CN117903719A - High-refractive-index EP composite packaging adhesive film and preparation method thereof - Google Patents

High-refractive-index EP composite packaging adhesive film and preparation method thereof Download PDF

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CN117903719A
CN117903719A CN202311853482.0A CN202311853482A CN117903719A CN 117903719 A CN117903719 A CN 117903719A CN 202311853482 A CN202311853482 A CN 202311853482A CN 117903719 A CN117903719 A CN 117903719A
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refractive index
high refractive
adhesive film
resin layer
parts
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CN117903719B (en
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潘俊
居俊杰
孟雪
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Suzhou Yisheng Optical Materials Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
    • C08G75/045—Polythioethers from mercapto compounds or metallic derivatives thereof from mercapto compounds and unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
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    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/08—Copolymers of ethene
    • C09J123/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C09J123/0815—Copolymers of ethene with aliphatic 1-olefins
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    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
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    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/322—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of solar panels
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    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/20—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself
    • C09J2301/208—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself the adhesive layer being constituted by at least two or more adjacent or superposed adhesive layers, e.g. multilayer adhesive
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    • C09J2423/04—Presence of homo or copolymers of ethene

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Abstract

The invention belongs to the technical field of photovoltaic materials, and particularly relates to a high-refractive-index EP composite packaging adhesive film and a preparation method thereof. The refractive index difference between the POE adhesive film and the EVA adhesive film is large, so that the haze of the EP composite adhesive film is increased, and the light transmittance is poor. The invention provides a high refractive index EP composite packaging adhesive film which is of a layered structure and is formed by compositing an EVA resin layer and a POE resin layer. The formula system of the EP composite packaging adhesive film with the high refractive index contains self-made high refractive index resin, the high refractive index resin takes nano oxide as a core, the outer layer is of a 'bead-string' structure with a fatty chain as a connecting chain, and the high refractive index resin structure contains nano zirconia, a carbon chain structure, an ester group structure, a benzene ring and sulfur element, so that the interlayer adhesion and the light transmittance of the EP composite adhesive film can be obviously improved.

Description

High-refractive-index EP composite packaging adhesive film and preparation method thereof
Technical Field
The invention belongs to the technical field of photovoltaic materials, and particularly relates to a high-refractive-index EP composite packaging adhesive film and a preparation method thereof.
Background
Solar modules (also called solar panels, photovoltaic modules) are the core in solar power generation systems. The photovoltaic packaging adhesive film is one of important materials in the photovoltaic industry, plays a role in bonding a solar cell with glass and a back plate, and has multiple functions of mechanical buffering, packaging protection and ultraviolet resistance protection of the back plate of a photovoltaic module. The photovoltaic packaging adhesive film is one of key materials affecting the service life and the generated power of the photovoltaic module.
At present, two main body packaging adhesive films of EVA and POE are mainly used in the market. The EVA adhesive film has the advantages of low processing temperature, strong impact resistance, high transmittance, good melt fluidity, excellent cohesiveness and the like, but has the problem of photo-thermal oxidation aging, and seriously affects the output power of the battery. The POE adhesive film has obvious advantages in the aspects of photo-thermal oxidation aging, PID resistance and the like, but the POE adhesive film has low polarity, weak adhesion with glass or backboard and easy occurrence of string deviation during lamination.
In order to solve the problems of slippage, bubbles and the like in the lamination process of POE (polyolefin elastomer) films, the EVA films on the surfaces of the POE films are studied to form the composite films with EPE or EP structures. The problem of precipitation of the auxiliary agent is solved by utilizing the characteristic of good compatibility of the additive and the EVA adhesive film, and the lamination efficiency and the yield of the battery assembly are improved. However, the EVA material and the POE material have larger refractive index difference, and the EVA material is easy to degrade under the actions of light, heat and oxygen, so that the light transmittance of the material is seriously reduced and is yellowing, and the long-term service life of the solar cell module is influenced.
DOI:10.3969/j.issn.1001-9731.2013.16.001 describes the absorption and loss of sunlight in a module as a function of the refractive index of the individual layers of the module. Light is directed onto a planar silicon wafer, wherein a portion of the light is reflected, and even for textured silicon surfaces, there is about 11% reflection loss due to increased absorption by multiple reflections of the incident light. According to the reflection minimum formula: Sunlight passes through the upper glass layer and passes through the EVA adhesive film to convert light energy into electric energy on the silicon wafer, if the refractive index of the intermediate material layer of the glass and the silicon wafer is the geometric average value/>, of the refractive indexes of the materials at two sides of the intermediate material layer The reflection value is zero and the utilization rate of sunlight by the silicon-based battery reaches the maximum value. Wherein n 0 = 1.52 is the refractive index of the glass; n 2 =3.8 is the refractive index of the silicon cell. Whereas EVA has a refractive index n=1.48, it is a very interesting task to increase the photoelectric conversion effect of the photovoltaic module by increasing the refractive index of the intermediate layer.
Disclosure of Invention
The problems in the prior art are: the refractive index difference between the POE adhesive film and the EVA adhesive film is large, so that the haze of the EP composite adhesive film is increased, and the light transmittance is poor. In view of the above problems, the present invention provides a method for preparing a high refractive index resin, comprising the steps of:
(1) Mixing oleic acid, absolute ethyl alcohol and water uniformly to obtain a mixed solution;
(2) Dispersing nano zirconia in water, and then adding the mixed liquid obtained in the step (1) into a reaction system in a dropwise manner to obtain oleic acid modified zirconia;
(3) Diallyl disulfide, 4 '-dimercapto diphenyl sulfide dimethyl methacrylate, oleic acid modified zirconia and 4', 4-dimercapto diphenyl sulfide react under the action of a photoinitiator to obtain the high refractive index resin.
Further, the dosage ratio of oleic acid to nano zirconia is 1mol:8-12mol.
Further, the dosage ratio of the diallyl disulfide to the 4,4' -dimercapto diphenyl sulfide to the methyl methacrylate, the oleic acid modified oxide and the N, N-dimethylformamide is 1-3g:1-5g:4-6g:400-500mL.
A high refractive index resin prepared by the preparation method.
The EP composite packaging adhesive film is of a layered structure and is formed by compounding an EVA resin layer and a POE resin layer, and is characterized in that the POE resin layer and/or the EVA resin layer contain the high-refractive-index resin.
Further, the POE resin layer comprises the following raw materials in parts by weight:
100 parts of POE resin;
0.5-4 parts of high refractive index resin;
0.5-1.2 parts of cross-linking agent;
1.0-2.0 parts of auxiliary cross-linking agent;
0.05-0.25 part of antioxidant;
0.05-0.3 part of light stabilizer;
0.3-0.5 part of silane coupling agent.
