Organosilicon modified polyacrylic acid-polyurethane resin and back coating liquid containing same

Abstract

The invention discloses organic silicon modified polyacrylic acid-polyurethane resin and a back coating liquid product of thermal transfer ribbon, thermal coding thermal transfer ribbon, banner, bar code and other thermal transfer ribbons prepared from the organic silicon modified polyacrylic acid-polyurethane resin. The organic silicon modified polyacrylic acid-polyurethane resin is prepared from the following raw materials in parts by mass: 10 to 30 parts of organic silicon oil, 2 to 10 parts of isocyanate, 40 to 80 parts of acrylic ester, 0.1 to 0.5 part of an initiator, 0.05 to 0.1 part of a catalyst and an organic solvent A. In addition, the invention also discloses a back coating liquid prepared from the synthetic resin, and the back coating liquid is prepared from the following components in parts by mass: 20-35 parts of resin, 0-1 part of a curing agent, 5-25 parts of an organic solvent and 20-45 parts of a diluent. The back coating liquid provided by the invention has excellent heat resistance, smoothness and adhesive force, and can be applied to high-end thermal printing ribbons, thermal coding thermal transfer ribbons, banners, bar code ribbons and other products in the hot stamping industry.

Description

Technical Field

[0001] The invention belongs to the technical field of back coating materials, and specifically relates to a synthetic silicone modified polyacrylic acid-polyurethane resin, and also relates to a back coating liquid containing the resin, which is mainly suitable for back coating liquids of thermal transfer ribbons, thermal transfer carbon ribbons, barcodes, banners and other carbon ribbons in the hot stamping industry. Background Art

[0002] With the rapid development of the Internet of Things in my country, the demand for barcode-related industries is increasing, and the requirements for thermal transfer ribbons are getting higher and higher. There are more and more varieties, from wax-based to mixed-based, and then to resin-based high-end ribbons. The ribbon mainly includes an ink layer, a release layer, a base ribbon and a back coating, etc. The transfer effect is provided by the ink layer, but it is also limited by the back coating. The back coating is a heat-resistant lubricating material applied to the back of the base ribbon. It can reduce the friction between the ribbon and the printer probe when the printer is working, increase the service life of the printer and improve the fineness of the transfer. It needs to have excellent heat resistance and thermal conductivity to ensure the continuity and clarity of the transfer, but the existing back coating materials cannot meet the use requirements of high-end ribbons. Therefore, it is urgent to develop a high-performance back coating material to meet the use requirements of high-end ribbons.

[0003] High-end heat-resistant lubricating adhesive backing material is a new type of polymer composite that combines high thermal conductivity, high heat resistance, high adhesion, low friction and smoothness. It is mainly used to coat the back of PET carbon ribbon to improve the heat resistance and smoothness of the carbon ribbon, so as to broaden the applicable energy level of the carbon ribbon printer and reduce the failure rate. At present, the back coating materials are mainly silicone polyurethane (patent CN103965431A), silicone polyacrylic resin (patent CN 101921363 A) and silicone modified polyester resin (patent CN115304743 B), etc. Among them, silicone polyurethane and silicone modified polyester resin back coating materials have good heat resistance, but their anti-sticking performance is poor, while silicone polyacrylic resin back coating materials have excellent smoothness, but their nature is slightly brittle and their adhesion is slightly poor.

[0004] In order to solve the above-mentioned problems in the prior art, the present application proposes a technical route with "brush"-shaped silicone-modified polyacrylate and silicone polyurethane as the main backing materials, and synthesizes a silicone-modified polyacrylic acid-polyurethane resin back coating material. This material combines the common advantages of silicone polyurethane resin and silicone acrylic resin, and gives the backing polymer coating material a variety of functionalities. The synergistic effect of the two components is used to solve a series of problems of traditional backing polymer coatings, such as high printing noise (poor lubricity), narrow printing energy level (poor heat resistance), easy glue falling off (poor adhesion), and printing energy level attenuation (poor stability). It can meet the needs of current high-end carbon ribbons, and the preparation process is simple and controllable, suitable for industrial large-area coating. Summary of the invention

[0005] The present invention aims to overcome the defects of the prior art and provides an organosilicon-modified polyacrylic acid-polyurethane resin, which combines organosilicon-modified polyurethane with organosilicon polyacrylic acid resin by chemical bonds, so that the resin has excellent temperature resistance. Compared with a single organosilicon acrylic acid resin, its temperature resistance can be increased by about 40°C (see Figure 1 ).

