CN101255324B - Trans-printing composition and preparation method thereof - Google Patents
Trans-printing composition and preparation method thereof Download PDFInfo
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- CN101255324B CN101255324B CN200710064073A CN200710064073A CN101255324B CN 101255324 B CN101255324 B CN 101255324B CN 200710064073 A CN200710064073 A CN 200710064073A CN 200710064073 A CN200710064073 A CN 200710064073A CN 101255324 B CN101255324 B CN 101255324B
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Abstract
The invention provides a transfer printing combination and preparation method thereof, belonging to printing technical field, in order to solve the problem that incompletely transfer printing, being easy to peel off after transfer and fading due to rubbing. The transfer printing combination comprises 10-30 weight% of polyacrylate copolymer, 1-10 weight% of modified resin and 60-80 weight% of organic solvent, wherein the modified resin is composed of 10-30 weight% of poluurethane resin, 20-50 weight% of chloroacetic resin, 30-60 weight% of tie resin, and the polyacrylate copolymer solution is produced by polymerizing the acr monomer in solution and the modified resin solution is produced by dissolving the modified resin in organic solvent. The transfer printing combination is obtained by mixing the above solution, with excellent performance of quickly drying, cleanly transferring, high fastness after transferring, antifriction and aging resistance.
Description
Technical field
The present invention relates to the high molecular polymer field, particularly relate to tackiness agent or tackiness agent that a kind of trans-printing of preparation is used.
Background technology
Trans-printing is meant that the surface of some stock presents the random fluctuation shape, or the object of moulding, or a kind of indirect printing process taked when being not easy to print on printing press such as flexible material.In order on these stock surfaces, also to stamp image and literal, just image and literal must be printed to earlier on a kind of material that is called the intermediate transfer carrier (plastic film or paper), and then by this carrier by some method, for example adopt heat, wetting, exert pressure etc. they transferred on the stock, finally form printed matter.
The range of application of trans-printing is very extensive.At first be that not only body is different for its stock, and material is also varied, is widely used in daily living article printings such as some molded container in irregular shape, toy for children, furniture, trade mark and other various potteries, glass, plastics, textiles, leather.Trans-printing almost can remedy many flexographies the printing of the various materials that can not undertake the printing of.
Trans-printing all is the off line printing, and promptly the intermediate transfer carrying agent is separately independently with the body of undertaking the printing of, and does not influence processing separately between they are mutual.Because trans-printing is applicable to plane or irregular convex-concave surface, as printing on multistage face, many curved surfaces, the various forming composition of polygonal planar, and can realize the exquisite printing of polychrome, therefore also play an important role in the packages printing field.As a big producing country, no matter be textiles, or other small item, all be big industry in China, to measure wide in varietyly greatly, trans-printing all has wide development prospect in China.
The transfer printing tackiness agent is that trans-printing composition is as the requisite a kind of material of trans-printing, in whole transfer process, play an important role, to the requirement of transfer printing tackiness agent is to shift will make things convenient for, rapidly, totally, literal or pattern chromatograph can be fixed on the object plane of undertaking the printing of after shifting, also will stand the certain frictional force and the test of climate change.Common printing binder does not reach such performance, more or less exist some indeterminable problems, not enough as bonding force, peeling phenomenon appears; Transfer printing is incomplete, has residual; Be subjected to extraneous weather effect the flavescence problem of fading to occur.
Summary of the invention
Purpose of the present invention be exactly for solve in the trans-printing process transfer printing not exclusively, problem such as peel off easily, be subjected to that friction is faded after shifting, a kind of trans-printing composition and preparation method thereof is provided, and it has rapidly dry, shifts clean, shift back fastness height, rub resistance, excellent properties such as ageing-resistant.
