Environment-friendly plate transfer film as well as preparation method and application thereof

Abstract

The invention discloses an environment-friendly plate transfer film as well as a preparation method and application thereof. The transfer printing film comprises the following structures which are stacked in sequence: a base film layer; a transfer layer; a protective layer; an adhesive layer; the raw material of the transfer printing layer comprises the following components: a carbon material; modifying epoxy resin with polyurethane; an acrylic resin; an initiator; an auxiliary agent; and a solvent. The transfer film has the advantages of being remarkable in scraping resistance, high temperature resistance and washing resistance, firstly, the base film layer serves as a base layer of the transfer film, and the strength and durability of a film body are improved; on the surface of the transfer printing film, the carbon material of the transfer printing layer plays a role in improving the surface hardness of the film layer, so that the transfer printing film can resist scraping in the use process, and the surface damage caused by external physical friction is reduced. And by adding the carbon material, particularly in the aspect of enhancing the surface hardness and wear resistance of the film, the scratch resistance of the film is favorably improved.

Description

Technical Field

[0001] The invention relates to the technical field of printing materials, and in particular to an environmentally friendly plate transfer film and a preparation method and application thereof. Background Art

[0002] Environmentally friendly sheet transfer film is a high-performance material used to decorate and protect the surface of sheets. With the gradual increase in environmental awareness and people's concern for healthy living, the shortcomings of traditional transfer films in terms of environmental protection and functionality have gradually become apparent. Environmentally friendly sheet transfer film has emerged as a green and environmentally friendly product to replace traditional materials. Environmentally friendly sheet transfer film not only has decorative functions, but also can improve the durability of sheets and reduce pollution to the environment. Therefore, it is widely used in home furnishings, building materials, automobiles and other fields, and has become one of the important materials for modern sheet decoration and surface treatment.

[0003] The structural design of the environmentally friendly sheet transfer film is the basis of its high performance. Usually, this transfer film is composed of multiple layers and has a complex multi-layer structure. Generally speaking, the basic structure of the environmentally friendly sheet transfer film can be divided into several parts, such as the base film layer, the transfer layer, the protective layer and the adhesive layer. The base film layer is usually a polyester film or other plastic film, which serves as the support of the film and provides stable physical properties; the transfer layer is the core layer of the film, usually composed of environmentally friendly inks, dyes, pigments, etc., and is responsible for the transfer and expression of patterns and images; the protective layer is to enhance the durability and protection of the film, and is usually made of polymer materials, which plays a role in anti-scratch, anti-ultraviolet, waterproof, etc.; the adhesive layer is used for the attachment of the film to the substrate, so that the film can be firmly attached to the surface of the sheet.

[0004] The materials that make up the environmentally friendly sheet transfer film mainly include base film materials, transfer inks, protective coating materials and adhesives. The base film materials usually select polyester film, polyolefin film, etc. These materials have good high temperature resistance, mechanical strength and weather resistance. The components of the transfer ink are mostly environmentally friendly water-based inks, solvent-based inks or UV-curing inks. These inks generally do not contain harmful substances, such as volatile organic compounds (VOCs), heavy metals, etc., and meet environmental protection standards. The protective coating generally uses high molecular polymer materials, such as acrylic resins, polyurethanes, polyvinyl fluoride, etc. These materials not only have good scratch resistance, but also provide high temperature resistance, UV resistance, water washing resistance and other protective functions. In terms of adhesives, environmentally friendly transfer films usually use water-based or solvent-based adhesives, which have good adhesion and stability, are non-toxic and harmless, and meet green environmental protection requirements.

[0005] However, despite the significant environmental advantages of environmentally friendly sheet transfer films, existing products still have certain shortcomings in practical applications, especially in terms of scratch resistance, high temperature resistance, and water washing resistance. First, the problem of insufficient scratch resistance is due to the insufficient hardness and toughness of the protective layer material of the transfer film itself. Although the protective layer can provide a certain anti-scratch effect, in actual use, due to the wear and friction of the external environment, scratches or wear easily appear on the surface of the film, affecting the appearance and service life. Secondly, the problem of poor high temperature resistance is mainly related to the heat resistance and thermal stability of the film material. Although some environmentally friendly transfer films can maintain good physical properties within a certain temperature range, in high temperature environments, especially under long-term high temperature, the transfer film may age, discolor or peel off, seriously affecting its use effect. The reason for poor water washing resistance is related to the material structure of the transfer film and the adhesion of the coating. Although the environmentally friendly transfer film uses water-based paint and environmentally friendly materials, the protective coating on the surface of the film may be damaged during frequent water washing, resulting in the shedding of the film layer or the fading of the pattern, thereby reducing its durability and decorativeness.

[0006] The key to these problems with existing environmentally friendly sheet transfer films lies in the limitations of their raw materials and processes. The polymer materials used in environmentally friendly transfer films are difficult to meet the requirements under extreme use conditions in some aspects of performance. For example, although polyester film has good mechanical properties and thermal stability, its scratch resistance is still limited; although water-based inks and environmentally friendly coatings meet environmental protection requirements, their durability is often insufficient under strong friction or extreme temperature environments. In addition, the production process of environmentally friendly transfer films may also affect the performance of the film. The current production processes are mostly based on traditional spraying, hot pressing and other methods. These processes have not yet been optimized in some aspects, resulting in insufficient adhesion between the film layer and the sheet, which in turn affects the film's high temperature resistance and water washability.

[0007] In addition, since the production process of environmentally friendly transfer films often uses green and environmentally friendly raw materials, these materials may compromise in performance compared to traditional transfer film materials. Environmentally friendly water-based inks and coating materials usually do not contain harmful chemicals, such as volatile organic compounds (VOCs), which limits their performance in certain extreme environments. For example, the high temperature resistance of some polymer materials is limited, making it difficult to maintain the structural stability of the film at high temperatures, and it is prone to thermal degradation or discoloration.

