Modification process of high-boiling silicone oil and application of high-boiling silicone oil in thermal transfer printing of bar code thermal transfer ribbon

Abstract

The invention relates to application in the technical field of secondary utilization and heat transfer printing of high-boiling silicone oil, in particular to a modification process of high-boiling silicone oil and application of the high-boiling silicone oil in the aspect of heat transfer printing of bar code thermal transfer ribbons. The invention provides a modification process for secondary utilization of high-boiling silicone oil. Taking an alcohol ether compound containing vinyl as a modifier, and carrying out alcoholysis reaction on the modifier and the high-boiling silicone oil in an alcohol-water solvent system, so that the high-boiling silicone oil is modified by the vinyl, and the modified high-boiling silicone oil modified by the vinyl is prepared. The vinyl group introduced high-boiling silicone oil is used for preparing the thermal transfer printing bar code thermal transfer ribbon back coating material, original chemically synthesized modified silicone oil can be well replaced, the adhesive force of the back coating material on a thermal transfer printing thermal transfer ribbon base layer can be remarkably improved, and the thermal transfer printing bar code thermal transfer ribbon back coating material has the advantages of being low in printing noise, good in stability, high in thermal conductivity and the like when applied to thermal transfer printing bar code thermal transfer ribbons. And therefore, an effective way is provided for recycling the high-boiling silicone oil.

Description

Technical Field

[0001] The invention relates to the technical field of secondary utilization of high-boiling silicone oil and thermal transfer printing, and in particular to a modification process of high-boiling silicone oil and its application in thermal transfer barcode carbon ribbon. Background Art

[0002] High-boiling organic silicon products refer to the part of the crude monomer product with a boiling point exceeding 80°C, which is mainly a mixture of various silanes based on Si-Si and Si-C-Si. High-boiling organic silicon products at room temperature and pressure are a brown, pungent and highly corrosive mixed liquid with a density of about 1.13 g / cm 3 , boiling range 80℃~215℃. At present, the mass fraction of high-boiling organic silicon in crude monomer products in China is about 7%~8%, while that in foreign countries is generally 3%~5%.

[0003] In recent years, with the rapid development of the organosilicon industry, the output of methylchlorosilane monomers has increased, and the resulting organosilicon high-boiling products have also increased. However, organosilicon high-boiling products are difficult to be made into valuable organochlorosilanes by simple methods, and their commercial value is low, resulting in a large backlog, which not only causes serious environmental problems and safety hazards, but also wastes resources. Therefore, in order to achieve healthy development of the organosilicon industry and maximize economic benefits, it is urgent to use organosilicon high-boiling products in a reasonable and feasible way for comprehensive utilization.

[0004] In order to improve the comprehensive utilization rate of high-boiling silicone products, alcoholysis is usually used to prepare high-boiling silicone oil from high-boiling silicone products, for example, CN101456955B. The prepared high-boiling silicone oil is usually used to produce silicone waterproofing agents, silicone oils, silicone resins, defoamers and release agents, etc., especially mainly to produce silicone waterproofing agents and defoamers. However, due to limited market capacity, only about one-fifth of the high-boiling silicone oil can be used each year. Therefore, the development of secondary applications of high-boiling silicone oil has become the research focus of scientific researchers in recent years. Summary of the invention

[0005] In order to solve the above problems, the purpose of the present invention is to provide a modification process of high boiling silicone oil and its application in thermal transfer barcode carbon ribbon. The present invention develops new applications of high boiling silicone oil by vinyl modification of high boiling silicone oil.

[0006] To achieve the above objectives, the technical solution of the present invention is as follows.

[0007] The first aspect of the present invention provides a modification process for high boiling silicone oil, comprising the following steps:

[0008] A vinyl-containing alcohol ether compound is used as a modifier to carry out alcoholysis reaction with a high-boiling organosilicon product in an alcohol-water solvent system, so that vinyl is modified on the high-boiling silicone oil to obtain a vinyl-modified high-boiling silicone oil; the high-boiling organosilicon product is a by-product of preparing a methylchlorosilane monomer.

[0009] The present invention mainly uses a vinyl alcohol ether compound as a modifier, introduces a vinyl group into a high-boiling silicone oil, and applies the modifier to prepare a thermal transfer bar code carbon ribbon back coating material, which can significantly improve the adhesion of the prepared thermal transfer bar code carbon ribbon back coating material on the thermal transfer carbon ribbon base layer, improve the use performance in the printing process, and provide a research and development basis for the use of high-boiling silicone oil in the thermal transfer bar code carbon ribbon back coating material.

[0010] Preferably, the temperature of the alcoholysis reaction is 40°C to 80°C, preferably 50°C to 70°C, and more preferably 60°C to 70°C.

[0011] Preferably, the preparation method of the modified high-boiling silicone oil comprises the following steps:

[0012] With a vinyl alcohol ether compound as a modifier, a high-boiling silicone oil and a vinyl alcohol ether compound-alcohol aqueous solution are subjected to alcoholysis reaction at 40°C to 80°C. After the reaction is completed, the lower layer of acidic silicone oil is allowed to stand for treatment, mixed with an alcohol solvent, a neutralizing agent and a co-solvent are added for neutralization reaction, and the lower layer of crude silicone oil is allowed to stand for treatment, filtered, and a vinyl-modified modified high-boiling silicone oil is obtained.

[0013] The present invention mainly prepares high-boiling silicone oil through alcoholysis reaction and neutralization reaction, and in the alcoholysis process, a vinyl-containing alcohol ether compound is used as a modifier to introduce a vinyl group into the high-boiling silicone oil to prepare a vinyl-modified modified high-boiling silicone oil. By introducing a vinyl group into the high-boiling silicone oil, the prepared vinyl-modified high-boiling silicone oil can significantly improve the adhesion of the prepared thermal transfer barcode carbon ribbon back coating material on the thermal transfer carbon ribbon base when used to prepare a thermal transfer barcode carbon ribbon back coating material, thereby providing a research and development basis for the use of high-boiling silicone oil in thermal transfer barcode carbon ribbon back coating materials.

[0014] Preferably, the termination condition of the neutralization reaction is: adjusting the pH to 6-8.

[0015] Preferably, the mass ratio of the high boiling silicone oil to the vinyl alcohol ether compound-alcohol aqueous solution is 1:0.7-1.6, preferably 1:0.8-1.5, and more preferably 1:1-1.4. The mass percentage of the vinyl glycol ether to the vinyl alcohol ether compound-alcohol aqueous solution is 47.6%-90.1%.

