WO2022217672A1 - Water-based low-temperature heat transfer printing adhesive and preparation method therefor - Google Patents

Water-based low-temperature heat transfer printing adhesive and preparation method therefor Download PDF

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Publication number
WO2022217672A1
WO2022217672A1 PCT/CN2021/092002 CN2021092002W WO2022217672A1 WO 2022217672 A1 WO2022217672 A1 WO 2022217672A1 CN 2021092002 W CN2021092002 W CN 2021092002W WO 2022217672 A1 WO2022217672 A1 WO 2022217672A1
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WIPO (PCT)
Prior art keywords
water
parts
based low
temperature
thermal transfer
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PCT/CN2021/092002
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French (fr)
Chinese (zh)
Inventor
朱清梅
吴坤斌
黄宏存
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海南必凯水性新材料有限公司
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Priority to CA3130987A priority Critical patent/CA3130987C/en
Publication of WO2022217672A1 publication Critical patent/WO2022217672A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/08—Copolymers of ethene
    • C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C09J123/0869—Acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives

Definitions

  • the invention relates to the technical field of printing materials, and more particularly, to an aqueous low-temperature thermal transfer adhesive and a preparation method thereof.
  • Thermal transfer is to directly contact the patterned transfer film with the substrate, and the graphic layer on the transfer film is dissolved and transferred to the substrate.
  • the thermal transfer film includes a carrier layer, a release layer, a protective layer,
  • the ink layer, the adhesive layer and the coatings are closely related and affect each other.
  • the adhesive layer is the substrate adhesive used to bond the ink information layer and various materials. It must have high adhesion, high temperature resistance, scratch resistance, washing resistance, and cooking resistance.
  • the problems existing in the thermal transfer adhesive in the prior art result in unsatisfactory scratch resistance, leveling, water resistance, high temperature resistance, and integrity of the low temperature transfer image and text.
  • the Chinese patent with publication number CN103289611A discloses an acrylic resin thermal transfer adhesive and a preparation method thereof, which is made from the following raw materials by weight: acrylic resin (AR-1520) 25-28, polyisobutylene 12-15, ammonia Sick group triethoxy silane 3-6, methyl triethoxy silane 3-5, diisophthalic benzene peroxide 2-3, dibutyl maleate 12-15, dodecyl mercaptan 4-6, rosin 5-8, crosslinking agent TAC1-2, dioctyl ester 3-5, 1-hydroxyethyl-2-oleylimidazoline 1-2, p-phenylenediamine 2-3, acetone 55- 60.
  • Xylene 40-45 it has the properties of firm bonding, not easy to break, fall off, and turn yellow.
  • the Chinese patent with publication number CN109517566A discloses a water-based thermal transfer PP adhesive, which includes the following components in mass fraction: water-based acrylic emulsion 5-15, water-based polyurethane dispersion 20-40, polyvinyl alcohol 5-15, water-based Coumarone resin 5-15, water-based adhesion promoter 0-5, fumed silica 0-1, ethanol 10-20, distilled water 10-20, leveling agent 0-0.001, defoamer 0-0.001; Has high adhesion and high edge trimming.
  • the leveling property, water resistance, scratch resistance and integrity of low-temperature transfer images and texts of the products disclosed in the prior art have not been improved, and the raw materials are not environmentally friendly.
  • the purpose of the present invention is to provide a water-based low-temperature thermal transfer adhesive and a preparation method thereof.
  • the low temperature transfer printing has good image and text integrity, and it is a pure water-based material, which is environmentally friendly and pollution-free.
  • the invention provides a water-based low-temperature thermal transfer adhesive, which is prepared from raw materials comprising the following components:
  • leveling aid 0.3-0.5 parts by weight of leveling aid
  • the plasticizer is selected from one or more of glycerol, dioctyl adipate and dioctyl sebacate.
  • the ethylene acrylic resin has a melt index of 300-1300, and a melting point of 75°C to 78°C.
  • the alkaline neutralizer is selected from one or more of ammonia water, KOH, NaOH and triethylamine.
  • the leveling aid is selected from one or more of Glide 410, Wet KL 245 and Glide 496.
  • the wax emulsion is selected from one or more of palm wax, polyethylene wax, oxidized polyethylene wax and micronized wax.
  • the present invention also provides a preparation method of the water-based low-temperature thermal transfer adhesive described in the above technical solution, comprising the following steps:
  • the stirring speed in step a) is 100r/min ⁇ 500r/min; the mixing time of the first amount of water, the second amount of alkaline neutralizer and plasticizer is 1min ⁇ 10min.
  • the first amount of water in step a) accounts for 70-90 wt% of the total amount of water; the second amount of alkaline neutralizer accounts for 70-80 wt% of the total alkaline neutralizer.
  • the temperature of the first reaction in step a) is 90°C to 100°C, and the time is 1h to 2h;
  • the temperature of the second reaction is 90°C ⁇ 100°C, and the time is 0.5h ⁇ 1h;
  • the temperature of the third reaction is 90°C to 100°C, and the time is 1 h to 2 h.
  • the cooling temperature in step a) is 20°C to 30°C.
  • the invention provides an aqueous low-temperature thermal transfer adhesive, which is prepared from raw materials comprising the following components: 20-30 parts by weight of ethylene acrylic resin; 3-10 parts by weight of alkaline neutralizer; 0.3-0.5 parts by weight of leveling aid 1-5 parts by weight of wax emulsion; 1-3 parts by weight of plasticizer; 0.01-0.05 parts by weight of defoamer; 65-80 parts by weight of water; the plasticizer is selected from glycerol, dioctyl adipate and one or more of dioctyl sebacate.
  • the water-based low-temperature thermal transfer adhesive provided by the present invention adopts a specific content of components to achieve overall better interaction, and the product has better leveling, water resistance, scratch resistance, and excellent The integrity of the low-temperature transfer image and text, and it is a pure water-based material, which is environmentally friendly and pollution-free.
  • the experimental results show that the water-based low-temperature thermal transfer adhesive provided by the present invention has good leveling properties, the formed coating does not turn white and swell after being washed with water at 45°C to 60°C for 1 hour, the appearance of the scratched coating remains intact, and the coating can be Stretching 2 to 2.6 times continuously, low temperature transfer at 110 ° C ⁇ 125 ° C, the image and text are complete, the printing performance is good, and the ink can not fall off and the color is bright.
  • the preparation method provided by the invention has simple process, mild conditions and easy control, and has broad application prospects.
  • the invention provides a water-based low-temperature thermal transfer adhesive, which is prepared from raw materials comprising the following components:
  • leveling aid 0.3-0.5 parts by weight of leveling aid
  • the plasticizer is selected from one or more of glycerol, dioctyl adipate and dioctyl sebacate.
  • the water-based low temperature thermal transfer adhesive is prepared from raw materials including ethylene acrylic resin, alkaline neutralizer, leveling aid, wax emulsion, plasticizer, defoamer and water, preferably ethylene acrylic acid Resin, alkaline neutralizer, leveling aid, wax emulsion, plasticizer, defoamer and water.
  • the melt index of the ethylene acrylic resin is preferably 300 to 1300, and the melting point is preferably 75°C to 78°C.
  • the source of the ethylene acrylic resin is not particularly limited in the present invention, and commercially available products or self-made products well-known to those skilled in the art can be used; Docosanol ester and methyl methacrylate are prepared as main components; it is sufficient to ensure that the EAA parameters meet the above-mentioned raw material requirements.
  • the water-based low temperature thermal transfer adhesive comprises 20-30 parts by weight of ethylene acrylic resin, preferably 20-28 parts by weight.
  • the alkaline neutralizer is preferably selected from one or more of ammonia water, KOH, NaOH and triethylamine, more preferably one or more of ammonia water, KOH, NaOH and triethylamine kind.
  • the present invention has no special limitation on the source of the alkaline neutralizer, and the commercially available products of the above-mentioned ammonia water, KOH, NaOH and triethylamine well known to those skilled in the art can be used.
  • the leveling aid is preferably selected from one or more of Glide 410, Wet KL 245 and Glide 496, more preferably Glide 410, Wet KL 245 or Glide 496.
  • the source of the leveling aid is not particularly limited in the present invention, and the commercially available products of the above-mentioned Glide 410, Wet KL 245 and Glide 496 well known to those skilled in the art can be used.
  • the wax emulsion is preferably selected from one or more of palm wax, polyethylene wax, oxidized polyethylene wax and micronized wax, more preferably palm wax, polyethylene wax, oxidized polyethylene wax or micronized powder wax.
  • the source of the wax emulsion is not particularly limited in the present invention, and the commercially available products of the above-mentioned palm wax, polyethylene wax, oxidized polyethylene wax and micronized wax well known to those skilled in the art can be used.
  • the water-based low temperature thermal transfer adhesive comprises 1-5 parts by weight of wax emulsion, preferably 2-5 parts by weight.
  • the plasticizer is selected from one or more of glycerol, dioctyl adipate and dioctyl sebacate, preferably glycerol, dioctyl adipate or dioctyl sebacate Octyl ester.
  • the present invention has no particular limitation on the source of the plasticizer, and the commercially available products of the above-mentioned glycerol, dioctyl adipate and dioctyl sebacate well known to those skilled in the art can be used.
