PVC (polyvinyl chloride) film excimer blister UV (ultraviolet) coating and preparation method thereof

Abstract

The invention provides a PVC film excimer blister UV coating and a preparation method thereof, and relates to the technical field of blister coating preparation. The coating is prepared from aliphatic polyurethane acrylate, difunctional polyester acrylate, acrylic acid modified organic silicon resin, modified nano silicon dioxide, a photoinitiator, an adhesion promoter and an auxiliary. The defects in the prior art are overcome, the wear resistance, oxidation resistance and corrosion resistance of the material can be improved while the toughness of a paint coating can be effectively guaranteed, and the PVC film is comprehensively protected.

Description

Technical Field

[0001] The present invention relates to the technical field of preparation of blister coatings, and specifically relates to a PVC film excimer blisterable UV coating and a preparation method thereof. Background Art

[0002] The PVC film excimer blisterable UV coating is specifically used for surface coating of PVC films. It can achieve rapid curing through UV light curing, and the cured coating can adapt to the blistering process. It is mainly used for surface coating of PVC films, especially for PVC film products that require blister molding. For example, in industries such as furniture, cabinets, and decorative boards, PVC films are commonly used for surface veneering and vacuum blistering, and UV coatings are used to protect the surface of PVC films.

[0003] Based on this, in order to improve the relevant properties of the PVC film surface and ensure the durability of the PVC film, it is necessary to design a blisterable UV coating that can improve the wear resistance and chemical resistance of the film. While ensuring good performance, it also needs to have high toughness to prevent cracks from occurring in the paint after blistering. Summary of the Invention

[0004] Aiming at the deficiencies of the prior art, the present invention provides a PVC film excimer blisterable UV coating and a preparation method thereof, which can effectively ensure the toughness of the paint coating while improving the wear resistance and antioxidant and corrosion resistance of the material, and comprehensively protect the PVC film.

[0005] To achieve the above object, the present invention is realized through the following technical solutions: The PVC film excimer blisterable UV coating, the coating comprises the following raw materials in parts by weight: 30-40 parts of aliphatic polyurethane acrylate, 10-15 parts of difunctional polyester acrylate, 8-12 parts of acrylic modified silicone resin, 1-2 parts of modified nano-silica, 3-4 parts of photoinitiator, 0.4-0.6 parts of adhesion promoter, 1-3 parts of auxiliary agent; the modified nano-silica is obtained by modifying nano-silica with fluorocarbon resin as a modifier.

[0006] Preferably, the specific preparation method of the modified nano-silica comprises the following steps: S1-1. Mix nano-silica and fluorocarbon resin according to a mass ratio of 10:0.2-0.4 to obtain a mixture; S1-2. Place the mixture in xylene and stir well, raise the pressure to 0.6-0.8 Mpa, continuously stir at a temperature of 80-90 °C for 40-50 min, then filter, wash with ethanol and dry to obtain modified nano-silica.

[0007] Preferably, the photoinitiator is obtained by mixing curing agent 1173 and curing agent TPO in a mass ratio of 2:1.

[0008] Preferably, the adhesion promoter is SYG-PM-2 methacrylate phosphate ester.

[0009] Preferably, the auxiliary agent is a mixture of a defoaming agent and a leveling agent in a mass ratio of 1:1, and the defoaming agent is at least one of fatty alcohol polyoxyethylene ether and alkylphenol polyoxyethylene ether; the leveling agent is obtained by mixing leveling agent SF-6432 and leveling agent HY-2500 in equal mass.

[0010] The preparation method of the PVC film excimer-absorbable UV coating comprises the following steps: (1) Thoroughly stir the aliphatic polyurethane acrylate mixed auxiliary agent evenly, then add difunctional polyester acrylate and acrylic acid modified silicone resin, raise the temperature and pressure for stirring treatment, and then relieve the pressure and stand for 1-2 h to obtain a premix for standby; (2) Add 1 / 2 of the above premix to the modified nano-silica, stir at a speed of 800-1000 r / min for 1 min, then adjust the speed to 120-400 r / min, dropwise add the remaining premix, then add a photoinitiator and an adhesion promoter, grind and filter to a fineness of ≤10 μm, and then stand to obtain an absorbable UV coating.

[0011] Preferably, in the step (1), the temperature for raising the temperature and pressure is 45-50 °C, the pressure is 2-4 Mpa, and the stirring speed for the stirring treatment is 120-600 r / min, and the stirring time is 20-30 min.

[0012] Preferably, in the step (1), the atmosphere is controlled to be nitrogen when raising the temperature and pressure.

[0013] Preferably, in the step (2), the time for dropwise adding the remaining premix is controlled within 30 min.

