UV transfer printing adhesive and preparation method thereof

Abstract

The invention provides a UV transfer printing adhesive and a preparation method thereof. The UV transfer printing adhesive comprises the following components in parts by weight: 20-40 parts of UV / thermal dual-curing resin containing epoxy groups and acryloyl groups; 10 to 30 parts of reaction type organic silicon modified acrylic ester; 30 to 60 parts of a reactive diluent; 3-8 parts of a photoinitiator; 2-5 parts of a blocked isocyanate curing agent; 1-5 parts of an auxiliary agent; and 1-3 parts of a closed amino silane coupling agent. The formula of the UV transfer printing adhesive provided by the invention contains UV / thermal dual-curing resin containing epoxy groups and acryloyl groups, so that the adhesive force of the UV transfer printing adhesive to glass is more excellent, and further the UV transfer printing adhesive can better meet boiling resistance, hardness, wear resistance and hydrophobicity required by a paint film.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of UV transfer glue, and particularly relates to a UV transfer glue and a preparation method thereof. BACKGROUND

[0002] The glass UV transfer glue is a light-cured forming glue, which is mainly formed on the surface of PC, PET and TPU and other polyester films through a mold, and can also be applied on the surface of the film alone. When applied on the surface of a glass plate, the UV glue is first injected onto the glass plate through a glue injection head, then the substrate to be printed is placed on the glass plate, and then the substrate and the glass plate are pressed by a pressing unit to make the UV glue between the substrate and the glass plate uniform, and then the light fixing unit is used for light fixing to complete the entire UV transfer process.

[0003] The UV glue curing principle is that the photoinitiator (or photosensitizer) in the UV curing material absorbs ultraviolet light to produce active free radicals or cations under the irradiation of ultraviolet light, which initiates monomer polymerization, crosslinking and branch chemical reaction, so that the adhesive is converted from liquid to solid within a few seconds.

[0004] Since the UV transfer glue is cured by absorbing ultraviolet light (only a few seconds are needed), the existing UV transfer glue needs to avoid contact with sunlight during storage, and the activity of the UV transfer glue is easily reduced due to absorption of indoor ultraviolet light when the UV transfer glue is just taken out, which affects the flowability, viscosity and other properties of the UV transfer glue. SUMMARY

[0005] In view of the problems in the prior art, the main purpose of the present application is to provide a UV transfer glue and a preparation method thereof. The UV transfer glue provided in the present application contains a UV / thermal dual-curing resin containing an epoxy group and an acryl group, which can make the glass adhesion more excellent, and thus can better meet the requirements of water boiling resistance, hardness, wear resistance and hydrophobicity of the paint film.

[0006] The purpose of the present application is achieved by the following technical solutions: The present application provides a UV transfer glue, which comprises the following components calculated by weight parts: UV / thermal dual-curing resin 20-40 parts; Reaction type organic silicon modified acrylate 10-30 parts; Active diluent 30-60 parts; Photoinitiator 3-8 parts; Blocked isocyanate curing agent 2-5 parts; Auxiliary agent 1-5 parts; Blocked amino silane coupling agent 1-3 parts; The UV / thermal dual-curing resin contains epoxy groups and acryl groups.

[0007] As a further description of the above technical solution, the epoxy equivalent weight of the UV / thermal dual-curing resin is 10000-15000 g / eq, and the UV / thermal dual-curing resin refers to a difunctional epoxy acrylate oligomer with a difunctional epoxy structure.

[0008] As a further description of the above technical solution, the glass transition temperature of the reaction-type silicone-modified acrylate is 40-60℃, and the reaction-type silicone-modified acrylate refers to a UV-cured silicone hybrid resin, and the hybrid part in the UV-cured silicone hybrid resin is a polydimethylsiloxane acrylate. In order to adjust the processing performance of the resin system, the resin system used for dilution can be one of DPHA, Changxing trademark No. 6195, TPGDA, and EM231, which respectively correspond to UV-cured silicone hybrid resins with Changxing trademark No. 601Q-35, 601X-35, 601A-35, and 601C-35.

