阅读说明：本技术 一种无醛纺织固色剂的制备方法 (A kind of preparation method of no aldehyde textile dye-Fixing agents ) 是由 陈桂川 于 2019-08-01 设计创作，主要内容包括：本发明涉及一种无醛纺织固色剂的制备方法,属于纺织技术领域。本发明通过添加羧甲基纤维素水凝胶,制备无醛纺织固色剂,羧甲基纤维素的基团可以与染料及纤维间产生形成氢键、配位键和范德华力结合,提高染料的固色率,羧甲基纤维素的分子量高,容易在织物表面形成一层薄膜,可对染料分子及其水溶性基团进行包覆,增加染料在水洗时从织物表面溶落的难度,提高湿处理牢度羧甲基纤维素可以与金属盐、无机盐经水解或解凝形成溶胶,微小的溶胶粒子具有极大的比表面积和较高的比表面能,促使粒子形成三维网状结构,在织物上形成一层氧化物薄膜,对染料分子及其水溶性基团进行包覆,增加染料在水洗时从织物表面溶落的难度,提高湿处理牢度。(The present invention relates to a kind of preparation methods of no aldehyde textile dye-Fixing agents, belong to textile technology field.The present invention passes through addition carboxymethyl cellulose hydrogel, preparation is without aldehyde textile dye-Fixing agents, the group of carboxymethyl cellulose can generate between dyestuff and fiber and form hydrogen bond, coordinate bond and Van der Waals force combine, improve the degree of fixation of dyestuff, the molecular weight of carboxymethyl cellulose is high, it is easy to form thin film in fabric surface, dye molecule and its water soluble group can be coated, increase dyestuff in washing from the molten difficulty fallen of fabric surface, improving wet colour fastness carboxymethyl cellulose can be with metal salt, inorganic salts, which are hydrolyzed or solved to coagulate, forms colloidal sol, small sol particles have great specific surface area and higher specific surface energy, particle is promoted to form tridimensional network, one layer of sull is formed on the fabric, dye molecule and its water soluble group are coated, increase dyestuff in washing from the molten difficulty fallen of fabric surface , improve wet colour fastness.)

1. a kind of preparation method of no aldehyde textile dye-Fixing agents, which is characterized in that specific preparation step are as follows:

(1) spermine, diethylenetriamine, triethylamine are added to absolute ethanol, under room temperature with 160 ~ 200r/min revolving speed stirring 10 ~ 20min obtains polyamines ethanol solution；

(2) polyamines ethanol solution is slowly added dropwise with the flow velocity of 20 ~ 30mL/min into bisphenol A type epoxy resin, at 30 ~ 40 DEG C Water bath condition under 20 ~ 30min is stirred to react with 200 ~ 240r/min revolving speed, then be warming up to 60 ~ 80 DEG C with 300 ~ 320r/min Revolving speed is stirred to react 20 ~ 30min, and heat preservation obtains ring-opening reaction liquid；

(3) sodium hydroxide is added in reaction solution, is stirred to react 30 in 60 ~ 80 DEG C of water bath conditions with 300 ~ 320r/min revolving speed ~ 40min obtains ring-closure reaction liquid；

(4) by carboxymethyl cellulose hydrogel be added ring-closure reaction liquid in, under room temperature with 200 ~ 240r/min revolving speed stirring 40 ~ 60min, the formic acid that mass concentration 10% is added dropwise adjust pH6 ~ 7, obtain no aldehyde textile dye-Fixing agents.

2. a kind of preparation method of no aldehyde textile dye-Fixing agents according to claim 1, which is characterized in that the bisphenol-A The weight of type epoxy resin, spermine, diethylenetriamine, triethylamine, carboxymethyl cellulose hydrogel, dehydrated alcohol, sodium hydroxide Part is 50 ~ 60 parts of bisphenol A type epoxy resins, 10 ~ 12 parts of spermine, 5 ~ 6 parts of diethylenetriamines, 5 ~ 6 parts of triethylamines, 20 ~ 24 parts of carboxylics Methyl cellulose hydrogel, 25 ~ 30 parts of dehydrated alcohols, 5 ~ 6 parts of sodium hydroxides.

