CN1720367B - Use of copolymers as auxiliaries for dyeing and printing textiles - Google Patents

Use of copolymers as auxiliaries for dyeing and printing textiles Download PDF

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Publication number
CN1720367B
CN1720367B CN200380104924.6A CN200380104924A CN1720367B CN 1720367 B CN1720367 B CN 1720367B CN 200380104924 A CN200380104924 A CN 200380104924A CN 1720367 B CN1720367 B CN 1720367B
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acid
azacyclo
pyridine
textiles
copolymer
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CN1720367A (en
Inventor
P·鲍姆
N·U·库尔策
F·芬克
A·巴斯蒂安
M·林格尔斯巴彻
H·埃斯来
G·罗伊特
R·康拉德
J·D·卡纳汉
K·西门斯迈尔
B·波特霍夫-卡尔
T·施奈德
J·米勒
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BASF SE
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BASF SE
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Priority claimed from DE2003121396 external-priority patent/DE10321396A1/en
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Priority claimed from PCT/EP2003/013463 external-priority patent/WO2004050982A1/en
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/02—After-treatment
    • D06P5/04—After-treatment with organic compounds
    • D06P5/08—After-treatment with organic compounds macromolecular
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
    • D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • D06P1/5214—Polymers of unsaturated compounds containing no COOH groups or functional derivatives thereof
    • D06P1/5242—Polymers of unsaturated N-containing compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/60—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing polyethers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/13—Fugitive dyeing or stripping dyes
    • D06P5/137—Fugitive dyeing or stripping dyes with other compounds

Abstract

The present invention provides an use of copolymers containing units derived from at least 2 monoethylenically unsaturated monomers B1 and B2 which each contain at least one nitrogenous heterocycle, as auxiliaries for textile dyeing and textile printing.

Description

Copolymer is as the purposes of textile dyeing and printing in textiles auxiliary agent
The present invention relates to the purposes of copolymer as textile dyeing and printing in textiles auxiliary agent, this copolymer comprises the unit that belongs to unsaturated monomer B1 and B2 derived from least 2 monoene that all comprised at least one azacyclo-.
Modern textile product dyeing not only adopts colouring agent also to use the textile dyeing auxiliary agent usually.The desired effects of textile dyeing auxiliary agent is for example to remove unwanted dyeing.All the other textile dyeing auxiliary agents also provide especially good and uniform dyeing and/or good colouring agent dye-uptake especially.
The object lesson of the textile dyeing auxiliary agent that the one skilled in the art is known is a dye leveller.All the other object lessons of the textile dyeing auxiliary agent that the one skilled in the art is known are removers.All the other object lessons of the textile dyeing auxiliary agent that the one skilled in the art is known are back soaping agents.
Textiles, for example natural or synthetic textiles, it is formed often is not fully uniformly, but on composition or thickness difference is arranged along wire length.A kind of possible consequence is that this dyed textiles has the relatively dark or relative more shallow zone of dyeing, and this is undesirable usually.For obtaining uniform dyeing, for example can use dye leveller.Dye leveller is to bring the reagent of level dyeing to the textiles zone of desiring to dye (and particularly along wire length).The dye leveller of prior art comprises oily sulfonate, aliphatic alcohol sulfonate, fatty acid condensation product, alkyl and alkylaryl polyglycol ether.
Dye leveller also influence the dyeing property of dyestuff and especially on dye characteristic.The dyestuff that fiber is had high-affinity should keep longer time and easier moving on the fiber in dye liquor.The expectation dye leveller finally causes the more dyeing of homogeneous (more even).
Known dye leveller comprises the dye leveller based on polyvinylpyrrolidone, sees Ullmann ' sEncyclopedia of Industrial Chemistry (the 5th edition) A26 volume, 291 pages, and left hurdle.Commercially available dye leveller also comprises for example H of adipic acid and amine 2N-CH 2CH 2-NH-(CH 2) 3-NH 2Or H 2N-CH 2CH 2-NH-(CH 2) 3-NH-CH 2CH 2-NH 2Condensation product.Yet, the performance of this conventional dye leveller, for example as homogenizing reduction, directly, during the dye leveller of activity or SULPHUR DYES, still need to improve.
Remover is a common agents, and it is used for by separating, change or destroying dyestuff and remove for example dyeing, trace and macerate.The Application Areas that remover is even more important is to revise aberration dyeing.It comprises that the aberration coloured portions to being illuminated dyes, and causes this aberration coloured portions to be able to once more or overstains.
Remover also is known as the composition of discharge printing paste.Discharge printing paste is used for removing certain color in discharge.In discharge, color is is normally evenly printed and dyed.Overstain with follow-up color then.Then remove this follow-up color by discharge printing paste in some zone.
Yet remover of the prior art is still needing improvement aspect its performance characteristic.
For reaching enough fastness levels, thus usually when dying operation finishes and before selling to active, directly or the textiles that dyes of vatting carry out the back and remove and remain in loose dyestuff on the fiber.The back is removed and being generally included at least once soap bath and repeatedly cleaning and neutralization bath.The chemical substance that exists in the dye liquor, especially salt burden influence the result of post rinse.The liquid of soaping that remove the back comprises the compound of DISPERSE DYES or dyestuff catabolite, and it is commonly called the back soaping agent.Known back soaping agent has a lot of inferior positions, wherein especially when the salt in dye liquor when for example Glauber salt and/or sodium chloride exist, finds that a lot of known back soaping agents are poor efficiencys.And known back soaping agent must at high temperature use, promptly near 98 ℃.In addition, still barely satisfactory as the polyacrylic acid and the polyvinylpyrrolidone performance of back soaping agent.
The purpose of this invention is to provide a kind of back removes through active, directly or the improving one's methods of textiles (after this also being referred to as dyed textiles) of vatting dyeing.Further aim of the present invention provides a kind of back soaping agent, and is effective when it has the salt that improves performance and high concentration is especially arranged when removing dyed textiles in the back in dye liquor.
For reaching enough fastness levels, thus also usually when the printing in textiles EO and before selling to through active, directly or the printing textile of vatting dyeing remove after carrying out and remaining in loose dyestuff on the fiber.The back is removed and being generally included at least once soap bath and repeatedly cleaning and neutralization bath.The chemical substance that exists in the dye liquor, especially salt burden influence the result of post rinse.The liquid of soaping that remove the back comprises the compound of DISPERSE DYES or dyestuff catabolite, and it is commonly called the back soaping agent.Known back soaping agent has a lot of inferior positions, wherein especially when the salt in dye liquor when for example Glauber salt and/or sodium chloride exist, finds that a lot of known back soaping agents are poor efficiencys.And known back soaping agent must at high temperature use, promptly near 98 ℃.In addition, still barely satisfactory as the polyacrylic acid and the polyvinylpyrrolidone performance of back soaping agent.
The purpose of this invention is to provide a kind of back removes through active, directly or the improving one's methods of printing textile (after this also being referred to as printing textile) of vatting dyeing.Further aim of the present invention provides a kind of back soaping agent, and is effective when it has the salt that improves performance and high concentration is especially arranged when removing printing textile in the back in dye liquor.
We find can realize this purpose by the textile dyeing and the printing in textiles auxiliary agent of above-mentioned qualification.
For the object of the invention textiles is the textiles of textile fabric, weaving intermediate product and end-product and manufactured goods prepared therefrom and clothing industry, also for example comprises carpet and all the other home textile and be used for the industrial purposes fabric construction.These also comprise unfashioned structure example such as staple fibre, line such as doublet cord, monofilament, yarn, rope, lace, braided fabric, rope and filament and three-dimensional structure such as felt, braided fabric, bondedfibre fabric and oakum.Textiles can be for example cotton, hair or flax of natural origin, or artificial synthetic, for example polyamide.
In one embodiment of the invention, the copolymer (after this also this copolymer being referred to as the copolymer used according to the present invention) that is used for textile dyeing and printing in textiles auxiliary agent of the present invention comprises derived from least 2 and has all comprised the monoethylenically unsaturated monomer B1 of at least one azacyclo-and the unit of B2.
Used copolymer can be random copolymer, block copolymer or graft copolymer according to the present invention.
In one embodiment of the invention, the B1 monomer that exists with copolymerized form in the used copolymer according to the present invention is the cyclic amide of at least a general formula I
Wherein
X be 1-6 integer and
R 1Be hydrogen or C 1-C 4Alkyl, for example methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl and the tert-butyl group.
The object lesson of the B1 monomer of copolymerization is N-vinylpyrrolidone, N-ethene-δ-valerolactam and N-ethene-epsilon-caprolactams, wherein preferred N-vinylpyrrolidone.
In one embodiment of the invention, used copolymer comprises the unit that comprises the B2 monomer of azacyclo-derived from least a according to the present invention, and this azacyclo-is selected from: pyrroles, pyrrolidines, pyridine, quinoline, isoquinolin, purine, pyrazoles, imidazoles, triazole, tetrazolium, indolizine, pyridazine, pyrimidine, pyrazine, indoles, iso-indoles,
Figure B2003801049246D00041
Azoles,
Figure B2003801049246D00042
Oxazolidone,
Figure B2003801049246D00043
Azoles alkane, morpholine, piperazine, piperidines, different Azoles, thiazole, isothiazole, indoxyl, isatin, dioxindole and hydantoins and derivative thereof, for example barbituric acid and uracil and derivative thereof.
Preferred heterocycle is imidazoles, pyridine and N-pyridine oxide, and especially preferred imidazoles.
Useful especially B2 comonomer example is N-vinyl imidazole, alkyl vinyl imidazoles (especially methyl ethylene imidazoles such as 1-ethene-glyoxal ethyline), 3-vinyl imidazole N oxide, 2-and 4-vinylpridine, 2-and 4-vinylpridine N-oxide and betaines derivative and quaternized products.
The B2 comonomer of especially preferred copolymerization is the 2-of betaine N-vinyl imidazole, general formula II c and II d of N-vinyl imidazole, II b of general formula II a and betaine 2-and the 4-vinylpridine of 4-vinylpridine and general formula II e and II f.
