CN113774691A - Printing ink auxiliary agent and preparation method thereof - Google Patents
Printing ink auxiliary agent and preparation method thereof Download PDFInfo
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- CN113774691A CN113774691A CN202111090575.3A CN202111090575A CN113774691A CN 113774691 A CN113774691 A CN 113774691A CN 202111090575 A CN202111090575 A CN 202111090575A CN 113774691 A CN113774691 A CN 113774691A
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- printing ink
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- auxiliary agent
- cyclodextrin
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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
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- D06P1/525—Polymers of unsaturated carboxylic acids or functional derivatives thereof
- D06P1/5257—(Meth)acrylic acid
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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
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
-
- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Discloses a printing ink auxiliary agent, which is obtained by copolymerization reaction of acrylic acid, sodium methacrylate sulfonate, 4-hydroxybutyl polyethylene glycol vinyl ether and a beta-cyclodextrin monomer with a polymerizable group; the beta-cyclodextrin monomer with a polymerizable group is selected from beta-cyclodextrin monomers of terminal acrylate. In addition, a preparation method of the printing ink auxiliary agent is also disclosed. The printing ink additive has better dispersion stability and storage stability.
Description
Technical Field
The invention belongs to the technical field of digital printing, and particularly relates to a printing ink auxiliary agent and a preparation method thereof.
Background
Digital printing is a new printing technology in the textile industry in the last two decades, and a printing pattern is digitalized through an input device such as a scanner and the like and is input into a computer; the micro-piezoelectric ink jet system is controlled by special software to directly jet printing ink onto a textile medium to form a required printing pattern. Compared with the traditional printing, the digital printing has the advantages of low energy consumption, low pollution, rapidness, flexibility and the like, can meet the customer requirements of personalized customization, small-batch production and the like while ensuring high printing quality, has wide market application prospect, and is an important development direction for printing production and processing. With the annual rise of labor cost and the stricter environmental regulations, more and more printing enterprises begin to transform production modes to the digital printing industry.
In the process of industrial development, some problems need to be solved, for example, a micro-piezoelectric nozzle is easy to block, the color of a printed fabric is not bright enough, the printed pattern is not clear, the edge of the printed fabric has a burr phenomenon, the fabric has poor rubbing fastness and washing fastness, the ink storage stability is poor, the ink is inconsistent with the performance parameters of the nozzle, and the printing cost is still high. These specific problems are more or less linked to the performance parameters of the printing inks and, in order to realize the fundamental changes in the textile industry, the solution of these specific problems must be used as a grip.
Printing ink is used as a key consumable in a digital printing process, the cost occupies about 40% of the total production cost, so that the printing ink is one of the key influencing factors of printing development, and the research and development of the ink must be emphasized in the digital printing industrialization process.
Textile inkjet printing inks are classified into dye inks and pigment inks, depending on the colorant used in the ink. Theoretically, all dyes for textile dyeing and printing can be prepared into digital printing ink, but the types of digital printing ink on the market are mainly reactive dye ink, acid dye ink and disperse dye ink. At present, reactive dye ink accounts for about 30%, acid dye ink accounts for about 7%, and disperse dye ink accounts for about 60% in the market.
Wherein, the molecular structure of the reactive dye contains reactive groups, and the reactive dye can react with certain groups on the fiber during dyeing to form covalent bonds to be combined with the fiber. Therefore, the reactive dye is firmly combined with the fiber, has better washing fastness and rubbing fastness, and is the dye with the largest textile dyeing dosage at present. The active dye is desalted to prepare ink, and is mainly used for digital printing of textiles such as cotton, real silk and the like.
Because the amount of reactive dye used in the printing process is large, the bath ratio is small, and the reactive dye is easy to aggregate, urea is usually added to improve the solubility of the reactive dye. The urea molecule has hydrophilic group, and can be combined with carboxylic acid group or sulfonic acid group chemical bond on the reactive dye molecule, so that the reactive dye aggregate is rapidly dissociated, thereby improving the solubility of the dye. However, when the solubility of the reactive dye is poor or the content of the reactive dye is high, the reactive dye is liable to form aggregates, resulting in deterioration of dispersion stability and storage stability of the printing ink.