  • the water-based low temperature thermal transfer adhesive includes 1-3 parts by weight of plasticizer, preferably 1-2 parts by weight.
  • the defoamer is preferably a polyether-modified organosilicon defoamer; the present invention has no special limitation on its source, and a commercially available commodity well known to those skilled in the art can be used.
  • the water is soft water well known to those skilled in the art, which is not particularly limited in the present invention.
  • the water-based low temperature thermal transfer adhesive comprises 65-80 parts by weight of water, preferably 72-80 parts by weight.
  • the solid content of the water-based low-temperature thermal transfer adhesive is preferably 20% to 30%; during storage, it is kept at a low temperature, protected from light, and sealed.
  • the water-based low-temperature thermal transfer adhesive provided by the present invention adopts specific content of components to achieve overall better interaction, and the product has better leveling, water resistance, scratch resistance, and excellent low-temperature transfer image and text integrity. It is a pure water-based material, and the completely water-based formula will not have any residue, which meets the market requirements of environmental protection, ease of use, and stability, and can be used with confidence; and the water-based low-temperature thermal transfer adhesive provided by the present invention can be coated on It has good product adaptability on substrates such as release film or release paper.
  • the experimental results show that the water-based low-temperature thermal transfer adhesive provided by the present invention has good leveling properties, the formed coating does not turn white and swell after being washed with water at 45°C to 60°C for 1 hour, the appearance of the scratched coating remains intact, and the coating can be Stretching 2 to 2.6 times continuously; compared to the transfer temperature of the product with the same solid content of 160 ° C to 180 ° C, the temperature required for the transfer of the product provided by the present invention is 110 ° C to 125 ° C, and the low temperature transfer temperature of 110 ° C to 125 ° C The picture and text are complete, the printing performance is good, and the ink can not fall off and the color is bright.
  • the present invention also provides a preparation method of the water-based low-temperature thermal transfer adhesive described in the above technical solution, comprising the following steps:
  • the water, alkaline neutralizer, plasticizer, ethylene acrylic resin, wax emulsion, defoamer, and leveling aid are the same as those in the above-mentioned technical solutions, and will not be repeated here.
  • the stirring conditions are continuously carried out in the whole preparation method; the rotation speed of the stirring is preferably 100r/min ⁇ 500r/min.
  • the device used in the preparation method is not particularly limited in the present invention, and a reaction kettle well-known to those skilled in the art can be used.
  • the mixing time of the first amount of water, the second amount of the alkaline neutralizer and the plasticizer is preferably 1 min to 10 min, more preferably 5 min.
  • the first amount of water preferably accounts for 70-90 wt% of the total amount of water; the second amount of the alkaline neutralizer preferably accounts for 70-80 wt% of the total alkaline neutralizer.
  • the temperature of the first reaction is preferably 90°C to 100°C, more preferably 90°C to 98°C; the time of the first reaction is preferably 1 h to 2 h.
  • the temperature of the second reaction is preferably 90°C to 100°C, more preferably 90°C to 98°C; the time of the second reaction is preferably 0.5h to 1h.
  • the temperature of the third reaction is preferably 90°C to 100°C, more preferably 95°C to 100°C; the time of the third reaction is preferably 1 h to 2 h.
  • the cooling temperature is preferably 20°C to 30°C, more preferably 25°C.
  • the preparation method provided by the invention has simple process, mild conditions and easy control, and has broad application prospects.
  • the invention provides an aqueous low-temperature thermal transfer adhesive, which is prepared from raw materials comprising the following components: 20-30 parts by weight of ethylene acrylic resin; 3-10 parts by weight of alkaline neutralizer; 0.3-0.5 parts by weight of leveling aid 1-5 parts by weight of wax emulsion; 1-3 parts by weight of plasticizer; 0.01-0.05 parts by weight of defoamer; 65-80 parts by weight of water; the plasticizer is selected from glycerol, dioctyl adipate and one or more of dioctyl sebacate.
  • the water-based low-temperature thermal transfer adhesive provided by the present invention adopts a specific content of components to achieve overall better interaction, and the product has better leveling, water resistance, scratch resistance, and excellent The integrity of the low-temperature transfer image and text, and it is a pure water-based material, which is environmentally friendly and pollution-free.
  • the experimental results show that the water-based low-temperature thermal transfer adhesive provided by the present invention has good leveling properties, the formed coating does not turn white and swell after being washed with water at 45°C to 60°C for 1 hour, the appearance of the scratched coating remains intact, and the coating can be Stretching 2 to 2.6 times continuously, low temperature transfer at 110 ° C ⁇ 125 ° C, the image and text are complete, the printing performance is good, and the ink can not fall off and the color is bright.
  • the preparation method provided by the invention has simple process, mild conditions and easy control, and has broad application prospects.
  • the melt index of the ethylene acrylic resin is 300, and the melting point is 77°C;
  • Described alkaline neutralizer is ammoniacal liquor
  • Described leveling aid is Glide 410;
  • the wax emulsion is oxidized polyethylene wax
  • the plasticizer is glycerol
  • the defoamer is a polyether-modified organosilicon defoamer.
  • the water-based low-temperature thermal transfer adhesive provided in Example 1 of the present invention was coated on the PET release film, the emulsion leveling was good, and a coating was formed after drying, and the dry glue amount was 50 g/m 2 .
  • the coating does not turn white and swell after being washed in warm water at 45°C for 1 hour, the appearance of the scratched coating remains intact, and the coating can be stretched 2 times continuously (using a tensile machine to test the peel strength, the coating length is stretched to 2 times without breaking ), 125 °C low temperature transfer image is complete, the printing performance is good, and the ink can not fall off and the color is bright.
  • the melt index of the ethylene acrylic resin is 300, and the melting point is 77°C;
  • the alkaline neutralizer is ammonia water and triethylamine with a weight ratio of 1:1;
  • Described leveling aid is Wet KL 245;
  • the wax emulsion is polyethylene wax
  • the plasticizer is dioctyl adipate
  • the defoamer is a polyether-modified organosilicon defoamer.
  • the water-based low-temperature thermal transfer adhesive provided in Example 2 of the present invention was coated on the PET release film, the emulsion leveling was good, and a coating was formed after drying, and the dry glue amount was 80 g/m 2 .
  • the coating does not turn white and swell after being washed with water at 50°C for 1 hour, the appearance of the scratched coating remains intact, and the coating can be stretched 2 times continuously (using a tensile machine to test the peel strength, the coating length is stretched to 2 times without breaking ), 125 °C low temperature transfer image is complete, the printing performance is good, and the ink can not fall off and the color is bright.
  • the melt index of the ethylene acrylic resin is 1300, and the melting point is 77°C;
  • the alkaline neutralizer is ammonia water and triethylamine with a weight ratio of 1:1;
  • Described leveling aid is Wet KL 245;
  • the wax emulsion is oxidized polyethylene wax
  • the plasticizer is glycerol
  • the defoamer is a polyether-modified organosilicon defoamer.
  • the water-based low-temperature thermal transfer adhesive provided in Example 3 of the present invention was coated on the release paper, the emulsion leveling was good, and a coating was formed after drying.
  • the dry glue amount was 60g/m 2 .
  • the coating was After washing with water at 60°C for 1 hour, it will not turn white and swell, the appearance of the scratched coating remains intact, and the coating can be stretched 2.6 times continuously (the method of using a tensile machine to test the peel strength, the coating length is stretched to 2.6 times without breaking) , 110 °C low temperature transfer image is complete, good printing performance, can achieve the ink does not fall off and the color is bright.
  • the melt index of the ethylene acrylic resin is 1300, and the melting point is 77°C;
  • the alkaline neutralizer is NaOH
  • Described leveling aid is Glide 496
  • the wax emulsion is oxidized polyethylene wax
  • the plasticizer is dioctyl sebacate
  • the defoamer is a polyether-modified organosilicon defoamer.
  • the water-based low-temperature thermal transfer adhesive provided in Example 4 of the present invention was coated on the PET release film, the emulsion leveling was good, and a coating was formed after drying, and the dry glue amount was 50 g/m 2 .
  • the coating does not turn white and swell after being washed with water at 50°C for 1 hour, the appearance of the scratched coating remains intact, and the coating can be stretched 2 times continuously (using a tensile machine to test the peel strength, the coating length is stretched to 2 times without breaking ), 120 °C low temperature transfer image is complete, the printing performance is good, and the ink can not fall off and the color is bright.
  • the melt index of the ethylene acrylic resin is 300, and the melting point is 77°C;
  • the alkaline neutralizer is triethanolamine and KOH in a weight ratio of 5:1;
  • Described leveling aid is Glide 410;
  • the wax emulsion is oxidized polyethylene wax
  • the plasticizer is dioctyl adipate
  • the defoamer is a polyether-modified organosilicon defoamer.
  • the water-based low-temperature thermal transfer adhesive provided in Example 5 of the present invention was coated on the release paper, the emulsion leveling was good, and a coating was formed after drying, and the dry glue amount was 70g/m 2 .
