CN100338298C - Fabric treatment - Google Patents

Abstract

A method of treating finished garments comprising cellulosic material so as to cause cross-linking, which comprises the step of treating fabrics with an effective amount of a blocked cross-linking agent for cellulose, said cross-linking agent being thermally activated. A composition for use in the said method which comprises an effective amount of a blocked cross-linking agent for cellulose, said cross-linking agent being thermally activated.

Description

Fabric treating

Technical field

The present invention relates to be applicable to the laundry treatment compositions of home laundry process, specifically relate to comprise can with the composition of cellulose crosslinked component.

Background of invention

Cellulose is the polysaccharide that β-1,4 links to each other, and the also main component of widely used material is widely known by the people in fabric production for cotton is this.Cellulose can be crosslinked by the hydrogen bond that forms between cellulose chain.

At least contain the cellulose fibre of some cottons or artificial silk form mostly available from clothing all over the world, these clothings for example in family's laundry processes, generally can run into because of fiber size and change shrink, distortion and the wrinkling problem that causes when contacting with water.This phenomenon is considered to opening of hydrogen bond and forms again cause.

So-called fabric " durable press " is handled and is used for overcoming these problems.Modal a kind of durable press method is with crosslinking agent anchoring fiber element on molecular level.The crosslinking agent that becomes known for whole cloth has formaldehyde and urea-glyoxal resin.Additive method comprises chloropropylene oxide, vinyl sulfone, acrylic compounds-acid amides (acrylo-amide) and acrylic compounds-acrylate (acrylo-acrylate).Up to now, there be not any being organized into to show any market viability in the clothing in these schemes in family.

The known commercial run that is used for the finished product fabric production process has a lot.

US 4588761 discloses the polyurethane coating composition that uses with transfer paper or other interim carriers.These compositions comprise the isocyanates that is preferably end-blocking.This is a kind of method of industrial process fabrics, just is not suitable for the home treated of ready-made clothes from the inherence.

JK 53035098 discloses with a kind of and has weaved or the method for sorting of knitted fibers cellulose fabric with the processing solution-treated, and this Treatment Solution comprises carbamate prepolymer, glyoxal-acid amide type crosslinking agent and the bromo-metal fluoride of band end-blocking isocyanate group.This method is unsuitable for family's ready-made clothes arrangement.

JP 6346374 discloses with the commercial run of substep fabric or sewings has been put in order, this method comprise with blocked isocyanate handle, heat treatment and use the gas phase crosslinking agent subsequently.JP 8127972 discloses similar method.

JP 55093882 discloses a kind of method that is used for the flocked fabric product, and this method is used blocked isocyanate.JP 9316781 discloses a kind of finishing agent that yarn, paper or film are produced that is used for that contains blocked isocyanate.JP 11131374 discloses a kind of commercial run that waterproof fabric is produced that is used for, this method use based on glyoxal resin cross-linking agent, organofluorine compound and handle based on the crosslinking agent of isocyanates, then again heat treatment 0.5-5 minute.JP 2000129573 discloses similar method.

Another kind of scheme is to use polyacid such as BTCA (BTCA) or citric acid as crosslinking agent.They can form covalent cross-linking with cellulosic hydroxyl generation esterification.This covalent cross-linking can so both not prevented fabric distortion by water destruct, helps fabric to recover smooth again.One of problem that this method exists is will esterification be carried out with the sodium hypophosphite catalyst usually, and the goods after handling need heat cure.In addition, these polyacids are high water solubles, are difficult to be deposited on the fabric.

The preferred durable press system that is fit to family expenses is the system of nontoxic, one pack system, catalyst-free, and lack flatiron-hardening time, with fabric face certain compatibility arranged, and can not cause the decline of fabric intensity.Also should avoid using professional equipment in addition and use the inconvenient material (as gaseous formaldehyde) that uses.

Summary of the invention

We have determined to use cellulose crosslinked dose of thermal activation and have handled the cross-linking effect that ready-made clothes can obtain excellence.

Therefore, the invention provides a kind of ready-made clothes of handling cellulose-containing material and make the method that generation is crosslinked, described method comprise the cellulose crosslinked dose of step of handling fabric with the end-blocking of effective dose, described crosslinking agent is the crosslinking agent of thermal activation.

In the context of the present invention, term " thermal activation " is meant that crosslinking agent is carried out to stop reaction by " end-blocking ", is subjected to thermal activation up to crosslinking agent.Crosslinked in order to finish, at least two active sites of preferred crosslinking agent are by heat-labile end-capping group end-blocking.

Preferably by the cross-linking part of end-blocking be selected from be easy to after those activation with cellulose in the position of the hydroxyl reaction that exists.More preferably cross-linking reaction forms " ester " key, and in the context of the present invention, " ester bond " comprises the key that the α-carbon of ester is replaced by hetero atom (preferred nitrogen atom).When α-carbon was so substituted, the formal name of this molecule was called carbamate.

It is desirable to need not catalyst and carry out this reaction.Can choose wantonly and have catalyst.According to the end-blocking electrochemical conditions of concrete use and for example comprise the catalyst that pH value, modifier and/or Metal Ion Selective Electrode are fit to.

Preferred described crosslinking agent is dual functional.

In an embodiment preferred of the present invention, described crosslinking agent is dual functional at least end-blocking polybasic carboxylic acid.

In another embodiment preferred of the present invention, described crosslinking agent is dual functional at least blocked isocyanate.

" dual functional " is meant the end-capping group of at least two energy of existence as cross-linking part.Preferred these two groups are blocked isocyanate or end-blocking carboxylic acid.

Preferred end-blocking carboxylic acid is the ester with more weak ester bond, and this ester bond can carry out ester exchange with cellulose.This realizes by forming polyester between polybasic carboxylic acid and this good leaving group of alcohol (this term comprises phenol).Alcohol is as heat-labile " end-capping reagent " of hydroxy-acid group.Adopt carboxylic acid/imido bonding can obtain essentially identical effect.

The invention provides a kind of ready-made clothes of handling cellulose-containing material and make crosslinked method takes place, described method comprises the step that dual functional at least end-blocking polybasic carboxylic acid and the described cellulosic material with effective dose carries out ester exchange.

Preferred described end-blocking polybasic carboxylic acid is with electrophilic alcohol or acid imide end-blocking.

The present invention also provides a kind of crosslinked method of the feasible generation of ready-made clothes of handling cellulose-containing material, and described method comprises the step of handling the ready-made clothes of cellulose-containing material with the dual functional at least blocked isocyanate of effective dose.

In the present invention, arrangement is as the part of the home washings of ready-made clothes operation and carry out.

Another aspect of the present invention provides a kind of composition that is used for said method.

Preferred described composition comprises the crosslinking agent that forms ester bond with cellulose.

Preferred described crosslinking agent comprises the blocked polyisocyanates or the end-blocking polybasic carboxylic acid of thermal activation.

Preferred method of the present invention is included in 50-250 ℃, more preferably passes through the step of heat treatment for solidification processed material 100-200 ℃ time.

Method more preferably of the present invention also comprises the step by flatiron or hot-press solidifying processed material.It is wondrous to press the good result that can obtain after the processing.

The inventive method preferably can and not have under the condition of known other components that are unsuitable for family expenses of prior art and implement at no gaseous formaldehyde.

Detailed Description Of The Invention

As mentioned above, described cellulose crosslinked dose can be end-blocking polybasic carboxylic acid or blocked isocyanate.Hereinafter this two classes crosslinking agent preferred embodiment is separately done further to discuss.

In some embodiments, the main chain of described crosslinking agent has polymeric character, that is contains the structure of repetition.This main chain comprises sufficiently long paradigmatic structure (preferred 2-12 carbon-to-carbon bond distance) usually to realize its function as bridging structure between two or more reactive groups.

A. end-blocking polybasic carboxylic acid:

Be applicable to polyester of the present invention comprise the esterification of " being left away " group polybasic carboxylic acid, described leaving group is alcohol or acid imide.But preferred described polybasic carboxylic acid contains the carboxyl of 2-6 esterification.Usually each carboxyl is all esterified and make polyester.

But most preferably described polybasic carboxylic acid contains the carbonyl of two esterifications, and these two carbonyls are usually located at the two ends of the polybasic carboxylic acid molecule of substantially linear.In a preferred embodiment, described polyester is:

R ₁O-CO-L-CO-OR ₂

Wherein, R ₁O-and-OR ₂Be identical or different pure residue ,-CO-L-CO-is the residue of polybasic carboxylic acid.L connects base, can be substituted, and contains 2-12 carbon atom on the skeleton usually.

