CN1177976A - Stabilized liquid fabric softener composition - Google Patents
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- CN1177976A CN1177976A CN 96192375 CN96192375A CN1177976A CN 1177976 A CN1177976 A CN 1177976A CN 96192375 CN96192375 CN 96192375 CN 96192375 A CN96192375 A CN 96192375A CN 1177976 A CN1177976 A CN 1177976A
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Abstract
Concentrated liquid fabric softener compositions which are unstable due to phase separation are stabilized by means of water-soluble polyesters. Stable liquid compositions comprising various fabric treatment electrolytes are provided. Compositions comprising terephthalate-ethylene oxide stabilizers in fabric softener compositions comprising various chelators such as ethylenediamine disuccinate, diethylenetriamine pentaacetate and various aminophosphonates restore softness and dye colors to fabrics which have been exposed to metal cations, especially copper or nickel. Compositions comprising cellulase enzymes are also disclosed.
Description
Invention field
The present invention relates to stable fabric softener composition and production method thereof in the presence of relative high density ionogen.
Background of invention
The preparation of liquid fabric softener composition generally comprises dispersion and the suspensoid of organic cation composition in liquid vehicle.Because its physico-chemical property, the cationic softener composition generally exists with the bubble form that has cationic charge in liquid vehicle.Because the result of its electric charge, bubble is tending towards being evenly dispersed in the carrier.
Traditional " single intensity " fabric sofetening agent formulation is quite general, and it generally contains about 5%～10% (weight) and is scattered in cationic softener in the water.But the preparation that contains up to the concentrated liquid fabric softener of about 30% cationic softener now is not to have no problem.When concentration was high, viscosity was restive.And, generally also need in this based composition, to add softening agent component other material in addition.For example, be used in this based composition to use multiple inorganic electrolyte to be lower than about 1% amount, so that the dehydration of softening agent bubble, and admixture spices in steeping toward positively charged ion, thereby stabilizing perfume.When in composition, adding, generally can observe it and can cause the bubble cohesion, and when storing, separate, thereby cause a kind of heterogeneous system undesirably more than about 1% ionogen.
In addition, for extra fabric nursing effect is provided, need in concentrated fabric softener compositions, add other water-soluble charged electrolyte.For example, various sterilant, sequestrant etc. if can be joined in the stable concentrate composition expediently, they will be useful to the user.But because the adding of this constituents has further increased the total electrolytical load of system, it can impel the cohesion of softening agent bubble undesirably and separate.
Now definite, some polymkeric substance can be added concentrated fabric softener compositions to improve stability.Bound by theory does not infer that this base polymer coats the cationic softener bubble to a certain extent, perhaps, otherwise interacts with the cationic softener bubble, suppresses the cohesion of steeping under the high ionic strength situation thus.Exist polymkeric substance also to stablize the viscosity of bulk fluid in the system.Obtained stable system thus.
Therefore, an object of the present invention is to provide the method for cationic fabric softener dispersion in a kind of stabilising liq carrier.Another object of the present invention provides to contain adds electrolytical stable cationic fabric softener composition.A further object of the invention provides shelf-stable and homogeneous concentrated fabric softener compositions.Can see that from following disclosure the present invention has reached these purposes and other purpose.
Background technology
In rinsing clothes additive or other products, be used for the various sequestrants of several open purposes and the use of poly-carboxyl composition and appear at following document: United States Patent (USP) U.S.3,756,950; United States Patent (USP) U.S.3,904,359; United States Patent (USP) U.S.3,954,630; German patent DE 3,312,328; European patent EP 165,138 (85:12:18); European patent application EP 168,889 (86:01:22); European patent application EP 271,004 (88:06:15); European patent application EP 534,009 (93:03:31; WO9,306,294); Canadian Patent CA 913,309 (00:01:00, right of priority 68:08:01 68, CA-026,440); With Japanese JP HEI4[1992] 275,956.Be used for preferred EDDS sequestrant of the present invention and be described in United States Patent (USP) U.S.4, in 704,233.Kymene is disclosed United States Patent (USP) U.S.2, in 926,154.Preferred stablizer is described in United States Patent (USP) U.S.4, in 702,857.Also can be with reference to the AATCC-161-1992 method " sequestrant: the dispersed dye color ligh modification that causes by metal; And control " (Chelating Agents:Disperse Dye Shade Change Caused by Metals; Control of).
Summary of the invention
The present invention includes a kind of composition, it comprises:
(a) stablizer of certain stable quantity, it comprises a kind of terephthalate/alkylene oxide copolymer;
(b) at least about a kind of fabric softener of 10% (weight), its preferred cationic type;
(c) greater than total ionogen of about 1% (weight); With
(d) a kind of fluid carrier, it comprises water.
Preferred concentrate composition of the present invention comprises about fabric softener of 15%～about 35% (weight) and about stablizer of 0.2%～about 1% (weight).
Composition of the present invention can comprise ionogen, and it is selected from water-soluble inorganic salt.Ionogen also can be a water-soluble organic compounds, and it is selected from sequestrant, intensity retention agent, sterilant, chlorine scavenger (NH particularly
4Cl) and composition thereof.
Inventive composition also can comprise the CAREZYME of cellulase, particularly NOVO.
The highly preferred concentrate composition of the present invention comprises:
(a) a kind of stablizer of about 0.2%～about 1% (weight), it is by terephthalic acid dimethyl ester/1, the multipolymer that the 2-propylene glycol/methyl blocking oxyethane obtains;
(b) about cationic fabric softener of 20%～about 30% (weight);
(c) amount is about 1% ionogen greater than composition weight, and it comprises CaCl
2Or MgCl
2, or its mixture and a kind of water miscible polycarboxylate or polyphosphonate sequestrant; With
(d) a kind of fluid carrier that comprises water.
The present invention also comprises a kind of by stablizing and contain electrolytical liquid softener method for compositions to wherein mixing a kind of stablizer that comprises water-soluble polyester.
Unless otherwise indicated, all per-cents of the present invention, ratio and umber all refer to weight.All all are incorporated herein by reference in the present invention at the document that relevant portion is quoted.
Detailed Description Of The Invention
The present invention uses composition known and that can buy, or uses the method press described in the document can the synthetic composition.
The sophisticated method preparation of stablizer (stabilizing agents) (stablizer (stablizer)) available techniques that stablizer-the present invention is used.The following describes this synthetic; Further details can be with reference to the United States Patent (USP) U.S.4 of the Gosselink that authorized on October 27th, 1987,702,857.
Stablizer is a water-soluble polyester, and it can be formed by following material: (1) ethylene glycol, 1,2-propylene glycol or its mixture; (2) a kind of polyoxyethylene glycol (PEG), an end is with C
1-C
4The alkyl group end-blocking; (3) a kind of dicarboxylic acid (or its diester).These components of selected respective amount, the polyester that has desired solvability and performance for stability with preparation.
The end-blocking PEG that is used to prepare polyester of the present invention is generally methyl blocking, can form by the oxyethylation of correspondent alcohol and oxyethane.The PEG of methyl blocking also can buy with poly-(ethylene glycol) methyl ether of title with trade(brand)name Methoxy Carbowax with from Aldrich chemical company (Aldrich ChemicalCompany) from Union Carbide.The molecular weight of these commercialization methyl blockings PEGs is 350 (n=about 7.5), 550 (n=about 12), 750 (n=about 16), 1900 (n=about 43) and 5000 (n=about 113).
Preferred unique dicarboxylic acid that uses is terephthalic acid or its diester.But can add a small amount of other aromatic dicarboxylic acid (or its diester) or aliphatic dicarboxylic acid (or its diester), to the degree that can keep stability basically.The illustrated example of other available aromatic dicarboxylic acid comprises m-phthalic acid, phthalic acid, naphthalene dicarboxylic acids, anthracene dicarboxylic acid, diphenyl dicarboxylic acid, oxydiphenyl formic acid etc., and these sour mixtures.The available aliphatic dicarboxylic acid comprises hexanodioic acid, pentanedioic acid, Succinic Acid, trimethyladipic acid, pimelic acid, nonane diacid, sebacic acid, suberic acid, 1,4-cyclohexyl dicarboxylic acid and/or dodecanedioic acid
The preferred method of used block polyester comprises lower dialkyl (methyl, ethyl, propyl group or the butyl) ester mixture of desired dicarboxylic acid and glycol (ethylene glycol, 1,2-propylene glycol or its mixture) mixture and end-blocking PEG is reacted among preparation the present invention.Then, diol ester and the oligopolymer that generates in this transesterification reaction is aggregated to desired degree.Transesterification reaction can be carried out according to the condition that generally is used for transesterification reaction.This transesterification reaction is 120 ℃～220 ℃ in temperature generally, carries out under the condition that esterifying catalyst exists.Reaction generates alcohol and will constantly remove alcohol, so that can be carried out fully.Control reaction temperature and pressure can not be distilled away from reaction mixture to avoid glycol aptly.Carry out if be reflected to add to depress, can adopt higher temperature.
Be used for the catalyzer that the catalyzer of transesterification reaction is known in the art.These catalyzer comprise the alkyl alkali earth metals, for example lithium, sodium, calcium and magnesium and transition metal and IIB family metal, and for example calcium halophosphate activated by antimony andmanganese, cobalt and zinc are normally with corresponding oxide compound, carbonate and acetate form.General ANTIMONY TRIOXIDE SB 203 99.8 PCT and the lime acetate of using.