Further, the EVA resin layer comprises the following raw materials in parts by weight:
100 parts of EVA resin;
0.5-4 parts of high refractive index resin;
0.5-1.5 parts of cross-linking agent;
0.5-2.0 parts of auxiliary cross-linking agent;
0.2-0.5 part of antioxidant;
0.1-0.4 part of light stabilizer;
0.3-0.5 part of silane coupling agent.
Further, the EP composite packaging adhesive film is of a double-layer co-extrusion composite layered structure, the single-layer thickness of the EVA resin layer is 50-100 mu m, and the single-layer thickness of the POE resin layer is 150-350 mu m.
Further, the co-crosslinking agent comprises at least one of a high refractive index monomer, a di-or tri-functional acrylate monomer, and the high refractive index monomer comprises at least one of diallyl disulfide, 4' -dimercaptodiphenyl sulfide bis methyl methacrylate.
Further, the antioxidant is a mixture of hindered phenol antioxidant and phosphite antioxidant; the light stabilizer is a mixture of hindered amine light stabilizer and benzophenone ultraviolet absorber.
The preparation method of the high-refractive-index EP composite packaging adhesive film comprises the following steps:
S1: mixing, namely adding raw materials of each layer of high-refractive-index EP composite packaging adhesive film into a mixer for mixing according to the formula amount to obtain mixed raw materials for later use;
s2: co-extrusion is carried out to obtain the product,
Placing POE resin layer raw materials into a double-screw extruder, and carrying out melt blending;
Placing EVA resin layer raw materials into a double-screw extruder, and melt blending;
co-extruding, compounding, casting and discharging POE resin layer raw materials and EVA resin layer raw materials through two double-screw extruders, and drawing, stretching and forming films;
s3: the film material is subjected to thickness measurement, edge pressing, shaping, trimming and rolling to obtain the high refractive index EP composite packaging adhesive film.
The invention has the following beneficial effects:
(1) The formula system of the EP composite packaging adhesive film with the high refractive index comprises self-made high refractive index resin, wherein the high refractive index resin takes nano oxide as a core, the outer layer is of a 'bead-string' structure with a fatty chain as a connecting chain, and the high refractive index resin structure simultaneously comprises nano zirconia, a carbon chain structure, an ester group structure, a benzene ring and sulfur elements;
the particle size of the nano zirconia is smaller than the wavelength, so that the light scattering at the interface can be reduced; meanwhile, the crystal structure determines that the film has high refractive index, which is very beneficial to improving the light transmittance of the EP composite adhesive film;
A large amount of benzene rings and sulfur elements have high refractive index, and are very beneficial to improving the light transmittance of the EP composite adhesive film;
After the nano zirconia is subjected to oleic acid surface modification, the problem that the nano zirconia is easy to agglomerate is solved, the dispersibility of the nano oxide is improved, in addition, the long carbon chain structure introduced by oleic acid has excellent compatibility with POE, and the light transmittance of a POE adhesive layer can be further improved;
the ester structure is beneficial to the dispersibility of the resin in EVA and also beneficial to improving the light transmittance of the POE adhesive layer;
The high refractive index resin is in a macromolecular structure, forms chain entanglement with the matrix resin, has no migration, and simultaneously contains the high refractive index resin in the POE resin layer and the EVA resin layer according to a similar compatibility principle, so that the interlayer adhesion and the light transmittance of the EP composite adhesive film can be effectively improved;
(2) The formula system of the EP composite packaging adhesive film with high refractive index is also added with a monomer with high refractive index as a crosslinking assistant,
The addition of the high refractive index monomer can form a cross-linked network structure with the high refractive index resin in the packaging adhesive film system to form a 'point-surface combination' effect, so that the refractive index of the whole EP composite packaging adhesive film is further improved;
The high refractive index monomer has high-efficiency reactivity and can be bonded into a resin system through chemical bonds;
meanwhile, the acrylic ester monomer auxiliary agent in the packaging adhesive film system has similar polarity to the self-made high refractive index resin, can be adsorbed on the surface of the high refractive index resin, and has low migration precipitation, so that the interlayer bonding stability of the EP adhesive film is further ensured, and the service life of the EP packaging adhesive film is prolonged.
The specific embodiment is as follows:
The present invention will be described in detail with reference to examples. It is to be understood that the following examples are illustrative of embodiments of the present invention and are not intended to limit the scope of the invention.
A preparation method of the high refractive index resin comprises the following steps:
(1) Fully stirring oleic acid and absolute ethyl alcohol until the oleic acid and absolute ethyl alcohol are completely mixed, adding deionized water, and continuously stirring to form uniform mixed solution;
(2) Adding nano zirconia into deionized water, performing ultrasonic dispersion for 20-30min, then placing the mixture at 78-80 ℃ for heating and stirring in a water bath, then adding the mixed liquid obtained in the step (1) into a reaction system, wherein the dropping speed is 25-20 drops/min, standing for 12-24h after the dropping is finished, filtering a reaction product, leaching by ethanol, taking insoluble substances, grinding, and placing the ground substances at 40-50 ℃ for vacuum drying for 12-24h to obtain oleic acid modified zirconia;
(3) Adding diallyl disulfide, 4 '-dimercapto diphenyl sulfide dimethyl methacrylate, oleic acid modified zirconia, 4', 4-dimercapto diphenyl sulfide and a photoinitiator into N, N-dimethylformamide, uniformly stirring, carrying out UV radiation for 5-30min, concentrating the reactant by reduced pressure distillation, adding absolute methanol to generate precipitate, filtering to obtain insoluble matters, leaching the insoluble matters with the absolute methanol, and carrying out vacuum drying at 40-50 ℃ for 12-24h to obtain the high refractive index resin.
In the preparation method, the dosage ratio of the oleic acid to the nano zirconia is 1mol:8-12mol.
In the preparation method, the dosage ratio of the diallyl disulfide, the 4,4' -dimercapto diphenyl sulfide dimethyl methacrylate, the oleic acid modified oxide and the N, N-dimethylformamide is 1-3g:1-5g:4-6g:400-500mL.
In the preparation method, the dosage of the 4' 4-dimercaptodiphenyl sulfide is added according to the molar ratio of the carbon-carbon double bond to the mercapto group in the reaction system of 1:1;
in the preparation method, the photoinitiator accounts for 0-3wt% of the total mass of the reactants.
In the preparation method, the average grain size of the nano zirconia is 10-50nm.
In the preparation method, the photoinitiator is a free radical type I photoinitiator.
