阅读说明：本技术 树脂组合物、含其母粒及应用 (Resin composition, master batch containing resin composition and application of master batch ) 是由 魏梦娟 周光大 侯宏兵 于 2021-09-01 设计创作，主要内容包括：本发明提供了一种树脂组合物、含其母粒及应用。该树脂组合物包括基体树脂和有机碱化合物及交联剂,有机碱化合物在25℃下的pKa为7.4～14.5,且基体树脂与有机碱化合物的重量比为100:(0.01～3)。通过加入特定含量的胍系化合物时,不仅能够提高树脂组合物形成的胶膜的透光率,同时还有较低的黄变率。同时由于胍系化合物具有较强的碱性,在应用过程中,其能够与乙烯-醋酸乙烯酯共聚物(EVA)发生Norrish typeⅡ脱乙酰反应产生的醋酸发生反应,从而提高上述树脂组合形成的胶膜的耐腐蚀性。综上所述,采用上述树脂组合物形成胶膜能够同时满足耐黄变性能好、光线透过率高和耐腐蚀等优点。(The invention provides a resin composition, a mother particle containing the same and application thereof. The resin composition comprises matrix resin, an organic base compound and a cross-linking agent, wherein the pKa of the organic base compound at 25 ℃ is 7.4-14.5, and the weight ratio of the matrix resin to the organic base compound is 100 (0.01-3). When the guanidine compound is added in a specific amount, the light transmittance of a film formed from the resin composition can be improved, and the yellowing rate can be reduced. Meanwhile, because the guanidine compound has stronger alkalinity, the guanidine compound can react with acetic acid generated by Norrish type II deacetylation reaction of ethylene-vinyl acetate copolymer (EVA) in the application process, thereby improving the corrosion resistance of the adhesive film formed by the resin combination. In conclusion, the adhesive film formed by the resin composition can simultaneously meet the advantages of good yellowing resistance, high light transmittance, corrosion resistance and the like.)

1. The resin composition is characterized by comprising a matrix resin, an organic base compound and a cross-linking agent, wherein the pKa of the organic base compound at 25 ℃ is 7.4-14.5, and the weight ratio of the matrix resin to the organic base compound is 100 (0.01-3).

2. The resin composition according to claim 1, wherein the organic base compound comprises a guanidine-based compound containing a guanidine group and at least one unsaturated bond;

preferably, the guanidine-based compound is one or more selected from the group consisting of (4-aminobutyl) guanidine, 2-vinyl-4, 6-diamino-triazine, 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene, 2, 4-diamino-6-phenyl-1, 3, 5-triazine, dodecyltetramethylguanidine carbonate and hexadecyltetramethylguanidine carbonate.

3. The resin composition according to claim 1 or 2, wherein the organic base compound further comprises an organic amine compound and/or an alcohol amine compound;

preferably, the weight ratio of the matrix resin to the organic amine compound and the alcohol amine compound is 100 (0.01-1): 0.02-3.

4. The resin composition according to claim 3, wherein the organic amine compound is selected from one or more of the group consisting of dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, melamine, triethylamine, triisobutylamine, hexamethylenetetramine, cyclohexylamine, tetraalkylammonium hydroxide, choline hydroxide and benzyltrimethylammonium hydroxide;

the alcohol amine compound is one or more selected from the group consisting of diethanolamine, triethanolamine, ethanolamine, diisopropanolamine, triisopropanolamine and N-ethyldiethanolamine.

5. The resin composition according to claim 3, wherein the organic base compound has a pKa of 8.4 to 14.5 at 25 ℃.

6. The resin composition according to claim 1, further comprising an inorganic filler selected from one or more of the group consisting of magnesium hydroxide, calcium hydroxide, zinc hydroxide, barium hydroxide, aluminum hydroxide, magnesium oxide, calcium oxide, zinc oxide, barium oxide, aluminum oxide, magnesium carbonate, calcium carbonate, zinc carbonate, barium carbonate, and hydrotalcite.