[0008] Therefore, how to further improve the durability, scratch resistance, high temperature resistance and water washability of the transfer film while maintaining environmental performance is still an urgent problem to be solved in the current field of environmentally friendly sheet transfer films. Summary of the invention

[0009] The object of the present invention is to provide an environmentally friendly plate transfer film which is scratch-resistant, high-temperature-resistant and water-washable.

[0010] A first aspect of the present invention is:

[0011] A transfer film is provided.

[0012] The second aspect of the present invention is:

[0013] Provided is a method for preparing a transfer film.

[0014] The third aspect of the present invention is:

[0015] Application of the transfer film.

[0016] The invention also provides a plate transfer film.

[0017] Specifically, the technical solution adopted according to the first aspect of the present invention is:

[0018] A transfer film, comprising the following structures stacked in sequence:

[0019] Basement membrane layer;

[0020] transfer layer;

[0021] Protective layer;

[0022] Adhesive layer;

[0023] The raw materials of the transfer layer include the following components:

[0024] Carbon materials;

[0025] Polyurethane modified epoxy resin;

[0026] Acrylic resin;

[0027] Initiator;

[0028] Additives;

[0029] Solvent.

[0030] According to the embodiments of the present invention, one of the technical solutions has at least one of the following advantages or beneficial effects:

[0031] The transfer film of the present invention has the characteristics of significant scratch resistance, high temperature resistance and water washability. First, the base film layer, as the base layer of the transfer film, provides the strength and durability of the film body. On top of that, the carbon material of the transfer layer plays a role in improving the surface hardness of the film layer, making the transfer film more resistant to scratches during use and reducing surface damage caused by external physical friction. The addition of carbon material, especially in enhancing the surface hardness and wear resistance of the film, helps to improve the scratch resistance of the film.

[0032] Secondly, the composite use of polyurethane-modified epoxy resin and acrylic resin in the transfer layer brings strong heat resistance and water washability. Polyurethane-modified epoxy resin not only improves the chemical and thermal stability of the film, but also maintains the integrity of the film layer under high temperature environment, while acrylic resin enhances the adhesion and water resistance of the film layer. The coordinated effect of these resins in the film layer makes the transfer film have excellent high temperature resistance, and the film layer is not easy to deform or lose performance even under high temperature conditions.

[0033] Finally, the transfer film of the present invention adopts a dual curing process of thermal curing and electron beam curing during the attachment application process. Among them, thermal curing is used as a pre-curing process, which can promote the formation of preliminary interface bonding between the transfer film and the substrate at a relatively low temperature; while electron beam curing can achieve rapid and deep cross-linking curing at room temperature. This innovative dual curing process design can not only ensure the formation of a stable interface bonding between the transfer film and the substrate, but also achieve rapid curing through electron beam curing, thereby improving production efficiency. Since thermal curing is only used as a pretreatment process, the required temperature and time are greatly reduced. Compared with the traditional full heat curing process, significant optimization has been achieved in terms of time consumption, energy consumption, and processing space requirements.

[0034] According to one embodiment of the present invention, the raw materials of the transfer layer include the following components in parts by weight:

[0035] Carbon material, 5-8 parts;

[0036] Polyurethane modified epoxy resin, 6-8 parts;

[0037] Acrylic resin, 20-30 parts;

[0038] Initiator, 2-5 parts;

[0039] Auxiliary agent, 1-10 parts;

[0040] Solvent, 100-200 parts.

[0041] According to one embodiment of the present invention, the raw materials of the transfer layer include the following components in parts by weight:

[0042] Carbon material, 5-8 parts;

[0043] Polyurethane modified epoxy resin, 6.5-8 parts;

[0044] Acrylic resin, 20-30 parts;

[0045] Initiator, 2-5 parts;

[0046] Auxiliary agent, 1-10 parts;

[0047] Solvent, 100-200 parts.

[0048] According to one embodiment of the present invention, the raw materials of the transfer layer include the following components in parts by weight:

[0049] Carbon material, 5-8 parts;

[0050] Polyurethane modified epoxy resin, 6.5-8 parts;

[0051] Acrylic resin, 25-30 parts;

[0052] Initiator, 2-5 parts;

[0053] Auxiliary agent, 1-10 parts;

[0054] Solvent, 100-200 parts.

[0055] According to one embodiment of the present invention, the raw materials of the transfer layer include the following components in parts by weight:

[0056] Carbon material, 5-8 parts;

[0057] Polyurethane modified epoxy resin, 6.5-8 parts;

[0058] Acrylic resin, 25-30 parts;

[0059] Initiator, 2-4 parts;

[0060] Auxiliary agent, 1-10 parts;

[0061] Solvent, 100-200 parts.

[0062] According to one embodiment of the present invention, the raw materials of the transfer layer include the following components in parts by weight:

[0063] Carbon material, 5-8 parts;

[0064] Polyurethane modified epoxy resin, 6.5-8 parts;

[0065] Acrylic resin, 25-30 parts;

[0066] Initiator, 2-4 parts;

[0067] Additives, 1-2 parts;

[0068] Solvent, 100-200 parts.

[0069] According to one embodiment of the present invention, the carbon material includes at least one of graphene, acetylene black and carbon nanotubes.

[0070] According to one embodiment of the present invention, the carbon material includes modified graphene, and the preparation method of the modified graphene includes the following steps: mixing graphene and hexadecyltrimethylammonium bromide, heating to react at 60-70°C, then adding 2-cyano-1,3,5-triazine and silicon nitride, and heating at 30-40°C to obtain the modified graphene.

[0071] The modified graphene is compounded with hexadecyltrimethylammonium bromide to form a long-chain alkyl coating effect on the graphene surface through electrostatic adsorption, thereby improving dispersion stability; compounded with 2-cyano-1,3,5-triazine to introduce a stable structure; and compounded with silicon nitride to form a three-dimensional network structure through electrostatic interaction. The modified graphene in the transfer layer of the present invention can greatly improve the stability of the system.

[0072] According to one embodiment of the present invention, the solvent includes at least one of ethyl acetate and butyl acetate.

