetic ester) is grafted on the graft copolymer that forms on the polyoxyalkylene skeleton.European patent application EP 0219048 referring to the people such as Kud that announced on April 22nd, 1987.The example of commercially available product comprises SOKALAN SRA such as SOKALAN HP-22, can buy from BASF AG of Germany.Other SRA has the polyester that contains 10-15% (weight) ethylene terephthalate and 90-80% (weight) polyoxyethylene terephthalate repeating unit, and it is that the polyoxyethylene glycol of 300-5000 is derived and obtained by molecular-weight average.Commercial examples comprises from the ZELCON 5126 of E.I.Du Pont Company with from the MILEASE of ICI.
Another preferred SRA has empirical formula (CAP) 2(EG/PG) 5(T) 5(SIP) 1Oligopolymer; wherein contain terephthaloyl (T); sulfo group isophthaloyl base (SIP); oxygen vinyloxy group and oxygen-1; 2-propenyl (EG/PG) unit and preferably use END CAPPED GROUP (CAP); preferably with the isethionic acid base end-blocking of improveing; as in oligopolymer, containing a sulfo group isophthaloyl base unit; 5 terephthaloyl unit; determine the oxygen vinyloxy group and the oxygen-1 of ratio; 2-propenyloxy group unit, this ratio preferably about 0.5: 1 to about 10: 1 and two are from 2-(2-hydroxyl-oxethyl) ethyl sulfonic acid sodium deutero-end-blocking unit.Described SRA preferably also contains the stablizer of the minimizing degree of crystallinity that accounts for oligopolymer 0.5% to 20% (weight), for example anion surfactant such as linear alkyl benzene sulphonate or be selected from dimethylbenzene-, cumene-, a kind of material with tosylate or their mixture, these stablizers or properties-correcting agent are to be added in the synthesis reactor, the Gosselink that all these are all authorized as May 16 nineteen ninety-five, Pan is described in the U.S. Pat 5415807 of Kellett and Hall.The suitable monomer of above-mentioned SRA comprises 2-(2-hydroxyl-oxethyl) ethylsulfonic acid sodium, DMT, 5-sulfoisophthalic acid dimethyl esters sodium, EG and PG.
Another preferred SRA is the oligomer ester that contains following part: (1) one skeleton, at least one is selected from following unit wherein to contain (a), they are dihydroxyl sulphonates, the poly-hydroxy sulphonate, at least the unit of three-functionality-degree, it forms ester bond to obtain branched oligomer skeleton and their mixture; (b) unit of at least one terephthaloyl base section; (c) at least one 1, the non-sulfonation unit of 2-oxyalkylene oxygen base section; (2) one or more end-blocking unit; be selected from nonionic end-blocking unit; negatively charged ion end-blocking unit such as alkoxylate (preferred ethoxylation) isethionate; alkoxylate propanesulfonic acid salt; alkoxylate third stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate; alkoxylate phenolsulfonate, sulfo group aromatic acyl derivative and their mixture.The ester that preferably has following empirical formula:
{ (CAP) x(EG/PG) Y '(DEG) Y "(PEG) Y ' "(T) z(SIP) Z '(SEG) q(B) mCAP wherein, EG/PG, PEG, T and SIP define as mentioned, (DEG) expression two (oxyalkylene) oxygen base unit, (SEG) the expression unit and relevant part unit of being derived and being obtained by the sulfo group ethyl ether of glycerine (B) represented to prop up a chain unit, and it is three-functionality-degree at least, thereby form ester bond to obtain the branched oligomer skeleton, x is about 1 to about 12, and y ' is about 0.5 to about 25, y " be 0 to about 12; y is 0 to about 10; y '+y "+y sum is about 0.5 to about 25, and z is about 1.5 to about 25, and z ' is 0 to about 12; Z+z ' sum is about 1.5 to about 25, and q is about 0.05 to about 12; M is about 0.01 to about 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, described ester has about 500 to about 5000 molecular weight.
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 } product of ethyl sulfonic acid sodium (" SE3 ") and its analogue and mixture and ethoxylation and sulfonation allyl alcohol.Preferred such SRA ester comprises 2-{2 (2-hydroxyl-oxethyl) oxyethyl group } 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-) ethyl sulfonic acid sodium, EG, and PG, at the transesterify and the oligomerization product that use under suitable Ti (IV) catalyzer, this product can be used (CAP) 2(T) 5(EG/PG) 1.4(SEG) 2.5(B) 0.13Expression, wherein CAP is (Na +O 3S[CH 2CH 2O] 3.5)-, B is the unit from glycerine, and the molar ratio of EG/PG is about 1.7: 1, and this ratio is by conventional gas Chromatographic Determination after complete hydrolysis.
Another kind of SRA comprises: (I) uses the vulcabond coupling agent to connect the nonionic terephthalate of polyester construction, referring to people's such as people's such as Violl and U.S. Pat 4201824 and Lagasse U.S. Pat 4240918; (II) has the SRA of carboxylate salt end group, and the conversion terminal hydroxy group becomes the trimellitate preparation among the known SRA by trimellitic acid 1,2-anhydride is added for it.By suitable selecting catalyst, trimellitic acid 1,2-anhydride forms the key that is connected with the end group of polymkeric substance by the ester of its isolated carboxylic acid rather than by opening the acid anhydride key.Nonionic or negatively charged ion SRA can be used as starting raw material, as long as have can esterified hydroxyl end groups for they, referring to people's such as Tung U.S. Pat 4525524; The anionic SRA based on terephthalate that (III) urethanum connects is referring to people's such as Violland U.S. Pat 4201824; (IV) poly-(caprolactam) and relevant and multipolymer monomer such as vinyl pyrrole ketone and/or dimethylaminoethyl acrylate methyl amino-ethyl ester comprise nonionic and cationic polymers, referring to people's such as Ruppert U.S. Pat 4579681; (V) graft copolymer except the SOKALAN type of BASF AG, also has the graft copolymer by the preparation of grafted propylene acid mono on sulfonated polyester.These SRA are considered to have detergency and the antiredeposition activity that is similar to the plain ether of known fiber; EP279134A in 1988 referring to Rhone-Poulenc; (VI) vinyl monomer such as vinylformic acid and the vinyl-acetic ester grafts on albumen such as casein is referring to the EP457205A (1991) of BASF AG; (VII) by the condensation hexanodioic acid, the polyester-polyamide SRA of hexanolactam and polyoxyethylene glycol preparation is in particular for handling tynex, referring to the DE2335044 of Unilever N.V. in 1974.Other useful SRA are described in U.S. Pat 4240918, and US4787989 is among US4525524 and the US4877896.
Remove great soil group dirt/anti redeposition agent
Composition of the present invention can also randomly contain the water-soluble ethoxylated amine with removal great soil group dirt and antiredeposition performance.The granular detergent composition that contains these compounds generally contains the water-soluble ethoxylated amine of 0.01% to 10.0% (weight); Liquid detergent composition generally contains the water-soluble ethoxylated amine of 0.01% to 5% (weight).
Most preferred removal dirt and anti redeposition agent are the ethoxylation tetrens.The example of ethoxylated amine has further description in the U.S. Pat 4597898 of the VanderMeer of mandate on July 1st, 1986.Another kind of preferred removal great soil group dirt-anti redeposition agent is a disclosed cation compound in the European patent application EP 111965 of on June 27th, 1984 disclosed 0h and Gosselink.Other that can use are in the present invention removed disclosed ethoxylated amine polymer in the european patent application 111984 that great soil group dirt/anti redeposition agents are included in disclosed Gosselink on the 27th June in 1984; July in 1984 disclosed Gosselink on the 4th European patent application EP 112592 in disclosed amphoteric ion polymer; With the amine oxide in the U.S. Pat 4548744 of the Connor that authorizes on October 22nd, 1985.As known in the art other remove the great soil group dirt and/or anti redeposition agent also can be used in the composition of the present invention.See the US4891160 of the VanderMeer that authorize January 2 nineteen ninety and the WO95/32272 of 30 announcements in November nineteen ninety-five.Another kind of preferred anti redeposition agent comprises carboxymethyl cellulose (CMC) material.These materials are well known in the art.
