CN109183467B - Hydrophilic alkali-resistant color fixing agent and preparation method thereof - Google Patents
Hydrophilic alkali-resistant color fixing agent and preparation method thereof Download PDFInfo
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- CN109183467B CN109183467B CN201811020643.7A CN201811020643A CN109183467B CN 109183467 B CN109183467 B CN 109183467B CN 201811020643 A CN201811020643 A CN 201811020643A CN 109183467 B CN109183467 B CN 109183467B
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/02—After-treatment
- D06P5/04—After-treatment with organic compounds
- D06P5/08—After-treatment with organic compounds macromolecular
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
- C08F8/24—Haloalkylation
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Abstract
The invention discloses a hydrophilic alkali-resistant color fixing agent containing a mol of copolymerization units shown as a formula (I), b mol of copolymerization units shown as a formula (II), c mol of copolymerization units shown as a formula (III) and d mol of copolymerization units shown as a formula (IV) and a preparation method thereof. The hydrophilic alkali-resistant color fixing agent disclosed by the invention is excellent in color fixing effect and alkali resistance, good in hydrophilicity and small in fabric color change.
Description
Technical Field
The invention relates to a color fixing agent and a preparation method thereof, in particular to a hydrophilic alkali-resistant color fixing agent and a preparation method thereof
Background
The cotton fabric is popular with consumers due to wide moisture absorption and air permeability, and the quality of the cotton fabric is more and more adapted to the increasingly improved wearing requirements of people through continuous development, wherein the mercerized cotton fabric is one of the products which are well received by the consumers, and the mercerized cotton fabric is comfortable to wear, has silky luster, stable, stiff and smooth in size and good in wrinkle resistance, and is widely applied to products such as T-shirts, moisture absorption and sweat releasing fabrics, high-grade shirts and the like.
The conventional mercerizing process of the cotton knitted fabric is carried out before dyeing, but in subsequent dyeing and post-finishing processing, the mercerizing effect of the cotton knitted fabric is obviously influenced under the long-time repeated physical friction extrusion and chemical action, and in order to keep the excellent performance of the cotton knitted fabric endowed with mercerizing and improve the product quality, a processing process route of dyeing firstly and then mercerizing is adopted for the cotton knitted fabric, but the processing method of dyeing firstly and then mercerizing enables the dyed fabric to be subjected to mercerizing concentrated alkali (NaOH 200-280 g/L), and the reactive dye is further hydrolyzed to cause flooding, so that the color fastness is seriously reduced, and the color fixing agent with excellent alkali resistance is required to carry out color fixing treatment on the dyed fabric, so that the improvement of the fabric quality is ensured.
Currently, most of dyeing and finishing workers at home and abroad research on formaldehyde-free fixing agents for cotton fabrics, such as polycations, polyamines, reactive fixing agents and the like. For example, chinese patent application No. CN201711160212.6 discloses a method for preparing a formaldehyde-free color fixing agent, which adopts allyl glycidyl ether, an intermediate of ethylenediamine reaction, and dimethyldiallylammonium chloride, and prepares a polycationic reactive color fixing agent under the action of an initiator, the color fixing effect is good, the soaping fastness reaches 4-5 levels, but the color fixing agent is not alkali-resistant, and the color fixing effect is greatly reduced under the condition of concentrated alkali; for example, chinese patent No. CN201711211179.5 discloses a method for preparing a formaldehyde-free color fixing agent, which is a polyamine-based reactive color fixing agent prepared from dimethylamine, epichlorohydrin, diethylenetriamine, dicyandiamide, etc., and has the advantages of simple process, convenient operation, and good alkali resistance, but the color fixing effect is general, and the color of the fabric is greatly affected by the color fixing agent due to dicyandiamide as one of the raw materials.