Polybasic carboxylic acid:

Preferably polybasic carboxylic acid comprises following one or more: malonic acid, methylmalonic acid, ethyl malonic acid, butylmalonic acid, dimethyl malonic acid, diethyl malonic acid, butanedioic acid, methylsuccinic acid, 2, the 2-dimethyl succinate, 2-ethyl-2-methylsuccinic acid, 2, the 3-dimethyl succinate, meso-2, the 3-dimethyl succinate, glutaric acid, the 2-methylglutaric acid, the 3-methylglutaric acid, 2, the 2-dimethylated pentanedioic acid, 3, the 3-dimethylated pentanedioic acid, adipic acid, 3-methyl adipic acid, 3-tert-butyl group adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, tridecandioic acid, heneicosanedioic acid, dodecanedioic acid, tetracosandioic acid, hexadecandioic acid (hexadecane diacid), docosandioic acid, tetracosandioic acid, tricarballylic acid, 1,2,3, the 4-BTCA, itaconic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, anti-glutaconate, instead-β-hydrogen muconic acid, instead-traumatic acid, instead, instead-muconic acid, suitable-aconitic acid, instead-aconitic acid, malic acid, citramalic acid, isopropylmolic acid, 3-hydroxy-3-methylglutaric acid, tartaric acid, glactaric acid, citric acid, Dihydroxyfumaric acid, diglycolic acid, 3,6-two oxa-suberic acids, 3,3 '-thio-2 acid, 3, the acid of 3 '-dithio dipropyl, instead-DL-1,2-encircles pentane dicarboxylic acid, 3,3-butylidene glutaric acid, camphoric acid, the cyclohexyl butanedioic acid, 1, the 1-cyclohexanediacetic, instead-1, the 2-cyclohexane cyclohexanedimethanodibasic, 1, the 3-cyclohexane cyclohexanedimethanodibasic, 1, the 4-cyclohexane cyclohexanedimethanodibasic, 1,3,5-cyclohexane tricarboxylic acid, 1,3,5-trimethyl-cyclohexane-1,3, the 5-tricarboxylic acid (Kemp ' s triacid), 1,2,3,4-cyclobutane tetracarboxylic acid, 1,2,3,4,5,6-cyclohexane pregnancy acid, 4-carboxyl phenoxyacetic acid, 1, the 4-phenylenediacetic Acid, 1,4-benzene dipropionic acid, 1,4-benzene diacrylate, 2-carboxyl benzenpropanoic acid, 4, the two benzoic acid of 4 '-oxo, phthalic acid, M-phthalic acid, terephthalic acid (TPA), 1,2, the 3-benzenetricarboxylic acid, 1,3, the 5-benzenetricarboxylic acid, 1,2,4, the 5-benzene tetracarboxylic acid, mellitic acid, 2-methoxyl group M-phthalic acid, diphenic acid, 4,4 '-biphenyl dicarboxylic acid, 2, the 6-naphthalenedicarboxylic acid, 3-carboxyl-1,4-dimethyl-2-pyrroles's acetate.

Can use the oligomer (and co-oligomer) of unsaturated carboxylic acid.The material that is fit to comprises the oligomer of acrylic acid, methacrylic acid, crotonic acid, vinyl acetic acid, 4-penetenoic acid and/or maleic acid.

Described acid can contain hetero atom.Nitrogen is preferred hetero atom.The nitrogen acid that is fit to comprises: iminodiacetic acid, the 3-aminophthalic acid, the amino terephthalic acid (TPA) of 2-, the amino M-phthalic acid of 5-, ethylenediamine-N, N '-oxalic acid, methyliminodiacetic acid, nitrilotriacetic acid, ethylenediamine tetra-acetic acid, 1,6-diamino hexane-N, N, N ', N '-tetraacethyl, instead-1,2-diamino-cyclohexane-N, N, N ', N '-tetraacethyl, triethylenetetraaminehexaacetic acid, 1,3-diaminourea-2-hydroxy propane-N, N, N ', N '-tetraacethyl, ethylenebis (oxygen base ethylidene nitrilo-) tetraacethyl, diethylene-triamine pentaacetic acid, aspartic acid, glutamic acid, 2-methyl glutamic acid, the 2-aminoadipic acid, the 3-aminoadipic acid, 2, the 6-diaminopimelic acid, cystine, N-benzyl iminodiacetic acid, N-(2-carboxyl phenyl) glycine, 2,2 '-(ethylidene dioxy base) dianil-N, N, N ', N '-tetraacethyl, porphobilinogen, 4,5-imidazoles dioctyl phthalate, 2,2 '-bipyridyl-4,4 '-dioctyl phthalate, 3, the 4-pyridinedicarboxylic acid, 2, the 5-pyridinedicarboxylic acid, 3, the 5-pyridinedicarboxylic acid, 2, the 6-pyridinedicarboxylic acid, 6-methyl-2,3-pyridinedicarboxylic acid and 2,6-dimethyl-3, the 5-pyridinedicarboxylic acid.

When in the acid nitrogen-atoms being arranged, available suitable quaternizing agent carries out quaternized.Known quaternizing agent comprises CH ₃Cl, CH ₃I and (CH ₃) ₂SO ₄

Alcohol:

Alcohol can have straight chain, side chain or circulus.

Preferred alcohol comprises 5 or 6 yuan of rings, and the ortho position of alcoholic extract hydroxyl group and contraposition have electron withdraw group on the ring.The example of this preferred alcohols comprises N-hydroxy-succinamide and hydroxybenzotriazole.In addition, described alcohol also can be the enol form of ketone.As mentioned above, for avoiding feeling uncertain, with regard to the purpose of this specification, think that phenol also is alcohol.

Suitable electron-withdrawing substituent comprises following one or more: NO on the ring ₂, CN, CO ₂H, CO ₂R, CONHR, CONR ₂, CHO, COR, SO ₂R, SO ₂OR, SO ₂OAr, NO, Ar, NR ₃ ⁺, SR ₂ ⁺, NH ₃ ⁺, F, Cl, Br, I, OAr, SH, SR, OH, OR and CH=CR ₂Electrophilic is attributable to inductive effect or resonance effects.

The amphyl that preferably contains at least one electron-withdrawing substituent.

Preferred amphyl comprises: vanillic aldehyde; ethyl vanillin; eugenol; isoeugenol; salicylic acid; salethyl; the 4-cyanophenol; hydroxyacetophenone; trichlorophenol, 2,4,6,-T; 2; the 6-syringol; 4-amino-phenol (and quaternary ammonium salt); dimethylamino phenol (and quaternary ammonium salt); chlorophenol; bromine phenol; iodine phenol; fluorine phenol; two chlorophenols; dibromophenol; phenol diiodide; difluoro phenol; the hydroxyl thiophenol; amino cresols; 4-amino-2; the 5-dimethyl phenol; 6-amino-2; 4-two chloro-3-sylvans; nitrophenol, dinitrophenol; hydroxypropiophenonepreparation; 2 '-hydroxyl-5 '-methyl acetophenone; 5 '-chloro-2 '-hydroxy acetophenone; Acetovanillone; the 4-hydroxy benzaldehyde; o-vanillin; 4-hydroxy-3-methyl benzaldehyde; 2-chloro-4-hydroxy benzaldehyde; 2-hydroxy-5-methyl oxygen benzaldehyde; vanirom; 5-nitro vanillic aldehyde; 3-methoxyl group-5-nitrosalicylaldehyde; the 4-hydroxybenzoic acid; cresotinic acid; chloro-salicylic acid; the methoxyl group salicylic acid; aminosalicylic acid; cresotinic acid; the formyl salicylic acid; the hydroxyl M-phthalic acid; methyl hydroxybenzoate; nipagin A; nipasol; 5-cresotinic acid methyl esters; 5-cresotinic acid acetoacetic ester; hydroxybenzamide; 5-chloro-2-hydroxybenzamide; 5-acetyl group salicylamide and 2-amino-4-(ethyl sulphonyl) phenol.

Particularly preferred alcohol comprises trichlorophenol, 2,4,6,-T, isoeugenol, vanillic aldehyde, 4-cyanophenol, salethyl, 2,6-syringol, 4-amino-phenol and dimethylamino phenol.As indicated above, acid imide also can use as " alcohol ".

A kind of preferred acid imide is a N-hydroxy-succinamide.

The alcohol leaving group can have functional characteristic, shows certain practicality after ester exchange reaction.A kind of such character is appreciable smell.For example, to obtaining significant cloves flavor after the isoeugenol ester heating (i.e. flatiron).This can be used as useful hint, and the hint customer responsiveness carries out.

Preferred polyester comprises butanedioic acid two (trichloro-benzenes phenolic ester), BTCA two (trichloro-benzenes phenolic ester), butanedioic acid two N-hydroxy-succinamide esters, butanedioic acid diisoeugenol ester and butanedioic acid two vanilla aldehydo-esters.

There are two or more dissimilar alcohol in " mixing " ester although can imagine, only have a kind of alcohol in the polyester usually.