The high-refractive-index EP composite packaging adhesive film is of a layered structure and is formed by compounding an EVA resin layer and a POE resin layer, wherein the POE resin layer comprises the following raw materials in parts by weight:
100 parts of POE resin;
0.5-4 parts of high refractive index resin;
0.5-1.2 parts of cross-linking agent;
1.0-2.0 parts of auxiliary cross-linking agent;
0.05-0.25 part of antioxidant;
0.05-0.3 part of light stabilizer;
0.3-0.5 part of silane coupling agent;
the EVA resin layer comprises the following raw materials in parts by weight:
100 parts of EVA resin;
0.5-4 parts of high refractive index resin;
0.5-1.5 parts of cross-linking agent;
0.5-2.0 parts of auxiliary cross-linking agent;
0.2-0.5 part of antioxidant;
0.1-0.4 part of light stabilizer;
0.3-0.5 part of silane coupling agent;
The high refractive index resin is in a macromolecular structure and is generated by oleic acid modified nano zirconia, diallyl disulfide, 4' -dimercapto diphenyl sulfide dimethyl methacrylate and dimercapto diphenyl sulfide through double bond photopolymerization and mercapto-alkene click chemical reaction;
the oleic acid modified nano zirconia is generated by esterification reaction of carboxyl of oleic acid and hydroxyl formed by adsorption on the surface of the nano zirconia.
In the packaging adhesive film, the single-layer thickness of the EVA resin layer is 50-100 mu m, and the single-layer thickness of the POE resin layer is 150-350 mu m.
In the packaging adhesive film, the EP composite packaging adhesive film is of a double-layer co-extrusion composite layered structure and is formed by compositing an EVA resin layer and a POE resin layer from top to bottom in sequence.
In the packaging adhesive film, the cross-linking agent comprises but is not limited to 1,1- (tert-butyl diperoxide) -3, 5-trimethylcyclohexane.
In the above packaging adhesive film, the auxiliary crosslinking agent includes a high refractive index monomer.
In the above packaging adhesive film, the high refractive index monomer includes, but is not limited to, at least one of diallyl disulfide and 4,4' -dimercapto diphenyl sulfide dimethyl methacrylate.
In the above packaging adhesive film, the auxiliary crosslinking agent further comprises at least one of difunctional or trifunctional acrylate monomers.
In the packaging adhesive film, the acrylate monomer comprises at least one of trimethylolpropane trimethacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated neopentyl glycol diacrylate and pentaerythritol triacrylate.
In the packaging adhesive film, the antioxidant is a mixture of hindered phenol antioxidant and phosphite antioxidant.
In the packaging adhesive film, the light stabilizer is a mixture of a hindered amine light stabilizer and a benzophenone ultraviolet absorber.
In the packaging adhesive film, the silane coupling agent comprises but is not limited to vinyl tri (beta-methoxyethoxy) silane.
The preparation method of the high-refractive-index EP composite packaging adhesive film comprises the following steps:
s1: mixing, namely adding the raw materials of each layer into a mixer according to the formula amount to mix, and mixing and stirring for 2 hours at the temperature of 40 ℃ and the rotating speed of 80rpm to obtain mixed raw materials for later use;
s2: co-extrusion is carried out to obtain the product,
Placing POE resin layer raw materials into a double-screw extruder, and melt-blending at 80-110 ℃ and a rotating speed of 45-50 rpm;
placing EVA resin layer raw material into a double screw extruder, and melt blending at 80-100deg.C and 45-50 rpm;
co-extruding, compounding, casting and discharging POE resin layer raw materials and EVA resin layer raw materials through two double-screw extruders, and drawing, stretching and forming films;
s3: the film material is subjected to thickness measurement, edge pressing, shaping, trimming and rolling to obtain the high refractive index EP composite packaging adhesive film.
POE resin in the following examples of the invention: XUS38660, purchased from the american dow chemical company.
EVA resin in the following examples of the invention: VA content 33%, melt Index (MI) 31, purchased from DuPont, U.S.A.
The average particle diameter of the nano zirconia in the following examples of the present invention was 10nm.
The crosslinker in the following examples of the invention is 1,1- (t-butyl diperoxide) -3, 5-trimethylcyclohexane.
The antioxidant in the following examples of the present invention is a composition of antioxidant 1076 and antioxidant 168 in a mass ratio of 1:2.
The light stabilizer in the following examples of the present invention is a composition of UV-292 and UV-950 in a mass ratio of 1:2.
The silane coupling agent in the following examples of the present invention is vinyltris (β -methoxyethoxy) silane.
Example 1
The EP composite packaging adhesive film with the high refractive index is of a layered structure and is formed by compounding an EVA resin layer and a POE resin layer, wherein the POE resin layer is composed of the following raw materials in parts by weight:
100 parts of POE resin;
2.5 parts of high refractive index resin;
1 part of cross-linking agent;
1.6 parts of auxiliary cross-linking agent;
0.1 part of antioxidant;
0.15 parts of light stabilizer;
0.4 parts of silane coupling agent.
The EVA resin layer is composed of the following raw materials in parts by weight:
100 parts of EVA resin;
2.8 parts of high refractive index resin;
1.1 parts of a cross-linking agent;
1.5 parts of auxiliary cross-linking agent;
0.36 parts of antioxidant;
0.3 parts of light stabilizer;
0.4 parts of silane coupling agent.
The EVA resin layer has a single layer thickness of 50 μm, and the POE resin layer has a single layer thickness of 150 μm.
The preparation method of the high refractive index resin comprises the following steps:
(1) Fully stirring oleic acid and absolute ethyl alcohol until the oleic acid and absolute ethyl alcohol are completely mixed, adding deionized water, and continuously stirring to form uniform mixed solution;
(2) Adding nano zirconia into deionized water, performing ultrasonic dispersion for 20min, then placing the mixture at 80 ℃ for heating and stirring in a water bath, then adding the mixed liquid obtained in the step (1) into a reaction system in a dropwise manner at a dropwise speed of 25 drops/min, standing for 12h after the dropwise addition is finished, filtering a reaction product, leaching with ethanol, taking insoluble matters, grinding, placing the ground matters at 40 ℃ for vacuum drying for 12h to obtain oleic acid modified zirconia, wherein the infrared data are as follows: 3434cm -1: -OH weakening; 2923cm -1: -C-H is present; 1622cm -1: -c=c-present;
The dosage ratio of oleic acid to absolute ethyl alcohol to deionized water is 1g:2g:2g:8g;
the dosage ratio of oleic acid to nano zirconia is 1mol:10mol;
(2) Adding diallyl disulfide, 4 '-dimercapto diphenyl sulfide dimethyl methacrylate, oleic acid modified zirconia, 4', 4-dimercapto diphenyl sulfide and a photoinitiator into N, N-dimethylformamide, uniformly stirring, radiating for 10min under the condition of UV light intensity of 400mJ/cm 2, concentrating the reactant by reduced pressure distillation, adding absolute methanol to generate precipitate, filtering to obtain insoluble matters, leaching the insoluble matters by the absolute methanol, and vacuum drying at 40 ℃ for 12h to obtain high refractive index resin, wherein the infrared data are as follows: 3434cm -1: -OH is present; 2923cm -1: -C-H is present; 3018cm -1: benzene ring-C-H is present; 1622cm -1: -c=c-absent; 1735m -1: -c=o present; 1603cm -1、810cm-1: -c=c-absent; 2550cm -1: SH is absent;
The dosage ratio of the diallyl disulfide to the 4,4' -dimercapto diphenyl sulfide to the methyl dimethacrylate to the oleic acid modified oxide to the N, N-dimethylformamide is 2g:3g:5g:400mL;
The dosage of the 4' 4-dimercaptodiphenyl sulfide is added according to the mol ratio of the carbon-carbon double bond to the mercapto in the reaction system of 1:1;
the photoinitiator was 2% of the total mass of the reactants.