Trans-printing composition of the present invention contains the acrylate copolymer of 10 quality %～30 quality %, the organic solvent of the modified resin of 1 quality %～10 quality % and 60 quality %～80 quality %, described modified resin is the urethane resin by 10 quality %～30 quality %, the vinyl chloride-vinyl acetate resin of 20 quality %～50 quality %, the mixture that the tackifying resin of 30 quality %～60 quality % is formed, prepare acrylate copolymer solution by acrylic ester monomer by solution polymerization process, make modified resin solution with organic solvent dissolution modified resin, described two kinds of solution mixing systems are got described trans-printing composition;
Preferably, described acrylic ester monomer comprises methyl methacrylate or methyl acrylate, the ethyl propenoate of 10 quality %～40 quality %, the butyl acrylate of 1 quality %～20 quality % and methacrylic acid or the vinylformic acid of 1 quality %～5 quality % of 30 quality %～60 quality %, above-mentioned monomer sum is 100 quality %, and the second-order transition temperature that monomeric ratio satisfies the acrylate copolymer that makes is 0～80 ℃, is preferably 10～60 ℃;
Preferably, the number-average molecular weight of described urethane resin is 10,000～100,000; Described vinyl chloride-vinyl acetate resin vinyl-chloride-containing amount is 60 quality %～90 quality %, and softening temperature is 50～130 ℃; Described tackifying resin is terpine resin or modified terpene resin, and softening temperature is 60～150 ℃.The effect of modified resin is to improve the cohesive strength of tackiness agent to various stocks, improves crocking resistance;
Described organic solvent is two kinds of mixed solvents that obtain with mass ratio mixing in 1: 1 in hydro carbons, ester class, the ketones solvent.Hydro carbons for example is toluene, hexanaphthene; The ester class for example is vinyl acetic monomer, N-BUTYL ACETATE; Ketone for example is acetone, butanone.
The preparation method of trans-printing composition of the present invention is as follows:
(1) with an organic solvent soluble modified resin is made the modified resin solution (b) of mass percent concentration 10%～30%;
(2), make the initiator solution of mass percent concentration 5%～20% with described organic solvent dissolution initiator; Drop into acrylic ester monomer earlier in polymerization unit, stir, be warmed up to 70～80 ℃, add 30%～50% initiator solution, isothermal reaction 0.5～1 hour drips remaining initiator solution then, drips off with 1～1.5 hour; Drip remaining organic solvent again, dripped off in 2～3 hours, be warmed up to 80～90 ℃ then, continue reaction 0.5～1 hour, cooling obtains acrylate copolymer solution (a);
(3) modified resin solution (b) is added in the acrylate copolymer solution (a) that makes, stirs, obtain described trans-printing composition.
Preparation acrylate copolymer used initiator is organic peroxy class initiator such as isopropyl benzene hydroperoxide, dicumyl peroxide, dibenzoyl peroxide (BPO), or azo-initiator such as Diisopropyl azodicarboxylate (AIBN), 2,2'-Azobis(2,4-dimethylvaleronitrile) (ABVN), consumption is 0.1%～2% of an acrylic ester monomer total mass.
The controlling index of the acrylate copolymer solution that the present invention makes is: solid masses content is 10%～40%, and viscosity is 200～1000cps (20 ℃, rotary viscosity design determining), and number-average molecular weight (Mn) is 10,000～200,000.
Use trans-printing composition of the present invention, for example the product that makes of example 1 carries out application experiment, transfer to respectively on wallpaper, PVC leather, the PU leather base material, the rate of transform can both reach 100%, shifting the back uses Pressuresensitive Tape to peel off, peel off area all less than 1%, put into washing machine and wash by rubbing with the hands continuously not have in 1500 minutes and come off.Compare with commercially available product, the stripping strength height, rub resistance will be got well.It has dry shifts totally rapidly, shifts back fastness height, rub resistance, excellent properties such as ageing-resistant.
Embodiment
Embodiment 1
Acrylate copolymer solution (a) preparation scheme is as follows, classifies mass fraction (back is together) down as:
Methyl methacrylate 40
Ethyl propenoate 44
Butyl acrylate 7
Vinylformic acid 9
Toluene 154
Butanone 154
BPO 0.5
Preparation process: in polymerization unit, drop into all monomers earlier, stir and be warmed up to 70～80 ℃.Dissolve initiator with mixed solvent, make initiator solution.After treating temperature-stable, add 40% initiator solution earlier, behind the isothermal reaction 1h, drip the residue initiator solution, 1h drips off.Drip remaining mixed solvent then, 2h drips off.After dripping off all raw materials, be warmed up to 80～90 ℃ and continue reaction 1h, cooling promptly obtained acrylate copolymer solution (a) after reaction finished.
