Transparent light-heat curing acrylic ester modified epoxy resin as well as preparation method and application thereof

Abstract

The invention relates to transparent light-heat curing acrylate modified epoxy resin and a preparation method and application thereof, and the transparent light-heat curing acrylate modified epoxy resin comprises the following components: aliphatic polyurethane acrylate oligomer, acrylate monomer, styrene-maleic anhydride copolymer, adhesion promoter, amino resin, photoinitiator, hydrogenated epoxy resin A and hydrogenated epoxy resin B, the composition is prepared from a thixotropic agent, an anti-aging agent, a UV absorbent, a light stabilizer, a curing agent and an accelerant. The problems that the requirement for glass fibers is high, holes are prone to occurring inside and the like due to insufficient infiltration of pure acrylic ester are solved, and the light photovoltaic flexible assembly prepared from the epoxy resin is excellent in performance and has good market application prospects.

Description

Technical Field

[0001] The invention belongs to the technical field of lightweight photovoltaic modules, and particularly relates to a transparent light-heat curing acrylate modified epoxy resin and a preparation method and application thereof. Background Art

[0002] Lightweight photovoltaic modules are used in areas such as roofs with limited load-bearing capacity, and usually require the addition of reinforced panels and back panels. The reinforced panels are required to be transparent, with a relative temperature index RTI> 115°C, and epoxy resin systems or acrylic resins are usually selected. The advantage of epoxy resin is good heat resistance, but in order to improve the heat resistance of pure epoxy resin, bisphenol A polyether epoxy is usually added. This product has poor UV resistance and tends to turn yellow when exposed to air and ultraviolet environments. Acrylic esters have high yellowing resistance, but acrylates are pure aliphatic chains, and their performance is relatively low at high temperatures. In addition, because free radical curing is difficult to control, the products prepared are usually well-cured products, and their glass fiber weight is generally <200g / m 2 , so its performance is only one-third of that of epoxy resin. In addition, high molecular weight acrylates are directly added to epoxy resins to achieve blended acrylate-modified epoxy prepolymers, but the prepolymer acrylate produced by this method is difficult to penetrate into the glass fiber cloth, and the acrylate will precipitate during the high-pressure accelerated aging life test PCT aging.

[0003] In the patent CN115466565B, light-cured pre-polyacrylate and glass fiber cloth with high air permeability are used, and a two-step curing method is adopted to enhance the wettability of acrylic resin. The product has good UV resistance, but its heat resistance is low, Tg<80°C. In the second heat curing stage, a laminator is used for thermal initiation to achieve better wettability. In the first step of the semi-cured sheet preparation process, a large amount of diluent is used during light curing to ensure wettability. The diluent is easy to explode during production and causes serious environmental pollution. In the second step of heat curing, the product needs an additional process, and many sheets are stacked, which makes the process difficult and bubbles are difficult to discharge.

[0004] In the patent CN117106214A, a simple photocurable resin is used. In order to ensure the impregnation type, it has high requirements on the glass fiber and needs to use glass fiber cloth post-treated with a coupling agent. In addition, due to the limitation of the molding pressure, the monomer content in its formula is relatively high, which also produces environmental problems such as hazardous monomer volatiles.

[0005] In the patent CN118206847A, light-curing acrylate is blended with epoxy resin, and light-curing is first used to increase viscosity, and an interpenetrating network structure is formed in the second stage of thermal curing, thereby improving the light transmittance and physical properties of the transparent composite material. However, in order to ensure the blending of epoxy resin and acrylate in the production process, 8wt%~14wt% of low-toxic diluent is still required, and high requirements are also placed on production environmental protection equipment, and a regenerative thermal incinerator RTO furnace is required to treat waste gas. In order to improve the compatibility of the Tg point of acrylate with epoxy resin, the formula also uses bisphenol A epoxy acrylate resin, which greatly reduces the UV resistance of the acrylate resin. Summary of the invention

[0006] The technical problem to be solved by the present invention is to provide a transparent light-heat curing acrylate modified epoxy resin and its preparation method and application, so as to overcome the problems that simple acrylate has high requirements on glass fiber and easily has holes inside due to insufficient infiltration.

[0007] The present invention provides a transparent light-heat curing acrylate modified epoxy resin, which comprises the following components in parts by mass: 10-40 parts of aliphatic polyurethane acrylate oligomer; Acrylate monomer 5-10 parts; 2-5 parts of styrene maleic anhydride copolymer; Adhesion promoter 1-5 parts; 2-6 parts of amino resin; Photoinitiator 0.5-1.5 parts; 30-40 parts of hydrogenated epoxy resin A; 10-20 parts of hydrogenated epoxy resin B; Thixotropic agent 0.5-1.5 parts; Anti-aging agent 0.5-1 part; 2-3 parts of UV absorber; Light stabilizer 0.5-1 part; 2-3 parts of curing agent; 1-2 parts of accelerator; The epoxy equivalent of the hydrogenated epoxy resin A is 500-750 g / eq; the epoxy equivalent of the hydrogenated epoxy resin B is 200-300 g / eq.