Plum preservation and the like uniformly mix the reactive dye, tetrahydrofuran, hydroxypropyl methacrylate and sodium hydroxide, stir and heat up, and keep the temperature for 8 hours to carry out substitution reaction to obtain the red macromolecular reactive dye. Then, the macromolecular reactive dye, ethylene glycol butyl ether, N-methyl-2-pyrrolidone, octyl phenol polyoxyethylene ether, ethylene glycol, a bactericide and deionized water are prepared into the macromolecular reactive dye ink. The physical and chemical parameters of the macromolecular reactive dye ink accord with the conventional parameters, and good adaptability is realized in the ink-jet printing process.
Chinese patent application CN106675093A discloses a reactive dye composition, a preparation method and application thereof. The reactive dye composition comprises a reactive dye, an auxiliary agent and water, but does not comprise a high-boiling-point solvent; the auxiliary agent comprises a macromolecular thickening agent and a macromolecular surfactant, the molecular weight of the macromolecular surfactant is 500-2000, the using amount of the macromolecular surfactant is 0.1-5%, the using amount of the macromolecular thickening agent is 0.3-10%, the using amount of the reactive dye is 3-15%, and the percentage is that the mass of each component accounts for the total mass of the reactive dye composition. The preparation method comprises mixing the above materials, and filtering. The reactive dye composition is applied to a wet printing digital printing process technology, can greatly reduce the line burr phenomenon of wet printing digital printing, improves the brightness degree and pattern definition of textiles and the color stability of the textiles printed in batches, and effectively solves the problem of print-through property of thick textiles.
However, the above prior art uses a high molecular reactive dye or a high molecular thickener and a high molecular surfactant, respectively, and the resulting printing ink still has the defect of poor dispersion stability and storage stability.
In view of the above-mentioned drawbacks of the prior art, there is still a need to find a printing ink additive with better dispersion stability and storage stability and a preparation method thereof.
Disclosure of Invention
The invention aims to provide a printing ink auxiliary agent for digital printing and a preparation method thereof. Compared with the prior art, the printing ink auxiliary agent has better dispersion stability and storage stability.
In order to solve the technical problems, the invention adopts the following technical scheme: a printing ink auxiliary agent is obtained by copolymerization reaction of acrylic acid, sodium methacrylate, 4-hydroxybutyl polyethylene glycol vinyl ether and a beta-cyclodextrin monomer with a polymerizable group; characterized in that the beta-cyclodextrin monomer with polymerizable group is selected from beta-cyclodextrin monomers of terminal acrylate.
The printing ink auxiliary agent provided by the invention is characterized in that the molar ratio of the beta-cyclodextrin monomer with the polymerizable group to the 4-hydroxybutyl polyethylene glycol vinyl ether is 1: (2-4).
Preferably, the molar ratio of the beta-cyclodextrin monomer having a polymerizable group to the 4-hydroxybutyl polyethylene glycol vinyl ether is 1: (2.5-3.5).
The printing ink auxiliary agent provided by the invention is characterized in that the beta-cyclodextrin monomer with the polymerizable group is prepared from beta-cyclodextrin and p-benzenesulfonyl chloride according to a molar ratio of 1: 1, and then sequentially reacting with 2-hydroxyethylamine and glycidyl methacrylate to obtain the compound.
The printing ink auxiliary agent provided by the invention is characterized in that the number average molecular weight Mn of 4-hydroxybutyl polyethylene glycol vinyl ether is 1500-3500 g/mol.
Preferably, the number average molecular weight Mn of the 4-hydroxybutyl polyethylene glycol vinyl ether is 1800-3000 g/mol.
The printing ink auxiliary agent provided by the invention is characterized in that the molar ratio of the beta-cyclodextrin monomer with the polymerizable group to the sodium acrylate and sodium methacrylate is 1: (5-9): (0.5-1.5).
Preferably, the molar ratio of the beta-cyclodextrin monomer having a polymerizable group to sodium acrylic acid and sodium methacrylate is 1: (6-8): (0.8-1.2).
The printing ink auxiliary agent provided by the invention is characterized in that the initiation system of the copolymerization reaction is a hydrogen peroxide/Vc system.
Advantageously, the molar ratio of hydrogen peroxide to Vc is (2.4-3.6): 1; preferably, the molar ratio of hydrogen peroxide to Vc is (2.7-3.3): 1.
the printing ink auxiliary agent provided by the invention is characterized in that the addition amount of hydrogen peroxide is 5-15% of the sum of all the comonomer moles.
Preferably, the hydrogen peroxide is added in an amount of 8 to 12% of the sum of all comonomer moles.
The printing ink auxiliary agent provided by the invention is characterized in that the reaction temperature of the copolymerization reaction is 40-80 ℃.
Preferably, the reaction temperature of the copolymerization reaction is 50 to 70 ℃.
