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

Abstract

The copolymer is used as an auxiliary agent for textile dyeing and textile printing, wherein the copolymer comprises units derived from at least two monoolefinic unsaturated monomers B1 and B2, each containing at least one nitrogen heterocycle.

Description

Use of copolymers as auxiliaries for textile dyeing and textile printing

The present invention relates to the use of copolymers comprising units derived from at least 2 monoethylenically unsaturated monomers B1 and B2 each comprising at least one nitrogen heterocycle, as textile dyeing and textile printing auxiliaries.

Modern textile dyeing processes usually use not only colorants but also textile dyeing auxiliaries. A desired effect of textile dyeing auxiliaries is, for example, the removal of unwanted dyeings. The remaining textile dyeing auxiliaries in particular also provide particularly good and uniform dyeing and/or good colorant uptake.

Specific examples of textile dyeing auxiliaries known to those skilled in the art are leveling agents. Other specific examples of textile dyeing auxiliaries known to those skilled in the art are stripping agents. Other specific examples of textile dyeing auxiliaries known to those skilled in the art are post-soaping agents.

Textiles, such as natural or synthetic textiles, are often not completely uniform in composition, but vary in composition or thickness along the length of the thread. One possible consequence is that the dyed textile has relatively dark or relatively lightly dyed areas, which is generally undesirable. In order to obtain a uniform dyeing, leveling agents can be used, for example. Leveling agents are agents that bring about an even coloring of the area of the textile to be dyed (and especially along the length of the thread). Prior art leveling agents include oil sulfonates, fatty alcohol sulfonates, fatty acid condensation products, alkyl and alkylaryl polyglycol ethers.

Leveling agents also influence the dyeing properties and especially the dyeing properties of the dyes. Dyes with a high affinity for fibers should remain in the dyebath longer and migrate to the fibers more easily. It is expected that the leveling agent will ultimately result in a more uniform (more uniform) dyeing.

Known leveling agents include those based on polyvinylpyrrolidone, see Ullmann's Encyclopedia of Industrial Chemistry (5th Edition) Vol. A26, p. 291, left column. Commercially available leveling agents also include adipic acid and amines such as _H2N - _{CH2CH2 -} NH-( _CH2 ) ₃ - _NH2 or _H2N - _{CH2CH2 -NH-} ( _CH2 ) Condensate of ₃ -NH-CH ₂ CH ₂ -NH ₂ . However, the performance of such conventional leveling agents, eg for use as leveling agents for leveling vat, direct, reactive or sulfur dyes, still needs improvement.

Strippers are common agents used to remove eg stains, blots and macerations by re-separating, altering or destroying dyes. A particularly important field of application for strippers is the correction of shading dyeing. It involves tinting the illuminated shade-dyed portion such that the shade-dyed portion is re- or over-dyed.

Release agents are also known as constituents of discharge printing pastes. Discharge printing paste is used to remove a certain color in discharge dyeing. In discharge dyeing, the colors are usually printed evenly. Then over-stain with follow-up colors. This subsequent color is then removed in certain areas by discharge printing paste.

However, prior art strippers still need improvement in their performance characteristics.

To achieve adequate fastness levels, reactive, direct or vat dyed textiles are usually post-cleaned to remove unfixed dye remaining on the fibers at the end of the dyeing operation and prior to sale. Post cleanup usually includes at least one soap bath and multiple cleaning and neutralizing baths. The presence of chemicals in the dyebath, especially the salt load, affects the results of post-rinsing. Post-cleaning soaping solutions include compounds that disperse dyes or dye breakdown products, and are often referred to as post-soaping agents. Known post-soaping agents have a number of disadvantages, among which many have been found to be ineffective especially when salts in the dyebath such as Glauber's salt and/or sodium chloride are present. Furthermore, known post-soaping agents must be used at high temperatures, ie around 98°C. In addition, the performance of polyacrylic acid and polyvinylpyrrolidone used as post-soaping agents is still not satisfactory.

It is an object of the present invention to provide an improved method of post-cleaning textiles dyed by reactive, direct or vat dyeing (hereinafter also referred to as dyed textiles). It is a further object of the present invention to provide a post-soaping agent which has improved performance in the post-cleaning of dyed textiles and which is especially effective when there is a high concentration of salt in the dye liquor.

To achieve adequate fastness levels, reactive, direct or vat dyed printed textiles are also typically post-cleaned at the end of the textile printing operation and prior to sale to remove unfixed dye remaining on the fibres. Post cleanup usually includes at least one soap bath and multiple cleaning and neutralizing baths. The presence of chemicals in the dyebath, especially the salt load, affects the results of post-rinsing. Post-cleaning soaping solutions include compounds that disperse dyes or dye breakdown products, and are often referred to as post-soaping agents. Known post-soaping agents have a number of disadvantages, among which many have been found to be ineffective especially when salts in the dyebath such as Glauber's salt and/or sodium chloride are present. Furthermore, known post-soaping agents must be used at high temperatures, ie around 98°C. In addition, the performance of polyacrylic acid and polyvinylpyrrolidone used as post-soaping agents is still not satisfactory.

It is an object of the present invention to provide an improved method of post-cleaning reactive, direct or vat dyed printed textiles (hereinafter also referred to as printed textiles). It is a further object of the present invention to provide a post-soaping agent which has improved performance in post-cleaning printed textiles and which is especially effective when there is a high concentration of salt in the dyebath.

We have found that this object is achieved by the textile dyeing and textile printing auxiliaries defined above.

Textiles for the purposes of the present invention are textile fibres, textile intermediate and end products as well as finished products made therefrom, and textiles of the clothing industry, also including eg carpets and other household fabrics and textile structures for industrial purposes. These also include unformed structures such as staple fibers, threads such as twins, monofilaments, yarns, cords, lace, braids, cords and filaments as well as three-dimensional structures such as felts, braids, nonwovens and wadding. Textiles can be of natural origin such as cotton, wool or linen, or synthetic such as polyamide.

In one embodiment of the present invention, the copolymer of the present invention for textile dyeing and textile printing auxiliaries (hereinafter also referred to as the copolymer used according to the present invention) comprises at least 2 compounds derived from Units of monoethylenically unsaturated monomers B1 and B2 containing at least one nitrogen heterocycle.

The copolymers used according to the invention may be random copolymers, block copolymers or graft copolymers.

In one embodiment of the invention, the B1 monomer present in copolymerized form in the copolymer used according to the invention is at least one cyclic amide of the general formula I

in

x is an integer from 1-6, and

R ¹ is hydrogen or C ₁ -C ₄ alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.

Specific examples of the copolymerized B1 monomers are N-vinylpyrrolidone, N-ethylene-δ-valerolactam and N-ethylene-ε-caprolactam, among which N-vinylpyrrolidone is preferred.

唑、

唑烷酮、

唑烷、吗啉、哌嗪、哌啶、异唑、噻唑、异噻唑、吲哚氧基、靛红、二氧吲哚、和乙内酰脲及其衍生物，例如巴比土酸和尿嘧啶及其衍生物。In one embodiment of the invention, the copolymer used according to the invention comprises units derived from at least one B2 monomer comprising a nitrogen heterocycle selected from: pyrrole, pyrrolidine, pyridine, quinoline, Isoquinoline, purine, pyrazole, imidazole, triazole, tetrazole, indolizine, pyridazine, pyrimidine, pyrazine, indole, isoindole,

azole,

oxazolidinone,

oxazolidine, morpholine, piperazine, piperidine, iso oxazole, thiazole, isothiazole, indoxyl, isatin, dioxindole, and hydantoin and derivatives thereof, such as barbituric acid and uracil and derivatives thereof.

Preferred heterocycles are imidazole, pyridine and pyridine N-oxide, and imidazole is especially preferred.

Examples of particularly useful B2 comonomers are N-vinylimidazole, alkylvinylimidazole (especially methylvinylimidazole such as 1-vinyl-2-methylimidazole), 3-vinylimidazole N-oxide, 2 - and 4-vinylpyridine, 2- and 4-vinylpyridine N-oxides and their betaine derivatives and quaternization products.