The degree of transesterification reaction can be monitored by the disappearance of diprotic acid dialkyl in alcohol amount that discharges or the reaction mixture, and this usable highly effective liquid chromatography (HPLC) or any other suitable method are measured.The transesterification reaction expectation proceeds to be finished more than 90%.Preferably finish more than 95%, to reduce the sublimate amount that obtains in the polymerization procedure.
When transesterification reaction is finished, then with the polymerization of diol ester product to make polyester.The desired polymerization degree can by HPLC and
13C-NMR analyzes and measures.For commercially producing, polyreaction generally is to have in the presence of the catalyzer, carries out under about 200 ℃～about 280 ℃ temperature.Can adopt higher temperature, but tend to produce the black product of color.The catalyzer illustrated example that is applicable to polymerization procedure comprises ANTIMONY TRIOXIDE SB 203 99.8 PCT, germanium dioxide, alkyl dioxide, hydration antimony pentaoxide and transesterification catalyst such as zinc salt, cobalt salt and manganese salt.Excess diol in the reaction and other volatile matter that discharges are removed by vacuum, as described in Gosselink.
Resultingly be used for preferred polymers of the present invention and can be expressed from the next:
Wherein, R
2Be selected from propylene (preferably), ethylidene or its mixture; Each X is C
1～C
4Alkyl (preferable methyl) 2 each n are about 12～about 43; With u be about 3～about 10.
The package stability of the present composition can be evaluated with simple visual examination.The preparation composition also is placed in the transparent vessel, is allowed to condition under the desired temperature and leaves standstill.Because the bubble of fabric softener is lighter than aqueous phase carriers, show stability problem in the formation of the limpid relatively phase of container bottom one.The stable composition prepared with present method can tolerate a few weeks longer under this condition for surveys, or even the several months, this depends on temperature in a way.In contrast, the unstable association thing will show and is separated generally in several days or less time.In addition, stability also can be evaluated by measuring storage back viscosity change.
The present invention is with " stable quantity ", and what promptly be enough to prevent above and mentioned is separated and prevents the amount that unacceptable finished product viscosity changes, and uses polymer stabilizer.This amount can change to a certain extent, and this depends on cationic fabric softener content and electrolyte content in the amount, amount of electrolyte, finished product of cationic fabric softener, selected ionogen type and concrete polymer stabilizer.For after illustrating a bit, with the prepared stable polyester agent of the method for Gosselink, it has about 3 terephthalate unit and is less than about 40 ethylene oxide units, to a certain extent, this stable polyester agent is effective not as the compound that comprises about 5 terephthalate unit and 40 ethylene oxide units.So under specified criteria, have to use the more not effective stabilizer of high density slightly, to reach the same stable effect that preferred stabilizer is provided.
The stability of composition finished product also is subjected to the influence of ionogen type or other ionic additive that may exist to a certain extent.But this soluble amount that why often needs to regulate polymer stabilizer.Hereinafter set forth this point in more detail.The composition that is stabilized comprise 26% (weight) tonsilon Dimethyl Ammonium two tallow alkyl esters and shown in various ionic additive.The amount of needed preferred 5 terephthalates of stable composition/40EO polyester is shown in Table 1.Table 1
MgCl
2ZnCl
2, HCl, ionogen
Or CaCl
2NaOH total amount sample additive (%) NH
4Cl (%) is stablizer 1 2.5%DETPA, 0.3～1 0.7～3.15 3.5～6.7 0.25～0.5 (%)
DETMP or
NTA
*2 1.25％EDDS
**0.5 0.75 2.5 0.53 0.5～1％ 1 1.7 3.2～3.7 0.2～0.8
KYMENE
***
*Sequestrant, as mentioned below
*Sequestrant, as mentioned below
* *The intensity retention agent, as mentioned below
The content of stablizer generally accounts for about 0.1%～about 1.5% (weight) of the present composition.Said composition shelf-stable, the amount of polyester add that the amount of other composition in the composition generally is enough to provide a preferred viscosities, and its scope is about 30 centipoises～about 80 centipoises, and passing in time keeps stable (BrookfieldLVT viscometer, #2 main shaft; 60 rev/mins; Room temperature, about 25 ℃).
Fabric softener/static inhibitor-the compositions and methods of the invention also comprise one or more fabric softeners or static inhibitor, so that extra fabric nursing benefit to be provided.This constituents generally accounts for the about more than 10% of present composition weight, reaches as high as about 35%.The preferred fabric softening agent that is used for the present composition is quaternary ammonium compound or amine precursor of the present invention, and its chemical formula is following (I) or (II).
Or
Q is-O-C (O)-or-C (O)-O-or-O-C (O)-O-or NR
4-C (O)-or-C (O)-NR
4, or its mixture, for example, with amide substituents in a part and ester substituting group; R
1Be (CH
2)
n-Q-T
2Or T
3R
2Be (CH
2)
m-Q-T
4Or T
5Or R
3R
3Be C
1～C
4Alkyl or C
1～C
4Hydroxyalkyl or hydrogen; R
4Be hydrogen or C
1～C
4Alkyl or C
1～C
4Hydroxyalkyl; T
1, T
2, T
3, T
4, T
5Be (identical or different) C
11～C
22Alkyl or alkenyl; N and m are 1～4 integer; With X be a negatively charged ion compatible with softening agent.
Alkyl or alkenyl, chain T
1, T
2, T
3, T
4, T
5Must comprise at least 11 carbon atoms, preferably at least 16 carbon atoms.Chain can be straight or branched.
Tallow is a convenient and cheap chain alkyl and an alkenyl material source.Especially preferred T wherein
1, T
2, T
3, T
4, T
5The compound of expression long-chain substance mixture refers generally to tallow.
The specific examples that is applicable to the quaternary ammonium compound of liquid fabric softening composition of the present invention comprises:
1) N, N-two (tallow base-oxygen base-ethyl)-N, N-alkyl dimethyl ammonium chloride;
2) N, N-two (tallow base-oxygen base-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium chloride or its corresponding amide (can VARISOFT 222 obtain);
3) N, N-two (2-tallow oxygen base-2-oxo-ethyl)-N, N-alkyl dimethyl ammonium chloride;
4) N, N-two (2-tallow oxygen base ethyl ketonic oxygen ethyl)-N, N-alkyl dimethyl ammonium chloride;
5) N-(2-tallow acyloxy-2-ethyl)-N-(2-tallow oxygen base-2-oxo-ethyl)-N, the N-alkyl dimethyl ammonium chloride;
6) N, N, N-three (tallow base-oxygen base-ethyl)-N-ammonio methacrylate;
7) N-(2-tallow base oxygen base-2-oxoethyl)-N-(tallow base-N, N-alkyl dimethyl ammonium chloride; With
8) 1, the 2-two tallow base oxygen bases-molten propane chloride of 3-trimethylammonium ammonia; And the mixture of above-mentioned any material.
In these compounds, compound 1～7 is the examples for compounds of chemical formula (I), and compound 8 is the example of chemical formula (II).
Particularly preferred is N, N-two (tallow acyl group-oxygen base-ethyl)-N, and the N-alkyl dimethyl ammonium chloride, wherein, the tallow chain is that part is unsaturated at least.
Tallow chain unsaturation degree can be measured by the iodine number (IV) of corresponding lipid acid, and it should preferred range be 5～100 under situation of the present invention, has the visibly different compound of two classes, its IV less than or greater than 25.
In fact, be 5～25 for IV, preferred 15～20 the chemical formula by beef fat acid preparation is the compound of (I), found that its suitable/trans isomer weight ratio is greater than about 30/70, be preferably greater than about 50/50, more preferably greater than about 70/30, so that the best dense property of carrying to be provided.
Be the compound of (I) for IV greater than 25 the chemical formula by beef fat acid preparation, finds that its suitable/trans isomer is stricter than not, unless the very high concentration of needs.
Chemical formula is other example of (I) and suitable quaternary ammonium (II), can obtain in the following way, for example,
-replace " tallow base " in the above-claimed cpds with for example cocoa, palm, lauryl, oleoyl, castor-oil plant acyl group, stearyl-, palmitoyl etc., described fatty acyl chain or all saturated, or preferred fractional saturation at least;
-use " methyl " in ethyl, oxyethyl group, propyl group, propoxy-, sec.-propyl, butyl, isobutyl-or the tertiary butyl replacement above-claimed cpd;
-use " muriate " in the replacement above-claimed cpds such as bromide, Methylsulfate, formate, vitriol, nitrate;
In fact, negatively charged ion only exists with the counter ion of positively charged quaternary ammonium compound.With respect to practice of the present invention, the character of counter ion is not crucial at all.
" its amine precursor " is meant secondary amine or the tertiary amine corresponding to above-mentioned quarternary ammonium salt compound, because the desired pH value of right, the amine described in the present composition is basically by protonated.
Quaternary ammonium of the present invention or the amount of amine precursor compound in the present composition are about 1%～about 80%, this depends on the use of composition, it can be diluted by the actives of about 5%～about 15% preferred amounts, or concentrated by the actives of about 15%～about 50% preferred amounts, most preferably concentrated by the actives of about 15%～about 35% amount.