Polymeric dispersant
Polymeric dispersant preferably is used for the present composition with the content of 0.1% to 7% (weight), especially when zeolite and/or layered silicate washing assistant exist.The polymeric dispersant that is fit to comprises polymeric multi-carboxylate and polyoxyethylene glycol, but other known polymeric dispersants of this area also can use.Do not limited by theoretical although do not wish, but can be sure of when polymeric dispersant with other washing assistants (comprising low-molecular-weight multi-carboxylate) when using, by the crystal growth restraining effect, free the peptization and the anti-redeposition of particulate fouling, can improve total detergent builders performance.
By making suitable unsaturated monomer, the polymerization of the unsaturated monomer of especially sour form or copolymerization can prepare the polymeric polycarboxylic acid salt material.Can comprise vinylformic acid, toxilic acid (or maleic anhydride), fumaric acid, methylene-succinic acid, equisetic acid, methylfumaric acid, citraconic acid and methylene radical propanedioic acid through the suitable multi-carboxylate polymer's of polymerization preparation unsaturated monomer acid.In multi-carboxylate polymer of the present invention, there are the monomer segment such as the vinyl methyl ether that do not contain carboxylate group, vinylbenzene, ethene etc. also are fit to, and are no more than 40% (weight) as long as this part is formed.
Especially the multi-carboxylate polymer of Shi Heing can obtain from vinylformic acid.Such that can be used for the present invention is the water-soluble salt of polymeric acrylic acid based on the polymerizing acrylic acid thing.The molecular-weight average of this base polymer that exists with sour form is preferably 2000-10000, and more preferably 4000-7000 most preferably is 4000-5000.The water-soluble salt of such acrylate copolymer can comprise, for example, and an alkali metal salt, ammonium salt and substituted ammonium salt.Such polymer soluble is known.Such application of polypropylene hydrochlorate in detergent composition is disclosed in the U.S. Pat 3308067 of the Diehl that on March 7th, 1967 authorized.
Multipolymer based on vinylformic acid/toxilic acid also can be as the preferred ingredient of dispersion/anti-deposition agent.This class material comprises the water-soluble salt of vinylformic acid and maleic acid.The molecular-weight average of this analog copolymer that exists with sour form is preferably 2000-100000, and more preferably 5000-75000 most preferably is 7000-65000.The ratio of acrylate moiety and toxilic acid part was generally more preferably 10: 1 to 2: 1 30: 1 to 1: 1 in this analog copolymer.The water-soluble salt of this class vinylformic acid/maleic acid can comprise, for example, and an alkali metal salt, ammonium salt and substituted ammonium salt.Vinylformic acid/the maleic acid of this class solubility is that the latter has also described this base polymer that comprises the hydroxypropyl acrylate at December 15 nineteen eighty-two disclosed European patent application EP 66915 and the known substance described on September 3rd, 1986 disclosed European patent EP 193360.Another kind of useful dispersion agent comprises toxilic acid/vinylformic acid/vinyl alcohol terpolymer.This material also is disclosed in EP193160, comprises, for example, vinylformic acid/toxilic acid of 45/45/10/vinyl alcohol terpolymer.
The another kind of polymeric material that can be comprised is polyoxyethylene glycol (PEG).PEG removes the performance that also has dispersion agent great soil group dirt-anti redeposition agent except can be used as.Molecular weight ranges as this purposes is generally 500-100000, is preferably 1000-50000, more preferably 1500-10000.
The present invention also can use polyaspartic acid salts and polyglutamic acid dipersant, especially is used in combination with zeolite builders.Dispersion agent such as polyaspartic acid salts preferably have 10000 molecular weight (on average).Whitening agent
Any white dyes well known in the art or other whitening agent generally can mix by the content of 0.01% to 1.2% (weight) in the detergent composition of the present invention.Can be used for commercially available white dyes of the present invention and can be divided into following group, include but not limited to: stilbene, pyrazoline, tonka bean camphor, carboxylic acid, methyne cyanines, dibenzothiophen-5,5-dioxide, pyrroles, 5-and 6-unit heterocyclic derivative, and other miscellaneous agents.The example of these whitening agent is disclosed in " production of white dyes and application (The Production and Application of FluorescentBrightening Agents) ", and M.Zahradnik is by John Wiley ﹠amp; Sons, New york publishes (1982).
The specific examples of the white dyes that uses in the present composition is those that confirm in the U.S. Pat 4790856 of the Wixon that authorized on December 13rd, 1988.These whitening agent comprise the PHORWHITE whitening agent series of Verona.Disclosed other whitening agent comprise in this reference: the Tinopal UNPA that can buy from Ciba-Geigy, Tinopal CBS and Tinopal5BM; Artic White CC and Artic White CWD, 2-(4-styryl phenyl)-2H-naphtho-[1,2-d] triazole; 4,4 '-two (1,2,3-triazoles-2-yl) stilbene; 4,4 '-two (styryl) biphenyl; And aminocoumarin.The specific examples of these whitening agent comprises: 4-methyl-7 diethyl amino coumarin; 1, the 2 pair of (ethene of benzimidazolyl-2 radicals-yl); 1, the 3-diphenylpyrazoline; 2, the two (benzoxazoles of 5--2-yl) thiophene; 2-styryl-naphtho-[1,2-d] oxazole; And 2-(stilbene-4-yl)-2H-naphtho-[1,2-d] triazole.In addition referring to the U.S. Pat 3646015 of the Hamilton that authorized on February 29th, 1972.
Dye transfer inhibitor
The present composition can comprise that also one or more effectively suppress the material that dyestuff shifts to another kind of fabric from a kind of fabric in cleaning process.Usually, this dye transfer inhibitor comprises polyvinylpyrrolidonepolymers polymers, polyamine N-oxide pllymers, the multipolymer of N-vinyl pyrrolidone and N-vinyl imidazole, magnesium phthalocyanine, peroxidase and their mixture.If you are using, the content of these reagent is generally 0.01% to 10% of composition weight, and is preferred 0.01% to 5%, and more preferably 0.05% to 2%.
More particularly, be preferred for polyamine N-oxide pllymers of the present invention and contain the unit with following structural: R-A x-P; Wherein P is a polymerizable unit, and the N-O base can be connected with this unit or the N-O base can constitute this polymerizable unit a part or N-O base can be connected with two unit; A be down a kind of in the array structure :-NC (O)-,-C (O) O-,-S-,-O-,-N=; X is 0 or 1; R is an aliphatic group, the ethoxylation aliphatic group, and aromatic group, heterocyclic radical or alicyclic radical or their any combinations, wherein the nitrogen-atoms in the N-O base can be connected with this group or the N-O group is the part of these groups.R is heterocyclic radical such as pyridine in the preferred polyamine N-oxide compound, pyrroles, imidazoles, tetramethyleneimine, piperidines and their derivative.
The N-O group can be represented with following formula: R wherein 1, R 2, R 3Be aliphatic series, aromatics, heterocycle or alicyclic group or their combination; X, y and z are 0 or 1; Can be connected on any aforementioned group with the nitrogen of N-O group or constitute the part of any aforementioned group.The unitary pK of the amine oxide of polyamine N-oxide＜10, preferred pK＜7, more preferably pK＜6.
