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CN1224449A - Liquid detergent compositions contg. specially selected modified polyamine polymers - Google Patents

Liquid detergent compositions contg. specially selected modified polyamine polymers Download PDF

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CN1224449A
CN1224449A CN 97196121 CN97196121A CN1224449A CN 1224449 A CN1224449 A CN 1224449A CN 97196121 CN97196121 CN 97196121 CN 97196121 A CN97196121 A CN 97196121A CN 1224449 A CN1224449 A CN 1224449A
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alkyl
agent
composition
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K·普拉莫德
R·K·帕南迪克
C·K·高希
R·A·沃森
J·L·贡－陈
F·德布扎卡里尼
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Procter and Gamble Co
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Procter and Gamble Co
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Abstract

Laundry detergent compositions that provide fabric appearance benefits to all fabric comprising modified polyamine agents and other selected fabric appearance agents, and a method for providing these benefits to fabric by contacting fabric articles with a water soluble and/or dispersible, modified polyamine having functionalized backbone moieties.

Description

The liquid detergent composition that comprises specially selected modified polyamine polymers
Right of priority history
The application's preference file is following pending application: US application serial No. 60/016,527 (applying date is 1996.5.3), US application serial No. 60/017,062 (applying date is 1996.5.3), US application serial No. 60/016,525 (applying date is 1996.5.3), US application serial No. 60/017,059 (applying date is 1996.5.3), US application serial No. 60/017,060 (applying date is 1996.5.3), US application serial No. 60/016,526 (applying date is 1996.5.3), US application serial No. 60/016,531 (applying date is 1996.5.3), US application serial No. 60/016,528 (applying date is 1996.5.3), US application serial No. 60/027,902 (applying date is 1996.10.7) and US application serial No. 60/027,899 (applying date is 1996.10.7).
Invention field
The present invention relates under various dirt conditions, all can provide the liquid laundry detergent composition of appearance of fabrics effect to fabric.Said composition comprises the agent of specially selected modified polyamine appearance of fabrics.The present invention also relates to by making fabric articles contact the method for fabric of giving with the modified polyamine of water-soluble and/or water dispersible with appearance effect.
Background of invention
Various appearance of fabrics agent known in the state of the art can be used for family expenses and technical fabric treating processes, process of dry fabric in the warm air clothes-drying machine etc. as laundry processes and fabric.Various appearance of fabrics agent comprise stain remover, dispersion agent, tensio-active agent, fabric softener and dye transfer inhibitor, and they have realized suitability for industrialized production, and routine is used for detergent composition and is used for fabric softener/static inhibitor product and composition.
The further investigation of having carried out already in this field is made remarkable improvement to the usefulness of various appearance of fabrics agent, has strengthened the performance and the preparation property of product.But single a kind of compound can not strengthen the various fabrics appearance effect definitely.Therefore, formulator also must select some kinds of technology to realize the desirable whole structure of human consumer and to reach cost-effectiveness.Owing to may interact between all ingredients in aqueous solution, thereby also there are some problems in liquid washing agent.
And then the conventional attractive in appearance dose of great majority of fabric that adopt of this class can't provide enhancing usefulness to hydrophobic and hydrophilic dirt and spot simultaneously.The tea spot is hydrophilic, and dirty and tomato spot is hydrophobic.
Therefore, up to the present, be used for laundry detergent effectively, the agent of Almightiness type appearance of fabrics can't be satisfactory.People attempt the example that the structure of the structure of using polymer and fabric is complementary and do not achieve success, and this method successfully is applied to the polyester soil release polymers field.
Now, be surprisingly found out that, can prepare effective appearance of fabrics agent from some modified polyamine.This beat all result has produced the composition that the inventive method that some kinds of appearance of fabrics effects are provided is played keying action, described composition only needs to use several discrete laundry additives, described soil-removing action, soil dispersion effect and the dye transfer restraining effect of acting as.Method of the present invention is also effective to all types of dirts and spot.
When laundry detergent compositions of the present invention was liquid, method of the present invention was effective especially.The range of viscosities of liquid washing agent can be very wide, and liquid washing agent can comprise heavy enriched material, dumpable " standby " washing composition or flexible fabric pretreating agent.
Described in the methods of the invention modified polyamine can be compatible with auxiliary agent with other laundry detergent additive.In fact, it is believed that in fact polyamine of the present invention can work in coordination with and strengthen other detergent additives such as tensio-active agent and may cause the effect of the additive of disadvantageous dye transfer problem in the past.
Background technology
USP4,548,744 (1985.10.22, Connor), USP4,597,898 (1986.7.1, Vander Meer), USP4,877,896 (1989.10.31, Maldonado etc.), USP4,891,160 (1990.1.2, Vander Meer), USP4,976,879 (Maldonado etc., 1990,12,11) USP5,415,807 (1995.5.16, Gosselink), USP4,235735 (1980.11.25, Marco etc.), WO95/32272 (1995.11.30), UKP1,537,288 (1978,12.29), UKP1,498,520 (1978.1.18), DE2829022 (1980.1.10), JP063-13271 (1994.4.27) is in addition referring to UK1,314,897, USP3,897,026, USP3,912,681, USP3,948,838 (Hinton etc. disclose the high molecular (500 as stain remover, 000-1,500,000) acrylic acid polymer), USP4,559,056, USP4,579,681, USP4,614,519.
The example of alkoxylate polyamine and quaternized alkoxylate polyamine is disclosed in EP-A-206, and 513, it is applicable to that as dirt dispersant still, and unexposed its can be used for cotton dirt stain remover.
Summary of the invention
The invention provides the liquid laundry detergent composition, it comprises:
(a) at least about the detersive surfactant of 0.1wt%, it is selected from anion surfactant, nonionogenic tenside or its mixture;
(b) at least about water-soluble or water dispersible, the modified polyamine reagent of 0.05wt%, described reagent comprises the polyamine backbone corresponding to following formula:
Figure A9719612100081
Wherein, R 1Be C independently of one another 2-C 5Alkylidene group, alkenylene or arylidene; R 2Be H or formula OH[(CH independently of one another) XO] nPart, wherein x is about 1-8, n is about 10-50; W is 0 or 1; X+y+z is about 5-30; The B representative is by the extension of this structure of branching; Wherein, the molecular-weight average of the polyamine before the alkylation is about 300-1200; With
(c) one or more additional detergent additives, it is selected from: amylase, decontamination amine, cats product, anti redeposition agent, anti-decolourant, laking agent, bead/fine hair reduce agent and its mixture.
Detergent composition of the present invention can comprise additional auxiliary component, and these compositions are selected from: washing assistant, white dyes, soil release polymer, dye transfer inhibitor, macromolecule dispersing agent, the enzyme except that amylase, suds suppressor, dyestuff, spices, tinting material, filling salt, hydrotropic solvent and its mixture.
In preferred embodiments, R 1Be C 2-C 4Alkylidene group, preferred ethylidene; R 2Be OH[CH 2CH 2O] n, wherein n is about 15-30, preferred n is about 20.The molecular-weight average of polyamine is about 300-1200 before alkylation, preferably about 500-900,600-700 more preferably from about, even 600-650 more preferably from about.
The invention still further relates to a kind of method of fabric of giving, comprise fabric is contacted with laundry compositions that described composition comprises with dye transfer restraining effect and other appearance of fabrics effect:
(a) at least about the above-mentioned water-soluble or water dispersible modified polyamine of 0.05wt%;
(b) one or more additional detergent additives, it is selected from: selected amylase, selected decontamination amine, selected cats product, anti redeposition agent, anti-decolourant, laking agent, bead/fine hair reduce agent and its mixture.
Detergent composition of the present invention can be liquid, gel or structuring liquid.
Except as otherwise noted, all percentage ratio, ratio and ratios all refer to weight among the present invention.All temperature be degree centigrade (℃).The document that all relevant portions are quoted all is incorporated herein by reference.
Detailed Description Of The Invention
The preferred laundry detergent compositions of the present invention comprises:
(a) anionic detersive surfactant of about 0.1-95wt% is preferably selected from: alkyl-sulphate, alkyl alkoxy (preferred oxyethyl group) vitriol and its mixture;
(b) at least about the non-ionic detersive surfactant of 0.1-95wt%, be preferably selected from: polyhydroxy fatty acid amide and alkylethoxylate;
(c) about 0.05-15wt%, the preferably of the present invention water-soluble or water dispersible of about 0.1-10wt%, the agent of modified polyamine appearance of fabrics;
(d) one or more additional detergent additives, it is selected from: amylase, decontamination amine, cats product, anti redeposition agent, anti-decolourant, laking agent, bead/fine hair reduce agent and its mixture; With
(e) balance carrier and auxiliary component.
When measuring with 10% aqueous solution, the pH value of the present composition preferred about 6-12, more preferably 7.0-10.5.
Modified polyamine
The present invention adopts the polyamine appearance of fabrics agent of " significant quantity " to improve the performance of the cleaning compositions that comprises other ancillary component.Herein, described " significant quantity " is meant that this consumption for some purpose dirt and spot at least, is enough under 90% degree of confidence, improves the performance of cleaning compositions just or significantly.Therefore, comprise in the composition of some food dirt that formulator will use the polyamine appearance of fabrics agent of capacity can improve clean-up performance to dirt at least just at its target directing.Importantly, in full preparation laundry detergent, the consumption of appearance of fabrics agent should be at least demonstrates minimum at least clean-up performance improvement effect to the dirt and the dirt of wide region, and these data that will provide from below as can be seen.
It may be noted that the appearance of fabrics agent that is used for detergent composition can be used in combination with detersive surfactant, the content of described detersive surfactant should reach the degree that can improve clean-up performance at least substantially effectively.For the fabric laundry compositions, " consumption " can change, and this not only depends on the type and the seriousness of dirt and spot, and depends on washing water temperature, the volume of bath water and the type of washing machine.
As seen from the above, be used for the consumption of the appearance of fabrics agent of machine washing of clothes can be according to user's custom and put into practice, the variations such as type of washing machine.And being it, the advantage that is not much accounted of of fabric attractive in appearance dose of settled the present can be at least the dirt and the spot of various scopes be all had minimum improvement.
Modified polyamine reagent of the present invention is the modified polyamine of water-soluble or water dispersible.These polyamine comprise the skeleton that can be straight chain or ring.This polyamine backbone also comprises the polyamine branched chain of different degrees of branching.Usually, polyamine backbone as herein described be modified as make the nitrogen-atoms of each polyamine chain all be substituted, quaternized or the two combine.
Among the present invention, " modification " is defined as by E unit (replacement) or by quaternized skeleton nitrogen (quaternized) and replaces skeleton-NH hydrogen atom.When relating to the process of the hydrogen atom that is connected with skeleton nitrogen with the replacement of E unit, term " modification " and " replacement " are interchangeable.Quaternized occurring in some situation except that replacement.
The preferred polymkeric substance of the present invention comprises can be by the equal polyamine skeletons that poly-ethylidene oxygen partly all replaces or part replaces, by the even polyamine backbone of all or part of replacement of quaternized amine, by whole even polyamine backbone and its mixtures that replace of nitrogen.But, be not all skeleton amine nitrogen atom modifications in the same manner, the selection mode of modification can be according to makers-up's special requirement.Ethoxylation degree is also determined by makers-up's specific requirement.
The preferred polyamine that comprises the The compounds of this invention skeleton is normally: polyalkylene amine (PAA), polyalkyleneimine (PAI), preferably poly-ethyleneamines (PEA), polyethylene imine based (PEI) or had PEA or the PEI that is connected than the unitary part of the longer R of parent PAA, PAI, PEA or PEI.Polyalkylene amine (PAA) commonly used is the four inferior tertiary butyl five amine.PEA is by making the reaction of ammonia and ethylene dichloride, obtaining through fractionation.The common PE A that obtains is Triethylenetetramine (TETA) (TETA) and tetren (TEP A).Be that hexamine, seven amine, eight amine and nine possible amine belong to the deutero-mixture jointly more than five amine, they are also failed by fractionation by distillation, can comprise other material, as cyclammonium, and piperazine especially.The cyclammonium that also can comprise the side chain nitrogen atom.Referring to USP2,792,372 (Dikinson, 1957.5.14), the document discloses the preparation process of PEA.
The preferred amines polymer backbone comprises the R unit, and it is C 2Alkylidene group (ethylidene) unit is also referred to as polyethylene imine based (PEI).Preferred PEI has moderate at least side chain, and promptly m and the ratio of n be less than 4: 1, and just more preferably the ratio of m and n is about 2: 1 PEI.
These polyamine for example, prepare by the polymerization ethyliminum in the presence of one of them at catalyzer such as carbonic acid gas, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetate etc.The method of concrete these polyamine backbone of preparation is referring to following document: USP2,182,306 (Ulrich etc., 1939.12.5), USP3,033,746 (Mayle etc., 1962.5.8), USP2,208,095 (Esselmann etc., 1940.7.16), USP2,806,839 (Crowther, 1957.9.17) and USP2,553,696 (Wilson, 1951.5.21), all these documents all are incorporated herein by reference.
Following formula shows the modified polyamine reagent that preferably comprises the PEI skeleton, and wherein, all commutable nitrogen are all by the polyoxy alkylidene oxygen unit-(CH with following formula 2CH 2O) 20H replaces hydrogen and modification,
Figure A9719612100111
Cats product is used for alkoxy quaternary ammonium of the present invention (AQA) tensio-active agent and has following general formula: Wherein, R 1For having about 8-18 carbon atom, preferably about 10-16 carbon atom, the more preferably from about alkyl of 10-14 carbon atom or alkenyl; R 2And R 3 'Independently of one another for having the alkyl of about 1-3 carbon atom, preferable methyl; R 3And R 4Can change independently, and be selected from hydrogen (preferably), methyl and ethyl, X-is for electroneutral negatively charged ion is provided, as chlorion, bromide anion, methylsulfate, sulfate radical etc.; A is selected from: C 1-C 4Alkoxyl group, particularly oxyethyl group (promptly-CH 2CH 2O-), propoxy-, butoxy and its mixture; To the formula I, p is that 2-is about 30, and preferred 2-is about 15, and more preferably 2-about 8; To II, p is that 1-is about 30, and preferred 1-is about 4, and q is that 1-is about 30, and preferred 1-is about 4, and more preferably p and q are 1.
The consumption that is used to prepare the AQA tensio-active agent of final laundry detergent compositions is about 0.1-5wt%, preferably about 0.45-2.5wt%.
Amylase
It is very difficult removing very hydrophobic " daily " dirt or " health " dirt fully, after washing, and usually can residual a spot of remaining dirt on the fabric.These resistatess are assembled, and play the effect of similar amorphous goo between fiber, and it can capture particular pollutant and make the fabric jaundice.Further find now, comprise the water-soluble polyamine reagent of the present invention and compare with the composition that only comprises one of above-mentioned two kinds of compositions with the detergent composition of amylase combination and have better cleaning and whitening performance.