[0014] The present invention provides a PVC film excimer-absorbable UV coating and its preparation method. Compared with the prior art, the advantages are as follows: The present invention uses aliphatic polyurethane acrylate, difunctional polyester acrylate, and acrylic acid modified silicone resin as the main base materials of the coating. While ensuring the adhesion of the coating, it controls a certain curing shrinkage rate, and the mixed modified nano-silica improves the wear resistance, oxidation resistance, and corrosion resistance effects, and at the same time does not cause cracks in the coating after thermoforming, ensuring the toughness of the material, and comprehensively improving the application value of the coating as a protective coating for PVC films. Specific embodiments

[0015] To make the objectives, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Apparently, the described embodiments are some, but not all, of the embodiments of the present invention. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0016] The aliphatic polyurethane acrylate used hereinafter is aliphatic polyurethane acrylate RU-2282B; the acrylic modified silicone resin is the acrylic modified silicone resin of Jipeng brand (model JP-024A), and the difunctional polyester acrylate is the two-functional polyurethane modified acrylate UV resin T-7005; the photoinitiator is obtained by mixing curing agent 1173 and curing agent TPO in a mass ratio of 2:1; the auxiliary agent is a mixture of defoaming agent and leveling agent in a mass ratio of 1:1, and the defoaming agent is alkylphenol polyoxyethylene ether, and the leveling agent is obtained by mixing leveling agent SF-6432, leveling agent HY-2500, etc. in equal mass; the adhesion promoter is SYG-PM-2 methacrylate phosphate.

[0017] The particle size range of the nano-silica used is 20-60 nm, and the preparation method of the modified nano-silica is as follows: first, mix nano-silica and fluorocarbon resin in a mass ratio of 10:0.3 to obtain a mixture; then place the mixture in an excessive amount (more than 5 times the total weight of the mixture) of xylene, stir well, boost the pressure to 0.7 Mpa, continuously stir at 85 °C for 45 min, then filter, wash with ethanol and dry at 45 °C to obtain the modified nano-silica.

[0018] Example 1: Preparation of PVC film excimer-absorbable UV coating: (1) Prepare materials according to the following parts by weight: 35 parts of aliphatic polyurethane acrylate, 13 parts of difunctional polyester acrylate, 10 parts of acrylic modified silicone resin, 1.5 parts of modified nano-silica, 3.5 parts of photoinitiator, 0.5 part of adhesion promoter, and 2 parts of auxiliary agent; (2) Stir the aliphatic polyurethane acrylate and the auxiliary agent evenly, then add the difunctional polyester acrylate and the acrylic modified silicone resin, place them in a sealed reaction kettle, displace the air in the reaction kettle with nitrogen, then raise the temperature to 45 °C, boost the pressure to 3 Mpa, adjust the stirring speed to 200 r / min, stir for 25 min, then relieve the pressure and stand for 1.5 h to obtain a premix for standby; (3) Add 1 / 2 of the above premix to the modified nano-silica, stir for 1 min at a rotation speed of 900 r / min, then adjust the rotation speed to 200 r / min, add the remaining premix dropwise within half an hour, then add the photoinitiator and adhesion promoter, grind and filter to a fineness of ≤10 μm, and then let it stand for 30 min to obtain the blisterable UV coating.

[0019] Comparative Example 1: Preparation of PVC film excimer blisterable UV coating: (1) Prepare materials according to the following parts by weight of raw materials: 35 parts of aliphatic polyurethane acrylate, 13 parts of difunctional polyester acrylate, 10 parts of acrylic acid modified silicone resin, 1.5 parts of nano-silica, 3.5 parts of photoinitiator, 0.5 part of adhesion promoter, and 2 parts of auxiliary agent; (2) Stir the aliphatic polyurethane acrylate and the auxiliary agent evenly, then add the difunctional polyester acrylate and the acrylic acid modified silicone resin into a sealed reaction kettle, displace the air in the reaction kettle with nitrogen, then heat up to 45 °C, increase the pressure to 3 Mpa, adjust the stirring speed to 200 r / min, stir for 25 min, and then relieve the pressure and let it stand for 1.5 h to obtain a premix for standby; (3) Add 1 / 2 of the above premix to the nano-silica, stir for 1 min at a rotation speed of 900 r / min, then adjust the rotation speed to 200 r / min, add the remaining premix dropwise within half an hour, then add the photoinitiator and adhesion promoter, grind and filter to a fineness of ≤10 μm, and then let it stand for 30 min to obtain the blisterable UV coating.

[0020] Comparative Example 2: Preparation of PVC film excimer blisterable UV coating: (1) Prepare materials according to the following parts by weight of raw materials: 35 parts of aliphatic polyurethane acrylate, 13 parts of difunctional polyester acrylate, 10 parts of acrylic acid modified silicone resin, 1.5 parts of modified nano-silica, 3.5 parts of photoinitiator, 0.5 part of adhesion promoter, and 2 parts of auxiliary agent; (2) Stir the aliphatic polyurethane acrylate and the auxiliary agent evenly, then add the difunctional polyester acrylate and the acrylic acid modified silicone resin into a sealed reaction kettle, adjust the stirring speed to 200 r / min, stir for 40 min, and then let it stand for 1.5 h to obtain a premix for standby; (3) Add 1 / 2 of the above premix to the modified nano-silica, stir for 1 min at a rotation speed of 900 r / min, then adjust the rotation speed to 200 r / min, add the remaining premix dropwise within half an hour, then add the photoinitiator and adhesion promoter, grind and filter to a fineness of ≤10 μm, and then let it stand for 30 min to obtain the blisterable UV coating.