Especially preferred copolymerized B2 comonomers are N-vinylimidazoles of the general formula IIa, betaine N-vinylimidazoles of the general formula IIb, 2- and 4-vinylpyridines of the general formulas IIc and IId and the general formulas IIe and IIf Betaine 2- and 4-vinylpyridine.

in

R ² , R ³ , R ⁴ , R ⁶ are independently hydrogen, C ₁ -C ₄ alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl; or phenyl, preferably hydrogen;

A ¹ is a C ₁ -C ₂₀ alkylene group, such as -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 -, preferably C ₁ -C ₃ alkylene; especially -CH ₂ -, -(CH ₂ ) ₂ -, -(CH ₂ ) ₃ -.

X ^- is -SO ₃ ^- -, -OSO ₃ ^- -, -COO ^- , -OPO(OH)O ^- , -OPO(OR ⁵ )O ^- or -PO(OH)O ^- ;

R ⁵ is C ₁ -C ₂₄ alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isopentyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl; especially preferred C ₁ - _C4 alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl.

Particularly preferred betaine copolymerized B2 monomers are those of the general formula IIb, IIe and IIf, wherein the A ¹ -X ^- moiety represents -CH ₂ -COO ^- , -(CH ₂ ) ₂ -SO ₃ ^- or (CH ₂ ) ₃ -SO ₃ - and the remaining symbols all represent hydrogen.

Useful B2 monomers further include vinylimidazoles and vinylpyridines that have been quaternized either before or after polymerization.

The quaternization process can be carried out especially by means of alkylating agents such as alkyl halides generally having an alkyl group of 1 to 24 carbon atoms or dialkyl sulfates generally comprising an alkyl group of 1 to 10 carbon atoms. Examples of useful alkylating agents are methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, propane chloride, hexyl chloride, dodecane chloride, and laurane chloride, as well as dimethyl sulfate and disulfate ethyl ester. Useful alkylating agents further include, for example: benzyl halides, especially benzyl chloride and benzyl bromide; chloroacetic acid; methyl fluorosulfate; diazomethane; Compounds such as trimethyloxytetrafluoroborate ; Alkylene oxides, such as ethylene oxide, propylene oxide and glycidol, which are used in the presence of acids; cationic epichlorohydrin. Preferred quaternizing agents are methyl chloride, dimethyl sulfate and diethyl sulfate.

甲氯化物。A particularly useful quaternized B2 monomer is 1-methyl-3-vinylimidazole methylsulfate and 1-methyl-3-vinylimidazole

Methyl chloride.

The weight ratio range of copolymerized B1 and B2 monomers is usually 99:1-1:99, preferably 90:10-30:70, more preferably 90:10-50:50, even more preferably 80:20-50:50 and Especially 80:20-60:40.

The copolymers used according to the invention may comprise units derived from one or more further monomers B3, for example carboxyl-containing monoethylenically unsaturated monomers, such as unsaturated _C2 - _C10 mono- or dicarboxylic acids and Its derivatives, such as salts, esters, amides and anhydrides. Examples that may be mentioned are:

Acids and their salts such as (meth)acrylic acid, fumaric acid, maleic acid and their respective alkali metal or ammonium salts; anhydrides such as maleic anhydride; esters such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, dimethyl maleate, diethyl maleate, dimethyl fumarate, diethyl fumarate, di-n-butyl fumarate.

Further examples of B3 are vinyl acetate and vinyl propionate and ethylenically unsaturated compounds of the general formulas IIIa to IIId,

here

^R1 is defined as above,

^Y is selected from oxygen or NH,

y is an integer selected from 1 or 0,

Y ² is [A ² -O] _s -[A ³ -O] _u -[A ⁴ -O] _v -R ⁸

A ² to A ⁴ are the same 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 ⁸ is hydrogen, amino-C ₁ -C ₆ -alkyl, where the amino group can be primary, secondary or tertiary amino, eg 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 ₂ H ₅ ) ₂ ; C ₁ -C ₂₄ alkyl; R ² -CO-, R ⁹ -NH-CO-;

R ⁹ is C ₁ -C ₂₄ alkyl;

R ¹⁰ is hydrogen, C ₁ -C ₂₄ alkyl, R ⁹ -CO-;

s represents an integer of 0-500;

u are in each case the same or different and represent in each case an integer from 1 to 5000;

v is in each case the same or different and represents in each case an integer from 0-5000;

w is in each case the same or different and represents in each case an integer from 0-5000;

The C ₁ -C ₂₄ alkyl groups in the general formulas IIIa to IIId may be branched or unbranched C ₁ -C ₂₄ alkyl groups, of which C ₁ -C ₁₂ alkyl groups are preferred and C ₁ -C ₆ are especially preferred alkyl. Examples that may be mentioned are methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl , n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1,1- Dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylpentyl Dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl 1-ethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methyl propyl, 1-ethyl-2-methylpropyl, n-heptyl, 2-ethylhexyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl and n-eicosyl.

In a particular embodiment, the method according to the invention comprises the use of one or more graft polymers as copolymers in the method of the invention.

Preferably used graft polymers include, for example, those which, in addition to the B1 and B2 monomers, also comprise units derived from such B3 comonomers according to the general formulas IIIa to IIId.

A preferred embodiment utilizes the graft base A from a polymer containing no monoethylenically unsaturated units, and from at least 2 monoethylenically unsaturated monomers B1 and B2 each containing at least one nitrogen heterocycle and optionally A further copolymer of comonomer B3 forms a graft polymer composed of polymerized side chains B.

The graft polymers used in the method embodiments according to the invention described below and which may have a comb-like structure can be characterized by their ratio of side chains B to polymeric graft base A. Based on the total graft polymer, the side chain B may account for more than 35% by weight. This fraction is preferably 55-95% by weight and more preferably 70-90% by weight.

The B1 monomer included in the side chain B of the graft polymer is preferably at least one cyclic amide of the general formula I

The symbols in the general formula I here are as defined above.

Specific examples of the copolymerized B1 monomers are N-vinylpyrrolidone, N-ethylene-δ-valerolactam and N-ethylene-ε-caprolactam, among which N-vinylpyrrolidone is preferred.

唑、

唑烷酮、

唑烷、吗啉、哌嗪、哌啶、异唑、噻唑、异噻唑、吲哚氧基、靛红、二氧吲哚、和乙内酰脲及其衍生物，例如巴比土酸和尿嘧啶及其衍生物。In one embodiment of the invention, the B branch advantageously comprises units derived from at least one monoethylenically unsaturated monomer B2 comprising a nitrogen heterocycle selected from: pyrrole, pyrrolidine, Pyridine, quinoline, isoquinoline, purine, pyrazole, imidazole, triazole, tetrazole, indolizine, pyridazine, pyrimidine, pyrazine, indole, isoindole,

azole,

oxazolidinone,

oxazolidine, morpholine, piperazine, piperidine, iso oxazole, thiazole, isothiazole, indoxyl, isatin, dioxindole, and hydantoin and derivatives thereof, such as barbituric acid and uracil and derivatives thereof.

Preferred heterocycles are imidazole, pyridine and pyridine N-oxide, and imidazole is especially preferred.

Examples of particularly useful B2 comonomers are N-vinylimidazole, alkylvinylimidazole (especially methylvinylimidazole such as 1-vinyl-2-methylimidazole), 3-vinylimidazole N-oxide, 2 - and 4-vinylpyridine, 2- and 4-vinylpyridine N-oxides and their betaine derivatives and quaternization products.

Especially preferred copolymerized B2 comonomers are N-vinylimidazoles of the general formula IIa, betaine N-vinylimidazoles of the general formula IIb, 2- and 4-vinylpyridines of the general formulas IIc and IId and the general formulas IIe and IIf Betaine 2- and 4-vinylpyridine.