The molecular weight of special preferred polyester is less than 1500 dalton.Think that the polyester of high molecular will make the cellulosic material hardening if use more.

Though polyester can be mixed in the nonaqueous solvents (as oxolane) and use, preferred way is to be mixed in to be entirely in water or the partially aqueous solvent to use.

B. blocked polyisocyanates

In another kind of embodiment of the present invention, finishing agent is a blocked isocyanate.

Blocked isocyanate has detailed description and definition in Progress in Organic Coatings (organic coating progress) among 36 (1999) 148-172.

Blocked isocyanate is preferred but be not can only be the chemical method end-blocking.Such molecule comprises the derivative that isocyanate compound and active dydrogen compounds reaction obtain.But the reaction that does not relate to isocyanates is also arranged and other approach that produce blocked isocyanate, these are also referred to as blocked isocyanate in the prior art.Equally, the reaction of the great majority of blocked isocyanate will generate the isocyanates intermediate when crosslinked, not generate the reaction scheme of this intermediate but existing people proposes the blocked isocyanate reaction.Also known isocyanates can form heat-labile dimer or higher condensate form, is commonly referred to " uretdione ", and with regard to purpose of the present invention, these also are considered to the example of blocked isocyanate.

Owing to above polybasic carboxylic acid and " end-blocking " alcohol that is fit to is described, hereinafter will polyisocyanates and the end-capping group that be fit to be described.

Polyisocyanates:

1,4-two isocyanate group butane, 1,6-two isocyanic acids 1, the own diester of 6-, 1,8-two isocyanate group octanes, 1,10-two isocyanate group decane, 1,12-two isocyanate group dodecanes, ten tetramethylene diisocyanate, the trimethyl cyclohexane vulcabond, the tetramethyl hexane diisocyanate, instead-1,4-cyclohexylidene vulcabond, isophorone diisocyanate, 1, two (isocyanate group methyl) cyclohexanes of 3-, 4,4 '-di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate), the trimethylolpropane tris isocyanates, 1-isocyanate group-2, two [(4-isocyanate group cyclohexyl) the methyl]-cyclohexanes of 4-, α, 4-benzal vulcabond, m xylene diisocyanate, Toluene-2,4-diisocyanate, the 4-vulcabond, Toluene-2,4-diisocyanate, the 5-isocyanates, 1, two (1-isocyanate group-1-Methylethyl) benzene of 3-, 1, the 3-phenylene vulcabond, 1, the 4-phenylene vulcabond, 2,6-benzal vulcabond, 4,4 '-oxygen two (phenyl isocyanate), naphthylene-1, the 5-vulcabond, triphenyl methane-4,4 '; 4 "-triisocyanate, 2,4-two isocyanate groups-1-(4-isocyanate group phenoxy group) benzene, 1,3,5-three isocyanate groups-2-methylbenzene, diphenyl methane-2,4,4 '-triisocyanate.

Also estimate suitable biuret-isocyanuric acid ester that above-mentioned simple polyisocyanates is arranged or the group modified product of amido-containing acid ester, as three-(6-isocyanate group hexyl) biuret and higher homologues thereof; The polyisocyanates that contains isocyanurate group that binary polymerization by aliphatic and/or aromatic diisocyanates (as two isocyanic acids 1, the own diester of 6-, isophorone diisocyanate, particularly three-(6-isocyanate group hexyl)-isocyanuric acid ester) obtains.

Obtain polyisocyanates by excessive vulcabond and polyol reaction, after excessive unreacted vulcabond is removed in distillation subsequently.

Simple examples of polyhydric alcohols comprises: glycerine, 1,2-propylene glycol, trimethylolpropane, pentaerythrite, ethylene glycol, diethylene glycol (DEG), triethylene glycol, tetraethylene glycol, five glycol, hexaethylene glycol, polyethylene glycol, polypropylene glycol, dipentaerythritol, triethanolamine (can choose wantonly by quaternized).

Also can make vulcabond and contain the polyalcohol of anionic group (as carboxylic acid, sulfonic acid and phosphoric acid), particularly carboxylic acid reaction, excessive unreacted vulcabond is removed in distillation in a similar fashion subsequently.The carboxylic acid that is fit to comprises: 2, and 2-two (methylol) acetate, 2,2-two (methylol) propionic acid, 2,2-two (methylol) butyric acid, 2,2,2-three (methylol) acetate and tartaric acid.

Can choose wantonly and acid groups partially or completely be neutralized so that contain the molecule of isocyanate groups and have water-soluble or water dispersible.

Polyisocyanates also can be removed excessive unreacted vulcabond and obtain by vulcabond and polyamine reaction, distillation subsequently.

The example of the polyamine that is fit to comprises: diethylenetriamines, N-(2-aminoethyl)-1,3-propane diamine, 3,3 '-diamino-N-methyl-di-n-propylamine, N-(3-aminopropyl)-1,3-propane diamine, spermidine, two (hexa-methylene) triamine, 2,2 '-(ethylenedioxy) two (ethamine), 4,7,10-trioxa-1,13-tridecane diamines, glycerine three (amine end-blocking polypropylene glycol) ether and chitosan.

Transforming the polyisocyanates that forms by polyamine also comprises as using the light gas disposal.

Two isocyanic acids 1, the own diester of 6-are the preferred especially isocyanates that uses among the present invention.

Polyisocyanate blocked dose:

These material types are similar to the above-mentioned heat-labile pure end-capping reagent that is used for ester.The same with the above-mentioned preferred material that is used for the end-blocking ester, the end-capping reagent of isocyanates also can be phenol.As mentioned above, the common and fibrin reaction generation carbamate of isocyanates, carbamate is considered to the more example of the ester of broad types.But some isocyanates will react formation " real " ester.

Preferred phenol also has electron-withdrawing substituent in the ortho position and/or the contraposition of pure proton.

Oxime (being generated by azanol and carbonyls reaction) can be used to blocked isocyanate.The example that generates the ketone that is fit to of oxime with azanol reaction has: tetramethyl-ring diacetyl, methyl-n-amyl ketone, methyl isoamyl ketone, methyl 3-ethyl heptyl ketone, methyl 2,4-dimethyl amyl group ketone, methyl ethyl ketone, cyclohexanone, methyl isopropyl Ketone, methyl isopropyl Ketone, methyl iso-butyl ketone (MIBK), diisobutyl ketone, methyl tertbutyl ketone, diisopropyl ketone and 2,2,6,6-tetramethyl-ring hexanone.

The non-phenolic alcohol end-capping reagent that is fit to comprises the monoether (as cellosolvo, 2-ethoxy ethoxy ethanol, 2-ethyl hexyl oxy ethanol, butoxy ethanol and 2-bu-toxyethoxy) and the N of ethylene glycol, N-hydroxyacetamide (as N, N-dibutyl hydroxyl acetamide and N-hydroxy-succinamide).

The acid amides and the acid imide end-capping reagent that are fit to comprise: monoacetylaniline, N-methylacetamide, caprolactam, 2-Pyrrolidone and succinimide.

The imidazoles and the amidine end-capping reagent that are fit to comprise: 2-ethyl-4-methylimidazole, glyoxal ethyline, 1,4,5,6-tetrahydropyrimidine, guanidine, 2,4-methylimidazole quinoline, 4-methylimidazole quinoline, 2-benzylimidazoline and 4-methyl-2-benzylimidazoline.

The pyrazoles that is fit to and triazole blocked dose comprise: pyrazoles, 3-methylpyrazole, 3,5-dimethyl pyrazole, 1,2,4-triazole and benzotriazole.

Secondary amine and particularly hindered amine can be used to blocked isocyanate.

The active methylene group end-capping reagent that is fit to comprises: diethyl malonate, malonic acid tert-butyl ester methyl esters, meldrum's acid (the different inferior propyl ester of malonic acid), ethyl acetoacetate and tert-butyl acetoacetate.

Particularly preferred end-capping reagent is meldrum's acid, phenol, 4-nitrophenol, 4-metoxyphenol and/or gaultherolin.Most preferred end-capping reagent is diethyl malonate, succinimide and sodium hydrogensulfite.

Above-mentioned isocyanates and carboxylic acid all can pass through only single feature active group and suitable end-capping reagent reaction coverlet end-blocking.Subsequently Sheng Xia active group freely can with another difunctional be connected base (as polyalcohol or polyamine) reaction, obtain the having following form closed-end structure of (acid and glycol with single end-blocking are example):

R ₁O-CO-L ₁-CO-OMO-CO-L ₂-CO-OR ₂

Wherein:

R ₁O-and-OR ₂Be identical or different pure residue ,-CO-L ₁-CO-and-CO-L ₂-CO-is the identical or different residue of polybasic carboxylic acid, and-OMO-is a residue of polyol.

