CN1811052A - Amphoteric water soluble color-fixing agent and its application - Google Patents
Amphoteric water soluble color-fixing agent and its application Download PDFInfo
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Abstract
The present invention relates to one kind of amphoteric water soluble polymer color-fixing agent and its synthesis and use. The amphoteric water soluble color-fixing agent is suitable for color fixing of direct active dye, and can form cation radical, reactant anion radical, hydrogen bond and some radical capable of increasing the intermolecular force in water solution. It can combine with dye anion and cellulose anion through electrostatic force like cationic color fixing agent, and has active cross-linking radical, structure unit with affinity to dye and molecular weight great enough to form protecting film combining with dye and fiber to close the hydrophilic radical, lower the water solubility of dye molecule and strengthen the force between dye molecule and cellulose molecule simultaneously, so as to raise color fastness in several aspects.
Description
Technical field
The invention belongs to the printing and dyeing assistant category, specifically a kind of amphoteric water soluble color-fixing agent and application thereof can be used for directly, the fixation of Dyeing of Cotton Fabric with Reactive Dyes fabric.
Background technology
Directly, REACTIVE DYES because bright in colour, chromatogram is complete, cost is cheap relatively, easy to use, in the dyeing of COTTON FABRIC, obtained using widely.But because in the direct dyes chemical constitution, many possess hydrophilic properties sulfonic group and carboxylic acid group, hydrophily is stronger, and only combines with fiber by hydrogen bond and Van der Waals force, so wet colour fastness is lower, and fade, the staining phenomenon is also very serious.Although and can form covalent bonds between REACTIVE DYES it and the fiber, the stability of a lot of dyestuffs and fiber bonding is not high, such as not acid and alkali resistance of REACTIVE DYES, oxidant and the heat of some type, takes place easily that look becomes, fades, the staining phenomenon.Therefore the dyeing of these two kinds of dyestuffs all is necessary to use color-fixing agent.
The color-fixing agent that uses in producing at present is based on cationic, but this class color-fixing agent in fact also just solves such as COLOR FASTNESS such as flatiron, washable, dry friction, and effect is not satisfactory improving on the wet colour fastness.Because when doing " wet friction " fastness, be that cotton long cloth that will wet and the dyeing cloth specimen of doing rub mutually, moisture content on this moment wet white cotton fine cloth does not only play lubricated, reduction and dry state painting cloth, the effect of coefficient of friction, raising flatness each other, is a kind of swelling, dissolving and adsorbent on the contrary.In friction process, make the unreacted set the dyestuff swelling, dissolve, come off, and be adsorbed on rapidly on the white cotton fine cloth of wet test.Cationic color-fixing agent molecule mainly combines with the dyestuff anion by ionic bond and Van der Waals force, makes the dye molecule increase and is insoluble in water, forms insoluble salt with fiber and dyestuff, generates the color lake, thereby improves the wet fastness of dyestuff.Cationic fixing agent or excessive its diffusion of color-fixing agent molecule of using is relatively poor at present, be difficult to infiltrate through fibrous inside, or the color-fixing agent molecule is less than normal, the color lake forms bad, film forming is poor, can not form the cross-linking system of height diversification, so can not well promote fastness to wet rubbing.
At this problem, the inventor imagines a kind of novel color-fixing agent that can effectively improve the wet fastness of rubbing of fabric of exploitation.
The amphoteric water-soluble macromolecule contains positive and negative two kinds of electric charge groups as a kind of novel polymer chemistry finishing agent on its strand, compare with water-soluble anionic polymer that only contains a kind of electric charge or cationic polymer, and its performance is more unique.At present, the amphoteric water-soluble macromolecule has been widely used in the Treatment of Industrial Water field as flocculant, its effect will be significantly higher than cationic flocculant, because it not only has electrical neutralization, the effect of adsorption bridging, and, produces intermolecular " windings " parcel effect owing to introduced the cross-linking system that anion can form the height diversification, make suitable of the mud of processing thick, dehydration property good.We utilize a kind of molecular weight of this good performance development of amphoteric water-soluble macromolecule moderate, can form the new type amphoteric color-fixing agent of the cross-linking system of height diversification.
Summary of the invention
The object of the invention provides a kind of amphoteric water soluble color-fixing agent and is using application direct, acid, Dyeing of Cotton Fabric with Reactive Dyes fabric fixation.