Particularly preferred examples of betaine copolymerized B2 monomers are those of the general formula IIb, IIe and IIf, where the A ¹ -X ^- moiety represents -CH ₂ -COO ^- , -(CH ₂ ) ₂ -SO ₃ ^- or ( CH ₂ ) ₃ —SO ₃ — and the rest of the symbols represent hydrogen.

Useful B2 monomers further include vinylimidazoles and vinylpyridines that are either quaternized before or after polymerization.

The quaternization process can be carried out as described above.

的甲基硫酸盐和1-甲基-3-乙烯基咪唑

甲氯化物。A particularly useful quaternized B2 monomer is 1-methyl-3-vinylimidazole

methylsulfate and 1-methyl-3-vinylimidazole

Methyl chloride.

The weight ratio range of copolymerized B1 and B2 monomers is usually 99:1-1:99, preferably 90:10-30:70, more preferably 90:10-50:50, even more preferably 80:20-50:50 and Especially 80:20-60:40.

The graft polymer branches used according to the invention may comprise units derived from one or more further monomers B3, for example carboxyl-containing monoethylenically unsaturated monomers, such as unsaturated _C2 - _C10 mono- or Dicarboxylic acids and their derivatives, such as salts, esters, anhydrides and substances as defined above.

The polymeric graft base A of the graft polymers used according to the invention is preferably a polyether. Here, the term "polymer" is also to be understood as meaning oligomers.

Particularly preferred polymeric graft bases A have an average molecular weight M _n of at least 300 g.

Particularly preferred polymeric graft bases A have the general formula IVa

or IVb

here

R ⁷ is carboxyl, amino, C ₁ -C ₂₄ alkoxy such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert Butoxy, n-pentyloxy, isopentyloxy, n-hexyloxy, isohexyloxy, R ⁹ -COO-, R ⁹ -NH-COO-, polyhydric alcohol groups such as glycerol;

A ² to A ⁴ are the same or different and are -(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 ⁸ is hydrogen, amino-C ₁ -C ₆ -alkyl, where the amino group can be primary, secondary or tertiary amino, eg 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 ₂ H ₅ ) ₂ ; C ₁ -C ₂₄ alkyl; R ⁹ -CO-, R ⁹ -NH-CO-;

^A5 is -CO-O-, -CO-B-CO-O, -CO-NH-B-NH-CO-O-;

A ⁶ is a C ₁ -C ₂₀ alkylene group, and its carbon chain can be inserted into 1-10 oxygen atoms as ether functional groups;

B is -(CH ₂ ) _t -, substituted or unsubstituted arylene such as p-phenylene, m-phenylene, o-phenylene, 1,8-naphthylene, 2,7-naphthylene;

n is 1 or 1-8 (when R ⁷ is a polyhydric alcohol group);

t represents an integer of 1-12;

And other symbols are defined as above.

The polymeric graft base A of the general formula IVa is preferably derived from polyepoxides based on ethylene oxide, propylene oxide and butylene oxide, polytetrahydrofuran and polyglycerol polyethers. Depending on the monomer, the resulting polymer contains the following structural units: -(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-

Both homopolymers and copolymers are useful, and the copolymers may be random or block copolymers.

The terminal primary hydroxyl groups of polyethers based on alkylene oxides or glycerol and the secondary OH groups of polyglycerols can exist in free form or be etherified with C ₁ -C ₂₄ alcohols, esterified with C ₁ -C ₂₄ carboxylic acids or with isocyanates The reaction forms urethane. Alcohols useful for this purpose may be, for example: primary aliphatic alcohols such as methanol, ethanol, propanol and butanol, primary aromatic alcohols such as phenol, isopropylphenol, tert-butylphenol, octylphenol, nonylphenol and naphthalene Phenols, aliphatic secondary alcohols such as isopropanol, aliphatic tertiary alcohols such as tert-butanol, and polyalcohols such as dihydric alcohols (e.g. ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol and butanediol) and Trihydric alcohols (eg glycerol, trimethylolpropane). However, the hydroxyl group can also be exchanged with a primary amino group (reductive amination by hydrogen-ammonia mixture under pressure) or ethylated with acrylonitrile cyano and hydrogenated to an aminopropene end group. The conversion of the terminal hydroxyl groups can occur not only later by reaction with alcohols or with aqueous alkali metal hydroxide solutions, amines and hydroxylamines, but can also be used as an initiator to initiate the polymerization, as Lewis acids such as boron trifluoride agent. Finally, the terminal hydroxyl groups can also be etherified by reaction with an alkylating agent such as dimethyl sulfate.

The C ₁ -C ₂₄ alkyl groups in the general formulas IVa and IVd can be branched or unbranched C ₁ -C ₂₄ alkyl groups, among which C ₁ -C ₁₂ alkyl groups are preferred and C ₁ -C ₆ alkyl groups are especially preferred. Examples that may be mentioned are methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl , n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1,1- Dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylpentyl Dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl 1-ethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methyl propyl, 1-ethyl-2-methylpropyl, n-heptyl, 2-ethylhexyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl and n-eicosyl.

The average molecular weight M _n of the polyethers of the general formula IVa is at least 300 g/mol and generally ≦100 000 g/mol. Preferably from 500 g/mol to 50000 g/mol, more preferably up to 10000 g/mol and most preferably up to 2000 g/mol. The polyethers of the general formula IVa have a low polydispersity, for example from 1.1 to 1.8 in most cases.

Homopolymers and copolymers of ethylene oxide, propylene oxide, butylene oxide and isobutylene oxide, each of which may be linear or branched, can be used as polymeric graft bases. As used herein, the term homopolymer is also understood to mean those polymers which, in addition to the polymerized alkylene oxide units, additionally include active molecules for initiating the polymerization of cyclic ethers or for capping the end groups of the polymers.

Branched polymers can be prepared, for example, by adding low molecular weight polyols (groups ^R of general formulas IVa and IVb), such as pentaerythritol, glycerol and sugars or sugar alcohols such as sucrose, D-sorbitol and D-mannitol , disaccharides, ethylene oxide, and if desired, propylene oxide and/or butylene oxide or polyglycerol.

In the polymer formed, at least one hydroxyl group present in the polyol molecule, preferably one to eight and more preferably one to five, may be linked in the form of an ether bond to a compound of formula IVa or IVb polyether group

Four-armed polymers can be obtained by adding alkylene oxides to diamines, preferably ethylenediamine.

Other branched polymers can be prepared by reacting alkylene oxides with higher amines, such as triamines, or especially polyethyleneimines. Suitable polyethyleneimines generally have an average molecular weight M _n of 300-20000 g, preferably 500-10000 and more preferably 500-5000 g. The weight ratio of alkylene oxide to polyethyleneimine is generally 100:1-0.1:1, and preferably 20:1-0.5:1.

Polyepoxides and aliphatic C ₁ -C ₁₂ -, preferably C ₁ -C ₆ -, dicarboxylic acids or aromatic dicarboxylic acids such as oxalic acid, succinic acid, adipic acid or terephthalic acid can also be used Polyesters with an average molecular weight _Mn of 1500-25000 g/mol were used as polymeric graft base A.

As an alternative to IVa and IVb, it is also possible to use polyepoxide-based polycarbonates or polyepoxide-based polyurethanes and aliphatic C ₁ -C ₁₂ diisocyanates and preferably C ₁ -C ₆ diisocyanates prepared by phosgenation Or aromatic diisocyanates, such as hexamethylene diisocyanate or phenylene diisocyanate, as polymeric graft base A.

These polyesters, polycarbonates or polyurethanes may contain up to 500 and preferably up to 100 polyepoxide units, in which case the polyepoxide units may consist not only of homopolymers but also of interpolymers of different alkylene oxides composition.

Particular preference is given to using homopolymers and copolymers of ethylene oxide and/or propylene oxide as polymeric graft base A in the process according to the invention, which can be terminated with terminal groups at one or both ends.

One effect of the copolymerization of alkylene oxide and polypropylene oxide with a high proportion of propylene oxide is that grafting readily occurs.