3. a kind of preparation method of no aldehyde textile dye-Fixing agents according to claim 1, which is characterized in that step (2) is described Heating rate be 1 ~ 2 DEG C/min.

4. a kind of preparation method of no aldehyde textile dye-Fixing agents according to claim 1, which is characterized in that step (4) is described PH adjust using mass concentration 10% formic acid.

5. a kind of preparation method of no aldehyde textile dye-Fixing agents according to claim 1, which is characterized in that step (4) is described Carboxymethyl cellulose hydrogel specific preparation step are as follows:

(1) carboxymethyl cellulose is added in deionized water, is stirred under conditions of 40 ~ 50 DEG C with 800 ~ 860r/min revolving speed strength 40 ~ 60min is mixed, cmc soln is obtained；

(2) glycerine is added in cmc soln, 1 ~ 2h is stirred with 400 ~ 500r/min revolving speed under room temperature, must be mixed Solution；

(3) mixed solution is placed in supercentrifuge, 5 ~ 10min is centrifugated with 2000 ~ 3000r/min revolving speed under room temperature, Obtain deaeration solution；

(4) deaeration solution is placed in convection oven, dry 4 ~ 6h, obtains solid under conditions of 40 ~ 60 DEG C；

(5) solid is added in aluminum sulfate solution, 1 ~ 3min is impregnated under room temperature, taken out, obtain carboxymethyl cellulose hydrogel.

6. a kind of preparation method of no aldehyde textile dye-Fixing agents according to claim 5, which is characterized in that the carboxymethyl Cellulose, glycerine, aluminum sulfate solution, deionized water parts by weight be 50 ~ 60 parts of carboxymethyl celluloses, 10 ~ 12 parts of glycerine, The aluminum sulfate solution of 100 ~ 120 parts of mass concentrations 0.1%, 100 ~ 120 parts of deionized waters.

7. a kind of preparation method of no aldehyde textile dye-Fixing agents according to claim 5, which is characterized in that step (1) is described Carboxymethyl cellulose specific preparation step are as follows:

(1) Cotton Pulp is placed in strong crusher, 40 ~ 60min is crushed under room temperature, obtains the Cotton Pulp of crushing；

(2) by the Cotton Pulp of crushing, sodium hydroxide dehydrated alcohol, it is placed in 2 ~ 3h of thermostatic ultrasonic in supersonic cleaning machine, must be alkalized Liquid；

(3) by chloroacetic acid be added alkaline solution in, under 70 ~ 80 DEG C of water bath condition with 200 ~ 240r/min stirring etherificate 3 ~ 5h, filtering, takes solid, obtains crude carboxymethyl cellulose；

(4) crude carboxymethyl cellulose is washed with the acetum of mass concentration 1% to neutrality, then washs 3 ~ 5 with dehydrated alcohol It is secondary, it is placed in baking oven dry 30 ~ 40min under conditions of 40 ~ 50 DEG C, obtains carboxymethyl cellulose.

8. a kind of preparation method of no aldehyde textile dye-Fixing agents according to claim 7, which is characterized in that the cotton pulp The dregs of rice, dehydrated alcohol, sodium hydroxide, chloroacetic parts by weight are 40 ~ 50 parts of Cotton Pulps, 120 ~ 150 parts of dehydrated alcohols, 20 ~ 25 parts Sodium hydroxide, 40 ~ 50 parts of monoxones.

9. a kind of preparation method of no aldehyde textile dye-Fixing agents according to claim 7, which is characterized in that step (2) is described Ultrasound condition be 40 ~ 50 DEG C, 3000 ~ 4000Hz.

10. a kind of preparation method of no aldehyde textile dye-Fixing agents according to claim 7, which is characterized in that step (4) is described The acetum washed crude carboxymethyl cellulose to neutrality using mass concentration 1%.