[0016] Preferably, the vinyl alcohol ether compound is vinyl glycol ether; the alcohol-water solvent is a mixed solution of an alcohol solvent and water; the alcohol solvent is methanol; in the vinyl alcohol ether compound-alcohol aqueous solution, the mass ratio of the vinyl alcohol ether compound to the alcohol solvent is 1:0.1-1; preferably 1:0.5-1. The mass ratio of the total mass of the vinyl alcohol ether compound and the alcohol solvent to water is 1:0.01-0.1; preferably 1:0.01-0.07.

[0017] Preferably, the vinyl-containing alcohol ether compound-alcohol aqueous solution is obtained by mixing vinyl glycol ether, methanol and water.

[0018] Preferably, the addition rate of the vinyl alcohol ether compound-alcohol aqueous solution is 0.2 mL / min to 30 mL / min; and as the addition time increases, the addition rate of the vinyl alcohol ether compound-alcohol aqueous solution gradually increases; when the addition amount of the vinyl alcohol ether compound-alcohol aqueous solution accounts for 50% of the preset total addition mass, the vacuum is turned on to remove the hydrogen chloride gas.

[0019] In the present invention, during the reaction, the speed of adding the vinyl glycol ether-methanol aqueous solution is 0.2 mL / min; as the time gradient increases, when the methanol and water are dripped to half, the dripping speed is 3 mL / min; thereafter, as the time gradient increases, the maximum does not exceed 30 mL / min. During the process of adding the vinyl glycol ether-methanol aqueous solution, the vacuum is slightly opened, the purpose of which is to prevent the hydrogen chloride gas in the reaction container from accumulating too much and causing excessive pressure, thereby causing danger.

[0020] During the alcoholysis reaction, nitrogen reflux is also performed to remove hydrogen chloride gas; the volume ratio of nitrogen gas to hydrogen chloride gas is 1 to 1.5:1; and the nitrogen reflux time is 10 to 40 minutes, preferably 20 to 40 minutes.

[0021] The purpose of the nitrogen reflux during the alcoholysis reaction of the present invention is to prevent excessive accumulation of hydrogen chloride gas in the reaction container, thereby preventing the gas pressure from being too high and causing danger. Therefore, the excessive hydrogen chloride gas in the reaction container is reduced by nitrogen reflux, and the volume ratio of the nitrogen gas to the hydrogen chloride gas in the reaction container is ensured to be 1-1.5:1, thereby ensuring the safe conduct of the reaction.

[0022] Preferably, during the mixing process of the lower layer acidic silicone oil and the alcohol solvent, the mass ratio of the lower layer acidic silicone oil to the alcohol solvent is 1:1-1.8; preferably 1:1-1.5. The mass ratio of the neutralizer to the cosolvent is 1:0.01-0.1; the neutralizer is at least one of ammonium bicarbonate, urea and ammonia; the cosolvent is at least one of zinc oxide and aluminum oxide.

[0023] In the present invention, the addition of the neutralizer is mainly used to adjust the pH of the solution to 6-8. The present invention selects ammonium bicarbonate, urea, and ammonia as neutralizers, mainly because these three substances are alkaline neutralizers and contain groups that produce ammonia, which can be removed by heating, thereby avoiding the introduction of impurities. The introduction of impurities will have a negative impact on the application of the prepared high-boiling silicone oil in the thermal transfer barcode carbon ribbon back coating material.

[0024] The second aspect of the present invention provides a vinyl-modified high-boiling silicone oil, which is prepared by the modification process of the high-boiling silicone oil described in the first aspect.

[0025] The third aspect of the present invention provides an application of the vinyl-modified high-boiling silicone oil described in the second aspect in thermal transfer barcode ribbons; the application of the vinyl-modified high-boiling silicone oil in preparing a back coating material for thermal transfer barcode ribbons.

[0026] A fourth aspect of the present invention provides a thermal transfer barcode carbon ribbon back coating material, which is prepared by mixing the following raw materials in weight percentage at room temperature:

[0027] 5% to 20% of acrylic monomer, 15% to 50% of epoxy resin, 10% to 40% of modified high-boiling silicone oil, 5% to 20% of diluent, 0.1% to 0.8% of cationic photoinitiator and 1% to 8% of free radical photoinitiator, totaling 100%; the modified high-boiling silicone oil is the vinyl-modified high-boiling silicone oil described in the second aspect.

[0028] In the present invention, acrylic monomers, diluents, cationic photoinitiators and free radical photoinitiators can all be selected according to actual needs. The present invention mainly adds modified high-boiling silicone oil to the thermal transfer bar code carbon ribbon back coating material, significantly improving the adhesion of the prepared thermal transfer bar code carbon ribbon back coating material on the thermal transfer carbon ribbon base layer, while developing a new application of high-boiling silicone oil in the field of thermal transfer carbon ribbons.

[0029] Preferably, the acrylic monomer is at least one of acrylic acid, methacrylic acid, acrylate, methacrylate and acrylic resin.

[0030] The molecular weight of the epoxy resin is 4000-10000; preferably, the epoxy resin is a bisphenol A epoxy resin with an average molecular weight of 5000-8000. The model of the bisphenol A epoxy resin is E51.

[0031] The diluent is at least one of vinyl glycol ether and divinyl glycol ether.

[0032] The cationic photoinitiator is at least one of diazonium salts, diaryliodonium salts, triarylsulfonium salts, alkylsulfonium salts, iron arene salts, sulfonyloxy ketones and triarylsiloxane ethers.

[0033] The free radical photoinitiator is at least one of methyl benzoylformate, dimethyl benzoate, photoinitiator 1173, 1-hydroxycyclohexyl phenyl ketone and photoinitiator 907.

[0034] The fourth aspect of the present invention provides a thermal transfer barcode carbon ribbon back coating material which is a UV-curable thermal transfer barcode carbon ribbon back coating material. The present invention is based on the existing thermal transfer barcode carbon ribbon back coating material, adds modified high-boiling silicone oil, and introduces vinyl groups into the high-boiling silicone oil, which can significantly improve the adhesion of the prepared thermal transfer barcode carbon ribbon back coating material on the thermal transfer carbon ribbon base layer.