The present invention can use any polymer backbone, as long as the amine oxide polymkeric substance that forms is water miscible and has the performance that suppresses dye transfer.The example of suitable polymeric skeleton comprises polyvinyls, polyalkenes hydrocarbon, polyester, polyethers, polymeric amide, polyimide, polyacrylate and their mixture.These polymkeric substance comprise random or segmented copolymer, and wherein a kind of monomer type is amine-N-oxide compound, and another kind of monomer type is the N-oxide compound.The amine n-oxide polymkeric substance generally has 10: 1 to 1: 1000000 the amine and the ratio of amine n-oxide.But the quantity that is present in the amine oxide group in the polyamine oxide polymer can change by suitable copolymerization or by suitable N-degree of oxidation.The polyamine oxide compound can obtain with any polymerization degree almost.Typically, average molecular weight range is 500-1000000; More preferably 1000-500000; 50000-100000 most preferably.Such preferable material can be called " PVNO ".
The most preferred polyamine N-oxide that can be used in the detergent composition of the present invention is poly-(4-vinylpridine-N-oxide compound), and its molecular-weight average is 50000, and the ratio of amine and amine n-oxide is 1: 4.
The multipolymer of N-vinyl pyrrolidone and N-vinyl imidazole polymkeric substance (being called " PVPVI ") also is preferred for the present invention.Preferred PVPVI has 5000-1000000, more preferably 5000-200000, the most preferably molecular-weight average of 10000-20000.(average molecular weight range by as at " chemical analysis " of Barth etc., the 113rd volume, light scattering method of describing in " modernism of polymer characterization " determines that the disclosed content this paper of the document quotes as a reference).The PVPVI multipolymer generally has 1: 1-0.2: 1, more preferably 0.8: 1-0.3: 1, most preferably 0.6: 1-0.4: 1 the N-vinyl imidazole and the molar ratio of N-vinyl pyrrolidone.These multipolymers can be straight chain or side chain.
The present composition can use also that to have molecular-weight average be 5000 to 400000, and is preferred 5000 to 200000, more preferably 5000 to 50000 Polyvinylpyrolidone (PVP) (" PVP ").PVP is known to the skilled in the detergent applications; For example, referring to EP-A-262897 and EP-A-256696, these two pieces of patents are quoted as a reference by this paper.It is 500 to 100000 that the composition that contains PVP also can contain molecular-weight average, preferred 1000 to 10000 polyoxyethylene glycol (" PEG ").Preferably, what discharge in washing soln is 2: 1 to 50: 1 by the PEG of ppm and the ratio of PVP, more preferably 3: 1 to 10: 1.
The hydrophilic white dyes that also can randomly contain some type of 0.005% to 5% (weight) in the detergent composition of the present invention, it also provides the effect that suppresses dye transfer.If you are using, this white dyes that preferably contains 0.01% to 1% (weight) in the present composition.
Can be used for hydrophilic white dyes of the present invention and have the following formula structure:
Figure A9719638100411
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 and amino; M is salt-forming cation such as sodium or potassium.
In following formula, work as R 1Be anilino, R 2Be N-2-two-when hydroxyethyl and M were positively charged ion such as sodium, whitening agent was 4,4 '-two [(4-anilino-6-(N-2-two-hydroxyethyl)-s-triazine-2-yl) amino]-2,2 '-stilbene disulfonic acid and disodium salt.Such special whitening agent can be bought from Ciba-Geigy company according to trade(brand)name Tinopal-UNPA-GX.Tinopal-UNPA-GX is the preferred hydrophilic white dyes that can be used in the detergent composition of the present invention.
In following formula, work as R 1Be anilino, R 2Be N-2-hydroxyethyl-N-2-methylamino-and M when being positively charged ion such as sodium, whitening agent is 4,4 '-two [(4-anilino-6-(N-2-hydroxyethyl-N-methylamino-)-s-triazine-2-yl) amino]-2,2 '-stilbene disulfonic acid disodium salt.Such special whitening agent can be bought from Ciba-Geigy company according to trade(brand)name Tinopal 5BM-GX.
In following formula, work as R 1Be anilino, R 2Be morpholino and M when being positively charged ion such as sodium, whitening agent is 4,4 '-two [(4-anilino-6-morpholino-s-triazine-2-yl) amino]-2,2 '-stilbene disulfonic acid sodium salt.Such special whitening agent can be bought from Ciba-Geigy company according to trade(brand)name Tinopal AMS-GX.
Selected these special white dyess that are used for the present invention provide the performance that especially effectively suppresses dye transfer when being used in combination with selected above-described polymeric dye transfer inhibitor.Selected this polymeric material (for example, PVNO and/or PVPVI) and selected this white dyes is (for example, Tinopal UNPA-GX, Tinopal 5BM-GX, and/or Tinopal AMS-GX) be used in combination in wash water solution than using any in these two kinds of detergent composition components that the dye transfer effect that obviously better suppresses all is provided separately.Do not want to be bound by theory, it is believed that it is because they have high-affinity to the fabric in the washing soln that such whitening agent works by this way, therefore relatively soon attached on these fabrics.This whitening agent can be by being called the parameter-definition of " exhaustion coefficient " attached to the degree on the fabric in washing soln.Exhaust coefficient usually as a) attached to whitening agent material and b on the fabric) ratio in the washing liq between the initial whitening agent concentration.For the present invention, the whitening agent with high relatively exhaustion coefficient is suitable for suppressing dye migration most.
Certainly, be understandable that the compound of the white dyes type that other are conventional can randomly be used for the present composition, so that the conventional fabric effect of " brightening " to be provided, rather than the effect of real inhibition dye transfer.This being applied in the detergent formulations is conventional with known.Sequestrant
Cleaning composition of the present invention can also contain the sequestrant of one or more iron and/or magnesium.This class sequestrant can be selected from aminocarboxylate, amino phosphonates do, and fragrant chelating agent of multifunctional replacement and composition thereof, all sequestrants are as definition hereinafter.Do not accept the restriction of opinion, it is believed that the advantage of these materials is that partly they have by forming the soluble chelating agent removes de-iron and magnesium from washing soln premium properties.
The aminocarboxylate that can be used as optional sequestrant comprises edetate, the N-hydroxyethyl-ethylenediamine triacetate, nitrilotriacetic acid(NTA) salt, ethylenediamine tetrapropionic acid(EDTP) salt, triethylenetetraaminehexaacetic acid salt, diethylentriamine pentacetate and ethanol Diglycocol, their an alkali metal salt, ammonium salt and substituted ammonium salt and their mixture.
When allowing at least to have low total phosphorous in the detergent composition, amino phosphonates do also is suitable as the sequestrant of the present composition, comprising: ethylenediamine tetraacetic (methylene phosphonic acid salt) is as DEQUEST.These amino phosphonates do preferably do not contain alkyl or the alkenyl above six carbon atom.
In the present composition, can also use the aromatic chelating agent of multifunctional replacement.Referring to people's U.S. Pat 3812044 such as Connor of authorizing on May 21st, 1974.The compound of preferred this class acid form be the dihydroxyl disulfobenzene as 1,2-dihydroxyl-3,5-disulfobenzene.
The preferred in the present invention biodegradable cheating agent of using is ethylenediamine disuccinate (" EDDS "), especially as [S, S] isomer of describing in the U.S. Pat 4704233 of Hartman that authorizes on November 3rd, 1987 and Perkins.
The present composition also can contain water miscible methylglycine oxalic acid (MGDA) salt (or sour form) to be used with for example insoluble washing assistant such as zeolite, layered silicate as sequestrant or auxiliary washing assistant.
If the use sequestrant, then its consumption is generally 0.1% to 15% of detergent composition weight of the present invention, and more preferably its consumption is 0.1% to 3.0% of a said composition weight.Suds suppressor
The compound that reduction or inhibition foam form can mix in the present composition.Particularly important in foam inhibition so-called " the high density washing methods " in as US4489455 and 4489574, described and under preceding charging type Europe class washing machine situation.