This kind both sexes color-fixing agent is a kind ofly to have molecular formula for (A)
x(N)
y(C)
zThe amphoteric water-soluble polyelectrolyte, wherein A is the anion chain link; N is the nonionic chain link; C is the CATION chain link; X, y, z then represent the degree of polymerization cloudy, non-, cation chain segments respectively, and x: y: z is (10～40): (0～30): (60～90), inherent viscosity are 33ml/g～320ml/g;
Synthetic method of the present invention can adopt copolymerization directly preparation and two kinds of schemes of copolymerization post-modification, and copolymerization process can adopt polymerisation in solution, suspension polymerization or emulsion polymerisation etc., and reaction can be undertaken by reaction mechanisms such as radical polymerization, condensation polymerization, anionic polymerisations.
The synthetic method of amphoteric water soluble color-fixing agent of the present invention is characterized in that adopting following method synthetic respectively:
1. the direct preparation method of copolymerization
Adopt methods such as polymerisation in solution, suspension polymerization or emulsion polymerisation, comprise water and nonaqueous phase disperse system.Is (10～40) with anionic monomer, non-ionic monomer and cationic monomer with mol ratio: (0～30): (60～90) are carried out copolymerization and are directly prepared polyampholyte.In the aqueous solution, adopt the direct preparation method of copolymerization often owing to the interaction of negative ions, be difficult to obtain the copolymer of completely random.In order to weaken this interaction, often neutral electrolyte need be added in water, for example: NaCl, KCl, Na
2SO
4, K
2SO
4Deng, salinity is at 0.1-0.5M;
2. the synthetic method of copolymerization post-modification:
Different monomers is copolymerized into the copolymer that only contains single kind ion earlier, then, on polymer chain, introduce the synthetic polyampholyte of method of second kind of ion by method of modifying such as hydrolysis, grafting, and make it anion, nonionic and cationic mol ratio and be (10～40): (0～30): (60～90).This method is owing to be to introduce second kind of ion by modification, so, more favourable to randomcopolymer.
The described anion chain link of this method is meant the part that contains groups such as carboxylic acid group, sulfate, sulfonic group, phosphate that directly obtains by copolymerization or modification.Copolymerization commonly used has acrylic acid, methacrylic acid, itaconic acid, maleic anhydride, vinyl sulfonic acid etc. with anionic monomer;
Described nonionic chain link is meant the part that does not contain electric charge that directly obtains by copolymerization or modification.Copolymerization commonly used has acrylamide, acrylate, acrylonitrile, styrene etc. with non-ionic monomer;
Described CATION chain link is meant directly by what copolymerization or modification obtained and contains primary amine, secondary amine, tertiary amine and quaternary ammonium salt thereof, morpholine, imidazoline and guanidine and biguanides etc.Copolymerization commonly used has the quaternary ammonium salt of dimethyl diallyl ammonium chloride (DMDAAC), diethyl diallyl ammonium chloride (DEDAAC), methylacryoyloxyethyl trimethyl ammonium chloride (DMC), acrylyl oxy-ethyl-trimethyl salmiac (DAC), dimethylamino propylene ethyl ester, the quaternary ammonium salt of dimethylamino methyl propylene ethyl ester etc. with cationic monomer.
After the described copolymerization again modification also divide three classes with monomer: modification generates anionic monomer acrylate, methacrylate and derivative thereof, acrylamide, Methacrylamide and derivative thereof etc.; Modification generates non-ionic monomer vinyl acetate and derivative thereof; Modification generates cationic monomer acrylamide, Methacrylamide and derivative thereof, N-vinyl acetamide and derivative thereof etc.
Described initator is the material that persulfate-bisulfites, persulfate-triethanolamine or azo diethyl butyronitrile or the like easily cause Raolical polymerizable.
The purposes of amphoteric water soluble color-fixing agent of the present invention is characterized in that being used for the fixation of direct dyes, Dyeing of Cotton Fabric with Reactive Dyes fabric.
The cloth specimen that specifically will dye is placed in the pH=5～7 dipping fixation liquid that contain 3%～4% both sexes color-fixing agent as claimed in claim 1, at room temperature and 1: 20 dipping of bath raio, soak two through two and roll, transfer the padding machine of pick-up 90% (scope), at 95 ℃～105 ℃ preliminary drying 2～4min, bake 3min at 150 ℃～180 ℃ then, washing and oven dry.