7. The resin composition according to claim 6, wherein the weight ratio of the matrix resin to the inorganic filler is 100 (0.01 to 5);

preferably, the weight ratio of the matrix resin to the inorganic filler is 100 (0.1-2).

8. A masterbatch comprising a matrix resin, characterized in that the matrix resin comprises the resin composition according to any one of claims 1 to 7.

9. A glue film comprising at least one single layer film, wherein the single layer film is prepared from a raw material comprising the resin composition of any one of claims 1 to 7 or the master batch of claim 8.

10. A photovoltaic module comprising a cell and a packaging adhesive film for packaging the cell, wherein the packaging adhesive film comprises the adhesive film of claim 9, and the adhesive film of claim 9 is disposed adjacent to the cell.

11. A display device comprising a light emitting unit and a sealing unit for sealing the light emitting unit, wherein the sealing unit comprises the adhesive film of claim 9.

Technical Field

The invention relates to the technical field of packaging adhesive films for solar cells, in particular to a resin composition, a mother particle containing the resin composition and application of the resin composition.

Background

When the photovoltaic module is used under the conditions of high temperature, high humidity and illumination, moisture or water gradually penetrates into the module, and under the action of light and heat, the ethylene-vinyl acetate copolymer (EVA) undergoes a Norrish type II deacetylation reaction to generate acetic acid. In the presence of acetic acid, a potential difference is formed between two metals of the tin-copper welding strip, and the metal with low potential is corroded. The standard electrode potentials of the two metals in the tin-coated copper welding strip are Sn²⁺：-0.136V，Pb²⁺: -0.126V, which are close in potential but still subject to galvanic corrosion that can yellow the tin-coated braze tape. In addition, acetic acid generated by EVA degradation can migrate into the holes of the electrode glass layer and react with lead oxide in the glass layer to generate lead acetate, so that metallization contact failure is caused. Therefore, the influence of the content of acetic acid in the adhesive film on the battery piece can be effectively reduced.

A prior patent (patent No. CN101542748B) discloses a solar cell sealing film comprising an ethylene-vinyl acetate copolymer, a crosslinking agent and an acid absorbent, wherein the acid absorbent is Mg (OH)₂. The EVA film contains acid absorbent magnesium hydroxide on the light receiving side, and contains acid absorbent magnesium hydroxide, magnesium oxide, calcium hydroxide and the like on the backlight side. The acid absorbent is a polar inorganic substance, has large surface energy, high surface activity and poor compatibility with EVA, easily causes interface defects, causes the performance reduction of materials, and cannot well ensure the durability of the solar cell; meanwhile, the addition of the inorganic acid absorbent can cause the reduction of the light transmittance of the EVA adhesive film, and further cause the reduction of the photoelectric conversion efficiency of the component.

The prior document (publication No. CN108610546A) provides a solar cell packaging material, which is characterized in that magnesium oxide is added to inhibit the generation of acetic acid of an ethylene-vinyl acetate copolymer, but unmodified magnesium oxide particles have relatively high surface energy, and the magnesium oxide particles attract each other to reduce the surface energy according to the principle of lowest energy, so that the magnesium oxide particles can be seriously agglomerated to form larger particles, thereby reducing the specific surface area of the magnesium oxide particles and further reducing the light transmittance of a packaging adhesive film.

On the basis, the EVA adhesive film which is high in light transmittance and good in corrosion resistance can be provided, and the EVA adhesive film has important significance for improving the photoelectric conversion efficiency of the photovoltaic module.

Disclosure of Invention

The invention mainly aims to provide a resin composition, a master batch containing the resin composition and an application of the master batch, and aims to solve the problem that an EVA adhesive film in the prior art cannot meet the requirements of high light transmittance and good corrosion resistance at the same time.

In order to achieve the above object, one aspect of the present invention provides a resin composition comprising a matrix resin, an organic base compound and a crosslinking agent, wherein the pKa of the organic base compound at 25 ℃ is 7.4 to 14.5, and the weight ratio of the matrix resin to the organic base compound is 100 (0.01 to 3).