[0021] Detection: 1. Select the same batch of PVC film materials with a thickness of 0.2 mm, and coat the surface of the film materials with the vacuum - forming UV coatings prepared in Example 1 and Comparative Examples 1 - 2 respectively, and cure them using the excimer curing process. The specific curing method is as follows: (1) Use an LED - UV lamp with a wavelength of 365 nm, an energy density of 200 mJ / cm 2 , a light intensity of 100 mW / cm 2 , and a curing time of 5 s to form a semi - cured coating; (2) Irradiate the semi - cured coating with 172 nm excimer laser for 5 s, and control the energy density at 100 mJ / cm 2 ; (3) Use a high - pressure mercury lamp for full curing, control the energy density at 1000 mJ / cm 2 , a light intensity of 300 mW / cm 2 , until the coating is completely cured to form a UV coating with a thickness of 0.05 ± 0.01 mm.

[0022] 2. Detect the hardness and wear resistance of the UV coating: Hardness detection: Taking the HB pencil hardness as the standard, a pencil with a load of 750 g is used to scratch - test on the coating with the sharpest edge; Wear resistance detection: Test according to the standard GB / T1768 - 2006, 100 r The specific results are shown in Table 1 below Table 1 As can be seen from the above table, the coating formed by the coating of Example 1 has better wear resistance.

[0023] 3. Detect the vacuum - forming performance of each group of coatings. Vacuum - form each group of materials at a temperature of 160 °C, control the vacuum - forming depth at 2 cm, 5 cm, and 8 cm, and observe whether there are cracking and peeling phenomena on the surface of the coating. The specific results are shown in Table 2 below: Table 2 4. Detect the antioxidant effect of each coating. Through the QUV accelerated aging test (340 nm, 0.76 W / m 2 , 60 °C / 50 °C, 8 h light exposure / 4 h condensation), detect the gloss retention rate and color difference ΔE at 200 h, 500 h, and 800 h. The specific results are shown in Table 3 below: Table 3 As can be seen from the above detections, the coating formed by the coating prepared in Example 1 has a better antioxidant effect.

[0024] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: they can still modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements on some of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the various embodiments of the present invention.

Claims

1. The PVC film excimer-absorbable UV coating is characterized in that The coating comprises the following raw materials in parts by weight: 30-40 parts of aliphatic polyurethane acrylate, 10-15 parts of difunctional polyester acrylate, 8-12 parts of acrylic modified silicone resin, 1-2 parts of modified nano-silica, 3-4 parts of photoinitiator, 0.4-0.6 part of adhesion promoter, and 1-3 parts of additives; the modified nano-silica is obtained by modifying nano-silica with fluorocarbon resin as a modifier.

2. The coating according to claim 1, wherein The specific preparation method of the modified nano-silica comprises the following steps: S1-1: Mix nano-silica and fluorocarbon resin in a mass ratio of 10:0.2-0.4 to obtain a mixture. S1-2: Place the mixture in xylene, stir well, boost the pressure to 0.6-0.8 Mpa, continuously stir at a temperature of 80-90 °C for 40-50 min, then filter, wash with ethanol and dry to obtain modified nano-silica.

3. The coating according to claim 1, characterized in that: The photoinitiator is obtained by mixing curing agent 1173 and curing agent TPO in a mass ratio of 2:

1.

4. The coating according to claim 1, characterized in that: The adhesion promoter is SYG-PM-2 methacrylate phosphate.

5. The coating according to claim 1, characterized in that: The additives are obtained by mixing a defoaming agent and a leveling agent in a mass ratio of 1:1, and the defoaming agent is at least one of fatty alcohol polyoxyethylene ether and alkylphenol polyoxyethylene ether; the leveling agent is obtained by mixing leveling agent SF-6432 and leveling agent HY-2500 in equal mass.

6. A method for preparing a coating as described in any one of claims 1-5, characterized in that, The preparation method comprises the following steps: (1) Stir the aliphatic polyurethane acrylate and additives evenly, then add difunctional polyester acrylate and acrylic modified silicone resin, raise the temperature and pressure and stir, then relieve the pressure and stand for 1-2 h to obtain a premix for standby. (2) Add 1 / 2 of the above premix to the modified nano-silica, stir at a speed of 800-1000 r / min for 1 min, then adjust the speed to 120-400 r / min, dropwise add the remaining premix, then add the photoinitiator and adhesion promoter, grind and filter until the fineness is ≤10 μm, and then stand to obtain a heat-absorbable UV coating.

7. The preparation method according to claim 6, characterized in that: In step (1), the temperature for raising the temperature and pressure is 45-50 °C, the pressure is 2-4 Mpa, and the stirring speed for the stirring treatment is 120-600 r / min, and the stirring time is 20-30 min.

8. The preparation method according to claim 6, characterized in that: In step (1), the atmosphere is controlled to be nitrogen when raising the temperature and pressure.

9. The preparation method according to claim 6, characterized in that: In step (2), the time for dropwise adding the remaining premix is controlled within 30 min.

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