Can prepare similar structure by isocyanates.

The method that forms single blocked isocyanate comprises having each isocyanate groups diisocyanate terminated of differential responses, thereby one or more group is preferentially by end-blocking.Perhaps, end-capping reagent can be added in a large amount of excessive vulcabond, unreacted vulcabond was removed in distillation immediately after question response was finished.Similarly method also is applicable to ester.

The reaction of single end-blocking crosslinking agent and polyalcohol or polyamine can comprise the reaction with all available hydroxyls or amido, obtains the polyalcohol or the polyamine of 100% modification.

By controlling the addition of single end-blocking crosslinking agent, can form hydroxyl and amido and all be changed and unaltered structure.After removing end-capping group, self-crosslinking can take place in this structure.

The polyalcohol that is fit to comprises that above-mentioned those are applicable to the alcohol of blocked isocyanate or carboxylic acid.

Particularly preferred polyalcohol comprises: carbohydrate as D-sorbite, mannitol, wood sugar, fructose, galactolipin, mannose, glucose, altrose, lactose, cellobiose, sucrose, oligosaccharides and polysaccharide, is preferably β-1, oligosaccharides and polysaccharide that 4-connects.

Particularly preferred polyalcohol is that cellulose and derivative thereof or other can be discerned cellulosic polysaccharide, and the example comprises locust bean gum and guar gum.

The polyamine that is fit to comprises: diethylenetriamines, N-(2-aminoethyl)-1,3-propane diamine, 3,3 '-diamino-N-methyl-di-n-propylamine, N-(3-aminopropyl)-1,3-propane diamine, spermidine, two (hexa-methylene) triamine, 2,2 '-(ethylenedioxy) two (ethamine), 4,7,10-trioxa-1,13-tridecane diamines, glycerine three (amine end-blocking polypropylene glycol) ether and chitosan.

Can choose wantonly with quaternizing agent (as iodomethane, dimethyl suflfate etc.) unreacted amino modified and give cationic.This cation-modified direct dyeing power (substantivity) of having improved material.

Can discern (situation of homopolysaccharide is the same) or otherwise connect (the same with cationic situation) auxiliary connection base " M " to the cellulose ground by using, the deposition efficiency of crosslinking agent can significantly improve.

Carrier and product form:

Composition of the present invention preferably is mixed with the Fabrid care composition that comprises the solution, dispersion or the emulsion that contain crosslinking agent.

Usually comprise a kind of carrier compatible in the composition of the present invention with fabric.

In the context of the present invention, term " carrier compatible " with fabric comprise can assist cellulose crosslinked dose with fabric interactional component takes place.Described carrier can be the solvent of crosslinking agent, although except the benefit that crosslinking agent provides, carrier also can provide other benefits (as softening, cleaning etc.).Preferred carrier is detergent-active compounds, fabric softener, conditioner or washing agent.

If said composition is used for laundry processes as the part of conventional fabrics treatment product (as rinse conditioner or main lotion), then preferred crosslinking agent accounts for the 0.01-10% of whole composition weight, more preferably 0.05-7.5%, most preferably 0.1-5%.

But,, then can use more substantial crosslinking agent if said composition is used for laundry processes as the special disposal fabric with the product that reduces wrinkle.Preferred its amount accounts for the 0.01-15% of whole composition weight, more preferably 0.05-10% (as 0.1-7.5% weight).

If said composition is used for spray product, then preferred crosslinking agent accounts for the 0.5-20% of whole composition weight, preferred 1-20%.

As mentioned above, method of the present invention generally includes following steps: the composition of crosslinking agent is applied on the clothing the preferred subsequently flatiron curing said composition that adopts.Can adopt conventional method (as dip in, spray or soak) that said composition is applied to fabric.

Fabrid care composition of the present invention preferably comprises solution, dispersion or the emulsion that contains crosslinking agent and the carrier compatible with fabric.The carrier compatible with fabric promotes contacting between fabric and the composition component.The carrier compatible with fabric can be water or surfactant, if but be water, preferably contain spices.

In an especially preferred embodiment, the form that said composition can be suitable for being sprayed onto on the fabric provides, and can dry fabric then in whizzer, solidifies said composition by flatiron more afterwards.

In this case, the amount of preferred polybasic carboxylic acid or derivatives thereof is the 0.5-20% of whole composition weight, is preferably 0.5-10%.If product is used for spraying, the existence of wetting agent (for example alcohol ethoxylates wetting agent, as Synperonic A7) also is good.

Can contain anion surfactant in the spray agent.

WO 96/15310 (Procter ﹠amp; Gamble) disclose the spray cloth apparatus that is fit in, this patent is attached to herein by reference.Perhaps, as described in EP 1201816 and WO 99/27176, said composition also can be applied to fabric by flatiron aqua storage tank, the independent spray booth that holds in jar or the flatiron.

Spray product can comprise as the water of carrier molecule and/or other solvents.

Advantageous particularly and surprisingly said composition can by in addition at home conditions flatiron solidify.In addition, can use the more satisfactory steam iron of smoothing wrinkle, and solidification process is not had adverse effect.

Another advantage of the inventive method is that when said composition is used as spray spray once is enough to tell on after washing.

In laundry processes, as the part of fabrics in general cleaning product (as composition of detergent), the carrier compatible with fabric is generally detergent-active compounds.Yet if this fabric treating product is a kind of rinse conditioner, the carrier compatible with fabric is fabric-softening and/or conditioning compound.These problems further go through below.

Crosslinking agent can be used in the washing cycle of laundry processes and handles fabric.Described crosslinking agent also can be used in the rinse cycle, perhaps preferably be used in the flatiron and/or hot pressing before or during.

Composition of the present invention can be liquid, solid (as powder or tablet), gel, lotion, spray, bar, foam or mousse form.The example comprises that (as conditioner or finishing agent) handled in infusion product, rinsing or the master washes product.Spray product is specially adapted in flatiron or the hot pressing.

Also can comprise the reagent that can produce pearlescent appearance in the various fluid compositions, as organic pearly-lustre compound (as diglycol stearate) or inorganic pearlescent pigment (as ultra-fine mica or titanium dioxide (TiO ₂) the coating mica).Various fluid compositions can be emulsion or emulsion precursor forms.

Detergent-active compounds:

If composition of the present invention is originally as the composition of detergent form, then compatible with fabric carrier can be selected from soap and non-soap anionic, CATION, nonionic, both sexes and zwitierionic detergent reactive compound and composition thereof.

The detergent active that is fit to has a lot, in the document they has been done sufficient description, as Schwartz, and Surface-Active Agents and Detergents (surfactant and the washing agent) I of Perry and Berch volume and II volume.

The preferred carrier compatible with fabric can be soap and synthetic non-soap anionic and non-ionic compound.

Anion surfactant is known for those skilled in the art.The example has alkylbenzenesulfonate, particularly alkyl chain length C ₈-C ₁₅Linear alkylbenzene sulfonate (LAS); Primary alkyl and secondary alkyl sulfate, particularly C ₈-C ₁₅Primary alkyl sulphates; Alkyl ether sulfate; Alkenyl sulphonate; Alkylxylene sulfonate; Dialkyl sulfosuccinates and fatty acid ester sulfonate.Common particular certain cancers.

Available ionic surfactant pack is drawn together primary alconol and secondary alcohol ethoxyl compound, the C of the oxirane ethoxylation that particularly average every mol of alcohol is the 1-20 mole ₈-C ₂₀Fatty alcohol, the C of the oxirane ethoxylation that more especially average every mol of alcohol is the 1-10 mole ₁₀-C ₁₅Uncle's fatty alcohol and secondary fatty alcohol.The ionic surfactant pack of non-ethoxylatedization is drawn together alkyl polyglycoside, glycerol monoethers and polyhydroxy amides (glucamide).

Available cationic surfactant comprises that general formula is R ₁R ₂R ₃R ₄N ⁺X ^-Quaternary ammonium salt, wherein the R base independently is C separately ₁-C ₂₂Hydrocarbyl chain, be generally the alkyl of alkyl, hydroxyalkyl or ethoxylation, X is the CATION (R wherein for example of solubilising ₁Be C ₈-C ₂₂Alkyl is preferably C ₈-C ₁₀Or C ₁₂-C ₁₄Alkyl, R ₂Be methyl, R ₃And R ₄Can be identical or different, be the compound of methyl or ethoxy), cationic ester (as cholinester) and pyridine  salt.

The total amount of surfactant is fit to account for the 0.1-60% of composition weight, for example 0.5-55% (as 5-50%).

Preferred anionic surfactant (when existing) accounts for the 1-50% of whole composition weight.More preferably anion surfactant accounts for the 3-35% (for example 5-30%) of whole composition weight.

Preferred nonionic surfactants (when existing) accounts for the 2-25% of whole composition weight, more preferably 5-20% weight.