  • the coating After washing with water at 60°C for 1 hour, it does not turn white and swell, the appearance of the scratched coating remains intact, and the coating can be stretched 2.2 times continuously (using a tensile machine to test the peel strength, the coating length is stretched to 2.2 times without breaking) , 110 °C low temperature transfer image is complete, good printing performance, can achieve the ink does not fall off and the color is bright.

Abstract

Provided in the present invention is a water-based low-temperature heat transfer printing adhesive, which is prepared from the following raw materials in parts by weight: 20-30 parts of an ethylene acrylic resin, 3-10 parts of an alkaline neutralizer, 0.3-0.5 parts of a leveling agent, 1-5 parts of a wax emulsion, 1-3 parts of a plasticizer, 0.01-0.05 parts of a defoaming agent and 65-80 parts of water, wherein the plasticizer is selected from one or more of glycerol, dioctyl adipate and dioctyl sebacate. Compared with the prior art, the water-based low-temperature heat transfer printing adhesive provided by the present invention utilizes components with specific contents and realizes relatively good overall interaction, and the product has a relatively good leveling property, water resistance, scratch resistance and excellent low-temperature transfer printing image-text integrity, is of a pure water-based material, and is environmentally friendly and pollution-free. Experiment results show that the water-based low-temperature heat transfer printing adhesive has a good leveling property, a formed coating layer does not whiten and swell after being washed with water at 45ºC-60ºC for 1 h, the outward appearance remains intact even when scratched, the coating layer can be stretched twofold to 2.6-fold without breaking, low-temperature transfer printing of images and text is completed at 110ºC -125ºC, and the printing performance is good.

Description

一种水性低温热转印胶及其制备方法A kind of water-based low temperature thermal transfer adhesive and preparation method thereof
本申请要求于2021年4月13日提交中国专利局、申请号为202110394442.9、发明名称为“一种水性低温热转印胶及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application claims the priority of the Chinese patent application with the application number 202110394442.9 and the invention titled "A water-based low temperature thermal transfer adhesive and its preparation method", which was submitted to the China Patent Office on April 13, 2021, the entire contents of which are by reference Incorporated in this application.
技术领域technical field
本发明涉及印刷材料技术领域，更具体地说，是涉及一种水性低温热转印胶及其制备方法。The invention relates to the technical field of printing materials, and more particularly, to an aqueous low-temperature thermal transfer adhesive and a preparation method thereof.
背景技术Background technique
热转印是将有图案的转印膜与承印物直接接触，转印膜上的图文层溶解并转移到承接物上，热转印膜上包括有载体层、离型层、保护层、油墨层、粘结层、各涂层间紧密联系，相互影响。其中，粘结层就是用来粘结油墨信息层和各种材料的基材胶黏剂，须具备高的粘附力、耐高温性能、耐刮擦性、耐水洗性、耐蒸煮性。现有的技术中热转印胶黏剂存在的问题，导致转印图文耐刮擦性、流平性、耐水性、耐高温性、低温转印图文完整性都不理想。Thermal transfer is to directly contact the patterned transfer film with the substrate, and the graphic layer on the transfer film is dissolved and transferred to the substrate. The thermal transfer film includes a carrier layer, a release layer, a protective layer, The ink layer, the adhesive layer and the coatings are closely related and affect each other. Among them, the adhesive layer is the substrate adhesive used to bond the ink information layer and various materials. It must have high adhesion, high temperature resistance, scratch resistance, washing resistance, and cooking resistance. The problems existing in the thermal transfer adhesive in the prior art result in unsatisfactory scratch resistance, leveling, water resistance, high temperature resistance, and integrity of the low temperature transfer image and text.
公开号为CN103289611A的中国专利公开了一种丙烯酸树脂热转印胶及其制备方法，由以下列重量份的原料制成：丙烯酸树脂(AR-1520)25-28、聚异丁烯12-15、氨病基三乙氧基硅烷3-6、甲基三乙氧基硅烷3-5、过氧化二异病苯2-3、顺丁烯二酸二丁酯12-15、十二烷基硫醇4-6、松香5-8、交联剂TAC1-2、二辛酯3-5、1-羟乙基-2-油基咪唑啉1-2、对苯二胺2-3、丙酮55-60、二甲苯40-45；其具有粘结牢固、不易破损、脱落、变黄等性能。而公开号为CN109517566A的中国专利公开了一种水性热转印PP胶黏剂，包括质量分数如下成分：水性丙烯酸乳液5-15、水性聚氨酯分散体20-40、聚乙烯醇5-15、水性古马隆树脂5-15、水性附着力促进剂0-5、气相二氧化硅0-1、乙醇10-20、蒸馏水10-20、流平剂0-0.001、消泡剂0-0.001；其具有高附着力、高切边性。但是，现有技术公开的产品流平性、耐水性、耐刮擦性以及低温转印图文完整性并没有得到改善，且原料不具有环保性。The Chinese patent with publication number CN103289611A discloses an acrylic resin thermal transfer adhesive and a preparation method thereof, which is made from the following raw materials by weight: acrylic resin (AR-1520) 25-28, polyisobutylene 12-15, ammonia Sick group triethoxy silane 3-6, methyl triethoxy silane 3-5, diisophthalic benzene peroxide 2-3, dibutyl maleate 12-15, dodecyl mercaptan 4-6, rosin 5-8, crosslinking agent TAC1-2, dioctyl ester 3-5, 1-hydroxyethyl-2-oleylimidazoline 1-2, p-phenylenediamine 2-3, acetone 55- 60. Xylene 40-45; it has the properties of firm bonding, not easy to break, fall off, and turn yellow. The Chinese patent with publication number CN109517566A discloses a water-based thermal transfer PP adhesive, which includes the following components in mass fraction: water-based acrylic emulsion 5-15, water-based polyurethane dispersion 20-40, polyvinyl alcohol 5-15, water-based Coumarone resin 5-15, water-based adhesion promoter 0-5, fumed silica 0-1, ethanol 10-20, distilled water 10-20, leveling agent 0-0.001, defoamer 0-0.001; Has high adhesion and high edge trimming. However, the leveling property, water resistance, scratch resistance and integrity of low-temperature transfer images and texts of the products disclosed in the prior art have not been improved, and the raw materials are not environmentally friendly.
发明内容SUMMARY OF THE INVENTION
有鉴于此，本发明的目的在于提供一种水性低温热转印胶及其制备方法，本发明提供的水性低温热转印胶具有较好的流平性、耐水性、耐刮擦性，同时低温转印图文完整性好，并且为纯水性材料，环保无污染。In view of this, the purpose of the present invention is to provide a water-based low-temperature thermal transfer adhesive and a preparation method thereof. The low temperature transfer printing has good image and text integrity, and it is a pure water-based material, which is environmentally friendly and pollution-free.
本发明提供了一种水性低温热转印胶，由包括以下组分的原料制得：The invention provides a water-based low-temperature thermal transfer adhesive, which is prepared from raw materials comprising the following components:
乙烯丙烯酸树脂20～30重量份；20-30 parts by weight of ethylene acrylic resin;
碱性中和剂3～10重量份；3-10 parts by weight of alkaline neutralizer;
流平助剂0.3～0.5重量份；0.3-0.5 parts by weight of leveling aid;
蜡乳液1～5重量份；1 to 5 parts by weight of wax emulsion;
增塑剂1～3重量份；1 to 3 parts by weight of plasticizer;
消泡剂0.01～0.05重量份；0.01-0.05 parts by weight of defoamer;
水65～80重量份；65-80 parts by weight of water;
所述增塑剂选自甘油、己二酸二辛酯和癸二酸二辛酯中的一种或多种。The plasticizer is selected from one or more of glycerol, dioctyl adipate and dioctyl sebacate.
优选的，所述乙烯丙烯酸树脂的熔融指数为300～1300，熔点为75℃～78℃。Preferably, the ethylene acrylic resin has a melt index of 300-1300, and a melting point of 75°C to 78°C.
优选的，所述碱性中和剂选自氨水、KOH、NaOH和三乙胺中的一种或多种。Preferably, the alkaline neutralizer is selected from one or more of ammonia water, KOH, NaOH and triethylamine.
优选的，所述流平助剂选自Glide 410、Wet KL 245和Glide 496中的一种或多种。Preferably, the leveling aid is selected from one or more of Glide 410, Wet KL 245 and Glide 496.
优选的，所述蜡乳液选自棕榈蜡、聚乙烯蜡、氧化聚乙烯蜡和微粉蜡中的一种或多种。Preferably, the wax emulsion is selected from one or more of palm wax, polyethylene wax, oxidized polyethylene wax and micronized wax.
本发明还提供了一种上述技术方案所述的水性低温热转印胶的制备方法，包括以下步骤：The present invention also provides a preparation method of the water-based low-temperature thermal transfer adhesive described in the above technical solution, comprising the following steps:
a)在搅拌条件下，将第一用量的水、第二用量的碱性中和剂、增塑剂混合后，加入乙烯丙烯酸树脂，进行第一次反应；然后以4g/s～6g/s的速度滴加剩余的碱性中和剂，进行第二次反应；之后，以45g/s～55g/s的速度加入剩余的水，进行第三次反应；冷却后加入消泡剂、流平助剂混合均匀，最后添加蜡乳液，得到水性低温热转印胶。a) Under stirring conditions, after mixing the first amount of water, the second amount of alkaline neutralizer and plasticizer, add ethylene acrylic resin to carry out the first reaction; Add the remaining alkaline neutralizer dropwise at a speed of 45g/s to carry out the second reaction; after that, add the remaining water at a speed of 45g/s～55g/s to carry out the third reaction; after cooling, add defoamer and leveling aid The agent is mixed evenly, and finally the wax emulsion is added to obtain a water-based low-temperature thermal transfer adhesive.