[0009] As a further description of the above technical solution, the active diluent can be a monofunctional acrylate monomer.

[0010] As a further description of the above technical solution, the active diluent is a cyclic structure acrylate monomer.

[0011] As a further description of the above technical solution, the monofunctional acrylate monomer is selected from one or more of isobornyl acrylate, 2-phenoxyethyl acrylate, tetrahydrofurfuryl acrylate, and hydroxyethyl methacrylate.

[0012] As a further description of the above technical solution, the ratio of the UV / thermal dual-curing resin and the reaction-type silicone-modified acrylate is 1.5:1-1:1 by weight.

[0013] As a further description of the above technical solution, the photoinitiator can be a cleavage-type photoinitiator or a hydrogen abstraction-type photoinitiator.

[0014] As a further description of the above technical solution, the blocked isocyanate curing agent is an HDI-type blocked isocyanate curing agent.

[0015] As a further description of the above technical solution, the auxiliary agent is a silicone leveling auxiliary agent, and is selected from one or more of BYK333 or tegO450.

[0016] The application also provides a preparation method of the UV transfer printing glue, which is used for preparing the UV transfer printing glue as described above, and the preparation method comprises the following steps: The active diluent is added to the photoinitiator under white light isolation of ultraviolet light, stirring at a speed of 300-600 rpm / min, and after uniform stirring, a first mixture is obtained; The UV / thermal dual-curing resin, the reactive organosilicon-modified acrylate, the blocked isocyanate curing agent, and the auxiliary agent are sequentially added to the first mixture, stirring at a speed of 800-1000 rpm / min, and after uniform stirring, a main agent is obtained; The blocked amino silane coupling agent is a matching agent; The main agent and the matching agent are uniformly mixed at a ratio of 100: (1-3) by weight parts, and the UV transfer adhesive is obtained.

[0017] As a further description of the above technical solution, the main agent and the matching agent are uniformly mixed at a ratio of 100:2 by weight parts.

[0018] Through the above technical solution, the application has the following advantages: The UV / thermal dual-curing resin containing epoxy groups and acryl groups in the formula of the UV transfer adhesive provided by the application has excellent glass adhesion, and can further meet the requirements of paint film for water boiling resistance, hardness, wear resistance, and hydrophobicity. BRIEF DESCRIPTION OF DRAWINGS

[0019] Fig. 1 is a schematic diagram of the sample obtained in Example 4 (left) subjected to 1h water boiling resistance test at a water temperature of 80℃ (middle) and 100℃ (right); Fig. 2 is a schematic diagram of the sample obtained in Example 4 subjected to water droplet angle test. DETAILED DESCRIPTION

[0020] The technical solutions in the embodiments of the application will be described clearly and completely below with reference to the drawings in the embodiments of the application. Obviously, the described embodiments are only a part of the embodiments of the application, rather than all the embodiments of the application. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the application.

[0021] In the description of the present application, it should be noted that the terms "upper", "middle", "lower", "inner", "outer", "front", "back", "left", "right" and the like indicate the orientation or positional relationship shown in the drawings, and are only for the convenience of describing the present application and simplifying the description, and do not indicate or imply that the devices or components referred to must have a particular orientation, be constructed and operated in a particular orientation, and therefore cannot be understood as a limitation on the present application. In addition, the terms "first", "second", "third" are only for the purpose of description, and cannot be understood as indicating or implying relative importance. For those of ordinary skill in the art, the specific meanings of the above terms in the present application can be understood according to the specific circumstances. The embodiments will be described below according to the overall structure of the present application.