The matrix resin is one or more of ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer and ethylene-methacrylic acid ionomer, and preferably ethylene-vinyl acetate.

Further, the organic base compound includes a guanidine-based compound containing a guanidine group and at least one unsaturated bond; preferably, the guanidine-based compound is one or more selected from the group consisting of (4-aminobutyl) guanidine, 2-vinyl-4, 6-diamino-triazine, 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene, 2, 4-diamino-6-phenyl-1, 3, 5-triazine, dodecyltetramethylguanidine carbonate, and hexadecyltetramethylguanidine carbonate.

Further, the organic base compound further includes an organic amine compound and/or an alcohol amine compound; preferably, the weight ratio of the matrix resin to the organic amine compound and the alcohol amine compound is 100 (0.01-1) to (0.02-3).

Further, the organic amine compound is selected from one or more of the group consisting of dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, melamine, triethylamine, triisobutylamine, hexamethylenetetramine, cyclohexylamine, tetraalkylammonium hydroxide, choline hydroxide and benzyltrimethylammonium hydroxide; the alcohol amine compound is one or more selected from the group consisting of diethanolamine, triethanolamine, ethanolamine, diisopropanolamine, triisopropanolamine and N-ethyldiethanolamine.

Further, the organic base compound has a pKa of 8.4 to 14.5 at 25 ℃.

Further, the resin composition further includes an inorganic filler selected from one or more of the group consisting of magnesium hydroxide, calcium hydroxide, zinc hydroxide, barium hydroxide, aluminum hydroxide, magnesium oxide, calcium oxide, zinc oxide, barium oxide, aluminum oxide, magnesium carbonate, calcium carbonate, zinc carbonate, barium carbonate, and hydrotalcite.

Further, the weight ratio of the matrix resin to the inorganic filler is 100 (0.01-5); preferably, the weight ratio of the matrix resin to the inorganic filler is 100 (0.1-2).

Another aspect of the present application also provides a master batch including a matrix resin including the resin composition provided herein.

The third aspect of the present application also provides a glue film, wherein the glue film comprises at least one single-layer film, and the single-layer film is prepared from the raw materials of the resin composition or the master batch provided by the present application.

The fourth aspect of this application still provides a photovoltaic module, including the battery piece and the encapsulation glued membrane that is used for encapsulating the battery piece, the encapsulation glued membrane includes the glued membrane that this application provided, and this glued membrane is close to the battery piece setting.

The fifth aspect of the present application further provides a display device, including a light emitting unit and a sealing unit, where the sealing unit is used to seal the light emitting unit, and the sealing unit is a glue film provided by the present application.

By applying the technical scheme of the invention, when the organic alkali compound with specific content and specific PKa is added, the light transmittance of the adhesive film formed by the resin composition can be improved, and the yellowing rate is low. Meanwhile, the organic alkali compound has stronger alkalinity, and can react with acetic acid generated by Norrish type II deacetylation reaction of ethylene-vinyl acetate copolymer (EVA) in the application process, so that the corrosion resistance of the adhesive film formed by the resin combination is improved. In conclusion, the adhesive film formed by the resin composition can simultaneously meet the advantages of good yellowing resistance, high light transmittance, corrosion resistance and the like.

Detailed Description

It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.

Generally, when the nitrogenous organic matter is added in the process of preparing the adhesive film, the nitrogenous organic matter has better compatibility with other components, so that the nitrogenous organic matter has better dispersibility in the adhesive film, and further can better improve the light transmittance of the adhesive film compared with inorganic filler. However, the addition of the nitrogen-containing organic substance makes the yellowing resistance of the adhesive film poor, so in order to improve the yellowing resistance of the adhesive film, the addition of the nitrogen-containing organic substance is usually avoided in the adhesive film preparation process. In order to enable the prepared adhesive film to simultaneously meet the advantages of high light transmittance, good yellowing resistance and corrosion resistance, the application provides a resin composition, which comprises a matrix resin, an organic base compound and a crosslinking agent, wherein the pKa of the organic base compound at 25 ℃ is 7.4-14.5, and the weight ratio of the matrix resin to the guanidine compound is 100 (0.01-2).