The present invention can use various materials as suds suppressor, and suds suppressor is known in those skilled in the art.Referring to, for example, Kirk Othmer Encyclopedia of ChemicalTechnology, the 3rd edition, the 7th volume, 430-447 page or leaf (John Wiley ﹠amp; Sons, Inc., 1979).The suds suppressor of one class particularly important comprises monocarboxylic acid lipid acid and its soluble salt.U.S. Pat 2954347 referring to the Wayne St.John that authorizes September 27 nineteen sixty.Generally have as the monocarboxylic acid lipid acid of suds suppressor and salt thereof and to contain 10 to about 24 carbon atoms, the hydrocarbyl chain of preferred 12 to 18 carbon atoms.The salt that is fit to comprises that alkali belongs to salt entirely, sodium salt for example, sylvite, and lithium salts, and ammonium salt and alkanol ammonium salts.
Detergent composition of the present invention can also contain the suds suppressor of nonsurfactant.The example of this class suds suppressor comprises: high-molecular-weight hydrocarbons, paraffin for example, fatty acid ester (as fatty acid triglyceride), the fatty acid ester of MHA, fatty C 18-40Ketone (as stearone) etc.Other suds suppressors comprise the alkylating aminotriazine of N-, for example three-to six-alkyl melamine or two-to four-alkyl diamine chloro triazine, they are cyanuric chloride and 2 or 3 moles of uncle or secondary amine that contain 1-24 carbon atom, propylene oxide, with single stearyl phosphoric acid ester, reaction product as single stearyl alcohol phosphoric acid ester and single stearyl phosphoric acid ester two basic metal (as K, Na, and Li) salt and phosphoric acid ester.Hydrocarbon such as paraffin and halo paraffin can use with liquid form.This liquid hydrocarbon should be liquid state under room temperature and normal atmosphere, and should have-40 ℃ to 50 ℃ pour point, and minimum boiling point is not less than 110 ℃ (under normal atmosphere).It is known using waxy hydrocarbon, and preferably its fusing point is lower than 100 ℃.Such hydrocarbon is the preferred suds suppressor of a class of detergent composition.In for example people's such as Gandolfo of mandate on May 5th, 1981 U.S. Pat 4265779, the hydrocarbon suds suppressor has been described.And this hydrocarbon comprises the aliphatic series that contains 12 to 70 carbon atoms, and is alicyclic, the saturated or unsaturated hydrocarbons of aromatics and heterocyclic.The term that uses in the discussion about such suds suppressor " paraffin " comprises the real paraffin and the mixture of cyclic hydrocarbon.
The suds suppressor of another kind of preferred nonsurfactant comprises the polysiloxane suds suppressor.Comprising using organopolysiloxane oil, polydimethylsiloxane for example, the dispersion of organopolysiloxane oil or resin or milk sap, and the mixture of organopolysiloxane and silica dioxide granule, polysiloxane wherein by chemisorption or consolidation to silicon-dioxide.The polysiloxane suds suppressor is known in the art, for example the people's such as Gandolfo that authorized on May 5th, 1981 U.S. Pat 4265779 and February 7 nineteen ninety disclosed Starch, disclosed in the european patent application 89307851.9 of M.S..
Other polysiloxane suds suppressor is disclosed in the U.S. Pat 3455839, and this patent relates to by mixing a small amount of polydimethylsiloxane fluid to eliminate aqueous solution foamy composition and method in composition.
The mixture of polysiloxane and silanized silica is for example being described among the German patent application DOS2124526 to some extent.Polysiloxane defoamers in the granulated detergent and Foam Control be disclosed in people's such as Bartolotta U.S. Pat 3933672 and the people's such as Baginski that authorized on March 24th, 1987 U.S. Pat 4652392 in.
Being used for the typical suds suppressor based on polysiloxane of the present invention is basically by the following Foam Control of forming with foam inhibition amount:
(ⅰ) at 25 ℃ of polydimethylsiloxane fluids with the about 20cs. of viscosity to about 1500cs.;
(ⅱ) by per 100 parts (weight) (ⅰ), about 5 to about 50 parts polyorganosiloxane resin, and this resin is by (CH 3) 3SiO 1/2Unit and SiO 2The unit is pressed about 0.6: 1 to about 1.2: 1 ratio composition; With
(ⅲ) by per 100 parts of (ⅰ) (weight), about 1 to about 20 parts of solid silicones;
In the preferred polysiloxane suds suppressor that the present invention uses, the solvent that is used for external phase is by some polyoxyethylene glycol or polyethylene glycol-propylene glycol copolymers or their mixture (preferably), or polypropylene glycol is formed.The polysiloxane suds suppressor mainly is branching/crosslinked, preferably is non-straight chain.
In order to further specify this point, typical liquid laundry detergent composition with control foaming effect randomly contains has an appointment 0.001% to about 1% (weight), preferred about 0.01% to about 0.7% (weight), 0.05% described polysiloxane suds suppressor most preferably from about to about 0.5% (weight), this suds suppressor contains the nonaqueous emulsion of (1) main suds suppressor, this suds suppressor is following (a), (b) mixture (c) and (d), wherein (a) is organopolysiloxane, (b) be arborescens polysiloxane or the polysiloxane compound that produces polyorganosiloxane resin, (c) be the broken filler of fine powder and (d) be to impel component of mixture (a) that (b) and (c) reaction is to generate the catalyzer of silane alkoxide; (2) at least a nonionic silicones tensio-active agent; (3) solubleness in water surpasses the polyoxyethylene glycol of 2% (weight) or the multipolymer of polyethylene glycol-propylene glycol under the room temperature; Wherein there is not polypropylene glycol.Similarly amount can be used for particulate composition, gelinite etc.In addition referring to the U.S. Pat 4978471 of the Starch that authorizes December 18 nineteen ninety, U.S. Pat 4983316 with the Starch that authorized on January 8th, 1991, people's such as the people's such as Huber that on February 22nd, 1994 authorized United States Patent (USP) 5288431 and Aizawa U.S. Pat 4639489 and US4749740, the 46th of first hurdle walks to the 35th row on the 4th hurdle.
Polysiloxane of the present invention is given as security the multipolymer that infusion preferably includes polyoxyethylene glycol and polyethylene/polypropylene glycol, and it is about 1000 that their molecular-weight average is lower than, and is preferably about 100-800.The multipolymer of polyoxyethylene glycol of the present invention and the polyethylene/polypropylene glycol at room temperature solubleness in water surpasses about 2% (weight), preferably surpasses about 5% (weight).
It is about 1000 that the preferred solvent of the present invention is that molecular-weight average is lower than, and more preferably about 100-800 most preferably is the polyoxyethylene glycol of 200-400 and the multipolymer of polyethylene/polypropylene glycol, preferred PPG200/PEG300.Polyoxyethylene glycol: the weight ratio of the multipolymer of polyethylene glycol-propylene glycol preferably about 1: 1-1: 10, most preferably be 1: 3-1: 6.
The polysiloxane suds suppressor that the present invention preferably uses does not contain polypropylene glycol, does not especially contain molecular weight and be 4000 polypropylene glycol.They also preferably do not contain the segmented copolymer of oxyethane and propylene oxide, as PLURONIC L101.
Can be used for the mixture that other suds suppressors of the present invention comprise secondary alcohol (as the 2-alkyl chain triacontanol) and these alcohol and polysiloxane oil, as be disclosed in U.S. Pat 4798679, the polysiloxane in US4075118 and the European patent EP 150872.Secondary alcohol comprises having C 1-16The C of chain 6-16Alkyl alcohol.Preferred alcohol is 2-butyl octanol, and this alcohol can obtain from Condea by the trade mark of ISOFOL 12.The secondary alcohol mixture can obtain from Enichem with the trade mark of ISALCHEM 123.It is 1 that the mixing suds suppressor generally contains weight ratio: 5-5: the mixture of 1 pure and mild polysiloxane.