Modified resin solution (b) preparation scheme is as follows:
Urethane resin (Mn is about 30,000) 16
Vinyl chloride-vinyl acetate resin (vinyl-chloride-containing amount 82 quality %) 45
Terpine resin (90 ℃ of softening temperatures) 39
Toluene 228
Butanone 228
Preparation process: organic solvent is put in the reaction vessel, started stirring, add urethane resin, vinyl chloride-vinyl acetate resin and terpine resin then successively, dissolving back restir is 30 minutes fully, and solvent back is standby.
The preparation of composition for transfer printing:
After acrylate copolymer solution (a) prepared, temperature dropped to 30～40 ℃, added modified resin solution (b), and stirring 1h can the discharging packing.
Embodiment 2
Acrylate copolymer solution (a) preparation scheme
Methyl acrylate 61
Ethyl propenoate 27
Butyl acrylate 9
Methacrylic acid 3
Butanone 185
Vinyl acetic monomer 185
AIBN 1.2
Modified resin solution (b) preparation scheme
Urethane resin (Mn is about 46,000) 25
Vinyl chloride-vinyl acetate resin (vinyl-chloride-containing amount 87 quality %) 40
Terpene phenolic resin (110 ℃ of softening temperatures) 35
Butanone 216
Vinyl acetic monomer 216
Preparation process makes composition for transfer printing with embodiment 1.
Embodiment 3
Acrylate copolymer solution (a) preparation scheme
Methyl methacrylate 52
Ethyl propenoate 37
Butyl acrylate 5
Vinylformic acid 6
Toluene 198
Vinyl acetic monomer 198
BPO 0.9
Modified resin solution (b) preparation scheme
Urethane resin (Mn is about 68,000) 28
Vinyl chloride-vinyl acetate resin (vinyl-chloride-containing amount 77%) 30
Modified terpene resin (100 ℃ of softening temperatures) 42
Toluene 200
Vinyl acetic monomer 200
Preparation process makes composition for transfer printing with embodiment 1.
Claims (3)
1. trans-printing composition, it is characterized in that, described trans-printing composition contains the acrylate copolymer of 10 quality %～30 quality %, the organic solvent of the modified resin of 1 quality %～10 quality % and 60 quality %～80 quality %, described modified resin is the urethane resin by 10 quality %～30 quality %, the vinyl chloride-vinyl acetate resin of 20 quality %～50 quality %, the mixture that the tackifying resin of 30 quality %～60 quality % is formed, the preparation method is: prepare acrylate copolymer solution by acrylic ester monomer by solution polymerization process, make modified resin solution with organic solvent dissolution modified resin, described two kinds of solution mixing systems are got described trans-printing composition;
Wherein, described acrylic ester monomer comprises methyl methacrylate or methyl acrylate, the ethyl propenoate of 10 quality %～40 quality %, the butyl acrylate of 1 quality %～20 quality % and methacrylic acid or the vinylformic acid of 1 quality %～5 quality % of 30 quality %～60 quality %, above-mentioned monomer sum is 100 quality %, and the second-order transition temperature of the satisfied acrylate copolymer that makes of monomeric ratio is 0～80 ℃;
The number-average molecular weight of described urethane resin is 10,000～100,000; Described vinyl chloride-vinyl acetate resin vinyl-chloride-containing amount is 60 quality %～90 quality %, and softening temperature is 50～130 ℃; Described tackifying resin is terpine resin or modified terpene resin, and softening temperature is 60～150 ℃;
Described organic solvent is two kinds of mixed solvents that obtain with mass ratio mixing in 1: 1 in hydro carbons, ester class, the ketones solvent.
2. the preparation method of the trans-printing composition described in the claim 1 is characterized in that described preparation method may further comprise the steps:
(1) with an organic solvent soluble modified resin is made the modified resin solution (b) of mass percent concentration 10%～30%;
(2) use the organic solvent dissolution initiator, make the initiator solution of mass percent concentration 5%～20%; Drop into acrylic ester monomer earlier in polymerization unit, stir, be warmed up to 70～80 ℃, add 30%～50% initiator solution, isothermal reaction 0.5～1 hour drips remaining initiator solution then, drips off with 1～1.5 hour; Drip remaining organic solvent again, dripped off in 2～3 hours, be warmed up to 80～90 ℃ then, continue reaction 0.5～1 hour, cooling obtains acrylate copolymer solution (a);
(3) modified resin solution (b) is added in the acrylate copolymer solution (a) that makes, stirs, obtain described trans-printing composition.