[0035] In the present invention, after the UV-curable thermal transfer barcode carbon ribbon back coating material is coated on the thermal transfer carbon ribbon base layer, a full-wavelength mercury lamp is used for UV curing, and the vertical distance between the full-wavelength mercury lamp and the thermal transfer carbon ribbon base layer to be cured is 0.8m to 2m; the UV curing time is 15s to 40s.

[0036] Preferably, the coating thickness of the thermal transfer barcode carbon ribbon back coating material is 0.1 g / m 2 -0.8g / m 2 .

[0037] The fifth aspect of the present invention provides a thermal transfer bar code carbon ribbon, comprising a thermal transfer carbon ribbon base layer and a thermal transfer bar code carbon ribbon back coating layer coated on one side of the thermal transfer carbon ribbon base layer, wherein the thermal transfer bar code carbon ribbon back coating layer is obtained by coating the thermal transfer bar code carbon ribbon back coating material described in the fourth aspect or the fifth aspect on one side of the thermal transfer carbon ribbon base layer and then curing it.

[0038] Beneficial effects of the present invention:

[0039] 1. The present invention mainly uses a vinyl-containing alcohol ether compound as a modifier, and obtains a vinyl-modified high-boiling silicone oil by introducing a vinyl group into the high-boiling silicone oil, so that the prepared vinyl-modified high-boiling silicone oil can be used to prepare a thermal transfer bar code carbon ribbon back coating material. The adhesion of the prepared thermal transfer bar code carbon ribbon back coating material on the thermal transfer carbon ribbon base layer can be significantly improved, and the use performance in the printing process can be improved, providing a research and development basis for the application of high-boiling silicone oil in thermal transfer bar code carbon ribbon back coating materials.

[0040] 2. The present invention introduces vinyl groups into high-boiling silicone oil by adding vinyl glycol ether during alcoholysis, thereby giving high-boiling silicone oil a new use, which can be used for heat-initiated free radical polymerization and UV light curing, so that the prepared back-coating resin shows excellent smoothness, weather resistance and thermal conductivity during the printing process. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1The curing condition diagrams of the thermal transfer barcode carbon ribbon back coating materials prepared with different addition amounts of vinyl glycol ether. Among them, (a) is a curing condition diagram of the thermal transfer barcode carbon ribbon back coating material prepared by using comparative example 4 without adding high boiling silicone oil; (b) is a curing condition diagram of the thermal transfer barcode carbon ribbon back coating material prepared by using comparative example 1; (c) is a curing condition diagram of the thermal transfer barcode carbon ribbon back coating material prepared by using comparative example 2; (d) is a curing condition diagram of the thermal transfer barcode carbon ribbon back coating material prepared by using example 2; (e) is a curing condition diagram of the thermal transfer barcode carbon ribbon back coating material prepared by using comparative example 3 with commercially available silicone oil; (f) is a curing condition diagram of the thermal transfer barcode carbon ribbon back coating material prepared by using example 3; (g) is a curing condition diagram of the thermal transfer barcode carbon ribbon back coating material prepared by using example 1. DETAILED DESCRIPTION

[0042] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0043] Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in the field without making any creative work shall fall within the scope of protection of the present invention.

[0044] The thermal transfer barcode ribbon is mainly provided with a thermal transfer ink layer on one side of the base film layer, and a back coating layer on the other side of the base film layer. The base film layer is a polyester film base layer, such as a PET base film, a PVC base film, a PP base film, and a PE base film. The thickness of the ink layer is generally required to be 1μm to 2μm. The back coating materials used in the back coating layer generally include solvent-based back coating materials and UV-curable back coating materials.

[0045] In order to develop new applications of high-boiling silicone oil, the present invention aims to provide the use of high-boiling silicone oil for preparing thermal transfer barcode ribbon back coating materials. However, in the subsequent experimental process, it was found that when the high-boiling silicone oil is directly prepared from high-boiling organic silicon substances by alcoholysis method similar to patent application CN101456955B and the high-boiling silicone oil is used to prepare thermal transfer barcode ribbon back coating materials, the thermal transfer barcode ribbon back coating materials are prone to poor adhesion on the thermal transfer ribbon base layer, thereby affecting the performance during printing.

[0046] In order to further improve the adhesion of high-boiling silicone oil on the thermal transfer bar code carbon ribbon base layer, the present invention mainly uses a vinyl-containing alcohol ether compound as a modifier, and introduces a vinyl group into the high-boiling silicone oil, so that the prepared vinyl-modified high-boiling silicone oil can be used to prepare the thermal transfer bar code carbon ribbon back coating material. The adhesion of the prepared thermal transfer bar code carbon ribbon back coating material on the thermal transfer carbon ribbon base layer can be significantly improved, the use performance in the printing process is improved, and a research and development basis is provided for the application of high-boiling silicone oil in the thermal transfer bar code carbon ribbon back coating material.

[0047] The invention provides a secondary utilization process of high-boiling silicone oil, a byproduct of methylchlorosilane monomer, wherein the high-boiling silicone oil is prepared by alcoholysis reaction and neutralization reaction, and a vinyl nitrogen alcohol ether compound is introduced into the alcoholysis reaction. By performing vinyl modification on the high-boiling silicone oil, the adhesion of the prepared thermal transfer bar code carbon ribbon back coating material on the thermal transfer carbon ribbon base layer is significantly improved, and a new application of the high-boiling silicone oil in the field of thermal transfer carbon ribbon is developed.

[0048] The present invention, through the secondary development and utilization of high-boiling silicone oil, not only effectively alleviates the serious environmental problems and safety hazards caused by the accumulation of high-boiling substances, but also increases its added value to generate good economic benefits, which has far-reaching significance for the overall development of the silicone industry.

[0049] The secondary utilization process of high-boiling organic silicon products provided by the present invention has basically no hazardous waste products, and realizes the full utilization of materials; it is simple and controllable in operation, easy to program and industrialize, and provides a good idea for the subsequent treatment and utilization of batches of high-boiling products. The present invention provides a formula and an embodiment for applying the obtained high-boiling silicone oil to thermal transfer carbon ribbons. Tests have proved that the back-coating resin prepared using the material shows excellent smoothness, weather resistance and thermal conductivity during the printing process, and can completely replace traditional silicone oil without side effects, and has high practicality.

[0050] The technical solution of the present invention is further described below through specific embodiments.

[0051] In the following examples, the methods described are conventional methods unless otherwise specified; the reagents and materials described are commercially available unless otherwise specified.