For any detergent composition that is used for automatic washing machine or wash up machine, the foam of formation can not reach the degree of overflowing washing machine or the washing mechanism of wash up machine is had negative impact.When using suds suppressor, preferably it exists with " foam inhibition amount "." foam inhibition amount " is meant that the prescription teacher of composition can select this Foam Control of some amount, and this amount is enough to control foam to obtain being used for the low foam laundry or the wash up washing composition of automatic washing machine or wash up machine.
Composition of the present invention contains 0% to 10% suds suppressor usually.When using monocarboxylic acid lipid acid and its salt as suds suppressor, its consumption is up to 5% of detergent composition weight usually.Preferred 0.5% to 3% the fatty monocarboxylate suds suppressor that uses.Although also can use higher consumption, the consumption of polysiloxane suds suppressor generally is up to 2.0% of detergent composition weight.This upper limit is a practicality, and main consideration is to make cost keep minimum and with the low efficient of measuring effective control foam.Preferred 0.01% to 1% the polysiloxane suds suppressor that uses, more preferably 0.25% to 0.5%.Among the present invention, comprise any silicon-dioxide that can use with organopolysiloxane and any additives material that may use in these weight percent numerical value.The consumption of single stearyl phosphoric acid ester suds suppressor is generally 0.1% to 2% of composition weight.Although can use the hydrocarbon suds suppressor of higher consumption, its consumption is generally 0.01% to 5.0%.The consumption of alcohol suds suppressor is generally the 0.2%-3% of final composition weight.The alkoxylate polycarboxylate
The alkoxylate polycarboxylate for example by the polyacrylate preparation those, is applicable to the present invention, so that extra degrease performance to be provided.This class material is described in WO91/08281 and PCT90/01815, page or leaf such as page 4 and back, and this paper quotes for referencial use.From chemically, these materials comprise that there is the polyacrylate of an oxyethyl group side chain every 7-8 acrylic unit.Side chain has formula :-(CH 2CH 2O) m(CH 2) nCH 3, wherein m is 2-3, n is 6-12.This side chain is connected with polyacrylate " skeleton " by ester bond, to form the polymkeric substance of " pectination " structure type.Its molecular weight can change, but generally in the 2000-50000 scope.This alkoxylate polycarboxylate can account for the 0.05%-10% of present composition weight.
Fabric softener
The fabric softener that adds in the time of can also randomly using various the washing in the present composition, particularly disclosed particulate montmorillonitic clay and other softening agent clays well known in the prior art in the U.S. Pat 4062647 of Storm that authorized on December 13rd, 1977 and Nirschl, thereby make the effect that obtains soft fabric in clean textile, the consumption of softening agent is generally 0.5% to 10% (weight) of the present composition.The clay softening agent can be used with amine and anionic softener, as the people's such as Crisp that authorize March 1 nineteen eighty-three U.S. Pat 4375416 and the people's such as Harris that authorized on September 22nd, 1981 U.S. Pat 4291071 discloses.
Spices
Be applicable to the spices in the present composition and the method and be with the component of fragrance to comprise multiple natural and synthetic chemical composition, include, but are not limited to aldehyde, ketone, ester.Also comprise various natural extracts and spices, they can comprise the complex mixture of some components, for example orange oil, lemon oil, rose extract, lavender, Moschus, Wrinkled Gianthyssop Herb, face cream essential oil, santal oil, pine tar, cedar(wood)oil.Finished product spices can comprise the extremely complicated mixture of these components.Finished product spices generally accounts for the 0.01%-2% (weight) of detergent composition of the present invention, and each can account for the 0.001%-90% (weight) of finished product flavor compositions with the component of fragrance.
The unrestricted example that is applicable to perfume composition of the present invention comprises: 7-ethanoyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl-naphthalene; Irone; γ-irone; Vertofix coeur; Methyl dihydrojasmonate; Methyl 1,6,10-trimethylammonium-2,5,9-cyclododecane triolefin-1-base ketone; 7-ethanoyl-1,1,3,4,4,6-hexamethyl 1,2,3,4-tetralin; 4 ethanoyl-6-the tertiary butyl-1,1-dimethyl 1,2-indane; To hydroxyl-phenyl-butanone; Benzophenone; Methyl β naphthyl ketone; 6-ethanoyl-1,1,2,3,3,5-hexamethyl 1,2-indane; 5 ethanoyl-3-sec.-propyl-1,1,2,6-tetramethyl-1,2-indane; The 1-dodecanal; 4-(4-hydroxy-4-methyl amyl group)-3-tetrahydrobenzene-1-formaldehyde; 7-hydroxyl-3,7-dimethyl octanal; 10-undecene-1-aldehyde; Dissident's thiazolinyl hexahydrobenzaldehyde; The formyl tristane; The condensation product of laurine and methyl o-aminobenzoate; The condensation product of laurine and indoles; The condensation product of phenyl acetaldehyde and indoles; 2-methyl-3-(to tert-butyl-phenyl) propionic aldehyde; Vanirone; Piperonylaldehyde; Hexyl cinnamic aldehyde; Amyl cinnamic aldehyde; 2-methyl-2-(right-isopropyl phenyl)-propionic aldehyde; Tonka bean camphor; γ-decalactone; Thibetolide; 16-hydroxyl-palmitoleic acid lactone; 1,3,4,6,7,8-six hydrogen-4,6,6,7,8,8-hexamethyl cyclopenta-γ-2-chromene; β-Nai Jiami; Ambroxane; Ten dihydro 3a, 6,6,9a-tetramethyl-naphtho-[2,1b] furans; Cypress camphor; 5 (2,2,3-front three basic ring penta 3 thiazolinyls)-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; Right-(tertiary butyl) cyclohexyl acetic acid ester.
Particularly preferred fragrance material is those fragrance materials of providing maximum smell to improve for the final product composition having that contains cellulase.These spices include, but are not limited to: cinnamic aldehyde in the hexyl; 2-methyl-3-(to 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 1,2,3,4 tetralines; Right-the tert-butylcyclohexyl acetic ester; Methyl dihydrojasmonate; β-Nai Jiami; Methyl β naphthyl ketone; 2-methyl-2-(p-isopropyl phenyl) propionic aldehyde; 1,3,4,6,7,8-six hydrogen-4,6,6,7,8,8-hexamethyl cyclopenta γ-2-chromene; Ten dihydros-3a, 6,6,9a-tetramethyl-naphtho-[2,1b] furans; Aubepine; Tonka bean camphor; Cypress camphor; Vanillin food grade,1000.000000ine mesh; The cyclopentadecane acid lactone; The tricyclo decene yl acetate; With the tricyclic decenyl propionic ester.
Other perfume composition comprises volatile oil, resinoid and the resin that obtains from various raw materials, include, but are not limited to: Surinam balsam, olibanum resinoid, st-yrax, ladanum resin, Semen Myristicae, cassia oil, styrax resinoid, Fructus Coriandri oil and Lavandula hybrida.Other flavor chemistry product comprise phenylethyl alcohol, Terpineol 350, phantol, phanteine, Geraniol, vernol, 2-(1, the 1-dimethyl ethyl)-adnoral acetate, jasmal and oxymethoxyallylbenzene.Carrier for example diethyl phthalate can be used in the finished product flavor compositions.
Other components
In the present composition, can be included in many other components useful in the detergent composition, comprise other active ingredients, carrier, hydrotropic agent, processing aid, dyestuff or pigment, the solvent of liquid preparation, the solid packing of stick preparation etc.If wish many bubbles, then can in said composition, mix suds booster such as C 10-16Alkanolamide, its content is generally 1%-10%.C 10-14Monoethanolamine and diglycollic amide are the representative instances of such suds booster.With this class suds booster and high foaming option list surface-active agent, as above-mentioned amine oxide, it also is favourable that trimethyl-glycine, sultaine use together.If necessary, also can add as MgCl 2, MgSO 4, CaCl 2, CaSO 4Remove the grease performance Deng water-soluble magnesium salt and/or calcium salt to obtain more foam and to strengthen, their usage quantity is generally 0.1%-2%.