Figure B2003801049246D00045
Figure B2003801049246D00051
Wherein
R 2, R 3, R 4, R 6Be independently hydrogen, C 1-C 4Alkyl such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl and the tert-butyl group; Or phenyl, preferred hydrogen;
A 1Be C 1-C 20Alkylidene, for example-CH 2-,-CH (CH 3)-,-(CH 2) 2-,-CH 2-CH (CH 3)-,-(CH 2) 3-,-(CH 2) 4-,-(CH 2) 5-,-(CH 2) 6-, preferred C 1-C 3Alkylidene; Especially-CH 2-,-(CH 2) 2-,-(CH 2) 3-.
X -Be-SO 3 --,-OSO 3 --,-COO -,-OPO (OH) O -,-OPO (OR 5) O -Or-PO (OH) O -
R 5Be C 1-C 24Alkyl, for example methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, isopentyl, sec-amyl, neopentyl, 1,2-dimethyl propyl, isopentyl, n-hexyl, isohesyl, Sec-Hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl; Especially preferred C 1-C 4Alkyl, for example methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl and the tert-butyl group.
Especially preferred betaine copolymerization B2 monomer is general formula II b, the monomer of II e and II f, wherein this A 1-X -Part representative-CH 2-COO -,-(CH 2) 2-SO 3 -Or (CH 2) 3-SO 3-and all the other symbols all represent hydrogen.
Useful B2 monomer all passes through quaternised vinyl imidazole and vinylpyridine before or after further being included in polymerization.
This quaternized process can be especially implemented by alkylating reagent (for example have the alkyl halide of 1 to 24 carbon atom alkyl usually or comprise the dialkylsulfates of 1 to 10 carbon atom alkyl usually).The example of useful alkylating reagent is chloromethanes, Celfume, iodomethane, chloroethanes, bromoethane, chloropropane, chlorohexane, chlorinated dodecane and chloro laurane and dimethyl suflfate and dithyl sulfate.Useful alkylating reagent for example further comprises: benzyl halogen, especially benzyl chlorine and benzyl bromine; Monoxone; The fluorosulfuric acid methyl esters; Diazomethane; Oxygen Compound, for example tetrafluoro boric acid trimethyl oxygen Alkylene oxide, for example oxirane, expoxy propane and glycidol, it uses under the situation that acid exists; The CATION epoxychloropropane.Preferred quaternizing agent is chloromethanes, dimethyl suflfate and dithyl sulfate.
Useful especially quaternized B2 monomer is 1-methyl-3-vinyl imidazole Methylsulfate and 1-methyl-3-vinyl imidazole
Figure B2003801049246D00064
Methochloride.
The B1 of copolymerization and B2 monomer weight ratio scope are generally 99: 1-1: 99, preferred 90: 10-30: 70, more preferably 90: 10-50: 50, even more preferably 80: 20-50: 50 and especially 80: 20-60: 40.
Used copolymer can comprise the unit derived from one or more further monomers B 3 according to the present invention, and for example carboxylic monoene belongs to unsaturated monomer, as unsaturated C 2-C 10List or dicarboxylic acids and derivative thereof are as salt, ester, acid amides and acid anhydride.The example that can mention is:
Acid and its salt is (methyl) acrylic acid, fumaric acid, maleic acid and its alkali metal or ammonium salt separately for example; Acid anhydride is maleic anhydride for example; Ester is (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, dimethyl maleate, diethyl maleate, fumaric acid dimethyl ester, fumaric acid diethylester, fumaric acid two-positive butyl ester for example.
Further the B3 example is the alefinically unsaturated compounds that vinylacetate and propionate and general formula III a represent to III d,
Figure B2003801049246D00065
Herein
R 1Define as above,
Y 1Be selected from oxygen or NH,
Y is selected from 1 or 0 integer,
Y 2Be [A 2-O] s-[A 3-O] u-[A 4-O] v-R 8
A 2To A 4Be identical or different and independently-(CH 2) 2-,-(CH 2) 3-,-(CH 2) 4-,-CH 2-CH (CH 3)-,-CH 2-CH (CH 2-CH 3)-,-CH 2-CHOR 10-CH 2-;
R 8Be hydrogen, amino-C 1-C 6-alkyl, wherein this amino group can be primary, the second month in a season or uncle's amino, for example CH 2-NH 2,-(CH 2) 2-NH 2,-CH 2-CH (CH 3)-NH 2,-CH 2-NHCH 3,-CH 2-N (CH 3) 2,-N (CH 3) 2,-NHCH 3,-N (C 2H 5) 2C 1-C 24Alkyl; R 2-CO-, R 9-NH-CO-;
R 9Be C 1-C 24Alkyl;
R 10Be hydrogen, C 1-C 24Alkyl, R 9-CO-;
S represents the integer of 0-500;
Identical or different in each case and integer expression 1-5000 under each situation of u;
Identical or different in each case and integer expression 0-5000 under each situation of v;
Identical or different in each case and integer expression 0-5000 under each situation of w;
The C of general formula III a to the III d 1-C 24Alkyl group can be branching or nonbranched C 1-C 24Alkyl, wherein preferred C 1-C 12Alkyl and especially preferred C 1-C 6Alkyl.The example that can mention is a methyl, ethyl, n-pro-pyl, the 1-Methylethyl, normal-butyl, the 1-methyl-propyl, the 2-methyl-propyl, 1, the 1-dimethyl ethyl, n-pentyl, the 1-methyl butyl, the 2-methyl butyl, the 3-methyl butyl, 2, the 2-dimethyl propyl, the 1-ethyl propyl, n-hexyl, 1, the 1-dimethyl propyl, 1, the 2-dimethyl propyl, the 1-methyl amyl, the 2-methyl amyl, the 3-methyl amyl, the 4-methyl amyl, 1, the 1-dimethylbutyl, 1, the 2-dimethylbutyl, 1, the 3-dimethylbutyl, 2, the 2-dimethylbutyl, 2, the 3-dimethylbutyl, 3, the 3-dimethylbutyl, the 1-ethyl-butyl, the 2-ethyl-butyl, 1,1,2-trimethyl propyl group, 1,2,2-trimethyl propyl group, 1-ethyl-1-methyl-propyl, 1-ethyl-2-methyl-propyl, n-heptyl, the 2-ethylhexyl, n-octyl, n-nonyl, positive decyl, the n-undecane base, dodecyl, the n-tridecane base, the n-tetradecane base, the n-pentadecane base, n-hexadecyl, the n-heptadecane base, the n-octadecane base, NSC 77136 base and n-eicosane base.
In specific embodiments, the method according to this invention comprises that one or more graft polymers of use are as the copolymer in the inventive method.
The preferred graft polymers that uses comprises that for example those also comprise the unit to this B3 comonomer of III d derived from general molecular formula III a except B1 and B2 monomer.
The embodiment preferred utilization belongs to the polymer graft matrix A of unsaturated unit and belongs to the graft polymers that polymeric side chains B that the copolymer of unsaturated monomer B1 and B2 and optional further comonomer B3 forms constitutes by at least 2 monoene that all comprised at least one azacyclo-by not comprising monoene.
Can take over for use in method embodiment as described below and the graft polymers that can have pectinate texture by the schedule of proportion of its side chain B and graft polymerization matrix A according to the present invention.Based on total graft polymers, described side chain B can account for more than the 35 weight %.This mark preferred 55-95 weight % and more preferably 70-90 weight %.
The B1 monomer that is included in pendant graft polymer chains B is preferably the cyclic amides of at least a general formula I
Figure B2003801049246D00081
Symbol in the general formula I all defines as above herein.
The object lesson of the B1 monomer of copolymerization is N-vinylpyrrolidone, N-ethene-δ-valerolactam and N-ethene-epsilon-caprolactams, wherein preferred N-vinylpyrrolidone.
In one embodiment of the invention, this B side chain advantageously comprises the unit that belongs to unsaturated monomer B2 derived from least a monoene that has comprised azacyclo-, and this azacyclo-is selected from: pyrroles, pyrrolidines, pyridine, quinoline, isoquinolin, purine, pyrazoles, imidazoles, triazole, tetrazolium, indolizine, pyridazine, pyrimidine, pyrazine, indoles, iso-indoles,
Figure B2003801049246D00082
Azoles,
Figure B2003801049246D00083
Oxazolidone,
Figure B2003801049246D00084
Azoles alkane, morpholine, piperazine, piperidines, different Azoles, thiazole, isothiazole, indoxyl, isatin, dioxindole and hydantoins and derivative thereof, for example barbituric acid and uracil and derivative thereof.
Preferred heterocycle is imidazoles, pyridine and N-pyridine oxide, and especially preferred imidazoles.
Useful especially B2 comonomer example is N-vinyl imidazole, alkyl vinyl imidazoles (especially methyl ethylene imidazoles such as 1-ethene-glyoxal ethyline), 3-vinyl imidazole N oxide, 2-and 4-vinylpridine, 2-and 4-vinylpridine N-oxide and betaines derivative and quaternized products.
The B2 comonomer of especially preferred copolymerization is the 2-of betaine N-vinyl imidazole, general formula II c and II d of N-vinyl imidazole, II b of general formula II a and betaine 2-and the 4-vinylpridine of 4-vinylpridine and general formula II e and II f.
Especially preferred betaine copolymerization B2 examples of monomers is general formula II b, the monomer of II e and II f, A herein 1-X -Part representative-CH 2-COO -,-(CH 2) 2-SO 3 -Or (CH 2) 3-SO 3-and all the other symbols all represent hydrogen.
Useful B2 monomer further is included in all quaternised vinyl imidazole and vinylpyridine before or after the polymerization.
This quaternized process can be according to implementing as mentioned above.
Useful especially quaternized B2 monomer is 1-methyl-3-vinyl imidazole
Figure B2003801049246D00091
Methylsulfate and 1-methyl-3-vinyl imidazole
Figure B2003801049246D00092
Methochloride.