[0022] The present embodiment discloses a UV transfer glue and a preparation method thereof. The UV transfer glue provided contains a UV / thermal dual-curing resin with epoxy and acryloyl groups, which can make the glass adhesion more excellent, and further make it more capable of meeting the requirements of paint film for water boiling resistance, hardness, wear resistance and hydrophobicity.

[0023] Specifically, the UV transfer glue disclosed by the present application comprises the following components calculated by weight parts: UV / thermal dual-curing resin 20-40 parts; Reactive silicone-modified acrylate 10-30 parts; Active diluent 30-60 parts; Photoinitiator 3-8 parts; Blocked isocyanate curing agent 2-5 parts; Auxiliary agent 1-5 parts; Blocked amino silane coupling agent 1-3 parts; The UV / thermal dual-curing resin contains epoxy and acryloyl groups.

[0024] The epoxy equivalent weight of the UV / thermal dual-curing resin used in the present application is 10000-15000 g / eq, and the molecular weight is 20-30 thousand. The UV / thermal dual-curing resin refers to a difunctional epoxy acrylate oligomer with a difunctional epoxy structure, such as but not limited to Changxing brand No. 6270, 6268, 6278, preferably Changxing brand No. 6278 product.

[0025] The reactive silicone-modified acrylate that can be used in the present application has a glass transition temperature of 40-60℃, and refers to a UV-cured silicone hybrid resin, wherein the hybrid part in the UV-cured silicone hybrid resin is a polydimethylsiloxane acrylate, and the reactive silicone-modified acrylate is, for example but not limited to, UV-cured silicone hybrid resins of the longxing brand 601Q-35, 601X-35, 601A-35, 601C-35, preferably the product of longxing brand 601X-35 / 601Q-35, wherein 601 represents the hybrid silicone part polydimethylsiloxane acrylate, and the resin system used for dilution can be one of DPHA (dipentaerythritol hexaacrylate), longxing brand 6195, EM223, EM231, in order to adjust the processing performance of the resin system.

[0026] The reactive diluent that can be used in the present application can be a monofunctional acrylate monomer, for example but not limited to EM70 (IBOA), EM210 (PHEA), EM214 (THFA), EM36 (HEMA), preferably a cyclic structure acrylate monomer EM70 (IBOA), EM210 (PHEA).

[0027] The monofunctional acrylate monomer that can be used in the present application is selected from one or more of isobornyl acrylate, 2-phenoxyethyl acrylate, tetrahydrofurfuryl acrylate, and hydroxyethyl methacrylate.

[0028] The ratio of the UV / thermal dual-curing resin and the reactive silicone-modified acrylate that can be used in the present application is 1.5:1~1:1 by weight.

[0029] The photoinitiator that can be used in the present application can be a cleavage type photoinitiator or a hydrogen abstraction type photoinitiator, for example but not limited to a hydroxybenzophenone type (model number 184), a phosphine oxide type such as TPO (diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide), a ketone type such as BP diphenyl ketone, and the like.

[0030] The blocked isocyanate curing agent that can be used in the present application is an HDI type blocked isocyanate curing agent, for example but not limited to Bayer 3175, SBN-70D of Downtex.

[0031] The auxiliary agent that can be used in the present application is a silicone leveling auxiliary agent, for example BYK333, tegO450.

[0032] The blocked amino silane coupling agent that can be used in the present application is, for example, SCA-MA10E.

[0033] The application further discloses a preparation method of the UV transfer printing glue. Firstly, the active diluent is added into the photoinitiator under white light shielding ultraviolet light, and stirring is performed at a speed of 300-600 rpm / min, and a first mixture is obtained after uniform stirring; the stirring duration is 30-60 min; Then, the UV / thermal dual-curing resin, the reactive organosilicon modified acrylate, the blocked isocyanate curing agent and the auxiliary agent are sequentially added into the first mixture, and stirring is performed at a speed of 800-1000 rpm / min, and a main agent is obtained after uniform stirring; the stirring duration is; The blocked amino silane coupling agent is a matching agent; Finally, the main agent and the matching agent are uniformly mixed at a ratio of 100: (1-3) by weight parts, and the UV transfer printing glue is obtained. Preferably, the main agent and the matching agent are uniformly mixed at a ratio of 100:2.