This amylase comprise WO95/26397 described those, and common pending application NovoNordisk PCT/DK96/00056 described those.Comprise the pure enzyme of 0.00018-0.060% with the total restatement detergent composition of composition, the pure enzyme of preferred 0.00024-0.048%.
Thereby the concrete amylase that is used for detergent composition of the present invention comprises:
(a) by Phadebas  alpha-amylase activity test, in 25-55 ℃ and the pH value 8-10 α-Dian Fenmei of the specific activity height at least 25% that records than Termamyl  of the specific activity of measurement down.The test of Phadebas  alpha-amylase activity is stated at the 9-10 page or leaf of WO95/26397.
(b) according to the α-Dian Fenmei of (a), be included in the aminoacid sequence that is shown in SEQ ID sequence table in the above-mentioned document of quoting, or at least with the aminoacid sequence 80% homologous α-Dian Fenmei that is shown in SEQ ID sequence table.
(c) according to the α-Dian Fenmei of (a), comprise following aminoacid sequence: His-His-Asn-Gly-Thr-Asn-Gly-Thr-Met-Met-Gln-Tyr-Phe-Glu-Trp-Tyr-Leu-Pro-Asn-Asp at the N-end.(Science) (1985,227, algorithm P1435) carries out the comparison of each aminoacid sequence, if show the identity property of X%, thinks that so this polypeptide and parent's amylase have the X% homology in " science " for example to adopt Lipman and Pearson.
(d) according to the α-Dian Fenmei of (a-c), wherein α-Dian Fenmei is obtained by close alkali (alkalophilic) genus bacillus; Particularly, from bacterial strain NCIB12289, NCIB12512, NCIB12513 and DSM935.
In the present invention, term " from ... obtain " be meant amylase not only by Bacillus strain production, and for by by the sequence encoding of this Bacillus strain separated DNA and by with described dna sequence dna host transformed biological production.
(e) show the α-Dian Fenmei of positive immunological cross-reaction with antibody, this antibody resists a certain α-Dian Fenmei, and this α-Dian Fenmei has and corresponds respectively to the identical aminoacid sequence of (a-d) α-Dian Fenmei.
(f) varient of parent's α-Dian Fenmei described below: (ⅰ) have the sequence of one of the aminoacid sequence of those α-Dian Fenmei that correspond respectively to (a-e), or (ⅱ) show with described one or more aminoacid sequences to have at least 80% homology, and/or show immunological cross-reaction with antibody, this antibody is anti-to have the α-Dian Fenmei of one of described aminoacid sequence, and/or by dna sequence encoding, this dna sequence dna and probe hybridization, this probe is identical with the dna sequence dna of the α-Dian Fenmei that one of coding has one of described aminoacid sequence; Varient wherein:
1. at least one amino-acid residue of described parent's α-Dian Fenmei lacks; And/or
2. at least one amino-acid residue of described parent's α-Dian Fenmei is substituted by a different amino-acid residue; And/or
3. for described parent's α-Dian Fenmei, inserted at least one amino-acid residue; Described varient has alpha-amylase activity and shows one of following properties at least for described parent's α-Dian Fenmei: thermostability increases, oxidation resistant stability increases, the calcium ion dependency reduces, stability when neutrality arrives very high pH value and/or Alpha-starch degrading activity increase, increase in high relatively temperature oc-amylolytic activity, and can increase or reduce with the pH of substratum its iso-electric point (pI) that is complementary better for the pI value that makes alpha-amylase variants.
Preferred amylase of the present invention is those that describe below:
(a) in temperature 25-55 ℃ scope and pH value time employing Phadebas in the 8-10 scope The specific activity of alpha-amylase activity measurements determination compares Termanyl The α-Dian Fenmei of specific activity high at least 25%;
(b) with antibody show positive immunological cross-reaction α-Dian Fenmei, the anti-α-Dian Fenmei of this antibody with aminoacid sequence of the α-Dian Fenmei that corresponds respectively to (a); With
(c) mixture of above-mentioned enzyme.
Described varient is described in patent application PCT/DK96/00056.
Be applicable to that other amylase of the present invention comprises the amylase that for example is described in GB1296839 (Novo); RAPIDASE  (International Bio-Synthetics) and TERMAMYL , the Novo.FUNGAMYL  that comes from Novo is especially suitable.
Be used for improving stability, for example the enzyme engineering method of oxidative stability is known.Referring to the biological example The Chemicals, the 260th volume, 11 phases, in June, 1985,6518-6521 page or leaf.The amylase that some embodiment preferred of the present composition will have the stability of improvement is used for washing composition, especially has the oxidative stability of improvement, for example with commercially available TERMAMYL  in 1993 as with reference to measuring.These preferred amylase of this paper are shared the diastatic characteristic of " stability increases ", it is characterized in that with respect to above-mentioned with reference to for the amylase, at least following measurable improvement arranged aspect one or more: oxidative stability, for example to the stability of the hydrogen peroxide in the buffered soln of pH value 9-10/tetrem acyl ethylene diamine; Thermostability, for example for example about 60 ℃ in common wash temperature; Or alkaline stability, for example stability when the about 8-11 of pH value.Utilize that disclosed any measuring technology can detect stability in this area.Referring to, for example be disclosed in the technology of WO9402597.
The amylase that stability increases can obtain from Novo or Genencor International.The particularly preferred kind of starch enzyme of this paper generally is to utilize the site-specific mutagenesis method from one or more bacillus amylases, genus bacillus α-Dian Fenmei deutero-especially, no matter be with a kind of, two or more amylase strains are as middle precursor.Described preferred amylase comprises the WO9402597 (Novo that (a) above introduces, 1994.2.3) amylase described, further illustrate by an one mutant, be positioned the α-Dian Fenmei of Bacillus licheniformis in the described mutant, 197 the methionine residues of the known TERMAMYL of being referred to as  utilizes L-Ala or Threonine, preferably Threonine substitutes, or similar parent's amylase bacillus amyloliquefaciens for example, the varient of the homology position of Bacillus subtilus or bacstearothermophilus; (b) be the stable enhanced amylase of describing in " α-Dian Fenmei " paper by Genencor International at its title with oxidation resistance, described paper is in the meeting of 207 countries of american chemical association, and 13-17 day in March, 1994 is submitted to by Mitchinson.Point out that wherein the SYNTHETIC OPTICAL WHITNER in the washing composition makes the α-Dian Fenmei inactivation, still, Genencor has improved oxidative stability by Bacillus licheniformis NCIB8061.Methionine(Met) (Met) is the residue that most possibly is modified.Met 8,15,197,256,304,366 and 438 replaces and to cause the specificity varient in the position at every turn, and particularly importantly M197L and M197T, M197T varient are the varients of stably express.Stability is measured by CASCADE  and SUNLIGHT ; (c) the particularly preferred amylase of the present invention is included in and adds the amylase variant of modifying among the direct parent, as the described amylase of WO9510603A, can be purchased with DURAMYL  from transferee Novo.Other particularly preferred oxidative stability enhanced amylase comprise WO9418314 (GenencorInternational) described those and WO9402597 (Novo) described those.Other oxidative stability enhanced amylase also can use, for example those that are obtained by positional mutation by known imaginary, the blended of available amylase or simple varient parent.Other preferred enzyme modification technology also can be utilized.Referring to WO9509909A (Novo).
Other enzyme
Detergent composition of the present invention can comprise the enzyme that is used for various uses, comprise from the surface as textiles or tableware with remove protein-based dirt, carbohydrate-based dirt or tri-glyceride base dirt, be used for preventing dye transfer, and be used for the fabric recovery in laundry processes.Other suitable enzyme comprises and derives from any suitable source such as plant, animal, bacterium, fungi and zymic proteolytic enzyme, lipase, peroxidase and its mixture.Preferred select to be subjected to following factor affecting, as pH value activity and/or stable optimum condition, thermostability and to the stability of activated detergent, washing assistant etc.At this on the one hand, preferred bacterium or fungal enzyme are as bacterial amylase and proteolytic enzyme.
" detergency enzymes " is meant any enzyme that has cleaning, decontamination or beneficial effect in laundry, hard-surface cleaning or use in personal care detergent composition herein.
The add-on of enzyme should be enough to provide " cleaning significant quantity " usually in washing composition or detergent composition.Term " cleaning significant quantity " is meant that consumption can clean, remove spot, removes dirt, brightens, eliminates the unusual smell or increase bright effect to generations such as substrate such as fabric, tablewares.With regard to the practical situation of present industrial application, the typical content of organized enzyme is usually up to about 5mg, more preferably 0.01-3mg in every gram detergent composition.In other words, composition of the present invention comprises 0.001-5wt% usually, the industrial enzyme preparation of preferred 0.01-1wt%.The content of proteolytic enzyme in industrial enzyme preparation should be enough to make the composition of every gram to have the activity of 0.005-0.1Anson unit (AU) usually.High reactivity content is ideal to the high concentration detergent prescription.
Peroxidase can be used in combination with oxygen source such as percarbonate, perborate, hydrogen peroxide etc., is used for " solution bleaching " or prevents to remove from substrate at washing process dyestuff or pigment and be transferred to other substrate the washing soln.Known peroxidase comprises horseradish peroxidase, lignoenzyme (ligninase) and halo peroxidase such as chloro or bromoperoxidase.The detergent composition that contains peroxidase is stated in following document: WO89099813A (1989.10.19, Novo) WO8909813A (Novo).
The scope of enzyme material also is disclosed in the following document with the method that is introduced into synthetic detergent composition: WO9307260A (Genencor International), WO8908694A (Novo), USP3,553,139 (McCarty etc., 1971.1.5).Enzyme also is disclosed in: USP4,101,457 (Place etc., 1978.7.18) and USP4,507,219 (Hughes, 1985.3.26).Be used for the enzyme material of liquid detergent formula and the method that they introduce described prescription is disclosed in: USP4,261,868 (Hora etc., 1981.4.14).The enzyme that is used for washing composition can carry out stabilization treatment by various technology.The enzyme stabilization technology for example is disclosed in: USP3,600,319 (Gedge etc., 1971.8.17), EP199,405 and EP200,586 (1986.10.29, Venegas).The enzyme stabilising system for example also is disclosed in: USP3,519,570.The useful genus bacillus sp.AC13 that provides proteolytic enzyme, zytase and cellulase is disclosed in WO9401532A (Novo).
Proteolytic enzyme
The subtilisin that the suitable example of proteolytic enzyme obtains for the specific bacterial strain by Bacillus subtilus and Bacillus licheniformis.A kind of suitable proteolytic enzyme is to obtain from the bacterial strain of bacillus, and it all has maximum activity between pH value 8-12, sells by Novo Industries A/S ofDenmark (hereinafter referred to as " Novo ") cultivation and with ESPERASE .The preparation method of this kind of enzyme and similar enzyme states among 243,784 (Novo) at GB1.Other suitable proteolytic enzyme comprises: available from ALCALASE  and the SAVINASE  of Novo, and available from InternationalBio-synthetics, the MAXATASE  of Inc. (Holland); And be disclosed in EP130, the protease A of 756A (1985.1.9) and be disclosed in EP303,761A (1987.4.28) and EP130, the proteolytic enzyme B of 756A (1985.1.9).Equally referring to the high pH proteolytic enzyme that is disclosed in WO9318140A (Novo) from bacillus NCIMB40338 bacterial strain.The enzyme-containing detergent that comprises proteolytic enzyme, one or more other enzymes and a kind of reversible protease inhibitors is stated in WO9203520A (Novo).Other preferred proteolytic enzyme comprises WO9510591A (Procter﹠amp; Gamble) those.When needs, can adopt to have the proteolytic enzyme that reduces absorption and strengthen hydrolysis, as WO9507791A (Procter ﹠amp; Gamble) described.Be applicable to that recombinant trypsin proteinoid enzyme of the present invention is disclosed in WO9425583 (Novo).
In more detail, particularly preferred proteolytic enzyme is so-called " proteolytic enzyme D ", and this proteolytic enzyme D is a kind of carbonylic hydrolase varient, it has a kind of at the undiscovered aminoacid sequence of nature, and it is a plurality of amino-acid residue replacement to be obtained with different amino acid at position+76 places corresponding to described carbonylic hydrolase by the precursor carbonylic hydrolase, and same preferred one or more amino acid residue positions with following position make up and replace :+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+274, according to angle bacillus amyloliquefaciens subtilisin numbering, as the US patent application serial number 08/322 of the US patent application serial number 08/322,676 (being entitled as " cleaning compositions that contains proteolytic enzyme ") of A.Baeck etc. and C.Ghosh etc., 677 (be entitled as " bleaching composition that contains proteolytic enzyme) described, both all apply in 1994.10.13.
Preferred proteolytic enzymes also is the bacterial serine proteolytic enzyme of modifying, as EP application serial 87 303,761.8 (1987.4.28 application) (particularly the 17th, 24 and 98 page) described those, these enzymes also are referred to as " proteolytic enzyme B "; (these enzymes are referred to as the bacterial serine proteolytic ferment of modification, are also referred to as " protease A " in the present invention for Venegas, 1986.10.29) described those enzymes with EP application 199,404; Protease A is as being disclosed in EP130, the protease A of 756A (1985.1.9) and be disclosed in EP303,761A (1987.4.28) and EP130, the proteolytic enzyme B of 756A (1985.1.9).
Same preferred proteolytic enzyme is subtilisin, particularly BPN ', and it makes a variation by the various nucleotide sequences to the enzyme coding and modifies, thereby the aminoacid sequence of enzyme is modified.Compare with the wild-type subtilisin, the subtilisin of these modifications reduces the absorption of insoluble substrate, and increases the hydrolysis of insoluble substrate.Suitable equally is the mutant gene that this BPN ' varient is encoded.
Preferred BPN ' mutation comprises the wild-type amino acid sequence, wherein, one or more positions of 199,200,201,202,203,204,205,206,207,208,209,210,211,212,213,214,215,216,218,219 or 220 are substituted the wild-type amino acid sequence in the position; Wherein, BPN ' compares with the wild-type subtilisin, and BPN ' mutation reduces the absorption of insoluble substrate, and increases the hydrolysis of insoluble substrate.The position that preferably has substituted amino acid is 199,200,201,202,205,207,208,209,210,211,212 or 215; More preferably 200,201,202,205 or 207.
Be preferred for proteolytic enzyme of the present invention and comprise subtilisin 309 mutation.These proteolytic enzyme comprise a few subtilisin-like protease 309 mutation.
A. ring zone 6 replaces varient
These subtilisin 309 varients have the aminoacid sequence of the modification of subtilisin 309 wild-type amino acid sequences, wherein, modified amino acid sequence is included in a position or multipoint replacement in the following position: 193,194,195,196,197,199,200,201,202,203,204,205,206,207,208,209,210,211,212,213 or 214; Compare with wild-type subtilisin 309, this subtilisin 309 varients can reduce the absorption of insoluble substrate, and increase the hydrolysis of insoluble substrate.Preferred these proteolytic enzyme are replaced amino acid in 193,194,195,196,199,201,202,203,204,205,206 or 209 positions.More preferably 194,195,196,199 or 200 positions.