优选的，步骤a)中所述搅拌的转速为100r/min～500r/min；所述第一用量的水、第二用量的碱性中和剂、增塑剂混合的时间为1min～10min。Preferably, the stirring speed in step a) is 100r/min～500r/min; the mixing time of the first amount of water, the second amount of alkaline neutralizer and plasticizer is 1min～10min.
优选的，步骤a)中所述第一用量的水占水总量的70～90wt％；所述第二用量的碱性中和剂占碱性中和剂总量的70～80wt％。Preferably, the first amount of water in step a) accounts for 70-90 wt% of the total amount of water; the second amount of alkaline neutralizer accounts for 70-80 wt% of the total alkaline neutralizer.
优选的，步骤a)中所述第一次反应的温度为90℃～100℃，时间为1h～2h；Preferably, the temperature of the first reaction in step a) is 90°C to 100°C, and the time is 1h to 2h;
所述第二次反应的温度为90℃～100℃，时间为0.5h～1h；The temperature of the second reaction is 90°C～100°C, and the time is 0.5h～1h;
所述第三次反应的温度为90℃～100℃，时间为1h～2h。The temperature of the third reaction is 90°C to 100°C, and the time is 1 h to 2 h.
优选的，步骤a)中所述冷却的温度为20℃～30℃。Preferably, the cooling temperature in step a) is 20°C to 30°C.
本发明提供了一种水性低温热转印胶，由包括以下组分的原料制得：乙烯丙烯酸树脂20～30重量份；碱性中和剂3～10重量份；流平助剂0.3～0.5重量份；蜡乳液1～5重量份；增塑剂1～3重量份；消泡剂0.01～0.05重量份；水65～80重量份；所述增塑剂选自甘油、己二酸二辛酯和癸二酸二辛酯中的一种或多种。与现有技术相比，本发明提供的水性低温热转印胶采用特定含量组分，实现整体较好的相互作用，产品具有较好的流平性、耐水性、耐刮擦性，以及优异的低温转印图文完整性，并且为纯水性材料，环保无污染。实验结果表明，本发明提供的水性低温热转印胶流平性良好，形成的涂层在45℃～60℃水水洗1h后不发白溶胀，刮擦涂层外观依然保持完好，涂层可以拉伸2～2.6倍不断，110℃～125℃低温转印图文完整，印刷性能好，可以实现油墨不脱落且色彩鲜艳。The invention provides an aqueous low-temperature thermal transfer adhesive, which is prepared from raw materials comprising the following components: 20-30 parts by weight of ethylene acrylic resin; 3-10 parts by weight of alkaline neutralizer; 0.3-0.5 parts by weight of leveling aid 1-5 parts by weight of wax emulsion; 1-3 parts by weight of plasticizer; 0.01-0.05 parts by weight of defoamer; 65-80 parts by weight of water; the plasticizer is selected from glycerol, dioctyl adipate and one or more of dioctyl sebacate. Compared with the prior art, the water-based low-temperature thermal transfer adhesive provided by the present invention adopts a specific content of components to achieve overall better interaction, and the product has better leveling, water resistance, scratch resistance, and excellent The integrity of the low-temperature transfer image and text, and it is a pure water-based material, which is environmentally friendly and pollution-free. The experimental results show that the water-based low-temperature thermal transfer adhesive provided by the present invention has good leveling properties, the formed coating does not turn white and swell after being washed with water at 45°C to 60°C for 1 hour, the appearance of the scratched coating remains intact, and the coating can be Stretching 2 to 2.6 times continuously, low temperature transfer at 110 ° C ~ 125 ° C, the image and text are complete, the printing performance is good, and the ink can not fall off and the color is bright.
另外，本发明提供的制备方法工艺简单，条件温和、易控，具有广阔的应用前景。In addition, the preparation method provided by the invention has simple process, mild conditions and easy control, and has broad application prospects.
具体实施方式Detailed ways
下面将结合本发明实施例，对本发明的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.
本发明提供了一种水性低温热转印胶，由包括以下组分的原料制得：The invention provides a water-based low-temperature thermal transfer adhesive, which is prepared from raw materials comprising the following components:
乙烯丙烯酸树脂20～30重量份；20-30 parts by weight of ethylene acrylic resin;
碱性中和剂3～10重量份；3-10 parts by weight of alkaline neutralizer;
流平助剂0.3～0.5重量份；0.3-0.5 parts by weight of leveling aid;
蜡乳液1～5重量份；1 to 5 parts by weight of wax emulsion;
增塑剂1～3重量份；1 to 3 parts by weight of plasticizer;
消泡剂0.01～0.05重量份；0.01-0.05 parts by weight of defoamer;
水65～80重量份；65-80 parts by weight of water;
所述增塑剂选自甘油、己二酸二辛酯和癸二酸二辛酯中的一种或多种。The plasticizer is selected from one or more of glycerol, dioctyl adipate and dioctyl sebacate.
在本发明中，所述水性低温热转印胶由包括乙烯丙烯酸树脂、碱性中和剂、流平助剂、蜡乳液、增塑剂、消泡剂和水的原料制得，优选由乙烯丙烯酸树脂、碱性中和剂、流平助剂、蜡乳液、增塑剂、消泡剂和水制得。In the present invention, the water-based low temperature thermal transfer adhesive is prepared from raw materials including ethylene acrylic resin, alkaline neutralizer, leveling aid, wax emulsion, plasticizer, defoamer and water, preferably ethylene acrylic acid Resin, alkaline neutralizer, leveling aid, wax emulsion, plasticizer, defoamer and water.
在本发明中，所述乙烯丙烯酸树脂的熔融指数优选为300～1300，熔点优选为75℃～78℃。本发明对所述乙烯丙烯酸树脂的来源没有特殊限制，采用本领域技术人员熟知的市售商品或自制品均可；如可采用本领域技术人员熟知的通过乙烯-醋酸乙烯共聚物、甲基丙烯酸二十二烷醇脂、甲基丙烯酸甲酯作为主要成分制备得到；保证EAA参数满足上述原料要求即可。在本发明中，所述水性低温热转印胶包括20～30重量份的乙烯丙烯酸树脂，优选为20～28重量份。In the present invention, the melt index of the ethylene acrylic resin is preferably 300 to 1300, and the melting point is preferably 75°C to 78°C. The source of the ethylene acrylic resin is not particularly limited in the present invention, and commercially available products or self-made products well-known to those skilled in the art can be used; Docosanol ester and methyl methacrylate are prepared as main components; it is sufficient to ensure that the EAA parameters meet the above-mentioned raw material requirements. In the present invention, the water-based low temperature thermal transfer adhesive comprises 20-30 parts by weight of ethylene acrylic resin, preferably 20-28 parts by weight.
在本发明中，所述碱性中和剂优选选自氨水、KOH、NaOH和三乙胺中的一种或多种，更优选为氨水、KOH、NaOH和三乙胺中的一种或两种。本发明对所述碱性中和剂的来源没有特殊限制，采用本领域技术人员熟知的上述氨水、KOH、NaOH和三乙胺的市售商品即可。In the present invention, the alkaline neutralizer is preferably selected from one or more of ammonia water, KOH, NaOH and triethylamine, more preferably one or more of ammonia water, KOH, NaOH and triethylamine kind. The present invention has no special limitation on the source of the alkaline neutralizer, and the commercially available products of the above-mentioned ammonia water, KOH, NaOH and triethylamine well known to those skilled in the art can be used.
在本发明中，所述流平助剂优选选自Glide 410、Wet KL 245和Glide 496中的一种或多种，更优选为Glide 410、Wet KL 245或Glide 496。本发明对所述流平助剂的来源没有特殊限制，采用本领域技术人员熟知的上述Glide 410、Wet KL 245和Glide 496的市售商品即可。In the present invention, the leveling aid is preferably selected from one or more of Glide 410, Wet KL 245 and Glide 496, more preferably Glide 410, Wet KL 245 or Glide 496. The source of the leveling aid is not particularly limited in the present invention, and the commercially available products of the above-mentioned Glide 410, Wet KL 245 and Glide 496 well known to those skilled in the art can be used.