[0052] In the following embodiments, the organosilicon high boiling product is a by-product of the direct synthesis of methylchlorosilane monomers, and is a mixture of various silanes with Si-Si, Si-O-Si, and Si-C-Si as the main chains. The mass fraction of the organosilicon high boiling product is about 7% to 8%, and the density is about 1.13 g / cm 3 , boiling range is about 80℃~215℃.

[0053] Example 1

[0054] A modification process for high-boiling silicone oil comprises the following steps:

[0055] 500g of high-boiling organosilicon was placed in a 2L three-necked flask, and the oil bath was heated to 70℃ under constant stirring. The vinyl glycol ether-methanol aqueous solution obtained by mixing 735g of vinyl glycol ether, 73.5g of methanol and 8.08g of water was slowly added dropwise to carry out alcoholysis reaction. When the addition started, the speed was controlled at 2mL / min to allow the hydrogen chloride gas to be absorbed as completely as possible. When the methanol and water were dripped to half, the dripping speed was increased to 10mL / min, and the vacuum was slightly opened to remove the hydrogen chloride gas. After the addition was completed, the system was heated to about 70℃, and nitrogen was refluxed to remove hydrogen chloride. The volume ratio of nitrogen to hydrogen chloride gas was 1:1, and the nitrogen reflux time was 20min. Then it was naturally cooled to room temperature, and the material was transferred to a separatory funnel and allowed to stand for stratification.

[0056] The lower layer of acidic silicone oil in the separatory funnel was separated and weighed to 539.28g; 540g of fresh methanol was added to the 539.28g lower layer of acidic silicone oil, and then ammonium bicarbonate and zinc oxide were added and stirred to adjust the solution pH to 7, wherein the mass ratio of ammonium bicarbonate to zinc oxide was 1:0.06. The lower layer of crude silicone oil product was separated and then filtered through activated carbon diatomaceous earth to finally obtain 530g of vinyl-modified high-boiling silicone oil.

[0057] Example 2

[0058] A modification process for high-boiling silicone oil comprises the following steps:

[0059] 500g of high-boiling organosilicon was placed in a 2L three-necked flask, and the oil bath was heated to 80℃ under constant stirring. Then, a vinyl glycol ether-methanol aqueous solution obtained by mixing 450g of vinyl glycol ether, 225g of methanol and 67.5g of water was slowly added dropwise to carry out alcoholysis reaction. When the addition started, the speed was controlled at 0.2mL / min to allow the hydrogen chloride gas to be absorbed as completely as possible. When the methanol and water were dripped to half, the dripping speed was increased to 30mL / min, and the vacuum was slightly opened to remove the hydrogen chloride gas. After the addition was completed, the system was heated to about 80℃, and nitrogen was refluxed to remove hydrogen chloride. The volume ratio of nitrogen to hydrogen chloride gas was 1.2:1, and the nitrogen reflux time was 10min. Then it was naturally cooled to room temperature, and the material was transferred to a separatory funnel and allowed to stand for stratification.

[0060] Separate the lower layer of acidic silicone oil in the separatory funnel and weigh 459.2g; add 688g of fresh methanol to the 459.2g lower layer of acidic silicone oil, and then add ammonium bicarbonate and zinc oxide and stir to adjust the solution pH to 7, wherein the mass ratio of ammonium bicarbonate to zinc oxide is 1:0.01. Stand and separate, separate the lower layer of crude silicone oil product, and then filter it through activated carbon diatomaceous earth to finally obtain 450g of vinyl-modified high-boiling silicone oil.

[0061] Example 3

[0062] A modification process for high-boiling silicone oil comprises the following steps:

[0063] 500g of high-boiling organosilicon was placed in a 2L three-necked flask, and the oil bath was heated to 70℃ under constant stirring. Then, a vinyl glycol ether-methanol aqueous solution obtained by mixing 150g of vinyl glycol ether, 150g of methanol and 30g of water was slowly added dropwise to carry out alcoholysis reaction. When the addition started, the speed was controlled at 1mL / min to allow the hydrogen chloride gas to be absorbed as completely as possible. When the methanol and water were dripped to half, the dripping speed was increased to 7mL / min, and the vacuum was slightly opened to remove the hydrogen chloride gas. After the addition was completed, the system was heated to about 70℃, and nitrogen was refluxed to remove hydrogen chloride. The volume ratio of nitrogen to hydrogen chloride gas was 1.5:1, and the nitrogen reflux time was 40min. Then it was naturally cooled to room temperature, and the material was transferred to a separatory funnel and allowed to stand for stratification.

[0064] The lower layer of acidic silicone oil in the separatory funnel was separated and weighed 493.25 g; 500 g of fresh methanol was added to the 493.25 g lower layer of acidic silicone oil, and then ammonium bicarbonate and zinc oxide were added and stirred to adjust the solution pH to 7, wherein the mass ratio of ammonium bicarbonate to zinc oxide was 1:0.1. The lower layer of crude silicone oil product was separated and then filtered through activated carbon diatomaceous earth to finally obtain 473.52 g of vinyl-modified high-boiling silicone oil.

[0065] Comparative Example 1

[0066] A modification process for high-boiling silicone oil comprises the following steps:

[0067] 500g of high-boiling organosilicon was placed in a 2L three-necked flask, and the oil bath was heated to 70℃ under constant stirring. A methanol aqueous solution obtained by mixing 636.36g of methanol and 63.64g of water was slowly added dropwise to carry out alcoholysis reaction. When the addition started, the speed was controlled at 2mL / min to allow the hydrogen chloride gas to be absorbed as completely as possible. When the methanol and water were halfway added, the addition speed was increased to 10mL / min, and the vacuum was slightly opened to remove the hydrogen chloride gas. After the addition was completed, the system was heated to about 70℃, and nitrogen was refluxed to remove hydrogen chloride. The volume ratio of nitrogen to hydrogen chloride gas was 1:1, and the nitrogen reflux time was 20min. Then it was naturally cooled to room temperature, and the material was transferred to a separatory funnel and allowed to stand for stratification.

[0068] Separate the lower layer of acidic silicone oil in the separatory funnel; add fresh methanol to the lower layer of acidic silicone oil in a mass ratio of 1:1, and then add ammonium bicarbonate and zinc oxide and stir to adjust the solution pH to 7, where the mass ratio of ammonium bicarbonate to zinc oxide is 1:0.06. Stand and separate the lower layer of crude silicone oil product, and then filter it through activated carbon diatomaceous earth to finally obtain high-boiling silicone oil.