[0006] The present invention also provides a back coating liquid containing the resin, which is applied on a PET film and tested by friction (see Figure 2 ) The average surface friction coefficient is 0.06, which can greatly reduce the friction coefficient of the PET film surface (0.34) and has excellent smoothness; after dilution, it is applied to the carbon ribbon. Through the printing test, its printing energy level on the Zebra 400 printer can reach 30, and there is no material residue near the panel and print head after continuous printing of 20,000 sheets. It also has excellent temperature resistance and adhesion, and has a wide range of uses.

[0007] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0008] An organosilicon-modified polyacrylic acid-polyurethane resin is mainly made of the following raw materials in parts by weight: 8-30 parts of organosilicon oil, 1-10 parts of isocyanate, 20-80 parts of acrylate, 0.1-0.5 parts of initiator, and 0.03-0.1 parts of organotin catalyst. The organosilicon-modified polyacrylic acid-polyurethane resin can be used as a resin for the back coating of a barcode carbon tape.

[0009] Specifically, the silicone oil may be one or both of ethylene / propylene terminated polydimethylsiloxane and hydroxyl / hydroxypropyl terminated polydimethylsiloxane, etc., and the molecular weight is between 2000 and 8000 g / mol.

[0010] Specifically, the isocyanate includes but is not limited to one or more of toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and the like.

[0011] Specifically, the acrylic acid ester includes but is not limited to one or more of methyl methacrylate, butyl acrylate, butyl methacrylate, hydroxyethyl methacrylate and the like.

[0012] Specifically, the initiator includes but is not limited to one or two of azobisisobutyronitrile, benzoyl peroxide, etc.; the catalyst can be dibutyltin dilaurate, etc.

[0013] The present invention provides a method for preparing the above-mentioned organosilicon-modified polyacrylic acid-polyurethane resin, which comprises the following steps:

[0014] 1) adding part of the organic silicone oil, isocyanate, organotin catalyst and part of the organic solvent A into a reaction kettle and sealing the reaction kettle at 60-85° C. for 4-12 hours to obtain an isocyanate-terminated organic silicone polyurethane prepolymer, which is sealed and stored away from light for later use;

[0015] 2) Mix part of the silicone oil, acrylate and part of the organic solvent A evenly and pour them into the reaction kettle as the reaction base liquid, and heat them to 60-85° C. under inert gas atmosphere and stirring;

[0016] 3) dissolving the remaining amount of silicone oil, the remaining amount of acrylate and the initiator in a proportion in a part of the organic solvent A, mixing them evenly and adding them to the reaction kettle in step 2) for 2-3 hours, stirring and reacting at 60-85° C. for 2-3 hours to obtain a silicone polyacrylic acid resin;

[0017] 4) The silicone polyurethane prepolymer of step 1) is used as a dropwise addition liquid, and part of the organic solvent A and the silicone polyacrylic resin of step 3) are used as a reaction liquid. The dropwise addition time is 2-3 hours. Stirring is continued at 40-60° C. for 5-14 hours. During the stirring process, the remaining organic solvent A is gradually added as the viscosity of the system increases, thereby obtaining a silicone-modified polyacrylic acid-polyurethane resin.

[0018] Specifically, the organic solvent A can be one or more of toluene, butanone, n-hexane, acetone, and the like.

[0019] The present invention also provides a barcode carbon ribbon back coating liquid, which comprises the organosilicon-modified polyacrylic acid-polyurethane resin, a curing agent, an organic solvent B and a diluent; the mass parts of the organosilicon-modified polyacrylic acid-polyurethane resin, the curing agent, the organic solvent B and the diluent are 15-35 parts, 0-1 part, 5-25 parts and 20-45 parts.

[0020] Furthermore, in the above-mentioned barcode carbon ribbon back coating liquid, the curing agent may be an isocyanate curing agent, such as hexamethylene diisocyanate trimer, polyphenyl polymethylene polyisocyanate, etc. The organic solvent B may be one or two of toluene, xylene, acetone, etc., and the diluent may be one or two of butanone, n-hexane, acetone, etc.

[0021] The present invention also provides application of the barcode carbon ribbon back coating liquid in the hot stamping industry.

[0022] The present invention also provides a method for preparing the barcode carbon ribbon back coating liquid, which comprises the following steps:

[0023] Mix the organosilicon-modified polyacrylic acid-polyurethane resin, organic solvent B and diluent evenly according to the proportion, add curing agent before coating, and mix well.