[0073] According to one embodiment of the present invention, the solvent is ethyl acetate and butyl acetate in a weight ratio of 1:1.

[0074] According to one embodiment of the present invention, the preparation method of the polyurethane-modified epoxy resin comprises the following steps: mixing hydroxy polydimethylsiloxane, diphenylmethane diisocyanate, 2,3-dichloropyridine and epoxy resin, heating for reaction, and obtaining the polyurethane-modified epoxy resin.

[0075] The polyurethane modified epoxy resin, by adding hydroxy polydimethylsiloxane, introduces flexible siloxy functional groups into the molecular chain structure, and the introduction of polyol segments further improves the toughness of the polyurethane modified epoxy resin; the compatibility between hydroxy polydimethylsiloxane, diphenylmethane diisocyanate and epoxy resin is fully utilized to achieve crosslinking, and the selection of diphenylmethane diisocyanate can further promote the mechanical properties of the polyurethane modified epoxy resin; the addition of 2,3-dichloropyridine further promotes the stability of the polyurethane modified epoxy resin, such as ultimately improving the chemical resistance and scratch resistance of the transfer film.

[0076] According to one embodiment of the present invention, the preparation method of the polyurethane modified epoxy resin comprises the following steps: in a protective atmosphere, hydroxy polydimethylsiloxane and diphenylmethane diisocyanate are mixed in a ratio of NCO:R(OH)=2:1.3, the temperature is raised to 75°C, and after 2 hours, the epoxy resin is added in a ratio of epoxy group:NCO=2.5:1.8, and then 0.5 parts by weight of 2,3-dichloropyridine is added, the temperature is raised to 110°C, and the reaction is carried out for 3 hours to obtain the polyurethane modified epoxy resin.

[0077] According to one embodiment of the present invention, the epoxy resin includes at least one of epoxy resin 197, epoxy resin 198, SM601, HM091, AG80, AFG90, E-51 and E-44. Preferably, the epoxy resin is E-44.

[0078] According to one embodiment of the present invention, the acrylic resin includes at least one of DM-55, Paraloid B-66, AR-2070 and AR-2630.

[0079] According to one embodiment of the present invention, the initiator includes at least one of a benzophenone initiator, an azo initiator and a nitrogen heterocyclic initiator.

[0080] According to one embodiment of the present invention, the auxiliary agent includes at least one of a fixing agent and an accelerator.

[0081] Specifically, the technical solution adopted according to the second aspect of the present invention is:

[0082] A method for preparing the transfer film comprises the following steps:

[0083] S1: mixing carbon material, polyurethane modified epoxy resin, acrylic resin, initiator and auxiliary agent in a solvent to obtain a transfer solution;

[0084] S2: coating a transfer solution on the base film layer and drying it to obtain a transfer layer;

[0085] S3: sequentially preparing a protective layer and an adhesive layer on the transfer layer to obtain the transfer film.

[0086] Another aspect of the present invention further provides a plate transfer film, including the transfer film as described in the first embodiment. Since the application adopts all the technical solutions of the transfer film, it has at least all the beneficial effects brought by the technical solutions of the above embodiment.

[0087] Another aspect of the present invention is to provide a special attachment process for the above-mentioned plate transfer film. Since the transfer film prepared by the above-mentioned technical solution has good electron beam irradiation reaction activity, the present invention has developed a dual curing process of thermal curing and electron beam curing, which has excellent curing effect and production efficiency, and specifically includes the following steps:

[0088] Pre-treating the plate transfer film by heat curing at 60 to 150° C. for 1 to 10 minutes;

[0089] The electron beam with an accelerating voltage of 80 to 200 kV is used for irradiation curing, and the dose range is 20 to 200 kGy;

[0090] The post-treatment is performed at a temperature of 60 to 150° C. for 2 to 5 minutes.

[0091] Preferably, a method for attaching a plate transfer film comprises the following steps:

[0092] 1. Clean the surface of the substrate to be attached to remove surface oil and impurities;

[0093] 2. Pre-position the transfer film and the substrate, and use a pressure roller for preliminary bonding;

[0094] 3. Thermal curing pretreatment process: thermal curing pretreatment is carried out at a temperature of 60-150°C for 1-10 minutes. The main purpose of this pretreatment process is to promote the formation of a preliminary interface between the transfer film and the substrate surface, creating good conditions for subsequent electron beam curing;

[0095] 4. Electron beam curing process: Use electron beam with acceleration voltage of 80-200kV for irradiation curing, and the dosage range is 20-200kGy. This process is the main curing link and can quickly achieve deep crosslinking at room temperature;

[0096] 5. Composite curing treatment: After the electron beam curing is completed, post-treatment at 60-100°C for 2-5 minutes can be selectively performed to optimize the interface bonding state.

[0097] The transfer film of the present invention adopts a dual curing process of thermal curing and electron beam curing during the attachment application process. Among them, thermal curing is used as a pre-curing process, which can promote the formation of preliminary interface bonding between the transfer film and the substrate at a relatively low temperature; while electron beam curing can achieve rapid and deep cross-linking curing at room temperature. This innovative dual curing process design can not only ensure the formation of a stable interface bonding between the transfer film and the substrate, but also achieve rapid curing through electron beam curing, thereby improving production efficiency. Since thermal curing is only used as a pretreatment process, the required temperature and time are greatly reduced. Compared with the traditional full thermal curing process, significant optimization has been achieved in terms of time consumption, energy consumption, and processing space requirements.

[0098] Other features and advantages of the present invention will be set forth in the description which follows, and in part will be apparent from the description, or may be learned by practice of the present invention. DETAILED DESCRIPTION

[0099] The words "preferred", "more preferred" and the like in the present invention refer to embodiments of the present invention that can provide certain beneficial effects in certain circumstances. However, other embodiments may also be preferred under the same circumstances or other circumstances. In addition, the description of one or more preferred embodiments does not imply that other embodiments are not applicable, nor is it intended to exclude other embodiments from the scope of the present invention.