One effect of the copolymerization of alkylene oxide and polyethylene oxide with a high ethylene oxide ratio is that after grafting has occurred and a grafted polymer having the same graft density as propylene oxide has been produced, the branched The weight ratio to the polymeric graft base is greater.

The K value of the graft polymer is usually 10-150, preferably 10-80 and more preferably 15-60 (by H. Fikentscher, Cellulose-Chemie, volume 13, pages 58-64 and pages 71-74 (1932) The method described is determined at 25° C. in water or in 3% by weight aqueous sodium chloride solution and at a polymer concentration of 0.1% by weight to 5% by weight (depending on the range of K values). The particular K value required can be set in a conventional manner by the composition of the materials used. For a theoretical degree of grafting of 100%, the molecular weight of the product is determined by the molecular weight of the graft base and the proportion of the copolymer reacting as branches. The greater the number of molecules in the graft base, the greater the number of final molecules obtained, and vice versa. The branching density can be controlled by the amount of initiator and reaction conditions.

A further process for preparing the graft polymers used according to the invention consists in the free-radical polymerization of the monomers B1 and B2 and optionally the further interpolymer B3 in the presence of the polymeric graft base A.

Polymerization can be performed, for example, in solution polymerization, bulk polymerization, emulsion polymerization, inverse emulsion polymerization, suspension polymerization, inverse suspension polymerization, or precipitation polymerization. Preference is given to bulk polymerization and especially solution polymerization, especially which is carried out in the presence of water.

The bulk polymerization process can be carried out by dissolving the monomers B1 and B2 in the polymerization graft base A, heating the mixture to the polymerization temperature and adding the free radical initiator before the mixture is completely polymerized. The polymerization process can also be carried out by first introducing part (for example 10% by weight) of the mixture of the polymerized graft base A, monomers B1 and B2 and free radical initiator and heating it to the polymerization temperature, after the start of the polymerization with the polymerization The reaction proceeds semi-continuously with the addition of the remainder of the mixture at a rate matching the progress of the reaction. However, it is also possible to initially charge the graft base A into the reactor, heat this initial charge to the polymerization temperature and add the monomers B1 and B2 (individually or as a mixture) all at once, batchwise or preferably continuously prior to the polymerization and free radical initiators.

The above-mentioned graft polymerization can be carried out in one or more solvents. Examples of suitable organic solvents are, for example, aliphatic and cycloaliphatic monohydric alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-hexanol and cyclohexanol, polyols , such as dihydric alcohols such as ethylene glycol, propylene glycol and butylene glycol and glycerol, alkyl ethers of polyols such as methyl ether and ethyl ether of the aforementioned diols, and ether alcohols such as diethylene glycol and triethylene glycol, and There are cyclic ethers such as di alkyl.

The graft polymerization process is preferably carried out with water as solvent. Here, A, B1 and B2 and optionally the further comonomer B3 are all dissolved with high or low efficiency, depending on the amount of water used. It is also possible to add water partially or completely during the polymerization. It should be understood that mixtures of water and the aforementioned organic solvents may also be used.

Typically 5 to 250% by weight, preferably 10 to 150% by weight, based on the graft polymer, of organic solvents, water or mixtures of water and organic solvents are used.

The polymerization process in water generally provides 10-70% by weight, preferably 20-50% by weight, of a solution or dispersion of the graft polymer according to the invention, which can be converted into powder form by various drying methods, such as Spray drying, fluidized spray drying, tumble drying or freeze drying. An aqueous solution or dispersion can easily be recovered by adding water at an appropriate time.

Useful free-radical initiators are peroxy compounds, azo compounds, redox initiator systems and reducing compounds. It should be understood that mixtures of free radical initiators may also be used.

Examples of suitable polymerization initiators are in particular: alkali metal peroxodisulfates such as sodium peroxodisulfate, ammonium peroxodisulfate, hydrogen peroxide, organic peroxides such as diacetyl peroxide, di-tert-butyl peroxide , dipentyl peroxide, dioctanoyl peroxide, didecanoyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, di(o-toluoyl) peroxide, succinyl peroxide, peracetic acid tert-butyl ester, tert-butyl permaleate, tert-butyl perisobutyrate, tert-butyl perpivalate, tert-butyl peroctoate, tert-butyl perneodecanoate, perbenzoate tert-butyl formate, tert-butyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl peroxy-2-ethylhexanoate and diisopropyl peroxydicarbonate; Azobis(2-aminopropane) dihydrochloride or 2,2'-azobis(2-methylbutyronitrile); sodium sulfite, sodium bisulfite, sodium formaldehyde sulfoxylate and Hydrazine and compounds of the above compounds with hydrogen peroxide; ascorbic acid/iron(II) sulfate/Na ₂ S ₂ O ₈ , tert-butyl hydroperoxide/sodium bisulfite, tert-butyl hydroperoxide/sodium hydroxymethanesulfinate.

Preferred free radical initiators are e.g. tert-butyl perpivalate, tert-butyl peroctoate, tert-butyl perneodecanoate, tert-butyl peroxide, tert-butyl hydroperoxide, azobis( 2-methylpentanoneamidine) dihydrochloride, 2,2'-azobis(2-methylbutyronitrile), hydrogen peroxide and sodium peroxodisulfate, to which a small amount of redox metal salt can be added, For example iron salts.

In general, 0.01 to 10% by weight, and preferably 0.1 to 5% by weight, of free-radical initiators are used, based on the monomers B1 and B2.

Polymerization regulators can also be used, if desired. Useful compounds are known to those skilled in the art and include, for example, sulfur compounds such as mercaptoethanol, 2-ethylhexyl thioglycolate, thioglycolic acid and dodecylmercaptan, and other types of regulators such as Hydrogen Sulfate and Hypophosphite. When polymerization regulators are used, their use level is generally 0.1 to 15% by weight, preferably 0.1 to 5% by weight and more preferably 0.1 to 2.5% by weight, based on monomers B1 and B2.

The polymerization temperature is usually 30-200°C, preferably 50-150°C and more preferably 75-110°C.

The polymerization is generally carried out at atmospheric pressure, but it can also be carried out under reduced or elevated pressure, for example at 0.5 or 5 bar.

According to the present invention, the above-mentioned copolymer can be used as, for example, a release agent. According to the invention, the abovementioned copolymers can be used as leveling agents.

A further embodiment of the invention comprises at least one graft polymer according to the invention as Use of textile dyeing and textile printing auxiliaries, monomers B1, B2 and B3 as defined above.

The present invention further provides auxiliaries for textile dyeing and textile printing (such as release agents, leveling agents and post-soaping agents) comprising the copolymers described above.

The textile dyeing and textile printing auxiliaries according to the invention, such as strippers, leveling agents and post-soaping agents, more preferably comprise at least one graft polymer grafted from a polymer which does not contain monoethylenically unsaturated units. Branch base A, and polymeric side chains B formed from copolymers of at least 2 monoethylenically unsaturated monomers B1 and B2 each containing at least one nitrogen heterocycle and optionally a further comonomer B3.

Preferably, the proportion of side chain B in the textile dyeing and textile printing auxiliary of the present invention (for example, in the release agent, leveling agent and post-soaping agent of the present invention) is 35% by weight or more.

Preferred textile dyeing and textile printing auxiliaries according to the invention, in addition to the abovementioned copolymers and especially the abovementioned graft polymers, also comprise further components, such as phosphorus compounds, complexing agents and ionic or nonionic surfaces Active agents, and examples of especially suitable phosphorus compounds are phosphonic acid compounds such as hydroxymethylene diphosphonic acid. Suitable complexing agents are aminocarboxylic acid derivatives and alkali metal salts thereof, such as nitrilotriacetic acid, ethylenediaminetetraacetic acid and the corresponding di- and trisodium salts and the tetrasodium salt of ethylenediaminetetraacetic acid. Suitable nonionic surfactants are ethoxylated products of long-chain alcohols. Preferred alcohols belong, for example, to 1-alkanols having 8-30 carbon atoms, preferably 8-18 carbon atoms, or to 2-alkanols having 8-30 carbon atoms, preferably 8-18 carbon atoms. The degree of ethoxylation is 4-30 and preferably 6-15.