在本发明中，所述蜡乳液优选选自棕榈蜡、聚乙烯蜡、氧化聚乙烯蜡和微粉蜡中的一种或多种，更优选为棕榈蜡、聚乙烯蜡、氧化聚乙烯蜡或微粉蜡。本发明对所述蜡乳液的来源没有特殊限制，采用本领域技术人员熟知的上述棕榈蜡、聚乙烯蜡、氧化聚乙烯蜡和微粉蜡的市售商品即可。在本发明中，所述水性低温热转印胶包括1～5重量份的蜡乳液，优选为2～5重量份。In the present invention, the wax emulsion is preferably selected from one or more of palm wax, polyethylene wax, oxidized polyethylene wax and micronized wax, more preferably palm wax, polyethylene wax, oxidized polyethylene wax or micronized powder wax. The source of the wax emulsion is not particularly limited in the present invention, and the commercially available products of the above-mentioned palm wax, polyethylene wax, oxidized polyethylene wax and micronized wax well known to those skilled in the art can be used. In the present invention, the water-based low temperature thermal transfer adhesive comprises 1-5 parts by weight of wax emulsion, preferably 2-5 parts by weight.
在本发明中，所述增塑剂选自甘油、己二酸二辛酯和癸二酸二辛酯中的一 种或多种，优选为甘油、己二酸二辛酯或癸二酸二辛酯。本发明对所述增塑剂的来源没有特殊限制，采用本领域技术人员熟知的上述甘油、己二酸二辛酯和癸二酸二辛酯的市售商品即可。在本发明中，所述水性低温热转印胶包括1～3重量份的增塑剂，优选为1～2重量份。In the present invention, the plasticizer is selected from one or more of glycerol, dioctyl adipate and dioctyl sebacate, preferably glycerol, dioctyl adipate or dioctyl sebacate Octyl ester. The present invention has no particular limitation on the source of the plasticizer, and the commercially available products of the above-mentioned glycerol, dioctyl adipate and dioctyl sebacate well known to those skilled in the art can be used. In the present invention, the water-based low temperature thermal transfer adhesive includes 1-3 parts by weight of plasticizer, preferably 1-2 parts by weight.
在本发明中，所述消泡剂优选为聚醚改性有机硅类消泡剂；本发明对其来源没有特殊限制，采用本领域技术人员熟知的市售商品即可。In the present invention, the defoamer is preferably a polyether-modified organosilicon defoamer; the present invention has no special limitation on its source, and a commercially available commodity well known to those skilled in the art can be used.
在本发明中，所述水为本领域技术人员熟知的软水，本发明对此没有特殊限制。在本发明中，所述水性低温热转印胶包括65～80重量份的水，优选为72～80重量份。In the present invention, the water is soft water well known to those skilled in the art, which is not particularly limited in the present invention. In the present invention, the water-based low temperature thermal transfer adhesive comprises 65-80 parts by weight of water, preferably 72-80 parts by weight.
在本发明中，所述水性低温热转印胶的固含量优选为20％～30％；储存时低温、避光、密封。In the present invention, the solid content of the water-based low-temperature thermal transfer adhesive is preferably 20% to 30%; during storage, it is kept at a low temperature, protected from light, and sealed.
本发明提供的水性低温热转印胶采用特定含量组分，实现整体较好的相互作用，产品具有较好的流平性、耐水性、耐刮擦性，以及优异的低温转印图文完整性，并且为纯水性材料，完全水性的配方不会有任何残留，符合环保、易用、稳定的市场要求，可以放心使用；并且，本发明提供的水性低温热转印胶可以涂布在离型膜或离型纸等基材上，具有良好的产品适应性。实验结果表明，本发明提供的水性低温热转印胶流平性良好，形成的涂层在45℃～60℃水水洗1h后不发白溶胀，刮擦涂层外观依然保持完好，涂层可以拉伸2～2.6倍不断；对比同等固含的产品转印温度为160℃～180℃，本发明提供的产品转印需要的温度为110℃～125℃，且110℃～125℃低温转印图文完整，印刷性能好，可以实现油墨不脱落且色彩鲜艳。The water-based low-temperature thermal transfer adhesive provided by the present invention adopts specific content of components to achieve overall better interaction, and the product has better leveling, water resistance, scratch resistance, and excellent low-temperature transfer image and text integrity. It is a pure water-based material, and the completely water-based formula will not have any residue, which meets the market requirements of environmental protection, ease of use, and stability, and can be used with confidence; and the water-based low-temperature thermal transfer adhesive provided by the present invention can be coated on It has good product adaptability on substrates such as release film or release paper. The experimental results show that the water-based low-temperature thermal transfer adhesive provided by the present invention has good leveling properties, the formed coating does not turn white and swell after being washed with water at 45°C to 60°C for 1 hour, the appearance of the scratched coating remains intact, and the coating can be Stretching 2 to 2.6 times continuously; compared to the transfer temperature of the product with the same solid content of 160 ° C to 180 ° C, the temperature required for the transfer of the product provided by the present invention is 110 ° C to 125 ° C, and the low temperature transfer temperature of 110 ° C to 125 ° C The picture and text are complete, the printing performance is good, and the ink can not fall off and the color is bright.
本发明还提供了一种上述技术方案所述的水性低温热转印胶的制备方法，包括以下步骤：The present invention also provides a preparation method of the water-based low-temperature thermal transfer adhesive described in the above technical solution, comprising the following steps:
a)在搅拌条件下，将第一用量的水、第二用量的碱性中和剂、增塑剂混合后，加入乙烯丙烯酸树脂，进行第一次反应；然后以4g/s～6g/s的速度滴加剩余的碱性中和剂，进行第二次反应；之后，以45g/s～55g/s的速度加入剩余的水，进行第三次反应；冷却后加入消泡剂、流平助剂混合均匀，最后添加蜡乳液，得到水性低温热转印胶。a) Under stirring conditions, after mixing the first amount of water, the second amount of alkaline neutralizer and plasticizer, add ethylene acrylic resin to carry out the first reaction; Add the remaining alkaline neutralizer dropwise at a speed of 45g/s to carry out the second reaction; after that, add the remaining water at a speed of 45g/s～55g/s to carry out the third reaction; after cooling, add defoamer and leveling aid The agent is mixed evenly, and finally the wax emulsion is added to obtain a water-based low-temperature thermal transfer adhesive.
在本发明中，所述水、碱性中和剂、增塑剂、乙烯丙烯酸树脂、蜡乳液、 消泡剂、流平助剂与上述技术方案中的相同，在此不再赘述。In the present invention, the water, alkaline neutralizer, plasticizer, ethylene acrylic resin, wax emulsion, defoamer, and leveling aid are the same as those in the above-mentioned technical solutions, and will not be repeated here.
在本发明中，所述搅拌条件在整个制备方法中持续进行；所述搅拌的转速优选为100r/min～500r/min。本发明对所述制备方法所用的装置没有特殊限制，采用本领域技术人员熟知的反应釜即可。In the present invention, the stirring conditions are continuously carried out in the whole preparation method; the rotation speed of the stirring is preferably 100r/min～500r/min. The device used in the preparation method is not particularly limited in the present invention, and a reaction kettle well-known to those skilled in the art can be used.
在本发明中，所述第一用量的水、第二用量的碱性中和剂、增塑剂混合的时间优选为1min～10min，更优选为5min。In the present invention, the mixing time of the first amount of water, the second amount of the alkaline neutralizer and the plasticizer is preferably 1 min to 10 min, more preferably 5 min.
在本发明中，所述第一用量的水优选占水总量的70～90wt％；所述第二用量的碱性中和剂优选占碱性中和剂总量的70～80wt％。In the present invention, the first amount of water preferably accounts for 70-90 wt% of the total amount of water; the second amount of the alkaline neutralizer preferably accounts for 70-80 wt% of the total alkaline neutralizer.
在本发明中，所述第一次反应的温度优选为90℃～100℃，更优选为90℃～98℃；所述第一次反应的时间优选为1h～2h。In the present invention, the temperature of the first reaction is preferably 90°C to 100°C, more preferably 90°C to 98°C; the time of the first reaction is preferably 1 h to 2 h.
在本发明中，所述第二次反应的温度优选为90℃～100℃，更优选为90℃～98℃；所述第二次反应的时间优选为0.5h～1h。In the present invention, the temperature of the second reaction is preferably 90°C to 100°C, more preferably 90°C to 98°C; the time of the second reaction is preferably 0.5h to 1h.
在本发明中，所述第三次反应的温度优选为90℃～100℃，更优选为95℃～100℃；所述第三次反应的时间优选为1h～2h。In the present invention, the temperature of the third reaction is preferably 90°C to 100°C, more preferably 95°C to 100°C; the time of the third reaction is preferably 1 h to 2 h.
在本发明中，所述冷却的温度优选为20℃～30℃，更优选为25℃。In the present invention, the cooling temperature is preferably 20°C to 30°C, more preferably 25°C.
本发明提供的制备方法工艺简单，条件温和、易控，具有广阔的应用前景。The preparation method provided by the invention has simple process, mild conditions and easy control, and has broad application prospects.