Amphoteric water soluble color-fixing agent of the present invention had both formed cation group in the aqueous solution, reactive anionic group has again can form hydrogen bond and some can increase the intermolecular force group.It both can utilize electrostatic attraction to combine with dyestuff anion and cellulose anion as cationic fixing agent like this; seal its part hydrophilic group; thereby reduce the water-soluble of dye molecule; also can interact between the color-fixing agent molecule; form network cross-linked; can add structural units that macromolecule or introduction and dyestuff have affinity again and strengthen intermolecular force between dye molecule and the cellulosic molecule; has active group simultaneously; can form covalent bonding; and molecular weight is even as big as forming diaphragm, thereby can utilize multiple factor acting in conjunction to improve COLOR FASTNESS.
This class new type amphoteric color-fixing agent is formed by cheap polymerizable raw material, the synthesis technique maturation, and it is simple, in the fixation process, taken all factors into consideration temperature, concentration, pH value, molecular weight or the like influence factor, and to the performance impact after the textile finishing, aspects such as environmental pollution have been optimized color fixing process as much as possible, have really accomplished economical and practical.
Five, the specific embodiment
What the both sexes high polymer adopted usually is cationic monomer, non-ionic monomer and anionic monomer copolymerization process make, of the present invention synthetic no exception, CATION can adopt dimethyl diallyl ammonium chloride (DMDAAC), diethyl diallyl ammonium chloride (DEDAAC), methylacryoyloxyethyl trimethyl ammonium chloride (DMC), acrylyl oxy-ethyl-trimethyl salmiac (DAC), the quaternary ammonium salt of dimethylamino propylene ethyl ester, the quaternary ammonium salt of dimethylamino methyl propylene ethyl ester or be modified as cation group or the like by acrylamide construction unit after the polymerization, anionic monomer can adopt acrylic acid, methacrylic acid, itaconic acid, maleic anhydride or generate anionic group or the like by the vinyl acetate alcoholysis, non-ionic monomer can adopt acrylate, acrylonitrile, acrylamide, styrene is with some alkene and derivative thereof, and initator can be used persulfate-bisulfites, persulfate-triethanolamine, azo diethyl butyronitrile or the like easily causes the material of Raolical polymerizable.
For example can carry out modification to obtain Amphiphatic high polymer with formaldehyde, diethylamine hydrochloride more earlier with acrylic acid and acrylamide copolymerization; Also can carry out radical polymerization with dimethyl diallyl ammonium chloride and itaconic acid; The methylacryoyloxyethyl trimethyl ammonium chloride is done cationic monomer, and styrene is done non-ionic monomer, and maleic anhydride is done anionic monomer, and the three carries out radical reaction and generates ampholyte copolymer; With acrylic acid, acrylamide and dimethyl diallyl ammonium chloride is that raw material carries out copolymerization or the like
The novel color-fixing agent of these class both sexes had both formed cation group in the aqueous solution, reactive anionic group has again can form hydrogen bond and some can increase the intermolecular force group.It both can utilize electrostatic attraction to combine with dyestuff anion and cellulose anion as cationic fixing agent like this; has active crosslinked group again; and contain the structural units that has affinity with dyestuff; and molecular weight is even as big as forming diaphragm; combine with the dye well fiber and can seal its part hydrophilic group; thereby reduce the water-soluble of dye molecule; strengthen the intermolecular force between dye molecule and the cellulosic molecule, thereby can utilize multiple factor acting in conjunction to improve COLOR FASTNESS.
This class new type amphoteric color-fixing agent is formed by cheap polymerizable raw material, the synthesis technique maturation, and it is simple, in the fixation process, taken all factors into consideration temperature, concentration, pH value, molecular weight or the like influence factor, and to the performance impact after the textile finishing, aspects such as environmental pollution have been optimized color fixing process as much as possible, have really accomplished economical and practical.
The specific embodiment
Following examples help to understand the present invention, but are not limited to content of the present invention.