[0034] Examples According to the components and proportions listed in Table 1, the component proportions of the UV transfer printing glue are adjusted.

[0035] Table 1: Components and proportions of the UV transfer printing glue in examples Comparative examples According to the components and proportions listed in Table 2, the component proportions of the UV transfer printing glue are adjusted.

[0036] Table 2: Components and proportions of the UV transfer printing glue in comparative examples According to the preparation method of the UV transfer printing glue described above, the examples 1-10 with different component proportions are prepared into UV transfer printing glue, and the prepared UV transfer printing glue is dripped onto a glass plate, and a PET film (containing a micro-concave structure) is covered above the UV transfer printing glue; then, the UV transfer printing glue is evenly coated in the effective area covered by the PET film through a wire bar impression roller, and the UV transfer printing glue is photocured by using a moving LED lamp, and the energy control is 1000-2000 mj / cm, so that the UV transfer printing glue is pre-cured on the glass plate; the pre-cured UV transfer printing glue and the PET film are demolded; then, the UV transfer printing glue is heat-cured at a temperature of 120-150 DEG C for 30-60 min, so that the UV transfer printing glue is completely cured. And the following tests are carried out: Demolding property: the difficulty of the film from the paint film after the film is UV-cured.

[0037] Adhesion: Using the standard ASTM D 3359-97, the sample is applied to the substrate to be tested. After it is fully cured, a grid is drawn on the surface of the paint film with a utility knife, with a spacing of 1mm between the lines. Then, 3M tape is pulled 5 times to observe the paint film peeling off within the grid. The results are recorded using international standards (5B is the best, 0B is the worst).

[0038] Hardness: Using the standard ASTM D 3363-100, after the coating has fully cured, its hardness is tested with a 1000g trolley. If the paint film is scratched, it means that its hardness is lower than the hardness of the pencil. Record the hardness of the two pencils that just made the paint film scratch.

[0039] Water resistance: In accordance with standard GB 1733-93, after the paint film has fully cured, it is placed in boiling water and the surface paint film is observed to see if cracking, blackening, blistering or other phenomena occur. The adhesion of the paint film before and after boiling is also tested.

[0040] Scratch resistance: Apply a 3kg load to the paint film with your index finger and record the severity of the scratches. If there are scratches, the paint film is not scratch-resistant; if there are no scratches, the paint film is scratch-resistant.

[0041] Abrasion resistance (RCA): Using standard ASTM F2357-04, with a load of 175g, the number of times the paint film was scratched (exposed to the substrate) was recorded using an RCA abrasion tester from Norman Tool in the United States.

[0042] Water droplet angle: A certain amount of water is dropped onto a material surface, and then any vibration or movement is immediately stopped. The angle of the water droplet is measured using a water droplet angle tester or computer software. The surface properties can be evaluated and determined based on the water droplet angle value. When the water droplet angle is between 0° and 90°, the material surface is hydrophilic; when the water droplet angle is greater than 90°, the material surface is hydrophobic.

[0043] Table 3 Test results for the Examples and Comparative Examples As shown in Table 3 (where Pass indicates success and NG indicates failure) and Figs. 1-2 As shown, the UV transfer adhesive obtained by the component ratio of the present invention uses a UV / thermal dual-curing resin containing epoxy and acryloyl groups, which can make its glass adhesion better, thereby making it better able to meet the requirements of the coating film such as water resistance, hardness, abrasion resistance and hydrophobicity.

[0044] The test results of Comparative Example 1 and Comparative Example 1 show that increasing the amount of UV / thermal dual-curing resin by more than 40 parts will result in a lower overall hardness of the coating film and poor scratch resistance.