[0069] Comparative Example 2

[0070] A modification process for high-boiling silicone oil comprises the following steps:

[0071] 500g of high-boiling organosilicon was placed in a 2L three-necked flask, and the oil bath was heated to 70℃ under constant stirring. Then, a vinyl glycol ether-methanol aqueous solution obtained by mixing 1080g of vinyl glycol ether, 108g of methanol and 11.88g of water was slowly added dropwise to carry out alcoholysis reaction. When the addition started, the speed was controlled at 2mL / min to allow the hydrogen chloride gas to be absorbed as completely as possible. When the methanol and water were dripped to half, the dripping speed was increased to 10mL / min, and the vacuum was slightly opened to remove the hydrogen chloride gas. After the addition was completed, the system was heated to about 70℃, and nitrogen was refluxed to remove hydrogen chloride. The volume ratio of nitrogen to hydrogen chloride gas was 1:1, and the nitrogen reflux time was 20min. Then it was naturally cooled to room temperature, and the material was transferred to a separatory funnel and allowed to stand for stratification.

[0072] Separate the lower layer of acidic silicone oil in the separatory funnel; add fresh methanol to the lower layer of acidic silicone oil in a mass ratio of 1:1, and then add ammonium bicarbonate and zinc oxide and stir to adjust the solution pH to 7, where the mass ratio of ammonium bicarbonate to zinc oxide is 1:0.06. Let stand and separate the lower layer of crude silicone oil product, and then filter it through activated carbon diatomaceous earth to finally obtain 530g of vinyl-modified high-boiling silicone oil.

[0073] Table 1 Mass ratio of high boiling silicone products to vinyl glycol ethers

[0074]

[0075]

[0076] In order to explore the use of the vinyl-modified high-boiling silicone oils prepared in Examples 1 to 3, the high-boiling silicone oils prepared in Comparative Example 1, and the vinyl-modified high-boiling silicone oils prepared in Comparative Example 2 in thermal transfer barcode ribbons, the following experiments were conducted.

[0077] Application Example 1

[0078] A method for preparing a back coating material for a thermal transfer barcode carbon ribbon, using the vinyl-modified high-boiling silicone oil prepared in Example 1 as the modified silicone oil, is applied to the preparation of a back coating material for a thermal transfer barcode carbon ribbon, and the specific preparation method comprises the following steps:

[0079] At room temperature, 5g of acrylic acid, 50g of bisphenol A epoxy resin, 20g of modified high-boiling silicone oil, 20g of diluent, 0.5g of cationic photoinitiator and 4.5g of free radical photoinitiator are added to a beaker, and stirred at room temperature for 20 minutes until the mixture is uniform, thereby obtaining a UV-curable thermal transfer barcode ribbon back coating material. The diluent is vinyl glycol ether; the cationic photoinitiator is triaryl siloxy ether; and the free radical photoinitiator is methyl benzoylformate. The molecular weight of bisphenol A epoxy resin is 5000-8000. The modified high-boiling silicone oil is the vinyl-modified high-boiling silicone oil prepared in Example 1.

[0080] The UV-curable thermal transfer barcode carbon ribbon back coating material prepared in Application Example 1 is directly used as a UV-curable back coating material. The specific application method is as follows:

[0081] The UV-curable thermal transfer barcode ribbon back coating material of Application Example 1 is evenly coated on one side of the thermal transfer ribbon base layer, with a thickness of about 0.4 g / m 2 The vertical distance between the fixed mercury lamp and the thermal transfer ribbon substrate to be cured is about 1.3m. The time from entering the light domain to leaving the light domain is about 25s. The curing process is completed to obtain the thermal transfer barcode ribbon. One side of the transfer barcode ribbon has a thermal transfer ink layer, such as CN115124883B; the thermal transfer ribbon substrate is a polyester film substrate, such as a PET base film.

[0082] Application Example 2

[0083] A method for preparing a back coating material for a thermal transfer barcode carbon ribbon, using the vinyl-modified high-boiling silicone oil prepared in Example 2 as the modified silicone oil, is applied to the preparation of a back coating material for a thermal transfer barcode carbon ribbon, and the specific preparation method comprises the following steps:

[0084] At room temperature, 5g of acrylic acid, 50g of bisphenol A epoxy resin, 20g of modified high-boiling silicone oil, 20g of diluent, 0.5g of cationic photoinitiator and 4.5g of free radical photoinitiator are added to a beaker, and stirred at room temperature for 20 minutes until the mixture is uniform, and the UV-curable thermal transfer barcode ribbon back coating material can be obtained. The diluent is vinyl glycol ether; the cationic photoinitiator is triaryl siloxy ether; and the free radical photoinitiator is methyl benzoylformate. The molecular weight of bisphenol A epoxy resin is 5000-8000. The modified high-boiling silicone oil is the vinyl-modified high-boiling silicone oil prepared in Example 2.

[0085] The UV-curable thermal transfer barcode carbon ribbon back coating material prepared in Application Example 2 is directly used as a UV-curable back coating material. The specific application method is as follows:

[0086] The UV-curable thermal transfer barcode ribbon back coating material of Application Example 2 is evenly applied to one side of the thermal transfer ribbon base layer, with a thickness of about 0.4 g / m 2 The vertical distance between the fixed mercury lamp and the thermal transfer ribbon substrate to be cured is about 1.3m. The time from entering the light domain to leaving the light domain is about 25s. The curing process is completed to obtain the thermal transfer barcode ribbon. One side of the transfer barcode ribbon has a thermal transfer ink layer, such as CN115124883B; the thermal transfer ribbon substrate is a polyester film substrate, such as a PET base film.

[0087] Application Example 3

[0088] A method for preparing a back coating material for a thermal transfer barcode carbon ribbon, using the vinyl-modified high-boiling silicone oil prepared in Example 3 as the modified silicone oil, is applied to the preparation of a back coating material for a thermal transfer barcode carbon ribbon, and the specific preparation method comprises the following steps:

[0089] At room temperature, 5g of acrylic acid, 50g of bisphenol A epoxy resin, 20g of modified high-boiling silicone oil, 20g of diluent, 0.5g of cationic photoinitiator and 4.5g of free radical photoinitiator are added to a beaker, and stirred at room temperature for 20 minutes until the mixture is uniform, thereby obtaining a UV-curable thermal transfer barcode ribbon back coating material. The diluent is vinyl glycol ether; the cationic photoinitiator is triaryl siloxy ether; and the free radical photoinitiator is methyl benzoylformate. The molecular weight of bisphenol A epoxy resin is 5000-8000. The modified high-boiling silicone oil is the vinyl-modified high-boiling silicone oil prepared in Example 3.