Technical field

The present invention relates to a kind of preparation methods of no aldehyde textile dye-Fixing agents, belong to textile technology field.

Background technique

With the raising of human material's civilization and people's environmental protection, the continuous enhancing of health perception, and country is to textile Hygienic requirements it is higher and higher, pass in succession through regulation nonimportation and sale containing carcinogen such as free formaldehyde etc. directly, The textile etc. for connecing and being potentially carcinogenic.Meanwhile with the increase that China Textile exports, textile enterprise is to formaldehyde-free color fixing agent Demand is also growing day by day.Traditional color fixing agent is synthesized by formaldehyde, dicyandiamide and ammonium chloride etc., easily causes discoloration, the hand of product dyed thereby Feel coarse etc., especially content of formaldehyde is higher, influences the health of human body dress, has not met International Textile requirement.

Color fixing agent, as the term suggests just refer to the one or moreization added to improve dyestuff fixed fastness on the fabric Close object.Currently, referring mainly to for reactive dye, acid dyes etc. after textile dyeing, keep dyestuff solid securely using color fixing agent On the fabric, enhance the fixing properties such as fastness to wet rubbing, the perspiration fastness of its color.Reactive dye, acid dyes etc. are water-soluble Property dye chromatography it is more complete, coloured light is more bright-coloured, but wet fastness is undesirable, fade, staining phenomenon it is serious, some dyes are from having contaminated It falls down on the wet fiber of color, fabric color itself is not only made to shoal, but also the other fibers for having dyed other colors can be stain, Cause color chaotic.In order to improve the fastness of dyed fabric, people often carry out fixation using certain auxiliary agents after textile dyeing Processing, this auxiliary agent that can improve wet fastness of dyed fabric etc. is color fixing agent.

Color fixing agent is one of indispensable important auxiliary agent in dyeing.For a long time, people continue to use always dicyandiamide Textile fixation treatment is carried out with the resin color fixing agent of formaldehyde condensation, fixation effect is good, but has research to send out from last century end Existing such color fixing agent contains very high free formaldehyde after arrangement, will lead to chafing even after its fixation of infantile clothes Ulcer occurs, so as to cause the attention that people study aldehyde-free colour stabilizer, at present volatilization of many countries to formaldehyde in textile Amount has stringent limitation.

The quality of color fixing agent performance directly affects the fastness of the dyestuff resistance to wet process of color on the fabric, determines fabric table The quality of face dyeing effect.The wet-milling fastness and color fastness to washing of existing aldehyde-free colour stabilizer are not ideal enough, the combination to dyestuff Power is bad, and the product dyed thereby for being especially difficult to fixation to bright red, emerald green orchid etc. is easy to appear the problem of hanging color loosely when arranging, and And existing color fixing agent all there are problems that having an impact reactive dyeing coloured light, affect fabric dye to a certain extent The color of color.

Aldehyde-free colour stabilizer experienced the condensation product of the condensation resin from dicyandiamide, epoxychloropropane to quaternary ammonium in China

The development course of salt compounds, synthesis process be all based on introduce cation group enable color fixing agent with it is various

Dyestuff (reactive dye, acid dyes, direct dyes etc.) is combined into salt and introduces reactive group, makes color fixing agent

It is crosslinked to reach fixation purpose with fabric fibre.The sixties in last century to the eighties is a height of color fixing agent research In peak period, the increasingly strict requirement with Overseas Textile Industry product market to the color fastness and content of formaldehyde of product dyed thereby, China is from upper The later period eighties in century reinforces development and the preferable formaldehydeless novel color fixing agent of the novel raising fastness properties of application, with substitution Traditional color fixing agent containing formaldehyde.Judging from the current situation, the aldehyde-free colour stabilizer used is made of amine and epoxychloropropane mostly Polycationic color fixing agent, and be further improved or be combined on this basis and improve fixation ability with comprehensive.From The development and application situation of color fixing agent is seen at present, and color fixing agent has a biggish achievement without hydroformylation and colour fixation, but still some It still needs further improvement for index such as wet rubbing fastness, light fastness and chlorine fastness etc..