The printing ink auxiliary agent provided by the invention has the weight average molecular weight Mw of 10000-18000 g/mol; the number average molecular weight Mn is 4000-6000 g/mol; PDI is 2.5-2.9.
Preferably, the weight average molecular weight Mw of the printing ink auxiliary agent is 12000-15000 g/mol; the number average molecular weight Mn is 4500-; PDI is 2.6-2.8.
In another aspect, the invention further provides a preparation method of the printing ink auxiliary agent, which comprises the following steps: acrylic acid, sodium methacrylate sulfonate, 4-hydroxybutyl polyethylene glycol vinyl ether and a beta-cyclodextrin monomer with a polymerizable group are subjected to copolymerization reaction in an inert atmosphere in the presence of an initiator system; after the reaction is finished, adjusting the pH value to be 6-7 to obtain a transparent solution; precipitating with precipitant, and vacuum drying.
The inventors have found that the printing ink auxiliaries are not only more dispersion-stable, but also more storage-stable than the prior art.
Detailed Description
The invention will be further illustrated with reference to specific embodiments.
It should be understood that the detailed description of the invention is merely illustrative of the spirit and principles of the invention and is not intended to limit the scope of the invention. Furthermore, it should be understood that various changes, substitutions, deletions, modifications or adjustments may be made by those skilled in the art after reading the disclosure of the present invention, and such equivalents are also within the scope of the invention as defined in the appended claims.
EXAMPLE 1 beta-Cyclodextrin monomers of terminal acrylates
To 350mL of a suspension containing 25g (22mmol) of β -cyclodextrin was added 160mL of NaOH solution (2.34M) over 30min, and the reaction was stirred vigorously at room temperature for 3h, then 8.39g (44mmol) of p-benzenesulfonyl chloride was added and the reaction was stirred vigorously at 4 ℃ for 5 h. Unreacted p-benzenesulfonyl chloride was removed by filtration, neutralized to pH 6.5 with hydrochloric acid, and allowed to stand overnight at 4 ℃. The white precipitate was obtained by suction filtration. Recrystallizing in water for 3 times, and vacuum drying at 60 ℃ for 24h to obtain a white solid 1.
20g (15.5mmol) of white solid 1, 20mL of DMMF and 20mL of 2-hydroxyethylamine were sequentially added to a round-bottom flask, and the reaction was stirred at 75 ℃ for 6h, cooled to room temperature, and the reaction was complete. The reaction solution was poured into 300mL of cold acetone to give a white precipitate as a crude product. The crude product was redissolved in water and reprecipitated using acetone; repeat for 3 times. Vacuum drying at 60 ℃ for 48h gave white solid 2.
30g (25.5mmol) of white solid 2 were dissolved in 80mL of a solvent in a volume ratio of 1: 1 DMF/H2To the O mixed solution was added 4.35g (30.6mmol) of glycidyl methacrylate, and the reaction was stirred at 80 ℃ for 10 hours. The reaction was cooled to room temperature and the reaction was complete. The reaction solution was poured into 400mL of cold acetone to obtain a white precipitate as a crude product. The crude product was redissolved in water and reprecipitated using acetone; repeat for 3 times. Vacuum drying for 48h at room temperature to obtain white solid 3, namely the beta-cyclodextrin monomer of the terminal acrylate.1H NMR(600MHz,DMSO-d6)δ:6.08(s,1H),5.97(d,1H),5.82-5.55(m,14H),4.87(s,5H),4.82(s,2H),4.53-4.35(m,7H),4.06(m,1H),3.98(m,1H),3.78-3.46(m,28H),3.45-3.22(m,16H),3.17(m,1H),2.94(m,1H),2.74-2.35(m,4H),1.89(s,2H),1.87(s,1H)。
EXAMPLE 2 Polymer printing ink adjuvant
23.8g (18mmol) of beta-cyclodextrin monomer of a terminal acrylate and 130g (54mmol) of 4-hydroxybutyl polyethylene glycol vinyl ether (number average molecular weight Mn 2400g/mol) were charged into a round-bottom flask, and 200mL of deionized water was added. Under the protection of nitrogen atmosphere, heating the mixture in water bath to 60 ℃, and stirring to obtain a transparent solution. 0.73g (21.6mmol) of hydrogen peroxide was added. 1.26g (7.2mmol) of Vc was dissolved in 50mL of deionized water to obtain an initiator solution. Then, 9.2g (126mmol) of acrylic acid and 2.9g (18mmol) of sodium methacrylate sulfonate were dissolved in 30mL of deionized water to obtain a monomer solution. And (3) dropwise adding the monomer solution and the initiator solution into the transparent solution, and continuing to react for 1 hour after the dropwise adding is finished. After the reaction, the reaction mixture was cooled to room temperature. pH 6.5 was adjusted using 30 wt% sodium hydroxide solution to give a light yellow transparent solution. The light yellow clear solution was poured into 500mL of cold anhydrous ethanol to give a light yellow precipitate as a crude product. The crude product was redissolved in water and reprecipitated using absolute ethanol; repeat for 3 times. And (5) vacuum drying for 48h at room temperature to obtain the polymer printing ink auxiliary agent. IR (KBr) v 3390cm-1，2930cm-1，1722cm-1，1643cm-1，1460cm-1，1340cm-1，1082cm-1，960cm-1. The weight average molecular weight Mw of the polymer printing ink auxiliary agent is 13684g/mol which is measured by Agilent PL-GPC 50; the number average molecular weight Mn is 5035 g/mol; PDI 2.71.