Also can use amphoteric surfactant, as amine oxide or betaine.

Builder:

The builder that can suitably comprise 10-70% weight, preferred 15-70% weight in the composition.The content of preferred builder is 15-50% weight.

Can comprise crystalline aluminosilicate in the described composition of detergent, the preferred as alkali aluminosilicate, more preferably sodium aluminosilicate is as builder.

The addition of aluminosilicate can be 10-70% weight (in anhydrous aluminosilicate) usually, preferred 25-50%.Aluminosilicate is the material with following general formula:

0.8-1.5 M ₂O.Al ₂O ₃.0.8-6 SiO ₂

Wherein, M is a monovalent cation, is preferably sodium.These materials contain some bound water, require its calcium ion exchange capacity to be at least 50mg CaO/g.Preferred sodium aluminosilicate contains 1.5-3.5 SiO in following formula ₂The unit.As the detailed description in the document, they can easily make by the reaction between sodium metasilicate and the sodium aluminate.

Except the aluminosilicate builder, optionally or additionally use phosphate builder.

Fabric-softening and/or conditioning compound:

If composition of the present invention is the fabric conditioner composition form, then compatible with fabric carrier is fabric-softening and/or conditioning compound (hereinafter referred to as " fabric softening compound "), and this compound can be CATION or non-ionic compound.

Described softening and/or conditioning compound can be water-fast quaternary ammonium compound.The amount of this compound reaches as high as 8% weight (based on the total of composition), and at this moment said composition is considered to rare; Perhaps the amount of this compound can reach 8-50% weight, and composition at this moment is considered to dense.

If use with suitable form, the composition that is adapted at transmitting during the rinsing can also be transmitted on the fabric in roller drier.Therefore, the composition (for example lotion) of another kind of product form for being suitable for being applied to that matrix (as soft thin slice or sponge or suitable distributor) goes up and transmitting from them in roller drier cycle period.

Suitable cationic fabric soften compound is water-fast substantially quaternary ammonium material, and this material comprises average chain length more than or equal to C ₂₀Monoalkyl or alkenyl long-chain.More preferably comprise polarity headgroup and average chain length more than or equal to C ₁₄Two alkyl or the soften compound of alkenyl chain.Preferred described fabric softening compound has two average chain lengths separately more than or equal to C ₁₆Chain alkyl or alkenyl chain.

Most preferably at least 50% chain alkyl or alkenyl have C ₁₈Or longer chain length.The chain alkyl of preferred fabric soften compound or alkenyl are mainly linear.

Quaternary ammonium compound with two long-chain aliphatic group, for example VARISOFT TA100 and two (hardened tallow alkyl) alkyl dimethyl ammonium chloride extensively is used in the commodity rinse conditioner composition.Other example of these cationic compounds can be referring to Schwartz, " the Surface-Active Agents and Detergents " of Perry and Berch, I and II volume.Any general type of this compounds all can be used in the composition of the present invention.

The preferred fabric soften compound is characterized in that for the compound of excellent emollescence is provided chain fusion L β-L α transition temperature is higher than 25 ℃, preferably is higher than 35 ℃, most preferably is higher than 45 ℃.This L β-L α changes and can measure by DSC, as in " Handbook of LipidBilayers (class lipid bilayer handbook) ", D Marsh, CRC Press, Boca Raton, Florida, the definition in 1990 (137 and 337 pages).

Basically water-fast fabric softening compound is defined as to have in 20 ℃ demineralized water less than 1 * 10 ^-3The fabric softening compound of the solubility of % weight.The solubility of preferred described fabric softening compound is less than 1 * 10 ^-4% weight is more preferably less than 1 * 10 ^-8% weight to 1 * 10 ^-6% weight.

Be preferably the cationic fabric soften compound of water-fast quaternary ammonium material especially, this compound has by at least one ester bond, and preferred two ester bonds are connected to two C on the molecule _12-22Alkyl or alkenyl.Particularly preferred the type compound is two (butter acyloxy ethyl) alkyl dimethyl ammonium chloride and/or its hardened tallow analogs.Other preferred materials comprise chlorination 1, two (hardened tallow the acyloxy)-3-trimethyl ammonium propane of 2-.Its preparation method is for example seen and is set forth in US 4,137 180 (Lever Brothers Co).As described in US 4 137 180, preferably these materials comprise a spot of corresponding monoesters, for example chlorination 1-hardened tallow acyloxy-2-hydroxyl-3-trimethyl ammonium propane.

Other useful cationic softener has the imidazolines of alkyl pyridine  salt and replacement.The primary, the condensation product of the second month in a season and tertiary amine and aliphatic acid and alkyl polyamine also is useful.

Described composition optionally or additionally comprises the water-soluble cationic fabric softener, as described in GB 2 039 556B (Unilever).

Described composition can comprise cationic fabric soften compound and oil, as disclosing in EP-A-0829531.

Described composition optionally or additionally comprises non-ionic fabric softener, as lanolin and derivative thereof.

Lecithin also is the soften compound that is fit to.

Non-ionic softener comprises the sugar ester that forms L β phase (as people such as M Hato at Langmuir12,1659,1666, described in (1996)) and relevant material (as glyceryl monostearate or sorbitan ester).These materials usually are used in combination with cationic substance to help deposition (referring to for example GB 2 202 244).In handling, rinsing in a similar manner polysiloxanes is used as the auxiliary softening agent (referring to for example GB 1 549 180) of cationic softener.

Described composition also can suitably comprise nonionic stabiliser.The nonionic stabiliser that is fit to is by the oxyalkylated straight chain C of 10-20 mole alkylene oxide ₈-C ₂₂Alcohol, C ₁₀-C ₂₀Alcohol or its mixture.

Preferably nonionic stabiliser is by the oxyalkylated straight chain C of 10-20 mole alkylene oxide ₈-C ₂₂Alcohol.The amount of preferred nonionic stabiliser is a 0.1-10% weight, more preferably 0.5-5% weight, most preferably 1-4% weight.The suitable mol ratio of quaternary ammonium compound and/or other cationic softener and nonionic stabiliser is 40: about 1: 1 of 1-is preferably 18: about 3: 1 of 1-.

Described composition also can comprise aliphatic acid, for example C ₈-C ₂₄Alkyl or alkenyl monocarboxylic acid or its polymer.The preferred saturated fatty acid, particularly hardened tallow C of using ₁₆-C ₁₈Aliphatic acid.Preferred fatty acid is non-saponification, and more preferably aliphatic acid dissociates, for example oleic acid, laurate or tallow acid.The preferred fatty acid amount of substance is greater than 0.1% weight, more preferably greater than 0.2% weight.Concentrate composition can contain 0.5-20% weight, more preferably the aliphatic acid of 1%-10% weight.The weight ratio of preferred quaternary ammonium material or other cationic softener and fatty acid material is 10: 1-1: 10.

Other components

Composition of the present invention can comprise soil release polymer, as the block copolymer of poly(ethylene oxide) and terephthalate.

Other optional components comprise electrolyte (as sodium chloride or calcium chloride), pH buffer and the essence (preferred 0.1-5% weight) of emulsifying agent, preferred 0.01-5% weight.

Other optional components comprise nonaqueous solvents, fluorescer, colouring agent, hydrotropic agent, defoamer, enzyme, fluorescent whitening agent and opacifier.

The bleaching agent that is fit to comprises peroxygen bleach.Preferred inorganic peroxy bleaching agent (as perborate and percarbonate) and bleach-activating coupling.Under the situation of using the inorganic peroxy bleaching agent, nonanoly acyloxy benzene sulfonate (NOBS) and tetraacetyl ethylene diamine (TAED) activator are commonly used and preferred activators.

The enzyme that is fit to comprises protease, amylase, lipase, cellulase, peroxidase and composition thereof.

In addition, also can comprise one or more anti-piping compounds, anti wrinkling agent, anti-fouling agent, bactericide, fungicide, antioxidant, ultra-violet absorber (sun-screening agent), heavy metal chelant, antichlor, dye-fixing agent, preservative agent, the pleat imparting agent (drape impartingagents) that hangs down, antistatic additive and flatiron auxiliary agent in the composition.Above-mentioned listed material is not whole.

In order further and better to understand the present invention, will be described some non-restrictive example below.

Embodiment

Synthetic embodiment

Embodiment 1: BTCA two (2,4,6-trichloro-benzenes phenolic ester) synthetic

(20.84g, 0.089mol) with 2,4, (35.80g is 0.18mol) in round-bottomed flask (250cm for the 6-trichlorophenol, 2,4,6,-T to take by weighing BTCA (BTCA) ³) in.With nitrogen purging flask 15 minutes, add distilled THF (150cm then ³).Under nitrogen, stir after 30 minutes, in 20 minutes, drip diisopropyl carbodiimides (29.0cm ³, 0.18mol).Stirring under nitrogen spends the night carries out reaction.This mixture is filtered,, stir 1 hour then to guarantee that the generation that precipitates reaches complete with the THF washing.Obtain crude product except that after desolvating.With the washed with dichloromethane crude product repeatedly, promptly get required product after removing solvent in the filtrate.