Further preference is given to the abovementioned alkanol ethoxylation products having an average degree of ethoxylation of 8-30 and preferably 8-18, provided that at least 1 mol of propylene oxide is used. The alkanol ethoxylation products mentioned in the examples are obtained by reacting the alkanols sequentially with propylene oxide and ethylene oxide.

Suitable ionic surfactants are based, for example, on sulfosuccinic acid mono- or diesters. Suitable alcohols for the preparation of the esters are branched or unbranched alcohols having a chain length of 2 to 30 carbon atoms and preferably 4 to 18 carbon atoms.

The textile dyeing and textile printing assistants according to the invention are available as powders. However, it can also be used as an aqueous formulation, in which case the water fraction can be from 5 to 95 and preferably from 20 to 90% by weight, based on the total amount of constituents. It is preferably used as a liquid formulation, the metering of which can be achieved, for example, by automatic metering equipment.

The present invention further provides a leveling method for color difference dyeing or uneven dyeing of fabrics, hereinafter also referred to as the leveling method of the present invention, which comprises the use of a leveling agent comprising at least one copolymer comprising a derivative Units from at least 2 monoethylenically unsaturated monomers B1 and B2 each comprising at least one nitrogen heterocycle.

In one embodiment of the present invention, the level dyeing method of the present invention involves the elimination of shading or uneven dyeing due to vat, direct, reactive or sulfur dyes.

One embodiment of the leveling method of the present invention utilizes a graft polymer as described above.

The leveling method of the present invention can be carried out under other known conditions.

Preferably, the leveling method of the invention is carried out in an aqueous solution, in which case the solution ratio is from 100:1 to 5:1 and preferably from 25:1 to 5:1.

Based on the aforementioned copolymer content, the leveling agent concentration according to the invention is 0.01-10 g/l solution, especially 0.1-1 g/l and especially 1 g/l solution.

In one embodiment of the invention, one or more dispersants are added to the solution. Examples of suitable dispersants are naphthalenesulfonic acid-formaldehyde condensation products which can be prepared by sulfonating naphthalene, for example with oleum, partially or completely neutralizing, for example, aqueous alkali metal hydroxide and reacting with formaldehyde. Other suitable dispersants are described, for example, in US 4,218,218. Suitable amounts are generally 0.1-5 g dispersant per liter of solution and preferably 1-2 g/liter.

In one embodiment of the invention, one or more reducing agents, such as sodium dithionite Na ₂ S ₂ O ₄ , are added to the solution. Suitable amounts are generally 0.1-10 g reducing agent per liter of solution and especially 1-6 g/liter.

In one embodiment of the invention, one or more protective colloids, for example based on partially or fully neutralized polyacrylic acid, are added to the solution. Suitable polyacrylic acids have an average molecular weight _Mw of, for example, 1000-200000 g/mol, preferably 1000-100000 g/mol and especially 3000-70000 g/mol. Especially preferred are fully neutralized polyacrylic acids. Suitable amounts are generally 0.1-5 g protective colloid per liter of solution and especially 1-2 g/liter.

The leveling method of the present invention is generally carried out at a pH of 9-13.

The leveling method of the invention is generally carried out at temperatures above room temperature. A temperature range of 50°C to boiling temperature, and preferably at least 60°C, is especially suitable.

The duration of leveling according to the invention is generally at least 5 minutes to 2 hours, and preferably 30 to 90 minutes.

Rinsing, washing and/or drying can be carried out after treatment with the leveling agent according to the invention. Neutralization with acids is also suitable, especially with low volatility acids such as succinic acid, adipic acid, tartaric acid or citric acid.

The present invention further provides a method of stripping color difference dyed matter from a fabric, hereinafter also referred to as the stripping method of the present invention, which comprises the use of a monoethylenically unsaturated Release agent of at least one copolymer of units of monomers B1 and B2.

In one embodiment of the invention, the stripping method of the invention involves the elimination of shading dyeing due to vat, direct, reactive or sulfur dyes.

One embodiment of the stripping method of the present invention utilizes a grafted polymer as described above.

The stripping method of the present invention can be carried out under otherwise known conditions.

Preferably, the stripping method of the invention is carried out in aqueous solution, in which case the solution ratio is from 100:1 to 5:1 and preferably from 25:1 to 5:1.

Based on the above copolymer content, the stripping agent concentration of the present invention is 0.5-10 g/L solution, especially 2-4 g/L solution.

In one embodiment of the invention, one or more dispersants are added. Examples of suitable dispersants are naphthalenesulfonic acid-formaldehyde condensation products which can be prepared by sulfonating naphthalene, for example with oleum, partially or completely neutralizing, for example, aqueous alkali metal hydroxide and reacting with formaldehyde. Other suitable dispersants are described eg in US 4,218,218. Suitable amounts are generally 0.1-5 g dispersant per liter of solution and preferably 1-2 g/liter.

In one embodiment of the invention, one or more reducing agents, such as sodium dithionite Na ₂ S ₂ O ₄ , are added to the solution. Suitable amounts are generally 0.1-10 g reducing agent per liter of solution and especially 1-6 g/liter.

In one embodiment of the invention, one or more protective colloids, for example based on partially or fully neutralized polyacrylic acid, are added to the solution. Suitable polyacrylic acids have an average molecular weight _Mw of, for example, 1000-200000 g/mol, preferably 1000-100000 g/mol and especially 3000-70000 g/mol. Especially preferred are fully neutralized polyacrylic acids. Suitable amounts are generally 0.1-5 g protective colloid per liter of solution and especially 1-2 g/liter.

The stripping method of the present invention is generally carried out at a pH of 9-13.

The stripping method of the present invention is usually carried out at a temperature higher than room temperature. A temperature range of 50°C to boiling temperature, and preferably at least 60°C, is especially suitable.

The duration of the stripping method according to the invention is generally at least 5 minutes to 2 hours, and preferably 30 to 90 minutes.

Rinsing, washing and/or drying may follow treatment with the stripper of the present invention. Neutralization with acids is also suitable, especially with low volatility acids such as succinic acid, adipic acid, tartaric acid or citric acid.

The invention further provides a method of post-cleaning dyed-printed textiles, hereinafter also referred to as the post-cleaning method of the invention or the post-soaping method of the invention.

The post-soaping method of the present invention is carried out by using one or more post-soaping agents of the present invention in a typical aqueous solution. The solution may comprise exogenous salts, such as NaCl or Glauber's salts, in amounts of up to 15% by weight, based on the solution. The water used to prepare the aqueous solution does not need to be softened; a water hardness of up to 30° German hardness is feasible.

The post-purge process of the present invention can be carried out at atmospheric pressure, however superatmospheric pressure such as 1.1-5 bar is also feasible.

To carry out the post-soaping method of the present invention, the dyed and printed textiles can be treated in one or more soaping baths, the temperature, pressure and pH conditions selected in each soaping bath being the same or different. Preferably one to three soaping washes are used and more preferably one or two soaping washes are used. Preferably, the temperature and pressure conditions of different soap baths are the same.

When multiple soaping baths are used, it is often necessary to dispose of the waste solution between each soaping wash and make up a new solution each time. Soaping solutions having the same composition or soaping solutions having different compositions can be used. However, at least one soap bath should contain one or more postsoaping agents of the present invention.

The concentration in the soaping solution of the post-soaping agent used according to the invention is generally 1-8 g/l and preferably 1-4 g/l.

The post-soaping process of the present invention can utilize at least one additional ingredient to further improve the post-cleaning of textiles.