Summary of the invention

The technical problems to be solved by the invention: for color fixing agent wet rubbing fastness, light fastness and chlorine fastness etc. The problem of it still needs further improvement provides a kind of preparation method of no aldehyde textile dye-Fixing agents.

In order to solve the above technical problems, the technical solution adopted by the present invention is that:

(1) spermine, diethylenetriamine, triethylamine are added to absolute ethanol, under room temperature with 160 ~ 200r/min revolving speed stirring 10 ~ 20min obtains polyamines ethanol solution；

(2) polyamines ethanol solution is slowly added dropwise with the flow velocity of 20 ~ 30mL/min into bisphenol A type epoxy resin, at 30 ~ 40 DEG C Water bath condition under 20 ~ 30min is stirred to react with 200 ~ 240r/min revolving speed, then be warming up to 60 ~ 80 DEG C with 300 ~ 320r/min Revolving speed is stirred to react 20 ~ 30min, and heat preservation obtains ring-opening reaction liquid；

(3) sodium hydroxide is added in reaction solution, is stirred to react 30 in 60 ~ 80 DEG C of water bath conditions with 300 ~ 320r/min revolving speed ~ 40min obtains ring-closure reaction liquid；

(4) by carboxymethyl cellulose hydrogel be added ring-closure reaction liquid in, under room temperature with 200 ~ 240r/min revolving speed stirring 40 ~ 60min, the formic acid that mass concentration 10% is added dropwise adjust pH6 ~ 7, obtain no aldehyde textile dye-Fixing agents.

It is the bisphenol A type epoxy resin, spermine, diethylenetriamine, triethylamine, carboxymethyl cellulose hydrogel, anhydrous Ethyl alcohol, sodium hydroxide parts by weight be 50 ~ 60 parts of bisphenol A type epoxy resins, 10 ~ 12 parts of spermine, 5 ~ 6 parts of diethylenetriamines, 5 ~ 6 Part triethylamine, 20 ~ 24 parts of carboxymethyl cellulose hydrogels, 25 ~ 30 parts of dehydrated alcohols, 5 ~ 6 parts of sodium hydroxides.

Heating rate described in step (2) is 1 ~ 2 DEG C/min.

PH described in step (4) adjusts the formic acid using mass concentration 10%.

The specific preparation step of carboxymethyl cellulose hydrogel described in step (4) are as follows:

(1) carboxymethyl cellulose is added in deionized water, is stirred under conditions of 40 ~ 50 DEG C with 800 ~ 860r/min revolving speed strength 40 ~ 60min is mixed, cmc soln is obtained；

(2) glycerine is added in cmc soln, 1 ~ 2h is stirred with 400 ~ 500r/min revolving speed under room temperature, must be mixed Solution；

(3) mixed solution is placed in supercentrifuge, 5 ~ 10min is centrifugated with 2000 ~ 3000r/min revolving speed under room temperature, Obtain deaeration solution；

(4) deaeration solution is placed in convection oven, dry 4 ~ 6h, obtains solid under conditions of 40 ~ 60 DEG C；

(5) solid is added in aluminum sulfate solution, 1 ~ 3min is impregnated under room temperature, taken out, obtain carboxymethyl cellulose hydrogel.

The carboxymethyl cellulose, glycerine, aluminum sulfate solution, deionized water parts by weight be 50 ~ 60 parts of carboxymethyls Cellulose, 10 ~ 12 parts of glycerine, the aluminum sulfate solution of 100 ~ 120 parts of mass concentrations 0.1%, 100 ~ 120 parts of deionized waters.