B. many rings zone replaces varient
These subtilisin 309 varients also can be the aminoacid sequences of the modification of subtilisin 309 wild-type amino acid sequences, wherein, the aminoacid sequence of modifying first, second, third, fourth or one or more zones in zone, five rings in, on one or more positions, comprise replacement.Thus, with respect to the subtilisin 309 of wild-type, subtilisin 309 variants have reduced the absorption of insoluble substrate, and have strengthened the hydrolysis of insoluble substrate.
C. the replacement of the position beyond the ring zone
In addition, the replacement of one or more wild-type subtilisins 309 can be carried out on the position beyond the division ring zone, for example 74 places in the position.If the additional replacement to subtilisin 209 only occurs in 74, preferably replace with Asn, Asp, Glu, Gly, His, Lys, Phe or Pro.More preferably His or Asp.But, can modify one or more ring positions and position 74, for example residue 97,99,101,102,105 and 121.
Subtilisin BPN ' varient and subtilisin 309 varients have further description in WO95/29979, WO95/30010 and WO95/30011 (all open in 1995.11.9), these three pieces of documents all are incorporated herein by reference.
Lipase
The lipase that is applicable to washing composition comprises the microorganism that is produced by Rhodopseudomonas, as Situ Ci Shi aeruginosa atcc 19.154 is produced those, as GB1,372,034 is described.Equally, also referring to JP-A-53-20487 (1978.2.24 is open).Other suitable lipase comprise produce by microorganism Pseudomonas fluorescens IAM1057 demonstrate those lipase of positive immunology cross reaction with lipase antibody.This lipase can trade(brand)name lipase P " Amano ", and from AmanoPharmaceutical Co.Ltd., Nagoya (Japan) is purchased, and below is referred to as " Amano-P ".Other suitable lipase is the lipase such as M1 Lipase  and Lipomax  (Gist-Brocades).Other suitable commercially available lipase comprises: Amano-CES, by ChromobacterViscosum, for example, and Chromobacter Viscosum mutation Lipolyticum NRRLB3673, the lipase that obtains is available from Toyo Jozo.Co., Tagata, Japan; ChromobacterViscosum lipase, available from U.S.Biochmical Corp., with Disoynth Co., Holland, and the lipase that obtains of gladiolus fat pseudomonas, the lipase LIPOLASE  that obtains by fetal hair (lanuginosa) pythium spp, available from Novo, referring to EP341,947, it is the preferred lipase of the present invention.Lipase variants to the superoxide enzyme stabilization is stated in WO9414951 (Novo).Equally referring to WO9205249 and RD359044.
Particularly preferred lipase is the D96L lipolytic enzyme variant of the natural lipase that obtained by the fetal hair pythium spp, as US application serial 08/341,826 is described (equally referring to patent application WO92/05249, promptly, wherein, in the natural lipase that is obtained by the fetal hair pythium spp, the aspartic acid of position 96 (D) residue becomes leucine (L).According to this nomenclature, described 96 aspartic acids (D) replace to leucine (L) and are shown in the position: D96L.).The preferred fetal hair pythium spp strain DSM 4106 that uses.
Although the report of existing a large amount of relevant lipase,, the lipase that only has the fetal hair pythium spp to obtain at present reaches the lipase that produces and has found that as main body can be used as additive is widely used in the fabric washing product in aspergillus oryzae.They can trade(brand)name Lipolase TMBe purchased from Novo Nordisk, in order to make the Lipolase detergency ability better, Novo Nordisk has prepared a large amount of varients.As described in WO92/05249, the D96L varient of natural fetal hair pythium spp can improve the removal usefulness of lard dirt, be higher than 4.4 times of wild-type lipase (content range 0.075-2.5mg protein/liter in enzyme is compared).Research Disclosure sequence number 35944 (1994.3.10 publishes, Novo Nordisk) shows that lipase variants (D96L) can add corresponding to the consumption of 0.001-100mg (5-500,000LU/ liter) lipase variants/1 liter washing lotion.
According to the present invention, the lipase content in the composition is that 50-8000LU/1 rises washing lotion, and the content of preferred varient D96L is that 100-7500LU/1 rises washing lotion, and more preferably content is that 150-5000LU/1 rises washing lotion.
In detergent composition of the present invention, in detergent composition weight, the normal add-on of lipase and/or at (cutinase) is for containing the 0.0001-2wt% organized enzyme.
Same suitable enzyme is at [EC3.1.1.50], and it is considered to a kind of special lipase, lipase that promptly need not interface activation.Adding in detergent composition states in WO-A-88/09367 (Genencor).
Cellulase
Laundry detergent compositions of the present invention can further comprise 0.001wt% at least, preferably at least about the cellulase of 0.01wt%.But the cellulase of significant quantity is enough to be used in laundry detergent compositions of the present invention.Term " significant quantity " is meant can be cleaned, remove spot, removal dirt to generations such as matrix such as fabric, tablewares, brightens, eliminates the unusual smell or increase bright improvement effect.Composition of the present invention comprises about 0.05-2wt% usually, preferably the commercially available zymin of about 0.1-1.5wt%.Cellulase of the present invention is generally comprised within the commercially available zymin, and it is 0.005-0.1Anson unit that its content should make the activity of every gram composition.The about 7-9.5 of optimal ph that preferably contains enzyme composition.
USP4,435,307 (Barbesgaard etc. 1984.3.6) disclose the cellulase of being produced by the insolen humicola lanuginosa.The example of the cellulase that other is suitable comprises the cellulase of being produced by insolen humicola lanuginosa, grey humicola lanuginosa bacterial strain through thermoidea, and the cellulase of being produced by genus bacillus or gas sporangium.Other useful cellulase is the cellulase by the hepatopancreas extraction of sea mollusk Dolabella Auricula Solander.Suitable cellulase is stated in following document: GB2,075,028 A (Nova Industri A/S); GB2, and 095,275 A (Kao Soap Co., Ltd.); With Horikoshi etc., USP3,844,890 (Rikagaku Kenkyusho).In addition, Shi Yi cellulase and its preparation method also are disclosed in the international open sequence number WO91/17243 (being disclosed in 1991.11.4, Novo NordiskA/S) of PCT.
Cellulase is known in the art, and can be provided with following trade(brand)name by supplier: Celluzyme , Endolase  and Carezyme .
For the suitability for industrialized production cellulase, preferably adopt recombinant DNA technology.But other technology that relates to the fermentation of regulating described microorganism or sudden change also can be used for guaranteeing the excessive generation of required enzyme activity.This method and technology also are known, and those skilled in the art is easy to implement.
Polymeric amide-polyamine
Detergent composition of the present invention another kind of optional but also be that preferred ingredient comprises one or more polymeric amide-polyamine fabric finishing agent.Have found that particularly when making up with modified polyamine appearance of fabrics agent of the present invention, adopt the bath water solution laundry of the detergent composition formation that comprises this combination, this material can be given fabric and a series of appearance effect of textiles.These appearance of fabrics effects can comprise, for example, improve the overall appearance effect of the fabric of washing, and minimizing balling-up and fluffing, prevent to fade etc.Do not suffered a loss or lost fewly to acceptable degree the time by the clean-up performance that laundry detergent compositions provided that has mixed this material, the polyamine-polymeric amide that is used for the compositions and methods of the invention can provide this appearance of fabrics effect.
Polymeric amide-the polyamine that comprises about 0.1-8wt% with composition weight meter composition of the present invention.Preferred composition comprises polymeric amide-polyamine of about 0.5-4wt%.More preferably composition comprises polymeric amide-polyamine of about 1-3wt%.
Being used for polymeric amide-polyamine of the present invention is corresponding to the following structural formula I, has the material of multiple substituted amide-amine unit:
Figure A9719612100201
The structural formula I in this structural formula I, R 1, R 2And R 5Be C independently of one another 1-C 4Alkylidene group, C 1-C 4Alkarylene or arylidene.Also cancellation R intactly 1, polymeric amide-polyamine is obtained by oxalic acid.
Equally in the structural formula I, R 3Be H, Epicholorohydrin base, azetidine group, epoxypropyl or dimethylamino hydroxypropyl, R 4Can be H, C 1-C 4Alkyl, C 1-C 4Alkaryl or aryl.R 4Also can be above-mentioned group and C 1-C 4The group that the oxyalkylene condensation forms.
R 1Preferred butylidene, R 2And R 5Preferred ethylidene.R 3Preferred Epicholorohydrin base.R 4Preferred H.
Used polymeric amide-the polyamine of the present invention can be by making polyamines such as diethylenetriamine, Triethylenetetramine (TETA), tetren or dipropylenetriamine and C 2-C 12Di-carboxylic acid such as oxalic acid, succsinic acid, pentanedioic acid, hexanodioic acid and diglycollic acid react and make.This material is further derived with for example Epicholorohydrin reaction.The preparation of this material has a detailed description in following document: Keim, USP2,296,116 (1960.2.23); Keim, USP2,296,154 (1960.2.23); Keim, UPS3,332,901 (1967.7.25).These documents all are incorporated herein by reference.
Being preferred for polymeric amide-polyamine of the present invention-Epicholorohydrin fabric finishing agent is following commercial goods: Hercules, Inc. trade(brand)name Kymene .Useful especially is Kymene557H  and Kymene557LX , and they are the polymeric amide-polyamine of diethylenetriamine and hexanodioic acid reaction product and the adducts of Epicholorohydrin.Other suitable material is the product available from Hercules, commodity Reten  by name and Delsette ; Available from the product of Sandoz, commodity are called Cartaretin .These commercially available polymeric amide-polyamine products are the aqeous suspension of polymer substance, comprise the solid of 12.5wt% according to appointment.
Laking agent
Optional but also be that the laking agent component that preferably is used for the present invention is selected from those and can form sedimentary material with anion surfactant.By comprising laundering of textile fabrics and textiles in this formed bath water solution of detergent composition that does not precipitate the laking agent material, this laking agent material that do not precipitate, particularly be used in combination, can provide colour fixation to fabric and textiles with modified polyamine outward appearance of the present invention agent.Other effect that these laking agent materials and modified polyamine appearance of fabrics of the present invention agent are made up comprises, for example, improves the outward appearance of laundering of textile fabrics and makes fabric colour-fast.Do not suffered a loss or lost fewly to acceptable degree the time by the clean-up performance that laundry detergent compositions provided that has mixed this material, the selected laking agent that is used for the present composition and method can provide this appearance of fabrics effect.
Be used for selected laking agent of the present invention and can be not polymeric material, oligopolymer or polymkeric substance.And then preferred laking agent is a cationic fixing agent.Usually the laking agent component that comprises about 0.1-5wt% with composition weight meter composition of the present invention.Preferred composition comprises the laking agent material of about 0.5-4wt%.The laking agent material that more preferably comprises about 1-3wt%.It is 10-100ppm that this concentration should be enough to make the concentration of laking agent in the wash water solution that is formed by laundry detergent compositions of the present invention.More preferably the concentration of laking agent is 20-60ppm, preferably 50ppm in the wash water solution.
The non-sedimentation type laking agent that is used for the present invention comprises available from CLARIANT company trade(brand)name following commercially available prod Sandofix , Sandolec  and Polymer VRN .They comprise, for example, and Sandofix SWE , Sandofix WA , Sandolec CT , SandolecCS , Sandolec Cl , Sandolec CF , Sandolec WA  and PolymerVRN .Other suitable laking agent be available from the product of Ciba-Geigy company commodity CassofixFRN-300  by name and is called the product of Tinofix EW  available from Hoechst Celanese company commodity.
Preferred non-sedimentation type laking agent is Sandofix SWE , and it has following structure:
Figure A9719612100221
Another kind of preferred non-sedimentation type laking agent is Sandofix WA , and it is the polymkeric substance with following structure:
Another kind of preferred non-sedimentation type laking agent is Cassofix FRN-300 , and it also is the polymkeric substance by following monomer preparation:
Figure A9719612100223
Be used for laking agent material of the present invention and be water-soluble substances usually.Thereby if necessary, they can aqueous solution form be used for the detergent composition preparation.
Alkyl alkoxylated suifate and/or alkyl-sulphate
Alkyl alkoxylated suifate of the present invention is a kind of following formula RO (A) mSO 3The water-soluble salt of M or acid, wherein, R is unsubstituted C 10-C 24Alkyl or have C 10-C 24The hydroxyalkyl of moieties, preferred C 12-C 18Alkyl or hydroxyalkyl, more preferably C 12-C 15Alkyl or hydroxyalkyl, A are oxyethyl group or propoxy-unit, and m is generally about 0.5-6 greater than 0,0.5-3 more preferably from about, and M is H or positively charged ion, positively charged ion for example can be metallic cation (as sodium, potassium, lithium, calcium, magnesium etc.), ammonium or replaces ammonium cation.Preferred alkyl ethoxylated sulfate and alkyl propoxylated sulphates.The specific examples of the ammonium cation that replaces comprises: ethanol-, three ethanol-, methyl-, dimethyl-, trimethylammonium-ammonium cation, quaternary ammonium cation such as tetramethyl-ammonium and lupetidine positively charged ion, and the group that obtains by alkylamine such as ethamine, diethylamine, triethylamine, or its mixture etc.Tensio-active agent is given an example: C 12-C 15Alkyl polyethoxylated (1.0) vitriol (C 12-C 15E (1.0) M), C 12-C 15Alkyl polyethoxylated (2.25) vitriol (C 12-C 15E (2.25) M) C 12-C 15Alkyl polyethoxylated (3.0) vitriol (C 12-C 15E (3.0) M) and C 12-C 15Alkyl polyethoxylated (4.0) vitriol (C 12-C 15E (4.0) M), wherein M is selected from sodium and potassium expediently.
Alkyl sulfate surfactant of the present invention is following formula ROSO 3The water-soluble salt of M or acid, wherein, R is C 8-C 18Alkyl, preferably have C 10-C 18The alkyl of moieties or hydroxyalkyl, preferred C 12-C 15Alkyl or hydroxyalkyl, more preferably C 12-C 15Alkyl or hydroxyalkyl, M is H or positively charged ion, alkali metal cation (as sodium, potassium, lithium) for example, ammonium or replace ammonium cation (as methyl-, dimethyl-, trimethylammonium-ammonium cation, quaternary ammonium cation such as tetramethyl-ammonium and lupetidine positively charged ion, and the quaternary ammonium cation that obtains by alkylamine such as ethamine, diethylamine, triethylamine, or its mixture etc.).
Commercially available alkyl alkoxylated suifate comprises the mixture of the compound with various degree of alkoxylation.For example, C 12-C 15(Shell Chemical Company, Houston TX) will comprise the molecule of 0-5 or bigger ethoxylation degree, average degree of ethoxylation=3 to polyoxyethylene (3) vitriol.The average degree of ethoxylation of the sample of giving is low more, and the content that then can be present in alkyl-sulphate in the mixture (EO=0) is high more.