[0008] Preferably, the acrylic acid ester monomer includes one or more of isobornyl methacrylate, tricyclodecane dimethanol diacrylate, and tricyclodecane dimethanol dimethacrylate.

[0009] Preferably, the weight average molecular weight of the styrene maleic anhydride copolymer is between Mw=4000 and 15000, wherein the molar ratio of styrene to maleic anhydride is 2-4:1.

[0010] Preferably, the adhesion promoter is an acrylate containing tripropylene glycol diacrylate TPGDA, and the TPGDA content is between 20wt% and 40wt%.

[0011] Preferably, the photoinitiator is one or more of benzoin and its derivatives, benzil and its derivatives, acetophenone derivatives, and α-hydroxyketone derivatives.

[0012] Preferably, the thixotropic agent is fumed silica.

[0013] Preferably, the antioxidant is one or more of the hindered phenol antioxidants 1076, 1098, and 1010.

[0014] Preferably, the UV absorber is one or more of the triazine UV absorbers UV1164, UV1577, and UV400.

[0015] Preferably, the light stabilizer is one or more of benzotriazole light stabilizers UV1130 and UV928.

[0016] Preferably, the curing agent is a hydrazide curing agent, such as sebacic dihydrazide curing agent, adipic dihydrazide curing agent, etc.

[0017] Preferably, the accelerator is an organic urea accelerator or a boron amine complex accelerator, more preferably an organic urea accelerator.

[0018] The present invention also provides a method for preparing a transparent light-heat curing acrylate modified epoxy resin, comprising the following steps: (1) Place aliphatic polyurethane acrylate oligomer, acrylate monomer, styrene-maleic anhydride copolymer, adhesion promoter, amino resin, photoinitiator, hydrogenated epoxy resin A, hydrogenated epoxy resin B, thixotropic agent, anti-aging agent, UV absorber, and light stabilizer into a planetary stirring reactor according to the formula ratio, heat to 60-80°C, stir for 20-30 minutes, and evacuate, with the vacuum degree controlled at >0.8 bar, and keep warm at 60-80°C after stirring; (2) Grind the curing agent and the accelerator according to the formula ratio, and then add them into the product of step (1) and stir to obtain a transparent light-heat curing acrylate modified epoxy resin.

[0019] The present invention also provides an application of a transparent light-heat curing acrylate modified epoxy resin in a lightweight photovoltaic flexible component.

[0020] Beneficial Effects (1) The formulation of the present invention does not use active diluents, and aliphatic polyurethane acrylate oligomers are used to blend with traditional hydrogenated epoxy resins at high temperature and in a vacuum to obtain a homogeneous resin mixture. The viscosity of aliphatic polyurethane acrylate oligomers and hydrogenated epoxy resins is similar at 30°C, and the viscosity of uncured aliphatic polyurethane acrylate oligomers at 60-80°C is 1 / 4-1 / 10 of the viscosity of hydrogenated epoxy resins. During the compounding process, the temperature of the reaction system rises, so that the low-viscosity aliphatic polyurethane acrylate oligomers preferentially infiltrate the glass fibers, and UV irradiation cross-links the aliphatic polyurethane acrylate oligomers to form a semi-cured sheet. The finished semi-cured sheet can be directly used for component packaging, and the hydrogenated epoxy resin further infiltrates and exhausts the glass fibers to obtain a transparent light-heat-cured acrylate-modified epoxy resin with low porosity.

[0021] (2) The present invention uses hydrogenated epoxy resin as the epoxy resin base material. In order to solve the problem of low heat of bisphenol A epoxy and improve the overall heat resistance, the reaction of octadecyl methacrylate (SMA) and acrylate is used to improve the heat resistance of acrylate, reduce the phase separation caused by high temperature and high humidity during PCT testing due to large differences in the main chains of the molecules and large differences in the Tg points, and improve the relative temperature index (RTI) value of the overall material.

[0022] (3) The curing agent of the present invention is thermally cured simultaneously with the amino resin, overcoming the disadvantages of low activity and slow curing of hydrogenated epoxy resin, and connecting the -OH terminal of acrylate with the hydroxyl terminal of hydrogenated epoxy resin to achieve a higher crosslinking degree. DETAILED DESCRIPTION

[0023] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall within the scope limited by the appended claims of the application equally.

[0024] Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art.

[0025] The preparation method of transparent light-heat curing acrylate modified epoxy resin comprises the following steps:

[0026] (1) Place aliphatic polyurethane acrylate oligomer, acrylate monomer, styrene-maleic anhydride copolymer, adhesion promoter, amino resin, photoinitiator, hydrogenated epoxy resin A, hydrogenated epoxy resin B, thixotropic agent, anti-aging agent, UV absorber, and light stabilizer into a planetary stirring reactor according to the formula ratio, heat to 60°C, stir for 20-30 minutes, and evacuate, with the vacuum degree controlled at >0.8 bar, and keep warm at 60°C after stirring;

[0027] (2) Grind the curing agent and the accelerator according to the formula ratio, and then add them into the product of step (1) and stir to obtain a transparent light-heat curing acrylate modified epoxy resin.