The synthetic of embodiment 1 polymer given an example:
1. the amphoteric polyacrylamide water soluble polymer is synthetic: a, polymerization: acrylic acid (needing refining) is pressed (10～40) with acrylamide monomer: (60～90) mixed in molar ratio becomes the aqueous solution; the concentration of monomer solution is controlled at 5-15%; then to wherein feeding nitrogen 10-30 minute; and under nitrogen protection under add ammonium persulfate-sodium bisulfite oxidation-reduction type initator; its consumption is the 0.001-0.008 molar fraction of monomer total amount; between 60 ℃～80 ℃ of the temperature; copolyreaction 3h～5h gets the anionic high polymer.B, modification: under pH=7-9, temperature is preferably 65 ℃ between 50 ℃～70 ℃, and this copolymer is carried out Mannich reaction with formaldehyde and diethylamine hydrochloride, and modification 2h～4h can get the aqueous solution of both sexes color-fixing agent.
2. make anionic monomer with itaconic acid, dimethyl diallyl ammonium chloride is made cationic monomer, and press (10～40): (60～90) mixed in molar ratio becomes the aqueous solution, and the concentration of monomer solution is controlled at 5-15%, makes both carry out radical polymerization.Caught up with oxygen in nitrogen 10-30 minute to wherein feeding then, and under nitrogen protection under add ammonium persulfate-sodium bisulfite oxidation-reduction type initator, its consumption is the 0.001-0.008 molar fraction of monomer total amount.Between 60 ℃～80 ℃ of the temperature, copolyreaction 3h～5h, cooling promptly gets the aqueous solution of both sexes color-fixing agent.
3. maleic anhydride is an anionic monomer, styrene is non-ionic monomer, the methylacryoyloxyethyl trimethyl ammonium chloride is cationic monomer (dissolving with small amount of ethanol), is (10～40) with anionic monomer, non-ionic monomer and cationic monomer with mol ratio: (0～30): (60～90), make solvent with acetone, the total concentration of monomer solution is 5-15%, is warming up to 60-90 ℃ and adds azodiisobutyronitrile, reaction 3h～5h, cooling promptly gets polymerizate.With the polymer water-soluble, then acetone is steamed, promptly get the aqueous solution of both sexes color-fixing agent.
4. with acrylic acid; acrylamide and dimethyl diallyl ammonium chloride are raw material; anionic monomer; non-ionic monomer and cationic monomer are (10～40) with mol ratio: (0～30): (60～90); and be dissolved in the NaCl aqueous solution of 0.1-0.5M; the total concentration of monomer saline solution is 5-15%; nitrogen was caught up with oxygen 10～30 minutes; under nitrogen protection, be warming up to 60-80 ℃; add potassium peroxydisulfate-triethanolamine oxidation-reduction type initator; its consumption is the 0.001-0.008 molar fraction of monomer total amount; cause copolymerization 3h～5h, get the saline solution of both sexes color-fixing agent.
2, the color fixing process of this class both sexes color-fixing agent is: dyeing cloth specimen → pad fixation liquid (two soak two rolls, and transfers pick-up about 90%) → preliminary drying (100 ℃～105 ℃/3～5min) → bake (150 ℃～175 ℃/3～4min) → washing → oven dry.
Fabric after 2 pairs of arrangements of embodiment carries out Performance Detection.
1. be example with the amphoteric polyacrylamide water soluble polymer, effect after the arrangement and color fixing agent Y effect are compared as follows:
The effect of table 1. polymer and color fixing agent Y relatively
| Laboratory sample | Former cloth | The both sexes color-fixing agent | Color fixing agent Y | ||||
| Direct pink 12B | Direct scarlet 4BS | Direct pink 12B | Direct scarlet 4BS | Direct pink 12B | Direct scarlet 4BS | ||
| The unlubricated friction fastness | 3-4 | 4-5 | 5 | 5 | 5 | 5 | |
| The wet fastness of rubbing | 2-3 | 2 | 5 | 4 | 4 | 2-3 | |
| Soaping fastness | Staining | 2 | 1 | 4 | 2-3 | 4 | 3 |
| Fade | 2 | 2-3 | 4 | 4 | 4 | 4 | |
| Perspiration fastness | Acid | 3 | 2-3 | 4 | 3 | 5 | 3 |
| Alkali | 3 | 3 | 4 | 3-4 | 5 | 4 | |
| Light fastness | 2-3 | 3 | 3 | 3-4 | 2 | 2 | |
| Stiffness | 2cm | 2.35cm | 2.60cm | 2.80cm | 2.50cm | 2.60cm | |
Dyeing and weaving thing to the direct pink 12B of above-mentioned arrangement carries out the test of free formaldehyde content, and proofreading and correct absorbance is 0.025, and free formaldehyde content is 68.1199ppm.