Useful additional ingredients include, for example, nonionic surfactants, such as polyalkoxylated fatty alcohols. It may be alkoxylated with, for example, ethylene oxide, propylene oxide or butylene oxide or mixtures thereof; ethylene oxide is preferred. Useful alcohols include C ₁₀ -C ₂₄ -alcohols, and especially C ₁₂ -C ₁₈ -alcohols. The degree of alkoxylation is from 10 to 40 equivalents of alkoxide per equivalent of fatty alcohol, especially from 15 to 30 equivalents of alkoxide per equivalent of fatty alcohol and especially from 20 to 25 equivalents of alkoxide per equivalent of fatty alcohol. The degree of alkoxylation must be understood here as an average value in each case.

Other ingredients that may be used in the post-soaping process of the present invention are complexing agents, for example phosphorus compounds such as polyphosphates or alkylene diphosphonic acid compounds such as hydroxymethylene diphosphonic acid. Also suitable are glycine derivatives such as nitrilotriacetic acid or ethylenediaminetetraacetic acid and the respective alkali metal salts thereof.

The quantitative ratios of the various ingredients in the post-soaping process of the invention are not critical per se.

The pH in the soaping solution used in the process of the invention is 4-12 and preferably 5-11. Especially preferably the pH is neutral or slightly acidic. The pH is usually set by organic carboxylic acids, for example aliphatic monocarboxylic acids such as acetic acid, formic acid, propionic acid, aliphatic dicarboxylic acids such as adipic acid, succinic acid, citric acid or polycarboxylic acids. Especially preferred are carboxylic acids which have only a very low vapor pressure at room temperature. Thus, aliphatic dicarboxylic acids, citric acid and polycarboxylic acids are preferred.

Preferably used aliphatic dicarboxylic acids have the general formula

HO ₂ C-(CH ₂ ) _i -(O-(CH ₂ ) _j ) _k -CO ₂ H

wherein i, j and k are independently 0-9. Especially preferred are carboxylic acids wherein k is 0 or 1 and i and j are independently 1-6. Carboxylic acids wherein i and j independently are 1-4 and k is 0 or 1 are especially preferred. Particular preference is given to mixtures of these carboxylic acids or mixtures of these carboxylic acids with citric acid.

Aliphatic dicarboxylic acids used with preference are succinic acid, glutaric acid, adipic acid, 2-methylsuccinic acid, 2-methylglutaric acid, 3-methylglutaric acid.

Polycarboxylic acids used with preference belong to polyacrylic acid and its copolymers with maleic acid. Their average molecular weight _Mn is 1000-150000 g/mol and preferably lies between 2000-70000 g/mol.

The post-soaping process of the present invention is generally carried out at elevated temperature. The feasible temperature range is 50-100°C and can be higher at superatmospheric pressure. The preferred temperature range is 60-98°C.

The mass ratio of the solution to the printed textile to be removed is generally 1:4 to 1:40 and preferably 1:6 to 1:20. The solution including the textile may be agitated during post-cleaning. The treatment time per soap bath is not critical per se and generally ranges from 5 minutes to 10 hours, and preferably 10-30 minutes.

After post soaping the textile is usually rinsed with water. Typically 1-6 and preferably 2-4 rinse cycles are used. The sole or first rinse solution is usually hot water, ie water at a temperature of 35-70°C. The last rinse operation usually takes place in the range of room temperature to 40°C.

The post-soaping process of the invention provides a very effective post-cleaning of textiles which contain only very low amounts of unfixed dyestuffs and thus have very high wash and contact fastnesses.

The invention further provides post-soaping agents, the use of which makes the method of the invention particularly effective. The post-soaping agent according to the invention comprises at least one copolymer comprising units derived from at least 2 monoethylenically unsaturated monomers B1 and B2 each comprising at least one nitrogen heterocycle. Exemplary copolymers are described above.

Preferably, the copolymers in the post-soaping agents of the present invention are graft polymers. Exemplary graft polymers are described above.

The post-soaping agents of the present invention more preferably comprise at least one graft polymer consisting of a polymeric graft base A that does not contain monoethylenically unsaturated units, and consists of at least 2 graft bases each containing at least one aza Polymerized side chains B formed from copolymers of cyclic monoethylenically unsaturated monomers B1 and B2 and optionally further comonomers B3.

Preferably, the side chain B accounts for more than 35% by weight of the post-soaping agent of the present invention.

Preferred post-soaping agents include, in addition to the graft polymers described above, other ingredients such as phosphorus compounds and nonionic surfactants. Particularly suitable phosphorus compounds and nonionic surfactants are as described above.

The post-soaping agents of the present invention are available as powders. However, it can also be used as an aqueous formulation, in which case the water content can be from 5 to 95% and preferably from 20 to 90% by weight, based on the total amount of components. It is preferably used as a liquid formulation, the metering of which can be achieved, for example, by automatic metering equipment.

The present invention further provides the use of post-soaping agents according to the invention for post-cleaning of textiles dyed with reactive, direct or vat dyes. Similarly, the present invention provides a method for post-cleaning reactive, direct or vat dyed textiles after dyeing and removing unfixed dyestuffs from the textiles.

The invention likewise relates to a method for post-cleaning reactive, direct or vat printed textiles, wherein the post-cleaning operation follows a coloring operation and serves to remove dyestuffs not fixed on the textile.

The invention is illustrated by the examples.

Example

Synthesis of the copolymers and graft polymers used according to the invention

1.1 Synthesis of grafted polymer 1

BASFAktiengesellschaft)和56.2g水加热至约85℃的内部温度。然后在3¹/₄小时的时间内连续加入27.5g的N-乙烯吡咯烷酮和12.5g的N-乙烯咪唑的混合物。同时如该混合物一样，在3¹/₄小时的时间内连续加入0.8g的2，2’-偶氮二(2-甲基丙脒)二盐酸盐(来自Wako Chemicals)。当完成添加时，将该批物料冷却至60℃。达到该温度时，加入含有0.3g叔丁基氢过氧化物的1.72ml水。随后添加含有0.2g Na₂S₂O₅的6.26ml水。获得清澈的微黄色聚合物溶液。固体量为42重量％。In a reactor equipped with nitrogen supply, reflux condenser, stirrer and metering device, 10 g of polyethylene _glycol (

BASFAktiengesellschaft) and 56.2 g of water were heated to an internal temperature of about 85°C. A mixture of 27.5 g of N-vinylpyrrolidone and 12.5 g of N-vinylimidazole was then added continuously over a period of 3 ^1/4 _hours . Simultaneously, like this _mixture , 0.8 g of 2,2'-azobis(2 ^- methylpropionamidine) dihydrochloride ( from Wako Chemicals). When the addition was complete, the batch was cooled to 60°C. When this temperature was reached, 1.72 ml of water containing 0.3 g of tert-butyl hydroperoxide was added. Then 6.26 ml of water containing 0.2 g _{of Na2S2O5 was} added. A clear yellowish polymer solution was obtained. The solids content was 42% by weight.

The K value was determined to be 40 by the method described in H. Fikentscher, Cellulose-Chemie, Vol. 13, pages 58-64 and 71-74 at 25° C. in 3% by weight aqueous NaCl.

1.2 Synthesis of Copolymer 1

A mixture of 125 g of N-vinylpyrrolidone, 125 g of N-vinylimidazole and 600 g of water was initially charged to the flask and heated to 85° C. with stirring under a nitrogen atmosphere. When 85[deg.] C. was reached, 1.53 g of 2,2'-azobis(2-aminopropane) dihydrochloride dissolved in 27 ml of water were added immediately within 2 hours. In addition, a solution of 5 g of mercaptoethanol dissolved in 27 ml of water was metered in over 1 hour. After the metered addition was complete, the reaction mixture was stirred at 85°C for 2 hours and then cooled to 60°C. 2.2 g of tert-butyl hydroperoxide (70% by weight in water) were diluted with 2 g of water and this dilution was added very quickly. Then 1.53 g of Na ₂ S ₂ 0 ₅ dissolved in water was added over 5 minutes and further stirred at 60° C. for 2 hours. A yellow, clear and slightly odorous polymer solution is obtained. The copolymer has a K value of 32. The molecular weight is 50000 g/mol. The aqueous solution has a solids content of 30% by weight.