The color fixing agent in the market is also mostly of the types, the traditional cotton fabric dyeing is realized, the dyeing process is carried out after mercerizing the common mercerized cotton fabric, the color fastness of the fabric can be effectively improved by the traditional color fixing agent through screening, but in the mercerizing process after dyeing with higher requirements, the color fixing agent in the market is poor in color fixing effect or poor in alkali resistance, the color fixing effect and the alkali resistance can not be considered by one color fixing agent, the fastness problem of the high-grade mercerized cotton fabric developed by the process of mercerizing the cotton fabric after dyeing is solved, and therefore, the development of the alkali-resisting color fixing agent for cotton with good color fixing effect has very important practical significance.
Disclosure of Invention
One aspect of the present invention provides a hydrophilic strong base resistant fixing agent comprising a moles of copolymerized units of formula (I), b moles of copolymerized units of formula (II), c moles of copolymerized units of formula (III), and d moles of copolymerized units of formula (IV):
in the formula:
R1、R4、R5、R6、R7、R8、R9、R11and R12Are each H or C1-C5An alkyl group;
R2is C1-C8Alkyl or C7-C11Aralkyl group;
R3is C1-C5An alkylene group;
R10is C1-C5Alkylene or C6-C10An arylene group;
R13is H, C1-C8Alkyl or C6-C10An aryl group;
the molar ratio of a to b to c to d is 1 (0.1-1) to (0.4-1.5), and the weight average molecular weight of the hydrophilic alkali-resistant fixing agent is 10000-150000.
Another aspect of the present invention is to provide a method for preparing the hydrophilic strong base-resistant color fixing agent, which comprises the following steps:
1) adding a moles of a comonomer represented by formula (V), b moles of a comonomer represented by formula (VI), c moles of a comonomer represented by formula (VII), d moles of a comonomer represented by formula (VIII) and water into a reaction kettle, and stirring;
in formula V:
R1is H or C1-C5Alkyl radical
R2Is C1-C8Alkyl or C7-C11Aralkyl group;
in formula VI:
R3is C1-C5An alkylene group;
R4and R5Are respectively C1-C5An alkyl group;
in formula VII:
R7、R8、R9、R11and R12Are each H or C1-C5An alkyl group;
R10is C1-C5Alkylene or C6-C10An arylene group;
in formula VIII:
R13is C1-C8Alkyl or C6-C10An aryl group;
2) adding a free radical initiator to carry out polymerization reaction; and
3) adding (alkyl) epichlorohydrin represented by the formula IX to perform quaternization reaction,
R6is H or C1-C5An alkyl group;
wherein the molar ratio of a to b to c to d is 1 (0.3-0.9) to (0.25-0.85) to (0.5-1.2).
Compared with the color fixing agent and the preparation method thereof which are disclosed now, the invention is originally reflected in the following aspects: (1) according to the invention, the special cationic monomer is adopted, so that the cationic density of the prepared color fixing agent is greatly improved, and the color fixing agent can be more effectively subjected to ionic bond combination with the cotton reactive dye, thereby obviously improving various fastnesses of the fabric; (2) introducing an amino-containing vinyl ether monomer to provide an active group amino for the next reaction with (alkyl) epichlorohydrin and provide hydrophilicity for a color fixing agent by utilizing an ether bond; (3) introducing enamine monomer and active group amido reacted with (alkyl) epoxy chloropropane to generate great amount of color fixing agent molecule
(R6Is H or C1-C5Alkyl) to form covalent bond combination with cotton fabric under alkaline condition, further improving various fastness of the fabric; (4) the unsaturated carboxylic acid monomer is introduced, so that strong alkali can be buffered, the change of the pH value on the surface of the fabric is small, the hydrolysis reaction of the strong alkali on the dye on the fabric is reduced, and the generation of loose color is reduced, thereby improving the color fastness of the fabric in a strong alkali environment. The hydrophilic alkali-resistant color fixing agent prepared by the invention has excellent color fixing effect and alkali resistance, good hydrophilicity and small fabric color change.