[0090] The UV-curable thermal transfer barcode carbon ribbon back coating material prepared in Example 3 is directly used as a UV-curable back coating material. The specific application method is as follows:

[0091] The UV-curable thermal transfer barcode ribbon back coating material of Application Example 3 is evenly coated on one side of the thermal transfer ribbon base layer, with a thickness of about 0.4 g / m 2 The vertical distance between the fixed mercury lamp and the thermal transfer ribbon substrate to be cured is about 1.3m. The time from entering the light domain to leaving the light domain is about 25s. The curing process is completed to obtain the thermal transfer barcode ribbon. One side of the transfer barcode ribbon has a thermal transfer ink layer, such as CN115124883B; the thermal transfer ribbon substrate is a polyester film substrate, such as a PET base film.

[0092] Application Comparative Example 1

[0093] A method for preparing a thermal transfer barcode carbon ribbon back coating material, wherein the high boiling silicone oil prepared in Comparative Example 1 is used in the preparation of the thermal transfer barcode carbon ribbon back coating material, and the specific preparation method comprises the following steps:

[0094] At room temperature, 5g of acrylic acid, 50g of bisphenol A epoxy resin, 20g of high boiling silicone oil, 20g of diluent, 0.5g of cationic photoinitiator and 4.5g of free radical photoinitiator are added to a beaker, and stirred at room temperature for 20 minutes until the mixture is uniform, thereby obtaining a UV-curable thermal transfer barcode ribbon back coating material. The diluent is vinyl glycol ether; the cationic photoinitiator is triaryl siloxy ether; and the free radical photoinitiator is methyl benzoylformate. The molecular weight of bisphenol A epoxy resin is 5000-8000. The high boiling silicone oil is the high boiling silicone oil prepared in Comparative Example 1.

[0095] The UV-curable thermal transfer barcode ribbon back coating material prepared in Comparative Example 1 is directly used as a UV-curable back coating material. The specific application method is as follows:

[0096] The UV-curable thermal transfer barcode ribbon back coating material of comparative example 1 is evenly applied to one side of the thermal transfer ribbon base layer, with a thickness of about 0.4 g / m 2 The vertical distance between the fixed mercury lamp and the thermal transfer ribbon substrate to be cured is about 1.3m. The time from entering the light domain to leaving the light domain is about 25s. The curing process is completed to obtain the thermal transfer barcode ribbon. One side of the transfer barcode ribbon has a thermal transfer ink layer, such as CN115124883B; the thermal transfer ribbon substrate is a polyester film substrate, such as a PET base film.

[0097] Application Comparative Example 2

[0098] A method for preparing a back coating material for a thermal transfer barcode carbon ribbon, using the vinyl-modified high-boiling silicone oil prepared in Comparative Example 2 as the modified silicone oil, and applying it to the preparation of a back coating material for a thermal transfer barcode carbon ribbon, the specific preparation method comprising the following steps:

[0099] At room temperature, 5g of acrylic acid, 50g of bisphenol A epoxy resin, 20g of modified high-boiling silicone oil, 20g of diluent, 0.5g of cationic photoinitiator and 4.5g of free radical photoinitiator are added to a beaker, and stirred at room temperature for 20 minutes until the mixture is uniform, thereby obtaining a UV-curable thermal transfer barcode ribbon back coating material. The diluent is vinyl glycol ether; the cationic photoinitiator is triaryl siloxy ether; and the free radical photoinitiator is methyl benzoylformate. The molecular weight of bisphenol A epoxy resin is 5000-8000. The modified high-boiling silicone oil is the vinyl-modified high-boiling silicone oil prepared in Comparative Example 2.

[0100] The UV-curable thermal transfer barcode ribbon back coating material prepared in Comparative Example 2 is directly used as a UV-curable back coating material. The specific application method is as follows:

[0101] The UV-curable thermal transfer barcode ribbon back coating material of comparative example 2 is evenly applied to one side of the thermal transfer ribbon base layer, with a thickness of about 0.4 g / m 2 The vertical distance between the fixed mercury lamp and the thermal transfer ribbon substrate to be cured is about 1.3m. The time from entering the light domain to leaving the light domain is about 25s. The curing process is completed to obtain the thermal transfer barcode ribbon. One side of the transfer barcode ribbon has a thermal transfer ink layer, such as CN115124883B; the thermal transfer ribbon substrate is a polyester film substrate, such as a PET base film.

[0102] Application Comparative Example 3

[0103] A method for preparing a thermal transfer barcode carbon ribbon back coating material, using commercially available vinyl silicone oil to prepare the thermal transfer barcode carbon ribbon back coating material, the specific preparation method comprises the following steps:

[0104] At room temperature, 5g of acrylic acid and 50g of bisphenol A epoxy resin, 20g of commercially available vinyl silicone oil, 20g of diluent, 0.5g of cationic photoinitiator and 4.5g of free radical photoinitiator are added to a beaker and stirred at room temperature for 20 minutes until the mixture is uniform. The UV-curable thermal transfer barcode ribbon back coating material can be obtained. The diluent is vinyl glycol ether; the cationic photoinitiator is triaryl siloxy ether; and the free radical photoinitiator is methyl benzoylformate. The molecular weight of bisphenol A epoxy resin is 5000-8000. The commercially available vinyl silicone oil is a commercially available vinyl silicone oil used in the production of thermal transfer ribbons, purchased from Guangdong Zhongke Hongtai New Materials Co., Ltd.

[0105] The UV-curable thermal transfer barcode ribbon back coating material prepared in Comparative Example 3 is directly used as a UV-curable back coating material. The specific application method is as follows:

[0106] The UV-curable thermal transfer barcode ribbon back coating material of comparative example 3 is evenly applied to one side of the thermal transfer ribbon base layer, with a thickness of about 0.4 g / m 2 The vertical distance between the fixed mercury lamp and the thermal transfer ribbon substrate to be cured is about 1.3m. The time from entering the light domain to leaving the light domain is about 25s. The curing process is completed to obtain the thermal transfer barcode ribbon. One side of the transfer barcode ribbon has a thermal transfer ink layer, such as CN115124883B; the thermal transfer ribbon substrate is a polyester film substrate, such as a PET base film.