The B1 of copolymerization and B2 monomer weight ratio scope are generally 99: 1-1: 99, preferred 90: 10-30: 70, more preferably 90: 10-50: 50, even more preferably 80: 20-50: 50 and especially 80: 20-60: 40.
Used graft polymers side chain can comprise the unit derived from one or more further monomers B 3 according to the present invention, and for example carboxylic monoene belongs to unsaturated monomer, as unsaturated C 2-C 10List or dicarboxylic acids and derivative thereof are as salt, ester, acid anhydride and material as defined above.
The graft polymerization matrix A preferred, polyethers of used graft polymers according to the present invention.Herein, term " polymerization " also should be understood to oligomer.
The grafting matrix A of especially preferred polymerization has the mean molecule quantity M of 300g at least n
The grafting matrix A of especially preferred polymerization has general formula IV a
Or IV b
Figure B2003801049246D00101
Herein
R 7Be carboxyl, amino, C 1-C 24Alkoxyl such as methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, isoamoxy, just own oxygen base, dissident's oxygen base, R 9-COO-, R 9-NH-COO-, polynary alcohol radical such as glyceryl;
A 2To A 4Be identical or different and be-(CH 2) 2-,-(CH 2) 3-,-(CH 2) 4-,-CH 2-CH (CH 3)-,-CH 2-CH (CH 2-CH 3)-,-CH 2-CHOR 10-CH 2-;
R 8Be hydrogen, amino-C 1-C 6-alkyl, wherein this amino group can be primary, the second month in a season or uncle's amino, for example CH 2-NH 2,-(CH 2) 2-NH 2,-CH 2-CH (CH 3)-NH 2,-CH 2-NHCH 3,-CH 2-N (CH 3) 2,-N (CH 3) 2,-NHCH 3,-N (C 2H 5) 2C 1-C 24Alkyl; R 9-CO-, R 9-NH-CO-;
A 5Be-CO-O-,-CO-B-CO-O ,-CO-NH-B-NH-CO-O-;
A 6Be C 1-C 20Alkylidene, its carbochain can insert 1-10 oxygen atom as the ether functional group;
B is-(CH 2) t-, replacement or unsubstituted arlydene be for example to phenylene, metaphenylene, adjacent phenylene, 1,8-naphthylene, 2,7-naphthylene;
N be 1 or 1-8 (work as R 7When being polynary alcohol radical);
T represents the integer of 1-12;
And other symbol all defines as above.
The graft polymerization matrix A of general formula IV a is preferably from the polyepoxide based on oxirane, expoxy propane and epoxy butane, the polyethers of PolyTHF and polyglycereol.According to this monomer, the polymer of gained comprises following construction unit :-(CH 2) 2-O-,-(CH 2) 3-O-,-(CH 2) 4-O-,-CH 2-CH (CH 3)-O-,-CH 2-CH (CH 2-CH 3)-O-,-CH 2-CHOR 8-CH 2-O-
Homopolymers and copolymer all are available, and copolymer can be random copolymer or block copolymer.
Can exist or by C with free form based on the secondary OH group of the terminal primary hydroxyl of the polyethers of alkylene oxide or glycerine preparation and polyglycereol 1-C 24Alcohol etherificate, C 1-C 24Carboxylic esterification or form urethane with isocyanate reaction.To the useful alcohol of this purpose for example can be: aliphatic primary alcohol is methyl alcohol, ethanol, propyl alcohol and butanols for example, the aromatics primary alconol is phenol, isopropyl-phenol, tert-butyl phenol, octyl phenol, nonyl phenol and naphthols for example, secondary aliphatic alcohols is isopropyl alcohol for example, the aliphatic tertiary alcohol is the tert-butyl alcohol for example, with polyalcohol for example dihydroxylic alcohols (for example ethylene glycol, diethylene glycol (DEG), propylene glycol, 1, ammediol and butanediol) and trihydroxylic alcohol (for example glycerine, trimethylolpropane).Yet the also available primary amino radical of oh group exchange (by under pressure, carrying out reductive amination) or with the acrylonitrile cyanoethylation and be hydrogenated to amino propylene end group with hydrogen-ammonia mixture.The conversion of this terminal hydroxyl not only can be later on by with alcohol or with aqueous alkali metal hydroxide solution, amine and azanol reaction after take place, and can use, as this initiator of polyreaction of initiation as lewis acid such as boron trifluoride.At last, also can by with alkylating reagent for example dimethyl suflfate reaction make this terminal hydroxyl group etherificate.
C among general formula IV a and the IVd 1-C 24Alkyl can be branching or nonbranched C 1-C 24Alkyl, wherein preferred C 1-C 12Alkyl and especially preferred C 1-C 6Alkyl.The example that can mention is a methyl, ethyl, n-pro-pyl, the 1-Methylethyl, normal-butyl, the 1-methyl-propyl, the 2-methyl-propyl, 1, the 1-dimethyl ethyl, n-pentyl, the 1-methyl butyl, the 2-methyl butyl, the 3-methyl butyl, 2, the 2-dimethyl propyl, the 1-ethyl propyl, n-hexyl, 1, the 1-dimethyl propyl, 1, the 2-dimethyl propyl, the 1-methyl amyl, the 2-methyl amyl, the 3-methyl amyl, the 4-methyl amyl, 1, the 1-dimethylbutyl, 1, the 2-dimethylbutyl, 1, the 3-dimethylbutyl, 2, the 2-dimethylbutyl, 2, the 3-dimethylbutyl, 3, the 3-dimethylbutyl, the 1-ethyl-butyl, the 2-ethyl-butyl, 1,1,2-trimethyl propyl group, 1,2,2-trimethyl propyl group, 1-ethyl-1-methyl-propyl, 1-ethyl-2-methyl-propyl, n-heptyl, the 2-ethylhexyl, n-octyl, n-nonyl, positive decyl, the n-undecane base, dodecyl, the n-tridecane base, the n-tetradecane base, the n-pentadecane base, n-hexadecyl, the n-heptadecane base, the n-octadecane base, NSC 77136 base and n-eicosane base.
The polyethers mean molecule quantity M of general formula IV a nBe 300g/mol and usually≤100000g/mol at least.Preferred 500g/mol to 50000g/mol, more preferably 10000g/mol and most preferably 2000g/mol at the most at the most.The polydispersity of the polyethers of general formula I Va is low, for example in most of the cases is 1.1-1.8.
Can use all can be that the homopolymerization of oxirane straight chain or branching, expoxy propane, epoxy butane and epoxy iso-butane and copolymer are as the graft polymerization matrix.As used in this, the term homopolymers also is interpreted as those alkylene oxide units except polymerization, comprises the polymer that is used to cause the polymerisation of cyclic ethers or is used for the bioactive molecule of polymer terminal group end-blocking in addition.
Branched polymer can be prepared as follows: for example add the low-molecular-weight polyalcohol (R of general formula I Va and IV b 7Group), pentaerythrite for example, glycerine and sugar or sugar alcohol such as sucrose, D-D-sorbite and D-mannitol, disaccharides, oxirane, and if need expoxy propane and/or epoxy butane or polyglycereol.
In formed polymer, at least a oh group that exists in this polyalcohol molecule, preferred a kind of to eight kinds and more preferably a kind of to five kinds, form that can ehter bond is connected to the polyether group of general formula IV a or IVb
By alkylene oxide is added diamine, preferred ethylenediamine can obtain four arm polymer.
By with alkylene oxide and the reaction of higher amine, triamine for example, or polymine especially can prepare other branched polymers.Suitable polymine has the mean molecule quantity M of 300-20000g usually n, preferably 500-10000 and more preferably 500-5000g.The weight ratio of alkylene oxide and polymine normally 100: 1-0.1: 1, and preferred 20: 1-0.5: 1.
Also can use polyepoxide and aliphatic C 1-C 12-, preferred C 1-C 6-, dicarboxylic acids or aromatic dicarboxylic acid, for example polyester of oxalic acid, butanedioic acid, adipic acid or terephthalic acid (TPA) (its mean molecule quantity M nBe 1500-25000g/mol) as graft polymerization matrix A.
As substituting of IVa and IV b, also can adopt the Merlon of polyepoxide of phosgenation preparation or the polyurethane and the aliphatic C of polyepoxide 1-C 12Vulcabond and preferred C 1-C 6Vulcabond or aromatic diisocyanates, for example hexamethylene diisocyanate or phenylene vulcabond are as graft polymerization matrix A.
These polyester, Merlon or polyurethane can comprise at the most 500 and preferred 100 polyepoxide unit at the most, and the polyepoxide unit not only can be made up of homopolymer in this case, also is made up of the copolymer of different alkylene oxides.
Especially preferably use the homopolymerization of oxirane and/or expoxy propane and copolymer graft polymerization matrix A as the method according to this invention, can be to its one or both ends tip group end capping.
Having the copolymerization alkylene oxide of high expoxy propane ratio and an effect of poly(propylene oxide) is that grafting takes place easily.
Having the copolymerization alkylene oxide of high ethylene oxide ratio and an effect of poly(ethylene oxide) is: after grafting had taken place and produced the graft polymers that has with the identical grafting density of expoxy propane, the weight ratio of side chain and graft polymerization matrix was bigger.
The K value of graft polymers is 10-150 normally, preferred 10-80 and more preferably 15-60 (by H.Fikentscher, Cellulose-Chemie, volume 13, the method described in 58-64 page or leaf and the 71-74 page or leaf (1932) is measured in water or in the sodium-chloride water solution of 3 weight % and under the polymer concentration (depending on K value scope) of 0.1 weight %-5 weight % in 25 ℃).Can set required special K value in the mode of routine by the composition of material therefor.Theoretical grafting degree for 100%, the molecular weight of product is determined by the grafting substrate molecule amount and the copolymer ratio of reacting as side chain.Grafting substrate molecule quantity is big more, and the final molecular amounts of gained is also just big more, and vice versa.Can control side chain density by amount of initiator and reaction condition.