Specifically, the photoinitiator is photoinitiator 184.
Specifically, the auxiliary cross-linking agent is a mixture formed by 4,4 '-dimercapto diphenyl sulfide dimethyl methacrylate and ethoxylated trimethylolpropane triacrylate and propoxylated neopentyl glycol diacrylate, the mass ratio of the ethoxylated trimethylolpropane triacrylate to the propoxylated neopentyl glycol diacrylate is 1:1, and the dosage ratio of the 4,4' -dimercapto diphenyl sulfide dimethyl methacrylate to the total amount of the mixture of the ethoxylated trimethylolpropane triacrylate and the propoxylated neopentyl glycol diacrylate is 2g:8g.
The preparation method of the high-refractive-index EP composite packaging adhesive film comprises the following steps:
s1: mixing, namely adding the raw materials of each layer into a mixer according to the formula amount to mix, and mixing and stirring for 2 hours at the temperature of 40 ℃ and the rotating speed of 80rpm to obtain mixed raw materials for later use;
s2: co-extrusion is carried out to obtain the product,
Placing POE resin layer raw materials into a double-screw extruder, and melt-blending at 90 ℃, 95 ℃, 105 ℃ and 50 rpm;
Placing EVA resin layer raw material into a double screw extruder, and melt blending at 80 ℃, 90 ℃, 100 ℃ and rotating speed of 45 rpm;
co-extruding, compounding, casting and discharging POE resin layer raw materials and EVA resin layer raw materials through two double-screw extruders, and drawing, stretching and forming films;
s3: the film material is subjected to thickness measurement, edge pressing, shaping, trimming and rolling to obtain the high refractive index EP composite packaging adhesive film.
Example 2
The EP composite packaging adhesive film with the high refractive index is of a layered structure and is formed by compounding an EVA resin layer and a POE resin layer, wherein the POE resin layer is composed of the following raw materials in parts by weight:
100 parts of POE resin;
4 parts of high refractive index resin;
0.5 parts of cross-linking agent;
2.0 parts of auxiliary cross-linking agent;
0.25 parts of antioxidant;
0.3 parts of light stabilizer;
0.3 parts of silane coupling agent.
The EVA resin layer is composed of the following raw materials in parts by weight:
100 parts of EVA resin;
4 parts of high refractive index resin;
0.5 parts of cross-linking agent;
2.0 parts of auxiliary cross-linking agent;
0.2 parts of antioxidant;
0.1 part of light stabilizer;
0.3 parts of silane coupling agent.
The EVA resin layer has a single-layer thickness of 100 mu m, and the POE resin layer has a single-layer thickness of 350 mu m.
The preparation method of the high refractive index resin comprises the following steps:
(1) Fully stirring oleic acid and absolute ethyl alcohol until the oleic acid and absolute ethyl alcohol are completely mixed, adding deionized water, and continuously stirring to form uniform mixed solution;
(2) Adding nano zirconia into deionized water, performing ultrasonic dispersion for 30min, then placing the mixture at 78 ℃ for heating and stirring in a water bath, then adding the mixed liquid obtained in the step (1) into a reaction system in a dropwise manner at a dropwise speed of 20 drops/min, standing for 24h after the dropwise addition is finished, filtering a reaction product, leaching with ethanol, taking insoluble matters, grinding, placing the ground matters at 50 ℃ for vacuum drying for 24h to obtain oleic acid modified zirconia, wherein the infrared data are as follows: 3434cm -1: -OH weakening; 2923cm -1: -C-H is present; 1622cm -1: -c=c-present;
The dosage ratio of oleic acid to absolute ethyl alcohol to deionized water is 1g:2g:2g:8g;
the dosage ratio of oleic acid to nano zirconia is 1mol:8mol;
(2) Adding diallyl disulfide, 4 '-dimercapto diphenyl sulfide dimethyl methacrylate, oleic acid modified zirconia and 4', 4-dimercapto diphenyl sulfide into N, N-dimethylformamide, uniformly stirring, radiating for 30min under the condition of UV light intensity of 400mJ/cm 2, concentrating the reactant by reduced pressure distillation, adding absolute methanol to generate precipitate, filtering to obtain insoluble matters, leaching the insoluble matters by the absolute methanol, and vacuum drying at 50 ℃ for 12h to obtain high refractive index resin, wherein the infrared data are as follows: 3434cm -1: -OH is present; 2923cm -1: -C-H is present; 3018cm -1: benzene ring-C-H is present; 1622cm -1: -c=c-absent; 1735m -1: -c=o present; 1603cm -1、810cm-1: -c=c-absent; 2550cm -1: SH is absent;
The dosage ratio of the diallyl disulfide to the 4,4' -dimercapto diphenyl sulfide dimethyl methacrylate to the oleic acid modified oxide to the N, N-dimethylformamide is 3g and 3g:4g:400mL;
The dosage of the 4' 4-dimercaptodiphenyl sulfide is added according to the mol ratio of the carbon-carbon double bond to the mercapto in the reaction system of 1:1;
Specifically, the auxiliary crosslinking agent is diallyl disulfide and a mixture formed by trimethylolpropane trimethacrylate and propoxylated neopentyl glycol diacrylate, the mass ratio of the trimethylolpropane trimethacrylate to the propoxylated neopentyl glycol diacrylate is 2:3, and the dosage ratio of the diallyl disulfide to the mixture of the trimethylolpropane trimethacrylate and the propoxylated neopentyl glycol diacrylate is 1g:3.6g:5.4g.
The preparation method of the high-refractive-index EP composite packaging adhesive film comprises the following steps:
s1: mixing, namely adding the raw materials of each layer into a mixer according to the formula amount to mix, and mixing and stirring for 2 hours at the temperature of 40 ℃ and the rotating speed of 80rpm to obtain mixed raw materials for later use;
s2: co-extrusion is carried out to obtain the product,
Placing POE resin layer raw materials into a double-screw extruder, and melt-blending at 90 ℃, 100 ℃, 110 ℃ and 50 rpm;
placing EVA resin layer raw material into a double screw extruder, and melt blending at 80 ℃, 90 ℃, 95 ℃ and a rotating speed of 50 rpm;
co-extruding, compounding, casting and discharging POE resin layer raw materials and EVA resin layer raw materials through two double-screw extruders, and drawing, stretching and forming films;
s3: the film material is subjected to thickness measurement, edge pressing, shaping, trimming and rolling to obtain the high refractive index EP composite packaging adhesive film.