[0107] Application Comparative Example 4

[0108] A method for preparing a thermal transfer barcode carbon ribbon back coating material, wherein the thermal transfer barcode carbon ribbon back coating material is prepared according to the method of Application Example 1 without adding high-boiling silicone oil.

[0109] The curing conditions of thermal transfer barcode ribbon back coating materials prepared with different addition amounts of vinyl glycol ether were analyzed. Figure 1 shown.

[0110] Figure 1 The curing condition diagrams of the thermal transfer barcode carbon ribbon back coating materials prepared with different addition amounts of vinyl glycol ether. Among them, (a) is a curing condition diagram of the thermal transfer barcode carbon ribbon back coating material prepared by using comparative example 4 without adding high boiling silicone oil; (b) is a curing condition diagram of the thermal transfer barcode carbon ribbon back coating material prepared by using comparative example 1; (c) is a curing condition diagram of the thermal transfer barcode carbon ribbon back coating material prepared by using comparative example 2; (d) is a curing condition diagram of the thermal transfer barcode carbon ribbon back coating material prepared by using example 2; (e) is a curing condition diagram of the thermal transfer barcode carbon ribbon back coating material prepared by using comparative example 3 with commercially available silicone oil; (f) is a curing condition diagram of the thermal transfer barcode carbon ribbon back coating material prepared by using example 3; (g) is a curing condition diagram of the thermal transfer barcode carbon ribbon back coating material prepared by using example 1.

[0111] (a) In the figure, no high-boiling silicone oil is added to the back-coating material of the thermal transfer barcode carbon ribbon in comparative example 4. (b) In the figure, the modified silicone oil used in the back-coating material of the thermal transfer barcode carbon ribbon in comparative example 1 is the high-boiling silicone oil prepared in comparative example 1 without adding vinyl glycol ether. (c) In the figure, the modified silicone oil used in the back-coating material of the thermal transfer barcode carbon ribbon in comparative example 2 is the vinyl-modified high-boiling silicone oil prepared in comparative example 2 with a mass ratio of high-boiling silicone to vinyl glycol ether of 1:2.16. (d) In the figure, the modified silicone oil used in the back-coating material of the thermal transfer barcode carbon ribbon in embodiment 2 is the vinyl-modified high-boiling silicone oil prepared in embodiment 2 with a mass ratio of high-boiling silicone to vinyl glycol ether of 1:0.9. (e) In the figure, the modified silicone oil used in the back-coating material of the thermal transfer barcode carbon ribbon in comparative example 3 is the commercially available silicone oil added. In the figure (f), the modified silicone oil used in the back coating material of the thermal transfer barcode carbon ribbon of Example 3 is a vinyl-modified high-boiling silicone oil prepared in Example 3 with a mass ratio of high-boiling silicone to vinyl glycol ether of 1:0.3. In the figure (g), the modified silicone oil used in the back coating material of the thermal transfer barcode carbon ribbon of Example 1 is a vinyl-modified high-boiling silicone oil prepared in Example 1 with a mass ratio of high-boiling silicone to vinyl glycol ether of 1:1.47.

[0112] Depend on Figure 1 It can be seen from the curing conditions that with the increase in the amount of vinyl glycol ether, the curing time of the thermal transfer barcode carbon ribbon back coating material gradually shortens. However, the excessive amount of vinyl glycol ether used in Comparative Example 2 and the addition of commercially available vinyl silicone oil in Comparative Example 3 require a relatively long curing time. The thermal transfer barcode carbon ribbon back coating material prepared without adding high-boiling silicone oil and high-boiling silicone oil prepared without adding vinyl glycol ether is difficult to cure.

[0113] From the above analysis, it can be seen that by introducing vinyl groups into high-boiling silicone oil and adjusting the amount of vinyl glycol ether added so that the mass ratio of high-boiling silicone to vinyl glycol ether is between 1:0.3 and 1:1.47, it is helpful to adjust the curing time of the thermal transfer barcode carbon ribbon back coating material.

[0114] The thermal transfer barcode ribbons prepared in Application Example 1 to Application Example 3 and Application Comparative Example 1 to Application Comparative Example 3 were collected and printed using a barcode ribbon printer. The specific criteria are as follows:

[0115] Heat resistance: Select low, medium and high speeds to print continuously for a specified time, with the appearance of no blurring of prints, ribbon rupture, etc. as the benchmark. The heat resistance level is the test standard for heat resistance.

[0116] Adhesion: The number of consecutive prints is measured until glue appears on the print head and affects printing. The more prints are made, the better the adhesion is. The number of consecutive prints and the glue loss are used as the test criteria for adhesion.

[0117] Static friction coefficient and dynamic friction coefficient: The test is carried out using the 10006-1988 plastic film and sheet friction coefficient determination method; the smaller the value, the smaller the friction and the better the lubricity. The GB / T 10006-1988 plastic film and sheet friction coefficient determination method is used as the test standard for static friction coefficient and dynamic friction coefficient.

[0118] Table 2 shows the comparison results of various properties of the thermal transfer barcode ribbons obtained by using Example 1 to Example 3 and Comparative Example 1 to Comparative Example 3.

[0119] Table 2 Comparison of various performances

[0120]

[0121] It can be seen from the results in Table 3 that in Application Examples 1 to Application Example 3 and Application Comparative Example 2, as the amount of vinyl glycol ether increases, there is a significant difference in the curing of the materials within the same illumination time. The more vinyl glycol ether, the more complete the curing. When the mass ratio of high-boiling organosilicon substances to vinyl glycol ether is 1:1.5, the combination of the two is relatively stable and the curing is best. When the mass ratio of high-boiling organosilicon substances to vinyl glycol ether is greater than 1.5, there is a state of excessive raw materials with poor curing effect.

[0122] Compared with the unmodified high-boiling silicone oil in comparative example 1, the high-boiling silicone oil modified with vinyl prepared in example 1 is added in example 1. By introducing vinyl groups into the high-boiling silicone oil, the prepared vinyl-modified high-boiling silicone oil can be used to prepare the thermal transfer bar code carbon ribbon back coating material. The adhesion, dynamic friction coefficient and static friction coefficient of the prepared thermal transfer bar code carbon ribbon back coating material on the thermal transfer carbon ribbon base layer can be significantly improved, thereby improving the performance during the printing process.