Among the present invention, the total amount that is present in the alkyl-sulphate in the detergent composition not only comprises the alkyl-sulphate that adds in the composition, also comprises the alkyl-sulphate that may be present in the alkyl alkoxylated sulfate surfactant mixture.
Amine
Be used for the amine that suitable amine tensio-active agent of the present invention comprises following formula:
R 3
R 1-X-(CH 2)n-N
R 4Wherein, R 1Be C 6-C 12Alkyl; N is about 2-4, and X is a bridged group, and it is selected from: NH, CONH, COO or O, and perhaps X can not exist; R 3And R 4Be independently selected from: H, C 1-C 4Alkyl or (CH 2-CH 2-O (R 5)), R wherein 5Be H or methyl.
Preferred amine comprises:
R 1-(CH 2) 2-NH 2
R 1-O-(CH 2) 3-NH 2
R 1-C(O)-NH-(CH 2) 3-N(CH 3) 2
CH 2-CH(OH)-R 5
R 1-N
CH 2-CH (OH)-R 5Wherein, R 1Be C 6-C 12Alkyl, R 5Be H or methyl.
In preferred embodiments, amine is as shown in the formula described:
R 1-C (O)-NH-(CH 2) 3-N (CH 3) 2Wherein, R 1Be C 8-C 12Alkyl.
Particularly preferred amine is selected from: octylame, hexylamine, decyl amine, n-Laurylamine, C 8-C 12Two (hydroxyethyl) amine, C 8-C 12Two (hydroxyl sec.-propyl) amine and C 8-C 12Amido propyl-dimethyl amine and its mixture.
Detersive surfactant
The consumption of anion surfactant is at least about 0.1wt% among the present invention, preferably about 0.1-95wt%, and 1-55wt% more preferably from about, its non-limiting example comprises conventional C 11-C 18Alkylbenzene sulfonate (" LAS "), uncle's side chain and C arbitrarily 10-C 20The C of alkyl-sulphate (" AS "), following formula 10-C 18Secondary (2,3) alkyl-sulphate: CH 3(CH 2) X(CHOSO 3 -M +) CH 3And CH 3(CH 2) y(CHOSO 3 -M +) CH 2CH 3, wherein, x and the integer that (y+1) is at least about 7, preferably at least about 9, M is water-soluble cationic, particularly sodium, unsaturated vitriol such as oleyl sulfate, C 10-C 18α-sulfonated fatty acid ester, C 10-C 18Sulfation alkyl poly glucoside, C 10-C 18Alkyl alkoxy sulfate (" AE XS ", EO1-7 ethoxy sulfate particularly) and C 10-C 18Alkyl alkoxy carboxylate salt (particularly EO1-5 ethoxy carboxylate).In Overall Group's compound, also can comprise C 12-C 18Trimethyl-glycine and sultaine (sulfobetaines) (sultaines), C 10-C 18Amine oxide etc.Also can use C 10-C 20Conventional soap.Foam is more if desired, then can use side chain C 10-C 16Soap.Other conventional tensio-active agent that adopts is listed in the standard body.
Nonionogenic tenside
The consumption of nonionogenic tenside is at least about 0.1wt% among the present invention, preferably about 0.1-95wt%, and 1-55wt% more preferably from about, its non-limiting example comprises: alcohol alcoxylates (AE ' S) and alkylphenol, polyhydroxy fatty acid amide (PFAA ' S), alkyl poly glucoside (APG ' S), C 10-C 18Glyceryl ether etc.
More specifically, be applicable to that nonionogenic tenside of the present invention is the condensation product of primary and secondary fatty alcohol and about 1-25 mole epoxy hexane (AE).The alkyl chain of fatty alcohol can be straight or branched, uncle or the second month in a season, by comprising about 8-22 carbon atom.Have about 8-20 carbon atom, the more preferably from about alcohol of 10-18 carbon atom alkyl and about 1-10 mole, preferred 2-7 mole, more preferably the condensation product of the oxyethane of 2-5 mole (in every mol of alcohol) is preferred.The example of commercially available such nonionogenic tenside comprises: Tergitol TM15-S-9 (C 11-C 15The condensation product of straight chain alcohol and 9 moles of ethylene oxide) and Tergitol TM24-L-6NMW (C 12-C 14The condensation product of primary alconol and 6 moles of ethylene oxide, it has narrow molecular weight distributions), they all are purchased the Corporation from Union Carbide; Neolol TM45-9 (C 14-C 15The condensation product of straight chain alcohol and 9 moles of ethylene oxide), Neolol TM23-3 (C 12-C 13The condensation product of straight chain alcohol and 3 moles of ethylene oxide), Neolol TM45-7 (C 14-C 15The condensation product of straight chain alcohol and 7 moles of ethylene oxide), Neolol TM45-5 (C 14-C 15The condensation product of straight chain alcohol and 5 moles of ethylene oxide), they all are purchased the Company from Shell Chemcal; Kyro TMEOB (C 13-C 15The condensation product of straight chain alcohol and 9 moles of ethylene oxide), it is purchased the ﹠amp from Procter; GambleCompany; With Genapol LA030 or 050 (C 12-C 14The condensation product of alcohol and 3 or 5 moles of ethylene oxide), they are purchased from Hoechst.The preferable range of these AE nonionogenic tensides HLB value is 8-11, more preferably 8-10.Also can use and the condensation product of propylene oxide and butylene oxide ring.
Another kind of to be preferred for nonionogenic tenside of the present invention be polyhydroxy fatty acid amide surfactant, and it has following formula:
Figure A9719612100261
Wherein, R 1Be H, C 1-C 4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or its mixture, R 2Be C 5-C 31Alkyl; Z is a polyhydroxy alkyl, and it has at least 3 hydrocarbyl chains that are connected directly to the hydroxyl on the chain, or its alkoxy derivative.Representative instance is as C 12-C 18And C 12-C 14The N-methyl glucose amide, referring to U.S.5,194,639 and 5,298,636.N-alkoxyl group polyhydroxy fatty acid amide also can use, referring to US.5, and 489,393.
Being equally applicable to nonionogenic tenside of the present invention is alkyl polysaccharide, as at USP4,565,647 (1986.1.21 is issued to Llenado) described those, they have the hydrophobic grouping that contains about 6-30 carbon atom.Preferred alkyl polysaccharide has following formula:
R 2O (C nH 2nO) t(glucosyl) X
Wherein, R 2Be selected from: alkyl, alkyl phenyl, hydroxyalkyl, hydroxyalkyl phenyl and its mixture, wherein, alkyl comprises about 10-18 carbon atom, preferably about 12-14 carbon atom; N is 2 or 3, preferred 2; T is 0-about 10, preferred 0; X is about 1.3-10, preferably about 1.3-3, more preferably from about 1.3-2.7.
The polyoxyethylene of alkylphenol, polyoxypropylene, polyoxy croton condensation thing also are applicable to the nonionogenic tenside as surfactant system of the present invention, preferred polyoxyethylene condenses.Such commercially available ionic surfactant pack is drawn together Igepal TMCO-630 is available from GAF company; Triton TMX-45, X-114, X-100 and X-102 are all available from Rohm ﹠amp; Haas company.These tensio-active agents are commonly called alkyl phenolic alkoxy thing (as alkylphenol ethoxylate).
The condensation product of oxyethane and hydrophobic alkali also is applicable to the additional nonionogenic tenside as the present invention, and described hydrophobic alkali is by propylene oxide and propylene glycol condensation and form.The molecular weight of the hydrophobic part of these compounds is preferably about 1500-1800, and shows as water-insoluble.The example of this compounds comprises the Pluronic that can be purchased from BASF TM
Same suitable nonionogenic tenside as nonionic surfactant system of the present invention also comprise oxyethane and the product that forms by propylene oxide and reacting ethylenediamine between condensation product.The example of this class nonionogenic tenside comprises the Tetronic that can be purchased from BASF TM
Washing assistant
Can be randomly in composition of the present invention but also preferably comprise washing assistant, it helps to control the mineral substance in the washing water, particularly Ca and/or Mg and hardness, helps to remove from the surface graininess dirt.The content range of washing assistant is very wide, depends on the physical form of end-use and composition.The washing composition that adds washing assistant comprises the washing assistant of about 1wt% usually at least.Liquid formulations comprises about 5-50wt% usually, the washing assistant of preferred 5-35wt%.The content of washing assistant lower or higher all be not precluded within outside.For example, some detergent additives or high surface agent prescription can not have washing assistant.
The preferred washing assistant of the present invention is a citrate compound, as citric acid and its soluble salt.It is believed that the combination of polyamine appearance of fabrics of the present invention agent and lemon acids washing assistant can improve clean-up performance.Therefore, in one embodiment of the invention, detergent composition comprises about 1-10wt%, preferably about 2-8wt%, more preferably from about the citric acid washing assistant of 4-7wt%.
The washing assistant that the present invention suits can be selected from: phosphoric acid salt and polyphosphate, particularly sodium salt; Silicate comprises water-soluble salt and aqueous solid type, comprise have chain, the silicate of stratiform or three-dimensional structure and unformed solid or non-structure kind of liquid; Carbonate except that yellow soda ash or concentrated crystal soda, supercarbonate, sesquicarbonate and carbonate minerals; Silico-aluminate; Organic single, two, three and the tetracarboxylic acid hydrochlorate, particularly with the water-soluble nonsurfactant carboxylate salt of acid, sodium, potassium or alkanol ammonium salts form, and oligomeric or water-soluble low molecular weight polymeric carboxylates, comprise aliphatic series and aromatics type; And phytic acid.But these washing assistants are the boron make-up hydrochlorate also, as is used for the buffer pH value, or vitriol, particularly sodium sulfate and other are for stabilized surfactant and/or contain the very important filler of detergent composition or the carrier of washing assistant.
Can use sometimes the washing assistant mixture that is called as " builder system ", described washing assistant mixture comprises two or more conventional washing assistants usually, randomly also can comprise sequestrant, pH damping fluid or filler, though these materials of back carry out separately making an explanation usually when quantity is described in the present invention.
The regional phosphorous washing assistant of Yun Xuing is usually preferred but be not limited to an alkali metal salt, ammonium salt and the alkanol ammonium salts of Tripyrophosphoric acid legally, and Tripyrophosphoric acid is as three condensed phosphates, pyrophosphate salt, glassy polymer metaphosphate; And phosphonate.
Suitable silicate-like builder comprises alkalimetal silicate, particularly SiO 2: Na 2O ratio is 1.6: 1-3.2: 1 liquid and solid alkali metal silicates, particularly for automatic washing machine, comprise that moisture ratio is 2 solid silicate, and available from Pq Corp., trade(brand)name BRITESIL  is as BRITESIL H2O; With lamination silicate, as at USP4,664,839 (1987.5.12, H.P.Rieck) described in those.Referring to the preparation method in the following document: DE-A-3,417,649 and DE-A-3,742,043.
Synthetic crystal type ion exchange material or its hydrate are equally applicable to the present invention, as USP5,427,711 (Sakaguchi etc., 1995.6.27) described.
Suitable carbonate builders comprises alkaline-earth metal and alkaline carbonate, as German patent application sequence number 2,321,001 (1973.11.15 is open).
The aluminosilicate washing assistant is specially adapted to detergent granules, but it also can mix in the liquid.Be applicable to that of the present invention is that empirical formula is [M z(AlO 2) z(SiO 2) v]-xH 2Those of O, wherein, z and v are at least 6 integer, and the mol ratio of z and v is 1.0-0.5, and x is the integer of 15-264.Aluminosilicate can be crystallization or unformed shape, can be natural product or synthetic product.USP3,985,669 (Krummel etc., 1976,10,12) disclose a kind of method of producing aluminosilicate.Preferred synthetic crystallization type aluminosilicate ion exchange material is zeolite A, zeolite P (B), X zeolite, no matter from which kind of degree, is different from zeolite P, promptly so-called zeolite MAP.
Suitable organic washing-assisting detergent comprises multi-carboxylate's compound, comprises water-soluble nonsurfactant dicarboxylate and tricarboxylate.More general washing assistant multi-carboxylate has a plurality of hydroxy-acid groups, preferably at least 3 hydroxy-acid groups.The carboxylate salt washing assistant can be mixed with acid, part neutrality, neutrality or high alkalinity form.When being salt form, preferred as alkali such as sodium, potassium and lithium, or alkanol ammonium salts.The multi-carboxy acid salt washing agent comprises ether multi-carboxylate such as oxygen di-succinate, referring to: USP3,128,287 (Berg, 1964.4.7); USP3,635,830 (Lamberti etc., 1972.1.18); USP4,663,071 (Bush etc., " TMS/TDS " washing assistants 1987.5.5); And other ether carboxylate, comprise ring compound and alicyclic compound, as USP3,923,679; 3,835,163; 4,158,635; 4,120,874; 4,102, those described in 903.
Other suitable washing assistant is an ether hydroxypolycarboxylic acid salt, the multipolymer of maleic anhydride and ethene or vinyl methyl ether; 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid; Carboxyl methoxyl group succsinic acid; Various an alkali metal salts, ammonium salt and the substituted ammonium salt of polyacetic acid such as ethylenediamine tetraacetic acid (EDTA) and nitrotrimethylolmethane acetate; And mellitic acid, succsinic acid, More Malay acid, benzene 1,3,5-tricarboxylic acid, carboxyl methoxyl group succsinic acid and its soluble salt.
Oxygen di-succinate also is specially adapted to composition of the present invention and its combination.
Some detersive surfactant or its short chain homologue also have to help washes activity.For the prescription that takes explicitly into account, when they had the tensio-active agent ability, these materials were summarized as detersive surfactant.Preferred type to the washing assistant function is illustrated by following substances: 3, and 3-dicarboxyl-4-oxa--1,6-adipate and relevant compound are disclosed in USP4,566,984 (Bush, 1986.1.28).The succsinic acid washing assistant comprises C 5-C 20Alkyl and alkenyl succinic and its salt.The succinate washing assistant also comprises: lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinic succinate (preferably), 2-15 carbene base succinates etc.The lauryl succinate is described in EP patent application serial number 86200690.5/0,200,263 (1986.11.5 is open).Lipid acid such as C 12-C 18Monocarboxylic acid also can mix and be used as tensio-active agent/washing assistant in the composition, can add separately, or add with above-mentioned washing assistant combination, particularly adds with Citrate trianion and/or the combination of succinate washing assistant, washes activity so that additional helping to be provided.Other suitable multi-carboxylate is disclosed in USP4,144,226 (Crutchfield etc., 1979.3.13) and USP3,308,067 (Diehl, 1,967 3,7).Referring to USP3,723,322 (Diehl).
The spendable inorganic builders material of other type has following formula (M x) iCa y(CO 3) z, wherein, x and i are integer 1-15, and y is integer 1-10, and z is integer 2-25, M iBe positively charged ion, one of them is water miscible at least, satisfies the equation ∑ I=1-15(x i* M iValence state)+2y=2z, thereby formula has neutrality or " balance " electric charge.These washing assistants are also referred to as " mineral washing assistant ".