The preparation graft polymers further method used according to the present invention is included in free yl polymerizating monomer B1 and B2 and optional further copolymer B3 under the situation that graft polymerization matrix A exists.
Polymerization can be carried out with for example polymerisation in solution, bulk polymerization, emulsion polymerisation, inverted emulsion polymerization, suspension polymerization, contrary suspension polymerization or precipitation polymerization.Preferred bulk polymerization and especially polymerisation in solution, particularly it carries out under the situation that water exists.
Bulk polymerisation process can followingly be implemented: monomers B 1 and B2 are dissolved in graft polymerization matrix A, with this mixture heated to polymerization temperature and mixture is being added radical initiator before the complete polymerization.This polymerization process also can be by at first introducing part (for example 10 weight %) this graft polymerization matrix A, monomers B 1 and B2 and radical initiator mixture and be heated polymerization temperature, begin the back in polymerization and add remaining mixture with the speed that is complementary with the polymerisation process and semi-continuously carry out.Yet, also can in reactor, initially add grafting matrix A, should add initially that part is heated to polymerization temperature and disposable before polymerization, in batches or preferred monomers B 1 and B2 (individually or as mixture) and the radical initiator of adding continuously.
Above-mentioned glycerol polymerization can be carried out in one or more solvents.The example of appropriate organic solvent is for example aliphatic and alicyclic monohydric alcohol, as methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol, sec-butyl alcohol, the tert-butyl alcohol, n-hexyl alcohol and cyclohexanol, polyalcohol, for example dihydroxylic alcohols such as ethylene glycol, propylene glycol and butanediol and glycerine, the alkyl ether of polyalcohol, the for example methyl ether of above-mentioned glycol and ethylether, and ether alcohol such as diethylene glycol (DEG) and triethylene glycol also have cyclic ether as two Alkane.
This glycerol polymerization process is preferably carried out as solvent with water.At this, A, B1 and B2 and optional further comonomer B3 are efficient or poor efficiency ground is dissolved, depend on the used water yield.Also can in polymerization process, partly or wholly add entry.Should be understood that the mixture that also can make water and above-mentioned organic solvent.
Usually use based on graft polymers 5-250 weight % organic solvent, water or the water of preferred 10-150 weight % and the mixture of organic solvent.
Polymerization process in water provides 10-70 weight % usually, solution or the dispersion of preferred 20-50 weight % according to graft polymers of the present invention, it can change into powder type by various drying meanss, as spray drying, fluidization and spray-drying, roller drying or freeze drying.Can be by adding water and regain the aqueous solution or dispersion easily in the suitable time.
Useful radical initiator is peralcohol, azo-compound, redox initiation system and reducing compound.Should be understood that the mixture that also can use radical initiator.
The example of suitable polymerization initiator is specially: peroxy-disulfuric acid alkali metal salt such as sodium peroxydisulfate, peroxo disulfate acid ammonium, hydrogen peroxide, organic peroxide such as diacetyl peroxide, di-tert-butyl peroxide, the diamyl peroxide, dioctanoyl peroxide, didecanoyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, peroxidating two (adjacent toluyl groups), succinyl peroxide, the peracetic acid tertiary butyl ester, cross the maleic acid tertiary butyl ester, cross the isobutyric acid tertiary butyl ester, cross the neopentanoic acid tertiary butyl ester, cross sad tertiary butyl ester, cross the neodecanoic acid tertiary butyl ester, t-butyl perbenzoate, tert-butyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, peroxide-2 ethyl hexanoic acid tertiary butyl ester and peroxide two dimethyl isopropyl esters; Azodiisobutyronitrile, azo two (2-aminopropane) dihydrochloride or 2,2 '-azo two (2-methylbutyronitrile); The compound of sodium sulfite, sodium hydrogensulfite, formaldehyde sodium sulfoxylate and hydrazine and above-claimed cpd and hydrogen peroxide; Ascorbic acid/ferric sulfate (II)/Na 2S 2O 8, tert-butyl hydroperoxide/sodium hydrogensulfite, tert-butyl hydroperoxide/hydroxyl methane sulfinic acid sodium.
Preferred radical initiator is for example to cross the neopentanoic acid tertiary butyl ester, cross sad tertiary butyl ester, cross neodecanoic acid tertiary butyl ester, tert-butyl peroxide, tert-butyl hydroperoxide, azo two (2-methylpentanone amidine) dihydrochloride, 2,2 '-azo two (2-methylbutyronitrile), hydrogen peroxide and sodium peroxydisulfate, can be to wherein adding small amounts reducing metal salt, for example molysite.
Based on monomers B 1 and B2, use 0.01-10 weight % usually, and the radical initiator of preferred 0.1-5 weight %.
If need, also can use polymerization regulator.Useful compound is that the one skilled in the art is known, and comprise for example sulphur compound, for example mercaptoethanol, TGA 2-ethylhexyl, TGA and lauryl mercaptan, and the conditioning agent of other type, for example bisulfites and hypophosphites.When using polymerization regulator, its usage level is 0.1-15 weight % normally, and preferably 0.1-5 weight % and more preferably 0.1-2.5 weight % are based on monomers B 1 and B2.
Polymerization temperature is generally 30-200 ℃, preferred 50-150 ℃ and more preferably 75-110 ℃.
Polymerization is carried out under atmospheric pressure usually, yet also can carry out under negative pressure or elevated pressure, for example at 0.5 or 5 crust.
According to the present invention, above-mentioned copolymer can be used as for example remover.According to the present invention, above-mentioned copolymer can be used as dye leveller.
The further embodiment of the present invention be included in comprised derived from least a graft polymers on the grafting matrix of the copolymer of the unit of monomers B 1 and B2 and optional further comonomer B3 according to the present invention as the purposes of textile dyeing and printing in textiles auxiliary agent, monomers B 1, B2 and B3 definition are as above.
The present invention further provides and comprised the auxiliary agent that is used for textile dyeing and printing in textiles of copolymer (for example remover, dye leveller and back soaping agent) as mentioned above.
Textile dyeing of the present invention and printing in textiles auxiliary agent, for example remover, dye leveller and back soaping agent, more preferably comprise at least a graft polymers, it belongs to the polymer graft matrix A of unsaturated unit and belongs to the polymeric side chains B that the copolymer of unsaturated monomer B1 and B2 and optional further comonomer B3 forms by at least 2 monoene that all comprised at least one azacyclo-and constitute by not comprising monoene.
Preferably, the ratio of side chain B is more than the 35 weight % in textile dyeing of the present invention and printing in textiles auxiliary agent (for example at remover of the present invention, dye leveller and back soaping agent).
Preferred textile dyeing and printing in textiles auxiliary agent according to the present invention, except above-mentioned copolymer and especially above-mentioned graft polymers, the component that also comprises other, for example phosphorus compound, complexing agent and ion-type or nonionic surface active agent, and especially the phosphorus compound example of Shi Yonging is a phosphinic acid compounds, for example the hydroxyl methylenediphosphonate.Suitable complexing agent is aminocarboxylic acid derivative and its alkali metal salt, for example nitrilotriacetic acid(NTA), ethylenediamine tetra-acetic acid and corresponding two-and the tetrasodium salt of trisodium salt and ethylenediamine tetra-acetic acid.Suitable nonionic surface active agent is the ethoxylated product of long-chain alcohol.Preferred alcohol belongs to the 1-alkanol that for example has 8-30 carbon atom and preferred 8-18 carbon atom or has 8-30 carbon atom and the 2-alkanol of preferred 8-18 carbon atom.Ethoxylation degree is 4-30 and preferred 6-15.
Further preferably have the above-mentioned alkanol ethoxylated product of the average degree of ethoxylation of 8-30 and preferred 8-18, condition is to use the 1mol expoxy propane at least.By with alkanol successively with expoxy propane and reacting ethylene oxide, can obtain alkanol ethoxylated product mentioned in the example.
Suitable ionic surfactant is based on for example sulfosuccinic acid list or diester.The suitable alcohol that is used to prepare this ester is branching or the nonbranched alcohol with 2-30 carbon atom and preferred 4-18 carbon atom chain length.
Textile dyeing of the present invention and printing in textiles auxiliary agent can be used as powder and use.Yet it also can be used as the aqueous formulation thing and uses, and the mark of water can be 5-95 and preferred 20-90 weight % in the case, based on the composition total amount.Preferably use as the liquid formulations thing, its metering can realize by for example automatic metering equipment.
The present invention further provides for the aberration dyeing of fabric or the equal dyeing method of uneven color, after this also be referred to as equal dyeing method of the present invention, comprised the dye leveller of at least a copolymer comprising use, this copolymer comprises the unit that belongs to unsaturated monomer B1 and B2 derived from least 2 monoene that all comprised at least one azacyclo-.
In one embodiment of the invention, equal dyeing method of the present invention relate to eliminate because reduction, directly, aberration dyeing or uneven dyeing due to activity or the sulphur dyestuff.
An embodiment of equal dyeing method of the present invention has been utilized aforesaid graft polymers.
Equal dyeing method of the present invention can be implemented under other known condition.
Preferably, equal dyeing method of the present invention is implemented in the aqueous solution, and in the case, this solution ratio is 100: 1-5: 1 and preferred 25: 1-5: 1.
Based on above-mentioned copolymer content, dye leveller concentration of the present invention is 0.01-10 grams per liter solution, especially 0.1-1 grams per liter and 1 grams per liter solution especially.
In one embodiment of the invention, in solution, add one or more dispersants.The example of suitable dispersant is naphthalene sulfonic acids-formaldehyde condensation products, and it can be by for example using the fuming sulphuric acid sulfonated naphthalene, partially or completely neutralizes with for example alkali metal hydroxide aqueous solution and with the formaldehyde reaction preparation and get again.All the other suitable dispersants are recorded in for example US4, in 218,218.Suitable consumption is 0.1-5g dispersant/rise solution and preferred 1-2 grams per liter normally.
In one embodiment of the invention, in solution, add one or more reductants, for example sodium dithionite Na 2S 2O 4Suitable amounts is generally 0.1-10g reductant/rise solution and particularly 1-6 grams per liter.