For most above-mentioned fabrics softening agents, the pH of the present composition is the main parameter of the present invention.In fact, pH influences the stability of quaternary ammonium or amine precursor compound, and influences the stability of cellulase, particularly under the long storage condition.
PH defined herein measures in 20 ℃ of clean compositions, or measure in the external phase behind 20 ℃ of super centrifugation disperse phase.For making the composition that comprises softening agent and ester bond have optimum hydrolysis stability, the clean pH that is measured under these conditions must be in about scope of 2.0～about 4.5, and preferred about 2.0～about 3.5.The pH of this based composition can regulate by adding protonic acid among the present invention.For non-ester softening agent, pH can be higher, and is general in 3.5～8.0 scope.
The example that is suitable for acid comprises mineral acid, carboxylic acid, particularly lower molecular weight (C
1～C
5) carboxylic acid and alkylsulphonic acid.The mineral acid that is suitable for comprises HCl, H
2SO
4, HNO
3And H
3PO
4The organic acid that is suitable for comprises formic acid, acetate, citric acid, methylsulfonic acid, ethyl sulfonic acid.Preferred acid is citric acid, hydrochloric acid, phosphoric acid, formic acid, methylsulfonic acid and phenylformic acid.
Nonionic fabric sofetening agent material also is suitable for the softening agent of doing in the present composition, preferably combines with cationic softener.The HLB of general this nonionic fabric sofetening agent material be about 2～about 9, be more generally about 3～about 7.This nonionic fabric sofetening agent material tends to or is easily disperseed by self, or when and other material, single-long-chain alkyl cats product As described in detail below in conjunction with the time, easily disperseed.By use more single-long-chain alkyl cats products, with hereinafter described other mixtures of material, and be coated with hotter water of use and/or more the stirring, can improve dispersiveness.Generally speaking, selected material should be relative crystalline, has higher melt (for example, greater than 40 ℃) and relative water-insoluble.
The amount of optional NON IONIC SOFTNER is generally about 0.1%～about 10%, preferred about 1%～about 5% in the present composition.
Preferred NON IONIC SOFTNER is part polyol ester or its acid anhydrides of lipid acid, and wherein, alcohol or acid anhydrides contain 2～18, preferred 2～8 carbon atoms, and each fatty acid part contains 12～30, preferred 16～20 carbon atoms.Generally speaking, this class softening agent per molecule contains 1～3, preferred 1～2 fatty acid group.
The polyol moiety of ester can be ethylene glycol, glycerine, poly-(for example, two, three, four, five and/or six) glycerine, Xylitol, sucrose, tetrahydroxybutane, five tetrahydroxybutanes, Sorbitol Powder or sorbitan.Preferred especially sorbitan ester and Polyglycerine monostearate.
The fatty acid part of ester is derived from usually has 12～30, and the lipid acid of preferred 16～20 carbon atoms, the representative instance of described lipid acid are lauric acid, tetradecanoic acid, palmitinic acid, stearic acid and docosoic acid.
Be applicable to that the highly preferred optional NON IONIC SOFTNER of the present invention is a sorbitan ester, it is the esterification dewatered product of Sorbitol Powder, and glyceryl ester.
The commercialization sorbitan monostearate is a kind of suitable material.Stearate/cetylate weight ratio variation range is about 10: 1～about 1: the 10 sorbitan stearate and the mixture of dehydrated sorbitol palmitate, and 1, the 5-sorbitan ester also is suitable for.
Preferably glycerine of the present invention and polyglycerol ester, the monoesters of special preferably glycerine, Glycerol dimer, triglycerin and Polyglycerine and/or diester (for example, the Polyglycerine monostearate of commodity Radiasurf 7248 by name).
The monoesters that glyceryl ester that is suitable for and polyglycerol ester comprise stearic acid, oleic acid, palmitinic acid, lauric acid, Unimac 5680, tetradecanoic acid and/or docosoic acid and the diester of stearic acid, oleic acid, palmitinic acid, lauric acid, Unimac 5680, docosoic acid and/or tetradecanoic acid.Know that general monoesters comprises some diester and three esters etc.
" glyceryl ester " also comprises Polyglycerine, for example, and double glyceride～eight glyceryl ester.The Polyglycerine polyvalent alcohol is by glycerine or epichlorohydrin condensation together, partly forms by ehter bond connection glycerine.The monoesters and/or the diester of preferred Polyglycerine polyvalent alcohol, the fatty acyl group group is generally hereinafter described those groups for sorbitan and glyceryl ester.
Be applicable to that other fabric softener of the present invention is described in the United States Patent (USP) 4,661,269 of Toan Trinh, the ErrolH.Wahl, Donald M.Swartley and the Ronald L.Hemingway that authorized on April 28th, 1987; The United States Patent (USP) 4,439,335 of the Burns that on March 27th, 1984 authorized; The United States Patent (USP) 3,861,870 of Ewards and Diehl; The United States Patent (USP) 4,308,151 of Cambre; The United States Patent (USP) 3,886,075 of Bernardino; The United States Patent (USP) 4,233,164 of Davis; The United States Patent (USP) 4,401,578 of Verbruggen; The United States Patent (USP) 3,974,076 of Wiersema and Rieke; With the United States Patent (USP) 4,237,016 of Rudkin, Clint, Young, all described patents are hereby incorporated by.
For example, be used for suitable fabrics softening agent of the present invention and can comprise a kind of, two kinds or whole following three kinds of fabric softeners:
(a) higher fatty acid and is selected from the reaction product (preferred about 10%～about 80%) of the polyamine of hydroxyalkyl Alkylenediamine and two alkylene triamine and composition thereof; And/or
(b) only contain a long-chain and do not have cyclic aliphatic C
15～C
22The positively charged ion of hydrocarbyl group contains nitrogen salt (preferred about 3%～about 40%); And/or
(c) positively charged ion contains nitrogen salt, and it contains two or more long-chains does not have cyclic aliphatic C
15～C
22Hydrocarbyl group, or a described group and an aromatic alkyl group (preferred about 10%～about 80%); Described (a) and (b) and preferred percent (c) are benchmark with the weight of the fabric softener component of the present composition.
Hereinafter be above-mentioned (a) and (b) and (c) general description of softening agent composition (comprise some the explanation specific embodiments of the invention, but do not limit the present invention).
Component (a): softening agent of the present invention (actives) can be the reaction product that higher fatty acid and is selected from the polyamine of hydroxyalkyl Alkylenediamine and two alkylene triamine and composition thereof.According to the polyfunctional structure of polyamine, these reaction product are mixtures of several compounds.
Preferred ingredient (a) is a kind of nitrogenous compound that is selected from selected component in mixture of reaction products or some mixture.More specifically, preferred ingredient (a) is for being selected from following compound:
(i) molecular ratio is the reaction product of about 2: 1 higher fatty acid and hydroxyalkyl Alkylenediamine, and described reaction product comprises the following composition of chemical formula:
Wherein, R
1Be no cyclic aliphatic C
15～C
21Hydrocarbyl group, R
2And R
3Be divalence C
1～C
3Alkylidene group;
The imidazolinium compounds that (ii) has the replacement of following chemical formula:
Wherein, R
1And R
2Definition as above;
The substituted imidazoline compound that (iii) has following chemical formula:
Wherein, R
1And R
2Definition as above;
(iv) molecular ratio is about 2: 1 higher fatty acid and the reaction product of two alkylene triamine, and described reaction product comprises the following composition of chemical formula:
Wherein, R
1, R
2And R
3Definition as above; With
(the substituted imidazoline compound that v) has following chemical formula:
Wherein, R
1And R
2Definition as above; With
(vi) its mixture.
Component (a) (i) can Mazamide
6 buy, sell by Mazer Chemicals, or with Ceranine
HC buys, by Sandoz Coors﹠amp; Chemicals sells; Higher fatty acid herein is a hydrogenated tallow fatty acid, and the hydroxyalkyl Alkylenediamine is the N-2-hydroxyethylethylene diamine, R
1Be aliphatic C
15～C
17Hydrocarbyl group, R
2And R
3Be divalence ethylidene group.
Component (a) example (ii) is octadecyl hydroxyethyl imidazole quinoline, wherein R
1Be aliphatic C
17Hydrocarbyl group, R
2Be divalence ethylidene group; This chemical is with trade(brand)name Alkazine
ST is by Alkaril Chemicals, and Inc. sells, or with Schercozoline
S is by Scher Chemicals, and Inc. sells.
Component (a) example (iv) is N, N " two tallow acyl group diethylenetriamine, wherein, R
1Be C
15～C
17Hydrocarbyl group, R
2And R
3Be divalence ethylidene group.
Component (a) (example v) is 1-tallow amido ethyl-2-tallow tetrahydroglyoxaline, wherein, and R
1Be C
15～C
17Hydrocarbyl group, R
2Be divalence ethylidene group.
(iii) and (a) (v) also can at first be dispersed in the pKa value is not more than in about 4 the protonic acid dispersing auxiliary component (a); Condition is that the pH of final composition is not more than about 5.Some preferred dispersing auxiliaries are hydrochloric acid, phosphoric acid or methylsulfonic acid.