2. Performance test

2.1 Performance test as leveling agent

Amounts listed as percentages are based on fiber weight.

Amounts not listed as percentages are based on solution volume.

Invention Embodiment 2.1.1:

Made of 0.3 wt% Indanthren Golden Organe G Colliosol, 0.5 wt% Indanthren Dark Blue BOA Colliosol, 12ml of 38°BE caustic soda, 0.5 g/l of graft polymer 1, 5 g/l _{of Na2S2O} The solution formed in ₄ , made up to a solution volume of 1 l, was treated in vats at 60° C. for 10 minutes without textiles.

25g of bleached cheesecloth (sample 1) was wrapped around a perforated metal basket and dyed at 60°C for 3 minutes and 40 seconds in a dye vat, which is a hermetically closeable stainless steel cylinder 15 cm in diameter and 30 cm high. Subsequently, the dye vat was opened and after a total dyeing time of 4 minutes, another 25 g of bleached cheesecloth (Sample 2) wrapped on a perforated metal basket was introduced into the dye vat. The vats were resealed and dyed at 60°C for 45 minutes. Subsequently, the dyed cheesecloth is removed and rinsed 3 times by dipping it in 1 1 of cold water.

Subsequently, the dyed cheesecloths (samples 1 and 2) were oxidized at 55° C. for 5 minutes in 1 1 of liquor containing 2 ml/liter of a 50% by weight hydrogen peroxide solution. This was followed by a water overflow rinse at room temperature for 5 minutes.

Samples 1 and 2 were then washed in a soaping solution for 15 minutes at 98°C. The composition of the soaping solution was as follows: 1 l solution containing 1 g/l of 90 wt% C ₁₃ H ₂₇ -(OCH ₂ CH ₂ ) ₄ -OH in water and 0.5 g/l of Na ₂ CO ₃ . Next, the samples were rinsed again at 55°C for 1 minute. Finally, samples 1 and 2 were centrifuged and dried. Level dyed samples 1 and 2 are thus provided.

To assess the effectiveness of graft polymer 1 as a leveling agent, samples 1 and 2 were compared in terms of shade depth.

The reflectance spectra of Sample 1 (as a reference) and the bleached cheesecloth were recorded with an X-rite CA22 spectrometer. Calculate the Kubelka-Munk K/S value for each spectrum. Subsequently, the K/S value of the bleached cheesecloth was subtracted from this value of Sample 1 to obtain the net contribution of dyeing to the K/S value of Sample 1 .

The same procedure was carried out for sample 2 to obtain the net contribution of dyeing to the K/S value of sample 2.

The ratio of the net contribution of the resulting staining to the K/S value was determined in the peak region of the wavelength-dependent graph of the K/S value for Sample 2. For this purpose, set the K/S value of sample 1 equal to 100%. Compared with the K/S value of sample 1, the higher the K/S value of sample 2, the better the leveling effect.

The excellent leveling performance of the leveling agent part examined should be such that Samples 1 and 2 have exactly the same shade.

Comparative example V2.1.2

Inventive example 2.1.1 was repeated except that instead of graft polymer 1 polyvinylpyrrolidone 1 with a molecular weight M _w of 45000 g/mol and a Fikentscher K value of 31 (measured in 1% by weight aqueous solution) was used.

The colorimetric value of table 1 leveling agent performance test

2.2 Performance test as a stripping agent

Performance as a stripper was tested based on pre-staining with vat dye.

Percentages are based on the weight of the bleached textile. The remaining amounts listed are based on solution volume.

Invention Embodiment 2.2.1:

Use of graft polymer 1 as release agent according to the invention

Perform prestaining according to the following method:

In a dye vat comprising a hermetically closable stainless steel cylinder 15 cm in diameter and 30 cm high, 1% by weight of Vat Orange 2, 0.5 g/l of the condensates of: 1 equivalent of adipic acid and 0.5 equivalents each of N3 -amine: H ₂ N-CH ₂ CH ₂ -NH-(CH ₂ ) ₃ -NH ₂ ; N4-amine: H ₂ N-CH ₂ CH ₂ -NH-(CH ₂ ) ₃ -NH-CH ₂ CH ₂ - NH ₂ , 12 ml of 38° BE caustic soda and 5 g/l of Na ₂ S ₂ O ₄ (88% by weight powder) are mixed, made up to 1 l with water and 50 g of bleached cheesecloth are added. Seal the vat. For the dyeing process, the temperature was raised from room temperature to 60° C. over 10 minutes and maintained at this temperature for 45 minutes. Subsequently, the pre-dried cheesecloth was removed and rinsed 3 times with 1 1 of room temperature water.

Next, the predyed cheesecloth was oxidized at 55° C. for 5 minutes in 1 1 of water containing 2 ml/liter of a 50% by weight hydrogen peroxide solution. This was followed by an overflow rinse at room temperature for 1 minute. It is then centrifuged and dried.

For the stripping process, a blank dyebath, ie a dyebath without _colorant , was prepared comprising 12 ml of 38° BE caustic soda, 6 g/L of _Na2S2O4 and 2 g/L of Graft Polymer ₁ . For the stripping process, 50 g of the above predyed cheesecloth were introduced into the blank dyebath, heated to 80°C over 20 minutes and treated at 80°C for 45 minutes. Subsequently, the temperature was lowered to 60° C. over 10 minutes and the cheesecloth thus pretreated was removed at 60° C. Rinse again 3 times in about 1 1 of cold water and then oxidize with 1 1 of liquid containing 2 ml/liter of a 50% by weight hydrogen peroxide solution at 55° C. for 5 minutes.

This was followed by an overflow rinse for 1 minute and subsequent soaping for 15 minutes at 98° C. in a solution comprising 1 g/L of 90% by weight C ₁₃ H ₂₇ —(OCH ₂ CH ₂ ) ₄ —OH in water and 0.5 g/L liters of Na ₂ CO ₃ . Finally, another overflow rinse with water was performed for 1 minute at 55°C. This is followed by centrifugation and drying to obtain a treated cheesecloth.

The reflectance spectra of the predyed cheesecloth (as a reference) and the bleached cheesecloth were recorded with an X-rite CA22 spectrometer. Calculate the Kubelka-Munk K/S value for each spectrum. Subsequently, the K/S value of the bleached cheesecloth is subtracted from that of the predyed cheesecloth to obtain the net contribution of dyeing to the K/S value of the predyed cheesecloth.

The net contribution of dyeing to the K/S value of the treated cheesecloth was obtained by performing the same procedure on the washed sample.

The resulting net contribution to the K/S value is determined in the peak region of the wavelength-dependent graph of the K/S value for the predyed denim. For this, set the K/S value of the predyed cheesecloth equal to 100%. The higher the K/S value of the treated cheesecloth compared to the K/S value of the pre-dyed cheesecloth, the poorer the release performance.

Excellent peel performance should mean that the sample has a shade comparable to the cotton fabric used or the staining is no longer measurable. The peel result values are reported as % pre-dyed cheesecloth shade.

Comparative example V2.2.2

Inventive example 2.2.1 was repeated except that instead of graft polymer 1 polyvinylpyrrolidone 1 had a molecular weight M _w of 45000 g/mol and a Fikentscher K value of 31 (measured in 1% by weight aqueous solution).

Table 2: Stripper Tests

2.3 Performance test as a post-soaping agent

2.3.1 General Instructions for Preparation of Hydrolyzed Reactive Dyes

A hydrolyzed reactive dye/reactive dye mixture for pre-dyeing was prepared as follows: the commercial reactive dyes listed in Table 1 (in the amounts reported in Table 1) were mixed with 40 ml of 38° BE aqueous sodium hydroxide solution, made up to 1 l with water and Adjust to 20° German hardness with CaCl ₂ . This was followed by heating from room temperature to 98°C over 30 minutes. The hydrolyzate thus obtainable was kept at 98° C. for 120 minutes and then cooled to room temperature over 30 minutes. The hydrolyzate was transferred to a brown glass bottle for storage. Table 3 lists the amount of dye used for hydrolysates H1-H8.