Detailed Description
In a preferred embodiment, the hydrophilic strong base resistant fixing agent of the present invention comprises a moles of copolymerized units of formula (I), b moles of copolymerized units of formula (II), c moles of copolymerized units of formula (III) and d moles of copolymerized units of formula (IV):
in formulae (I) to (IV):
R1、R4、R5、R6、R7、R8、R9、R11and R12Are each H or C1-C3An alkyl group;
R2is C1-C3Alkyl or benzyl;
R3is C1-C2An alkylene group;
R10are respectively C1-C2Alkylene or phenylene;
R13is C1-C3Alkyl or phenyl;
the molar ratio of a to b to c to d is 1 (0.3-0.9) to (0.25-0.85) to (0.5-1.2), and the weight average molecular weight of the hydrophilic alkali-resistant color fixing agent is 25000-100000.
In a more preferred embodiment, R1、R4、R5、R6、R7、R8、R9、R11And R12Are each H, methyl or ethyl;
R2is methyl or benzyl;
R3is C1-C2An alkylene group;
R10are respectively C1-C2Alkylene or m-phenylene;
R13is methyl or phenyl;
the molar ratio of a to b to c to d is 1 (0.4-0.8) to (0.3-0.7) to (0.6-1.0), and the weight average molecular weight of the hydrophilic alkali-resistant color fixing agent is 30000-80000.
In a more preferred embodiment, the hydrophilic alkali-resistant fixing agent of the present invention is a block copolymer or a random copolymer.
In a preferred embodiment of the present invention, the present invention provides a method for preparing the above hydrophilic strong base-resistant fixing agent, which comprises the following steps:
1) adding a mol of (methyl) acryloyl oxygen quaternary ammonium salt cationic monomer represented by the formula (V), b mol of vinyl ether monomer containing amino group represented by the formula (VI), c mol of enamine monomer represented by the formula (VII), d mol of unsaturated carboxylic acid monomer represented by the formula (VIII) and water (preferably deionized water) into a reaction kettle for stirring. Preferably, the stirring is carried out at 40 to 80 ℃ for 10 to 20 minutes. In the above monomer mixture, it is preferable to optionally add 10 to 25 mass% of an acid agent and 20 to 60 mass% of water, based on the total weight of the monomers. The above acid agent is preferably a strong acid, and more preferably an inorganic strong acid such as hydrochloric acid and sulfuric acid.
2) Based on the total weight of the monomers, dripping 1-2 mass percent of free radical initiator to initiate free radical polymerization reaction, and finishing dripping within 1-3 hours;
3) raising the temperature to 50-100 ℃, preferably raising the temperature to 60-90 ℃, and keeping the temperature for about 1-4 hours;
4) cooling to 25-80 ℃, preferably cooling to 30-70 ℃, adjusting the pH value to 7-8 by NaOH, dropwise adding (alkyl) epichlorohydrin, preferably (methyl) epichlorohydrin or epichlorohydrin, finishing dropwise adding for 1-2 hours, and keeping the temperature for 2-3 hours to obtain the hydrophilic alkali-resistant color fixing agent.
In a more preferred embodiment of the present invention, the amount of (alkyl) epichlorohydrin used is greater than or equal to the total moles of the amine group-containing vinyl ether monomer represented by formula (VI) and the enamine monomer represented by formula (VII), i.e., greater than or equal to the moles of b + c.
In a more preferred embodiment of the invention, the free radical initiator comprises a peroxyacid salt, such as ammonium persulfate or percarbonate. More preferably, a reducing agent such as sodium sulfite, sodium bisulfite and the like is added in addition to the peroxyacid salt.
In another preferred embodiment of the present invention, the amine group-containing vinyl ether monomer represented by (VI) and the enamine monomer represented by formula (VII) may be prepared by quaternizing with (alkyl) epichlorohydrin represented by formula (IX), and then free-radically polymerizing with the (meth) acryloyloxy quaternary ammonium salt cationic monomer represented by formula (V) and the unsaturated carboxylic acid monomer represented by formula (VIII) in water, respectively or simultaneously.