N; N " two tallow acyl group diethylenetriamine and 1-tallow (amido ethyl)-2-tallow tetrahydroglyoxaline; the two all is reaction product of tallow fatty acids and diethylenetriamine; the precursor that is cationic fabric softener methyl isophthalic acid-tallow amido ethyl-2-tallow imidazoles Methylsulfate is (referring to " as the cats product of fabric softener " of R.R.Egan; " U.S.'s oiling is learned association's magazine " (Journal of the American Oil Chemicals ' is in January, 1978 Society), the 118th～121 page).N, " two tallow acyl group diethylenetriamine and 1-tallow amido ethyl-2-tallow tetrahydroglyoxaline can obtain with experimental chemistry product form from Witco Chemical Company N.Methyl isophthalic acid-tallow amido ethyl-2-tallow imidazoles Methylsulfate by Witco chemical company (Witco ChemicalCompany) with trade(brand)name Varisoft
475 sell.
Component (b): preferred ingredient (b) is for positively charged ion contains nitrogen salt, and it comprises one and is selected from following long-chain and does not have cyclic aliphatic C
15～C
22Hydrocarbyl group:
(i) have the acyclic quaternary ammonium salt of following chemical formula:
Wherein, R
4Be no cyclic aliphatic C
15～C
22Hydrocarbyl group, R
5And R
6Be C
1～C
4Saturated alkyl or hydroxyalkyl group and A are negatively charged ion;
The imidazole salts that (ii) has the replacement of following chemical formula:
Wherein, R
1Be no cyclic aliphatic C
15～C
21Hydrocarbyl group, R
7Be hydrogen or C
1～C
4Saturated alkyl or hydroxyalkyl group, and A
-Be negatively charged ion;
The substituted imidazole salt that (iii) has following chemical formula:
Wherein, R
2Be divalence C
1～C
3Alkylidene group, R
1, R
5And A
-Definition as above;
The Fixanol that (iv) has following chemical formula:
Wherein, R
4Be no cyclic aliphatic C
16～C
22Hydrocarbyl group, and A
-Be negatively charged ion; With
(V) have the alkylamide alkylidene group pyridinium salt of following chemical formula:
Wherein, R
1Be no cyclic aliphatic C
15～C
21Hydrocarbyl group, R
2Be divalence C
1～C
3Alkylidene group and A are ionic group;
(the monoesters quaternary ammonium compound that vi) has following chemical formula:
[(R)
3-N
+-(CH
2)
n-Y-R
2]A
Wherein,
Each Y is-O-(O) C-or-C (O)-O-
Each n is 1～4;
Each R substituting group is a short chain C
1～C
6, preferred C
1～C
3Alkyl or hydroxyalkyl group, for example, methyl (most preferably), ethyl, propyl group, hydroxyethyl etc., benzyl or its mixture;
R
2Be C
10～C
22Alkyl or substituted hydrocarbon radical, substituting group, preferred C
12～C
19Alkyl and/or alkenyl, most preferably C
12～C
18Straight chained alkyl and/or alkenyl (in the preparation, chain is short more, and is stable more); Counter ion A
-Can be any negatively charged ion compatible with softening agent, for example, muriate, bromide, Methylsulfate, formate, vitriol, nitrate etc.; With
(vii) its mixture.
Component (b) example (i) is a monoalkyltrimethyl ammonium salts, as single tallow base trimethyl ammonium chloride, list (hydrogenated-tallow group) trimethyl ammonium chloride, palmityl trimethyl ammonium chloride and soybean trimethyl ammonium chloride, by Sherex chemical company (Sherex Chemical Comnpany) respectively with trade(brand)name Adogen
471, Adogen
441, Adogen
444 and Adogen
415 sell.In these salt, R
4Be no cyclic aliphatic C
16～C
18Hydrocarbyl group, R
5And R
6Be methyl group, preferred single (hydrogenated-tallow group) trimethyl ammonium chloride and single tallow base trimethyl ammonium chloride.
Component (b) other example (i) is an INCROQUAT TMC-80, wherein, and R
4Be C
22Hydrocarbyl group, by the Humko of Witco chemical company Division of Chemistry (Humko Chemical Division ofWitco Chemical Corporation) with trade(brand)name Kemamine
Q2803-C sells; Soybean dimethyl ethyl QAE quaternary aminoethyl vitriol, wherein, R
4Be C
16～C
18Hydrocarbyl group, R
5Be monomethyl group, R
6Be an ethyl group, A
-Be the ethylsulfuric acid salt anionic, by Jordan chemical company (JordanChemical Corporation) with trade(brand)name Jordaquat
1033 sell; And methyl-two (2-hydroxyethyl)-octadecyl ammonium chloride, wherein, R
4Be C
18Hydrocarbyl group, R
5Be 2-hydroxyethyl groups, R
6Be methyl group, can trade(brand)name Ethoquad
18/12 obtains from Armak company.
Component (b) example (iii) is 1-ethyl-1-(2-the hydroxyethyl)-different heptadecyl imidazole ethyl of 2-vitriol, wherein, and R
1Be C
17Hydrocarbyl group, R
2Be ethylidene group, R
5Be ethyl group, A is the ethylsulfuric acid salt anionic.It can (Mona Industries be Inc.) with trade(brand)name Monaquat from Mona industrial
ISIES buys.
(example vi) is single (tallow acyl group oxygen ethyl) hydroxyethyl dimethyl ammonium chloride to component (b); it is the monoesters of tallow fatty acids and two (hydroxyethyl) alkyl dimethyl ammonium chloride; make a kind of by product of tallow fatty acids and two (hydroxyethyl) alkyl dimethyl ammonium chloride diester; i.e. two (tallow acyl group oxygen ethyl) alkyl dimethyl ammonium chloride, a kind of (c) component (vide infra) (iii).
Component (c): preferred cation contains nitrogen salt to be had two or more long-chains and not to have cyclic aliphatic C
15～C
22Hydrocarbyl group or a described group and an aromatic alkyl group, it can use separately, or uses as the part of mixture, and it is selected from:
(i) have the acyclic quaternary ammonium salt of following chemical formula:
Wherein, R
4Be no cyclic aliphatic C
15～C
22Hydrocarbyl group, R
5Be C
1～C
4Saturated alkyl or hydroxyalkyl group, R
8Be selected from R
4And R
5Group, and A
-Be definition negatively charged ion as above;
The diamido quaternary ammonium salt that (ii) has following chemical formula:
Wherein, R
1Be no cyclic aliphatic C
15～C
21Hydrocarbyl group, R
2For having the divalent alkyl group of 1～3 carbon atom, R
5And R
9Be C
1～C
4Saturated alkyl or hydroxyalkyl group and A are a negatively charged ion;
The diamino alkoxy quaternary ammonium salt that (iii) has following chemical formula:
Wherein, n=1～about 5, and R
1, R
2, R
5Define as above with A;
The quaternary ammonium compound that (iv) has following chemical formula:
R wherein
4Be no cyclic aliphatic C
15～C
22Hydrocarbyl group, R
5Be C
1～C
4Saturated alkyl or hydroxyalkyl group, A are a negatively charged ion;
(the substituted imidazole salt that v) has following chemical formula:
Wherein, R
1Be no cyclic aliphatic C
15～C
21Hydrocarbyl group, R
2For having the divalent alkyl group of 1～3 carbon atom, R
5Define as above with A; With
(the substituted imidazole salt that vi) has following chemical formula:
Wherein, R
1, R
2And A
-Definition as above;
(diester quat (DEQA) that vii) has following chemical formula:
(R)
4-m-N
+-[(CH
2)
n-Y-R
2]
mA
Wherein,
Each Y is-O-(O) C-or-C (O)-O-;
M is 2 or 3;
Each n is 1～4;
Each R substituting group is a short chain C
1～C
6, preferred C
1～C
3Alkyl or hydroxyalkyl group, for example, methyl (most preferably), ethyl, propyl group, hydroxyethyl etc., benzyl or its mixture;
Each R
2Be a long-chain C
10～C
22Alkyl, or substituted hydrocarbon radical substituting group, preferred C
15～C
19Alkyl and/or alkenyl, most preferably C
15～C
18Straight chained alkyl and/or alkenyl; With
Counter ion A
-Can be any negatively charged ion compatible with softening agent, for example, muriate, bromide, Methylsulfate, formate, vitriol, nitrate etc.; With
(vii) its mixture.
Component (c) example (i) is well-known dialkyl dimethyl ammonium salt, as Varisoft DHT, two tallow base Dimethyl Ammonium Methylsulfates, two (hydrogenated-tallow group) alkyl dimethyl ammonium chloride, distearyl acyl group alkyl dimethyl ammonium chloride, two docosyl alkyl dimethyl ammonium chlorides.Preferred two (hydrogenated-tallow group) alkyl dimethyl ammonium chloride and Varisoft DHTs.The example that can be used for dialkyl dimethyl ammonium salt of the present invention that can buy is two (hydrogenated-tallow group) alkyl dimethyl ammonium chloride (trade(brand)name Adogen
442), Varisoft DHT (trade(brand)name Adogen
470), distearyl acyl group alkyl dimethyl ammonium chloride (trade(brand)name Arosurf
TA-100), all can obtain from Witco chemical company.R wherein
4Be no cyclic aliphatic C
22Two docosyl alkyl dimethyl ammonium chlorides of hydrocarbyl group, by the Humko of Witco chemical company Division of Chemistry with trade(brand)name Kemamine
Q-2802C sells.