The various decontamination components of using in the present composition can also be randomly by these components are absorbed on the porous hydrophobic matrix, and then with hydrophobicity apply agent with this matrix coated with further making its stabilization.Preferably before absorbing, this decontamination component is mixed with tensio-active agent with porous matrix.In use, this decontamination component is discharged into the wash water solution from matrix, and finishes the decontamination effect of its expection in this washing soln.
In order to illustrate in greater detail this technology, with porous hydrophobic silicon-dioxide (trade mark SIPERNATD10, DeGussa) with contain 3%5% C 13-15The proteolysis enzyme solution of ethoxylated alcohol (EO 7) nonionogenic tenside mixes.The amount of this enzyme/surfactant soln generally is 2.5 times of silica weight.The gained powder (can use the various polysiloxane oils of viscosity as 500-12500) through dispersed with stirring in polysiloxane oil.Add in the final washing composition matrix with the polysiloxane oil dispersion emulsification of gained or with it.By this method, enzyme as the aforementioned, SYNTHETIC OPTICAL WHITNER, bleach-activating agent; bleaching catalyst, light activating agent, dyestuff; white dyes, fabric regulator and hydrolyzable surface active agent composition can be used for washing composition with " protected form ", comprise being used for liquid laundry detergent compositions.
Can contain water and other solvents in the liquid detergent composition as carrier.What be fit to is lower molecular weight uncle or secondary alcohol, for example methyl alcohol, ethanol, propyl alcohol and Virahol.The preferred monohydroxy-alcohol that uses comes solubilizing surfactant, but also can use polyvalent alcohol as the alcohol that contains 2 to 6 carbon atoms and 2 to 6 hydroxyls (for example, 1, ammediol, ethylene glycol, glycerine and 1,2-propylene glycol).Composition generally contains 5%-90%, typically such carrier of 10%-50%.
Detergent composition of the present invention preferably is formulated into and is being used for washing operation, and the pH value of washing water is 6.5 to 11, is preferably 7.5 to 10.5.It is 6.8 to 9.0 that liquid wash up product formulation preferably has the pH value.Laundry product general pH value is 9-11.Control pH comprises the use buffer reagent in the method under the use value of recommending, alkali, and acid etc., these all are that those skilled in the art are familiar with.Granule manufacture
With the present invention two-the alkoxylate cats product adds and mixes in the machine, then by conventional spraying drying, helps any residual short chain amine pollutent possible frowzy of removal.If but prescription Shi Xiwang preparation is used for for example composite grain that contains the alkoxylate cats product of high density granular detergent, preferably this particulate composition is not overbasic.Preparation high-density (being higher than 650g/l) particulate method is described among the US5366652.The effective pH value that this particle can be mixed with when using is 9 or lower, to avoid the smell of impurity amine.This can pass through to add a small amount of acid source for example boric acid, citric acid etc. in this particle, or suitable pH buffer reagent is realized.In another embodiment, relevant with amine stink expection problem can hide by using as perfume composition disclosed herein.
Embodiment
Following examples are to be used to illustrate the present invention, rather than the restriction or the regulation scope of the invention.Unless otherwise indicated, all umbers used herein, percentage ratio and ratio are that percentage ratio is represented by weight.
In following examples, the component symbol of writing a Chinese character in simplified form has to give a definition: LAS: straight chain C 12Sodium alkyl benzene sulfonate TAS: tallow alkyl sodium sulfate C45AS: C 14-C 15Straight-chain alkyl sulfate C XyE zS: with the C of Z moles of ethylene oxide condensation 1x-C 1YBranched-chain alkyl sulfuric acid
Sodium C45E7: with average 7 moles of ethylene oxide condensations mainly be C 14-15Directly
Chain primary alconol C25E3: with the C of average 3 moles of ethylene oxide condensations 12-15Branched-chain primary alcohol C25E5: with the C of average 5 moles of ethylene oxide condensations 12-15Branched-chain primary alcohol coconut EO2: R 1N +(CH 3) (C 2H 4OH) 2, R 2=C 12-C 14Soap: the straight chained alkyl that obtains by 80/20 butter and coconut oil blend
Carboxylic acid sodium TFAA: C 16-C 18Alkyl N-methyl glucose amide TPKFA: C 12-C 14The full cut STPP of lipid acid topping: anhydrous sodium tripolyphosphate zeolite A: formula Na 12(AlO 2SiO 2) 1227H 2The hydrated sodium aluminosilicate of O,
Primary particle size is 0.1-10 micron NaSKS-6: formula δ-NaSi 2O 5The crystalline layered silicate citric acid: Citric Acid, usp, Anhydrous Powder carbonate: granularity is a 200-900 micron anhydrous sodium carbonate supercarbonate: size-grade distribution is at the anhydrous sodium bicarbonate silicate of 400-1200 micron: amorphous sodium silicate (SiO 2: Na 2O ratio=2.0) sodium sulfate: anhydrous slufuric acid na citrate: size-grade distribution at the active matter content of 425-850 micron is
86.4% citrate trisodium dihydrate MA/AA: 1: 4 toxilic acid/acrylic copolymer, molecular-weight average 70000CMC: Xylo-Mucine proteolytic enzyme: by NOVO Industries A/S with trade(brand)name Savinase
The proteolytic ferment of selling, active 4KNPU/gAlcalase: the activity of being sold by NOVO Industries A/S is 3AU/g
The proteolytic ferment cellulase: by NOVO Industries A/S with trade(brand)name Carezyme
The cellulolytic enzyme of selling, active 1000CEVU/g amylase: by NOVO Industries A/S with trade(brand)name Termamyl
The amylolytic enzyme that 60T sells, active 60KNU/g lipase: with the lipolytic enzyme that trade(brand)name Lipolase sells, activity
100KLU/gEndolase: the activity of being sold by NOVO Industries A/S is
The endoglucanase PB of 3000CEVU/g 4: general formula NaBO 2.3H 2O.H 2O 2Sodium perborate tetrahydrate PB 1: nominal formula NaBO 2.H 2O 2Anhydrous sodium perborate SYNTHETIC OPTICAL WHITNER percarbonate: formula 2NaCO 33H 2O 2SPC-D NOBS: nonanoly acyloxy benzene sulfonate, sodium-salt form TAED: tetraacetyl ethylene diamine DTPMP: diethylenetriamine five (methylene phosphonic acid), by Meng Shan all with merchant
Name of an article Dequest 2060 sells floating of photoactivation: the sulfonated phthalocyanine zinc white agent whitening agent of usefulness soluble dextrins polymeric encapsulate 1: 4,4 '-two (2-sulfo group styryl) biphenyl disodium whitening agent 2: 4,4 '-two (4-phenylaminos-6-morpholino-1,3,5-triazines-2-
Base) stilbene-2: 2 '-disulfonic acid disodium HEDP amino): hydroxyl ethane 1,1-di 2 ethylhexyl phosphonic acid PVNO: polyvinylpyridine N-oxide compound PVPVI: the multipolymer SRA1 of Polyvinylpyrolidone (PVP) and vinyl imidazole: the sulfo group benzoyl is end capped to have the oxygen vinyloxy group and to benzene two
The ester SRA2 of acyl group skeleton: poly-(terephthalic acid 1, the inferior propyl ester of 2-) short embedding of diethoxyization
Section polymer poly siloxanes disappears: polydimethylsiloxane foam control agent and siloxanes infusion-oxyalkylene copolymers as dispersion agent, the weight of described foam control agent and dispersion agent
Than being 10: 1-100: 1
In following examples, all content are to represent by the % that accounts for composition weight.
The embodiment I
Preparation is according to following detergent body of the present invention, and wherein A and C are the phosphorated detergent composition, and B is the detergent composition that contains zeolite.