The hydrophilic alkali-resistant color fixing agent prepared by the method has excellent color fixing effect and alkali resistance, good hydrophilicity and small color change of fabrics.
Examples
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
In each example, all the materials and fabrics were commercially available.
The weight average molecular weight of the prepared product and the application and performance of the product on textiles are determined as follows:
1) weight average molecular weight determination: measurement was carried out by using HLC-8320GPC type gel permeation chromatography (Nippon Tosoh Co., Ltd.).
2) The application process in the textile comprises the following steps:
sample preparation: red cotton knitted fabric
The process comprises the following steps: dipping color fixing liquid (1% o.w.f., bath ratio of 1:20, 40 ℃ x 30min) → dewatering → drying.
3) Textile performance determination standards:
and (3) fastness to water bubbles: heating the cocoon washing powder to 90 ℃ at a bath ratio of 1:50, placing a cloth sample treated by a color fixing agent, oscillating the cloth sample in a dyeing oscillator for 5min, taking out the cloth sample, and determining the color depth of the working solution according to a grey sample card for color change evaluation of GB/T250 + 2008 textile color fastness test;
fastness to soaping: measured according to GB/T3921-;
color fastness to perspiration: measuring according to the color fastness to perspiration of GB/T3922 and 2013 textile color fastness test;
color fastness to rubbing: the determination is carried out according to GB/T3920 and 2008 textile color fastness test rubbing color fastness;
color change: determining according to a grey sample card for evaluating color change in GB/T250 + 2008 textile color fastness test;
hydrophilicity: the shorter the time, the better the hydrophilicity, as measured by AATCC 79-2010.
Example 1
30g of acryloyloxyethyl trimethyl ammonium chloride (80%; M193.67; n 0.1239mol), 8g of 2- (diethylamine) ethanol vinyl ether (M143; n 0.05594mol), 4.6g N-ethyl methyl allylamine (M99.17; n 0.04638mol), 10g of crotonic acid (M86.09; n 0.1162mol), 11g of hydrochloric acid (37%; M36.46; n 0.1116mol) and 26.4g of deionized water were placed in a four-neck flask equipped with a stirrer, a thermometer and a reflux condenser, and after stirring at 60 ℃ for 10min, 1% ammonium persulfate aqueous solution was added dropwise, 1.5h of dropwise addition was completed, the temperature was increased to 80 ℃, the temperature was maintained for 2.5h, the temperature was decreased to 40 ℃, the pH was adjusted to 7-8 with NaOH, 10g of epichlorohydrin (M92.52; n 0.1081mol) was added dropwise, the temperature was maintained for 1.5h, and the temperature was maintained for 3 h. Obtaining the hydrophilic alkali-resistant color fixing agent 1. The application effects are shown in tables 1 and 2. The weight average molecular weight of the hydrophilic alkali-resistant color fixing agent 1 is 35000.
Example 2
37g of methacryloyloxyethyl trimethyl ammonium chloride (75%; M207.7; n. 0.1336mol), 10g of 2- (diethylamine) ethanolic vinyl ether (M143; n. 0.06993mol), 5g N-methyl-2-methylallylamine (M. 85.15; n. 0.05872mol), 8g of crotonic acid (M. 86.09; n. 0.09293mol), 12g of hydrochloric acid (37%; M. 36.46; n. 0.1218mol) and 16g of deionized water were placed in a four-neck flask equipped with a stirrer, a thermometer and a reflux condenser, and after stirring at 70 ℃ for 10min, 1h of an aqueous ammonium persulfate solution was added dropwise, the temperature was raised to 75 ℃, the temperature was maintained for 3h, the temperature was lowered to 50 ℃, the pH was adjusted to 7-8 with NaOH, 12g of epichlorohydrin (M. 92.52; n. 0.1297mol) was added dropwise, the temperature was maintained for 2h, and the temperature was maintained for 2.5 h. And obtaining the hydrophilic alkali-resistant color fixing agent 2. The application effects are shown in tables 1 and 2. The weight average molecular weight of the hydrophilic strong base resistant color fixing agent 2 is 67000.