[0100] When a numerical range is disclosed herein, the above range is considered to be continuous and includes the minimum and maximum values ​​of the range, as well as every value between such minimum and maximum values. Further, when a range refers to an integer, every integer between the minimum and maximum values ​​of the range is included. In addition, when multiple ranges are provided to describe features or characteristics, the ranges can be combined. In other words, unless otherwise indicated, all ranges disclosed herein should be understood to include any and all subranges included therein.

[0101] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of the present invention.

[0102] Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art.

[0103] In the embodiments and comparative examples, the epoxy resin is E-44.

[0104] In the embodiments and comparative examples, DM-55 is used as the acrylic resin.

[0105] Example 1

[0106] A transfer film, comprising the following structures stacked in sequence:

[0107] Basement membrane layer;

[0108] Transfer layer;

[0109] Protective layer;

[0110] Adhesive layer;

[0111] The raw materials of the transfer layer include the following components in parts by weight:

[0112] Carbon material, 5 parts;

[0113] Polyurethane modified epoxy resin, 6 parts;

[0114] Acrylic resin, 20 parts;

[0115] Initiator, 2 parts;

[0116] Auxiliary agent, 1 part;

[0117] Solvent, 100 parts.

[0118] The carbon material is modified graphene.

[0119] The acrylic resin is DM-55.

[0120] The auxiliary agents include fixing agents and accelerators.

[0121] The solvent is ethyl acetate and butyl acetate in a weight ratio of 1:1.

[0122] The graphene is modified graphene, and the preparation method of the modified graphene comprises the following steps:

[0123] Graphene and hexadecyltrimethylammonium bromide are mixed, heated at 60° C. for reaction, and then 2-cyano-1,3,5-triazine and silicon nitride are added, and heated at 40° C. to obtain the modified graphene.

[0124] The preparation method of the polyurethane modified epoxy resin comprises the following steps:

[0125] In a protective atmosphere, hydroxy polydimethylsiloxane and diphenylmethane diisocyanate are mixed in a ratio of NCO:R(OH)=2:1.3, the temperature is raised to 75°C, cooled to room temperature after 2 hours, epoxy resin is added in a ratio of epoxy group:NCO=2.5:1.8, and then 0.5 parts by weight of 2,3-dichloropyridine is added, the temperature is raised to 110°C, and the reaction is carried out for 3 hours to obtain the polyurethane modified epoxy resin.

[0126] The method for preparing the transfer film comprises the following steps:

[0127] S1: mixing carbon material, polyurethane modified epoxy resin, acrylic resin, initiator and auxiliary agent in a solvent to obtain a transfer solution;

[0128] S2: coating a transfer solution on the base film layer and drying it to obtain a transfer layer;

[0129] S3: sequentially preparing a protective layer and an adhesive layer on the transfer layer to obtain the transfer film.

[0130] Example 2

[0131] The difference between Example 2 and Example 1 is that in Example 2, the carbon material is carbon nanotubes.

[0132] Specific:

[0133] A transfer film, comprising the following structures stacked in sequence:

[0134] Basement membrane layer;

[0135] Transfer layer;

[0136] Protective layer;

[0137] Adhesive layer;

[0138] The raw materials of the transfer layer include the following components in parts by weight:

[0139] Carbon material, 5 parts;

[0140] Polyurethane modified epoxy resin, 6 parts;

[0141] Acrylic resin, 20 parts;

[0142] Initiator, 2 parts;

[0143] Auxiliary agent, 1 part;

[0144] Solvent, 100 parts.

[0145] The carbon material is carbon nanotube.

[0146] The acrylic resin is DM-55.

[0147] The auxiliary agents include fixing agents and accelerators.

[0148] The solvent is ethyl acetate and butyl acetate in a weight ratio of 1:1.

[0149] The preparation method of the polyurethane modified epoxy resin comprises the following steps:

[0150] In a protective atmosphere, hydroxy polydimethylsiloxane and diphenylmethane diisocyanate are mixed in a ratio of NCO:R(OH)=2:1.3, the temperature is raised to 75°C, cooled to room temperature after 2 hours, epoxy resin is added in a ratio of epoxy group:NCO=2.5:1.8, and then 0.5 parts by weight of 2,3-dichloropyridine is added, the temperature is raised to 110°C, and the reaction is carried out for 3 hours to obtain the polyurethane modified epoxy resin.

[0151] The method for preparing the transfer film comprises the following steps:

[0152] S1: mixing carbon material, polyurethane modified epoxy resin, acrylic resin, initiator and auxiliary agent in a solvent to obtain a transfer solution;

[0153] S2: coating a transfer solution on the base film layer and drying it to obtain a transfer layer;

[0154] S3: sequentially preparing a protective layer and an adhesive layer on the transfer layer to obtain the transfer film.

[0155] Example 3

[0156] The difference between Example 3 and Example 1 is that in Example 3, the carbon material is unmodified graphene.

[0157] Specific:

[0158] A transfer film, comprising the following structures stacked in sequence:

[0159] Basement membrane layer;

[0160] Transfer layer;

[0161] Protective layer;

[0162] Adhesive layer;

[0163] The raw materials of the transfer layer include the following components in parts by weight:

[0164] Carbon material, 5 parts;

[0165] Polyurethane modified epoxy resin, 6 parts;

[0166] Acrylic resin, 20 parts;

[0167] Initiator, 2 parts;

[0168] Auxiliary agent, 1 part;

[0169] Solvent, 100 parts.

[0170] The carbon material is graphene.

[0171] The acrylic resin is DM-55.

[0172] The auxiliary agents include fixing agents and accelerators.

[0173] The solvent is ethyl acetate and butyl acetate in a weight ratio of 1:1.