Powder STPP 24.0-24.0 zeolite A-24.0-C45AS, 8.0 5.0 11.0MA/AA, 2.0 4.0 2.0LAS, 6.0 8.0 11.0TAS 1.5 of A B C blowing--coconut MeEO2 *1.5 1.0 2.0 silicate, 7.0 3.0 3.0CMC, 1.0 1.0 0.5 brightening agents, 2 0.2 0.2 0.2 soaps, 1.0 1.0 1.0DTPMP 0.4 0.4 0.2 spray bleaching agent 0.05 0.05 0.05 protease 1.0 1.0 1.0 lipase 0.4 0.4 0.4 amylase, 0.25 0.30 0.15 sodium sulphate, 3.0 3.0 5.0 surpluses (water and other) of C45E7 2.5 2.5 2.0C25E3 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 15.0PB4-4.0 10.0PB1 4.0-0 percarbonate 18.0 18.0 21.0TAED 3.0 3.0-photoactivation to 100.0 100.0 100.0 density (g/l) 630 670 670
* two-AQA-2 of this embodiment's two-AQA-1 (coconut MeEO2) tensio-active agent available equivalents quantity replaces to other two-AQA tensio-active agent of any tensio-active agent of two-AQA-22 or this paper.
The embodiment II
Preparation is according to following detergent body of the present invention:
D E F zeolite A 30.0 22.0 6.0 sodium sulfate 19.0 5.0 7.0MA/AA 3.0 3.0 6.0LAS 13.0 11.0 21.0C45AS 8.0 7.0 7.0 coconut MeEO2 *1.0 bleaching agent 1.05 0.5 0.2 sodium sulphate of 1.0 1.0 silicate-1.0 5.0 soap--2.0 brightening agents, 1 0.2 0.2 0.2 carbonate, 8.0 16.0 20.0DTPMP-0.4 0.4C45E7,1.0 1.0 1.0PVPVI/PVNO, 0.5 0.5 0.5 protease, 1.0 1.0 1.0 lipase, 0.4 0.4 0.4 amylase, 0.1 0.1 0.1 cellulases, 0.1 0.1 0.1NOBS-6.1 4.5PB1-2.0,4.1 photoactivation-6.0-surplus (water and other) is to 100 100 100
* two-AQA-2 of this embodiment's two-AQA-1 (coconut MeEO2) tensio-active agent available equivalents quantity replaces to other two-AQA tensio-active agent of any tensio-active agent of two-AQA-22 or this paper.
The embodiment III
Preparation is according to following high density detergent goods of the present invention:
The powdery zeolite A 15.0 15.0 15.0 sodium sulfate 0.0 5.0 0.0LAS 3.0 3.0 3.0 coconut MeEO2 of G H I blowing *1.0 1.5 1.5DTPMP, 0.4 0.4 0.4CMC, 0.4 0.4 0.4MA/AA, 4.0 2.0 2.0 aggregate LAS, 5.0 5.0 5.0TAS, 2.0 2.0 1.0 silicate, 3.0 3.0 4.0 Wessalith CSs, 8.0 8.0 8.0 carbonate 8.0 8.0 4.0 are sprayed poly-epoxy--0.2 ethane bentonite--10.0 protease 1.0 1.0 1.0 lipase 0.4 0.4 0.4 amylase 0.6 0.6 0.6 cellulases 0.6 0.6 0.6 polysiloxane defoamers 5.0 5.0 5.0 dried additive sulfuric acid sodium 0.0 3.0 0.0 surpluses (water and other) of bleaching agent 1.0 0.75 0.5MW5000000 of spices 0.3 0.3 0.3C45E7 2.0 2.0 2.0C25E3 2.0--thousand additive citric acid salt 5.0-2.0 bicarbonates-3.0-carbonate 8.0 15.0 10.0TAED 6.0 2.0 5.0PB1-2.0 3.6 photoactivation to 100.0 100.0 100.0 density (g/l) 850 850 850
* two-AQA-2 of this embodiment's two-AQA-1 (coconut MeEO2) tensio-active agent available equivalents quantity replaces to other two-AQA tensio-active agent of any tensio-active agent of two-AQA-22 or this paper.
The embodiment IV
Preparation is according to following high density detergent goods of the present invention:
The powdery zeolite A 2.5 2.5 sodium sulfate 1.0 1.0 coconut MeEO2 of M N blowing *1.5 1.5 aggregate C45AS, 11.0 14.0 Wessalith CSs, 15.0 6.0 sodium carbonate, 4.0 8.0MA/AA, 4.0 2.0CMC, 0.5 0.5DTPMP 0.4 0.4 sprays bleaching agent 0.27 0.8SRA1 0.3 0.3 protease 1.4 1.4 lipase 0.4 0.4 cellulases 0.6 0.6 amylase 0.6 0.6 polysiloxane defoamers 5.0 5.0 brightening agent 1 10.2 0.2 brightening agents, the 2 0.2-surpluses (water and other) of C25E5 5.0 5.0 spices 0.5 0.5 thousand additive HEDP 0.5 0.3SKS6 13.0 10.0 citrates 3.0 1.0TAED 5.0 7.0PB1 8.0 15.0 photoactivation to 100 100 density (g/l) 850 850
* two-AQA-2 of this embodiment's two-AQA-1 (coconut MeEO2) tensio-active agent available equivalents quantity replaces to other two-AQA tensio-active agent of any tensio-active agent of two-AQA-22 or this paper.
The embodiment V
By being mixed preparation following hand washing the according to the present invention by weight percentage shown below, each component uses detergent body:
A B C DLAS 15.0 12.0 15.0 12.0TFAA 1.0 2.0 1.0 2.0C25E5 4.0 2.0 4.0 2.0AQA-9* 2.0 3.0 3.0 2.0STPP 25.0 25.0 15.0 15.0MA/AA 3.0 3.0 3.0 3.0CMC 0.4 0.4 0.4 0.4DTPMP 1.0 1.6 1.6 1.6 carbonate 2.0 2.0 5.0 5.0 bicarbonates--bleaching agent 0.3 0.3 0.3 0.3 sulfate 2.2 2.2 2.2 2.2PB1 4.0 5.4 4.0 2.3NOBS 2.6 3.1 2.5 1.7SRA1,0.3 0.3 0.7 0.3 brightening agents, 1 0.15 0.15 0.15 0.15 surpluses (water and other) of 2.0 2.0 silicate, 7.0 7.0 7.0 7.0 protease 1.0-1.0,1.0 amylase, 0.4 0.4 0.4-lipase, 0.12 0.12-0.12 photoactivation are to 100.0 100.0 100.0 100.0
AQA-9* can replace with any AQA tensio-active agent described herein.The preferred AQA tensio-active agent that is used for this embodiment is to have those of 10 15 oxyethyl groups; AQA-10 for example, AQA-16.
Following examples have illustrated the present composition that relates to laundering of textile fabrics, but do not mean that and limit them.