[0028] Table 1 Formula of transparent light-heat curing acrylate modified epoxy resin (parts by weight)

[0029]

[0030] Table 2 Formula of transparent light-heat curing acrylate modified epoxy resin (parts by weight)

[0031]

[0032] Table 3 Formula of transparent light-heat curing acrylate modified epoxy resin (parts by weight)

[0033]

[0034] The application method of transparent light-heat curing acrylate modified epoxy resin comprises the following steps:

[0035] (1) Use a coating machine to reverse coat the resin on the release paper. The resin weight is 54~68g / m 2 between;

[0036] (2) Use a laminating machine with a roll weight of 160g / m 2 ~250g / m 2 Twill woven glass fiber cloth, using two coatings and one dip method to prepare prepreg, the compounding temperature is 60~70℃; after compounding, the film is laminated, and LED 365nm 1~3kW / cm is used after lamination 2 The irradiation intensity photocures the cross-linked prepreg to form a semi-prepreg photo-thermal curing acrylate modified epoxy resin prepreg;

[0037] (3) Simulating the packaging conditions of lightweight flexible components, the prepreg is vacuum-formed and thermally cured at 150°C / 20min, and the physical properties and other reliability properties are tested after thermal curing.

[0038] Table 4 Test results

[0039]

[0040] Table 5 Test results

[0041]

[0042] Table 6 Test results

[0043]

Claims

1. A transparent light-heat curing acrylate modified epoxy resin, characterized in that: By mass, it includes the following components: 10-40 parts of aliphatic polyurethane acrylate oligomer; Acrylate monomer 5-10 parts; 2-5 parts of styrene maleic anhydride copolymer; Adhesion promoter 1-5 parts; 2-6 parts of amino resin; Photoinitiator 0.5-1.5 parts; 30-40 parts of hydrogenated epoxy resin A; 10-20 parts of hydrogenated epoxy resin B; Thixotropic agent 0.5-1.5 parts; Anti-aging agent 0.5-1 part; 2-3 parts of UV absorber; Light stabilizer 0.5-1 part; 2-3 parts of curing agent; 1-2 parts of accelerator; The epoxy equivalent of the hydrogenated epoxy resin A is 500-750 g / eq; the epoxy equivalent of the hydrogenated epoxy resin B is 200-300 g / eq.

2. The transparent light-heat curing acrylate modified epoxy resin according to claim 1, characterized in that: The acrylic acid ester monomer includes one or more of isobornyl methacrylate, tricyclodecane dimethanol diacrylate, and tricyclodecane dimethanol dimethacrylate.

3. The transparent light-heat curing acrylate modified epoxy resin according to claim 1, characterized in that: The weight average molecular weight of the styrene maleic anhydride copolymer is between Mw=4000 and 15000, wherein the molar ratio of styrene to maleic anhydride is 2-4:

1.

4. The transparent light-heat curing acrylate modified epoxy resin according to claim 1, characterized in that: The adhesion promoter is an acrylate containing tripropylene glycol diacrylate.

5. The transparent light-heat curing acrylate modified epoxy resin according to claim 1, characterized in that: The photoinitiator is one or more of benzoin and its derivatives, benzil and its derivatives, acetophenone derivatives, and α-hydroxyketone derivatives.

6. The transparent light-heat curing acrylate modified epoxy resin according to claim 1, characterized in that: The thixotropic agent is fumed silica; the anti-aging agent is one or more of the hindered phenol anti-aging agents 1076, 1098, and 1010; the UV absorber is one or more of the triazine UV absorbers UV1164, UV1577, and UV400; the light stabilizer is one or more of the benzotriazole light stabilizers UV1130 and UV928.

7. The transparent light-heat curing acrylate modified epoxy resin according to claim 1, characterized in that: The curing agent is a hydrazide curing agent; the accelerator is an organic urea accelerator or a boron amine complex accelerator.

8. A method for preparing the transparent light-heat curing acrylate modified epoxy resin according to any one of claims 1 to 7, comprising the following steps: (1) Place aliphatic polyurethane acrylate oligomer, acrylate monomer, styrene-maleic anhydride copolymer, adhesion promoter, amino resin, photoinitiator, hydrogenated epoxy resin A, hydrogenated epoxy resin B, thixotropic agent, anti-aging agent, UV absorber, and light stabilizer into a planetary stirring kettle according to the formula ratio, heat to 60-80°C, stir for 20-30 minutes, and evacuate, with the vacuum degree controlled at >0.8 bar, and keep warm at 60-80°C after stirring; (2) Grind the curing agent and the accelerator according to the formula ratio, and then add them into the product of step (1) and stir to obtain a transparent light-heat curing acrylate modified epoxy resin.

9. Use of the transparent light-heat curing acrylate modified epoxy resin according to any one of claims 1 to 7 in a lightweight photovoltaic flexible component.

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