In one embodiment of the invention, in solution, add one or more protecting colloids, for example based on the polyacrylic protecting colloid that partially or completely neutralizes.Suitable polyacrylic mean molecule quantity M wBe for example 1000-200000g/mol, preferred 1000-100000g/mol and especially 3000-70000g/mol.Especially the preferred polyacrylic acid of neutralization fully.Suitable amounts is generally 0.1-5g protecting colloid/rise solution and especially 1-2 grams per liter.
Equal dyeing method of the present invention carries out under the pH of 9-13 usually.
Equal dyeing method of the present invention is implemented being higher than under the temperature of room temperature usually.Temperature range be 50 ℃ to boiling temperature, and preferably, at least 60 ℃ is especially suitable.
According to normally at least 5 minutes-2 hours duration of levelling of the present invention, and preferred 30-90 minute.
After handling, can carry out rinsing, washing and/or drying with dye leveller of the present invention.With the acid neutralization also is suitable, especially uses low volatility acid for example butanedioic acid, adipic acid, tartaric acid or citric acid.
The present invention further provides the method that the aberration product dyed thereby is separated fabric, after this also be referred to as stripping means of the present invention, comprised the remover of at least a copolymer that belongs to the unit of unsaturated monomer B1 and B2 derived from least 2 monoene that all comprised at least one azacyclo-comprising use.
In one embodiment of the invention, stripping means of the present invention relate to eliminate because reduction, directly, the aberration dyeing due to activity or the sulphur dyestuff.
An embodiment of stripping means of the present invention has been utilized aforesaid graft polymers.
If not stripping means of the present invention can be implemented under so known condition.
Preferably, stripping means of the present invention is implemented in the aqueous solution, and in the case, this solution ratio is 100: 1-5: 1 and preferred 25: 1-5: 1.
Based on above-mentioned copolymer content, remover concentration of the present invention is 0.5-10 grams per liter solution, especially 2-4 grams per liter solution.
In one embodiment of the invention, add one or more dispersants.Suitable dispersant example is naphthalene sulfonic acids-formaldehyde condensation products, and it can be by for example using the fuming sulphuric acid sulfonated naphthalene, partially or completely neutralizes with for example alkali metal hydroxide aqueous solution and with the formaldehyde reaction preparation and get again.Other suitable dispersants are recorded in for example US4, in 218,218.Suitable consumption is 0.1-5g dispersant/rise solution and preferred 1-2 grams per liter normally.
In one embodiment of the invention, in solution, add one or more reductants, for example sodium dithionite Na 2S 2O 4Suitable amounts is generally 0.1-10g reductant/rise solution and particularly 1-6 grams per liter.
In one embodiment of the invention, in solution, add one or more protecting colloids, for example based on the polyacrylic protecting colloid that partially or completely neutralizes.Suitable polyacrylic mean molecule quantity M wBe for example 1000-200000g/mol, preferred 1000-100000g/mol and especially 3000-70000g/mol.Especially the preferred polyacrylic acid of neutralization fully.Suitable amounts is generally 0.1-5g protecting colloid/rise solution and especially 1-2 grams per liter.
Stripping means of the present invention carries out under the pH of 9-13 usually.
Stripping means of the present invention is implemented being higher than under the temperature of room temperature usually.Temperature range be 50 ℃ to boiling temperature, and preferably, at least 60 ℃ is especially suitable.
According to normally at least 5 minutes-2 hours stripping means of the present invention duration, and preferred 30-90 minute.
After handling, can carry out rinsing, washing and/or drying with remover of the present invention.With the acid neutralization also is suitable, especially uses low volatility acid for example butanedioic acid, adipic acid, tartaric acid or citric acid.
The present invention further provides the method for back removing through the textiles of dye transfer, after this also be referred to as back of the present invention sweep-out method or of the present invention after the method for soaping.
The method of soaping is by using one or more back soaping agents of the present invention to implement in typical water solution after of the present invention.This solution can comprise based on the solution external salt of the amount of 15 weight %, for example NaCl or Glauber salt at the most.The water that is used to prepare this aqueous solution does not need to soften; The water hardness of 30 ° of Deutschland hardnesss is feasible at the most.
Back of the present invention reset procedure can under atmospheric pressure be implemented, however super-atmospheric pressure for example the 1.1-5 crust also be feasible.
For implementing the method for soaping after of the present invention, can in one or more soap liquid, handle textiles through dye transfer, soap each time bathe in selected temperature, pressure and pH condition all may be identical or different.Preferred use to soap for one to three time bathe and more preferably one or soap for twice.Preferably, the soap temperature and pressure condition of bathing of difference is all identical.
When bath is repeatedly soaped in use, need usually between each time soaped, dispose waste liquid and all need prepare new liquid at every turn.Can use the liquid or have the different liquid of forming of soaping soaped with same composition.Yet at least a soap body lotion should comprise one or more back of the present invention soaping agents.
Concentration according to the present invention in the solution of soaping of used back soaping agent is 1-8 grams per liter and preferred 1-4 grams per liter normally.
The process of soaping can be utilized assign to further the improve back removing of textiles of at least a other one-tenth after of the present invention.
Other useful compositions comprise for example nonionic surface active agent, for example the aliphatic alcohol of poly-alkoxylation.Available for example oxirane, expoxy propane or epoxy butane or its mixture are with its alkoxylate; Optimization ethylene oxide.Useful alcohol comprises C 10-C 24-alcohol, and C especially 12-C 18-alcohol.Degree of alkoxylation is the alkoxide/equivalent aliphatic alcohol of alkoxide/equivalent aliphatic alcohol and particularly 20-25 equivalent of alkoxide/equivalent aliphatic alcohol, especially the 15-30 equivalent of 10-40 equivalent.Degree of alkoxylation must all be interpreted as mean value in each case herein.
Other the composition that can be used for the method for soaping behind the present invention is a complexing agent, for example phosphorus compound such as polyphosphate or alkylidene di 2 ethylhexyl phosphonic acid compound such as oxidronic acid.Aminobenzoic acid derivative for example nitrilotriacetic acid(NTA) or ethylenediamine tetra-acetic acid and its separately corresponding alkali metal salt also be suitable.
The quantity of various compositions is also more non-key than itself in the method for soaping after of the present invention.
PH in the solution of soaping that method of the present invention is used is 4-12 and preferred 5-11.Especially preferred pH is neutrality or subacidity.PH sets by organic carboxyl acid usually, for example aliphatic monocarboxylic acid such as acetate, formic acid, propionic acid, aliphatic dicarboxylic acid such as adipic acid, butanedioic acid, citric acid or polycarboxylic acids.Especially the preferred carboxylic acid that at room temperature only has low-down vapour pressure.Therefore, preferred aliphat dicarboxylic acids, citric acid and polycarboxylic acids.
The preferred aliphatic dicarboxylic acid that uses has general formula
HO 2C-(CH 2) i-(O-(CH 2) j) k-CO 2H
Wherein i, j and k are 0-9 independently.Especially preferred wherein k be 0 or 1 and i and j be the carboxylic acid of 1-6 independently.Preferred especially wherein i and j are that 1-4 and k are 0 or 1 carboxylic acids independently.The mixture of especially preferred these carboxylic acids or the mixture of these carboxylic acids and citric acid.
The preferred aliphatic dicarboxylic acid that uses is butanedioic acid, glutaric acid, adipic acid, 2-methylsuccinic acid, 2-methylglutaric acid, 3-methylglutaric acid.
The preferred polycarboxylic acids that uses belongs to the copolymer of polyacrylic acid and itself and maleic acid.Its mean molecule quantity M nBe 1000-150000g/mol and preferably be in 2000-70000g/mol.
The method of soaping after of the present invention is implemented usually at elevated temperatures.Feasible temperature range is 50-100 ℃ and can be higher under superatmospheric pressure.Preferred range is 60-98 ℃.
This solution with desire that the back removes through the mass ratio of the textiles of printing and dyeing normally 1: 4-1: 40 and preferred 1: 6-1: 20.During removing, the back can stir the solution that has comprised this textiles.Soap at every turn processing time of bathing itself and and non-key and be in usually in 5 minutes to 10 hours the scope, and preferred 10-30 minute.
After soap after usually with this textiles of water rinse.Usually adopt 1-6 time and preferred 2-4 rinse cycle.Unique or for the first time rinsing solution adopt hot water usually, promptly temperature is 35-70 ℃ a water.Last rinsing operation takes place in room temperature to 40 ℃ scope usually.
The process of soaping provides the back very effectively of textiles to remove after of the present invention, and it only comprises the loose dyestuff of extremely low quantity and therefore has very high washing and contact fastness.
The present invention further provides back soaping agent, its application makes method of the present invention especially effective.Back of the present invention soaping agent comprises at least a copolymer, and this copolymer has comprised the unit that belongs to unsaturated monomer B1 and B2 derived from least 2 monoene that all comprised at least a azacyclo-.Exemplary copolymer as mentioned above.
Preferably, the copolymer in the back soaping agent of the present invention is a graft polymers.Exemplary graft polymers as mentioned above.
Back of the present invention soaping agent more preferably comprises at least a graft polymers, it is constructed as follows: do not comprise monoene and belong to the graft polymerization matrix A of unsaturated unit and belong to the polymeric side chains B that the copolymer of unsaturated monomer B1 and B2 and optional further comonomer B3 forms by at least 2 monoene that all comprised at least one azacyclo-.
Preferably, this side chain B accounts for more than the 35 weight % of back of the present invention soaping agent.
Preferred back soaping agent except aforesaid graft polymers, also comprises other composition, for example phosphorus compound and nonionic surface active agent.Especially suitable phosphorus compound and nonionic surface active agent are as mentioned above.
Back of the present invention soaping agent can be used as powder and uses.Yet it also can be used as the aqueous formulation thing and uses, and the content of water can be 5-95% and preferred 20-90 weight % in the case, based on the component total amount.Preferably use as the liquid formulations thing, its metering can realize by for example automatic metering equipment.