The enzyme stabilising system
The enzyme composition that contains of the present invention can randomly comprise about 0.001-10wt%, preferably about 0.005-8wt%, the enzyme stabilising system of first-selected about 0.01-6wt%.The enzyme stabilising system can be any and decontamination with the compatible stabilising system of enzyme.This system can be provided by other active ingredient self of filling a prescription, perhaps as the makers-up by detergent enzyme or the producer add all the other components separately and provide.For example, this stabilising system can comprise calcium ion, boric acid, propylene glycol, short chain carboxy acid, boronicacid and its mixture, and is designed type and the different stable problem of physical form processing according to detergent composition.
Borate substance is used in another kind of stable research.Referring to USP (Severson, 4,537,706).
The stabilising system of some cleaning composition also comprises the about 10wt% of 0-, and preferably the chlorine scavenger of about 0.01-6wt% adds this scavenging agent and is used for preventing to be present in the chlorine bleaching composition attack enzyme of many supplied water and to make enzyme deactivation, particularly under the alkali condition.
Also can use antioxidant such as carbamate, ascorbate salt etc., organic amine such as ethylenediamine tetraacetic acid (EDTA) (EDTA) or its an alkali metal salt, monoethanolamine (MEA) and its mixture.Similarly, concrete enzyme inhibition system can mix, thereby makes different enzymes have maximum consistency.If necessary, also can use other conventional scavenging agent such as sulphite, 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 its mixture.
Macromolecule decontaminant
Known macromolecule decontaminant (hereinafter referred to as " SRA " or " SRA ' S ") can randomly be used for detergent composition of the present invention.If adopt, composition comprises about 0.01-10.0wt% usually, preferred 0.1-5wt%, more preferably SRA ' S of 0.2-3.0wt%.
SRA ' S can comprise various charged as anionic monomer unit or cationic monomer unit (seeing USP4,956,447), and uncharged monomeric unit, and its structure can be straight chain, side chain or star.They can comprise the end-blocking part that can control molecular weight especially effectively or change physics or some surface active property.Structure can be adapted to different fibers or type of textiles with charge distribution, and is adapted to various washing composition or washing composition interpolation product.
Suitable SRA ' S comprises the sulfonated products of the ester oligomer of basic straight chain; described oligopolymer is made up of terephthaloyl oligomer ester skeleton and the multiple unit of oxygen connection alkylidene group oxygen basic weight, as USP4, and 968; 451 (1990.11.6, J.J.Scheibel and E.P.Gosselink).Referring to, USP4,7l1,730 (1987.12.8, Gosselink etc.), for example, by gathering those products that (ethylene glycol) methyl ether, DMT, PG and poly-(ethylene glycol) (" PEG ") obtain by transesterification/oligomerization.Part and whole end capped oligomer esters of negatively charged ion, USP4,721,580 (1988.1.26, Gosselink), as by ethylene glycol (" EG "), PG, DMT and 3, the oligopolymer of 6-two oxa-s-8-hydroxyl perfluorooctane sulfonate; The end capped block polyester oligomeric compound of nonionic, USP4,702,857 (1987.10.27, Gosselink), for example, produce by the PEG of DMT, methyl blocking and EG and/or PG, perhaps those of the PEG of DMT, EG and/or PG, methyl blocking and dimethyl-5-sulfoisophthalic acid sodium combination results; And negatively charged ion, the particularly end capped terephthalate of sulfo group aroyl, USP4,877,896 (1989.10.31, Maldonado, Gosselink etc.).
SRA ' S also comprises the simple copolymerization block of ethylene glycol terephthalate or propylene glycol ester terephthalate and polyethylene oxide or poly(propylene oxide) terephthalate, referring to USP3, and 959,230 (Hays, 1976.5.25) and USP3,893,929 (1975.7.8, Basadur); Derivatived cellulose such as hydroxy ethers cellulose polymer compound, with trade(brand)name METHOCEL available from Dow company; C 1-C 4Alkylcellulose and C 4Hydroxy alkyl cellulose; Referring to USP4,000,093 (Nicol etc., 1976.12.28).Suitable SRA ' SFeature be that poly-(vinyl ester) hydrophobic section comprises poly-(vinyl ester) as C 1-C 6Vinyl ester, preferred poly-(vinyl-acetic ester) grafts to the graft copolymer that forms on the polyoxyalkylene skeleton.Referring to asking 0219048 (Kud etc., 1987.4.22 is open) among the EP.Commercially available example comprises: SOKALAN SRA ' S, as SOKALAN HP-22, available from BASF AG of Germany.Other SRA ' S is the polyester with the repeating unit that contains 10-15wt% ethylene glycol terephthalate and 90-80wt% polyoxyethylene terephthalate, is 300-5 by molecular-weight average, and 000 polyoxyethylene glycol obtains.Commercially available example comprises available from the ZELCON5126 of Dupont with available from the MILEASE T of ICI.
USP5,415,807 (Gosselink, Pan, Kellett and Hall, 1995.5.16).Be used for above-mentioned SRA suitable monomer and comprise 2-(2-hydroxyl-oxethyl)-ethyl sulfonic acid sodium, DMT, dimethyl-5-sulfoisophthalic acid sodium, EG and PG.
SRA ' the S of other classification comprises (I) nonionic terephthalate, uses the vulcabond coupler to be connected on the macromolecule ester structure, referring to USP4, and 201,824 (Violland etc.) and USP4,240,918 (Lagasse etc.); (II) has the SRA ' of carboxylic end group S, by benzenetricarboxylic anhydride being added to known SRA ' SOn, terminal hydroxyl is changed into the benzenetricarboxylic acid ester.Adopt the catalyzer of suitably selecting, the carboxylic acid by isolating benzenetricarboxylic anhydride but not, make benzenetricarboxylic anhydride form the key that is connected with polymer ends by opening anhydride bond.Nonionic SRA ' SOr negatively charged ion SRA ' SAll can be used as raw material, as long as have can esterified hydroxyl end groups for it.Referring to USP4,525,524 (Tung etc.); (III) connects the SRA ' of kind based on the urethanum of negatively charged ion terephthalic acid S, referring to USP4,201,824 (Violland etc.); (IV) has as vinyl pyrrolidone and/or dimethylaminoethyl methacrylate monomeric poly-(caprolactam) and related copolymers, comprises nonionic and cationic polymers, referring to USP4, and 579,681 (Ruppert etc.); (V) grafts on the sulfonated polyester Acrylic Acid Monomer and makes except that from the graft copolymer the SOKALAN type of BASF; These SRA ' SSimilar with known ether of cellulose, have the active and antiredeposition activity of decontamination, referring to EP279,134A (1988, Rhone-Poulenc Chemie); (VI) vinyl monomer such as vinylformic acid and vinyl-acetic ester graft to the grafts that forms on protein such as the casein, referring to EP457, and 205A (BASF, 1991); The polyester-polyamide SRA ' that (VII) makes by condensation hexylene glycol, hexanolactam and polyoxyethylene glycol S, especially for handling polyamide fabric, referring to DE2,335,044 (Bevan etc., Unilever N.V., 1974).The SRA ' that other is useful SIn following document, state: USP4,240,918,4,787,989,4,525,524 and 4,877,896.
Clay soil remover/anti redeposition agent
Composition of the present invention also optionally comprises the water-soluble ethoxylated amine with clay soil removal and antiredeposition performance.The liquid detergent composition that comprises these compounds comprises the water-soluble ethoxylated amine of about 0.01-5wt% usually.
Most preferred stain remover and anti redeposition agent are the ethoxylation tetren.The example of ethoxylated amine is at USP4, and 597,898 (VanderMeer states in 1986.7.1).Another organizes preferred clay soil remover and anti redeposition agent is a positively charged ion, and it is disclosed in EP-A111,965 (Oh and Gosselink, 1984.6.27).Other adoptable clay soil remover/anti redeposition agent comprises ethoxylated amine polymer, is disclosed in EP-A111,984 (Gosselink, 1984.6.27); Amphoteric ion polymer is disclosed in EP-A112,592 (Gosselink, 1984.7.4); And amine oxide, be disclosed in USP4,584,744 (Connor, 1985.10.22).Other clay soil remover well known in the art and/or anti redeposition agent also can be used in the present composition.Referring to USP4,891,160 (VanderMeer, 1990.1.2) and WO95/32272 (1995.11.30).Another kind of preferred anti redeposition agent comprises carboxymethyl cellulose (CMC) material.These materials are known in the art.
Randomly, being used for preferred anti redeposition agent of the present invention is the alkoxylate season diamines with following general formula:
Figure A9719612100321
Wherein, R is selected from the C of straight or branched 2-C 12Alkylidene group, C 3-C 12Hydroxy alkylidene, C 4-C 12Alkyl sub-dihydroxy, C 8-C 12Dialkyl group arylidene, [(CH 2CH 2O) qCH 2CH 2]-and [CH 2CH (OH) CH 2O-(CH 2CH 2O) qCH 2CH (OH) CH 2]-, wherein, q is about 1-100.Each R 1Be independently from each other C 1-C 4Alkyl, C 7-C 12Alkylaryl or A.A has following formula:
Figure A9719612100322
Wherein, R 3Be selected from H or C 1-C 3Alkyl, n are about 5-100, and B is selected from H, C 1-C 4Alkyl, acetyl or benzoyl base; X is a water soluble anion.
In preferred embodiments, R is selected from C 4-C 8Alkylidene group, R 1Be selected from C 1-C 2Alkyl or C 2-C 3Hydroxyalkyl, A is:
Figure A9719612100323
Wherein, R 3Be selected from H or methyl, n is about 10-50.
In another preferred embodiment, R is straight or branched C 6, R 1Be methyl, R 3Be H, n is about 20-50.
Another kind of optional but preferred anti redeposition agent is the alkoxylate season polyamines of following formula:
Figure A9719612100331
Wherein, R is selected from the C of straight or branched 2-C 12Alkylidene group, C 3-C 12Hydroxy alkylidene, C 4-C 12Alkyl sub-dihydroxy, C 8-C 12Dialkyl group arylidene, [(CH 2CH 2O) qCH 2CH 2]-and [CH 2CH (OH) CH 2O-(CH 2CH 2O) qCH 2CH (OH) CH 2]-, wherein, q is about 1-100.R 1If there is each R 1Be independently from each other C 1-C 4Alkyl, C 7-C 12Alkylaryl or A.Can there be R on some nitrogen-atoms 1Yet at least three nitrogen-atoms are had following formula by quaternized A:
Figure A9719612100332
Wherein, R 3Be selected from H or C 1-C 3Alkyl, n are about 5-100, and B is selected from H, C 1-C 4Alkyl, acetyl or benzoyl base; M is about 1-4, and X is a water soluble anion.
In preferred embodiments, R is selected from C 4-C 8Alkylidene group, R 1Be selected from C 1-C 2Alkyl or C 2-C 3Hydroxyalkyl, A is:
Figure A9719612100333
Wherein, R 3Be selected from H or methyl, n is about 10-50, and m is 1.
In another preferred embodiment, R is straight or branched C 6, R 1Be methyl, R 3Be H, n is about 20-50, and m is 1.
These anti redeposition agents can be according to USP4, and 664,848 listed method or employings well known to a person skilled in the art that method is synthetic.
Be used to prepare laundry detergent compositions and comprise about 0.1-10wt%, preferably the deposition agent again of about 0.4-5wt%.
Macromolecule dispersing agent
Composition of the present invention preferably comprises the macromolecule dispersing agent of about 0.1-7wt%, particularly when having zeolite and/or layered silicate washing assistant.Suitable macromolecule dispersing agent comprises polymeric polycarboxylic acid salt and polyoxyethylene glycol, can certainly adopt well known in the art those.It is believed that, though be not bound by any theory, macromolecule dispersing agent with other washing assistant (comprising the lower molecular weight multi-carboxylate) when being used in combination, by crystalline growth suppress, particulate fouling removes peptization and anti-redeposition, and strengthened washing assistant usefulness.
Polymeric polycarboxylic acid salt material can preferably carry out polymerization or copolymerization with its sour form by making suitable unsaturated monomer.Can be aggregated the unsaturated monomer acid that forms suitable polymeric polycarboxylic acid salt comprises: vinylformic acid, toxilic acid (or maleic anhydride), fumaric acid, methylene-succinic acid, equisetic acid, methylfumaric acid, citraconic acid, methylene radical propanedioic acid.In polymeric polycarboxylic acid salt, exist the monomer fragment comprise non-hydroxy-acid group such as vinyl methyl ether, vinylbenzene, ethene etc. to suit, as long as this segmental amount is no more than about 40wt%.
Shi Yi polymeric polycarboxylic acid salt can be made by vinylformic acid especially.Being used for this acrylic acid based polymer of the present invention is the acrylic acid water-soluble salt of polymeric.The molecular-weight average of this acid-based polymer is about 2,000-10, and 000, preferred about 4,000-7,000, more preferably from about 4,000-5,000.The example of the water-soluble salt of this acrylate copolymer comprises an alkali metal salt, ammonium salt and substituted ammonium salt.Such soluble polymer is known.Such polyacrylate is used for detergent composition and is disclosed in for example USP3,308,067 (Diehl, 1967.3.7).
Vinylformic acid/maleic copolymer also can be used as preferred dispersing agent/anti redeposition agent component.This material comprises the water-soluble salt of the multipolymer of vinylformic acid and toxilic acid.The molecular-weight average of this acid type multipolymer is about 2,000-100, and 000, preferred about 5,000-75,000, more preferably from about 7,000-65,000.The ratio of vinylformic acid and toxilic acid is generally about 30 in this multipolymer: 1-1: 1, preferred about 10: 1-2: 1.The example of the water-soluble salt of this vinylformic acid/maleic acid comprises an alkali metal salt, ammonium salt and substituted ammonium salt.Such solubility vinylformic acid/maleic acid is disclosed in EP-A66915 (1982,12.15) and EP193,360 (1986.9.3), and the document has also been described the polymkeric substance that comprises the hydroxypropyl acrylate.Another kind of useful dispersion agent comprises the terpolymer of toxilic acid/vinylformic acid/vinyl alcohol.This material also is disclosed in EP193, and 360, for example, comprise the terpolymer of 45/45/10 toxilic acid/vinylformic acid/vinyl alcohol.
Another kind of adoptable polymer substance is polyoxyethylene glycol (PEG).PEG can demonstrate dispersing agent performance, also can be used as clay soil remover-anti redeposition agent.The typical molecular weight that is used for this purposes is about 500-100,000, and preferably about 1,000-50,000, more preferably from about 1,500-10,000.
Polyaspartic acid salts and polyglutamic acid dipersant also can use, and especially are used in combination with zeolite builders.Dispersion agent, as aspartate preferred molecular weight (on average) about 10,000.