Example 3
The EP composite packaging adhesive film with the high refractive index is of a layered structure and is formed by compounding an EVA resin layer and a POE resin layer, wherein the POE resin layer is composed of the following raw materials in parts by weight:
100 parts of POE resin;
0.5 parts of high refractive index resin;
1.2 parts of cross-linking agent;
1.0 parts of auxiliary cross-linking agent;
0.05 parts of antioxidant;
0.05 parts of light stabilizer;
0.5 part of silane coupling agent.
The EVA resin layer is composed of the following raw materials in parts by weight:
100 parts of EVA resin;
1 part of high refractive index resin;
1.5 parts of cross-linking agent;
0.5 part of auxiliary cross-linking agent;
0.5 parts of antioxidant;
0.4 parts of light stabilizer;
0.5 part of silane coupling agent.
The EVA resin layer has a single-layer thickness of 100 mu m, and the POE resin layer has a single-layer thickness of 200 mu m.
The preparation method of the high refractive index resin comprises the following steps:
(1) Fully stirring oleic acid and absolute ethyl alcohol until the oleic acid and absolute ethyl alcohol are completely mixed, adding deionized water, and continuously stirring to form uniform mixed solution;
(2) Adding nano zirconia into deionized water, performing ultrasonic dispersion for 20min, then placing the mixture at 80 ℃ for heating and stirring in a water bath, then adding the mixed liquid obtained in the step (1) into a reaction system in a dropwise manner at a dropwise speed of 25 drops/min, standing for 12h after the dropwise addition is finished, filtering a reaction product, leaching with ethanol, taking insoluble matters, grinding, placing the ground matters at 45 ℃ for vacuum drying for 12h to obtain oleic acid modified zirconia, wherein the infrared data are as follows: 3434cm -1: -OH weakening; 2923cm -1: -C-H is present; 1622cm -1: -c=c-present;
The dosage ratio of oleic acid to absolute ethyl alcohol to deionized water is 1g:2g:2g:8g;
the dosage ratio of oleic acid to nano zirconia is 1mol:12mol;
(2) Adding diallyl disulfide, 4 '-dimercapto diphenyl sulfide dimethyl methacrylate, oleic acid modified zirconia, 4', 4-dimercapto diphenyl sulfide and a photoinitiator into N, N-dimethylformamide, uniformly stirring, radiating for 5min under the condition of UV light intensity of 400mJ/cm < 2 >, concentrating the reactant by reduced pressure distillation, adding absolute methanol to generate precipitate, filtering to obtain insoluble matters, leaching the insoluble matters by the absolute methanol, and vacuum drying at 50 ℃ for 12h to obtain high refractive index resin, wherein the infrared data are as follows: 3434cm -1: -OH is present; 2923cm -1: -C-H is present; 3018cm -1: benzene ring-C-H is present; 1622cm -1: -c=c-absent; 1735m -1: -c=o present; 1603cm -1、810cm-1: -c=c-absent; 2550cm -1: SH is absent;
The dosage ratio of the diallyl disulfide to the 4,4' -dimercapto diphenyl sulfide to the methyl dimethacrylate to the oleic acid modified oxide to the N, N-dimethylformamide is 1g:3g:6g:400mL;
The dosage of the 4' 4-dimercaptodiphenyl sulfide is added according to the mol ratio of the carbon-carbon double bond to the mercapto in the reaction system of 1:1;
the photoinitiator is 1% of the total mass of the reactants.
The photoinitiator is a photoinitiator TPO.
The auxiliary crosslinking agent is diallyl disulfide and a mixture formed by ethoxylated pentaerythritol tetraacrylate and propoxylated neopentyl glycol diacrylate, the mass ratio of the ethoxylated pentaerythritol tetraacrylate to the propoxylated neopentyl glycol diacrylate is 1:1, and the using amount ratio of the diallyl disulfide to the mixture of the ethoxylated pentaerythritol tetraacrylate and the propoxylated neopentyl glycol diacrylate is 3g:7g.
The preparation method of the high-refractive-index EP composite packaging adhesive film comprises the following steps:
s1: mixing, namely adding the raw materials of each layer into a mixer according to the formula amount to mix, and mixing and stirring for 2 hours at the temperature of 40 ℃ and the rotating speed of 80rpm to obtain mixed raw materials for later use;
s2: co-extrusion is carried out to obtain the product,
Placing POE resin layer raw materials into a double-screw extruder, and melt-blending at 90 ℃, 95 ℃, 105 ℃ and 50 rpm;
Placing EVA resin layer raw material into a double screw extruder, and melt blending at 80 ℃, 90 ℃, 100 ℃ and a rotating speed of 50 rpm;
co-extruding, compounding, casting and discharging POE resin layer raw materials and EVA resin layer raw materials through two double-screw extruders, and drawing, stretching and forming films;
s3: the film material is subjected to thickness measurement, edge pressing, shaping, trimming and rolling to obtain the high refractive index EP composite packaging adhesive film.
Example 4
The EP composite packaging adhesive film with the high refractive index is of a layered structure and is formed by compounding an EVA resin layer and a POE resin layer, wherein the POE resin layer is composed of the following raw materials in parts by weight:
100 parts of POE resin;
2 parts of high refractive index resin;
1 part of cross-linking agent;
1.6 parts of auxiliary cross-linking agent;
0.1 part of antioxidant;
0.15 parts of light stabilizer;
0.4 parts of silane coupling agent.
The EVA resin layer is composed of the following raw materials in parts by weight:
100 parts of EVA resin;
3 parts of high refractive index resin;
1.1 parts of a cross-linking agent;
1.5 parts of auxiliary cross-linking agent;
0.36 parts of antioxidant;
0.3 parts of light stabilizer;
0.4 parts of silane coupling agent.
The EVA resin layer has a single-layer thickness of 50 μm, and the POE resin layer has a single-layer thickness of 250 μm.
The preparation method of the high refractive index resin is the same as in example 1.
Specifically, the auxiliary cross-linking agent is diallyl disulfide, 4' -dimercapto diphenyl sulfide dimethyl methacrylate, trimethylolpropane trimethacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated neopentyl glycol diacrylate and pentaerythritol triacrylate.
The preparation method of the high-refractive-index EP composite packaging adhesive film comprises the following steps:
s1: mixing, namely adding the raw materials of each layer into a mixer according to the formula amount to mix, and mixing and stirring for 2 hours at the temperature of 40 ℃ and the rotating speed of 80rpm to obtain mixed raw materials for later use;
s2: co-extrusion is carried out to obtain the product,
Placing POE resin layer raw materials into a double-screw extruder, and melt-blending at 80 ℃, 90 ℃, 100 ℃ and a rotating speed of 45 rpm;
Placing EVA resin layer raw material into a double screw extruder, and melt blending at 80 ℃, 85 ℃, 90 ℃ and rotating speed of 45 rpm;
co-extruding, compounding, casting and discharging POE resin layer raw materials and EVA resin layer raw materials through two double-screw extruders, and drawing, stretching and forming films;
s3: the film material is subjected to thickness measurement, edge pressing, shaping, trimming and rolling to obtain the high refractive index EP composite packaging adhesive film.