The present invention further provides back of the present invention soaping agent has been used for the application that the textiles that dyes through REACTIVE DYES, direct dyes or vat dye is removed in the back.Similarly, the invention provides and a kind ofly be used for after dyeing back and remove through active, directly or the textiles that dyes of vatting and remove the method that is not fixed in the dyestuff on this textiles.
The present invention relates to a kind of back that is used for equally and removes through active, directly or the method for the textiles of reduction stamp, wherein this back clear operation paint operate after and be used to remove the dyestuff that is not fixed on this textiles.
The present invention sets forth by embodiment.
Embodiment
Used copolymer and graft polymers is synthetic according to the present invention
1.1 graft polymers 1 is synthetic
In the reactor of being furnished with nitrogen supply (NS), reflux condenser, agitator and metering device, under nitrogen with 10g mean molecule quantity M wFor the polyethylene glycol of 600g/mol (
Figure B2003801049246D00211
BASFAktiengesellschaft) and 56.2g water be heated to about 85 ℃ internal temperature.Then 3 1/ 4Hour time in add continuously the mixture of the N-ethene imidazoles of the N-vinylpyrrolidone of 27.5g and 12.5g.Simultaneously as this mixture, 3 1/ 4Hour time in add continuously 2 of 0.8g, 2 '-azo two (2-methyl-prop amidine) dihydrochloride ( From Wako Chemicals).When finishing interpolation, this batch materials is cooled to 60 ℃.When reaching this temperature, add the 1.72ml water that contains the 0.3g tert-butyl hydroperoxide.Add subsequently and contain 0.2g Na 2S 2O 56.26ml water.Obtain limpid little yellow polymer solution.Amount of solid is 42 weight %.
The K value is by H.Fikentscher, Cellulose-Chemie, and volume 13, the method described in 58-64 page or leaf and the 71-74 page or leaf and in the NaCl aqueous solution of 3 weight %, measure in 25 ℃, its value is 40.
1.2 copolymer 1 is synthetic
At the beginning the N-vinylpyrrolidone of 125g, the N-ethene imidazoles of 125g and the mixture of 600g water are added flask and be heated with stirring to 85 ℃ under nitrogen atmosphere.When reaching 85 ℃, in 2 hours, will be dissolved in the 1.53g 2 in the 27ml water immediately, 2 '-azo two (2-aminopropane) dihydrochloride adds.In addition, with being metered into the 5g mercaptoethanol solution that is dissolved in 27ml water in 1 hour.After the metering interpolation is finished reactant mixture was stirred 2 hours at 85 ℃, be cooled to 60 ℃ then.With 2g water dilution 2.2g tert-butyl hydroperoxide (70 weight % in water) and very rapidly with this dilution adding.Then with adding the 1.53g Na be dissolved in the water in 5 minutes 2S 20 5, and in 60 ℃ of further stirrings 2 hours.Obtain polymer solution yellow, limpid and the summary scent of.This copolymer K value is 32.Molecular weight is 50000g/mol.This aqueous solution has the solids content of 30 weight %.
2. performance test
2.1 performance test as dye leveller
The quantity of listing as percentage is based on fibre weight.
The quantity of listing as percentage is not based on liquor capacity.
Inventive embodiments 2.1.1:
By the Indanthren Golden Organe G Colliosol of 0.3 weight %, the Indanthren Dark Blue BOA Colliosol of 0.5 weight %, 38 ° of BE caustic soda of 12ml, the Na of graft polymers 1,5 grams per liter of 0.5 grams per liter 2S 2O 4The solution that constitutes complements to the liquor capacity of 1l, and tun was handled 10 minutes under 60 ℃ of situations that do not having a textiles.
On the perforated metal basket, twine 25g jhuganat (sample 1) and in 60 ℃ of dyeing 3 minutes and 40 seconds in dye vat, this dye vat be diameter 15cm and high 30cm can hermetic closed stainless steel cylinder.Subsequently, open dye vat and after total dyeing time of 4 minutes, another 25g jhuganat (sample 2) that is wrapped on the perforated metal basket is introduced dye vat.Dye vat seals once more and dyeed 45 minutes in 60 ℃.Subsequently, take out this dyed garrha also by it is immersed the 1l cold rinse 3 times.
Subsequently, this dyed garrha of oxidation (sample 1 and 2) 5 minutes in 55 ℃ of 1l liquid that comprised the 50 weight % hydrogenperoxide steam generators that 2ml/ rises.Then room temperature water overflow rinsing 5 minutes.
Then, sample 1 and 2 was cleaned 15 minutes in soaping liquid in 98 ℃.The liquid of soaping is composed as follows: 1l solution, it comprises 90 weight %C of 1 grams per liter 13H 27-(OCH 2CH 2) 4The Na of-OH the aqueous solution and 0.5 grams per liter 2CO 3Then, in 55 ℃ of rinsing samples 1 minute once more.At last, centrifugation and drying sample 1 and 2.The sample 1 and 2 of levelling so is provided.
Be the validity of assessment graft polymers 1, sample 1 and 2 is made colorimetric relatively with depth of color as dye leveller.
Write down the reflectance spectrum of the garrha of sample 1 (as reference) and this bleaching with X-rite CA22 spectrometer.Calculate the Kubelka-Munk K/S value of each spectrum.Subsequently, thus the K/S value of garrha of bleaching is deducted acquisition from this value of sample 1 dye to the net contribution of the K/S value of sample 1.
Implement same steps as and obtain to dye for sample 2 net contribution of the K/S value of sample 2.
Peak region at the figure line of the dependence wavelength of the K/S of sample 2 value is obtained the net contribution ratio of the dyeing of gained to the K/S value.For this reason, the K/S value of setting sample 1 equals 100%.Than the K/S value of sample 1, the K/S value of sample 2 is high more, and then levelling effect is good more.
The excellent levelling performance of the dye leveller part of being checked should make sample 1 and 2 have identical colourity.
Comparative Examples V2.1.2
Except using molecular weight M wFor 45000g/mol and Fikentscher K value are that the polyvinylpyrrolidone 1 of 31 (measuring in the 1 weight % aqueous solution) replaces repeating inventive embodiments 2.1.1 beyond the graft polymers 1.
The colourimetric number of table 1 dye leveller performance test
Figure B2003801049246D00241
2.2 performance test as remover
Based on the performance of testing with the vat dye pre-staining as remover.
Percentage is based on the weight of bleaching textiles.All the other listed quantity are based on liquor capacity.
Inventive embodiments 2.2.1:
Graft polymers used according to the invention 1 is as remover
Implement pre-staining according to following method:
Comprise diameter 15cm and high 30cm can the dye vat of hermetic closed stainless steel cylinder in, with the condensation product of the following material of 1 weight %Vat Orange, 2,0.5 grams per liters: the N3-amine of the adipic acid of 1 equivalent and each 0.5 equivalent: H 2N-CH 2CH 2-NH-(CH 2) 3-NH 2N4-amine: H 2N-CH 2CH 2-NH-(CH 2) 3-NH-CH 2CH 2-NH 2, the 38 ° of BE caustic soda of 12ml and the Na of 5 grams per liters 2S 2O 4(powder of 88 weight %) mix, and water complements to 1l and adds the 50g jhuganat.The sealing dye vat.For dyeing course, with 10 minutes temperature is increased to 60 ℃ from room temperature, this temperature maintenance 45 minutes.Subsequently, take out pre-dried garrha also with 1l room temperature water rinsing 3 times.
Then, should be through prestained garrha 5 minutes in 55 ℃ in the 1l water oxygenizations that comprised the 50 weight % hydrogenperoxide steam generators that 2ml/ rises.Then room temperature overflow rinsing 1 minute.Centrifugation and dry then.
For stripping process, preparation comprises 38 ° of BE caustic soda of 12ml, the Na of 6 grams per liters 2S 2O 4With the blank dye liquor of the graft polymers 1 of 2 grams per liters, promptly there is not the dye liquor of colouring agent.For stripping process, the garrha that the above-mentioned warp of 50g dyes is in advance introduced blank dye liquor, with being heated to 80 ℃ and handled 45 minutes in 20 minutes in 80 ℃.Subsequently, with 10 minutes temperature is reduced to 60 ℃ and take out pretreated garrhas like this at 60 ℃.Cleaning also uses for 3 times the 1l liquid of the 50 weight % hydrogenperoxide steam generators that contain the 2ml/ liter 55 ℃ of oxidations 5 minutes subsequently in about 1l cold water once more.
Then the overflow rinsing was also carried out soaping in 15 minutes in solution in 98 ℃ in 1 minute subsequently, and this solution comprises 90 weight %C of 1 grams per liter 13H 27-(OCH 2CH 2) 4The Na of-OH the aqueous solution and 0.5 grams per liter 2CO 3Finally, in 55 ℃ of water overflow rinsings 1 minute once more.Follow centrifugation and drying and obtain treated garrha.
Write down the reflectance spectrum of the garrha of prestained garrha (as reference) and this bleaching with X-rite CA22 spectrometer.Calculate the Kubelka-Munk K/S value of each spectrum.Subsequently, thus the K/S value of garrha of bleaching is deducted acquisition from this value of prestained garrha dye to the net contribution of the K/S value of prestained garrha.
Implement same steps as and obtain to dye for sample after cleaning the net contribution of the K/S value of the garrha after this processing.
Obtain the net contribution ratio to the K/S value of gained at the peak region of the figure line of the dependence wavelength of the K/S of prestained garrha value.For this reason, the K/S value of setting prestained garrha equals 100%.Than the K/S value of prestained garrha, the K/S value of the garrha after the processing is high more, and then stripping performance is poor more.
Excellent stripping performance should mean that this sample has with comparable colourity or the dyeing of used COTTON FABRIC and no longer can survey.The peel results value record is the prestained garrha colourity of %.
Comparative Examples V2.2.2
Except using molecular weight M wFor 45000g/mol and Fikentscher K value are that the polyvinylpyrrolidone 1 of 31 (measuring in the 1 weight % aqueous solution) replaces repeating inventive embodiments 2.2.1 beyond the graft polymers 1.