[0024] Compared with the prior art, the present invention has the following beneficial effects:

[0025] The present invention proposes a technical route using "brush"-shaped silicone modified polyacrylate and silicone polyurethane as the main backing materials, and synthesizes a silicone modified polyacrylic acid-polyurethane resin back coating material. The synthetic resin has excellent heat resistance. Compared with a single silicone acrylic resin, its temperature resistance can be increased by about 40°C (see Figure 1 The present invention also provides a back coating liquid containing the resin, which is applied on a PET film and tested by friction (see Figure 2 ) The average surface friction coefficient is 0.06, which can greatly reduce the friction coefficient of the PET film surface (0.34), and has excellent smoothness; after dilution, it is applied to the carbon ribbon. Through the printing test, its printing energy level on the Zebra 400 printer is 17-30, up to 30, and the printing noise is 86-87.5dB, and there is no material residue near the panel and the print head after continuous printing of 20,000 sheets, and it has excellent temperature resistance and adhesion. In addition, the organosilicon-modified polyacrylic acid-polyurethane resin of the present invention combines the common advantages of organosilicon polyurethane resin and organosilicon acrylic resin, and gives the back-adhesive polymer coating material a variety of functionalities. The synergistic effect of the two components is used to solve a series of problems of the traditional back-adhesive polymer coating, such as high printing noise (poor lubricity), narrow printing energy level (poor heat resistance), easy glue falling (poor adhesion), and printing energy level attenuation (poor stability). It can meet the needs of current high-end carbon ribbons and has a wide range of uses. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] The present invention will be further described in detail below in conjunction with the accompanying drawings and specific embodiments.

[0027] Figure 1 This is a schematic diagram of the friction coefficient after the back coating liquid of the organosilicon-modified polyacrylic acid-polyurethane resin synthesized in Example 1 is coated on the PET surface;

[0028] Figure 2 Schematic diagram of thermal analysis of the organosilicon-modified polyacrylic acid-polyurethane resin synthesized in Examples 1 and 2. DETAILED DESCRIPTION

[0029] The organosilicon-modified polyacrylic acid-polyurethane resin provided by the present invention and the back coating liquid prepared using the resin are described in detail below in conjunction with the embodiments. The described embodiments are part of the embodiments of the present invention, rather than all of the embodiments, and they should not be understood as limiting the scope of protection of the present invention.

[0030] In the following examples, the raw materials used are all common commercial products that can be directly purchased or prepared using conventional techniques in the art. The molecular weight of the organic silicone oil used is between 2000 and 8000 g / mol.

[0031] Synthetic resin and back coating liquid embodiment 1

[0032] The silicone-modified polyacrylic acid-polyurethane resin and the back coating liquid prepared using the resin described in this embodiment include the following steps:

[0033] 1. Preparation of synthetic resin

[0034] A synthetic resin is prepared from the following raw materials: 4 g of vinyl-terminated polydimethylsiloxane, 5 g of hydroxypropyl-terminated polydimethylsiloxane, 1.2 g of isophorone diisocyanate, 10 g of methyl methacrylate, 5 g of butyl acrylate, 6 g of hydroxyethyl methacrylate, 5 g of butyl methacrylate, 0.4 g of azobisisobutyronitrile, 0.04 g of dibutyltin dilaurate, 215 g of toluene and 210 g of butanone.

[0035] The preparation method of the synthetic resin specifically comprises the following steps:

[0036] 1) 1.2 g of isophorone diisocyanate, 0.04 g of dibutyltin dilaurate and 5 g of toluene were added to a reaction bottle, the temperature was set to 75° C. 5 g of hydroxypropyl-terminated polydimethylsiloxane was uniformly added dropwise to the reaction bottle for 0.5 h. The bottle was sealed and stirred for 5 h to obtain an isocyanate-terminated silicone polyurethane prepolymer, which was sealed and stored away from light for later use.

[0037] 2) Take 2g of vinyl-terminated polydimethylsiloxane, 3g of butyl acrylate, and 10g of toluene, mix well, pour into a reaction bottle as a reaction base liquid, stir and heat to 85°C under N2 atmosphere;

[0038] 3) Take 10g methyl methacrylate, 2g butyl acrylate, 6g hydroxyethyl methacrylate, 2g vinyl-terminated polydimethylsiloxane, 5g butyl methacrylate, 0.4g azobisisobutyronitrile, and 50g toluene, mix well and slowly add dropwise to the reaction base liquid for 2-3h, continue stirring and reacting for 2 hours, then cool to 50°C to obtain a silicone acrylic resin for standby use;

[0039] 4) Take 60g of butanone and add it to the silicone polyacrylic resin. When the temperature is constant at 50°C, take the silicone polyurethane prepolymer in step 1) as a drop solution and add it dropwise to the diluted silicone polyacrylic resin for 2-3h. After continuous stirring at 50°C for 2h, add 150g of toluene and 150g of butanone, and continue stirring and reacting for 12h to obtain a silicone-modified polyacrylic acid-polyurethane resin.