Example 3
38g of methacryloyloxyethyl dimethylbenzyl ammonium chloride (60%; M: 281.78; n: 0.08091mol), 8g of 2- (diethylamine) ethanol vinyl ether (M: 143; n: 0.05594mol), 5g N-ethyl methallylamine (M: 99.17; n: 0.0504mol), 12g of cinnamic acid (M: 148.16; n: 0.0810mol), 11g of hydrochloric acid (37%; M: 36.46; n: 0.1116mol), and 14g of deionized water were added to a four-neck flask equipped with a stirrer, a thermometer, and a reflux condenser, and after stirring at 80 ℃ for 10min, 1% ammonium persulfate and 1% sodium bisulfite aqueous solution were added dropwise, 2h of dropwise addition was completed, the temperature was raised to 90 ℃, the temperature was maintained for 2h, the temperature was reduced to 60 ℃, the pH was adjusted to 7-8 with NaOH, and 12g of methyl epichlorohydrin (M: 106.55; n: 0.1126mol) was added dropwise, and the temperature was maintained for 2 h. Obtaining the hydrophilic alkali-resistant color fixing agent 3. The application effects are shown in tables 1 and 2. The weight average molecular weight of the hydrophilic strong-base-resistant color fixing agent 3 is 55000.
Example 4
15g of methacryloxyethyl trimethyl ammonium chloride (75%; M207.7; n 0.05416mol), 20g of methacryloxyethyl dimethyl benzyl ammonium chloride (60%; M281.78; n 0.04259mol), 9g of 2- (diethylamine) ethanol vinyl ether (M143; n 0.06294mol), 6.6g of 3-vinylaniline (M119.16; n 0.05539mol), 10g of cinnamic acid (M148.16; n 0.06749mol), 13g of hydrochloric acid (37%; M36.46; n 0.1319mol) and 13.4g of deionized water are placed in a four-neck flask equipped with a stirrer, a thermometer and a reflux condenser, 1% ammonium persulfate and 1% aqueous sodium sulfite are added dropwise after stirring at 70 ℃ for 10min, the addition is completed for 2h, the temperature is increased to 85 ℃, the temperature is maintained for 2.5h, the temperature is then decreased to 70 ℃, the pH is adjusted to 7-8 with NaOH, the addition is started, the addition is completed for 2h, the temperature is increased to 13.8, the pH is adjusted to 13g of epichlorohydrin (M106.55; M586; n 0.1220mol), after the dropwise addition is finished within 1.5h, the temperature is kept for 2.5 h. And obtaining the hydrophilic alkali-resistant color fixing agent 4. The application effects are shown in tables 1 and 2. The weight average molecular weight of the hydrophilic alkali-resistant color fixing agent 4 is 43000.
The application effect of each example is compared with the application effect of a commercial fixing agent, and is shown in tables 1 and 2.
TABLE 1 Effect of application (acid fixation pH 5)
TABLE 1 Effect of application (alkaline fixation)
As can be seen from tables 1 and 2, the color fixing agent prepared by the invention has excellent color fixing effect no matter under acidic color fixing conditions or alkaline color fixing conditions, the color fixing effect is still outstanding even under NaOH 300g/L, and meanwhile, fabric color is reduced and hydrophilicity is good. The color fixing effect of the color fixing agent prepared by the invention is better than that of a common color fixing agent A sold in the market and a commercially available alkali-resistant color fixing agent B sold in the market.