Whitening agent
Any white dyes or other whitening agent well known in the art all can mix in the detergent composition of the present invention, and its content is generally about 0.01-1.2wt%.Be used for the commercially available white dyes of the present invention and can be divided into some groups, include but not limited to the derivative of following compounds: toluylene, pyrazoline, tonka bean camphor, carboxylic acid, methyne cyanine, dibenzothiophene-5,5-dioxide, pyrroles, 5 yuan and 6 yuan of ring heterocyclic compounds and other reagent.The example of this whitening agent is disclosed in " production of white dyes and application ", and (M.Zahradnik is by JohnWiley ﹠amp; Sons publishes, New York, 1982).
The selected white dyes specific examples that is used for the present composition is in USP4,790,856 (Wixon, 1988.12.13) identical those.These whitening agent comprise the PHORWHITE whitening agent series from Verona.Other whitening agent that is disclosed in the document comprises: TinopalUNPA, Tinopal CBS and Tinopal 5BM; Be purchased from Ciba-Geigy; Artic WhiteCC and Artic White CWD, 2-(4-styryl-phenyl)-2H-naphtho-[1,2-d] triazole; 4,4 '-two-(1,2,3-triazoles-2-yl) toluylene; 4,4 '-two (styryl) biphenyl; And aminocoumarin.Referring to USP3,646,015 (1972.2.29, Hamilton).
Dye transfer inhibitor
Composition of the present invention also can comprise one or more and can suppress dyestuff in the cleaning course effectively and be transferred to material on the another kind of fabric from a kind of fabric.Usually, this dye transfer inhibitor comprises multipolymer, manganese phthalocyanine, peroxidase and its mixture of polyvinyl pyrrolidone polymers, polyamine N-oxide pllymers, N-vinyl pyrrolidone and N-vinyl imidazole.If you are using, comprise about 0.01-10wt% usually, preferably about 0.01-5wt%, the more preferably from about dye transfer inhibitor of 0.05-2wt% with the composition weight meter composition.
More particularly, be preferred for polyamine N-oxide pllymers of the present invention and comprise the unit with following structural formula: R-A X-P; Wherein P is a polymerizable unit, and the N-O group can be connected on it, or the N-O group can form the part of polymerizable unit, or the N-O group can be connected on two unit; A is a kind of in the following structure :-NC (O)-,-C (O) O-,-S-,-O-,-N=; X is 0 or 1; R is aliphatic group, ethoxylation aliphatic group, aromatic group, heterocycle or alicyclic group or its any combination, and the N-O group can be connected on it, or the N-O group is the part of these groups.Preferred polyamine N-oxide compound be R be heterocyclic those, as pyridine, pyrroles, imidazoles, tetramethyleneimine, piperidines and its derivative.
The N-O group can be represented by the following formula structure:
Be used for the most preferred polyamine N-oxide of detergent composition of the present invention and be poly-(4-vinylpridine-N-oxide compound), its molecular-weight average is about 50,000, and the ratio of amine and amine n-oxide is 1: 4.
The multipolymer of N-vinyl pyrrolidone and N-vinyl imidazole polymkeric substance (being referred to as " PVPVI " class) also is preferred for the present invention.The molecular weight of PVPVI is preferably 5,000-1, and 000,000, more preferably 5,000-200,000, first-selected 10,000-20,000.(average molecular weight range is by light scattering measurement, as Barth etc., and chemical analysis, 113 volumes, " modernism of polymer property " (Modern Methods of PolymerCharcterization), the document is incorporated herein by reference).The N-vinyl imidazole of PVPVI multipolymer and the mol ratio of N-vinyl pyrrolidone are generally 1: 1-0.2: 1, preferred 0.8: 1-0.3: 1, more preferably 0.6: 1-0.4: 1.These multipolymers can be straight or branched.
Detergent composition of the present invention also can adopt a kind of Polyvinylpyrolidone (PVP) (" PVP "), and its molecular-weight average is about 5,000-400, and 000, preferred about 5,000-200,000, more preferably from about 5,000-about 50,000.PVP is known in the art, for example, referring to, EP-A-262,897 and EP-A-256,696, they all are incorporated herein by reference.The composition that comprises PVP also can comprise polyoxyethylene glycol (" PEG "), and its molecular-weight average is about 500-100, and 000, preferred about 1,000-10,000.Carrying PEG in washings and the ratio of PVP with ppm is about 2: 1-50: 1, preferred about 3: 1-10: 1.
Detergent composition of the present invention also can randomly comprise the hydrophilic white dyes of some type of about 0.005-5wt%, and it also has dye transfer simultaneously and suppresses active.If you are using, composition will preferably comprise the white dyes of about 0.01-1wt%.
When in following formula, R 1Be phenylamino, R 2Be the N-2-dihydroxy ethyl, M is positively charged ion such as sodium, whitening agent be 4,4 '-two [(4-phenylamino-6-(N-2-dihydroxy ethyl)-s-triazine-2-yl) amino]-2,2 '-diphenylethyllene disulfonic acid and disodium salt.This specific whitening agent can be purchased with trade(brand)name Tinopal-UNPA-GX from Ciba-Geigy company.Tinopal-UNPA-GX is a kind of hydrophilic white dyes that preferably is used for detergent composition of the present invention.
When in following formula, R 1Be phenylamino, R 2Be N-2-hydroxyethyl-N-2-methylamino, M is positively charged ion such as sodium, whitening agent be 4,4 '-two [(4-phenylamino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl) amino]-2,2 '-the diphenylethyllene disulfonic acid disodium salt.This specific whitening agent can be purchased with trade(brand)name Tinopal-5BM-GX from Ciba-Geigy company.
When in following formula, R 1Be phenylamino, R 2Be morpholino, M is positively charged ion such as sodium, whitening agent be 4,4 '-two [(4-phenylamino-6-morpholino-s-triazine-2-yl) amino]-2,2 '-the diphenylethyllene disulfonic acid, sodium salt.This specific whitening agent can be purchased with trade(brand)name Tinopal-AMS-GX from Ciba-Geigy company.
Sequestrant
Detergent composition of the present invention also can randomly comprise one or more iron and/or manganese sequestrant.This sequestrant can be selected from: the aromatic chelating agent of aminocarboxylate, amino phosphonates do, multiple functionalized replacement and its mixture.Although be not bound by any theory, the agency part that it is believed that these materials comes from them can be by forming the soluble chelating thing and remove de-iron and mn ion from washing soln.
Aminocarboxylate as optional sequestrant comprises edetate, N-hydroxyethyl ethylene diamine triacetate, nitrilotriacetic acid(NTA) salt, ethylenediamine tetrapropionic acid(EDTP) salt, triethylenetetraaminehexaacetic acid salt, diethylentriamine pentacetate and ethanol Diglycocol, its an alkali metal salt, ammonium salt and substituted ammonium salt and its mixture.
In the time can allowing in detergent composition that the total phosphorus of low levels exists at least, amino phosphonates do also is suitable for the sequestrant as the present composition, comprises ethylene diamine four (methylene phosphonic acid salt) (DEQUEST).Preferred these amino phosphonates do do not comprise alkyl or the alkenyl that surpasses 6 carbon atoms.
The aromatic chelating agent of multifunctional replacement also can be used for composition of the present invention.Referring to USP3,812,044 (Connor etc., 1974.5.21).The preferred acid type compound of the type be the dihydroxyl disulfobenzene as 1,2-dihydroxyl-3,5-disulfobenzene.
Being preferred for biodegradable cheating agent of the present invention is ethylenediamine disuccinate (" EDDS "), [S, S] isomer particularly, and as USP4,704,233 (Hartman andPerkins, 1987.11.3) described.
Composition of the present invention also can comprise water-soluble methylglycine oxalic acid (MGDA) salt (or sour form) as sequestrant or totally one washing assistant, and uses with for example insoluble washing assistant such as zeolite, layered silicate etc.
If necessary, detergent composition of the present invention comprises the sequestrant of about 0.1-15wt% usually.More preferably, if necessary, detergent composition of the present invention comprises the sequestrant of about 0.1-3.0wt% usually.
Suds suppressor
Can mix the compound that reduces or suppress foam formation in the composition of the present invention.Foam inhibition at USP4, in 489,455 and 4,489,574 described so-called " the high density cleaning courses " and the meaning that in European front-loading washing machine, has particularly important.
Have multiple material to can be used as suds suppressor, suds suppressor is known in the art.For example, referring to Kirk Othmer encyclopedia of chemical technology (Kirk Othmer Encyclopedia ofChemical Technology), the third edition, the 7th volume, 430-447 page or leaf (John Wiley ﹠amp; Sons, Inc., 1979).A significant especially class suds suppressor comprises unary fatty acid and its soluble salt.Referring to USP2,954,347 (Wayne St.John, 1960.9.30).Unary fatty acid as suds suppressor has 10-24 carbon atom usually, the alkyl of preferred 12-18 carbon atom.Suitable salt comprises an alkali metal salt such as sodium, potassium, lithium salts and ammonium salt and alkanol ammonium salts.
Detergent composition of the present invention also can comprise the nonsurfactant suds suppressor.Specific examples is: high-molecular-weight hydrocarbons such as paraffinic hydrocarbons, fatty acid ester (as triglyceride), the fatty acid ester of monohydroxy-alcohol, aliphatic C 18-C 40Ketone (as stearone) etc.Other suds suppressor comprise N-alkylation aminotriazine as three to six alkyl melamines or two to the tetraalkyl diammonium chloride for triazine, it is the product by the reaction of cyanuric acid and following compound: the two or three moles of uncles or secondary amine, propylene oxide and the single stearyl phosphoric acid ester/salt that comprise 1-24 carbon atom.As single stearyl-alcohol phosphoric acid ester and single stearyl-two basic metal (as potassium, sodium and lithium) phosphoric acid salt and phosphoric acid ester.Hydrocarbon such as paraffinic hydrocarbons and halogenated paraffin can use by liquid form.Hydrocarbon suds suppressor such as USP4,265,779 (Gandolfo etc., 1981.5.5) described.
Another kind of preferred nonsurfactant suds suppressor comprises silicone suds suppressor.This class suds suppressor comprises use organopolysiloxane oil, as polydimethylsiloxane, the dispersion liquid of organopolysiloxane oil or resin or emulsion, and the combination of organopolysiloxane and silica dioxide granule, wherein, organopolysiloxane by chemisorption to silicon-dioxide or be fired on the silicon-dioxide.Silicone suds suppressor is well known in the art, for example, is disclosed in USP4, and 265,779 (1981.5.5, Gandolfo etc.) and EP application serial 89307851.9 (1990.2.7 is open, Starch, M.S.).
Other silicone suds suppressor is disclosed in USP3, and 455,839, this patent relates to by mixing a small amount of polydimethylsiloxane fluid makes the composition and the method for aqueous solution skimming.
The mixture of siloxanes and silanization (silanated) silicon-dioxide is at German Patent DOS2, states in 214,526.Silicone antifoam agent in the granular detergent composition and Foam Control be at USP3,933,672 (Bartolotta etc.) and USP4, and 652,392 (Baginski etc. state in 1987.3.24).
Other suds suppressor that is used for the present invention comprises the mixture of secondary alcohol (as the 2-alkyl chain triacontanol) and this alcohol and silicone oil, as is disclosed in USP4,798,679,4,075,118 and EP150, and 872 siloxanes.Secondary alcohol includes C 1-C 16The C of chain 6-C 16Alkyl alcohol.Preferred alcohol is 2-butyl octanol, and it can be purchased with trade(brand)name ISOFOL12 from Condea.The mixture of secondary alcohol can be purchased with trade(brand)name ISALCHEM123 from Enichem.The mixture suds suppressor comprises usually with weight ratio 1: 5-5: the mixture of alcohol+siloxanes of 1.
Alkane hydrogen base polycarboxylate
Alkoxylate multi-carboxylate is used for the present invention so that additional degreasing performance to be provided as those that are made by polyacrylate.This material is stated in WO91/08281 and PCT90/01815 (page 4), and the document is incorporated herein by reference.From chemically, the every 7-8 of these a materials acrylic acid units comprises the polyacrylate with an oxyethyl group side chain.Side chain has following formula-(CH 2CH 2O) m(CH 2) nCH 3, wherein m is 2-3, n is 6-12.The side chain ester is connected on the polyacrylic acid " skeleton ", and a kind of " comb shape " polymer-type structure is provided.Molecular weight can change, but is generally about 2000-50,000.Mixture of the present invention can comprise the alkoxylate polycarboxylate of about 0.05-10wt%.
Fabric softener
In composition of the present invention, various washings (through-the-wash) fabric softener that can randomly comprise about 0.5-10wt%, in fabric washing, can provide fabric sofetening usefulness, described softening agent is special in USP4,062,647 (Storm and Nirschl, 1977.12.13) the deoil terre verte behind the dirt and other softening agent clays known in the art of described imperceptible montmorillonite.The clay softening agent can be used in combination with amine and cationic softener, as USP4,375,416 (Crisp, 1983.3.1) and USP4,291,071 (Harris etc., 1981.9.22) described.
Spices
The spices and the flavour ingredient that are used for the present composition and method comprise various natural and synthetic chemistry compositions, and it includes but not limited to: aldehyde, ketone, ester etc.Equally, comprise various natural extracts and essence, it can comprise the compounding mixture of each composition, as orange oil, lemon oil, rose extract, lavender, Moschus, patchouli, balm matter essence, santal oil, pine tar, cdear wet goods.Final spices can comprise each extremely complicated mixture of ingredients.Detergent composition of the present invention comprises the final spices of about 0.01-2wt% usually, and various fragrance components can account for about 0.0001-90% of final flavor compositions weight.
The non-limiting example that is used for fragrance component of the present invention comprises: 7-ethanoyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl-naphthalene; The methyl ionone; γ-methyl ionone; Vertofix coeur; Methyl dihydro jasmonate; Methyl 1,6,10-trimethylammonium-2,5,9-cyclododecatriene (cyclododecatrien)-1-base ketone; 7-ethanoyl-1,1,3,4,4,6-hexamethyl naphthane; 4-ethanoyl-6-the tertiary butyl-1,1-two-methyl indane; The p-hydroxybenzene butanone; Benzophenone; Methyl betanaphthyl ketone; 6-ethanoyl-1,1,2,3,3,5-hexamethyl indane; 5-ethanoyl-3-sec.-propyl-1,1,2,6-tetramethyl-indane; The 1-lauric aldehyde, 4-(4-hydroxy-4-methyl amyl group)-3-tetrahydrobenzene-1-carboxylic formaldehyde; 7-hydroxyl-3,7-dimethyl octanal; 10-hendecene-1-aldehyde; Dissident's thiazolinyl cyclohexyl carboxylic formaldehyde; The formyl radical tristane; The condensation product of laurine and methyl o-aminobenzoate; The condensation product of laurine and indoles, the condensation product of phenylacetic aldehyde and indoles; 2-methyl-3-(to tert-butyl-phenyl) propionic aldehyde; Vanillal; Piperonylaldehyde; Hexyl cinnamic aldehyde; Amyl cinnamic aldehyde; 2-methyl-2-(p-isopropyl phenyl) propionic aldehyde; Tonka bean camphor; The γ decalactone; Cyclopentadecane lactide (cyclopentadecanolide); 16-hydroxyl-palmitoleic acid lactone; 1,3,4,6,7,8-six hydrogen-4,6,6,7,8,8-hexamethyl pentamethylene-γ-2-chromene; The 2-Naphthol methyl ether; Dodecane hydrogen-3a, 6,6,9a-tetramethyl-naphtho-[2,1-b] furans; Cypress camphor, 5-(2,2,3-front three basic ring penta-3-thiazolinyl)-3-methylpent-2-alcohol; 2-ethyl-4-(2,2,3-trimethylammonium-3-cyclopentenes-1-yl)-2-butylene-1-alcohol; Caryophyllenol; The tricyclic decenyl propionic ester; The tricyclo decene yl acetate; Benzyl salicylate, cedryl acetate; With right-(tertiary butyl) cyclohexyl acetic acid ester.