Component (c) example (ii) is two (tallow base amido ethyl) (2-hydroxyethyl) ammonium methyl sulphates of methyl and two (hydrogenated-tallow group amido ethyl) (2-hydroxyethyl) ammonium methyl sulphates of methyl, wherein, and R
1Be no cyclic aliphatic C
15～C
17Hydrocarbyl group, R
2Be ethylidene group, R
5Be methyl group, R
9Be hydroxyalkyl group, A is the methylsulfuric acid salt anionic; These materials can be from Witco chemical company respectively with trade(brand)name Varisoft
222 and Varisoft
110 obtain.
Component (c) example (iv) is a dimethyl stearyl-benzyl ammonium chloride, wherein, and R
4Be no cyclic aliphatic C
18Hydrocarbyl group, R
5Be methyl group, A
-Be chloride anion, by Witco chemical company with trade(brand)name Varisoft
SDC and Onyx chemical company (Onyx Chemical Company) are with trade(brand)name Ammonyx
490 sell.
Component (c) (example v) is 1-methyl isophthalic acid-tallow amido ethyl-2-tallow base imidazoles Methylsulfate and 1-methyl isophthalic acid-(hydrogenated-tallow group amido ethyl)-2-(hydrogenated-tallow group) imidazoles Methylsulfate, wherein, and R
1Be no cyclic aliphatic C
15～C
17Hydrocarbyl group, R
2Be ethylidene group, R
5Be methyl group, A
-Be chloride anion; They by Witco chemical company respectively with trade(brand)name Varisoft
475 and Varisoft
445 sell.
Know (vii), above-mentioned substituent R and R for (c)
2Can be randomly replaced, and/or can be saturated, undersaturated, straight chain and/or side chain, as long as R by various groups such as alkoxyl group or oh group
2Group can keep hydrophobic character substantially.Preferred softening compound thing is biodegradable, as component (c) (vii).These preferred compounds can be counted as the diester variations of Varisoft DHT (DTDMAC), and it is widely used on the fabric softener.
Following be (c) (non-limiting example vii) (wherein, all chain alkyl substituting group be straight chain):
[CH
3]
2 +N[CH
2CH
2OC(O)R
2]
2Cl
-
[HOCH(CH
3)CH
2][CH
3]
+N[CH
2CH
2OC(O)C
15H
31]
2Br
[C
2H
5]
2 +N[CH
2CH
2OC(O)C
17H
35]
2Cl
-
[CH
3][C
2H
5]
+N[CH
2CH
2OC(O)C
13H
27]
2I
-
[C
3H
7][C
2H
5]
+N[CH
2CH
2OC(O)C
15H
31]
2 -SO
4CH
3 
[CH
2CH
2OH] [CH
3]
+N[CH
2CH
2OC (O) R
2]
2Cl
-Wherein ,-C (O) R
2Be derived from soft tallow and/or hard tallow fatty acids.The diester of preferred especially soft and/or hard tallow fatty acids and two (hydroxyethyl) alkyl dimethyl ammonium chloride also can be called two (tallow acyl group oxygen ethyl) alkyl dimethyl ammonium chloride.
Because more aforesaid compounds (diester) are easy to hydrolysis to a certain extent, when using it for preparation composition of the present invention, should quite carefully operate.For example, stable liquid compositions of the present invention is to prepare in pH is about scope of 2～about 5, preferred about 2～about 4.5, more preferably from about 2～about 4.PH can regulate by adding protonic acid.Preparation contains the pH scope of stable softener composition of diester quaternary ammonium fabric softening compound thing, is disclosed in the United States Patent (USP) 4,767,547 of the Straathof that authorized on August 30th, 1988 and Konig, is incorporated herein by reference herein.
(c) (diester quaternary ammonium fabric softening compound thing (DEQA) vii) also can have general formula:
Wherein, each R, R
2And A
-Have and former identical implication.This compounds comprises those compounds with following chemical formula:
[CH
3]
3 +N[CH
2CH (CH
2OC (O) R
2) OC (O) R
2] Cl wherein ,-OC (O) R
2Be derived from soft tallow and/or hard tallow fatty acids.
Preferred each R is methyl or ethyl group, preferably each R
2At C
15～C
19Scope in.Branching to a certain degree, replacement and/or unsaturated may reside in the alkyl chain.The preferred strong acid anion of negatively charged ion A in the molecule for example, can be muriate, bromide, vitriol and Methylsulfate; Negatively charged ion can have double charge, in such cases, and A
-Represent group half.Generally speaking these compounds are difficult to make stable concentrated liquid composition.
Three types the compound and the general method of preparation thereof are disclosed in the people's such as Naik that authorized on January 30th, 1979 the United States Patent (USP) 4,137,180, are incorporated herein by reference herein.
A kind of preferred compositions contains about 10%～about 80% the component (a) that accounts for present composition fabric sofetening composition weight, about 3%～about 40% component (b) and about 10%～about 80% component (c).A kind of preferred composition contains and is selected from (i) two (hydrogenated-tallow group) alkyl dimethyl ammonium chloride; (v) methyl isophthalic acid-tallow base amido ethyl-2-tallow base imidazoles Methylsulfate; (vii) two tallow base ethanol ester alkyl dimethyl ammonium chlorides; And composition thereof component (c).
A kind of even preferred composition contains component (a): the reaction product of about 2 moles of hydrogenated tallow fatty acids and about 1 mole of N-2-hydroxyethylethylene diamine, its amount are about 20～about 70% of present composition fabric sofetening composition weight; Component (b): single (hydrogenated-tallow group) trimethyl ammonium chloride, its amount is about 3%～about 30% of a present composition fabric sofetening composition weight; Component (c): be selected from two (hydrogenated-tallow group) alkyl dimethyl ammonium chloride, Varisoft DHT, methyl isophthalic acid-tallow base amido ethyl-2-tallow base imidazoles Methylsulfate, diethyl alcohol ester alkyl dimethyl ammonium chloride and composition thereof; Wherein, the amount of component (c) is about 20～about 60% of a present composition fabric sofetening composition weight; Wherein, the weight ratio of described two (hydrogenated-tallow group) alkyl dimethyl ammonium chlorides and described methyl isophthalic acid-tallow base amido ethyl-2-tallow base imidazoles Methylsulfate is about 2: 1～about 6: 1.
Also can use those components (for example, Varisoft DHT or two tallow base ethanol ester alkyl dimethyl ammonium chlorides) of above-mentioned each component, particularly I (c) independently.
Described hereinafter positively charged ion contains in the nitrogen salt, negatively charged ion A
-Electric neutrality is provided.The most frequent is that being used to provide electroneutral negatively charged ion in these salt is halogenide, as muriate or bromide.But, also can use other negatively charged ion, as Methylsulfate, sulfovinate, oxyhydroxide, acetate, formate, Citrate trianion, vitriol, carbonate etc.Preferred muriate of the present invention and Methylsulfate are as negatively charged ion A.Reduce further to increase product stability and soft effect because the foam of finished product is long-pending, so available traditional high-shear grinding equipment is milled fabric softener.Preferred 1 micron or the littler particle of milling.
Sequestrant-stable composition of the present invention and method are preferably used one or more copper and/or nickel sequestrant (chelating agents) (" sequestrant (chelators) ").This class water-soluble chelator can be selected from aminocarboxylate, phosphoro-amidate, multifunctional replacement aromatic chelating agent and composition thereof, all these such as hereinafter definition.Without being limited by theory, the benefit of believing these materials partly is because they can remove copper and mickel ionic special ability by forming the soluble chelating thing from rinsing solution.Be unexpectedly, as if these sequestrants also interact on fabric with dyestuff and white dyes, described fabric in laundry processes with copper or nickel cation (or other positively charged ion, as manganese, iron or transition metal) interacting is influenced undesirably, and be accompanied by variable color and/or filbert effect.By contacting with sequestrant, the whiteness of these affected fabrics and/or brightness improve basically or have recovered.
The aminocarboxylate that is suitable for use as sequestrant of the present invention comprises edetate (EDTA), N-hydroxyethyl-ethylenediamine triacetate, nitrilotriacetic acid(NTA) salt (NTA), ethylenediamine tetrapropionic acid(EDTP) salt, quadrol-N, N '-two glutaminate, 2-hydroxyl propylene diamine-N, N '-disuccinate, triethylenetetraaminehexaacetic acid salt, diethylentriamine pentacetate (DETPA) and ethanol diamino-acetic acid, comprise its water-soluble salt, as its an alkali metal salt, ammonium salt, substituted ammonium salt and composition thereof.
When in detergent composition, allowing a small amount of at least total phosphorus, amino phosphonates do also is suitable for use as the sequestrant of the present composition, it comprises ethylenediamine tetraacetic (methylene phosphonic acid salt), diethylenetriamine-N, N, N ', N ", N " five (phosphonic salts) (DETMP) and 1-hydroxyethyl-1,1-diphosphonate (HEDP).These phosphoro-amidates preferably do not comprise alkyl or the kiki alkenyl group that has more than about 6 carbon atoms.
Usually, the chelating dosage that is used for rinse method of the present invention is about 2ppm～about 25ppm, soak time be 1 minute up to several hours.