[0040] 2. Back coating liquid example 1

[0041] A back coating liquid prepared by using the above synthetic resin is composed of the following raw materials: 20g of the synthetic resin in Example 1, 0.5g of a curing agent hexamethylene diisocyanate trimer, 15g of an organic solvent toluene and 25g of a diluent butanone.

[0042] The preparation method of the back coating liquid is as follows: the synthetic resin, toluene and butanone are mixed evenly according to a certain proportion, packaged for standby use, and a curing agent is added before the coating step.

[0043] 3. Performance Testing

[0044] The prepared back coating liquid is applied to the carbon ribbon, with a coating amount of about 0.2-0.5g / m 2 , the tape base thickness is 4um, the release layer thickness is 1um, and the ink layer thickness is 1um (the specific composition of the tape base, release layer, ink layer, etc. can be referred to the existing patent document CN111791614A). The printing energy level on the Zebra ZM 400 printer is 17-26, and the average printing noise is 86.3dB.

[0045] The silicone modified polyacrylic acid-polyurethane resin back coating liquid (i.e., the synthetic resin in Example 1) was applied to a PET film (thickness 0.8 mm) and dried to test the friction coefficient. A 4 mm diameter steel ball with a load of 1 N was used to rub the PET film with a wear distance of 6 mm. The friction curve is shown in FIG. Figure 1 As shown, the average friction coefficient of the blank base tape is 0.34, and the friction coefficient is reduced to 0.06 after coating with the back coating liquid described in Example 1, indicating that the coating of the back coating liquid effectively improves the smoothness of PET. When coated on the carbon ribbon, it can not only provide good protection for the print head during printing, but also significantly reduce the noise generated by the carbon ribbon during daily use.

[0046] The organosilicon-modified polyacrylic acid-polyurethane resin (i.e., the synthetic resin in Example 1) was subjected to thermal gravimetric and differential scanning calorimetric analysis tests on a thermal analyzer. The heating rate was 10°C / min under a nitrogen atmosphere. The curve is as follows: Figure 2 As shown in the figure, compared with silicone acrylic resin, the mass loss starting temperature of silicone modified polyacrylic acid-polyurethane resin is higher (about 200°C for silicone acrylic resin and about 300°C for silicone modified polyacrylic acid-polyurethane resin), and the thermal decomposition temperature is higher (326°C for silicone acrylic resin and 366°C for silicone modified polyacrylic acid-polyurethane resin). This shows that the introduction of silicone polyurethane component greatly improves the temperature resistance of synthetic resin, and the diluted back coating liquid also has excellent heat resistance.

[0047] Synthetic resin example 2

[0048] A synthetic resin is prepared from the following raw materials: 6 g of vinyl-terminated polydimethylsiloxane, 5 g of hydroxypropyl-terminated polydimethylsiloxane, 1.2 g of isophorone diisocyanate, 10 g of methyl methacrylate, 5 g of butyl acrylate, 6 g of hydroxyethyl methacrylate, 5 g of butyl methacrylate, 0.4 g of azobisisobutyronitrile, 0.04 g of dibutyltin dilaurate, 215 g of toluene, and 210 g of butanone.

[0049] The preparation method of the synthetic resin specifically comprises the following steps:

[0050] 1) 1.2 g of isophorone diisocyanate, 0.04 g of dibutyltin dilaurate and 5 g of toluene were added to a reaction bottle, the temperature was set to 75° C. 5 g of hydroxypropyl-terminated polydimethylsiloxane was uniformly added dropwise to the reaction bottle for 0.5 h. The bottle was sealed and stirred for 5 h to obtain an isocyanate-terminated silicone polyurethane prepolymer, which was sealed and stored away from light for later use.

[0051] 2) Take 3g of vinyl-terminated polydimethylsiloxane, 3g of butyl acrylate, and 10g of toluene, mix well, pour into a reaction bottle as a reaction base liquid, stir and heat to 85°C under N2 atmosphere;

[0052] 3) Take 10g methyl methacrylate, 2g butyl acrylate, 6g hydroxyethyl methacrylate, 3g vinyl-terminated polydimethylsiloxane, 5g butyl methacrylate, 0.4g azobisisobutyronitrile, and 50g toluene, mix well and slowly add dropwise to the reaction base liquid for 2-3h, continue stirring and reacting for 2 hours, then cool to 50°C to obtain a silicone acrylic resin for standby use;

[0053] 4) Take 60g of butanone and add it to the silicone polyacrylic resin. When the temperature is constant at 50°C, take the silicone polyurethane prepolymer in step 1) as a drop solution and add it dropwise to the diluted silicone polyacrylic resin for 2-3h. After continuous stirring at 50°C for 2h, add 150g of toluene and 150g of butanone, and continue stirring and reacting for 12h to obtain a silicone-modified polyacrylic acid-polyurethane resin.