The embodiment VI
Two-AQA the surfactant mixture that can be used for replacing two-AQA tensio-active agent listed in any the foregoing description below has been described.As above disclosed; This mixture improvement in performance is provided providing widely and/or the cleaning combination that is suitable for working conditions miscellaneous is provided.Preferably; The two-AQA tensio-active agent difference at least 1.5 in this mixture, the limiting examples of this mixture of preferred 2.5-20 total EO unit.The proportional range of mixture (weight) generally is 10:1-1:10. is as follows: component ratio (weight) is two-AQA-1+ is two-1: 1 couple-AQA-1+ of AQA-5 is two-1: 1 couple-AQA-1+ of AQA-10 is two-1: 2 couple-AQA-1+ of AQA-15 is two-AQA-5+ is two-1: 1: 1 couple-AQA-2+ of AQA-20 is two-3: 1 couples-AQA-5+ of AQA-5 is two-5 1.5: 1 couple-AQA-1+ of AQA-1 is two-AQA-20 1: 3
Can also use the two-AQA tensio-active agent and the mixture that only contains the corresponding cats product of single ethoxylation chain of this paper.For example, the present invention can use formula R 1N +CH 3[EO] x[EO] yX and R 1N +(CH 3) 2[EO] zThe mixture of the ethoxylation cats product of X, wherein R 1The same with X, and wherein a kind of (x+y) in this cats product or z are in the 1-5 scope, and preferred 1-2, alternative (x+y) or z be in the 3-100 scope, preferred 10-20, most preferably 14-16.This composition is than using cats product of the present invention that the water hardness of wide region has more advantageously been improved scourability (particularly in laundering of textile fabrics) separately.Now the cats product (for example EO2) of finding shorter EO has improved the cleaning performance of anion surfactant in soft water, and the cats product of higher EO (for example EO15) has the effect that improves the anti-hardness of anion surfactant, has improved the cleaning performance of anion surfactant in hard water thus.The conventional knowledge of washing technology proposes the performance " window " that washing assistant can be optimized anion surfactant.But also this window can not be expanded to all water hardness conditions that consist essentially of so far.
Use the laundry detergent composition of the above mixtures preparation of one or more of each component can be randomly with any nonphosphate or phosphate builders or its mixture as washing assistant, generally account for the 5%-70% of final product composition having weight.
The embodiment VII
Below illustrated the conventional non--AQA tensio-active agent that can use with the two-AQA combinations-of surfactants in any the foregoing description mixture, but do not mean that and limit them.The ratio of non-in mixture-AQA tensio-active agent is to represent by accounting for the surfactant mixture parts by weight.
Mixture A-C
Component ratio
AS*/LAS 1∶1
AS/LAS 10: 1 (preferred 4: 1)
AS/LAS 1: 10 (preferred 1: 4)
* more than, uncle's type AS tensio-active agent of straight chain can be with secondary type AS or side chain AS, oleyl sulfate and/or its mixture of equivalent basically, comprise with above shown in straight chain, the mixture of uncle's type AS, replace.The AS of " butter " chain length is being a particularly suitable under the ebullient hot water conditions." coconut " AS is preferred for colder wash temperature.
The mixture of above-mentioned alkyl-sulphate/anion surfactant is modified by the nonionogenic tenside that mixes non-AQA, and wherein the weight ratio of anion surfactant (always) and nonionogenic tenside is 25: 1-1: 5 scopes.Nonionogenic tenside can comprise the ethoxylated alcohol of any general type or alkylphenol, alkyl polyglycoside or polyhydroxy fatty acid amide (if there is LAS, then being less preferred) or its mixture, for example those disclosed above.
Mixture D-F
AS*/AES 1∶1
AS/AES 10: 1 (preferred 4: 1)
AS/AES 1: 10 (preferred 1: 4)
* can with as above-mentioned second month in a season, side chain or oil base AS replace.
Above-mentioned AS/AES mixture can be by being modified to wherein mixing LAS, and wherein the weight ratio of AS/AES (always) and LAS is 1: 10-10: 1 scope.
The AS/AES/LAS mixture that AS/AES mixture or their form also can with the nonionic surfactant combinations described in the mixture A-C, the weight ratio of negatively charged ion (always) and nonionogenic tenside is 25: 1-1: 5 scopes.
Any said mixture all can be by being modified to wherein mixing amine oxide surfactant, and wherein amine oxide accounts for the 1%-50% of total surfactant mixture.
Above-mentioned non--the most preferred combination of AQA tensio-active agent accounts for the 3%-60% of total finished product laundry detergent composition weight.Final product composition having preferably comprises 0.25%-3.5% (weight) two-AQA tensio-active agent.

Claims (19)

1. composition wherein comprises following component or is mixed with by following component: two-alkoxy quaternary ammonium of the following formula of optical white, non--AQA tensio-active agent and significant quantity (two-AQA) cats product: R wherein 1Be C 8-C 18Alkyl or alkenyl part, R 2Be C 1-C 3Moieties, R 3And R 4Can change and be selected from hydrogen, methyl, ethyl separately, X is a negatively charged ion, and A and A ' can change and each C naturally separately 1-C 4Alkoxyl group, p and q can change and be the integer of 1-30 separately.
2. according to the composition of claim 1, said composition is by being mixed with non--AQA tensio-active agent and AQA tensio-active agent.
3. according to the composition of claim 1 or 2, wherein non--AQA tensio-active agent is an anion surfactant.
4. according to the composition of any claim 1-3, wherein-ratio of AQA and non--AQA tensio-active agent is 1: 15-1: 8.
5. according to the composition of any claim 1-4, wherein comprise other SYNTHETIC OPTICAL WHITNER.
6. according to the composition of any claim 1-5, wherein also comprise the SYNTHETIC OPTICAL WHITNER and the bleach-activating agent that discharge oxygen.
7. according to each composition among the claim 1-6, wherein also comprise bleaching catalyst.
8. according to the composition of any claim 1-7, wherein said two-AQA tensio-active agent formula in R 1Be C 8-C 18Alkyl, R 2Be methyl, A and A ' are oxyethyl group or propoxy-, and p and q respectively are the integers of 1-8.
9. according to the composition of any claim 1-8, wherein said two-AQA tensio-active agent formula in R 1Be C 8-C 18Alkyl, R 2Be methyl, A and A ' are oxyethyl group or propoxy-, and p and q respectively are the integers of 1-4.
10. according to the composition of any claim 1-9, wherein-AQA cats product formula in p and/or q be the integer of 10-15 scope.
11., wherein comprise two or more pairs-AQA tensio-active agent, or the mixture of two-AQA tensio-active agent and monosubstituted ethoxy cats product according to the composition of any claim 1-10.
12., wherein comprise two or more non--AQA tensio-active agents and two or more pairs-AQA surfactant mixtures according to the composition of any claim 1-11.
13. according to the composition of any claim 1-12, said composition is particle, stick, water fluid or non-aqueous liquid or sheet form.
14. a method of removing dirt and spot, this method are to make said dirt and spot and contact according to the detergent composition of claim 1-13 arbitrarily or the water-bearing media that comprises this detergent composition.
15. according to being used for of claim 14 from the method for fabric removal to the dirt of SYNTHETIC OPTICAL WHITNER sensitivity.
16. according to the method for claim 14 or 15, this method is undertaken by manual.
17. according to the method for any claim 14-16, this method is carried out in automatic washing machine.
18. one kind is improved spices or perfume composition deposits or the method for weather resistance on fabric or other surface, be included in two-AQA tensio-active agent and exist down said surface is contacted with spices or perfume composition.
19. according to the method for claim 18, this method is carried out with spices or perfume composition and the detergent composition combination that comprises two-AQA tensio-active agent.
CN 97196381 1996-05-17 1997-05-16 Detergent composition Pending CN1225122A (en)

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CN 97196381 CN1225122A (en) 1996-05-17 1997-05-16 Detergent composition

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US60/017,883 1996-05-17
CN 97196381 CN1225122A (en) 1996-05-17 1997-05-16 Detergent composition

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CN1225122A true CN1225122A (en) 1999-08-04

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1103363C (en) * 2000-03-13 2003-03-19 上海华珏精细化工实业有限公司 Super-concentration phosphorus-free bleaching washing liquid
CN101855331B (en) * 2007-09-08 2013-01-23 荷兰联合利华有限公司 Improvements relating to fabric conditioners

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1103363C (en) * 2000-03-13 2003-03-19 上海华珏精细化工实业有限公司 Super-concentration phosphorus-free bleaching washing liquid
CN101855331B (en) * 2007-09-08 2013-01-23 荷兰联合利华有限公司 Improvements relating to fabric conditioners

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