Being used for preferred EDDS sequestrant of the present invention (being also referred to as quadrol-N, N '-disuccinate) is to be described in United States Patent (USP) 4,704, and the material in 233 is quoted as mentioned, and its chemical formula (representing with free acid form) is:
As disclosed in this patent, EDDS can prepare with maleic anhydride and quadrol.Preferred biodegradable EDDS[S, S] isomer can be by making L-aspartic acid and glycol dibromide prepared in reaction.EDDS is that it is all effective to chelated copper and nickel cation than the advantage that other sequestrant had, can biodegradable form obtain, and not phosphorous.The EDDS that is used for the present invention as a kind of sequestrant is normally with the form of its salt, i.e. one or more by a kind of water-soluble cationic M, as replacements such as sodium, potassium, ammonium, triethanol ammoniums in four acidic hydrogens wherein.As previously mentioned, the EDDS sequestrant generally also is used in the rinse method of the present invention, and its amount is for about 2ppm～about 25ppm, soak time be 2 minutes up to several hours.As hereinafter mentioning, when certain pH value, EDDS preferably is used in combination with zinc cation.
Can see that from aforementioned the present invention can use multiple sequestrant.In fact, also can use simple polycarboxylate, as Citrate trianion, oxygen di-succinate etc., although on weight basis, this class sequestrant is effective like that not as aminocarboxylate and phosphonate.So consider its chelating validity degree difference, can adjust its consumption.Sequestrant of the present invention preferably has-cupric ion stability constant (all stability constants of ionization sequestrants), and it is about 5 that this stability constant is at least, and preferably is at least about 7.Sequestrant accounts for the about 0.5% of present composition weight at least, is generally about 0.75%～about 15%, preferred about 1%～about 5%.Preferred sequestrant comprises DETMP, DETPA, NTA, EDDS or its mixture.
Chlorine scavenger-many in the world areas make water sterilization with chlorine.For guaranteeing that water is safe, the small amount of residual chlorine of generally staying in the water is per approximately 1/1000000th～2 parts (ppm).Sometimes, at least about containing have an appointment 2ppm or more chlorine in the 10% American family tap water.Find that a spot of like this chlorine also can cause some dye for fabrics to fade or variable color in the tap water.Therefore, chlorine causes fabric color and subtracts in time that to take off be to exist residual chlorine to cause in the rinse water.So stable composition of the present invention also can comprise a kind of chlorine scavenger.And, use this chlorine scavenger, because it can eliminate or reduce the chlorine flavor on the fabric, can provide a kind of ancillary benefit.
Chlorine scavenger is to react with chlorine or the material such as the hypochlorite that generate chlorine, and eliminates or reduce the material of the bleaching activity of chloride material.For the color fidelity, generally be suitable for adding the chlorine scavenger of capacity, with in and the chlorine of about 1～10ppm in the rinse water, usually at least in and the chlorine of about 1ppm in the rinse water.Eliminate or reduce owing to use the fabric chlorine flavor that chlorine bleach caused in washings for additional, composition should comprise the chlorine scavenger of capacity, with in and in the rinse water at least about the chlorine of 10ppm.
This composition of the present invention provides about 0.1ppm～about 40ppm, preferably about 0.2ppm～about 20ppm, the more preferably chlorine scavenger of 0.3ppm～about 10ppm in common rinsing is bathed.The chlorine scavenger amount that is suitable in the present composition be total composition weight about 0.01%～about 10%, preferred about 0.02%～about 5%, most preferably from about 0.03%～about 4%.If the positively charged ion of remover and negatively charged ion all with chlorine reaction, this is desired, then can regulate the remover amount so that itself and normal available chlorine react.
The non-limiting example of chlorine scavenger comprises primary amine and secondary amine, comprises uncle's aliphatic amine and secondary aliphatic amine; Ammonium salt, for example muriate, vitriol; The functional polymkeric substance of amine; Amino acid homopolymer and salt thereof with amino group are as poly arginine, polylysine, polyhistidyl; Amino acid copolymer and salt thereof with amino group; Amino acid and salt thereof preferably have the amino group more than in its per molecule, as arginine, Histidine, do not comprise Methionin reduction negatively charged ion, as sulphite, hydrosulphite, thiosulphate, nitrite; Oxidation inhibitor is as xitix, carbamate, phenol; With its mixture.Ammonium chloride is a kind of cheap chlorine scavenger of the present invention that is preferred for.
Other useful chlorine scavenger comprises the primary amine and the secondary amine of water-soluble low molecular weight, low volatility, for example, and monoethanolamine, diethanolamine, three (methylol) aminomethane, vulkacit H.The functional chlorine scavenger polymkeric substance of amine that is suitable for comprises: water-soluble poly ethyleneimine, polyamine, polyvinylamine, polyamine acid amides and polyacrylamide.Preferred polymkeric substance is poly-ethyleneimine, polyamine and polyamine acid amides.The molecular weight of preferred poly-ethyleneimine is less than about 2000, and more preferably from about 200～about 1500.
Intensity retention agent-well-known, fabric may be subjected to the destruction of mechanical force and various chemical.Specifically, known fiber cellulose fiber such as cotton can be degraded to protofibril and microfibril, and its eventual failure makes fabric seem " grinding old ".Have now found that some material, particularly KYMENE can join in the composition of the present invention with being stabilized.In case touch protofibril and microfibril, KYMENE it seems can provide crosslinked action, before fibril breakage, helps to recover intensity thus.
KYMENE is the material of a kind of polymeric amide/polyamine/Epicholorohydrin type, is described in United States Patent (USP) U.S.2,926,154 (2/23/60; License to G.I.Keim), details can also can be with reference to United States Patent (USP) U.S.5,200,036 with reference to this patent.If use, its account for present composition weight at least about 0.1%, be generally about 0.1%～about 1.5%, preferred about 0.5%～about 1%.
Dye transfer inhibitor-stable composition of the present invention also can comprise one or more in rinse cycle, can effectively suppress the material that dyestuff shifts to another kind of fabric from a kind of fabric.Generally speaking, this dye transfer inhibitor comprises multipolymer, manganese phthalocyanine, peroxidase of polyvinyl pyrrolidone polymers, polyamine N-oxide pllymers, N-vinyl pyrrolidone and N-vinyl imidazole and composition thereof.If use, these reagent generally account for composition weight about 0.01%～about 10%, preferred about 0.01%～about 5%, more preferably from about 0.05%～about 2%.
More particularly, be preferred for polyamine N-oxide pllymers of the present invention and comprise the unit with following structural formula: R-Ax-Z; Wherein Z is a kind of polymerizable unit, and the N-O group can be connected on this polymerizable unit, and perhaps the N-O group can form the part of this polymerizable unit, and perhaps the N-O group can be connected on these two unit; A be one of following structure :-NC (O)-,-C (O) O-,-S-,-O-,-N=; X is 0 or 1; With R be aliphatic series, aliphatic, the aromatics of ethoxylation, heterocycle or alicyclic group or its arbitrary combination, the N of N-O group can be connected thereto or the N-O group is the part of these groups.Preferred polyamine N-oxide compound is a heterocyclic group for R wherein, as those polyamine N-oxide of pyridine, pyrroles, imidazoles, tetramethyleneimine, croak pyridine and derivative thereof.
The N-O group can be represented with following general structure:
Wherein, R
1, R
2, R
3Be aliphatic series, aromatics, heterocycle or alicyclic group or its combination; X, y and z are 0 or 1; With the N of N-O group can be coupled or form the part of any aforementioned group.The unitary pKa of the amine oxide of polyamine N-oxide＜10, preferred pKa＜7, more preferably pKa＜6.
As long as formed amine oxide polymers is water-soluble and has the dye transfer rejection, just can adopt any polymer backbone.The example of suitable polymers skeleton is polyethylene, polyalkylene, polyester, polyethers, polymeric amide, polyimide, polyacrylic ester and composition thereof.These polymkeric substance comprise random copolymers or segmented copolymer, and one of them monomer type is an amine n-oxide, and other monomer type is the N-oxide compound.The ratio of common amine that has of amine n-oxide polymkeric substance and amine n-oxide is 10: 1～1: 1,000,000.But the quantity that is present in the amine oxide group in the polyamine oxide polymer can change by suitable co-polymerization or suitable N-degree of oxidation.The polyamine oxide compound can almost obtain with any polymerization degree.Generally speaking, its molecular-weight average is 500～1, in 000,000 the scope; More preferably 1,000～500,000; Most preferably 5,000～100,000.The preferred material of this class can be known as " PVNO ".
The most preferably polyamine N-oxide that is applicable to rinse added compositions of the present invention and method is poly-(4-vinylpridine-N-oxide compound), and its molecular-weight average is about 50,000, and the ratio of amine and amine n-oxide is about 1: 4.
The present invention also can preferably use the multipolymer (class that is called " PVPVI ") of N-vinyl pyrrolidone and N-vinyl imidazole polymkeric substance.The average molecular weight range of preferred PVPVI is 5,000～1,000,000, more preferably 5,000～200,000, most preferably 10,000～20,000.(average molecular weight range is by light scattering determining, is described in " chemical analysis " the 113rd volume of people such as Barth, and " modernism of polymer characterization ", its disclosure is hereby incorporated by).General N-vinyl imidazole that has of PVPVI multipolymer and N-vinyl pyrrolidone mol ratio are 1: 1～0.2: 1, more preferably 0.8: 1～0.3: 1, and most preferably 0.6: 1～0.4: 1.These multipolymers or be straight chain or for side chain.