[0054] Synthetic resin example 3

[0055] A synthetic resin is prepared from the following raw materials: 4 g of vinyl-terminated polydimethylsiloxane, 5 g of hydroxypropyl-terminated polydimethylsiloxane, 1.1 g of toluene diisocyanate, 10 g of methyl methacrylate, 5 g of butyl acrylate, 6 g of hydroxyethyl methacrylate, 5 g of butyl methacrylate, 0.4 g of azobisisobutyronitrile, 0.04 g of dibutyltin dilaurate, 215 g of toluene, and 210 g of butanone.

[0056] The preparation method of the synthetic resin specifically comprises the following steps:

[0057] 1) Take 1.1g toluene diisocyanate, 0.04g dibutyltin dilaurate and 5g toluene and add them into a reaction bottle, set the temperature to 60°C, uniformly add 5g hydroxypropyl-terminated polydimethylsiloxane into the reaction bottle, add the mixture for 0.5h, seal and stir to react for 4h, and obtain an isocyanate-terminated silicone polyurethane prepolymer, which is sealed and stored away from light for later use.

[0058] 2) Take 2g of vinyl-terminated polydimethylsiloxane, 3g of butyl acrylate, and 10g of toluene, mix well, pour into a reaction bottle as a reaction base liquid, stir and heat to 85°C under N2 atmosphere;

[0059] 3) Take 10g methyl methacrylate, 2g butyl acrylate, 6g hydroxyethyl methacrylate, 2g vinyl-terminated polydimethylsiloxane, 5g butyl methacrylate, 0.4g azobisisobutyronitrile, and 50g toluene, mix well and slowly add dropwise to the reaction base liquid for 2-3h, continue stirring and reacting for 2 hours, then cool to 50°C to obtain a silicone acrylic resin for standby use;

[0060] 4) Take 60g of butanone and add it to the silicone polyacrylic resin. When the temperature is constant at 50°C, take the silicone polyurethane prepolymer in step 1) as a drop solution and add it dropwise to the diluted silicone polyacrylic resin for 2-3h. After continuous stirring at 50°C for 2h, add 150g of toluene and 150g of butanone, and continue stirring and reacting for 12h to obtain a silicone-modified polyacrylic acid-polyurethane resin.

[0061] Synthetic resin example 4

[0062] A synthetic resin is prepared from the following raw materials: 4 g of vinyl-terminated polydimethylsiloxane, 5 g of hydroxypropyl-terminated polydimethylsiloxane, 1 g of hexamethylene diisocyanate, 10 g of methyl methacrylate, 5 g of butyl acrylate, 6 g of hydroxyethyl methacrylate, 5 g of butyl methacrylate, 0.4 g of azobisisobutyronitrile, 0.04 g of dibutyltin dilaurate, 215 g of toluene, and 210 g of butanone.

[0063] The preparation method of the synthetic resin specifically comprises the following steps:

[0064] 1) Take 1g of hexamethylene diisocyanate, 0.04g of dibutyltin dilaurate and 5g of toluene and add them into a reaction bottle. Set the temperature to 75°C, uniformly add 5g of hydroxypropyl-terminated polydimethylsiloxane into the reaction bottle for 0.5h. Seal and stir the reaction for 5h to obtain an isocyanate-terminated silicone polyurethane prepolymer, which is sealed and stored away from light for later use.

[0065] 2) Take 2g of vinyl-terminated polydimethylsiloxane, 3g of butyl acrylate, and 10g of toluene, mix well, pour into a reaction bottle as a reaction base liquid, stir and heat to 85°C under N2 atmosphere;

[0066] 3) Take 10g methyl methacrylate, 2g butyl acrylate, 6g hydroxyethyl methacrylate, 2g vinyl-terminated polydimethylsiloxane, 5g butyl methacrylate, 0.4g azobisisobutyronitrile, and 50g toluene, mix well and slowly add dropwise to the reaction base liquid for 2-3h, continue stirring and reacting for 2 hours, then cool to 50°C to obtain a silicone acrylic resin for standby use;

[0067] 4) Take 60g of butanone and add it to the silicone polyacrylic resin. When the temperature is constant at 50°C, take the silicone polyurethane prepolymer in step 1) as a drop solution and add it dropwise to the diluted silicone polyacrylic resin for 2-3h. After continuous stirring at 50°C for 2h, add 150g of toluene and 150g of butanone, and continue stirring and reacting for 12h to obtain a silicone-modified polyacrylic acid-polyurethane resin.