Embodiment 2: butanedioic acid two (2,4,5-trichloro-benzenes phenolic ester) synthetic

(1.5g 0.013mol) is dissolved in DMSO (50cm with butanedioic acid ³) in.Add 1, (5.0g 0.03mol), at room temperature stirred this mixture 30 minutes 1 '-carbonyl dimidazoles.Add 2,4 then, (5.05g's 5-trichlorophenol, 2,4,6,-T 0.026mol), and spends the night this mixture stirring under room temperature.This mixture is poured in the water, filters, washes, washed with ether, obtain white solid (2.03g, 33%).

δ _H(500MHz; CDCl ₃) 3.07 (4H, s, CH ₂-CH ₂-C (O)-O-) and 7.55 ﹠amp; 7.29 (4H, s, Ph).

Embodiment 3: butanedioic acid two (N-hydroxy-succinamide ester) synthetic

(2.0g 0.017mol) is dissolved in THF (50cm with butanedioic acid ³) in.Add 1, (5.49g 0.034mol), at room temperature stirred this mixture 30 minutes 1 '-carbonyl dimidazoles.(3.89g 0.034mol), and at room temperature stirs this mixture and spends the night to add N-hydroxy-succinamide.This mixture is poured in the water, after filtering, wash, washing with ether again, obtained white solid (2.0g, 38%).

δ _H(500MHz; CDCl ₃) 2.59 (8H, s, CH ₂-CH ₂-CO-N-) and 2.89 (4H, s, CH ₂-CH ₂-C (O)-O-)

Embodiment 4: butanedioic acid two vanilla aldehydo-esters synthetic

(1) organic solvent method:

(9.82g 64.5mmol) is dissolved in anhydrous THF (100cm with vanillic aldehyde at room temperature, nitrogen atmosphere and under stirring ³) in.Add natrium carbonicum calcinatum (8.2g, 77.4mmol, 1.2 equivalents) then, continue to stir 30 minutes.In 20 minutes, in the slurry that obtains, drip succinyl chloride (5g, 32.25mmol, 0.5 equivalent), in the dark place this mixture is continued to stir 18 hours then.Filter this mixture, decompression obtains linen solid after removing solvent in the filtrate.Subsequently this crude product is recrystallized in IPA, obtains white solid (2.7g, 24%).

δ _H(500MHz; CDCl ₃) 3.08 (2H, s ,-CH ₂-C (O)-O-), 3.89 (3H, s ,-OCH ₃), 7.27-7.50 (3H, m, Ph) and 9.95 (1H, s ,-CHO).

(2) Schotten-Baumann method:

(1.3g 32.5mmol) is dissolved in distilled water (100cm with NaOH ³) in.(4.91g 32.5mmol), stirs and obtains pale yellow solution to add vanillic aldehyde in this solution.This solution is cooled to 0 ℃, drip then succinyl chloride (2.5g, 16.25mmol).Allow this mixture rise to room temperature, continue subsequently to stir 10 minutes, obtain light-yellow precipitate.Pour this mixture into water (200cm subsequently ³) in, at room temperature stirred 30 minutes.Filter this solution, collect solids.With the crude product recrystallization, obtain white solid (0.84g, 13%) subsequently.

Embodiment 5: butanedioic acid two (4-cyan phenol ester) synthetic

(7.7g 64.5mmol) is dissolved in anhydrous THF (100cm with the 4-cyanophenol at room temperature, nitrogen atmosphere and under stirring ³).Add natrium carbonicum calcinatum (8.2g, 77.4mmol, 1.2 equivalents) then, continue to stir 10 minutes.In 20 minutes, drip succinyl chloride subsequently, under nitrogen, continue to stir 18 hours in the dark place.Filter grey slurry, the solvent in the filtrate is removed in decompression, obtains gray solid.Subsequently crude product is recrystallized in IPA, obtains pale solid (3.7g, 36%).

δ _H(500MHz；CDCl ₃)3.03(2H，s，-CH ₂-C(O)-O-)，7.24(2H，d，J8，Ph).& 7.69(2H，d，J8.5，Ph).

Embodiment 6: butanedioic acid diisoeugenol ester synthetic

(25g 0.15mol) is dissolved in THF (100cm with isoeugenol ³) in, (16.14g 0.15mol), at room temperature stirs this mixture to add sodium carbonate.(11.8g 0.075mol), continues this mixture to stir 90 minutes subsequently to add succinyl chloride in 20 minutes in the stirred mixture.Then this reactant mixture is heated to 50 ℃, kept 60 minutes, at room temperature stir again and spend the night.Filter this mixture, removal of solvent under reduced pressure obtains the oil that dark placement is solidified.This crude product is recrystallized in ethyl acetate and ether, obtains pale solid (4.67g, 8%).

δ _H(500MHz; CDCl ₃) 1.86 (6H, d ,-CH ₃-CH=CH-), 3.80 (6H, s, PhCH ₃), 6.34-6.14 (4H, m, CH=CHCH ₃) and 6.70-6.88 (6H, m, Ph).

Embodiment 7: two isocyanic acids 1 of meldrum's acid end-blocking, and the own diester of 6-synthetic synthetic:

At room temperature with triethylamine (12.9ml, 92.75mmol, 3.0 equivalent) drop to two isocyanic acids 1, own diester of 6-(5.0ml, 30.92mmol, 1 equivalent) and meldrum's acid (9.36g, 64.92mmol, 2.1 in carrene equivalent) (100ml) solution, continue to stir 15 hours, TLC analyzes the meldrum's acid that (EtOAc) shows noresidue.Add silica (about 25g), removal of solvent under reduced pressure subsequently.Adopt the rapid column chromatography purifying, obtain the diamides (7.33g, 55%) of colorless solid shape.

R _f＝0.1(EtOAc)；δ _H(400MHz，CDCl ₃)1.42-1.46(4H，m，CH ₂)，1.59-1.68(4H，m，CH ₂)，1.69-1.74(12H，s(br)，CH ₃)，3.42(4H，q，J 6.5Hz，CH ₂)，9.25-9.34(2H，s(br)，NH)，14.95-15.0(2H，s(br)，OH)；δ _C(100MHz，CDCl ₃)26.2(CH ₂)，26.2(CH ₃)，28.9，40.3(CH ₂)，72.8(C-quat)，104.6，164.2(C＝)，170.25，170.3(CO)；m/z(ES ⁺)477(M-H ⁺+2Na ⁺，100％)；

Measured value: C, 51.49; H, 6.05; N, 5.98; C ₁₈H ₂₈N ₂O ₁₀Theoretical value: C, 50.00; H, 6.48; N, 6.48.

Embodiment 8: two isocyanic acids 1 of phenol end-blocking, and the own diester of 6-synthetic synthetic:

Triethylamine (2.7ml, 19.37mmol, 3.1 equivalents) is dropped to two isocyanic acids 1, in carrene (25ml) solution of own diester of 6-(1.0ml, 6.18mmol, 1 equivalent) and phenol (1.26g, 13.39mmol, 2.1 equivalents), continue to stir 15 minutes.Removal of solvent under reduced pressure, the solid that obtains are dry in vacuum desiccator, obtain the title compound (2.16g, 98%) of white solid.

δ _H(400MHz，CDCl ₃)1.36-1.44(4H，m，CH ₂)，1.54-1.65(4H，m，CH ₂)，3.26(4H，q(br)，J 6.5Hz，CH ₂)，5.05(2H，m(br)，NH)，7.12(4H，d，J 7.5Hz，ArH)，7.18(2H，t，J 7.5Hz，ArH)，7.34(4H，t，J 7.5Hz，ArH)；δ _C(100MHz，CDCl ₃)26.2，29.7，41.0(CH ₂)，121.6(CH)，125.2(C-ipso)，129.2(CH)，151.1(C-ipso)，154.6(CO)；

Measured value: C, 66.00; H, 7.02; N, 8.27; C ₂₀H ₂₄N ₂O ₄Theoretical value: C, 67.42; H, 6.74; N, 7.87.

Embodiment 9: two isocyanic acids 1 of succinimide end-blocking, and the own diester of 6-synthetic synthetic:

At room temperature triethylamine (18.8ml, 135.0mmol, 3.0 equivalents) is dropped to two isocyanic acids 1, own diester of 6-(7.57g, 45.01mmol, 1 equivalent) and succinimide (8.90g, 90.01mmol, 2.0 equivalents) carrene (100ml) solution in, continue to stir 1 hour.Filter and collect the white precipitate that forms, (3 * 50ml) wash, dry in vacuum desiccator subsequently, obtain the pulverous title product of white (colourless) (14.93g, 90%) with carrene.