Particularly preferred fragrance material is that those can provide the finished product composition that the comprises cellulase material with high wind flavor improvement effect.These spices include but not limited to: hexyl cinnamic aldehyde; 2-methyl-3-(right-tert-butyl-phenyl)-propionic aldehyde; 7-ethanoyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl-naphthalene; Benzyl salicylate, 7-ethanoyl-1,1,3,4,4,6-hexamethyl naphthane; To (tertiary butyl) cyclohexyl acetic acid ester; Methyl dihydro jasmone; The 2-Naphthol methyl ether; Methyl betanaphthyl ketone; 2-methyl-2-(p-isopropyl phenyl) propionic aldehyde; 1,3,4,6,7,8-six hydrogen-4,6,6,7,8,8-hexamethyl pentamethylene-γ-2-chromene; Dodecane hydrogen-3a, 6,6,9a-tetramethyl-naphtho-[2,1-b] furans; Aubepine; Tonka bean camphor; Cypress camphor; Vanillin food grade,1000.000000ine mesh; The cyclopentadecane lactide; The tricyclo decene yl acetate; The tricyclic decenyl propionic ester.
Other fragrance material comprises the volatile oil from various sources, thermosetting resin and resin, these sources include but not limited to: Surinam balsam, frankincense thermosetting resin, Styrox, labdanum resin, Semen Myristicae, Oleum Cinnamomi, styrax resinoid, coriander, Lavandula hybrida.Other flavor chemistry material comprises phenylethyl alcohol, Terpineol 350, coriandrol, linalyl acetate, Geraniol, vernol, 2-(1,1-two-methylethyl)-adnoral acetate, jasmal and oxymethoxyallylbenzene.Carrier such as diethyl phthalate also can be used in the whole flavor compositions.
Other composition
Various other compositions that are used for detergent composition all can be used for composition of the present invention, comprise other activeconstituents, carrier, hydrotropic solvent, processing aid, dyestuff or pigment, liquid formulations with solvent, bar composition with solid packing etc.High if desired foam can add suds booster, as C in composition 10-C 16Alkanolamide, add-on is 1-10wt% usually.C 10-C 14Monoethanolamine and diglycollic amide demonstrate and are typical such suds booster.It is very favorable using this suds booster with high foaming surfactant auxiliary agent such as above-mentioned amine oxide, trimethyl-glycine and sultaine.If necessary, water soluble magnesium and/or calcium salt such as magnesium chloride, sal epsom, calcium chloride, calcium sulfate etc. can add provides additional foaming effect, and strengthens degreasing effect, and its add-on is generally 0.1-2%.
(trade mark SIPERNAT D10 is DeGussa) with the proteolysis enzyme solution (C that comprises 3-5wt% for porous hydrophobic silicon-dioxide 13-C 15Ethoxylated alcohol (EO7) nonionogenic tenside) mixes.Usually, enzyme/surfactant soln is 2.5 times of silica weight.With the powder that forms by dispersed with stirring in silicone oil (spendable various silicone oil range of viscosities are 500-12,500).With the silicone oil dispersion liquid emulsification that forms or add in the final detergent base.Like this, be used for washing composition after various compositions such as above-mentioned enzyme, photosensitizers, dyestuff, fluorescent agent, fabric finishing agent and hydrolyzable tensio-active agent are " protected ", comprise the liquid laundry detergent composition.
Liquid detergent composition can comprise water and other solvent as carrier.Low molecular weight primary or secondary alcohol are to suit as methyl alcohol, ethanol, propyl alcohol and Virahol.Preferred monohydroxy-alcohol is used for solubilizing surfactant, but polyvalent alcohol is as also being used by the alcohol that comprises 2-6 carbon atom and 2-6 hydroxyl (as 1, ammediol, ethylene glycol, glycerine and 1,2-propylene glycol).Composition can comprise 5-90%, the carrier of preferred 10-50%.
The preferred preparation like this of detergent composition of the present invention: be used for the aqueous cleaning operating process, the pH value of washing water is about 6.5-11, preferably about 7.5-10.5.Liquid dishwashing is with the preferred 6.8-9.0 of pH value of washing composition.Clothing is generally 9-11 with the pH value of product.Be used to control the pH value and comprise use damping fluid, alkali, acid etc. in the technology of recommending use range, they are well known to a person skilled in the art.
Liquid washing agent
The production of heavy duty liquid detergent compositions, the product that particularly is designed for fabric washing comprises the nonaqueous carrier medium, and they can prepare according to the described method of following document: USP4,753,570; 4,767,558; 4,772,413; 4,889,652; 4,892,673; GB-A-2,158,838; GB-A-2,195,125; GB-A-2,195,649; USP4,988,462; USP5,266,233; EP-A-225,654 (6/16/87); EP-A-510,762 (10/28/92); EP-A-540,089 (5/5/93); EP-A-540,090 (5/5/93); USP4,615,820; EP-A-565,017 (10/13/93); EP-A-030,096 (6/10/81), all these documents all are incorporated herein by reference.This composition can comprise various stable suspersions in particulate stain removal composition wherein.Thereby this non-aqueous composition comprises liquid phase (LIQUID pHASE) and randomly but preferred a kind of solid phase (SOLID pHASE), the reference of quoting and below description in will be described in more detail.The agent of modified polyamine appearance of fabrics is mixed in the composition, its content and method such as other laundry detergent compositions of above-mentioned production.
Composition of the present invention can be used for forming the washing that aqueous cleaning solution is used for fabric.Usually, the said composition of significant quantity is added in the water, preferably add in the common fabric automatic washing machine, to form moisture laundry solution.Then, the aqueous cleaning solution of formation is contacted with the fabric of desire washing, preferably under agitation contact.
The liquid detergent composition of significant quantity adds to and forms aqueous cleaning solution in the water, and this significant quantity is enough to form about 500-7, the aqueous solution of the composition of 000ppm.More preferably form about 800-3, the aqueous solution of the composition of 000ppm.
Following embodiment is used to illustrate the present invention, but is not the qualification to protection domain of the present invention.Except as otherwise noted, all umber, percentage ratio and ratios all are expressed as weight percentage.
In the following embodiments, all content are benchmark in the weight % of composition all.
The embodiment I
Preparation PEI600E 20
Carry out ethoxylation in one 2 gallons the stainless steel autoclave that is equipped with whipping appts, autoclave is provided with temperature survey and control device, stress measuring device, vacuumometer and inert blowing gas sweeping device, injection port, is used to introduce liquid epoxy ethane.The steel cylinder of about 20 pounds of oxyethane (ARC) is set, and will transfer to as the oxyethane of liquid in the autoclave by pump, steel cylinder is positioned over a certain scale place, thereby can detect the changes in weight of steel cylinder.
(Nippon Shokubai, the molecular-weight average that has is 600, is equivalent to the nitrogen functional group of about 0.417 moles of polymer and 6.25 moles) adds in the autoclave with the polymine (PEI) of 250g.Then, with autoclave sealing, charge into air (vacuum is placed 28 " under the Hg, subsequently with nitrogen pressure to 250psia, then to atmosphere emptying).Autoclave contents is heated to 130 ℃, applies vacuum simultaneously.After about 1 hour, charge into nitrogen, making autoclave is 250psia, simultaneously autoclave is cooled to about 105 ℃.Then, the mode with increment in for some time adds oxyethane in autoclave, closely detects the flow velocity of autoclave pressure, temperature and oxyethane simultaneously.Turn off the oxyethane pump, cooling off with restriction is increased by the temperature that thermopositive reaction causes.Temperature is remained on 100-110 ℃, simultaneously stagnation pressure is increased gradually.The oxyethane of 275g altogether add to (roughly be equivalent to 1 moles of ethylene oxide/1 mole PEI nitrogen functional group) in the autoclave after, temperature is increased to 110 ℃, again autoclave was stirred 1 hour.At this moment, apply vacuum to remove the unreacted ethylene oxide of any remnants.
Below, apply vacuum continuously, make autoclave be cooled to about 50 ℃ simultaneously, add the methanol solution (0.625 mole in the PEI nitrogen functional group, reaches 10% catalyst cupport) of 25% sodium methylate of 135g simultaneously.By vacuum methanol solution is sucked in the autoclave, then, the temperature regulator of autoclave is made as increases to 130 ℃.A device is used to detect the power that agitator consumes.Along with methyl alcohol is discharged from autoclave, the power and the temperature value of agitator increase gradually, and the viscosity of mixture increases and stablized 1 hour, shows that most methyl alcohol is discharged.Again mixture is heated under vacuum and stirred 30 minutes.
Remove vacuum, autoclave is cooled to 105 ℃, fill simultaneously with nitrogen, lead to environmental stress then to 250psia.Charge in the autoclave to 200psia with nitrogen.Mode with increment adds oxyethane in autoclave again, closely detects pressure, temperature and the ethylene oxide flow rate of autoclave simultaneously, maintains the temperature at 100-110 ℃ simultaneously, and restriction is increased by the temperature that thermopositive reaction causes.The oxyethane that adds about 5225g (forming the oxyethane/1 mole PEI nitrogen functional group of 20 moles of total amounts)) after several hours, temperature is increased to 110 ℃, again mixture was stirred 1 hour.
Then, collect reaction mixture and enter in the container that nitrogen purging crosses, and finally be transferred to 22L and have in the three neck round-bottomed flasks of heating and whipping appts.By add 60g methylsulfonic acid (0.625 mole) with in and alkali catalyst.Make about 100 cubic feet rare gas element (argon gas or nitrogen) by disperseing the soft porcelain materials,, reaction mixture is removed flavor, stir simultaneously and heated mixt to 130 ℃ again by reaction mixture.
Last reaction product is slightly cooled off, and is collected in the Glass Containers of crossing with nitrogen purging.
In other preparation process, before discharging product, carry out neutralization reaction and taste removal reaction.
The following description of embodiment II liquid detergent composition of the present invention:
?????????????????????wt％
Composition ?????A ?????B ?????C ?????D
Poly-hydroxy fatty acid distribution of coconut oil acid amides ????3.5 ????3.5 ????3.5 ????3.5
NEODOL23-9 1 ????2.0 ????2.0 ????2.0 ????2.0
C 25Alkyl ethoxylated sulfate ????19.0 ????19.0 ????19.0 ????19.0
C 25Alkyl-sulphate ????-- ????-- ????3.5 ????2.0
C 10The aminopropyl acid amides ????-- ????0.5 ????1.5 ????0.5
Citric acid ????3.0 ????5.0 ????3.0 ????5.0
Tallow fatty acid ????2.0 ????-- ????2.0 ????--
Ethanol ????3.5 ????3.5 ????3.5 ????3.5
Propylene glycol ????6.0 ????6.0 ????6.0 ????6.0
One carbinolamine ????0.5 ????0.5 ????0.5 ????0.5
Sodium hydroxide ????3.0 ????2.5 ????3.5 ????2.5
Paratoluenesulfonic acid sodium salt ????2.5 ????2.5 ????2.5 ????2.5
Borax ????2.5 ????2.5 ????2.5 ????2.5
Proteolytic enzyme 2 ????0.8 ????0.8 ????0.8 ????0.8
Lipase 3 ????0.1 ????0.1 ????0.1 ????0.1
Duramyl 4 ????0.1 ????0.1 ????-- ????--
α-Dian Fenmei 5 ????-- ????-- ????0.1 ????0.1
CAREZYME ????0.05 ????0.05 ????0.05 ????0.05
White dyes 6 ????0.1 ????0.1 ????0.1 ????0.1
Modified polyamine 7 ????1.2 ????1.2 ????1.2 ????1.2
Stain remover 8 ????0.2 ????0.2 ????0.2 ????0.1
Calcined silica ????0.1 ????0.1 ????0.1 ????0.1
On a small quantity, aestetics, water Balance to 100%
1.C 12-C 13Alkyl E9 ethoxylate is available from Shell Oil Co.
2. the bacillus amyloliquefaciens subtilisin as described in WO95/10615, is disclosed in 1995.4.20, Genencor International.
3. obtain by the fetal hair humicola lanuginosa, available from Novo.
4. be disclosed in WO9510603A, available from Novo.
5. α-Dian Fenmei disclosed by the invention comprises: TERMAMYL , RAPIDASE , FUNGAMYL , DURAMYL .
6. whitening agent is selected from: whitening agent 49 (Tinopal CBS), inopal UNPA, Tinopal CBS, Tinopal 5BM, Artic White CC, Artic White CWD, 2-(4-styryl-phenyl)-2H-naphtho-[1,2-d] triazole; 4,4 '-two-(1,2,3-triazoles-2-yl)-toluylene, 4,4 '-two (styryl) biphenyl and aminocoumarin.
7.PEI600E 20, as previously mentioned.
8. terephthaldehyde's acid copolymer, as USP4,968,451 (Scheibel etc., 1990.11.6) described.
The following description of embodiment III liquid detergent composition of the present invention:
??????????????????wt％
Composition ?????A ?????B ?????C
Poly-hydroxy fatty acid distribution of coconut oil acid amides ????3.5 ????3.5 ????--
NEODOL23-9 1 ????2.0 ????2.0 ????2.0
C 25Alkyl ethoxylated sulfate ????15.0 ????15.0 ????15.0
C 25Alkyl-sulphate ????2.0 ????2.0 ????--
C 10The aminopropyl acid amides ????-- ????-- ????0.5
Linear alkylbenzene sulfonate ????4.0 ????4.0 ????4.0
Citric acid ????3.0 ????5.0 ????5.0
Tallow fatty acid ????2.0 ????2.0 ????2.0
Ethanol ????3.4 ????3.4 ????3.4
Propylene glycol ????6.0 ????6.0 ????6.0
One carbinolamine ????0.5 ????0.5 ????0.5
Sodium hydroxide ????3.0 ????2.5 ????2.5
Paratoluenesulfonic acid sodium salt ????2.5 ????2.5 ????2.5
Borax ????2.5 ????2.5 ????2.5
Proteolytic enzyme 2 ????0.8 ????0.8 ????0.8
Lipolase 3 ????0.1 ????0.1 ????0.1
α-Dian Fenmei 5 ????0.1 ????0.1 ????0.1
CAREZYME ????0.05 ????0.05 ????0.05
White dyes ????0.1 ????0.1 ????0.1
Modified polyamine 6 ????1.2 ????1.2 ????1.2
The ethoxylation tetren ????3.0 ????3.0 ????3.0
Stain remover 7 ????0.2 ????0.2 ????0.2
Calcined silica ????0.1 ????0.1 ????0.1
Vinylformic acid/maleic acid ????-- ????-- ????0.05
The ethylenediamine disuccinate sequestrant ????-- ????1.0 ????--
Fabric integrity agent 8 ????2.0 ????3.5 ????0.75
On a small quantity, aestetics, water Balance to 100%
1.C 12-C 13Alkyl E9 ethoxylate is available from Shell Oil Co.