[0123] Compared with the commercially available vinyl silicone oil in Application Comparative Example 3, Application Examples 1 to Application Examples 3 modify the high-boiling silicone oil into a new silicone oil raw material having a photocurable active grafting group by adding vinyl-modified high-boiling silicone oil, and apply it to the back coating material of the thermal transfer carbon ribbon. The ultraviolet light technology is used to achieve rapid curing of the back coating material and the PET base layer, which greatly improves the preparation rate of the thermal transfer barcode carbon ribbon. At the same time, the printing adhesion and the static / dynamic friction during the printing operation are significantly reduced, which has the effects of extending the continuous printing time, reducing adhesion, and ensuring the printing effect and stability.

[0124] From the above analysis, it can be seen that Examples 1 to 3 of the present invention add vinyl glycol ether during alcoholysis, thereby introducing vinyl groups into high-boiling silicone oil, thereby giving high-boiling silicone oil a new use, which can be used for thermally initiated free radical polymerization and UV light curing, so that the prepared back-coating resin shows excellent smoothness, weather resistance and thermal conductivity during the printing process.

[0125] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A modification process for high boiling silicone oil, characterized in that: The following steps are involved: Using a vinyl alcohol ether compound as a modifier, an alcoholysis reaction is carried out with a high-boiling silicone product in an alcohol-water solvent system to modify the high-boiling silicone oil with vinyl, thereby obtaining a vinyl-modified high-boiling silicone oil; The organosilicon high boiling point is a by-product of preparing methylchlorosilane monomer.

2. The modification process of high boiling silicone oil according to claim 1, characterized in that: The preparation method of the modified high-boiling silicone oil comprises the following steps: With a vinyl alcohol ether compound as a modifier, an alcoholysis reaction is carried out between a high-boiling organosilicon product and a vinyl alcohol ether compound-alcohol aqueous solution at 40°C to 80°C. After the reaction is completed, the lower layer of acidic silicone oil is taken out and mixed with an alcohol solvent after standing. A neutralizing agent and a co-solvent are added to carry out a neutralization reaction. After standing, the lower layer of crude silicone oil is taken out and filtered to obtain a vinyl-modified modified high-boiling silicone oil.

3. The modification process of high boiling silicone oil according to claim 2, characterized in that: The mass ratio of the high-boiling organosilicon substance to the vinyl-containing alcohol ether compound-alcohol aqueous solution is 1:0.7-1.6; The mass percentage of the vinyl glycol ether to the vinyl alcohol ether compound-alcohol aqueous solution is 47.6% to 90.1%; The vinyl alcohol ether compound is vinyl glycol ether; the alcohol-water solvent is a mixed solution of an alcohol solvent and water; the alcohol solvent is methanol; In the vinyl alcohol ether compound-alcohol aqueous solution, the mass ratio of the vinyl alcohol ether compound to the alcohol solvent is 1:0.1-1; the mass ratio of the total mass of the vinyl alcohol ether compound and the alcohol solvent to water is 1:0.01-0.

1.

4. The modification process of high boiling silicone oil according to claim 2, characterized in that: The addition rate of the vinyl alcohol ether compound-alcohol aqueous solution is 0.2 mL / min to 30 mL / min; and as the addition time increases, the addition rate of the vinyl alcohol ether compound-alcohol aqueous solution gradually increases; When the amount of the vinyl-containing alcohol ether compound-alcohol aqueous solution added accounts for 50% of the preset total added mass, the vacuum is turned on to remove the hydrogen chloride gas; The alcoholysis reaction process also includes nitrogen reflux to remove hydrogen chloride gas; the volume ratio of nitrogen gas to hydrogen chloride gas is 1 to 1.5:1; the nitrogen reflux time is 10 minutes to 40 minutes.

5. The modification process of high boiling silicone oil according to claim 2, characterized in that: During the mixing process of the lower layer acidic silicone oil and the alcohol solvent, the mass ratio of the lower layer acidic silicone oil to the alcohol solvent is 1:1-1.8; the mass ratio of the neutralizer to the co-solvent is 1:0.01-0.1; The neutralizing agent is at least one of ammonium bicarbonate, urea and ammonia; the co-solvent is at least one of zinc oxide and aluminum oxide.

6. A vinyl-modified high-boiling silicone oil, characterized in that: The silicone oil is prepared by the modification process of the high boiling silicone oil described in any one of claims 1 to 5.

7. An application of the vinyl-modified high-boiling silicone oil according to claim 6 in thermal transfer barcode ribbons; characterized in that: The vinyl-modified high-boiling silicone oil is used for preparing thermal transfer barcode carbon ribbon back coating materials.

8. A thermal transfer barcode carbon ribbon back coating material, characterized in that: The method is prepared by mixing the following raw materials in weight percentage at room temperature: Acrylic monomer 5% to 20%, epoxy resin 15% to 50%, modified high boiling silicone oil 10% to 40%, diluent 5% to 20%, cationic photoinitiator 0.1% to 0.8% and free radical photoinitiator 1% to 8%, totaling 100%; The modified high-boiling silicone oil is the vinyl-modified high-boiling silicone oil as described in claim 6.

9. The thermal transfer barcode carbon ribbon back coating material according to claim 8, characterized in that: The acrylic monomer is at least one of acrylic acid, methacrylic acid, acrylate, methacrylate and acrylic resin; The molecular weight of the epoxy resin is 4000 to 10000; The diluent is at least one of vinyl glycol ether and divinyl glycol ether; The cationic photoinitiator is at least one of a diazonium salt, a diaryl iodonium salt, a triaryl sulfonium salt, an alkyl sulfonium salt, an iron arene salt, a sulfonyloxy ketone and a triaryl siloxane ether; The free radical photoinitiator is at least one of methyl benzoylformate, dimethyl benzoate, photoinitiator 1173, 1-hydroxycyclohexyl phenyl ketone and photoinitiator 907.

10. A thermal transfer barcode carbon ribbon, comprising a thermal transfer carbon ribbon base layer and a thermal transfer barcode carbon ribbon back coating layer coated on one side of the thermal transfer carbon ribbon base layer, characterized in that: The thermal transfer barcode carbon ribbon back coating layer is obtained by coating the thermal transfer barcode carbon ribbon back coating material according to claim 8 or 9 on one side of the thermal transfer carbon ribbon base layer and then curing it.

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