δ _H(270MHz，d ₆-DMSO)1.12-1.45(8H，m，CH ₂)，2.64(8H，s，CH ₂)，3.01(4H，q，J 6.5Hz，CH ₂)，9.25-9.34(2H，t，J 6.5Hz，NH)；

Measured value: C, 52.28; H, 6.04; N, 15.30; C ₁₆H ₂₂N ₄O ₆Theoretical value: C, 52.46; H, 6.01; N, 15.30.

Embodiment 10: two isocyanic acids 1 of sodium hydrogensulfite end-blocking, and the own diester of 6-synthetic synthetic:

In having the 100ml round-bottomed flask of magnetic stir bar, add two isocyanic acids 1, (6.73g 0.04mol), adds the sodium pyrosulfite (8.36g that is dissolved in the 16ml water to the own diester of 6-again, 0.044mol), turbid solution is covered and stirred 17 hours down in room temperature (20 ℃).This product is precipitated in acetone (100ml), filters and drying.With in this product water-soluble (30ml), use acetone (350ml) precipitation more then, filter the final vacuum drying, obtain trickle white powder, productive rate is 93% ^*

FT-IR has confirmed CONH (1680cm ^-1) generation and isocyanate-free peak (2275cm ^-1), show that not having free vulcabond in the product exists.

^*NMR analyzes (internal standard compound: three  alkane) show that degree of purity of production is 57.43%.Impurity may be sodium pyrosulfite.

¹H NMR-(D ₂O): δ (ppm) 1.36 (4H, m); 1.55 (water, s); 1.59 (4H, m); 2.23 (acetone, s); 3.29 (4H, t); 4.74 (D ₂O); 5.23 (three  alkane, 6H, s).

Two isocyanic acids 1 of embodiment 11:4-nitrophenol end-blocking, the own diester of 6-synthetic synthetic:

Triethylamine (7.1ml, 50.75mmol, 2.0 equivalents) is dropped to two isocyanic acids 1, own diester of 6-(4.1ml, 25.35mmol, 1 equivalent) and 4-nitrophenol (7.06g, 50.75mmol, 2.0 equivalents) carrene (100ml) solution in, continue to stir 2 hours.The light-yellow precipitate that filter to collect forms, with carrene (2 * 50ml) and ether (1 * 50ml) washing is drying in vacuum desiccator also, obtains the pulverous title compound of yellow-white (11.25g, 100%).

δ _H(400MHz，d ₆-DMSO)1.31-1.45(4H，m，CH ₂)，1.46-1.59(4H，m，CH ₂)，3.10(4H，t(br)，J 6.5Hz，CH ₂)，7.40(4H，d，J 9.0Hz，ArH)，(2H，t(br)，J 6.5Hz，NH)，8.28(4H，d，J 9.0H2，ArH)；

Measured value: C, 52.28; H, 6.04; N, 15.30; C ₁₆H ₂₂N ₄O ₆Theoretical value: C, 52.46; H, 6.01; N, 15.30.

Two isocyanic acids 1 of embodiment 12:4-metoxyphenol end-blocking, the own diester of 6-synthetic synthetic:

Triethylamine (9.0ml, 64.76mmol, 3.0 equivalents) is dropped to two isocyanic acids 1, own diester of 6-(3.5ml, 21.58mmol, 1 equivalent) and 4-metoxyphenol (5.36g, 43.17mmol, 2.0 equivalents) carrene (50ml) solution in, continue to stir 15 hours.Filter and collect the white precipitate that forms, (2 * 50ml) washings are also dry in vacuum desiccator, obtain the title compound (5.0g, 59%) of white powder with carrene.

δ _H(400MHz，d ₆-DMSO)1.25-1.42(4H，m，CH ₂)，1.45-1.55(4H，m，CH ₂)，3.07(4H，q(br)，J 6.0Hz，CH ₂)，3.36(6H，s，CH ₃)，6.90(4H，d，J 9.0Hz，ArH)，7.02(4H，d，J 9.0Hz，ArH)，7.61(2H，t(br)，J 6.0Hz，NH)；δ _C(100MHz，d ₆-DMSO)26.3，29.5，40.7(CH ₂)，55.7(CH ₃)，114.5，122.9(CH)，144.9，155.1(C-ipso)，156.6(CO)；

Measured value: C, 62.58; H, 7.08; N, 7.66; C ₂₀H ₂₈N ₂O ₆Theoretical value: C, 61.22; H, 7.14; N, 7.14.

Embodiment 13: two isocyanic acids 1 of gaultherolin end-blocking, the own diester of 6-synthetic

Triethylamine (2.3ml, 16.69mmol, 3.0 equivalents) is dropped to two isocyanic acids 1, in carrene (50ml) solution of own diester 1 of 6-(0.9ml, 5.57mmol, 1 equivalent) and phenol 2 (1.50g, 10.38mmol, 1.9 equivalents), continue to stir 15 hours.Removal of solvent under reduced pressure adopts rapid column chromatography with this crude product mixture purifying (hexane/ethyl acetate 2: 1 → 1: 1), obtains white (colourless) crystalline solid title compound (4) (0.725g, 29%).Rf=0.15 (hexane-ethyl acetate: 1: 1);

m/z(ES ⁺)463(MNa ⁺，100％)；.δ _H(250MHz，CDCl ₃)1.32-1.95(8H，m，CH ₂)，3.23(2H，q，J 6.5Hz，CH ₂)，3.82(3H，s，CH ₃)，4.02(2H，t，J 7.O Hz，CH ₂)，5.29(1H，m(br)，NH)，7.12(1H，d，J 7.5Hz，ArH)，7.20-7.34(3H，m，ArH)，7.51(1H，dt，J 1.5，7.5Hz，ArH)，7.69(1H，dt，J1.5，7.5Hz，ArH)，7.96(1H，dd，J 1.5，7.5Hz，ArH)，8.08(1H，dd，J 1.5，7.5Hz，ArH)；

Measured value: C, 61.9; H, 5.5; N, 6.2%, C ₂₃H ₂₄O ₇N ₂Theoretical value: C, 62.7; H, 5.45; N, 6.4%;

Application Example

Among the embodiment 14-19 and 27 that provides below, synthetic ester pads the Oxford cotton (on 18 * 6cm) fully from solvent (as THF and/or water).With the cloth specimen drying, the time in accordance with regulations is in higher setting (cotton/flax) flatiron curing down more then.

After the curing, under 20 ℃ and 65% relative humidity,, measure elastic recovery angle (CRA) (according to BS1553086) then with the cloth specimen damping.(25mm * 50mm) is folded to form tangible wrinkle, and continues 1 minute under the load of 1kg with fabric sample.After unclamping cloth specimen, wrinkle are unfolded to certain angle.Lax this angle of measuring after 1 minute.(therefore maximum CRA is 180 °) only carried out in test at warp-wise.Therefore higher CRA shows and does not crease easily.

In embodiment 19-26, blocked isocyanate pads cotton (on 18 * 6cm) fully from appropriate solvent.With the cloth specimen drying, the time in accordance with regulations is in higher setting (cotton/flax) flatiron curing down more then.

After the curing, under 20 ℃ and 65% relative humidity,, measure elastic recovery angle (CRA) (using improving one's methods) then based on BS1553086 with the cloth specimen damping.(25mm * 50mm) is folded to form tangible wrinkle, and continues 1 minute under the load of 1kg with fabric sample.After unclamping cloth specimen, wrinkle are unfolded to certain angle.Lax this angle of measuring after 1 minute.(therefore maximum CRA is 180 °) only carried out in test at warp-wise.The wrinkling degree that higher CRA correspondence is lower.

Embodiment 14: the application of BTCA two (2,4,6-trichloro-benzenes phenolic ester)

The CRA that the THF solution (19g THF contains the 1g diester) of the diester of employing 5% obtains the results are shown in following table 1:

Table 1

	CRA
						Press 10s	Press 20s	Press 30s	Press 60s
The untreated control sample	79	-	-	-
					5% diester	92	99	98	103

From these results as can be seen, cloth specimen (untreated control sample) crease intensity little (CRA height) that the cloth specimen of handling is more untreated is also found handling the cloth specimen flatiron time longly more, has then further improved the effect of folding test (carrying out after the flatiron).

Embodiment 15: the application of butanedioic acid two (2,4,5-trichloro-benzenes phenolic ester)

The CRA that the THF solution of the diester of employing 7.65% obtains the results are shown in following table 2:

Table 2

	CRA
						Press 10s	Press 20s	Press 30s	Press 60s
The untreated control sample	78	-	-	-
					7.65% diester	92	99	102	113

Can find out once more from these results, cloth specimen (untreated control sample) crease intensity little (CRA height) that the cloth specimen of handling is more untreated, in addition, make anti-wrinkle effect that further raising be arranged long hardening time.