2. the bacillus amyloliquefaciens subtilisin as described in WO95/10615, is disclosed in 1995.4.20, Genencor International.
3. obtain by the fetal hair humicola lanuginosa, available from Novo.
4. α-Dian Fenmei disclosed by the invention comprises: TERMAMYL , RAPIDASE , FUNGAMYL , DURAMYL .
5.PEI600E 20, as previously mentioned.
6. terephthaldehyde's acid copolymer, as USP4,968,451 (Scheibel etc., 1990.11.6) described.
7. fabric integrity agent is selected from bead/fine hair and reduces agent, anti redeposition agent, anti-decolourant, laking agent and its mixture.
????wt％
Composition ?????D ?????E ??????F
Poly-hydroxy fatty acid distribution of coconut oil acid amides ????4.0 ????5.0 ?????5.0
NEODOL23-9 1 ????4.0 ????4.0 ?????2.0
C 25Alkyl ethoxylated sulfate ????4.0 ????17.0 ?????25.0
C 25Alkyl-sulphate ????14.0 ????7.0 ?????--
C 10The aminopropyl acid amides ????1.0 ????2.0 ?????1.0
Linear alkylbenzene sulfonate ????-- ????-- ?????4.0
Citric acid ????5.0 ????5.0 ?????5.0
Tallow fatty acid ????7.0 ????5.0 ?????5.0
Ethanol ????2.0 ????5.5 ?????10.0
Propylene glycol ????9.0 ????8.0 ?????8.0
One carbinolamine ????5.0 ????9.0 ?????7.0
Sodium hydroxide ????2.0 ????1.5 ?????0.5
Paratoluenesulfonic acid sodium salt ????0.1 ????2.0 ?????2.0
Borax ????2.0 ????3.5 ?????3.5
Proteolytic enzyme 2 ????0.2 ????1.5 ?????1.5
Lipolase 3 ????0.06 ????0.2 ?????--
α-Dian Fenmei 5 ????0.2 ????0.1 ?????0.1
CAREZYME ????-- ????0.1 ?????0.1
White dyes ????0.15 ????0.1 ?????0.1
Modified polyamine 6 ????1.2 ????1.2 ?????1.2
The ethoxylation tetren ????1.0 ????3.0 ?????3.0
Stain remover 7 ????0.2 ????0.5 ?????0.5
Calcined silica ????0.2 ????0.1 ?????--
Vinylformic acid/maleic acid ????0.05 ????-- ?????--
The ethylenediamine disuccinate sequestrant ????1.0 ????0.5 ?????--
Fabric integrity agent 8 ????1.0 ????1.5 ?????--
On a small quantity, aestetics, water Balance to 100%
1.C 12-C 13Alkyl E9 ethoxylate is available from Shell Oil Co.
2. the bacillus amyloliquefaciens subtilisin as described in WO95/10615, is disclosed in 1995.4.20, Genencor International.
3. obtain by the fetal hair humicola lanuginosa, available from Novo.
4. α-Dian Fenmei disclosed by the invention comprises: TERMAMYL , RAPIDASE , FUNGAMYL , DURAMYL .
5.PEI600E 20, as previously mentioned.
6. terephthaldehyde's acid copolymer, as USP4,968,451 (Scheibel etc., 1990.11.6) described.
7. fabric integrity agent is selected from bead/fine hair and reduces agent, anti redeposition agent, anti-decolourant, laking agent and its mixture.
The embodiment IV describes below structured liquids detergent composition of the present invention:
?????????????wt％
Composition ??????A ??????B
NEODOL45-7 1 ?????2.0 ?????2.0
C 25Alkyl ethoxylated sulfate ?????16.0 ?????16.0
C 25Alkyl-sulphate ?????-- ?????--
Cats product 2 ?????5.0 ?????4.0
C 12-C 16The alkyl dimethyl amino oxide ?????-- ?????1.0
Citric acid ?????5.0 ?????5.0
Ethanol ?????-- ?????--
Propylene glycol ?????6.4 ?????2.0
One carbinolamine ?????-- ?????0.5
Sodium hydroxide To pH8.0 To pH6.7
Borax ?????2.0 ?????1.0
Proteolytic enzyme 2 ?????0.5 ?????1.0
Lipolase 3 ?????0.06 ?????0.2
α-Dian Fenmei 5 ?????1.2 ?????0.5
CAREZYME ?????-- ?????0.5
White dyes ?????0.2 ?????0.1
Modified polyamine 6 ?????1.0 ?????1.5
Fabric integrity agent 7 ?????1.0 ?????3.0
Stain remover 8 ?????0.2 ?????0.5
Calcined silica ?????0.2 ?????0.1
Vinylformic acid/maleic acid ?????0.05 ?????--
The ethylenediamine disuccinate sequestrant ?????1.0 ?????0.5
On a small quantity, aestetics, water Balance to 100%
1.C 14-C 15Alkyl E7 ethoxylate is available from Shell Oil Co.
2. lauryl trimethyl ammonium chloride.
3. the bacillus amyloliquefaciens subtilisin as described in WO95/10615, is disclosed in 1995.4.20, Genencor International.
4. obtain by the fetal hair humicola lanuginosa, available from Novo.
5. α-Dian Fenmei disclosed by the invention comprises: TERMAMYL , RAPIDASE , FUNGAMYL , DURAMYL .
6.PEI600E 20, as previously mentioned.
7. fabric integrity agent is selected from bead/fine hair and reduces agent, anti redeposition agent, anti-decolourant, laking agent and its mixture.
8. terephthaldehyde's acid copolymer, as USP4,968,451 (Scheibel etc., 1990.11.6) described.

Claims (9)

1. liquid laundry detergent composition, it comprises:
(a) decontamination negatively charged ion and the nonionogenic tenside of 0.1wt% at least are selected from the following substances one or more: alkyl-sulphate, alkyl alkoxy sulfate, linear alkylbenzene sulfonate, polyhydroxy fatty acid amide and its mixture;
(b) the water-soluble or water dispersible of 0.05wt%, the agent of modified polyamine appearance of fabrics at least, described reagent comprises the polyamine backbone corresponding to following formula: [(R 2) 2-N] W-[R 1-N] X-[R 1-N] Y-[R 1-N] Z
B R 2(R 2) 2Wherein, R 1Be C independently of one another 2-C 5Alkylidene group, alkenylene or arylidene; R 2Be H or formula OH[(CH independently of one another 2) xO] nPart, wherein x is 1-8, n is 10-50; W is 0 or 1; X+y+z is 5-30; The B representative is by the extension of this structure of branching; Wherein, the molecular-weight average of the polyamine before the alkylation is 300-1200; With
(c) one or more other detergent additives, it is selected from: α-Dian Fenmei, decontamination amine, cats product, anti redeposition agent, anti-decolourant, laking agent, bead/fine hair reduce agent and its mixture; Wherein said decontamination amine is following formula: compound:
R 3
R 1-X-(CH 2)n-N
R 4Wherein, R 1Be C 6-C 12Alkyl; N is 2-4, and X is a bridged group, is selected from: NH, CONH, COO or O, or X can not exist; R 3And R 4Be selected from respectively: H, C 1-C 4Alkyl or (CH 2-CH 2-O (R 5)), wherein, R 5Be H or methyl.
2. according to the composition of claim 1, wherein, detergent composition also comprises supplementary component, and these compositions are selected from: washing assistant, white dyes, soil release polymer, dye transfer inhibitor, macromolecule dispersing agent, the enzyme except that amylase, suds suppressor, dyestuff, spices, tinting material, filling salt, hydrotropic solvent and its mixture.
3. according to the composition of claim 2, wherein, described supplementary component is the Citrate trianion washing assistant; Wherein, described composition comprises the described Citrate trianion of 2-8wt%.
4. according to the composition of claim 1, wherein, additional detergent additive is an amylase; Wherein, described amylase is selected from:
(a) in temperature 25-55 ℃ scope and the specific activity of pH value time employing Phadebas  alpha-amylase activity measurements determination in the 8-10 scope than the α-Dian Fenmei of the specific activity high at least 25% of Termamyl ;
(b) show the α-Dian Fenmei of positive immunity fork reaction with antibody, this antibody is anti-to have the α-Dian Fenmei of the aminoacid sequence that corresponds respectively to (a) α-Dian Fenmei; With
(c) mixture of above-mentioned enzyme.
5. according to the composition of claim 1, wherein, described amine is selected from: octylame, hexylamine, decyl amine, n-Laurylamine, C 8-C 12Two (hydroxyethyl) amine, C 8-C 12Two (hydroxyl sec.-propyl) amine, C 8-C 12Amido propyl-dimethyl amine and its mixture.
6. according to the composition of claim 1, wherein, other detergent additive is the cats product of following formula:
Figure A9719612100031
Figure A9719612100032
Wherein, R 1Be alkyl or alkenyl with 8-18 carbon atom; R 2And R 3 'Independently of one another for comprising the alkyl of about 3 carbon atoms of 1-; R 3And R 4Can change independently, they are selected from: hydrogen, methyl and ethyl; X-is for electroneutral negatively charged ion is provided, as chlorion, bromide anion, methylsulfate, sulfate radical etc.; A is selected from: C 1-C 4Alkoxyl group; To the formula I, p is 2-30; To formula II, p is 1-30, and q is 1-30.
7. according to the composition of claim 1, wherein, additional detergent additive is a kind of anti redeposition agent, and described anti redeposition agent is selected from the material of following formula:
Figure A9719612100033
Wherein, R is selected from: the C of straight or branched 2-C 12Alkylidene group, C 3-C 12Hydroxy alkylidene, C 4-C 12Alkyl sub-dihydroxy, C 8-C 12Dialkyl group arylidene, [(CH 2CH 2O) qCH 2CH 2]-and-CH 2CH (OH) CH 2O-(CH 2CH 2O) qCH 2CH (OH) CH 2]-, wherein q is 1-100; R 1Be independently from each other: C 1-C 4Alkyl, C 7-C 12Alkaryl or A, wherein A has following formula: Wherein, R 3Be selected from: H or C 1-C 3Alkyl, n are 5-100; B is selected from: H, C 1-C 4Alkyl, acetyl or benzoyl base; X is a water soluble anion; With
Figure A9719612100042
Wherein, R is selected from: the C of straight or branched 2-C 12Alkylidene group, C 3-C 12Hydroxy alkylidene, C 4-C 12Alkyl sub-dihydroxy, C 8-C 12Dialkyl group arylidene, [(CH 2CH 2O) qCH 2CH 2]-and-CH 2CH (OH) CH 2O-(CH 2CH 2O) qCH 2CH (OH) CH 2]-, wherein q is 1-100; If present, R 1Be independently from each other: C 1-C 4Alkyl, C 7-C 12Alkaryl or A; R 1Can not exist in the time of on some nitrogen; But at least three nitrogen must be quaternized; A has following formula:
Figure A9719612100043
Wherein, R 3Be selected from: H or C 1-C 3Alkyl, n are 5-100; B is selected from: H, C 1-C 4Alkyl, acetyl or benzoyl base; M is 1-4, and X is a water soluble anion.
8. according to the composition of claim 1, wherein additional detergent additive is a kind of anti-stripping agent, comprise the laking agent of 0.1-5wt%, it is selected from: Cassofix FRN-300 , SandofixSWE , Sandofix WA , Tinofix EW , Polymer VRN , SandolecCF , Sandolec WA , Sandolec CT , Sandolec CS  and SandolecCl ; Wherein said Sandofix SWE  has following formula:
Figure A9719612100051
Wherein said Cassofix FRN-300  polymkeric substance is made by the monomer with following formula structure:
Figure A9719612100052
Wherein said Sandofix WA  polymkeric substance has the following formula structure:
Figure A9719612100053
9. according to the composition of claim 1, wherein, additional detergent additive is that bead/fine hair reduces agent, comprises polymeric amide-polyamine fabric finishing agent of about 0.1-8wt%, and it is that repeating unit by the following formula structure forms:
Figure A9719612100054
Wherein, R 1, R 2And R 5Be C independently of one another 1-C 4Alkylidene group, C 1-C 4Alkarylene or arylidene, perhaps, R wherein 1Can not exist; R 3Be H, Epicholorohydrin base, azetidinyl, epoxypropyl, dimethylin hydroxypropyl; R 4Be H, C 1-C 4Alkyl, C 1-C 4Alkaryl or aryl; Described R 4Can be randomly and C 1-C 4The oxyalkylene condensation.
CN 97196121 1996-05-03 1997-04-25 Liquid detergent compositions contg. specially selected modified polyamine polymers Pending CN1224449A (en)

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US60/027,902 1996-05-03
US60/017,060 1996-05-03
US60/016,526 1996-05-03
US60/027,899 1996-05-03
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105586165A (en) * 2016-01-29 2016-05-18 广州康钰生物科技有限公司 Laundry sheet with color protecting function and preparation method thereof
CN110891931A (en) * 2017-06-30 2020-03-17 凯米拉公司 Method of preparing a chelant mixture, chelant mixture and method of using same
CN112449651A (en) * 2018-08-24 2021-03-05 宝洁公司 Treatment compositions comprising low levels of oligoamines
US11274266B2 (en) 2018-08-24 2022-03-15 The Procter & Gamble Company Treatment compositions comprising a surfactant system and an oligoamine

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105586165A (en) * 2016-01-29 2016-05-18 广州康钰生物科技有限公司 Laundry sheet with color protecting function and preparation method thereof
CN110891931A (en) * 2017-06-30 2020-03-17 凯米拉公司 Method of preparing a chelant mixture, chelant mixture and method of using same
CN110891931B (en) * 2017-06-30 2022-11-08 凯米拉公司 Method of preparing a chelant mixture, chelant mixture and method of using same
CN112449651A (en) * 2018-08-24 2021-03-05 宝洁公司 Treatment compositions comprising low levels of oligoamines
US11274266B2 (en) 2018-08-24 2022-03-15 The Procter & Gamble Company Treatment compositions comprising a surfactant system and an oligoamine
US11279901B2 (en) 2018-08-24 2022-03-22 The Procter & Gamble Company Treatment compositions comprising low levels of an oligoamine

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