3. the preparation method of trans-printing composition as claimed in claim 2, it is characterized in that, the used initiator of preparation acrylate copolymer is organic peroxy class initiator or azo-initiator, and consumption is 0.1%～2% of an acrylic ester monomer total mass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710064073A CN101255324B (en) | 2007-02-26 | 2007-02-26 | Trans-printing composition and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN200710064073A CN101255324B (en) | 2007-02-26 | 2007-02-26 | Trans-printing composition and preparation method thereof |
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| CN101255324A CN101255324A (en) | 2008-09-03 |
| CN101255324B true CN101255324B (en) | 2010-05-19 |
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| CN200710064073A Expired - Fee Related CN101255324B (en) | 2007-02-26 | 2007-02-26 | Trans-printing composition and preparation method thereof |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2395064A1 (en) * | 2010-06-08 | 2011-12-14 | Bayer MaterialScience AG | Linerless label |
| CN103174018A (en) * | 2013-03-28 | 2013-06-26 | 南通市鸿瑞化工有限公司 | Method for producing artificial leather surface treating agent |
| CN103468174B (en) * | 2013-09-29 | 2015-04-08 | 云南玉溪东魅包装材料有限公司 | Low-temperature hot stamping hot melt adhesive for alumite and preparation method thereof |
| CN104673140B (en) * | 2015-03-05 | 2017-11-21 | 深圳市格莱特印刷材料有限公司 | A kind of peelable glue and preparation method thereof |
| CN105647435B (en) * | 2016-01-13 | 2018-08-28 | 广州慧谷工程材料有限公司 | A kind of adhesive of IML and the preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4389458A (en) * | 1981-03-26 | 1983-06-21 | Tdk Electronics Co., Ltd. | Magnetic recording medium |
| CN1062014A (en) * | 1990-11-29 | 1992-06-17 | 青州铝箔纸总厂 | Pre-treating adhesive of metallized paper and uses thereof |
| US6358660B1 (en) * | 1999-04-23 | 2002-03-19 | Foto-Wear, Inc. | Coated transfer sheet comprising a thermosetting or UV curable material |
-
2007
- 2007-02-26 CN CN200710064073A patent/CN101255324B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4389458A (en) * | 1981-03-26 | 1983-06-21 | Tdk Electronics Co., Ltd. | Magnetic recording medium |
| CN1062014A (en) * | 1990-11-29 | 1992-06-17 | 青州铝箔纸总厂 | Pre-treating adhesive of metallized paper and uses thereof |
| US6358660B1 (en) * | 1999-04-23 | 2002-03-19 | Foto-Wear, Inc. | Coated transfer sheet comprising a thermosetting or UV curable material |
Non-Patent Citations (4)
| Title |
|---|
| 林柏亨，石晓燕，钟彤炜.双组份丙烯酸聚氨酯胶粘剂研制总结.广州化工1988年 第1期.1988,1988年(第1期),4-9. |
| 林柏亨,石晓燕,钟彤炜.双组份丙烯酸聚氨酯胶粘剂研制总结.广州化工1988年 第1期.1988,1988年(第1期),4-9. * |
| 黄云翔.用途广泛的氯乙烯/醋酸乙烯共聚物.广州化工1991年 第2期.1991,1991年(第2期),53-58. |
| 黄云翔.用途广泛的氯乙烯/醋酸乙烯共聚物.广州化工1991年 第2期.1991,1991年(第2期),53-58. * |
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Address after: 100070 Fengtai District Science City, Beijing Feng Feng Road, room 2, room 209, level 8 Patentee after: Beijing Comens New Materials Co., Ltd. Address before: 100070 Fengtai District Science City, Beijing Feng Feng Road, room 2, room 209, level 8 Patentee before: Beijing Comens Chemical Co., Ltd. |
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Effective date of registration: 20170217 Address after: 226407 Rudong Coastal Economic Development Zone, Jiangsu, Nantong port chemical industrial park Patentee after: Nantong Gaomeng New Material Co., Ltd. Address before: 100070 Fengtai District Science City, Beijing Feng Feng Road, room 2, room 209, level 8 Patentee before: Beijing Comens New Materials Co., Ltd. |
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