2. be that the product that raw material carries out copolymerization is an example with acrylic acid, acrylamide and dimethyl diallyl ammonium chloride, effect after the arrangement and color fixing agent Y effect are compared as follows:
| Laboratory sample | Former cloth | The both sexes color-fixing agent | Color fixing agent Y |
| Direct pink 12B | Direct pink 12B | Direct pink 12B | |
| The unlubricated friction fastness | 3～4 | 4～5 | 5 |
| The wet fastness of rubbing | 2～3 | 3～4 | 2～3 |
| Laboratory sample | Former cloth | The both sexes color-fixing agent | Color fixing agent Y |
| Direct pink 12B | Direct pink 12B | Direct pink 12B | |
| The unlubricated friction fastness | 3～4 | 4～5 | 5 |
| The wet fastness of rubbing | 2～3 | 3 | 2～3 |
Claims (6)
1, this kind both sexes color-fixing agent is a kind ofly to have molecular formula for (A)
x(N)
y(C)
zThe amphoteric water-soluble polyelectrolyte, wherein A is the anion chain link; N is the nonionic chain link; C is the CATION chain link; X, y, z then represent the degree of polymerization cloudy, non-, cation chain segments respectively, and x: y: z is (10～40): (0～30): (60～90), inherent viscosity are 33ml/g～320ml/g;
Described anion chain link is meant the part that contains carboxylic acid group, sulfate, sulfonic group or phosphate group that directly obtains by copolymerization or modification; Copolymerization commonly used has acrylic acid, methacrylic acid, itaconic acid, maleic anhydride or vinyl sulfonic acid with anionic monomer;
Described nonionic chain link is meant the part that does not contain electric charge that directly obtains by copolymerization or modification; Copolymerization commonly used has acrylamide, acrylate, acrylonitrile or styrene with non-ionic monomer;
Described CATION chain link is meant directly by what copolymerization or modification obtained and contains primary amine, secondary amine, tertiary amine and quaternary ammonium salt thereof, morpholine, imidazoline and guanidine or biguanides; Copolymerization commonly used has the quaternary ammonium salt of dimethyl diallyl ammonium chloride, diethyl diallyl ammonium chloride, methylacryoyloxyethyl trimethyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac, dimethylamino propylene ethyl ester or the quaternary ammonium salt of dimethylamino methyl propylene ethyl ester with cationic monomer;
After the described copolymerization again modification also divide three classes with monomer: modification generates anionic monomer acrylate, methacrylate and derivative thereof, acrylamide, Methacrylamide and derivative thereof etc.; Or modification generates non-ionic monomer, and vinyl acetate and derivative thereof are arranged; Modification generates cationic monomer acrylamide, Methacrylamide and derivative thereof, N-vinyl acetamide or derivatives thereof;
Described initator is the material that persulfate-bisulfites, persulfate-triethanolamine or azo diethyl butyronitrile easily cause Raolical polymerizable.
2, the synthetic method of amphoteric water soluble color-fixing agent as claimed in claim 1 is characterized in that adopting following method synthetic respectively:
3. the direct preparation method of copolymerization
Adopt methods such as polymerisation in solution, suspension polymerization or emulsion polymerisation, comprise water and nonaqueous phase disperse system; Is (10～40) with anionic monomer, non-ionic monomer and cationic monomer with mol ratio: (0～30): (60～90) are carried out copolymerization and are directly prepared polyampholyte; In water, add neutral electrolyte NaCl, KCl, Na in case of necessity
2SO
4Or K
2SO
4, salinity is at 0.1-0.5M;
4. the synthetic method of copolymerization post-modification:
Different monomers is copolymerized into the copolymer that only contains single kind ion earlier, then, on polymer chain, introduce the synthetic polyampholyte of method of second kind of ion by hydrolysis or graft-modification method, and make it anion, nonionic and cationic mol ratio and be (10～40): (0～30): (60～90).
3, the synthetic method of amphoteric water soluble color-fixing agent as claimed in claim 2 is characterized in that described water is the water of anaerobic.
4, the purposes of amphoteric water soluble color-fixing agent as claimed in claim 1 is characterized in that being used for the fixation of direct dyes, Dyeing of Cotton Fabric with Reactive Dyes fabric.