本发明提供了一种水性低温热转印胶，由包括以下组分的原料制得：乙烯丙烯酸树脂20～30重量份；碱性中和剂3～10重量份；流平助剂0.3～0.5重量份；蜡乳液1～5重量份；增塑剂1～3重量份；消泡剂0.01～0.05重量份；水65～80重量份；所述增塑剂选自甘油、己二酸二辛酯和癸二酸二辛酯中的一种或多种。与现有技术相比，本发明提供的水性低温热转印胶采用特定含量组分，实现整体较好的相互作用，产品具有较好的流平性、耐水性、耐刮擦性，以及优异的低温转印图文完整性，并且为纯水性材料，环保无污染。实验结果表明，本发明提供的水性低温热转印胶流平性良好，形成的涂层在45℃～60℃水水洗1h后不发白溶胀，刮擦涂层外观依然保持完好，涂层可以拉伸2～2.6倍不断，110℃～125℃低温转印图文完整，印刷性能好，可以实现油墨不脱落且色彩鲜艳。The invention provides an aqueous low-temperature thermal transfer adhesive, which is prepared from raw materials comprising the following components: 20-30 parts by weight of ethylene acrylic resin; 3-10 parts by weight of alkaline neutralizer; 0.3-0.5 parts by weight of leveling aid 1-5 parts by weight of wax emulsion; 1-3 parts by weight of plasticizer; 0.01-0.05 parts by weight of defoamer; 65-80 parts by weight of water; the plasticizer is selected from glycerol, dioctyl adipate and one or more of dioctyl sebacate. Compared with the prior art, the water-based low-temperature thermal transfer adhesive provided by the present invention adopts a specific content of components to achieve overall better interaction, and the product has better leveling, water resistance, scratch resistance, and excellent The integrity of the low-temperature transfer image and text, and it is a pure water-based material, which is environmentally friendly and pollution-free. The experimental results show that the water-based low-temperature thermal transfer adhesive provided by the present invention has good leveling properties, the formed coating does not turn white and swell after being washed with water at 45°C to 60°C for 1 hour, the appearance of the scratched coating remains intact, and the coating can be Stretching 2 to 2.6 times continuously, low temperature transfer at 110 ° C ~ 125 ° C, the image and text are complete, the printing performance is good, and the ink can not fall off and the color is bright.
另外，本发明提供的制备方法工艺简单，条件温和、易控，具有广阔的应用前景。In addition, the preparation method provided by the invention has simple process, mild conditions and easy control, and has broad application prospects.
为了进一步说明本发明，下面通过以下实施例进行详细说明。本发明以下实施例所用原料均为市售。In order to further illustrate the present invention, the following examples are used for detailed description. The raw materials used in the following examples of the present invention are all commercially available.
实施例1Example 1
(1)原料重量配比及具体种类限定：(1) Raw material weight ratio and specific type limitation:
Figure PCTCN2021092002-appb-000001
Figure PCTCN2021092002-appb-000001
所述乙烯丙烯酸树脂的熔融指数为300，熔点77℃；The melt index of the ethylene acrylic resin is 300, and the melting point is 77°C;
所述碱性中和剂为氨水；Described alkaline neutralizer is ammoniacal liquor;
所述流平助剂为Glide 410；Described leveling aid is Glide 410;
所述蜡乳液为氧化聚乙烯蜡；The wax emulsion is oxidized polyethylene wax;
所述增塑剂为甘油；The plasticizer is glycerol;
所述消泡剂为聚醚改性有机硅类消泡剂。The defoamer is a polyether-modified organosilicon defoamer.
(2)制备方法步骤如下：(2) the preparation method steps are as follows:
取总水量70wt％的软水加入反应釜中，开启搅拌并将搅拌速度控制为100r/min，加80wt％的碱性中和剂、全部的增塑剂搅拌5min，再加入全部的乙烯丙烯酸树脂，控制温度为90℃，保温反应1h；然后以5g/s的速度缓慢滴加剩余20wt％的碱性中和剂，再将乳液温度控制为95℃，保温反应0.5h；之后，以50g/s的速度加入剩余30wt％的软水，再将乳液温度控制为95℃，保温反应2h；最后降温至25℃后加入所有的消泡剂、流平助剂混合均匀，最后添加所有蜡乳液，得到水性低温热转印胶；所得水性低温热转印胶的固含为21.5wt％。Take soft water with a total water volume of 70wt% and add it into the reaction kettle, start stirring and control the stirring speed to be 100r/min, add 80wt% of alkaline neutralizer and all plasticizers and stir for 5min, then add all ethylene acrylic resin, The temperature was controlled at 90°C, and the reaction was incubated for 1 h; then the remaining 20wt% alkaline neutralizer was slowly added dropwise at a rate of 5g/s, and the temperature of the emulsion was controlled to 95°C, and the reaction was incubated for 0.5h; Add the remaining 30wt% soft water at the same speed, then control the temperature of the emulsion to 95 °C, and keep the reaction for 2 h; finally, cool down to 25 °C, add all the defoaming agents and leveling aids and mix evenly, and finally add all the wax emulsion to obtain a water-based low temperature Thermal transfer adhesive; the solid content of the obtained water-based low-temperature thermal transfer adhesive is 21.5 wt %.
将本发明实施例1提供的水性低温热转印胶涂布在PET离型膜上，乳液流平性良好，烘干后形成涂层，干胶量为50g/m 2，经检测，该涂层在45℃温水水洗1h后不发白溶胀，刮擦涂层外观依然保持完好，涂层可以拉伸2倍不断(使用拉伸机测试剥离强度的方法，涂层长度拉到2倍不断裂)，125℃低温 转印图文完整，印刷性能好，可以实现油墨不脱落且色彩鲜艳。 The water-based low-temperature thermal transfer adhesive provided in Example 1 of the present invention was coated on the PET release film, the emulsion leveling was good, and a coating was formed after drying, and the dry glue amount was 50 g/m 2 . The coating does not turn white and swell after being washed in warm water at 45°C for 1 hour, the appearance of the scratched coating remains intact, and the coating can be stretched 2 times continuously (using a tensile machine to test the peel strength, the coating length is stretched to 2 times without breaking ), 125 ℃ low temperature transfer image is complete, the printing performance is good, and the ink can not fall off and the color is bright.
实施例2Example 2
(1)原料重量配比及具体种类限定：(1) Raw material weight ratio and specific type limitation:
Figure PCTCN2021092002-appb-000002
Figure PCTCN2021092002-appb-000002
所述乙烯丙烯酸树脂的熔融指数为300，熔点77℃；The melt index of the ethylene acrylic resin is 300, and the melting point is 77°C;
所述碱性中和剂为重量比为1：1的氨水和三乙胺；The alkaline neutralizer is ammonia water and triethylamine with a weight ratio of 1:1;
所述流平助剂为Wet KL 245；Described leveling aid is Wet KL 245;
所述蜡乳液为聚乙烯蜡；The wax emulsion is polyethylene wax;
所述增塑剂为己二酸二辛酯；The plasticizer is dioctyl adipate;
所述消泡剂为聚醚改性有机硅类消泡剂。The defoamer is a polyether-modified organosilicon defoamer.
(2)制备方法步骤如下：(2) the preparation method steps are as follows:
取总水量80wt％的软水加入反应釜中，开启搅拌并将搅拌速度控制为300r/min，加70wt％的碱性中和剂、全部的增塑剂搅拌5min，再加入全部的乙烯丙烯酸树脂，控制温度为95℃，保温反应1h；然后以5g/s的速度缓慢滴加剩余30wt％的碱性中和剂，再将乳液温度控制为95℃，保温反应0.5h；之后，以50g/s的速度加入剩余20wt％的软水，再将乳液温度控制为99℃，保温反应2h；最后降温至25℃后加入所有的消泡剂、流平助剂混合均匀，最后添加所有蜡乳液，得到水性低温热转印胶；所得水性低温热转印胶的固含为26.3wt％。Take soft water with a total water volume of 80wt% and add it to the reaction kettle, start stirring and control the stirring speed to 300r/min, add 70wt% of alkaline neutralizer and all plasticizers and stir for 5min, then add all ethylene acrylic resin, The temperature was controlled to 95°C, and the reaction was kept for 1 h; then the remaining 30wt% alkaline neutralizer was slowly added dropwise at a rate of 5g/s, and the temperature of the emulsion was controlled to 95°C, and the reaction was kept for 0.5h; Add the remaining 20wt% of soft water at the same speed, then control the temperature of the emulsion to 99°C, and keep the reaction for 2h; finally, cool down to 25°C, add all the defoaming agents and leveling aids and mix evenly, and finally add all the wax emulsion to obtain a water-based low temperature Thermal transfer adhesive; the solid content of the obtained water-based low-temperature thermal transfer adhesive is 26.3 wt %.
将本发明实施例2提供的水性低温热转印胶涂布在PET离型膜上，乳液流平性良好，烘干后形成涂层，干胶量为80g/m 2，经检测，该涂层在50℃水水洗1h后不发白溶胀，刮擦涂层外观依然保持完好，涂层可以拉伸2倍不断(使用拉伸机测试剥离强度的方法，涂层长度拉到2倍不断裂)，125℃低温转印图文完整，印刷性能好，可以实现油墨不脱落且色彩鲜艳。 The water-based low-temperature thermal transfer adhesive provided in Example 2 of the present invention was coated on the PET release film, the emulsion leveling was good, and a coating was formed after drying, and the dry glue amount was 80 g/m 2 . The coating does not turn white and swell after being washed with water at 50°C for 1 hour, the appearance of the scratched coating remains intact, and the coating can be stretched 2 times continuously (using a tensile machine to test the peel strength, the coating length is stretched to 2 times without breaking ), 125 ℃ low temperature transfer image is complete, the printing performance is good, and the ink can not fall off and the color is bright.