[0045] Comparing the test results of Comparative Example 2 and Example 4, it is evident that when the amount of reactive silicone-modified acrylate exceeds 30 parts, water resistance tends to deteriorate. Appropriately increasing the amount of reactive silicone-modified acrylate can improve hardness and abrasion resistance while also maintaining water resistance; however, excessive dosage can lead to increased internal stress in the paint film, causing the film to become brittle and deteriorating in water resistance. Comparing the test results of Sample Example 3 and Comparative Example 3, it is evident that reducing the amount of sealing HDI leads to a deterioration in the water resistance of the paint film and the substrate, indicating that sealing HDI can effectively improve adhesion to the glass substrate.

[0046] Comparative results of tests in Examples 8, 9, and 10 with those in Comparative Examples 4 and 5 show that too much or too little aminosilane coupling agent has no effect on water resistance. Too little amino coupling agent hydrolyzes to form a small amount of Si-OH, resulting in fewer anchoring groups with the substrate. Too much coupling agent hydrolyzes to form a large amount of hydrophilic Si-OH, a small amount of which anchors with the substrate, while the remainder either shrinks and self-polymerizes or remains in the system, resulting in poor water resistance.

[0047] Finally, it should be noted that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any changes, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A UV transfer adhesive, characterized in that, The UV transfer adhesive is composed of the following components in parts by weight: 20-40 parts of UV / thermal dual-curing resin; 10-30 parts of reactive organosilicon-modified acrylate; 30-60 parts of reactive diluent; 3-8 parts of photoinitiator; 2-5 parts of blocked isocyanate curing agent; 1-5 parts of auxiliary agent; 1-3 parts of blocked aminosilane coupling agent; The UV / thermal dual-curing resin contains epoxy groups and acryloyl groups.

2. The UV transfer adhesive according to claim 1, characterized in that, The epoxy equivalent of the UV / thermal dual-curing resin is 10000-15000 g / eq.

3. The UV transfer adhesive according to claim 1, characterized in that, The glass transition temperature of the reactive organosilicon-modified acrylate is 40-60℃.

4. The UV transfer adhesive according to claim 1, characterized in that, The reactive diluent is a monofunctional acrylate monomer.

5. The UV transfer adhesive according to claim 4, characterized in that, The monofunctional acrylate monomer is an acrylate monomer with a cyclic structure.

6. The UV transfer adhesive according to claim 4, characterized in that, The monofunctional acrylate monomer is selected from one or more of isobornyl acrylate, 2-phenoxyethyl acrylate, tetrahydrofuran acrylate, and hydroxyethyl methacrylate.

7. The UV transfer adhesive according to claim 1, characterized in that, The ratio of the UV / thermal dual-curing resin to the reactive silicone-modified acrylate is 1.5:1 to 1:1 by weight.

8. The UV transfer adhesive according to claim 1, characterized in that, The blocked isocyanate curing agent is an HDI type blocked isocyanate curing agent.

9. A method for preparing a UV transfer adhesive, characterized in that, It is used to prepare the UV transfer adhesive as described in any one of claims 1-8, wherein the preparation method includes the following steps: Under a white light that isolates ultraviolet light, the reactive diluent is added to the photoinitiator and stirred at a speed of 300~600 rpm / min until the mixture is homogeneous, thus obtaining the first mixture. The UV / thermal dual-curing resin, reactive silicone-modified acrylate, blocked isocyanate curing agent, and additives are added sequentially to the first mixture, and the mixture is stirred at a speed of 800~1000 rpm / min until it is uniformly stirred to obtain the main agent. The blocked aminosilane coupling agent is a formulation; The main agent and the additives are mixed uniformly in a ratio of 100:(1~3) by weight to obtain the UV transfer adhesive.

10. The method for preparing the UV transfer adhesive according to claim 9, characterized in that, The main agent and the additives are mixed uniformly in a ratio of 100:2 by weight.

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