The specific preparation step of carboxymethyl cellulose described in step (1) are as follows:

(1) Cotton Pulp is placed in strong crusher, 40 ~ 60min is crushed under room temperature, obtains the Cotton Pulp of crushing；

(2) by the Cotton Pulp of crushing, sodium hydroxide dehydrated alcohol, it is placed in 2 ~ 3h of thermostatic ultrasonic in supersonic cleaning machine, must be alkalized Liquid；

(3) by chloroacetic acid be added alkaline solution in, under 70 ~ 80 DEG C of water bath condition with 200 ~ 240r/min stirring etherificate 3 ~ 5h, filtering, takes solid, obtains crude carboxymethyl cellulose；

(4) crude carboxymethyl cellulose is washed with the acetum of mass concentration 1% to neutrality, then washs 3 ~ 5 with dehydrated alcohol It is secondary, it is placed in baking oven dry 30 ~ 40min under conditions of 40 ~ 50 DEG C, obtains carboxymethyl cellulose.

The Cotton Pulp, dehydrated alcohol, sodium hydroxide, chloroacetic parts by weight are 40 ~ 50 parts of Cotton Pulps, 120 ~ 150 Part dehydrated alcohol, 20 ~ 25 parts of sodium hydroxides, 40 ~ 50 parts of monoxones.

Ultrasound condition described in step (2) is 40 ~ 50 DEG C, 3000 ~ 4000Hz.

Crude carboxymethyl cellulose washed to neutrality described in step (4) molten using the acetic acid of mass concentration 1% Liquid.

The present invention is compared with other methods, and advantageous effects are:

(1) present invention is using bisphenol A type epoxy resin and spermine, diethylenetriamine, triethylamine as raw material, and preparation is without aldehyde weaving fixation Agent, spermine, diethylenetriamine, triethylamine belong to polyamine compounds, contain cation group in molecule, these cations The fiber that surface is negatively charged in alkalinity bath can be made to combine a large amount of cation groups, promote the surface cation of fiber hole Change, barrier potential when reducing dyeing, makes dye anion be easier to adsorb, improve dyeability, and these cation groups can also With the anionic group of dyestuff with ionic bond in conjunction with, formed insoluble or indissoluble macromolecule color lake, enclose the water of dye molecule Soluble group and be deposited on inside and outside fiber, to improve the Washing of dyed fabric, polyamine compounds can also be with epoxy Epoxy group in resin reacts, epoxy group can under the high temperature conditions open loop and in cellulose fibre hydroxyl occur Reaction, meanwhile, through the cation group of polyamine compounds in conjunction with anionic dye, enhance between dyestuff and fiber significantly Binding force, greatly improve fixation ability, improve the crocking resistance of dyestuff, the reactive group energy in polyamine compounds Carry out self-crosslinking and form the protective film with some strength, formed and the dyestuff in not formed color lake all anchors at fiber surface and Enhance colour fixation, and on the active group and fiber in dye molecule hydroxyl or amido crosslink, color fixing agent serves as Function served as bridge, reduces the water solubility of dyestuff, to improve the wet boiling hot, soaping fastness of dye object；

(2) present invention is prepared by addition carboxymethyl cellulose hydrogel without aldehyde textile dye-Fixing agents, the group of carboxymethyl cellulose It can generate and be formed in conjunction with hydrogen bond, coordinate bond and Van der Waals force between dyestuff and fiber, improve the degree of fixation of dyestuff, carboxymethyl is fine The molecular weight for tieing up element is high, is easy to form thin film in fabric surface, can coat to dye molecule and its water soluble group, Increase dyestuff in washing from the molten difficulty fallen of fabric surface, improve wet colour fastness carboxymethyl cellulose can with metal salt, Inorganic salts, which are hydrolyzed or solved to coagulate, forms colloidal sol, and small sol particles have great specific surface area and higher specific surface energy, Promote particle to form tridimensional network, forms one layer of sull on the fabric, this tunic is three-dimensional fixed by dyestuff, with saturating The form of bright film is bonded and is closed to dyestuff, is coated to dye molecule and its water soluble group, is increased dyestuff and is existed From the molten difficulty fallen of fabric surface when washing, wet colour fastness is improved.