[0068] Synthetic resin example 5

[0069] A synthetic resin is prepared from the following raw materials: 4 g of vinyl-terminated polydimethylsiloxane, 5 g of hydroxypropyl-terminated polydimethylsiloxane, 1.2 g of isophorone diisocyanate, 10 g of methyl methacrylate, 5 g of butyl acrylate, 6 g of hydroxyethyl methacrylate, 5 g of butyl methacrylate, 0.4 g of benzoyl peroxide, 0.04 g of dibutyltin dilaurate, 215 g of toluene and 210 g of butanone.

[0070] The preparation method of the synthetic resin specifically comprises the following steps:

[0071] 1) 1.2 g of isophorone diisocyanate, 0.04 g of dibutyltin dilaurate and 5 g of toluene were added to a reaction bottle, the temperature was set to 75° C. 5 g of hydroxypropyl-terminated polydimethylsiloxane was uniformly added dropwise to the reaction bottle for 0.5 h. The bottle was sealed and stirred for 5 h to obtain an isocyanate-terminated silicone polyurethane prepolymer, which was sealed and stored away from light for later use.

[0072] 2) Take 2g of vinyl-terminated polydimethylsiloxane, 3g of butyl acrylate, and 10g of toluene, mix well, pour into a reaction bottle as a reaction base liquid, stir and heat to 65°C under N2 atmosphere;

[0073] 3) Take 10g methyl methacrylate, 2g butyl acrylate, 6g hydroxyethyl methacrylate, 2g vinyl-terminated polydimethylsiloxane, 5g butyl methacrylate, 0.4g benzoyl peroxide, and 50g toluene, mix well, and slowly add dropwise to the reaction base liquid for 2-3h. Continue stirring and reacting for 3 hours, then cool to 50°C to obtain a silicone acrylic resin for standby use;

[0074] 4) Take 60g of butanone and add it to the silicone polyacrylic resin. When the temperature is constant at 50°C, take the silicone polyurethane prepolymer in step 1) as a drop solution and add it dropwise to the diluted silicone polyacrylic resin for 2-3h. After continuous stirring at 50°C for 2h, add 150g of toluene and 150g of butanone, and continue stirring and reacting for 12h to obtain a silicone-modified polyacrylic acid-polyurethane resin.

[0075] Synthetic Resin Example 6

[0076] A synthetic resin is prepared from the following raw materials: 4 g of propylene-terminated polydimethylsiloxane, 5 g of hydroxypropyl-terminated polydimethylsiloxane, 1.2 g of isophorone diisocyanate, 10 g of methyl methacrylate, 5 g of butyl acrylate, 6 g of hydroxyethyl methacrylate, 5 g of butyl methacrylate, 0.4 g of benzoyl peroxide, 0.04 g of dibutyltin dilaurate, 215 g of toluene, and 210 g of butanone.

[0077] The preparation method of the synthetic resin specifically comprises the following steps:

[0078] 1) 1.2 g of isophorone diisocyanate, 0.04 g of dibutyltin dilaurate and 5 g of toluene were added to a reaction bottle, the temperature was set to 75° C. 5 g of hydroxypropyl-terminated polydimethylsiloxane was uniformly added dropwise to the reaction bottle for 0.5 h. The bottle was sealed and stirred for 5 h to obtain an isocyanate-terminated silicone polyurethane prepolymer, which was sealed and stored away from light for later use.

[0079] 2) Take 2g of propylene-terminated polydimethylsiloxane, 3g of butyl acrylate, and 10g of toluene, mix well, pour into a reaction bottle as a reaction base liquid, stir and heat to 65°C under N2 atmosphere;

[0080] 3) Take 10g methyl methacrylate, 2g butyl acrylate, 6g hydroxyethyl methacrylate, 2g propylene-terminated polydimethylsiloxane, 5g butyl methacrylate, 0.4g benzoyl peroxide, and 50g toluene, mix well, and slowly add dropwise to the reaction base liquid for 2-3h. Continue stirring and reacting for 3 hours, then cool to 50°C to obtain a silicone acrylic resin for standby use;

[0081] 4) Take 60g of butanone and add it to the silicone polyacrylic resin. When the temperature is constant at 50°C, take the silicone polyurethane prepolymer in step 1) as a drop solution and add it dropwise to the diluted silicone polyacrylic resin for 2-3h. After continuous stirring at 50°C for 2h, add 150g of toluene and 150g of butanone, and continue stirring and reacting for 12h to obtain a silicone-modified polyacrylic acid-polyurethane resin.

[0082] Synthetic resin example 7

[0083] A synthetic resin is prepared from the following raw materials: 4 g of vinyl-terminated polydimethylsiloxane, 5 g of hydroxyl-terminated polydimethylsiloxane, 1.2 g of isophorone diisocyanate, 10 g of methyl methacrylate, 6 g of hydroxyethyl methacrylate, 5 g of butyl acrylate, 5 g of butyl methacrylate, 0.4 g of azobisisobutyronitrile, 0.04 g of dibutyltin dilaurate, 215 g of toluene, and 210 g of n-hexane.