[0174] The preparation method of the polyurethane modified epoxy resin comprises the following steps:

[0175] In a protective atmosphere, hydroxy polydimethylsiloxane and diphenylmethane diisocyanate are mixed in a ratio of NCO:R(OH)=2:1.3, the temperature is raised to 75°C, cooled to room temperature after 2 hours, epoxy resin is added in a ratio of epoxy group:NCO=2.5:1.8, and then 0.5 parts by weight of 2,3-dichloropyridine is added, the temperature is raised to 110°C, and the reaction is carried out for 3 hours to obtain the polyurethane modified epoxy resin.

[0176] The method for preparing the transfer film comprises the following steps:

[0177] S1: mixing carbon material, polyurethane modified epoxy resin, acrylic resin, initiator and auxiliary agent in a solvent to obtain a transfer solution;

[0178] S2: coating a transfer solution on the base film layer and drying it to obtain a transfer layer;

[0179] S3: sequentially preparing a protective layer and an adhesive layer on the transfer layer to obtain the transfer film.

[0180] Example 4

[0181] The difference between Example 4 and Example 1 is that the usage amounts of the raw material components of the transfer layer are different.

[0182] A transfer film, comprising the following structures stacked in sequence:

[0183] Basement membrane layer;

[0184] transfer layer;

[0185] Protective layer;

[0186] Adhesive layer;

[0187] The raw materials of the transfer layer include the following components in parts by weight:

[0188] Carbon material, 8 parts;

[0189] Polyurethane modified epoxy resin, 6 parts;

[0190] Acrylic resin, 20 parts;

[0191] Initiator, 2 parts;

[0192] Auxiliary agent, 2 parts;

[0193] Solvent, 110 parts.

[0194] The carbon material is modified graphene.

[0195] The acrylic resin is DM-55.

[0196] The auxiliary agents include fixing agents and accelerators.

[0197] The solvent is ethyl acetate and butyl acetate in a weight ratio of 1:1.

[0198] The graphene is modified graphene, and the preparation method of the modified graphene comprises the following steps:

[0199] Graphene and hexadecyltrimethylammonium bromide are mixed, heated at 60° C. for reaction, and then 2-cyano-1,3,5-triazine and silicon nitride are added, and heated at 40° C. to obtain the modified graphene.

[0200] The preparation method of the polyurethane modified epoxy resin comprises the following steps:

[0201] In a protective atmosphere, hydroxy polydimethylsiloxane and diphenylmethane diisocyanate are mixed in a ratio of NCO:R(OH)=2:1.3, the temperature is raised to 75°C, cooled to room temperature after 2 hours, epoxy resin is added in a ratio of epoxy group:NCO=2.5:1.8, and then 0.5 parts by weight of 2,3-dichloropyridine is added, the temperature is raised to 110°C, and the reaction is carried out for 3 hours to obtain the polyurethane modified epoxy resin.

[0202] The method for preparing the transfer film comprises the following steps:

[0203] S1: mixing carbon material, polyurethane modified epoxy resin, acrylic resin, initiator and auxiliary agent in a solvent to obtain a transfer solution;

[0204] S2: coating a transfer solution on the base film layer and drying it to obtain a transfer layer;

[0205] S3: sequentially preparing a protective layer and an adhesive layer on the transfer layer to obtain the transfer film.

[0206] Example 5

[0207] The difference between Example 5 and Example 1 is that the usage amounts of the raw material components of the transfer layer are different.

[0208] A transfer film, comprising the following structures stacked in sequence:

[0209] Basement membrane layer;

[0210] Transfer layer;

[0211] Protective layer;

[0212] Adhesive layer;

[0213] The raw materials of the transfer layer include the following components in parts by weight:

[0214] Carbon material, 6 parts;

[0215] Polyurethane modified epoxy resin, 6.5 parts;

[0216] Acrylic resin, 25 parts;

[0217] Initiator, 2 parts;

[0218] Auxiliary agent, 1 part;

[0219] Solvent, 100 parts.

[0220] The carbon material is modified graphene.

[0221] The acrylic resin is DM-55.

[0222] The auxiliary agents include fixing agents and accelerators.

[0223] The solvent is ethyl acetate and butyl acetate in a weight ratio of 1:1.

[0224] The graphene is modified graphene, and the preparation method of the modified graphene comprises the following steps:

[0225] Graphene and hexadecyltrimethylammonium bromide are mixed, heated at 60° C. for reaction, and then 2-cyano-1,3,5-triazine and silicon nitride are added, and heated at 40° C. to obtain the modified graphene.

[0226] The preparation method of the polyurethane modified epoxy resin comprises the following steps:

[0227] In a protective atmosphere, hydroxy polydimethylsiloxane and diphenylmethane diisocyanate are mixed in a ratio of NCO:R(OH)=2:1.3, the temperature is raised to 75°C, cooled to room temperature after 2 hours, epoxy resin is added in a ratio of epoxy group:NCO=2.5:1.8, and then 0.5 parts by weight of 2,3-dichloropyridine is added, the temperature is raised to 110°C, and the reaction is carried out for 3 hours to obtain the polyurethane modified epoxy resin.

[0228] The method for preparing the transfer film comprises the following steps:

[0229] S1: mixing carbon material, polyurethane modified epoxy resin, acrylic resin, initiator and auxiliary agent in a solvent to obtain a transfer solution;

[0230] S2: coating a transfer solution on the base film layer and drying it to obtain a transfer layer;

[0231] S3: sequentially preparing a protective layer and an adhesive layer on the transfer layer to obtain the transfer film.

[0232] Example 6

[0233] The difference between Example 6 and Example 1 is that the usage amounts of the raw material components of the transfer layer are different.

[0234] A transfer film, comprising the following structures stacked in sequence:

[0235] Basement membrane layer;

[0236] transfer layer;

[0237] Protective layer;

[0238] Adhesive layer;

[0239] The raw materials of the transfer layer include the following components in parts by weight:

[0240] Carbon material, 6 parts;

[0241] Polyurethane modified epoxy resin, 6.5 parts;

[0242] Acrylic resin, 20 parts;

[0243] Initiator, 2 parts;

[0244] Auxiliary agent, 1 part;

[0245] Solvent, 100 parts.