Table 2: remover test
Figure B2003801049246D00251
2.3 performance test as the back soaping agent
2.3.1 the general remark of preparation hydrolysed reactive dye
Being used for prestained hydrolysed reactive dye/reactive dye mixture is prepared as follows: the commercial REACTIVE DYES (by the amount that table 1 write down) that table 1 is listed is mixed with 38 ° of BE sodium hydrate aqueous solutions of 40ml, and water complements to 1l and uses CaCl 2Be adjusted to 20 ° of Deutschland hardnesss.Be heated to 98 ℃ with 30 minutes from room temperature subsequently.Will be thus obtainable hydrolysate kept 120 minutes and subsequently with being cooled to room temperature in 30 minutes at 98 ℃.This hydrolysate is transferred to Brown Glass Brown glass bottles and jars only to be stored.Enumerated the dyestuff use amount that is used for hydrolysate H1-H8 in the table 3.
The abbreviation implication that is used for reactive systems is as follows:
MCT monochloro triazine
The single Cyanuric trifluoride of MFT
DA-MCT dual-active monochloro triazine
The VS vinyl sulfone(Remzaol
Table 3: hydrolysate H1 to H8
Figure B2003801049246D00271
2.3.2 prepare prestained general remark with hydrolysate
Water complements to the dyeing hydrolysate amount from table 3 1l and uses CaCl 2Be adjusted to 20 ° of Deutschland hardnesss.Use HVF12085 from Mathis to pad padding mangles the dilution water hydrolysis products of gained is imposed on cotton goods.The contact pressure of roller is 2.6 crust.The gained wet pickup is 80%.Application rate is 2m/min.Subsequently in from the LTF89534 circulating air case of Mathis in 125 ℃ and do not have under the situation of air circulation dry this textiles 4 minutes.Measure thus obtained pad dyeing textiles colourity and by calculating as mentioned above with X-rite CA22 reflectance spectrometer.After this claim also that the textiles of the not back removing of this pad dyeing is the pad dyeing textiles.
2.3.3 the general description of flushing REACTIVE DYES (test V1-60)
Dissolve the back soaping agent (with table 2 usage level) of table 2 and use CaCl with the 50g sodium chloride in the 1l water 2Be adjusted to 10 ° of Deutschland hardnesss.The temperature of the 200ml solution that so obtains is controlled to 60 ℃.If need, the numerical value that uses citric acid that the pH value is adjusted in the table 5 to be write down.In solution, add 10g pad dyeing textiles and with being heated to the listed temperature of table 5 in 10 minutes.Be cooled to before 60 ℃, the effect 15 minutes that allows at every turn to soap, and under the situation of soaping more than those have used once, after first soaps, all solution is handled and is set the new solution of soaping.In this test, to the last second to soap all be identical under each situation.Take out this textiles and extruding with hand.Use 200ml cold rinse twice subsequently respectively, each 5 minutes.Then at room temperature centrifugation and drying sample.
It is as follows that recruitment evaluation is removed in the back:
With X-rite CA22 spectrometer write down this pad dyeing, dry textiles reflectance spectrum as with reference to and measure untreated textiles subsequently.Calculate the Kubelka-Munk K/S value of two kinds of textiless.Subsequently, thus the K/S value of untreated textiles deducted from this pad dyeing, dry textiles obtain the net contribution of dyeing the K/S value of this pad dyeing, dry textiles.
To this through after the sample removed implement same step, obtain dyeing to this net contribution through the K/S value of the textiles of back removing.
Obtain the net contribution ratio to the K/S value of the dyeing of gained at the peak region of the figure line of the dependence wavelength of the K/S value of this pad dyeing, dry textiles.For this reason, the K/S value of setting this pad dyeing, dry textiles equals 100%.The K/S value of the pad dyeing of removing, dry textiles than back not, the K/S value of the textiles of back removing is high more, and the performance of soaping after then is poor more.
Used back soaping agent is listed material or mixture S1-S8 in the following table 4.
Table 4: the composition of invention back soaping agent S2-S7 and contrast back soaping agent S1
Back soaping agent S1 S2 S3 S4 S5 S6 S7
Polyacrylic acid 100
The 1-oxidronic acid 25 10 31.5
Copolymer 1 100
Graft polymers 1 25 10 35 35 100
n-C 16H 33-(OCH 2CH 2) 25-OH 2.5 2.5 3.5
Water 47.5 77.5 30 65
Being used for the used polyacrylic acid of Comparative Examples back soaping agent S1 is the M of NaOH neutralization wPolyacrylic acid for 70000g passes through gel permeation chromatography measurement; PH8.5, the aqueous solution of 45 weight %.Comparative Examples V2, V4, V6 and V8 use the liquid of soaping of soaping agent without issue, and promptly the processing to the pad dyeing textiles is to adopt the hot water with the pH that is write down to carry out.
N-C 16H 33-(OCH 2CH 2) 25-OH is the hexadecanol according to the ethyl oxidation of following explanation preparation.
In the autoclave of 100 ℃ and 1 millibar, 242g octadecanol and 0.1molKOH thin slice were dewatered 2 hours, with the nitrogen decompression and in autoclave, be heated to 130 ℃ for 3 times then with purging with nitrogen gas.When reaching 130 ℃, with 3 hours 20 minutes under 6.1 bar pressures at the most continuous metering add 1100g oxirane.Finish when adding, begin to react until reaching constant voltage.Be cooled to 100 ℃ subsequently.
Table 5: invention back soaping agent example and Comparative Examples
Figure B2003801049246D00301
Table 5 (continuing)
Table 5 (continuing)
Figure B2003801049246D00321
Table 5 (continuing)
Figure B2003801049246D00331
Table 5 (continuing)
Figure B2003801049246D00341
Table 5 (continuing)
Figure B2003801049246D00351
2.3.4 printing in textiles
Manutex F700 by stirring 80g) Na of p-nitrofulfonic acid sodium (p-nitrosulfonate), 100g urea and the 25g of alginates, 10g 2CO 3With 5g calgon water softener with according to the 20g dyestuff hydrolysis products of table 1, thereby form printing paste D1-D8.The printing paste D1-D8 that can so obtain has the dynamic viscosity of 3Pas.
Be equipped with magnetic roller system (roller bearing diameter 10mm; 12m/min; 6 strokes) on the MBK flat screen printing platen, by E50-55 tulle flat screen with each printing paste D1-D8 stamp to 100% cotton goods.Dry under 80 ℃ in from the circulating air case of Mathis subsequently, up to the drying of finishing these stamp product.
Steam in the device at Mathis GD laboratory HT then, fixation is 10 minutes under 102 ℃ steam-laden atmosphere.After steaming, soap after this stamp sample sent to.
2.3.5 after the test of soaping
Dissolve the back soaping agent (with table 3 use amount) of table 2 and use CaCl with the 50g sodium chloride in the 1l water 2Be adjusted to 10 ° of Deutschland hardnesss.The temperature of the 200ml solution that so obtains is controlled to 60 ℃.If need, the numerical value that uses citric acid that the pH value is adjusted in the table 3 to be write down.In solution, add the 10g printing textile and with being heated to the listed temperature of table 3 in 10 minutes.Be cooled to before 60 ℃, allowing the every kind of liquid effect 15 minutes of soaping, and in the example of the liquid of soaping more than those have used once, after first soaps, all solution is being handled and set the new liquid of soaping.In this test, to the last second to soap all be identical in every respect.Take out this textiles and extruding with hand.Use 200ml cold rinse twice subsequently respectively, each 5 minutes.Then at room temperature centrifugation and drying sample.
It is as follows that recruitment evaluation is removed in the back:
With X-rite CA22 spectrometer write down this through stamp, dry textiles reflectance spectrum as with reference to and measure untreated textiles subsequently.Calculate the Kubelka-Munk K/S value of two kinds of textiless.Subsequently, thus the K/S value of untreated textiles deducted through stamp, dry textiles from this obtain the net contribution of dyeing the K/S value of this stamp, dry textiles.
To this through after the sample removed implement same step, obtain dyeing to this net contribution through the K/S value of the textiles of back removing.
Obtain the net contribution ratio to the K/S value of gained at this peak region through the figure line of the dependence wavelength of the K/S value of the textiles of stamp, drying.For this reason, the K/S value of setting this stamp, dry textiles equals 100%.The K/S value of removing than back through stamp, dry textiles, through after the K/S value of textiles of removing high more, the performance of soaping after then is poor more.
Used back soaping agent is listed material or mixture S1-S8 in the following table 4.
Table 6: the back removing embodiment of invention and contrast (V) example
V61 V62 V63 64 65 66 67
The hydrolysate sequence number H5 H5 H5 H5 H5 H5 H5
Hydrolysate consumption [grams per liter] 20 20 20 20 20 20 20
Textiles colourity % through stamp 100 100 100 100 100 100 100
V61 V62 V63 64 65 66 67
Back soaping agent S1 S1 S7 S5 S5 S5
The number of times of soaping 1 1 1 1 1 1 1
Soap liquid temp [℃] 98 98 98 98 98 98 98
Soaping agent consumption [grams per liter] 1 2 1 1 2 1
pH 6.5 6.5 6.5 6.5 6.5 6.5 6.5
Processing time [min] 10 10 10 10 10 10 10
The liquid NaCl content [grams per liter] of soaping - - - - - - 15
Through after the K/S value of the sample removed 0.38 0.43 0.50 0.02 0.04 0.02 0.05

Claims (34)

1. graft copolymer is as the purposes of textile dyeing and printing in textiles dye leveller, and described graft copolymer comprises the unit that belongs to unsaturated monomer B1 and B2 derived from least 2 monoene that all comprised at least one azacyclo-
Wherein, the B1 monomer is the cyclic amide of general formula I
Wherein
X be 1-6 integer and
R 1Be hydrogen or C 1-C 4Alkyl,
B2 is the comonomer that contains azacyclo-, and described azacyclo-is selected from by pyrroles, pyrrolidines, pyridine, quinoline, isoquinolin, purine, pyrazoles, imidazoles, triazole, tetrazolium, indolizine, pyridazine, pyrimidine, pyrazine, indoles, iso-indoles, oxazole, oxazolidone, oxazolidine, morpholine, piperazine, piperidines, isoxazole, thiazole, isothiazole, indoxyl, isatin, dioxindole and hydantoins and is selected from barbituric acid and group that the derivative of uracil is formed.