Claims (7)
1. A method for preparing a hydrophilic alkali-resistant color fixing agent comprises the following steps:
1) adding a mol of a comonomer represented by the formula (V), b mol of a comonomer represented by the formula (VI), c mol of a comonomer represented by the formula (VII), d mol of a comonomer represented by the formula (VIII), water and inorganic strong acid into a reaction kettle, and stirring;
in the formula (V):
R1is H or C1-C5An alkyl group, a carboxyl group,
R2is C1-C8Alkyl or C7-C11Aralkyl group;
in formula (VI):
R3is C1-C5An alkylene group or a substituted alkylene group,
R4and R5Are each H or C1-C5An alkyl group;
in formula (VII):
R7、R8、R9、R11and R12Are each H or C1-C5An alkyl group, a carboxyl group,
R10is C1-C5Alkylene or C6-C10An arylene group;
in formula (VIII):
R13is C1-C8Alkyl or C6-C10An aryl group;
2) adding a free radical initiator to carry out polymerization reaction; and
3) adjusting the pH value to 7-8 by NaOH, adding epichlorohydrin or alkyl epichlorohydrin represented by a formula (IX) to perform quaternization reaction,
in formula (IX):
R6is H or C1-C5An alkyl group;
wherein the molar ratio of a to b to c to d is 1 (0.1-1) to (0.4-1.5).
2. The method of claim 1, wherein: r1、R4、R5、R7、R8、R9、R11And R12Are each H or C1-C3An alkyl group;
R2is C1-C3Alkyl or benzyl;
R3is C1-C2An alkylene group;
R10are respectively C1-C2Alkylene or phenylene;
R13is C1-C3Alkyl or phenyl;
the molar ratio of a, b, c and d is 1 (0.3-0.9) to (0.25-0.85) to (0.5-1.2), the temperature of the polymerization reaction in the step 2) is 50-100 ℃, and the temperature of the quaternization reaction in the step 3) is 25-80 ℃.
3. The method of claim 2, wherein R is1、R4、R5、R7、R8、R9、R11And R12Are each H, methyl or ethyl;
R2is methyl or benzyl;
R3is C1-C2An alkylene group;
R10are respectively C1-C2Alkylene or m-phenylene;
R13is methyl or phenyl;
the molar ratio of a, b, c and d is 1 (0.4-0.8) to (0.3-0.7) to (0.6-1.0), the polymerization temperature in the step 2) is 60-90 ℃, and the quaternization temperature in the step 3) is 30-70 ℃.
4. The process of claim 1, wherein the moles of epichlorohydrin or alkyl epichlorohydrin exceed the total moles of b + c.
5. The method of claim 1, wherein the free radical initiator comprises ammonium persulfate.
6. The method of claim 1, wherein the water used in step a) is deionized water.
7. A hydrophilic strong base resistant fixing agent prepared by the method of any one of claims 1-6.
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| CN102797170A (en) * | 2012-09-06 | 2012-11-28 | 苏州联胜化学有限公司 | Formaldehyde-free fixing agent and preparation method thereof |
| CN104313926A (en) * | 2014-11-17 | 2015-01-28 | 上海雅运纺织助剂有限公司 | Preparation method for hydrophilic dye-fixing agent for reactive dyeing |
| CN107216428A (en) * | 2017-07-07 | 2017-09-29 | 苏州联胜化学有限公司 | Cotton perspiration resistance aldehyde-free colour stabilizer and its preparation method and application |
| JP2018104850A (en) * | 2016-12-27 | 2018-07-05 | 日東紡績株式会社 | Dye fixing agent for cellulose fiber |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102797170A (en) * | 2012-09-06 | 2012-11-28 | 苏州联胜化学有限公司 | Formaldehyde-free fixing agent and preparation method thereof |
| CN104313926A (en) * | 2014-11-17 | 2015-01-28 | 上海雅运纺织助剂有限公司 | Preparation method for hydrophilic dye-fixing agent for reactive dyeing |
| JP2018104850A (en) * | 2016-12-27 | 2018-07-05 | 日東紡績株式会社 | Dye fixing agent for cellulose fiber |
| CN107216428A (en) * | 2017-07-07 | 2017-09-29 | 苏州联胜化学有限公司 | Cotton perspiration resistance aldehyde-free colour stabilizer and its preparation method and application |
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