Application example 1-composition comprising Polymer printing ink auxiliary and reactive dye
Weighing 12 wt% of C.I. reactive red 111, 1.5 wt% of polymer printing ink auxiliary agent and deionized water, and adjusting the pH to 8; stirring for 2 hours by using a stirrer (400rpm) and sanding for 8 hours by using a sand mill (1200 rpm); and taking out the product, standing for 48h, and filtering by using a filter membrane with the pore diameter of 0.45 mu m to obtain the composition containing the polymer printing ink auxiliary agent and the reactive dye.
Application example 2-composition comprising Polymer printing ink auxiliary and reactive dye
Weighing 12 wt% of C.I. reactive red 111, 0.8 wt% of polymer printing ink auxiliary agent and deionized water, and adjusting the pH to 8; stirring for 2 hours by using a stirrer (400rpm) and sanding for 8 hours by using a sand mill (1200 rpm); and taking out the product, standing for 48h, and filtering by using a filter membrane with the pore diameter of 0.45 mu m to obtain the composition containing the polymer printing ink auxiliary agent and the reactive dye.
Comparative example 1 composition comprising polymeric printing ink adjuvant and reactive dye
Weighing 12 wt% of C.I. reactive red 111, 0.4 wt% of polymer printing ink auxiliary agent and deionized water, and adjusting the pH to 8; stirring for 2 hours by using a stirrer (400rpm) and sanding for 8 hours by using a sand mill (1200 rpm); and taking out the product, standing for 48h, and filtering by using a filter membrane with the pore diameter of 0.45 mu m to obtain the composition containing the polymer printing ink auxiliary agent and the reactive dye.
Comparative example 2 composition comprising polymeric printing ink adjuvant and reactive dye
The polymer printing ink assistant of comparative example 2 was prepared under the same conditions as in example 2 without adding the terminal acrylate β -cyclodextrin monomer. Then 12 wt% of c.i. reactive red 111, 2 wt% of the polymer printing ink auxiliary of comparative example 2 and deionized water were weighed, and the pH was adjusted to 8; stirring for 2 hours by using a stirrer (400rpm) and sanding for 8 hours by using a sand mill (1200 rpm); and taking out the product, standing for 48h, and filtering by using a filter membrane with the pore diameter of 0.45 mu m to obtain the composition containing the polymer printing ink auxiliary agent and the reactive dye.
Performance testing
A certain amount of the composition containing the polymer printing ink auxiliary agent and the reactive dye is added into a centrifuge tube and centrifuged for 30min at the rotating speed of 8000 rpm. Taking the supernatant, diluting with a certain factor, and measuring its absorbance at the maximum absorption wavelength using a spectrophotometer. Dispersion stability the specific absorbance R, which is the ratio of the absorbances of the system before and after centrifugation1Evaluation was carried out. R1Absorbance of the centrifuged system/absorbance of the non-centrifuged system 100%.
A certain amount of the composition containing the polymer printing ink auxiliary agent and the reactive dye is put into a glass bottle and is put into an oven at 40 ℃ for aging for one week. The supernatant was taken and diluted by a certain factor, and the absorbance thereof was measured at the maximum absorption wavelength using a spectrophotometer. Storage stability the ratio of the absorbance of the system before and after aging, i.e. the specific absorbance R2Evaluation was carried out. R2Absorbance of the aged system/absorbance of the unaged system 100%.
See table 1 for results.