The present composition also can use a kind of molecular-weight average for about 5,000～about 400,000, preferred about 5,000～about 200,000 and more preferably from about 5,000～about 50,000 polyvinylpyrrolidone (" PVP ").The technician of detergent applications knows PVP ' s; For example, referring to European patent application EP-A-262,897 and European patent application EP-A-256,696, be incorporated herein by reference herein.The composition that contains PVP also can comprise molecular-weight average be about 500～about 100,000, preferred about polyoxyethylene glycol of 1,000～about 10,000 (" PEG ").The ratio that preferably is released into PEG in the washing soln and PVP with ppm count about 2: 1～about 50: 1, more preferably from about 3: 1～about 10: 1.
Composition of the present invention also can randomly comprise the wetting ability white dyes of certain type of about 0.005%～5% (weight), and it also provides a kind of dye transfer restraining effect.If use, preferably comprise this white dyes of about 0.001%～1% (weight) in the composition of the present invention.
Be applicable to that wetting ability white dyes of the present invention is the material with following structural formula:
Wherein, R
1Be selected from anilino, N-2-two-hydroxyethyl and NH-2-hydroxyethyl; R
2Be selected from N-2-pair-hydroxyethyl, N-2-hydroxyethyl-N-methylamino-, morpholino, chlorine and amino; With M be the salifiable positively charged ion of shape, as sodium or potassium.
In above-mentioned chemical formula, R
1Be anilino, R
2For N-2-two-when hydroxyethyl and M were a positively charged ion such as sodium, whitening agent was 4,4 '-two [(4-anilino-6-(N-2-two-hydroxyethyl)-s-triazine-2-yl) amino]-2,2 '-stilbene disulfonic acid and disodium salt.The whitening agent material that this class is concrete is commercially available with trade(brand)name Tinopal-UNPA-GX by Ciba-GeigyCorporation.Tinopal-UNPA-GX is applicable to that the present invention adds the preferred hydrophilic white dyes in the composition.
In above-mentioned chemical formula, R
1Be anilino, R
2When being positively charged ion such as sodium for N-2-hydroxyethyl-N-2-methylamino-and M, whitening agent is 4,4 '-two [(4-benzene) base-6-(N-2-hydroxyethyl-N-methylamino-)-s-triazine-2-yl) amino]-2,2 '-the stilbene disulfonic acid disodium salt.The whitening agent material that this class is concrete is commercially available with trade(brand)name Tinopal-5BM-GX by Ciba-Geigy Corporation.
In above-mentioned chemical formula, R
1Be anilino, R
2When being a positively charged ion such as sodium for morpholino and M, whitening agent is 4,4 '-two [(4-anilino-6-morpholino-s-triazine-2-yl) amino]-2,2 '-the stilbene disulfonic acid disodium salt.The whitening agent material that this class is concrete is commercially available with trade(brand)name Tinopal-AMS-GX by Ciba-Geigy Corporation.
Be selected to this concrete white dyes of the present invention, when being used in combination with selected polymeric dye transfer inhibitor as described above, can providing especially effectively, dye transfer suppresses benefit.With this selected polymer material (for example, PVNO and/or PVPVI) and this selected white dyes is (for example, Tinopal UNPA-GX, Tinopal 5BX-GX and/or Tinopal AMS-GX) be used in combination, it is better significantly that the dye transfer that is provided separately when separately using these two kinds of components in the aqueous solution suppresses effect.Be not bound by theory, it is believed that it is because it has high-affinity to fabric in the aqueous solution that this whitening agent produces effect like this, so very fast under deposition on the fabric.Whitening agent is deposited in the solution degree on the fabric and can be called " exhausting coefficient (exhaustioncoefficient) " parameter with one and defines.Exhaust coefficient and be generally whitening agent material and the b that a) is deposited on the fabric) ratio of initial whitening agent concentration in the washings.Have the high relatively whitening agent that exhausts coefficient and be suitable for suppressing dye transfer within the scope of the invention most.
Certainly to recognize that the optical brightener compounds of other general type can randomly be used for composition of the present invention, " brighten " effect so that conventional fabric to be provided, rather than real dye transfer restraining effect.
Cellulase-cellulase also can improve the overall appearance of fabric, can randomly be used for composition of the present invention.There is multiple cellulase well-known in washing, food and field of papermaking.
Useful cellulase can be any bacterium or fungal cellulase in the present composition and method.The plain enzyme of useful fiber is disclosed, and for example UK Patent Application GB-A-2075028, UK Patent Application GB-A-2095275 and German DE-OS-2447832 are incorporated herein all as a reference.
The example of this cellulase is by Humicola insolens bacterial strain (grey humicola lanuginosa variant thermoidea), particularly the Humicola strain DSM 1800, with the mycetogenetic cellulase of the generation cellulase 212 that belongs to Aeromonas, and extraction is from the cellulase of sea mollusk (the truncation sea hare belongs to the atrium spire) hepatopancreas.
The cellulase that adds in the present composition can be non-dusting particle form, for example, " marumes " or " bead ", or with liquid form, for example a kind of cellulase that is wherein provided is the liquid that is suspended in for example a kind of nonionogenic tenside or is dissolved in the cellulase enriched material in the aqueous media.
Be used for preferred cellulose enzyme of the present invention and be characterised in that, cellulase protein matter is 25 * 10 in the laundry testing liquid
-6During % (weight), according to the C that is described among the European patent application EP A350098 (all being incorporated herein by reference) at this
14The CMC method, it can be removed at least about 10% immobilized radiolabeled carboxymethyl cellulose.
Most preferred cellulase is the enzyme that is described in the International Patent Application WO 91/17243, is incorporated herein all as a reference.For example, a kind of cellulase preparation that is used for the present composition can mainly be made up of a homogeneous phase endo-dextranase component, it has immune response with the antibody that the highly purified 43kD cellulase that is derived from Humicolainsolens and DSM1800 is produced, or itself and described 43kD endo-dextranase homology.
Cellulase of the present invention should be that the amount that about 0.1～about 125CEVU/ restrains composition is used for the present composition [CEVU=cellulase (equivalent) viscosity unit to be equivalent to vigor, for example, described in the WO91/13136, introduce it herein all as a reference], most preferably from about 5～about 100.In machine-washing rinse cycle process, select the cellulase of this amount, so that the preferred cellulose enzyme activity of certain amount of the present invention to be provided, make composition discharge to improve the cellulase amount of outward appearance and/or fabric softness, this amount rises rinsing solution less than about 50CEVU ' s/, preferably less than about 30CEVU ' s/ liter, be more preferably less than about 25CEVU ' s/ liter and most preferably less than about 20CEVU ' s/ liter.The preferred present composition is used for rinse cycle to provide about 1CEVU ' s/ to rise the amount that rinsing solution～about 50CEVU ' s/ rises rinsing solution, 2CEVU ' s/ liter～about 30CEVU ' s/ liter more preferably from about, even more preferably from about 5CEVU ' s/ liter～about 25CEVU ' s/ liter and most preferably from about 5CEVU ' s/ liter～about 15CEVU ' s/ liter.
CAREZYME and BAN cellulase, those cellulases as obtaining from NOVO are specially adapted to the present invention.If use, this commercial enzyme preparation generally accounts for about 0.001%～about 2% of this composition weight.
The present composition provides with the liquid form that is used for water-bath.Water or water/alcohol are the common carrier of liquid composition, generally its account for present composition weight up to about 89%.In pH is about scope of 3～about 8, compositions formulated expediently.In case dilute in solution, the pH scope during use is generally about 6.0～6.5.Know that the liquid composition preparation that contains EDDS and biodegradable (usually, containing ester) fabric softener is not really common, because it is, require the pH of product low, general in 3.0～3.5 scope for making biodegradable softening agent have best package stability.Under low like this pH condition, EDDS can form needle crystal in composition.If need, can be with the pH regulator of this composition to up to about 4.5, to dissolve EDDS again.But in this pH scope, total package stability of product will suffer damage.
Have now found that, can for example, prepare by zinc cation is provided in composition by adding water-soluble zinc salt at the liquid composition that contains EDDS of acid ph value scope 3.0～3.5.Particularly, zinc chloride also has ZnBr
2And ZnSO
4, all can be used for this purpose.The mol ratio of zinc cation and EDDS generally in about 1: 1～about 2: 1 scope, preferred about 3: 2.Therefore, when so that hereinafter described method is suitably prepared, the EDDS spicule of formation will reduce to minimum.
Hereinafter illustrate according to the compositions and methods of the invention, but do not mean and be confined to this:
Example I
With DEEDMAC (two tallow alkyl esters of ethyl alkyl dimethyl ammonium chloride; Mainly being two (the stearyl-oxygen ethyl) ammonium chlorides of dimethyl) raw material liquefies in 76 ℃ water-bath.To also comprise free-water in the composition of polysiloxane defoamers and about 0.02 part of HCl separately at an encloses container internal heating to 76 ℃.Under 72～75 ℃ and turbine mixer stir, the DEEDMAC raw material is transferred in the aqueous portion lentamente.CaCl with 1.2 part 25% (moisture)
2Solution splashes into disperse phase, so that the heavy-gravity lotion is made thin fluids.With the rotor-stator detecting element this system was milled 2 minutes 55 ℃ of following high-shears then.Under medium stirring, will make it in 5 minutes, drop to room temperature in this system immersion ice bath.