In the present invention, "pKa" generally means "acid dissociation constant in water", but "acid dissociation constant in dimethyl sulfoxide (DMSO)" means "acid dissociation constant in dimethyl sulfoxide (DMSO) for a case where the pKa cannot be measured in water", and "acid dissociation constant in acetonitrile" means for a case where the pKa cannot be measured in DMSO. Preferably, it means "acid dissociation constant in water".

Through creative research for many years, the applicant finds that when the base resin is crosslinked under the action of the crosslinking agent and the organic base compound with specific content and specific PKa is added, the light transmittance of a glue film formed by the resin composition can be improved, and the yellowing rate is low. Meanwhile, the organic alkali compound has stronger alkalinity, and can react with acetic acid generated by Norrish type II deacetylation reaction of ethylene-vinyl acetate copolymer (EVA) in the application process, so that the corrosion resistance of the adhesive film formed by the resin combination is improved. In conclusion, the adhesive film formed by the resin composition can simultaneously meet the advantages of good yellowing resistance, high light transmittance, corrosion resistance and the like.

The matrix resin can be selected from the types commonly used in the field, and comprises one or more of ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer and ethylene-methacrylic acid ionomer which are mixed according to any proportion, and preferably is ethylene-vinyl acetate.

In order to further improve the yellowing resistance and light transmittance of the adhesive film composition formed of the above resin composition, in a preferred embodiment, the organic base compound includes a guanidine-based compound having a guanidine group and at least one unsaturated bond. More preferably, the guanidine-based compound includes, but is not limited to, one or more of the group consisting of (4-aminobutyl) guanidine, 2-vinyl-4, 6-diamino-triazine, fatty acid guanidine salts, 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene, 2, 4-diamino-6-phenyl-1, 3, 5-triazine, dodecyltetramethylguanidine carbonate, hexadecyltetramethylguanidine carbonate. Compared with other guanidine compounds, the guanidine compounds have better compatibility with other components and better promotion effect on the yellowing resistance of the adhesive film.

Preferably, the organic base compound further includes an organic amine compound and/or an alcohol amine compound. Because the guanidine compound has stronger alkalinity, after the organic amine compound and/or the alcohol amine compound are added, the yellowing of the adhesive film can be inhibited to a certain extent; meanwhile, the corrosion resistance of the adhesive film formed by the resin composition can be further improved by adding the organic amine compound and/or the alcohol amine compound. In order to further improve the overall performance of the adhesive film formed by the resin composition, the weight ratio of the matrix resin to the organic amine compound and the alcohol amine compound is more preferably 100 (0.01-1) to (0.02-3).

In a preferred embodiment, the organic amine compound includes, but is not limited to, one or more of the group consisting of dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, melamine, triethylamine, triisobutylamine, hexamethylenetetramine, cyclohexylamine, tetraalkylammonium hydroxide, choline hydroxide, and benzyltrimethylammonium hydroxide; the alcohol amine compound includes, but is not limited to, one or more of the group consisting of diethanolamine, triethanolamine, ethanolamine, diisopropanolamine, triisopropanolamine and N-ethyldiethanolamine.

In order to further improve the yellowing resistance and the light transmittance of the resin composition provided by the present application, more preferably, the organic base compound has a pKa of 8.4 to 14.5 at 25 ℃.

In a preferred embodiment, the resin composition further comprises an inorganic filler. The inorganic filler can exert a synergistic effect with an organic basic compound such as a guanidine compound, an organic amine compound and/or an alcohol amine compound, thereby further improving the overall performance of a glue film formed by the resin composition. The inorganic filler may be selected from those conventionally used in the art. More preferably, the inorganic filler includes, but is not limited to, one or more of the group consisting of magnesium hydroxide, calcium hydroxide, zinc hydroxide, barium hydroxide, aluminum hydroxide, magnesium oxide, calcium oxide, zinc oxide, barium oxide, aluminum oxide, magnesium carbonate, calcium carbonate, zinc carbonate, barium carbonate, and hydrotalcite.