TABLE 1
| R1 | R2 | |
| Application example 1 | 98％ | 97％ |
| Application example 2 | 96％ | 94％ |
| Comparative example 1 | 91％ | 87％ |
| Comparative example 2 | 82％ | 79％ |
As can be seen from Table 1, the printing ink assistant of the present invention of practical examples 1 and 2 is not only superior in dispersion stability but also superior in storage stability, as compared to comparative examples 1 and 2.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (10)
1. A printing ink auxiliary agent is obtained by copolymerization reaction of acrylic acid, sodium methacrylate, 4-hydroxybutyl polyethylene glycol vinyl ether and a beta-cyclodextrin monomer with a polymerizable group; characterized in that the beta-cyclodextrin monomer with polymerizable group is selected from beta-cyclodextrin monomers of terminal acrylate.
2. The printing ink auxiliary according to claim 1, wherein the molar ratio of the beta-cyclodextrin monomer having a polymerizable group to 4-hydroxybutyl polyethylene glycol vinyl ether is 1: (2-4).
3. The printing ink auxiliary according to claim 1, wherein the beta-cyclodextrin monomer having a polymerizable group is prepared from beta-cyclodextrin and p-benzenesulfonyl chloride in a molar ratio of 1: 1, and then sequentially reacting with 2-hydroxyethylamine and glycidyl methacrylate to obtain the compound.
4. The printing ink assistant according to claim 1, wherein the number average molecular weight Mn =1500-3500g/mol of 4-hydroxybutyl polyethylene glycol vinyl ether.
5. The printing ink assistant according to claim 1, wherein the molar ratio of the beta-cyclodextrin monomer having a polymerizable group to sodium acrylate and sodium methacrylate is 1: (5-9): (0.5-1.5).
6. The printing ink auxiliary according to claim 1, wherein the initiation system of the copolymerization reaction is a hydrogen peroxide/Vc system; advantageously, the molar ratio of hydrogen peroxide to Vc is (2.4-3.6): 1.
7. the printing ink assistant according to claim 6, wherein the hydrogen peroxide is added in an amount of 5 to 15% of the sum of all the comonomer moles.
8. The printing ink aid according to claim 1, wherein the reaction temperature of the copolymerization reaction is 40-80 ℃.
9. The printing ink assistant according to claim 1, wherein the printing ink assistant has a weight average molecular weight Mw = 10000-; the number average molecular weight Mn = 4000-; PDI = 2.5-2.9.
10. A method for preparing the printing ink assistant according to any one of claims 1 to 9, comprising: acrylic acid, sodium methacrylate sulfonate, 4-hydroxybutyl polyethylene glycol vinyl ether and a beta-cyclodextrin monomer with a polymerizable group are subjected to copolymerization reaction in an inert atmosphere in the presence of an initiator system; after the reaction is finished, adjusting the pH =6-7 to obtain a transparent solution; precipitating with precipitant, and vacuum drying.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1789345A (en) * | 2004-12-18 | 2006-06-21 | 青岛大学 | Method for preparing polyocarboxy acid type pigment ink |
| CN104817663A (en) * | 2015-04-10 | 2015-08-05 | 广州市建筑科学研究院有限公司 | Preparation method of polycarboxylate water-reducer capable of inhibiting side-effect of montmorillonite and polymeric monomer |
| CN106480753A (en) * | 2016-08-31 | 2017-03-08 | 浙江德誉进出口有限公司 | A kind of real silk blend polyester fabric digit printing ink and preparation method thereof |
| CN111499775A (en) * | 2017-11-27 | 2020-08-07 | 湖南辰砾新材料有限公司 | Polyamino modified cyclodextrin and application thereof |
-
2021
- 2021-09-17 CN CN202111090575.3A patent/CN113774691B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1789345A (en) * | 2004-12-18 | 2006-06-21 | 青岛大学 | Method for preparing polyocarboxy acid type pigment ink |
| CN104817663A (en) * | 2015-04-10 | 2015-08-05 | 广州市建筑科学研究院有限公司 | Preparation method of polycarboxylate water-reducer capable of inhibiting side-effect of montmorillonite and polymeric monomer |
| CN106480753A (en) * | 2016-08-31 | 2017-03-08 | 浙江德誉进出口有限公司 | A kind of real silk blend polyester fabric digit printing ink and preparation method thereof |
| CN111499775A (en) * | 2017-11-27 | 2020-08-07 | 湖南辰砾新材料有限公司 | Polyamino modified cyclodextrin and application thereof |
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