[0246] The carbon material is modified graphene.

[0247] The acrylic resin is DM-55.

[0248] The auxiliary agents include fixing agents and accelerators.

[0249] The solvent is ethyl acetate and butyl acetate in a weight ratio of 1:1.

[0250] The graphene is modified graphene, and the preparation method of the modified graphene comprises the following steps:

[0251] Graphene and hexadecyltrimethylammonium bromide are mixed, heated at 60° C. for reaction, and then 2-cyano-1,3,5-triazine and silicon nitride are added, and heated at 40° C. to obtain the modified graphene.

[0252] The preparation method of the polyurethane modified epoxy resin comprises the following steps:

[0253] In a protective atmosphere, hydroxy polydimethylsiloxane and diphenylmethane diisocyanate are mixed in a ratio of NCO:R(OH)=2:1.3, the temperature is raised to 75°C, cooled to room temperature after 2 hours, epoxy resin is added in a ratio of epoxy group:NCO=2.5:1.8, and then 0.5 parts by weight of 2,3-dichloropyridine is added, the temperature is raised to 110°C, and the reaction is carried out for 3 hours to obtain the polyurethane modified epoxy resin.

[0254] The method for preparing the transfer film comprises the following steps:

[0255] S1: mixing carbon material, polyurethane modified epoxy resin, acrylic resin, initiator and auxiliary agent in a solvent to obtain a transfer solution;

[0256] S2: coating a transfer solution on the base film layer and drying it to obtain a transfer layer;

[0257] S3: sequentially preparing a protective layer and an adhesive layer on the transfer layer to obtain the transfer film.

[0258] Example 7

[0259] The difference between Example 7 and Example 1 is that the amounts of the raw material components of the transfer layer are different.

[0260] A transfer film, comprising the following structures stacked in sequence:

[0261] Basement membrane layer;

[0262] Transfer layer;

[0263] Protective layer;

[0264] Adhesive layer;

[0265] The raw materials of the transfer layer include the following components in parts by weight:

[0266] Carbon material, 5-10 parts;

[0267] Polyurethane modified epoxy resin, 7 parts;

[0268] Acrylic resin, 20 parts;

[0269] Initiator, 2 parts;

[0270] Auxiliary agent, 1 part;

[0271] Solvent, 100 parts.

[0272] The carbon material is modified graphene.

[0273] The acrylic resin is DM-55.

[0274] The auxiliary agents include fixing agents and accelerators.

[0275] The solvent is ethyl acetate and butyl acetate in a weight ratio of 1:1.

[0276] The graphene is modified graphene, and the preparation method of the modified graphene comprises the following steps:

[0277] Graphene and hexadecyltrimethylammonium bromide are mixed, heated at 60° C. for reaction, and then 2-cyano-1,3,5-triazine and silicon nitride are added, and heated at 40° C. to obtain the modified graphene.

[0278] The preparation method of the polyurethane modified epoxy resin comprises the following steps:

[0279] In a protective atmosphere, hydroxy polydimethylsiloxane and diphenylmethane diisocyanate are mixed in a ratio of NCO:R(OH)=2:1.3, the temperature is raised to 75°C, cooled to room temperature after 2 hours, epoxy resin is added in a ratio of epoxy group:NCO=2.5:1.8, and then 0.5 parts by weight of 2,3-dichloropyridine is added, the temperature is raised to 110°C, and the reaction is carried out for 3 hours to obtain the polyurethane modified epoxy resin.

[0280] The method for preparing the transfer film comprises the following steps:

[0281] S1: mixing carbon material, polyurethane modified epoxy resin, acrylic resin, initiator and auxiliary agent in a solvent to obtain a transfer solution;

[0282] S2: coating a transfer solution on the base film layer and drying it to obtain a transfer layer;

[0283] S3: sequentially preparing a protective layer and an adhesive layer on the transfer layer to obtain the transfer film.

[0284] Example 8

[0285] The difference between Example 8 and Example 1 is that the amounts of the raw material components of the transfer layer are different.

[0286] A transfer film, comprising the following structures stacked in sequence:

[0287] Basement membrane layer;

[0288] Transfer layer;

[0289] Protective layer;

[0290] Adhesive layer;

[0291] The raw materials of the transfer layer include the following components in parts by weight:

[0292] Carbon material, 10 parts;

[0293] Polyurethane modified epoxy resin, 8 parts;

[0294] Acrylic resin, 30 parts;

[0295] Initiator, 5 parts;

[0296] Auxiliary agent, 10 parts;

[0297] Solvent, 200 parts.

[0298] The carbon material is modified graphene.

[0299] The acrylic resin is DM-55.

[0300] The auxiliary agents include fixing agents and accelerators.

[0301] The solvent is ethyl acetate and butyl acetate in a weight ratio of 1:1.

[0302] The graphene is modified graphene, and the preparation method of the modified graphene comprises the following steps:

[0303] Graphene and hexadecyltrimethylammonium bromide are mixed, heated at 60° C. for reaction, and then 2-cyano-1,3,5-triazine and silicon nitride are added, and heated at 40° C. to obtain the modified graphene.

[0304] The preparation method of the polyurethane modified epoxy resin comprises the following steps:

[0305] In a protective atmosphere, hydroxy polydimethylsiloxane and diphenylmethane diisocyanate are mixed in a ratio of NCO:R(OH)=2:1.3, the temperature is raised to 75°C, cooled to room temperature after 2 hours, epoxy resin is added in a ratio of epoxy group:NCO=2.5:1.8, and then 0.5 parts by weight of 2,3-dichloropyridine is added, the temperature is raised to 110°C, and the reaction is carried out for 3 hours to obtain the polyurethane modified epoxy resin.

[0306] The method for preparing the transfer film comprises the following steps:

[0307] S1: mixing carbon material, polyurethane modified epoxy resin, acrylic resin, initiator and auxiliary agent in a solvent to obtain a transfer solution;

[0308] S2: coating a transfer solution on the base film layer and drying it to obtain a transfer layer;

[0309] S3: sequentially preparing a protective layer and an adhesive layer on the transfer layer to obtain the transfer film.