Specific embodiment

According to parts by weight, respectively weigh 40 ~ 50 parts of Cotton Pulps, 120 ~ 150 parts of dehydrated alcohols, 20 ~ 25 parts of sodium hydroxides, Cotton Pulp is placed in strong crusher by 40 ~ 50 parts of monoxones, and 40 ~ 60min is crushed under room temperature, the Cotton Pulp of crushing is obtained, by powder It in broken Cotton Pulp, sodium hydroxide dehydrated alcohol, is placed in supersonic cleaning machine, under 40 ~ 50 DEG C, the adjusting of 3000 ~ 4000Hz 2 ~ 3h of thermostatic ultrasonic, obtains alkaline solution, chloroacetic acid is added in alkaline solution, with 200 ~ 240r/ under 70 ~ 80 DEG C of water bath condition Min stirring 3 ~ 5h of etherificate, filtering take solid, obtain crude carboxymethyl cellulose, by crude carboxymethyl cellulose mass concentration 1% Acetum wash to neutrality, then washed 3 ~ 5 times with dehydrated alcohol, be placed in baking oven dry 30 under conditions of 40 ~ 50 DEG C ~ 40min obtains carboxymethyl cellulose, then according to parts by weight, weighs 50 ~ 60 parts of carboxymethyl celluloses, 10 ~ 12 parts the third three respectively Alcohol, the aluminum sulfate solution of 100 ~ 120 parts of mass concentrations 0.1%, 100 ~ 120 parts of deionized waters, by carboxymethyl cellulose addition go from In sub- water, with 800 ~ 860r/min revolving speed 40 ~ 60min of strong stirring under conditions of 40 ~ 50 DEG C, it is molten to obtain carboxymethyl cellulose Glycerine is added in cmc soln liquid, stirs 1 ~ 2h under room temperature with 400 ~ 500r/min revolving speed, must mix molten Mixed solution is placed in supercentrifuge by liquid, is centrifugated 5 ~ 10min under room temperature with 2000 ~ 3000r/min revolving speed, is obtained de- Solution is steeped, deaeration solution is placed in convection oven, dry 4 ~ 6h, obtains solid, sulphur is added in solid under conditions of 40 ~ 60 DEG C In sour aluminum solutions, 1 ~ 3min is impregnated under room temperature, is taken out, is obtained carboxymethyl cellulose hydrogel, then according to parts by weight, weigh respectively 50 ~ 60 parts of bisphenol A type epoxy resins, 10 ~ 12 parts of spermine, 5 ~ 6 parts of diethylenetriamines, 5 ~ 6 parts of triethylamines, 20 ~ 24 parts of carboxymethyls Anhydrous second is added in spermine, diethylenetriamine, triethylamine by cellulose aquagel, 25 ~ 30 parts of dehydrated alcohols, 5 ~ 6 parts of sodium hydroxides In alcohol, 10 ~ 20min is stirred with 160 ~ 200r/min revolving speed under room temperature, obtains polyamines ethanol solution, by polyamines ethanol solution with 20 ~ The flow velocity of 30mL/min is slowly added dropwise into bisphenol A type epoxy resin, with 200 ~ 240r/min under 30 ~ 40 DEG C of water bath condition Revolving speed is stirred to react 20 ~ 30min, then is warming up to 60 ~ 80 DEG C with 1 ~ 2 DEG C of rate and is stirred to react 20 with 300 ~ 320r/min revolving speed ~ 30min, heat preservation, obtains ring-opening reaction liquid, and sodium hydroxide is added in reaction solution, 60 ~ 80 DEG C of water bath conditions with 300 ~ 320r/min revolving speed is stirred to react 30 ~ 40min, obtains ring-closure reaction liquid, and ring-closure reaction liquid is added in carboxymethyl cellulose hydrogel In, 40 ~ 60min is stirred with 200 ~ 240r/min revolving speed under room temperature, the formic acid that mass concentration 10% is added dropwise adjusts pH2 ~ 3, obtains no aldehyde Textile dye-Fixing agents.