5, the purposes of amphoteric water soluble color-fixing agent as claimed in claim 4, it is characterized in that the dyeing cloth specimen is placed in the pH=5～7 dipping fixation liquid that contain 3%～4% both sexes color-fixing agent as claimed in claim 1, at room temperature and 1: 20 dipping of bath raio, soaking two through two rolls, at 95 ℃～105 ℃ preliminary drying 2～4min, bake 3min at 150 ℃～180 ℃ then, washing and oven dry.
6, the purposes of amphoteric water soluble color-fixing agent as claimed in claim 4, it is characterized in that described two, to soak two pick-ups that roll be 90%.
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| CN101280032B (en) * | 2007-11-06 | 2010-09-01 | 江苏工业学院 | Preparation of quaternaries hyper branched polycation electrolyte |
| CN102912661A (en) * | 2012-11-07 | 2013-02-06 | 愉悦家纺有限公司 | Fixation treating method for fabric |
| CN103147327A (en) * | 2013-03-26 | 2013-06-12 | 无锡嘉德纺织制品有限公司 | Dye fixing agent and preparation method thereof |
| CN103669041A (en) * | 2013-11-27 | 2014-03-26 | 江苏中新资源集团有限公司 | Fabric formaldehyde-free fixing agent and preparation method thereof |
| CN103922944A (en) * | 2014-04-01 | 2014-07-16 | 浙江传化股份有限公司 | Cross-linkable quaternary ammonium salt water-soluble cationic monomer as well as preparation method and application thereof |
| CN104004383A (en) * | 2014-06-19 | 2014-08-27 | 北京泛博化学股份有限公司 | Leather dye and preparing method thereof |
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| CN104047192A (en) * | 2014-06-10 | 2014-09-17 | 盐城市印染有限公司 | Color-fixing anti-wrinkle finishing agent as well as preparation method and application thereof |
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| CN101280032B (en) * | 2007-11-06 | 2010-09-01 | 江苏工业学院 | Preparation of quaternaries hyper branched polycation electrolyte |
| CN102912661A (en) * | 2012-11-07 | 2013-02-06 | 愉悦家纺有限公司 | Fixation treating method for fabric |
| CN102912661B (en) * | 2012-11-07 | 2015-03-18 | 愉悦家纺有限公司 | Fixation treating method for fabric |
| CN103147327B (en) * | 2013-03-26 | 2014-12-17 | 江苏高博智融科技有限公司 | Dye fixing agent and preparation method thereof |
| CN103147327A (en) * | 2013-03-26 | 2013-06-12 | 无锡嘉德纺织制品有限公司 | Dye fixing agent and preparation method thereof |
| CN103669041A (en) * | 2013-11-27 | 2014-03-26 | 江苏中新资源集团有限公司 | Fabric formaldehyde-free fixing agent and preparation method thereof |
| CN103922944A (en) * | 2014-04-01 | 2014-07-16 | 浙江传化股份有限公司 | Cross-linkable quaternary ammonium salt water-soluble cationic monomer as well as preparation method and application thereof |
| CN103922944B (en) * | 2014-04-01 | 2016-08-17 | 浙江传化股份有限公司 | A kind of crosslinkable quaternary ammonium salt water-soluble cationic monomer and its preparation method and application |
| CN104018372A (en) * | 2014-05-22 | 2014-09-03 | 浙江莱美纺织印染科技有限公司 | Washing process for ink-jet printed ultrafine fiber polyester /brocade blended fabric |
| CN104047192A (en) * | 2014-06-10 | 2014-09-17 | 盐城市印染有限公司 | Color-fixing anti-wrinkle finishing agent as well as preparation method and application thereof |
| CN104004383A (en) * | 2014-06-19 | 2014-08-27 | 北京泛博化学股份有限公司 | Leather dye and preparing method thereof |
| CN104878629A (en) * | 2015-05-08 | 2015-09-02 | 陕西科技大学 | Anionic dye fixing agent with formaldehyde removal function and preparation method thereof |
| CN106498785A (en) * | 2016-12-07 | 2017-03-15 | 郑州源冉生物技术有限公司 | A kind of active alkaline-resisting aldehyde-free colour stabilizer and preparation method thereof |
| CN106758411A (en) * | 2016-12-07 | 2017-05-31 | 郑州源冉生物技术有限公司 | A kind of alkaline-resisting environmentally friendly color fixing agent of activity and preparation method thereof |
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