Example 5
The EP composite packaging adhesive film with the high refractive index is of a layered structure and is formed by compounding an EVA resin layer and a POE resin layer, wherein the POE resin layer is composed of the following raw materials in parts by weight:
100 parts of POE resin;
3 parts of high refractive index resin;
1 part of cross-linking agent;
1.6 parts of auxiliary cross-linking agent;
0.1 part of antioxidant;
0.15 parts of light stabilizer;
0.4 parts of silane coupling agent.
The EVA resin layer is composed of the following raw materials in parts by weight:
100 parts of EVA resin;
3.3 parts of high refractive index resin;
1.1 parts of a cross-linking agent;
1.5 parts of auxiliary cross-linking agent;
0.36 parts of antioxidant;
0.3 parts of light stabilizer;
0.4 parts of silane coupling agent.
The EVA resin layer has a single-layer thickness of 50 μm, and the POE resin layer has a single-layer thickness of 300 μm.
The preparation method of the high refractive index resin is the same as in example 1.
Specifically, the auxiliary cross-linking agent is 4,4 '-dimercapto diphenyl sulfide dimethyl methacrylate and a mixture formed by ethoxylated trimethylolpropane triacrylate and propoxylated neopentyl glycol diacrylate, the mass ratio of the ethoxylated trimethylolpropane triacrylate to the propoxylated neopentyl glycol diacrylate is 1:1, and the using amount ratio of the 4,4' -dimercapto diphenyl sulfide dimethyl methacrylate to the mixture of the ethoxylated trimethylolpropane triacrylate and the propoxylated neopentyl glycol diacrylate is 2g:8g.
The preparation method of the high refractive index EP composite packaging adhesive film is the same as that of the embodiment 1.
Example 6 the same as example 1, except that the ratio of the total amount of 4,4' -dimercaptodiphenyl sulfide dimethacrylate to the ethoxylated trimethylolpropane triacrylate, propoxylated neopentyl glycol diacrylate mixture in the co-crosslinker of example 6 was 3g:7g.
Example 7 the same as in example 1, except that the ratio of the amount of methyl 4,4' -dimercaptodiphenyl sulfide dimethacrylate to the total amount of the ethoxylated trimethylolpropane triacrylate, propoxylated neopentyl glycol diacrylate mixture in the co-crosslinking agent of example 7 was 1g:9g.
Example 8 the same as example 1, except that the preparation method of the high refractive index resin in example 8 was as follows:
(1) Fully stirring oleic acid and absolute ethyl alcohol until the oleic acid and absolute ethyl alcohol are completely mixed, adding deionized water, and continuously stirring to form uniform mixed solution;
(2) Adding nano zirconia into deionized water, performing ultrasonic dispersion for 20min, then placing the mixture at 80 ℃ for heating and stirring in a water bath, then adding the mixed liquid obtained in the step (1) into a reaction system in a dropwise manner at a dropwise speed of 25 drops/min, standing for 12h after the dropwise addition is finished, filtering a reaction product, leaching with ethanol, taking insoluble matters, grinding, placing the ground matters at 40 ℃ for vacuum drying for 12h to obtain oleic acid modified zirconia, wherein the infrared data are as follows: 3434cm -1: -OH weakening; 2923cm -1: -C-H is present; 1622cm -1: -c=c-present;
The dosage ratio of oleic acid to absolute ethyl alcohol to deionized water is 1g:2g:2g:8g;
the dosage ratio of oleic acid to nano zirconia is 1mol:10mol;
(2) Adding diallyl disulfide, 4 '-dimercapto diphenyl sulfide dimethyl methacrylate, oleic acid modified zirconia, 4', 4-dimercapto diphenyl sulfide and a photoinitiator into N, N-dimethylformamide, uniformly stirring, radiating for 10min under the condition of UV light intensity of 400mJ/cm 2, concentrating the reactant by reduced pressure distillation, adding absolute methanol to generate precipitate, filtering to obtain insoluble matters, leaching the insoluble matters by the absolute methanol, and vacuum drying at 40 ℃ for 12h to obtain high refractive index resin, wherein the infrared data are as follows: 3434cm -1: -OH is present; 2923cm -1: -C-H is present; 3018cm -1: benzene ring-C-H is present; 1622cm -1: -c=c-absent; 1735m -1: -c=o present; 1603cm -1、810cm-1: -c=c-absent; 2550cm -1: SH is absent;
the dosage ratio of the diallyl disulfide to the 4,4' -dimercapto diphenyl sulfide to the methyl dimethacrylate to the oleic acid modified oxide to the N, N-dimethylformamide is 1g:5g:4g:400mL;
The dosage of the 4' 4-dimercaptodiphenyl sulfide is added according to the mol ratio of the carbon-carbon double bond to the mercapto in the reaction system of 1:1;
the photoinitiator was 3% of the total mass of the reactants.
Specifically, the photoinitiator is photoinitiator 184.
Example 9 the same as example 1, except that the preparation method of the high refractive index resin in example 9 was as follows:
(1) Fully stirring oleic acid and absolute ethyl alcohol until the oleic acid and absolute ethyl alcohol are completely mixed, adding deionized water, and continuously stirring to form uniform mixed solution;
(2) Adding nano zirconia into deionized water, performing ultrasonic dispersion for 20min, then placing the mixture at 80 ℃ for heating and stirring in a water bath, then adding the mixed liquid obtained in the step (1) into a reaction system in a dropwise manner at a dropwise speed of 25 drops/min, standing for 12h after the dropwise addition is finished, filtering a reaction product, leaching with ethanol, taking insoluble matters, grinding, placing the ground matters at 40 ℃ for vacuum drying for 12h to obtain oleic acid modified zirconia, wherein the infrared data are as follows: 3434cm -1: -OH weakening; 2923cm -1: -C-H is present; 1622cm -1: -c=c-present;
The dosage ratio of oleic acid to absolute ethyl alcohol to deionized water is 1g:2g:2g:8g;
the dosage ratio of oleic acid to nano zirconia is 1mol:10mol;
(2) Adding diallyl disulfide, 4 '-dimercapto diphenyl sulfide dimethyl methacrylate, oleic acid modified zirconia, 4', 4-dimercapto diphenyl sulfide and a photoinitiator into N, N-dimethylformamide, uniformly stirring, radiating for 10min under the condition of UV light intensity of 400mJ/cm 2, concentrating the reactant by reduced pressure distillation, adding absolute methanol to generate precipitate, filtering to obtain insoluble matters, leaching the insoluble matters by the absolute methanol, and vacuum drying at 40 ℃ for 12h to obtain high refractive index resin, wherein the infrared data are as follows: 3434cm -1: -OH is present; 2923cm -1: -C-H is present; 3018cm -1: benzene ring-C-H is present; 1622cm -1: -c=c-absent; 1735m -1: -c=o present; 1603cm -1、810cm-1: -c=c-absent; 2550cm -1: SH is absent;
The dosage ratio of the diallyl disulfide to the 4,4' -dimercapto diphenyl sulfide to the methyl dimethacrylate to the oleic acid modified oxide to the N, N-dimethylformamide is 1g:3g:6g:400mL;
The dosage of the 4' 4-dimercaptodiphenyl sulfide is added according to the mol ratio of the carbon-carbon double bond to the mercapto in the reaction system of 1:1;
the photoinitiator is 1% of the total mass of the reactants.