[0310] Example 9

[0311] The difference between Example 9 and Example 1 is that the usage amounts of the raw material components of the transfer layer are different.

[0312] A transfer film, comprising the following structures stacked in sequence:

[0313] Basement membrane layer;

[0314] Transfer layer;

[0315] Protective layer;

[0316] Adhesive layer;

[0317] The raw materials of the transfer layer include the following components in parts by weight:

[0318] Carbon material, 8 parts;

[0319] Polyurethane modified epoxy resin, 7 parts;

[0320] Acrylic resin, 25 parts;

[0321] Initiator, 3 parts;

[0322] Auxiliary agent, 2 parts;

[0323] Solvent, 150 parts.

[0324] The carbon material is modified graphene.

[0325] The acrylic resin is DM-55.

[0326] The auxiliary agents include fixing agents and accelerators.

[0327] The solvent is ethyl acetate and butyl acetate in a weight ratio of 1:1.

[0328] The graphene is modified graphene, and the preparation method of the modified graphene comprises the following steps:

[0329] Graphene and hexadecyltrimethylammonium bromide are mixed, heated at 60° C. for reaction, and then 2-cyano-1,3,5-triazine and silicon nitride are added, and heated at 40° C. to obtain the modified graphene.

[0330] The preparation method of the polyurethane modified epoxy resin comprises the following steps:

[0331] In a protective atmosphere, hydroxy polydimethylsiloxane and diphenylmethane diisocyanate are mixed in a ratio of NCO:R(OH)=2:1.3, the temperature is raised to 75°C, cooled to room temperature after 2 hours, epoxy resin is added in a ratio of epoxy group:NCO=2.5:1.8, and then 0.5 parts by weight of 2,3-dichloropyridine is added, the temperature is raised to 110°C, and the reaction is carried out for 3 hours to obtain the polyurethane modified epoxy resin.

[0332] The method for preparing the transfer film comprises the following steps:

[0333] S1: mixing carbon material, polyurethane modified epoxy resin, acrylic resin, initiator and auxiliary agent in a solvent to obtain a transfer solution;

[0334] S2: coating a transfer solution on the base film layer and drying it to obtain a transfer layer;

[0335] S3: sequentially preparing a protective layer and an adhesive layer on the transfer layer to obtain the transfer film.

[0336] Example 10

[0337] The difference between Example 10 and Example 1 is that the usage amounts of the raw material components of the transfer layer are different.

[0338] A transfer film, comprising the following structures stacked in sequence:

[0339] Basement membrane layer;

[0340] Transfer layer;

[0341] Protective layer;

[0342] Adhesive layer;

[0343] The raw materials of the transfer layer include the following components in parts by weight:

[0344] Carbon material, 6.5 parts;

[0345] Polyurethane modified epoxy resin, 6.5 parts;

[0346] Acrylic resin, 25 parts;

[0347] Initiator, 3 parts;

[0348] Auxiliary agent, 2 parts;

[0349] Solvent, 120 parts.

[0350] The carbon material is modified graphene.

[0351] The acrylic resin is DM-55.

[0352] The auxiliary agents include fixing agents and accelerators.

[0353] The solvent is ethyl acetate and butyl acetate in a weight ratio of 1:1.

[0354] The graphene is modified graphene, and the preparation method of the modified graphene comprises the following steps:

[0355] Graphene and hexadecyltrimethylammonium bromide are mixed, heated at 60° C. for reaction, and then 2-cyano-1,3,5-triazine and silicon nitride are added, and heated at 40° C. to obtain the modified graphene.

[0356] The preparation method of the polyurethane modified epoxy resin comprises the following steps:

[0357] In a protective atmosphere, hydroxy polydimethylsiloxane and diphenylmethane diisocyanate are mixed in a ratio of NCO:R(OH)=2:1.3, the temperature is raised to 75°C, cooled to room temperature after 2 hours, epoxy resin is added in a ratio of epoxy group:NCO=2.5:1.8, and then 0.5 parts by weight of 2,3-dichloropyridine is added, the temperature is raised to 110°C, and the reaction is carried out for 3 hours to obtain the polyurethane modified epoxy resin.

[0358] The method for preparing the transfer film comprises the following steps:

[0359] S1: mixing carbon material, polyurethane modified epoxy resin, acrylic resin, initiator and auxiliary agent in a solvent to obtain a transfer solution;

[0360] S2: coating a transfer solution on the base film layer and drying it to obtain a transfer layer;

[0361] S3: sequentially preparing a protective layer and an adhesive layer on the transfer layer to obtain the transfer film.

[0362] Comparative Example 1

[0363] The difference between Comparative Example 1 and Example 1 is that in the process of preparing modified graphene, silicon nitride is not added in Comparative Example 1.

[0364] Comparative Example 2

[0365] The difference between Comparative Example 2 and Example 1 is that in the process of preparing modified graphene, Comparative Example 2 adds 2-amino-1,3,5-triazine to replace 2-cyano-1,3,5-triazine.

[0366] Comparative Example 3

[0367] The difference between Comparative Example 3 and Example 1 is that in the process of preparing the polyurethane-modified epoxy resin, no 2,3-dichloropyridine is added in Comparative Example 3.

[0368] Comparative Example 4

[0369] The difference between Comparative Example 4 and Example 1 is that in the process of preparing the polyurethane-modified epoxy resin, polytetramethylene glycol is added in Comparative Example 4 to replace hydroxypolydimethylsiloxane.

[0370] Performance Testing:

[0371] The transfer films prepared in Examples 1-4 and Comparative Examples 1-4 were subjected to performance tests. The test results are shown in Table 1.

[0372] The wear resistance test is carried out in accordance with the provisions of Section 6.8 of GB / T 7705-2008.

[0373] Among them, the water washability test is carried out according to the method specified in GB / T 8629.