[0084] The preparation method of the synthetic resin specifically comprises the following steps:

[0085] 1) 1.2 g of isophorone diisocyanate, 0.04 g of dibutyltin dilaurate and 5 g of toluene were added to a reaction bottle, the temperature was set to 75° C. 5 g of hydroxyl-terminated polydimethylsiloxane was uniformly added dropwise to the reaction bottle for 0.5 h. The bottle was sealed and stirred for 5 h to obtain an isocyanate-terminated silicone polyurethane prepolymer, which was sealed and stored away from light for later use.

[0086] 2) Take 2g of vinyl-terminated polydimethylsiloxane, 3g of butyl acrylate, and 10g of toluene, mix well, pour into a reaction bottle as a reaction base liquid, stir and heat to 85°C under N2 atmosphere;

[0087] 3) Take 10g methyl methacrylate, 2g butyl acrylate, 6g hydroxyethyl methacrylate, 2g vinyl-terminated polydimethylsiloxane, 5g butyl methacrylate, 0.4g azobisisobutyronitrile, and 50g toluene, mix well and slowly add dropwise to the reaction base liquid for 2-3h, continue stirring and reacting for 2 hours, then cool to 50°C to obtain a silicone acrylic resin for standby use;

[0088] 4) Take 60g of n-hexane and add it to the silicone polyacrylic acid resin. When the temperature is constant at 50°C, take the silicone polyurethane prepolymer in step 1) as a drop solution and add it dropwise to the diluted silicone polyacrylic acid resin for 2-3h. After stirring continuously at 50°C for 2h, add 150g of toluene and 150g of n-hexane, and continue stirring and reacting for 12h to obtain the silicone modified polyacrylic acid-polyurethane resin.

[0089] Synthetic resin example 8

[0090] A synthetic resin is prepared from the following raw materials: 8 g of vinyl-terminated polydimethylsiloxane, 5 g of hydroxypropyl-terminated polydimethylsiloxane, 1.2 g of isophorone diisocyanate, 10 g of methyl methacrylate, 6 g of hydroxyethyl methacrylate, 5 g of butyl acrylate, 5 g of butyl methacrylate, 0.4 g of azobisisobutyronitrile, 0.04 g of dibutyltin dilaurate, 215 g of toluene, and 210 g of acetone.

[0091] The preparation method of the synthetic resin specifically comprises the following steps:

[0092] 1) 1.2 g of isophorone diisocyanate, 0.04 g of dibutyltin dilaurate and 5 g of toluene were added to a reaction bottle, the temperature was set to 75° C. 5 g of hydroxypropyl-terminated polydimethylsiloxane was uniformly added dropwise to the reaction bottle for 0.5 h. The bottle was sealed and stirred for 5 h to obtain an isocyanate-terminated silicone polyurethane prepolymer, which was sealed and stored away from light for later use.

[0093] 2) Take 4g of vinyl-terminated polydimethylsiloxane, 3g of butyl acrylate, and 10g of toluene, mix well, pour into a reaction bottle as a reaction base liquid, stir and heat to 85°C under N2 atmosphere;

[0094] 3) Take 10g methyl methacrylate, 2g butyl acrylate, 6g hydroxyethyl methacrylate, 4g vinyl-terminated polydimethylsiloxane, 5g butyl methacrylate, 0.4g azobisisobutyronitrile, and 50g toluene, mix well and slowly add dropwise to the reaction base liquid for 2-3h, continue stirring and reacting for 2 hours, then cool to 50°C to obtain a silicone acrylic resin for standby use;

[0095] 4) Take 60g of acetone and add it to the silicone polyacrylic resin. When the temperature is constant at 50°C, take the silicone polyurethane prepolymer in step 1) as a drop solution and add it dropwise to the diluted silicone polyacrylic resin for 2-3h. After stirring continuously at 50°C for 2h, add 150g of toluene and 150g of acetone, and continue stirring and reacting for 12h to obtain a silicone-modified polyacrylic acid-polyurethane resin.

[0096] Back coating liquid examples 2 to 16

[0097] The back coating liquid prepared by using the synthetic resin of Examples 1-8 above has its weight components shown in Table 1. The preparation method of the back coating liquid is: the synthetic resin, organic solvent and diluent are mixed evenly according to a certain proportion, and a curing agent is added before coating.