Specifically, the photoinitiator is photoinitiator 184.
Example 10 the same as example 1, except that the ratio of diallyl disulfide, 4' -dimercaptodiphenyl sulfide dimethacrylate, oleic acid modified oxide, N-dimethylformamide used in example 10 was 1g:4g:5g:400mL.
Example 11 the same as in example 1 was repeated, except that in example 11, diallyl disulfide, 4' -dimercaptodiphenyl sulfide dimethyl methacrylate, oleic acid modified oxide, N-dimethylformamide were used in an amount ratio of 3g:2g:5g:400mL.
Comparative example 1 the same as example 1 was different in that the inventive self-made high refractive index resin was not added to both the POE resin layer and the EVA resin layer of comparative example 1, and the auxiliary crosslinking agent in the POE resin layer and the EVA resin layer was a mixture of ethoxylated trimethylolpropane triacrylate and propoxylated neopentyl glycol diacrylate in a mass ratio of 1:1.
Comparative example 2 is different from example 1 in that the inventive homemade high refractive index resin was not added to both the POE resin layer and EVA resin layer of comparative example 2.
Comparative example 3 the same as example 1, except that the high refractive index resin of comparative example 3 was prepared as follows:
Adding diallyl disulfide, 4 '-dimercapto diphenyl sulfide dimethyl methacrylate, oleic acid, nano zirconia, 4', 4-dimercapto diphenyl sulfide and a photoinitiator 184 into N, N-dimethylformamide, stirring, performing ultrasonic dispersion for 20min, radiating for 10min under the condition of UV light intensity of 400mJ/cm 2, performing reduced pressure distillation, concentrating, adding absolute methanol to generate precipitate, filtering, leaching insoluble substances with the absolute methanol, and performing vacuum drying at 40 ℃ for 12h to obtain high-refraction resin, wherein the infrared data are as follows: 3434cm -1: -OH is present; 2923cm -1: -C-H is present; 3018cm -1: benzene ring-C-H is present; 1622cm -1: -c=c-absent; 1735m -1: -c=o present; 1603cm -1、810cm-1: -c=c-absent; 2550cm -1: SH is absent;
the dosage ratio of oleic acid to nano zirconia is 1mol:10mol;
The dosage ratio of the diallyl disulfide to the 4,4' -dimercapto diphenyl sulfide to the methyl dimethacrylate to the oleic acid to the N, N-dimethylformamide is 2g:3g:0.93g:400mL;
The dosage of the 4' 4-dimercaptodiphenyl sulfide is added according to the mol ratio of the carbon-carbon double bond to the mercapto group in the reaction system of 1:1;
The photoinitiator 184 is 2% of the total mass of the reactants.
Comparative example 4 the same as example 1 except that oleic acid-modified zirconia was used in comparative example 4 instead of the high refractive index resin in example 1.
Comparative example 5 the same as example 1 was different in that step (2) in the preparation of the high refractive index resin in comparative example 5 was as follows:
Adding diallyl disulfide, oleic acid modified zirconia, 4' 4-dimercapto diphenyl sulfide and a photoinitiator 184 into N, N-dimethylformamide, uniformly stirring, radiating for 10min under the condition of UV light intensity of 400mJ/cm 2, performing reduced pressure distillation, concentrating, adding absolute methanol to generate precipitate, filtering to obtain insoluble substances, leaching the insoluble substances with the absolute methanol, and performing vacuum drying at 40 ℃ for 12h to obtain high-refractive-index resin;
the dosage ratio of the diallyl disulfide to the oleic acid modified zirconia to the N, N-dimethylformamide is 5g:5g:400mL;
The dosage ratio of the diallyl disulfide to the oleic acid modified zirconia to the 4' 4-dimercapto diphenyl sulfide is added according to the molar ratio of the carbon-carbon double bond to the mercapto of 1:1;
The photoinitiator 184 is 2% of the total mass of the reactants;
The infrared data are as follows: 3434cm -1: -OH is present; 2923cm -1: -C-H is present; 3018cm -1: benzene ring-C-H is present; 1622cm -1: -c=c-absent; 2550cm -1: SH is absent.
Comparative example 6 the same as example 1 was different in that step (2) in the preparation of the high refractive index resin in comparative example 6 was as follows:
Adding 4,4 '-dimercaptodiphenyl sulfide dimethyl methacrylate, oleic acid modified zirconia, 4', 4-dimercaptodiphenyl sulfide and a photoinitiator 184 into N, N-dimethylformamide, uniformly stirring, radiating for 10min under the condition of UV light intensity of 400mJ/cm 2, concentrating the reactant by reduced pressure distillation, adding absolute methanol to generate precipitate, filtering to obtain insoluble matters, leaching the insoluble matters by the absolute methanol, and vacuum drying at 40 ℃ for 12h to obtain high-refractive-index resin, wherein the infrared data are as follows: 3434cm -1: -OH is present; 2923cm -1: -C-H is present; 3018cm -1: benzene ring-C-H is present; 1622cm -1: -c=c-absent; 1735m -1: -c=o present; 1603cm -1、810cm-1: -c=c-absent; 2550cm -1: SH is absent;
The dosage ratio of the 4,4' -dimercaptodiphenyl sulfide dimethyl methyl methacrylate, the oleic acid modified oxide and the N, N-dimethylformamide is 5g:5g:400mL;
The dosage of the 4' 4-dimercaptodiphenyl sulfide is added according to the mol ratio of the carbon-carbon double bond to the mercapto in the reaction system of 1:1;
The photoinitiator 184 is 2% of the total mass of the reactants.
Comparative example 7 is different from example 1 in that the average particle diameter of the nano zirconia in comparative example 7 is 100nm.
Comparative example 8 the same as in example 1 was conducted except that comparative example 8 used the same quality of nano-silica instead of nano-zirconia in example 1 (average particle diameter: 10 nm).
Comparative example 9 the same as example 1 was repeated except that the co-crosslinking agent in comparative example 9 was a mixture of ethoxylated trimethylolpropane triacrylate and propoxylated neopentyl glycol diacrylate in a mass ratio of 1:1.
Performance testing
The packaging films obtained in examples 1 to 11 and comparative examples 1 to 9 of the present invention were subjected to the relevant performance test, and the test results are shown in Table 1.