[0374] The fading rate test method is as follows: before washing, measure the color density according to Section 6.5.3 of GB / T 7705-2008, and after washing, measure the color density again and calculate the fading rate.

[0375] Table 1

[0376] Wear resistance % Washable Fading rate% Example 1 95.32 No debonding, wrinkling or breaking 0 Example 2 86.51 No degumming, some wrinkles 8 Example 3 87.80 No degumming, some wrinkles 8.5 Example 4 96.84 No debonding, wrinkling or breaking 0 Comparative Example 1 90.28 No degumming, some wrinkles 3 Comparative Example 2 92.52 No debonding, wrinkling or breaking 4 Comparative Example 3 69.41 There is degumming and wrinkles 7 Comparative Example 4 80.77 There is degumming and wrinkles 12

[0377] From Table 1, it can be seen that the presence of silicon nitride in the modified graphene can form a protective layer on the surface of the transfer film. In the process of preparing the modified graphene in Comparative Example 1, silicon nitride is not added, resulting in a decrease in the wear resistance of the transfer film. In addition, silicon nitride helps to stabilize the dispersion of graphene and can also provide additional ultraviolet shielding effect, reduce the damage of ultraviolet rays to the surface structure of graphene, and delay color fading. If silicon nitride is not added, graphene is easy to aggregate, resulting in color instability, thereby increasing the fading rate.

[0378] In the process of preparing modified graphene in Comparative Example 2, relative to Example 1, 2-amino-1,3,5-triazine is added to replace 2-cyano-1,3,5-triazine. 2-cyano-1,3,5-triazine can form a stable cyano-graphene complex with the graphene surface through a strong chemical reaction. This complex usually has better water resistance and chemical corrosion resistance. When replaced, it will affect the performance of the transfer film.

[0379] In the process of preparing polyurethane-modified epoxy resin in Comparative Example 3, 2,3-dichloropyridine is not added in Comparative Example 3. The addition of 2,3-dichloropyridine helps to optimize the compatibility and interfacial bonding between polyurethane and epoxy resin, avoid phase separation between the polyurethane part and the epoxy resin part, and improve the overall performance of the composite material. In addition, the failure to add 2,3-dichloropyridine will also result in insufficient cross-linking density of the resin, resulting in reduced wear resistance of the film layer. The wear resistance of the resin is affected by its hardness, cross-linking structure and molecular arrangement. The absence of 2,3-dichloropyridine will cause the surface of the film layer to be relatively soft and easily damaged by friction and external forces.

[0380] In the process of preparing the polyurethane-modified epoxy resin in Comparative Example 4, polytetramethylene ether glycol is added to replace hydroxypolydimethylsiloxane in Comparative Example 4. Since polytetramethylene ether glycol is subject to certain degradation under thermal oxidation conditions, the fading rate of the transfer film increases; in addition, the hydroxypolydimethylsiloxane structure contains flexible functional groups, which enhance the toughness of the material, while polytetramethylene ether glycol does not contain them, resulting in a decrease in the wear resistance of Comparative Example 4.

[0381] The above are only embodiments of the present invention, and are not intended to limit the patent scope of the present invention. Any equivalent transformations made using the contents of the present invention specification, or directly or indirectly applied in related technical fields, are also included in the patent protection scope of the present invention.

Claims

1. A transfer film, characterized in that: The invention comprises the following structures which are stacked in sequence: Basement membrane layer; transfer layer; Protective layer; Adhesive layer; The raw materials of the transfer layer include the following components: Carbon materials; Polyurethane modified epoxy resin; Acrylic resin; Initiator; Additives; Solvent.

2. A transfer film according to claim 1, characterized in that: The raw materials of the transfer layer include the following components in parts by weight: Carbon material, 5-10 parts; Polyurethane modified epoxy resin, 6-8 parts; Acrylic resin, 20-30 parts; Initiator, 2-5 parts; Auxiliary agent, 1-10 parts; Solvent, 100-200 parts.

3. A transfer film according to claim 1, characterized in that: The carbon material includes modified graphene. The preparation method of the modified graphene includes the following steps: mixing graphene and hexadecyltrimethylammonium bromide, heating at 60-70°C for reaction, then adding 2-cyano-1,3,5-triazine and silicon nitride, and heating at 30-40°C to obtain the modified graphene.

4. The transfer film according to claim 1, characterized in that: The preparation method of the polyurethane modified epoxy resin comprises the following steps: mixing hydroxy polydimethylsiloxane, diphenylmethane diisocyanate, 2,3-dichloropyridine and epoxy resin, and heating for reaction to obtain the polyurethane modified epoxy resin.

5. The transfer film according to claim 1, characterized in that: The acrylic resin includes at least one of DM-55, Paraloid B-66, AR-2070 and AR-2630.

6. The transfer film according to claim 1, characterized in that: The initiator includes at least one of a benzophenone initiator, an azo initiator and a nitrogen heterocyclic initiator.

7. The transfer film according to claim 1, characterized in that: The auxiliary agent includes at least one of a fixing agent and an accelerator.

8. A method for preparing a transfer film according to any one of claims 1 to 7, characterized in that: The following steps are involved: S1: mixing carbon material, polyurethane modified epoxy resin, acrylic resin, initiator and auxiliary agent in a solvent to obtain a transfer solution; S2: coating a transfer solution on the base film layer and drying it to obtain a transfer layer; S3: sequentially preparing a protective layer and an adhesive layer on the transfer layer to obtain the transfer film.

9. A sheet transfer film, characterized in that: The invention comprises the transfer film according to any one of claims 1 to 7.

10. A method for attaching a plate transfer film, characterized in that: The following steps are involved: Pre-treating the plate transfer film of claim 9 by heat curing at a temperature of 60 to 150° C. for 1 to 10 minutes; The electron beam with an accelerating voltage of 80 to 200 kV is used for irradiation curing, and the dose range is 20 to 200 kGy; The post-treatment is performed at a temperature of 60 to 150° C. for 2 to 5 minutes.