Under room temperature and medium stirring, join following compositions in the product successively:
1.25 the polymer stabilizer solution of part a kind of 40% is (by Gosselink; By dimethyl terephthalate (DMT)/1, the polyoxyethylene glycol of 2-propylene glycol/methyl blocking obtains, and comprises about 5 terephthalate unit in the preferred skeleton, and " afterbody " comprises 40 EO unit);
The mixture of a kind of 6.1 parts of 41%NaDETPA solution and 1.5 parts of dense HCl;
Spices up to 1.35 parts;
0.1 the ammonium chloride of part;
CAREZYME solution (choosing wantonly) up to 0.5 part;
2.8 the moisture CaCl of part 25%
2Solution.
Need enough mixing times to diffuse in the DEEDMAC bubble to promote spices.Mixing time is directly proportional with the batch processing amount.The addition sequence of said components is most important for the physical stability of final dispersion.Spices should be at CaCl
2Add before.Polymkeric substance should add sequestrant and preferably other ionogen added in the past.When the softening agent that uses the pH sensitivity, sequestrant should be mixed into pH near softening agent with acid or alkali, to avoid the partial pH variation that may influence softening agent stability and influence product viscosity stability.Finished product comprises 2.5% DETPA.
Example II
When a kind of product liquid that comprises DEEDMAC softening agent and EDDS sequestrant of preparation, the following improvement of Application Example I.1. generally use MgCl
2CaCl in the alternate sets compound
2With 1.0 parts of 25%MgCl
2The aqueous solution splashes in the dissipation of heat body, mills then, when proceeding to the final step of products production, adds this salt of equivalent.2. behind the adding stabilization of polymer, under medium stirring, replace adding DETPA/HCl, in product, add a kind of 3.8 parts of 33%NaEDDS aqueous solution and 1.25 parts～about 1.50 parts of 50%ZnCl
2The mixture of the aqueous solution.Contain 1.25%EDDS in the finished product.
EXAMPLE III
A kind of interpolation rinsing liquid chelant composite with fabric sofetening performance is prepared with biodegradable EDDS and a kind of Biodegradable fabric softener by following prescription.Finished product pH, " same as before " is determined as 3.5.
Component % (weight)
DEEDMAC 25
EDDS[S, S], Na salt 1.25
ZnCl
2 0.75
Polymkeric substance
*0.5
Water and small amount of matter
*Surplus
*By dimethyl terephthalate (DMT), 1, the polyoxyethylene glycol of 2-propylene glycol and methyl blocking is synthetic, and as disclosed by Gosselink, ibid.
*Spices, ionogen, souring agent.
EXAMPLE IV
A kind of Biodegradable fabric softener that contains, and in pH3～3.5 time preparation is as follows with the interpolation rinsing liquid chelant composite that package stability is provided:
Component % (weight)
DEEDMAC 25
DETPA，Na 2.5
KYMENE 1.0
Polymkeric substance
*0.5
Water and small amount of matter
*Surplus
*Polymkeric substance as EXAMPLE III.
*Spices, ionogen, souring agent.
The flowability and the homogeneity of the softener composition of the above-mentioned general type of table 2 explanation, it contains sequestrant DETPA, EDDS, DETMP and NTA respectively.
Table 2
Fresh aged 1.50 0 95 centipoises 390 centipoises (7 days) 2.50 0 250 centipoises of the viscosity %DETPA % polymer stabilizer of 74 (23 ℃) 2.50 0.25 32 centipoises, 40 centipoises (15 days), 2.50 0.50 28 centipoises, 36 centipoises (15 week) %EDDS that is separated in 1 day
*1.25 0.5 42 centipoises, 55 centipoises (1 week)
69 centipoises (3 week)
78 centipoises (6 week)
*Contain 0.63%ZnCl
2And MgCl
2With replaced C aCl
2Product; Viscosimetric analysis is carried out at ambient temperature.%DETMP2.5 0.5～0.75---44～77 centipoises
* *Fresh and under 40 of temperature (4 ℃)～74 (23 ℃) after 4 weeks.At storage temperature is under 110 °F (47 ℃), and in 3 week of experience, spread of viscosity is 44 centipoises～294 centipoises.%NTA2.5 0.5---58～71 centipoises
* *Measure same DETMP.Under 110 °F (47 ℃), spread of viscosity is 58 centipoises～491 centipoises (3 weeks).
Composition of the present invention can randomly comprise various other components, includes, but are not limited to: dyestuff; Defoamer (being generally polysiloxane defoamers) as Dow Corning 2210; Sanitas is as KATHON etc.This class component generally accounts for about 0.01%～about 1% of present composition total amount.For avoiding external metallic cation and ionogen, preferably use the deionized water compositions formulated.If use alcohol, as ethanol, its generally account for composition weight about 5% or still less.
The present composition is planned pending fabric and is contacted with a kind of water-bearing media that contains any above-mentioned composition and use.Contacting and to be undertaken by any method easily between fabric and treatment soln, comprise spraying, dip-dye, some processing, or preferably fabric is immersed in the water-bath that contains composition, for example usually at about 70 °F (20 ℃), be immersed in traditional pH and be in about 6.5～8.0 the rinsing water-bath at least about 1 minute, carry out other conventional washing operation then.The consumption of fabric softener is conventional, is generally 1～20mls or higher, and this depends on user's needs, processed fabric load and fabric type.The ethyl diformazan ammonium salt that preferably comprises a kind of dialkyl group esterification is a fabric softener, and ammonium chloride is chlorine scavenger and a kind of combination of chelating agents thing, and said composition keeps for the fabric of handling with this provides unusual fabric sofetening and color.
Claims (13)
1. composition, it comprises:
(a) a kind of stablizer that comprises terephthalate/alkylene oxide copolymer of a stable quantity;
(b) at least about a kind of fabric softener of 10% (weight);
(c) greater than total ionogen of about 1% (weight); With
(d) the aqueous fluid carrier of a kind of bag.
2. composition according to claim 1, wherein fabric softener is cationic, and contains ester bond.
3. composition according to claim 2, wherein fabric softener is the ethyl dimethyl ammonium of dialkyl group esterification.
4. composition according to claim 1, it comprises about fabric softener of 15%～about 35% (weight).
5. composition according to claim 2, it comprises about stablizer of 0.2%～about 1% (weight).
6. composition according to claim 1, wherein ionogen is a kind of compound that is selected from water-soluble inorganic salt.
7. composition according to claim 1, wherein ionogen is a kind of water-soluble organic compounds that is selected from sequestrant, intensity retention agent, sterilant, chlorine scavenger and composition thereof.
8. composition according to claim 1, it comprises:
(a) about 0.2%～about 1% (weight) is a kind of by dimethyl terephthalate (DMT)/1, the stablizer that the multipolymer of the oxyethane of 2-propylene glycol/methyl blocking obtains;
(b) about cationic fabric softener of 20%～about 30% (weight);
(c) amount for greater than composition weight about 1% comprise CaCl
2Or MgCl
2, or the ionogen of its mixture and a kind of water-soluble chelator; With
(d) the aqueous fluid carrier of a kind of bag.
9. composition according to Claim 8, wherein sequestrant is a kind of diethylenetriamine-N that is selected from, N, N ', N ", the N " compound of five (phosphonic salts), diethylentriamine pentacetate, nitrilotriacetic acid(NTA) salt and composition thereof.
10. composition according to Claim 8, wherein sequestrant is an ethylenediamine disuccinate, and said composition also comprises zinc cation.
11. the composition according to claim 1, it also comprises ammonium chloride as chlorine scavenger.
12. the composition according to claim 1, it also comprises a kind of cellulase.
13. one kind by to wherein mixing the method that a kind of stablizer that comprises water-soluble polyester comes stable liquid compositions, described liquid composition comprises a kind of cationic fabric softener at least about 10% (weight), total ionogen and the aqueous fluid carrier of a kind of bag greater than about 1% (weight).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96192375 CN1177976A (en) | 1995-01-12 | 1996-01-02 | Stabilized liquid fabric softener composition |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/372,490 | 1995-01-12 | ||
| CN 96192375 CN1177976A (en) | 1995-01-12 | 1996-01-02 | Stabilized liquid fabric softener composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1177976A true CN1177976A (en) | 1998-04-01 |
Family
ID=5128234
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 96192375 Pending CN1177976A (en) | 1995-01-12 | 1996-01-02 | Stabilized liquid fabric softener composition |
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| Country | Link |
|---|---|
| CN (1) | CN1177976A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113481063A (en) * | 2017-12-01 | 2021-10-08 | 宝洁公司 | Granular laundry softening detergent additive |
-
1996
- 1996-01-02 CN CN 96192375 patent/CN1177976A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113481063A (en) * | 2017-12-01 | 2021-10-08 | 宝洁公司 | Granular laundry softening detergent additive |
| CN113481063B (en) * | 2017-12-01 | 2024-03-22 | 宝洁公司 | Granular laundry softening detergent additive |
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