实施例3Example 3
(1)原料重量配比及具体种类限定：(1) Raw material weight ratio and specific type limitation:
Figure PCTCN2021092002-appb-000003
Figure PCTCN2021092002-appb-000003
所述乙烯丙烯酸树脂的熔融指数为1300，熔点77℃；The melt index of the ethylene acrylic resin is 1300, and the melting point is 77°C;
所述碱性中和剂为重量比为1：1的氨水和三乙胺；The alkaline neutralizer is ammonia water and triethylamine with a weight ratio of 1:1;
所述流平助剂为Wet KL 245；Described leveling aid is Wet KL 245;
所述蜡乳液为氧化聚乙烯蜡；The wax emulsion is oxidized polyethylene wax;
所述增塑剂为甘油；The plasticizer is glycerol;
所述消泡剂为聚醚改性有机硅类消泡剂。The defoamer is a polyether-modified organosilicon defoamer.
(2)制备方法步骤如下：(2) the preparation method steps are as follows:
取总水量90wt％的软水加入反应釜中，开启搅拌并将搅拌速度控制为100r/min，加80wt％的碱性中和剂、全部的增塑剂搅拌5min，再加入全部的乙烯丙烯酸树脂，控制温度为90℃，保温反应1h；然后以5g/s的速度缓慢滴加剩余20wt％的碱性中和剂，再将乳液温度控制为95℃，保温反应0.5h；之后，以50g/s的速度加入剩余10wt％的软水，再将乳液温度控制为95℃，保温反应2h；最后降温至25℃后加入所有的消泡剂、流平助剂混合均匀，最后添加所有蜡乳液，得到水性低温热转印胶；所得水性低温热转印胶的固含为30.0wt％。Take soft water with a total water volume of 90wt% and add it to the reaction kettle, start stirring and control the stirring speed to 100r/min, add 80wt% of alkaline neutralizer and all plasticizers and stir for 5min, then add all ethylene acrylic resin, The temperature was controlled at 90°C, and the reaction was incubated for 1 h; then the remaining 20wt% alkaline neutralizer was slowly added dropwise at a rate of 5g/s, and the temperature of the emulsion was controlled to 95°C, and the reaction was incubated for 0.5h; Add the remaining 10wt% of soft water at the same speed, then control the temperature of the emulsion to 95°C, and keep the reaction for 2h; finally, cool down to 25°C, add all the defoaming agents and leveling aids and mix evenly, and finally add all the wax emulsion to obtain a water-based low temperature Thermal transfer adhesive; the solid content of the obtained water-based low-temperature thermal transfer adhesive is 30.0 wt %.
将本发明实施例3提供的水性低温热转印胶涂布在离型纸上，乳液流平性良好，烘干后形成涂层，干胶量为60g/m 2，经检测，该涂层在60℃水水洗1h后不发白溶胀，刮擦涂层外观依然保持完好，涂层可以拉伸2.6倍不断(使用拉伸机测试剥离强度的方法，涂层长度拉到2.6倍不断裂)，110℃低温转印图文完整，印刷性能好，可以实现油墨不脱落且色彩鲜艳。 The water-based low-temperature thermal transfer adhesive provided in Example 3 of the present invention was coated on the release paper, the emulsion leveling was good, and a coating was formed after drying. The dry glue amount was 60g/m 2 . After testing, the coating was After washing with water at 60°C for 1 hour, it will not turn white and swell, the appearance of the scratched coating remains intact, and the coating can be stretched 2.6 times continuously (the method of using a tensile machine to test the peel strength, the coating length is stretched to 2.6 times without breaking) , 110 ℃ low temperature transfer image is complete, good printing performance, can achieve the ink does not fall off and the color is bright.
实施例4Example 4
(1)原料重量配比及具体种类限定：(1) Raw material weight ratio and specific type limitation:
Figure PCTCN2021092002-appb-000004
Figure PCTCN2021092002-appb-000004
所述乙烯丙烯酸树脂的熔融指数为1300，熔点77℃；The melt index of the ethylene acrylic resin is 1300, and the melting point is 77°C;
所述碱性中和剂为NaOH；The alkaline neutralizer is NaOH;
所述流平助剂为Glide 496；Described leveling aid is Glide 496;
所述蜡乳液为氧化聚乙烯蜡；The wax emulsion is oxidized polyethylene wax;
所述增塑剂为癸二酸二辛酯；The plasticizer is dioctyl sebacate;
所述消泡剂为聚醚改性有机硅类消泡剂。The defoamer is a polyether-modified organosilicon defoamer.
(2)制备方法步骤如下：(2) the preparation method steps are as follows:
取总水量80wt％的软水加入反应釜中，开启搅拌并将搅拌速度控制为500r/min，加80wt％的碱性中和剂、全部的增塑剂搅拌5min，再加入全部的乙烯丙烯酸树脂，控制温度为98℃，保温反应2h；然后以5g/s的速度缓慢滴加剩余20wt％的碱性中和剂，再将乳液温度控制为95℃，保温反应0.5h；之后，以50g/s的速度加入剩余20wt％的软水，再将乳液温度控制为100℃，保温反应1h；最后降温至25℃后加入所有的消泡剂、流平助剂混合均匀，最后添加所有蜡乳液，得到水性低温热转印胶；所得水性低温热转印胶的固含为27.5wt％。Take the soft water with a total water volume of 80wt% and add it to the reaction kettle, start the stirring and control the stirring speed to 500r/min, add 80wt% of the alkaline neutralizer and all the plasticizers and stir for 5min, then add all the ethylene acrylic resin, The temperature was controlled at 98°C, and the reaction was incubated for 2h; then the remaining 20wt% alkaline neutralizer was slowly added dropwise at a rate of 5g/s, and the temperature of the emulsion was controlled to 95°C, and the reaction was incubated for 0.5h; Add the remaining 20wt% of soft water at the same speed, then control the temperature of the emulsion to 100 °C, and keep the reaction for 1 h; finally, cool down to 25 °C, add all the defoaming agents and leveling aids and mix evenly, and finally add all the wax emulsion to obtain a water-based low temperature Thermal transfer adhesive; the solid content of the obtained water-based low-temperature thermal transfer adhesive is 27.5 wt %.
将本发明实施例4提供的水性低温热转印胶涂布在PET离型膜上，乳液流平性良好，烘干后形成涂层，干胶量为50g/m 2，经检测，该涂层在50℃水水洗1h后不发白溶胀，刮擦涂层外观依然保持完好，涂层可以拉伸2倍不断(使用拉伸机测试剥离强度的方法，涂层长度拉到2倍不断裂)，120℃低温转印图文完整，印刷性能好，可以实现油墨不脱落且色彩鲜艳。 The water-based low-temperature thermal transfer adhesive provided in Example 4 of the present invention was coated on the PET release film, the emulsion leveling was good, and a coating was formed after drying, and the dry glue amount was 50 g/m 2 . The coating does not turn white and swell after being washed with water at 50°C for 1 hour, the appearance of the scratched coating remains intact, and the coating can be stretched 2 times continuously (using a tensile machine to test the peel strength, the coating length is stretched to 2 times without breaking ), 120 ℃ low temperature transfer image is complete, the printing performance is good, and the ink can not fall off and the color is bright.
实施例5Example 5
(1)原料重量配比及具体种类限定：(1) Raw material weight ratio and specific type limitation:
Figure PCTCN2021092002-appb-000005
Figure PCTCN2021092002-appb-000005
所述乙烯丙烯酸树脂的熔融指数为300，熔点77℃；The melt index of the ethylene acrylic resin is 300, and the melting point is 77°C;
所述碱性中和剂为重量比为5：1的三乙醇胺和KOH；The alkaline neutralizer is triethanolamine and KOH in a weight ratio of 5:1;
所述流平助剂为Glide 410；Described leveling aid is Glide 410;
所述蜡乳液为氧化聚乙烯蜡；The wax emulsion is oxidized polyethylene wax;
所述增塑剂为己二酸二辛酯；The plasticizer is dioctyl adipate;
所述消泡剂为聚醚改性有机硅类消泡剂。The defoamer is a polyether-modified organosilicon defoamer.
(2)制备方法步骤如下：(2) the preparation method steps are as follows:
取总水量70wt％的软水加入反应釜中，开启搅拌并将搅拌速度控制为300r/min，加80wt％的碱性中和剂、全部的增塑剂搅拌5min，再加入全部的乙烯丙烯酸树脂，控制温度为92℃，保温反应2h；然后以5g/s的速度缓慢滴加剩余20wt％的碱性中和剂，再将乳液温度控制为98℃，保温反应1h；之后，以50g/s的速度加入剩余30wt％的软水，再将乳液温度控制为95℃，保温反应2h；最后降温至25℃后加入所有的消泡剂、流平助剂混合均匀，最后添加所有蜡乳液，得到水性低温热转印胶；所得水性低温热转印胶的固含为25.5wt％。Take soft water with a total water volume of 70wt% and add it into the reaction kettle, start stirring and control the stirring speed to 300r/min, add 80wt% of alkaline neutralizer and all plasticizers and stir for 5min, then add all ethylene acrylic resin, The temperature was controlled at 92°C, and the reaction was incubated for 2h; then the remaining 20wt% alkaline neutralizer was slowly added dropwise at a rate of 5g/s, and the temperature of the emulsion was controlled at 98°C, and the reaction was incubated for 1h; The remaining 30wt% soft water was added at a speed, and then the temperature of the emulsion was controlled to 95 ℃, and the reaction was kept for 2 h; finally, the temperature was lowered to 25 ℃, and all the defoaming agents and leveling aids were added to mix evenly, and finally all the wax emulsion was added to obtain an aqueous low-temperature heat Transfer adhesive; the solid content of the obtained water-based low-temperature thermal transfer adhesive is 25.5 wt %.