2. the purposes of claim 1, wherein B2 is selected from imidazoles, pyridine and pyridine N-oxides.
3. graft polymers is as the purposes of the auxiliary agent of textile dyeing and printing in textiles, and wherein at least a graft polymers is made of following material:
Do not comprise monoene belong to unsaturated unit graft polymerization matrix A and
Belong to the polymeric side chains B that the copolymer of unsaturated monomer B1 and B2 and optional further comonomer B3 forms by at least 2 monoene that all comprised at least one azacyclo-, and described side chain B accounts for more than the 35 weight % of described graft polymers, and the auxiliary agent that wherein is used for textile dyeing and printing in textiles is selected from remover, dye leveller and back soaping agent.
4. the purposes of claim 3, wherein said graft polymerization matrix A is a polyethers.
5. the aberration product dyed thereby is separated the method for textile material, comprise the remover of at least a graft polymers comprising use, this polymer comprises the unit that belongs to unsaturated monomer B1 and B2 derived from least 2 monoene that all comprised at least one azacyclo-,
Wherein, the B1 monomer is the cyclic amide of general formula I
Figure F2003801049246C00021
Wherein
X be 1-6 integer and
R 1Be hydrogen or C 1-C 4Alkyl,
B2 is the comonomer that contains azacyclo-, and described azacyclo-is selected from by pyrroles, pyrrolidines, pyridine, quinoline, isoquinolin, purine, pyrazoles, imidazoles, triazole, tetrazolium, indolizine, pyridazine, pyrimidine, pyrazine, indoles, iso-indoles, oxazole, oxazolidone, oxazolidine, morpholine, piperazine, piperidines, isoxazole, thiazole, isothiazole, indoxyl, isatin, dioxindole and hydantoins and is selected from barbituric acid and group that the derivative of uracil is formed.
6. the method for claim 5, wherein B2 is selected from imidazoles, pyridine and pyridine N-oxides.
7. the method for levelling on textile material comprises the dye leveller of at least a graft copolymer comprising use, and described graft copolymer comprises the unit that belongs to unsaturated monomer B1 and B2 derived from least 2 monoene that all comprised at least one azacyclo-,
Wherein, the B1 monomer is the cyclic amide of general formula I
Figure F2003801049246C00022
Wherein
X be 1-6 integer and
R 1Be hydrogen or C 1-C 4Alkyl,
B2 is the comonomer that contains azacyclo-, and described azacyclo-is selected from by pyrroles, pyrrolidines, pyridine, quinoline, isoquinolin, purine, pyrazoles, imidazoles, triazole, tetrazolium, indolizine, pyridazine, pyrimidine, pyrazine, indoles, iso-indoles, oxazole, oxazolidone, oxazolidine, morpholine, piperazine, piperidines, isoxazole, thiazole, isothiazole, indoxyl, isatin, dioxindole and hydantoins and is selected from barbituric acid and group that the derivative of uracil is formed.
8. the method for claim 7, wherein B2 is selected from imidazoles, pyridine and pyridine N-oxides.
9. the method for the textiles of dyed or stamp is removed in the back, and comprising using at least a copolymer, described copolymer comprises the unit that belongs to unsaturated monomer B1 and B2 derived from least 2 monoene that all comprised at least one azacyclo-,
Wherein, the B1 monomer is the cyclic amide of general formula I
Figure F2003801049246C00031
Wherein
X be 1-6 integer and
R 1Be hydrogen or C 1-C 4Alkyl,
B2 is the comonomer that contains azacyclo-, and described azacyclo-is selected from by pyrroles, pyrrolidines, pyridine, quinoline, isoquinolin, purine, pyrazoles, imidazoles, triazole, tetrazolium, indolizine, pyridazine, pyrimidine, pyrazine, indoles, iso-indoles, oxazole, oxazolidone, oxazolidine, morpholine, piperazine, piperidines, isoxazole, thiazole, isothiazole, indoxyl, isatin, dioxindole and hydantoins and is selected from barbituric acid and group that the derivative of uracil is formed.
10. the method for claim 9, wherein B2 is selected from imidazoles, pyridine and pyridine N-oxides.
11. the method for claim 9, wherein at least a copolymer is a graft polymers.
12. the method for claim 11, wherein at least a graft polymers is made of following material: do not comprise monoene belong to unsaturated unit graft polymerization matrix A and
Belong to the polymeric side chains B that the copolymer of unsaturated monomer B1 and B2 and optional further comonomer B3 forms by at least 2 monoene that all comprised at least one azacyclo-,
Wherein, B3 is selected from unsaturated C 2-C 10The alefinically unsaturated compounds that list or dicarboxylic acids and derivative thereof, vinylacetate and propionate and general formula III a represent to III d
Figure F2003801049246C00041
Herein
R 1Define as above,
Y 1Be selected from oxygen or NH,
Y is selected from 1 or 0 integer,
Y 2Be [A 2-O] s-[A 3-O] u-[A 4-O] v-R 8
A 2To A 4Be identical or different and independently-(CH 2) 2-,-(CH 2) 3-,-(CH 2) 4-,-CH 2-CH (CH 3)-,-CH 2-CH (CH 2-CH 3)-,-CH 2-CHOR 10-CH 2-;
R 8Be hydrogen, amino-C 1-C 6-alkyl, wherein this amino group can be primary, the second month in a season or uncle's amino; C 1-C 24Alkyl; R 9-CO-, R 9-NH-CO-;
R 9Be C 1-C 24Alkyl;
R 10Be hydrogen, C 1-C 24Alkyl, R 9-CO-;
S represents the integer of 0-500;
Identical or different in each case and integer expression 1-5000 under each situation of u;
Identical or different in each case and integer expression 0-5000 under each situation of v;
Identical or different in each case and integer expression 0-5000 under each situation of w.
13. the method for claim 12, wherein R 8Be CH 2-NH 2,-(CH 2) 2-NH 2,-CH 2-CH (CH 3)-NH 2,-CH 2-NHCH 3,-CH 2-N (CH 3) 2,-N (CH 3) 2,-NHCH 3Or-N (C 2H 5) 2
14. the method for claim 12, wherein unsaturated C 2-C 10The derivative of list or dicarboxylic acids is salt, ester, acid amides and acid anhydride.
15. the method for claim 12, wherein B3 is selected from vinylacetate, propionate, (methyl) acrylic acid, fumaric acid, maleic acid and its alkali metal or ammonium salt separately; Maleic anhydride; (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, dimethyl maleate, diethyl maleate, fumaric acid dimethyl ester, fumaric acid diethylester, fumaric acid two-positive butyl ester.
16. each method among the claim 12-15, wherein said side chain B accounts for more than the 35 weight % of described graft polymers.
17. the method for claim 11, wherein said graft polymerization matrix A is a polyethers.
18. each method among the claim 12-15, wherein said graft polymerization matrix A is a polyethers.
19. the method for claim 16, wherein said graft polymerization matrix A is a polyethers.
20. each method among the claim 11-15, it further comprises at least a other compositions that are selected from complexing agent and nonionic surface active agent of use.
21. the method for claim 16, it further comprises at least a other compositions that are selected from complexing agent and nonionic surface active agent of use.
22. the method for claim 17, it further comprises at least a other compositions that are selected from complexing agent and nonionic surface active agent of use.
23. the method for claim 18, it further comprises at least a other compositions that are selected from complexing agent and nonionic surface active agent of use.
24. the method for claim 19, it further comprises at least a other compositions that are selected from complexing agent and nonionic surface active agent of use.
25. each method among the claim 11-15 is implemented to neutral pH at pH 5.
26. the method for claim 16 is implemented to neutral pH at pH 5.
27. the method for claim 17 is implemented to neutral pH at pH 5.
28. the method for claim 18 is implemented to neutral pH at pH 5.
29. the method for claim 19 is implemented to neutral pH at pH 5.
30. the method for claim 20 is implemented to neutral pH at pH 5.
31. the method for claim 21 is implemented to neutral pH at pH 5.
32. the method for claim 22 is implemented to neutral pH at pH 5.
33. the method for claim 23 is implemented to neutral pH at pH 5.
34. the method for claim 24 is implemented to neutral pH at pH 5.
CN200380104924.6A 2002-12-03 2003-11-28 Use of copolymers as auxiliaries for dyeing and printing textiles Expired - Fee Related CN1720367B (en)

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DE2002156618 DE10256618A1 (en) 2002-12-03 2002-12-03 Method for after-cleaning dyed textiles, i.e. to remove unfixed dye, involves using copolymers of at least two mono-unsaturated monomers containing nitrogen heterocycles, e.g. N-vinylpyrrolidone and N-vinylimidazole
DE10256618.6 2002-12-03
DE2002161190 DE10261190A1 (en) 2002-12-20 2002-12-20 Processing aid for textile dyeing and printing comprises a copolymer of at least 2 monoethylenically unsaturated monomers containing at least one nitrogen containing heterocycle
DE10261190.4 2002-12-20
DE2003121396 DE10321396A1 (en) 2003-05-12 2003-05-12 Processing aid for textile dyeing and printing comprises a copolymer of at least 2 monoethylenically unsaturated monomers containing at least one nitrogen containing heterocycle
DE10321396.1 2003-05-12
PCT/EP2003/013463 WO2004050982A1 (en) 2002-12-03 2003-11-28 Use of copolymers as auxiliaries for dyeing and printing textiles

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CN107828533A (en) * 2017-11-13 2018-03-23 东莞市古川纺织助剂有限公司 A kind of fabric disperse dyes cleaning agent

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