[0098] Table 1 Composition of raw materials, friction coefficient and printing conditions of back coating liquid examples 2-16 on a Zebra ZM 400 printer

[0099]

[0100]

[0101] Referring to Example 1, the synthetic resin of Example 2-8 was subjected to thermal weight loss and differential scanning calorimetry analysis on a thermal analyzer, under a nitrogen atmosphere, with a heating rate of 10°C / min; the back coating liquid of Example 2-16 was applied to a PET film (thickness 0.8mm) and dried to test the friction coefficient, using a 4mm diameter steel ball, a load of 1N and a PET friction film, with a wear distance of 6mm. The experimental results show that the initial thermal decomposition temperature of the synthetic resin is basically the same, both higher than that of pure silicone polyacrylic resin, indicating that the introduction of silicone polyurethane prepolymer improves the heat resistance of the resin; the diluted back coating liquid also has excellent heat resistance and maintains a low surface friction coefficient (below 0.1), which is much smaller than the average friction coefficient of the blank base tape of 0.34, indicating that the coating of the back coating liquid effectively improves the smoothness of PET, and coating it on the carbon tape can not only protect the print head well during printing, but also greatly reduce the noise generated by the carbon tape during daily use.

[0102] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A silicone-modified polyacrylic acid-polyurethane resin, characterized in that: The invention is mainly prepared from the following raw materials in parts by weight: 8-30 parts of organic silicone oil, 1-10 parts of isocyanate, 20-80 parts of acrylate, 0.1-0.5 parts of initiator and 0.03-0.1 parts of organic tin catalyst.

2. The organosilicon-modified polyacrylic acid-polyurethane resin according to claim 1, characterized in that: The organic silicone oil is one or both of ethylene / propylene terminated polydimethylsiloxane and hydroxyl / hydroxypropyl terminated polydimethylsiloxane, and has a molecular weight between 2000 and 8000 g / mol.

3. The organosilicon-modified polyacrylic acid-polyurethane resin according to claim 1, characterized in that: The isocyanate is one or more of toluene diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate.

4. The organosilicon-modified polyacrylic acid-polyurethane resin according to claim 1, characterized in that: The acrylic acid ester is one or more of methyl methacrylate, butyl acrylate, butyl methacrylate, and hydroxyethyl methacrylate.

5. The organosilicon-modified polyacrylic acid-polyurethane resin according to claim 1, characterized in that: The initiator is one or both of azobisisobutyronitrile and benzoyl peroxide; the catalyst is dibutyltin dilaurate.

6. The method for preparing the organosilicon-modified polyacrylic acid-polyurethane resin according to any one of claims 1 to 5, characterized in that: The following steps are involved: 1) Take part of the silicone oil, isocyanate, organotin catalyst and part of the organic solvent A and add them into a reaction kettle, seal and react at 60-85 ºC for 4-12 hours to obtain an isocyanate-terminated silicone polyurethane prepolymer, and seal and store it away from light for later use; 2) Take part of the silicone oil, acrylate and part of the organic solvent A and mix them evenly, then pour them into the reactor as the reaction base liquid, and heat them to 60-85 ºC under inert gas atmosphere and stirring; 3) Take the remaining amount of silicone oil, the remaining amount of acrylate and the initiator and dissolve them in part of the organic solvent A in proportion, mix them evenly and add them to the reaction kettle in step 2) for 2-3 hours. Stir and react continuously at 60-85 ºC for 2-3 hours to obtain silicone polyacrylic acid resin; 4) Take the organosilicon polyurethane prepolymer of step 1) as the dropwise addition liquid, take part of the organic solvent A and the organosilicon polyacrylic resin of step 3) as the reaction liquid, add the dropwise addition liquid for 2-3 hours, continue stirring at 40-60 ºC for 5-14 hours, and gradually add the remaining organic solvent A as the viscosity of the system increases during the stirring process to obtain the organosilicon modified polyacrylic acid-polyurethane resin.

7. The method for preparing the organosilicon-modified polyacrylic acid-polyurethane resin according to claim 6, characterized in that: The organic solvent A is one or more of toluene, butanone, n-hexane and acetone.

8. A barcode carbon ribbon back coating liquid, characterized in that: The invention comprises the organosilicon-modified polyacrylic acid-polyurethane resin according to any one of claims 1 to 5, a curing agent, an organic solvent B and a diluent; the mass parts of the organosilicon-modified polyacrylic acid-polyurethane resin, the curing agent, the organic solvent B and the diluent are 15-35 parts, 0-1 parts, 5-25 parts and 20-45 parts.

9. The barcode carbon ribbon back coating liquid according to claim 8, characterized in that: The curing agent is an isocyanate curing agent; the organic solvent B is one or two of toluene and xylene; and the diluent is one or two of butanone, n-hexane and acetone.

10. Application of the barcode carbon ribbon back coating liquid according to any one of claims 8 to 9 in the hot stamping industry.

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