The test method comprises the following steps:
(1) Refractive index: the optical film refractive index and thickness tester assay procedures in GJB 8687-2015 were referenced for testing.
(2) Transmittance, haze: the test was performed as described in GB/T2410-2008.
(3) Wet heat aging performance: after the EP composite packaging adhesive film is placed at the temperature of 85 ℃ and the relative humidity of 85% for 2000 hours, observing whether delamination phenomenon occurs in the packaging adhesive film; and its peel strength was measured according to IEC61215 standard.
(4) Ultraviolet aging: the EP adhesive film obtained was subjected to ultraviolet irradiation aging test in accordance with the requirements specified in International electrotechnical Commission standard IEC 61345. Test conditions: the surface temperature of the test piece is 60+/-5 ℃, the ultraviolet wavelength range is 280-400nm, the irradiation intensity is 15 kW.h/m 2, and the ultraviolet irradiation test time is 2000hr.
The yellowing index (. DELTA.YI) before and after the test was measured according to HG/T3862-2006.
TABLE 1
First, as can be seen from examples 1 to 11 in table 1, the high refractive index EP composite packaging film obtained in the present invention has excellent light transmittance, is not liable to delamination and has a high refractive index.
Comparing example 1 with comparative examples 1 and 2, it is clear that the use of self-made high refractive index resin for the high refractive index EP composite packaging film of the present invention has positive effects on improving light transmittance, reducing haze, improving interlayer adhesion, and aging resistance.
Comparing example 1 with comparative examples 3-6, the high refractive index EP composite packaging adhesive film obtained by the invention has excellent dispersibility by using self-made high refractive resin and excellent performance in interlayer compatibility (no delamination and peeling strength). It can also be observed from example 1 and comparative examples 5-6 that the benzene-containing structure has a positive effect on the refractive index increase, but is detrimental to the aging resistance improvement.
As can be seen from comparing example 1 with comparative examples 7-8, the self-made high refractive index resin in the high refractive index EP composite packaging adhesive film obtained by the invention adopts nano zirconia, has higher refractive index than nano silica, and has better influence on optical performance due to proper particle size.
As can be seen from comparison of example 1 and comparative example 9, the auxiliary crosslinking agent for the EP composite packaging adhesive film with high refractive index contains a high refractive index monomer, and the auxiliary crosslinking agent is compounded with high refractive index resin for use, so that the auxiliary crosslinking agent has high-efficiency synergistic effect, and the refractive index of the whole EP composite packaging adhesive film is further improved.
In conclusion, the self-made high-refractive-index resin and the high-refractive-index monomer are compounded for use through special formula design, so that the high-refractive-index EP composite packaging adhesive film has high light transmittance, low haze and high refractive index, is excellent in interlayer adhesion, and effectively prolongs the service life.
With the above-described preferred embodiments according to the present invention as an illustration, the above-described descriptions can be used by persons skilled in the relevant art to make various changes and modifications without departing from the scope of the technical idea of the present invention. The technical scope of the present invention is not limited to the description, but must be determined according to the scope of claims.

Claims (11)

1. A method for preparing a high refractive index resin, comprising the steps of:
(1) Mixing oleic acid, absolute ethyl alcohol and water uniformly to obtain a mixed solution;
(2) Dispersing nano zirconia in water, and then adding the mixed liquid obtained in the step (1) into a reaction system in a dropwise manner to obtain oleic acid modified zirconia;
(3) Diallyl disulfide, 4 '-dimercapto diphenyl sulfide dimethyl methacrylate, oleic acid modified zirconia and 4', 4-dimercapto diphenyl sulfide react under the action of a photoinitiator to obtain the high refractive index resin.
2. A high refractive index resin according to claim 1, wherein the oleic acid to nano zirconia ratio is 1mol:8-12mol.
3. The high refractive index resin according to claim 1, wherein the ratio of the amount of diallyl disulfide, 4' -dimercaptodiphenyl sulfide dimethyl methacrylate, oleic acid modified oxide, N-dimethylformamide is 1 to 3g:1-5g:4-6g:400-500mL.
4. A high refractive index resin produced by the production method according to any one of claims 1 to 3.
5. An EP composite packaging adhesive film with a high refractive index, which is a layered structure and is formed by compounding an EVA resin layer and a POE resin layer, wherein the POE resin layer and/or the EVA resin layer contains the high refractive index resin according to claim 4.
6. The high refractive index EP composite packaging adhesive film according to claim 5, wherein the POE resin layer comprises the following raw materials in parts by weight:
100 parts of POE resin;
0.5-4 parts of high refractive index resin;
0.5-1.2 parts of cross-linking agent;
1.0-2.0 parts of auxiliary cross-linking agent;
0.05-0.25 part of antioxidant;
0.05-0.3 part of light stabilizer;
0.3-0.5 part of silane coupling agent.
7. The high refractive index EP composite packaging film according to claim 5, wherein the EVA resin layer comprises the following raw materials in parts by weight:
100 parts of EVA resin;
0.5-4 parts of high refractive index resin;
0.5-1.5 parts of cross-linking agent;
0.5-2.0 parts of auxiliary cross-linking agent;
0.2-0.5 part of antioxidant;
0.1-0.4 part of light stabilizer;
0.3-0.5 part of silane coupling agent.
8. The high refractive index EP composite packaging film according to any one of claims 5 to 7, wherein the EP composite packaging film has a double-layer co-extrusion laminated structure, the EVA resin layer has a single-layer thickness of 50 to 100 μm, and the POE resin layer has a single-layer thickness of 150 to 350 μm.
9. The high refractive index EP composite packaging film according to claim 6 or 7, wherein the co-crosslinking agent comprises at least one of a high refractive index monomer comprising at least one of diallyl disulfide, 4' -dimercaptodiphenyl sulfide bis-methyl methacrylate, a di-functional or tri-functional acrylate monomer.
10. The high refractive index EP composite packaging film according to claim 6 or 7, wherein the antioxidant is a mixture of hindered phenol antioxidant and phosphite antioxidant; the light stabilizer is a mixture of hindered amine light stabilizer and benzophenone ultraviolet absorber.
11. The preparation method of the high-refractive-index EP composite packaging adhesive film is characterized by comprising the following steps of:
S1: mixing, namely adding raw materials of each layer of high-refractive-index EP composite packaging adhesive film into a mixer for mixing according to the formula amount to obtain mixed raw materials for later use;
s2: co-extrusion is carried out to obtain the product,
Placing POE resin layer raw materials into a double-screw extruder, and carrying out melt blending;
Placing EVA resin layer raw materials into a double-screw extruder, and melt blending;
co-extruding, compounding, casting and discharging POE resin layer raw materials and EVA resin layer raw materials through two double-screw extruders, and drawing, stretching and forming films;
s3: the film material is subjected to thickness measurement, edge pressing, shaping, trimming and rolling to obtain the high refractive index EP composite packaging adhesive film.
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