The abbreviations used for active systems have the following meanings:

MCT Monochlorotriazine

MFT Monofluorotriazine

DA-MCT Dual active monochlorotriazine

VS vinyl sulfone

Table 3: Hydrolysates H1 to H8

2.3.2 General instructions for preparing prestains with hydrolyzate

The amount of dyed hydrolyzate from Table 3 was made up to 1 l with water and adjusted to 20° German hardness with CaCl ₂ . The resulting diluted hydrolyzate was applied to cotton fabrics using a HVF12085 pad padding machine from Mathis. The contact pressure of the rollers was 2.6 bar. The liquid absorption of the obtained fiber was 80%. The application rate was 2 m/min. The textile was then dried for 4 minutes at 125° C. without air circulation in a LTF89534 circulating air oven from Mathis. The shade of the pad dyed textile thus obtained was measured with an X-rite CA22 reflectance spectrometer and calculated as described above. Hereinafter, the pad-dyed non-cleaned textile is also referred to as pad-dyed textile.

2.3.3 General description of flushing reactive dyes (Test V1-60)

Dissolve the _post -soaping agents of Table 2 (at the levels used in Table 2) with 50 g of sodium chloride in 1 l of water and adjust to 10° German hardness with CaCl. The temperature of 200 ml of the solution thus obtained was controlled to 60°C. If necessary, adjust the pH to the value reported in Table 5 using citric acid. 10 g of pad dyed textile was added to the solution and heated to the temperature listed in Table 5 for 10 minutes. Each soaping was allowed to act for 15 minutes before cooling to 60°C, and in those cases where more than one soaping was used, the solution was processed after the first soaping and a new soaping solution was set. In this test, until the last second soaping was in each case identical. The textile is removed by hand and squeezed. Then rinse twice with 200ml of cold water for 5 minutes each. The samples were then centrifuged and dried at room temperature.

Post-clearance effects were evaluated as follows:

The reflectance spectrum of the pad-dyed, dried textile was recorded with an X-rite CA22 spectrometer as a reference and the untreated textile was subsequently measured. Calculate the Kubelka-Munk K/S values for two textiles. Subsequently, the K/S value of the untreated textile was subtracted from the padded, dried textile to obtain the net contribution of dyeing to the K/S value of the padded, dried textile.

The same procedure was carried out on the cleaned sample to obtain the net contribution of dyeing to the K/S value of the cleaned textile.

The net contribution ratio of the resulting dyeing to the K/S value is determined in the peak region of the wavelength-dependent graph of the K/S value of the pad-dyed, dried textile. For this purpose, the K/S value of the pad-dyed, dried textile is set equal to 100%. The higher the K/S value of the post-cleaned textile, the worse the post-soaping performance compared to the K/S value of the pad-dyed, dried textile without post-cleaning.

The post-soaping agents used were the substances or mixtures S1-S8 listed in Table 4 below.

Table 4: Composition of Soaping Agent S2-S7 after Invention and Soaping Agent S1 after Comparison

post soaping agent S1 S2 S3 S4 S5 S6 S7 Polyacrylic acid 100 1-Hydroxymethylene diphosphonic acid 25 10 31.5 Copolymer 1 100 Graft polymer 1 25 10 35 35 100 n-C₁₆H₃₃-(OCH₂CH₂)₂₅-OH 2.5 2.5 3.5 water 47.5 77.5 30 65

The polyacrylic acid used for the post-soaping agent S1 in the comparative example was a NaOH-neutralized polyacrylic acid with a _Mw of 70000 g, measured by gel permeation chromatography; pH 8.5, 45 wt % aqueous solution. Comparative examples V2, V4, V6 and V8 used soaping liquors without post-soaping agent, ie the treatment of the pad dyed textiles was carried out with hot water at the recorded pH.

_nC16H33- ( _OCH2CH2 ) ₂₅ -OH is ethyloxylated cetyl alcohol prepared according to _{the following} instructions.

242 g of stearyl alcohol and 0.1 mol KOH flakes were dehydrated in an autoclave at 100°C and 1 mbar for 2 hours, depressurized with nitrogen and purged 3 times with nitrogen in the autoclave and then heated to 130°C. When 130° C. was reached, 1100 g of ethylene oxide were metered in continuously at a pressure of up to 6.1 bar over 3 hours and 20 minutes. When the addition was complete, the reaction was started until constant pressure was reached. It was then cooled to 100°C.

Table 5: Soaping agent examples and comparative examples after the invention

Table 5 (continued)

Table 5 (continued)

Table 5 (continued)

Table 5 (continued)

Table 5 (continued)

2.3.4 Textile printing

By stirring 80 g of Manutex F700) alginate, 10 g of p-nitrosulfonate (p-nitrosulfonate), 100 g of urea and 25 g of Na ₂ CO ₃ and 5 g of sodium hexametaphosphate water softener and 20 g of sodium hexametaphosphate according to Table 1 Dye hydrolysates to form printing pastes D1-D8. The printing pastes D1-D8 thus obtainable have a dynamic viscosity of 3 Pa·s.

On the MBK flat screen printing table equipped with a magnetic roller system (roller diameter 10mm; 12m/min; 6 strokes), each printing paste D1-D8 was printed through an E50-55 tulle flat screen onto 100% cotton top. It was subsequently dried at 80° C. in a circulating air cabinet from Mathis until drying of the print was complete.

Then in the Mathis GD laboratory HT steamer, the color was fixed for 10 minutes in a water vapor saturated atmosphere at 102 °C. After steaming, the print samples were sent for post-soaping.

2.3.5 Post-soaping test

Dissolve the post-soaping agent of Table 2 (in the amount used in Table 3) with 50 g of sodium chloride in 1 l of water and adjust to 10° German hardness with CaCl ₂ . The temperature of 200 ml of the solution thus obtained was controlled to 60°C. If necessary, adjust the pH to the value reported in Table 3 using citric acid. 10 g of the printed textile was added to the solution and heated to the temperature listed in Table 3 over 10 minutes. Allow each soaping solution to act for 15 minutes before cooling to 60°C, and in those instances where more than one soaping solution was used, process the solution after the first soaping and set a new soaping liquid. In this test, until the last second soaping was identical in all respects. The textile is removed by hand and squeezed. Then rinse twice with 200ml of cold water for 5 minutes each. The samples were then centrifuged and dried at room temperature.

Post-clearance effects were evaluated as follows:

The printed, dried textile reflectance spectrum was recorded with an X-rite CA22 spectrometer as a reference and the untreated textile was subsequently measured. Calculate the Kubelka-Munk K/S values for two textiles. Subsequently, the K/S value of the untreated textile was subtracted from the printed, dried textile to obtain the net contribution of dyeing to the K/S value of the printed, dried textile.

The same procedure was carried out on the cleaned sample to obtain the net contribution of dyeing to the K/S value of the cleaned textile.

The resulting net contribution to the K/S value is determined in the peak region of the wavelength-dependent graph of the K/S value of the printed, dried textile. For this, the K/S value of the printed, dried textile is set equal to 100%. The higher the K/S value of the post-cleaned textile, the worse the post-soaping performance compared to the K/S value of the printed, dried textile without post-cleaning.

The post-soaping agents used were the substances or mixtures S1-S8 listed in Table 4 below.

Table 6: Invented post-clearing examples and comparative (V) examples

V61 V62 V63 64 65 66 67 Hydrolyzate No. H5 H5 H5 H5 H5 H5 H5 Amount of hydrolyzate [g/L] 20 20 20 20 20 20 20 Printed textile color % 100 100 100 100 100 100 100

V61 V62 V63 64 65 66 67 post soaping agent S1 S1 S7 S5 S5 S5 Soaping times 1 1 1 1 1 1 1 Soap solution temperature [°C] 98 98 98 98 98 98 98 Amount of soaping agent [g/L] 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 NaCl content of soaping liquid [g/L] - - - - - - 15 The K/S value of the sample after cleaning 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

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

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

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

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.