Embodiment 16: the application of butanedioic acid two (N-hydroxy-succinamide ester)

The CRA that obtains in the aqueous solution of the THF solution of the diester of employing 5.25% and 5.25% diester the results are shown in following table 3:

Table 3

	CRA
						Press 10s	Press 20s	Press 30s	Press 60s
The untreated control sample	71
					5.25% diester (THF)	87	88	93	95
5.25% diester (water)	93	95	92	92

From these results as can be seen, more untreated cloth specimen (untreated control sample) crease intensity little (CRA height) of the cloth specimen of handling (THF and water are two kinds of situations of carrier).When being carrier with water, curing/result is better under the flatiron time short and long.

Embodiment 17: the application of butanedioic acid two vanilla aldehydo-esters

Begin to be adopted as the THF solution (19cm of 6.55% diester ³) add the CRA that big yield obtains subsequently and the results are shown in following table 4:

Table 4

	CRA-presses 60s
		The untreated control sample	77
The THF of 6.55% diester (not adding water)	82
		The THF+1cm of 6.55% diester 3Water	86
The THF+2cm of 6.55% diester 3Water	85
		The THF+3cm of 6.55% diester 3Water	88
The THF+5cm of 6.55% diester 3Water	91

From these results as can be seen, more untreated cloth specimen (untreated control sample) crease intensity little (CRA height) of the cloth specimen of handling (THF and THF+ water are two kinds of situations of carrier).

Embodiment 18: the application of butanedioic acid two (4-cyan phenol ester)

The CRA that the THF solution of the diester of employing 5.45% obtains the results are shown in following table 5:

Table 5

	CRA-presses 60s
		The untreated control sample	77
5.45% diester	84

From these results as can be seen, more untreated cloth specimen (untreated control sample) crease intensity little (CRA height) of the cloth specimen of handling.

Embodiment 19: two isocyanic acids 1 of diethyl malonate end-blocking, the application of the own diester biuret of 6-

The structure of this molecule is as follows:

Two isocyanic acids 1 of diethyl malonate end-blocking, the 1-methoxyl group-2-propanol solution of the own diester biuret of 6-(commodity are called BI7963, available from Baxenden Chemicals Ltd) with 70% obtains, and with the THF dilution, obtains 2% solution subsequently.The results are shown in following table 6:

Table 6:CRA result

The flatiron time	CRA
		The untreated control sample	76
Flatiron (being shorter than 2s) a little	90
		2s	92
4s	93
		6s	92
8s	95
		10s	97

For the cloth specimen of handling, as can be seen, wrinkle are restorative to increase significantly even if very of short duration flatiron also makes.We think that this belongs to the cross-linking reaction between this material and the cellulose.This is considered to also that isocyanates and fibrin reaction generate real ester but not one of example of the isocyanate reaction of carbamate.

Embodiment 20: two isocyanic acids 1 of meldrum's acid end-blocking, the application of the own diester of 6-

Use 2% solution to use according to the method described above.The results are shown in following table 6.As can be seen, compare with the untreated control sample, elastic recovery angle makes moderate progress.

Table 6:CRA (2% DCM solution)

The flatiron time	CRA
		The untreated control sample	73
2s	83
		6s	85
10s	84
		20s	85

Embodiment 21: two isocyanic acids 1 of phenol end-blocking, the application of the own diester of 6-

Use 2% solution to use according to the method described above.The results are shown in following table 7.As can be seen, compare with the untreated control sample, elastic recovery angle makes moderate progress.

Table 7:CRA (2% THF solution)

The flatiron time	CRA
		The untreated control sample	73
2s	84
		6s	94
10s	89
		20s	89

Embodiment 22: two isocyanic acids 1 of succinimide end-blocking, the application of the own diester of 6-

Use 2% solution to use according to the method described above.The results are shown in following table 8.As can be seen, compare with the untreated control sample, elastic recovery angle makes moderate progress.

Table 8:CRA (2% DMAc solution)

The flatiron time	CRA
		The untreated control sample	73
2s	94
		6s	98
10s	99
		20s	102

Embodiment 23: two isocyanic acids 1 of sodium hydrogensulfite end-blocking, the application of the own diester of 6-

Use 1% solution to use according to the method described above.The results are shown in following table 9.As can be seen, compare with the untreated control sample, elastic recovery angle makes moderate progress.

Table 9:CRA (1% the aqueous solution)

The flatiron time	CRA
		The untreated control sample	75
2s	78
		6s	83
10s	85
		20s	85

Two isocyanic acids 1 of embodiment 24:4-nitrophenol end-blocking, the application of the own diester of 6-

Use 2% solution to use according to the method described above.The results are shown in following table 10.As can be seen, compare with the untreated control sample, elastic recovery angle makes moderate progress.

Table 10:CRA (2% DMAc solution)

The flatiron time	CRA
		The untreated control sample	73
2s	77
		6s	83
10s	95
		20s	92

Two isocyanic acids 1 of embodiment 25:4-metoxyphenol end-blocking, the application of the own diester of 6-

Use 2% solution to use according to the method described above.The result provides in following table 11.As can be seen, compare with the untreated control sample, except that the very short flatiron time, elastic recovery angle makes moderate progress.

Table 11:CRA (2%, DMAc)

The flatiron time	CRA
		The untreated control sample	73
2s	73
		6s	73
10s	84
		20s	90

Embodiment 26: two isocyanic acids 1 of gaultherolin end-blocking, the application of the own diester of 6-

Use 2% solution to use according to the method described above.The results are shown in following table 12.As can be seen, compare with the untreated control sample, elastic recovery angle makes moderate progress.

Table 12:CRA (2% THF solution)

The flatiron time	CRA
		The untreated control sample	73
2s	87
		6s	86
10s	87
		20s	86

Embodiment 27: the application of butanedioic acid diisoeugenol ester

This isoeugenol diester is used for cotton and after flatiron, has cloves fragrance to emit owing to the ester exchange cross-linking reaction takes place.

Claims (10)

1. a ready-made clothes of handling cellulose-containing material makes crosslinked method takes place, described method comprises the cellulose crosslinked dose of step of handling fabric with the end-blocking of effective dose, described crosslinking agent is the crosslinking agent of thermal activation, cellulose crosslinked dose of wherein said end-blocking comprises polybasic carboxylic acid, described polybasic carboxylic acid is by forming polyester and end-blocking with electrophilic alcohol or imido esterification, and wherein is used for the alcohol of end-blocking or acid imide and comprises following one or more:

A) trichlorophenol, 2,4,6,-T,

B) isoeugenol,

C) menthol,

D) 4-cyanophenol,

E) salethyl,

F) 2, the 6-syringol,

G) 4-amino-phenol,

H) dimethylamino phenol and

I) N-hydroxy-succinamide.

2. the process of claim 1 wherein that described polybasic carboxylic acid is butanedioic acid, BTCA (BTCA), 3,6-two oxa-suberic acids, tartaric acid, glactaric acid, glutamic acid, methylamino oxalic acid or nitrilotriacetic acid.

3. the process of claim 1 wherein that described polyester comprises following one or more:

A) butanedioic acid two (trichloro-benzenes phenolic ester),

B) BTCA two (trichloro-benzenes phenolic ester),

C) butanedioic acid two (N-hydroxy-succinamide ester),

D) butanedioic acid diisoeugenol ester and

E) butanedioic acid two menthol esters.

4. the method for claim 1, described method also comprises the step of the described cellulosic material of heat cure.

5. the method for claim 4, wherein heat treatment is carried out under 50-250 ℃.

6. the process of claim 1 wherein that the molecular weight of described crosslinking agent is less than 1500 dalton.

7. one kind is used for each the composition of method of aforesaid right requirement, described composition comprises cellulose crosslinked dose of end-blocking of effective dose, described crosslinking agent is the crosslinking agent of thermal activation, cellulose crosslinked dose of wherein said end-blocking comprises polybasic carboxylic acid, described polybasic carboxylic acid is by forming polyester and end-blocking with electrophilic alcohol or imido esterification, and wherein is used for the alcohol of end-blocking or acid imide and comprises following one or more:

A) trichlorophenol, 2,4,6,-T,

B) isoeugenol,

C) menthol,

D) 4-cyanophenol,

E) salethyl,

F) 2, the 6-syringol,

G) 4-amino-phenol,

H) dimethylamino phenol and

I) N-hydroxy-succinamide.

8. the composition of claim 7, described composition also comprises the carrier compatible with fabric.

9. the composition of claim 8, the wherein said carrier compatible with fabric comprises surfactant.

10. the composition of claim 7, described composition is packed with spray form.