将本发明实施例5提供的水性低温热转印胶涂布在离型纸上，乳液流平性良好，烘干后形成涂层，干胶量为70g/m 2，经检测，该涂层在60℃水水洗1h后不发白溶胀，刮擦涂层外观依然保持完好，涂层可以拉伸2.2倍不断(使用拉伸机测试剥离强度的方法，涂层长度拉到2.2倍不断裂)，110℃低温转印图文完整，印刷性能好，可以实现油墨不脱落且色彩鲜艳。 The water-based low-temperature thermal transfer adhesive provided in Example 5 of the present invention was coated on the release paper, the emulsion leveling was good, and a coating was formed after drying, and the dry glue amount was 70g/m 2 . After testing, the coating After washing with water at 60°C for 1 hour, it does not turn white and swell, the appearance of the scratched coating remains intact, and the coating can be stretched 2.2 times continuously (using a tensile machine to test the peel strength, the coating length is stretched to 2.2 times without breaking) , 110 ℃ low temperature transfer image is complete, good printing performance, can achieve the ink does not fall off and the color is bright.
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰， 这些改进和润饰也应视为本发明的保护范围。The above are only the preferred embodiments of the present invention. It should be pointed out that for those skilled in the art, without departing from the principles of the present invention, several improvements and modifications can also be made. It should be regarded as the protection scope of the present invention.

Claims (10)

  1. 一种水性低温热转印胶，由包括以下组分的原料制得：A water-based low-temperature thermal transfer adhesive is prepared from raw materials comprising the following components:
    乙烯丙烯酸树脂20～30重量份；20-30 parts by weight of ethylene acrylic resin;
    碱性中和剂3～10重量份；3-10 parts by weight of alkaline neutralizer;
    流平助剂0.3～0.5重量份；0.3-0.5 parts by weight of leveling aid;
    蜡乳液1～5重量份；1 to 5 parts by weight of wax emulsion;
    增塑剂1～3重量份；1 to 3 parts by weight of plasticizer;
    消泡剂0.01～0.05重量份；0.01-0.05 parts by weight of defoamer;
    水65～80重量份；65-80 parts by weight of water;
    所述增塑剂选自甘油、己二酸二辛酯和癸二酸二辛酯中的一种或多种。The plasticizer is selected from one or more of glycerol, dioctyl adipate and dioctyl sebacate.
  2. 根据权利要求1所述的水性低温热转印胶，其特征在于，所述乙烯丙烯酸树脂的熔融指数为300～1300，熔点为75℃～78℃。The water-based low temperature thermal transfer adhesive according to claim 1, wherein the ethylene acrylic resin has a melt index of 300-1300 and a melting point of 75°C to 78°C.
  3. 根据权利要求1所述的水性低温热转印胶，其特征在于，所述碱性中和剂选自氨水、KOH、NaOH和三乙胺中的一种或多种。The water-based low-temperature thermal transfer adhesive according to claim 1, wherein the alkaline neutralizer is selected from one or more of ammonia water, KOH, NaOH and triethylamine.
  4. 根据权利要求1所述的水性低温热转印胶，其特征在于，所述流平助剂选自Glide 410、WetKL 245和Glide 496中的一种或多种。The water-based low temperature thermal transfer adhesive according to claim 1, wherein the leveling aid is selected from one or more of Glide 410, WetKL 245 and Glide 496.
  5. 根据权利要求1所述的水性低温热转印胶，其特征在于，所述蜡乳液选自棕榈蜡、聚乙烯蜡、氧化聚乙烯蜡和微粉蜡中的一种或多种。The water-based low-temperature thermal transfer adhesive according to claim 1, wherein the wax emulsion is selected from one or more of palm wax, polyethylene wax, oxidized polyethylene wax and micropowder wax.
  6. 一种权利要求1～5任一项所述的水性低温热转印胶的制备方法，包括以下步骤：A preparation method of the water-based low-temperature thermal transfer adhesive according to any one of claims 1 to 5, comprising the following steps:
    a)在搅拌条件下，将第一用量的水、第二用量的碱性中和剂、增塑剂混合后，加入乙烯丙烯酸树脂，进行第一次反应；然后以4g/s～6g/s的速度滴加剩余的碱性中和剂，进行第二次反应；之后，以45g/s～55g/s的速度加入剩余的水，进行第三次反应；冷却后加入消泡剂、流平助剂混合均匀，最后添加蜡乳液，得到水性低温热转印胶。a) Under stirring conditions, after mixing the first amount of water, the second amount of alkaline neutralizer and plasticizer, add ethylene acrylic resin to carry out the first reaction; then use 4g/s～6g/s Add the remaining alkaline neutralizer dropwise at a speed of 45g/s to carry out the second reaction; after that, add the remaining water at a speed of 45g/s～55g/s to carry out the third reaction; after cooling, add defoamer, leveling aid The agent is mixed evenly, and finally the wax emulsion is added to obtain a water-based low temperature thermal transfer adhesive.
  7. 根据权利要求6所述的制备方法，其特征在于，步骤a)中所述搅拌的转速为100r/min～500r/min；所述第一用量的水、第二用量的碱性中和剂、增塑剂混合的时间为1min～10min。The preparation method according to claim 6, wherein the stirring speed in step a) is 100r/min～500r/min; the water of the first amount, the alkaline neutralizer of the second amount, The mixing time of the plasticizer is 1 min to 10 min.
  8. 根据权利要求6所述的制备方法，其特征在于，步骤a)中所述第一用量的水占水总量的70～90wt％；所述第二用量的碱性中和剂占碱性中和剂总量的70～80wt％。The preparation method according to claim 6, wherein the first amount of water in step a) accounts for 70-90 wt% of the total amount of water; the second amount of alkaline neutralizer accounts for 70-80wt% of the total amount of the blending agent.
  9. 根据权利要求6所述的制备方法，其特征在于，步骤a)中所述第一次反应的温度为90℃～100℃，时间为1h～2h；The preparation method according to claim 6, wherein the temperature of the first reaction in step a) is 90°C to 100°C, and the time is 1h to 2h;
    所述第二次反应的温度为90℃～100℃，时间为0.5h～1h；The temperature of the second reaction is 90°C～100°C, and the time is 0.5h～1h;
    所述第三次反应的温度为90℃～100℃，时间为1h～2h。The temperature of the third reaction is 90°C to 100°C, and the time is 1 h to 2 h.
  10. 根据权利要求6所述的制备方法，其特征在于，步骤a)中所述冷却的温度为20℃～30℃。The preparation method according to claim 6, wherein the cooling temperature in step a) is 20°C to 30°C.
PCT/CN2021/092002 2021-04-13 2021-05-07 Water-based low-temperature heat transfer printing adhesive and preparation method therefor WO2022217672A1 (en)

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WO1999065998A2 (en) * 1998-06-18 1999-12-23 Ato Findley, Inc. A synthetic based self seal adhesive system for packaging
JP2000177252A (en) * 1998-12-16 2000-06-27 Dainippon Printing Co Ltd Thermal transfer sheet
CN102876250A (en) * 2012-09-24 2013-01-16 无锡市科麦特光电材料有限公司 Ethylene acrylic glue for composite metal strip
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CN111332056A (en) * 2019-11-19 2020-06-26 江苏学泰印务有限公司 Antibacterial corrosion-resistant heat transfer printing film and production process thereof

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US6042931A (en) * 1998-06-08 2000-03-28 Avery Dennison Corporation Heat-transfer label including improved acrylic adhesive layer
CN109517566A (en) * 2018-11-19 2019-03-26 香洋新材料（江苏）有限公司 A kind of aqueous thermal transfer PP adhesive and preparation method thereof

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WO1999065998A2 (en) * 1998-06-18 1999-12-23 Ato Findley, Inc. A synthetic based self seal adhesive system for packaging
JP2000177252A (en) * 1998-12-16 2000-06-27 Dainippon Printing Co Ltd Thermal transfer sheet
CN102876250A (en) * 2012-09-24 2013-01-16 无锡市科麦特光电材料有限公司 Ethylene acrylic glue for composite metal strip
CN106381063A (en) * 2016-08-30 2017-02-08 杭州天地数码科技股份有限公司 Thermal transfer ribbon used for proximal margin printing and production method thereof
CN111332056A (en) * 2019-11-19 2020-06-26 江苏学泰印务有限公司 Antibacterial corrosion-resistant heat transfer printing film and production process thereof

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