In a preferred embodiment, the weight ratio of the matrix resin to the inorganic filler is 100 (0.01-5); more preferably, the weight ratio of the matrix resin to the inorganic filler is 100 (0.1-2).

In order to improve the overall performance of the resin composition, in a preferred embodiment, the raw materials forming the resin composition further include one or more of the group consisting of a co-crosslinking agent, an antioxidant, an ultraviolet absorber, a light stabilizer, an adhesion promoter, and a pigment. Furthermore, relative to 100 parts by weight of the matrix resin, the raw materials for forming the resin composition also comprise 0.01-3 parts by weight of a cross-linking agent, 0.01-10 parts by weight of an auxiliary cross-linking agent, 0-0.4 part by weight of an ultraviolet absorber, 0-0.5 part by weight of an antioxidant, 0-1.0 part by weight of a light stabilizer, 0-3.0 parts by weight of a tackifier and 0-20 parts by weight of a pigment.

The crosslinking agent is a molecule having a plurality of ethylenically unsaturated groups, and can promote crosslinking of the polymer to achieve a higher degree of crosslinking. The cross-linking agent in the above composition may be selected from those commonly used in the art, and preferably, the cross-linking agent includes, but is not limited to, isopropyl t-butylperoxycarbonate, 2, 5-dimethyl-2, 5- (di-t-butylperoxy) hexane, 2-ethylhexyl t-butylperoxycarbonate, 1-bis (t-butylperoxy) -3,3, 5-trimethylcyclohexane, 1-bis (t-amylperoxy) -cyclohexane, 1-bis (t-butylperoxy) cyclohexane, 2-bis (t-butylperoxy) butane, t-amyl peroxy-2-ethylhexylcarbonate, 2, 5-dimethyl-2, 5-bis (benzoylperoxy) -hexane, tert-amyl peroxycarbonate, tert-butyl peroxy3, 3, 5-trimethylhexanoate.

In a preferred embodiment, the co-crosslinking agent includes, but is not limited to, triallyl isocyanurate, triallyl cyanurate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, ethoxylated glycerol triacrylate, propoxylated glycerol triacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, trimethylolpropane tetraacrylate, ditrimethylolpropane tetramethacrylate, propoxylated pentaerythritol tetraacrylate, 2,4, 6-tris (2-propenyloxy) -1,3, 5-triazine, poly (allyl methacrylate), poly (vinyl, One or more of the group consisting of tricyclodecane dimethanol diacrylate, propoxylated neopentyl glycol diacrylate, ethoxylated bisphenol A dimethacrylate, 2-butyl-2-ethyl-1, 3-propanediol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate and polyethylene glycol dimethacrylate.

Antioxidants are used to improve the stability of the polymer during extrusion processing and long term use, and to retard degradation due to the action of hot oxygen. In a preferred embodiment, the antioxidant is a hindered phenol-based compound and/or a phosphite-based compound. Compared with other antioxidants, the antioxidant has better stability and oxidation resistance. More preferably, the hindered phenol-based compound includes, but is not limited to, 2, 6-di-tert-butyl-4-ethylphenol, 2 ' -methylene-bis- (4-methyl-6-tert-butylphenol), 2 ' -methylene-bis- (4-ethyl-6-tert-butylphenol), 4 ' -butylidene-bis- (3-methyl-6-tert-butylphenol), octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythritol-tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 7-octadecyl-3- (4 ' -hydroxy-3 ', one or more of the group consisting of 5 '-di-tert-butylphenyl) propionate, tetrakis- [ methylene-3- (3', 5 '-di-tert-butyl-4' -hydroxyphenyl) propionate ] methane; phosphite based compounds include, but are not limited to, one or more of the group consisting of tris (2, 4-di-t-butylphenyl) phosphite, bis [2, 4-bis (1, 1-dimethylethyl) -6-methylphenyl ] ethyl ester phosphite, tetrakis (2, 4-di-t-butylphenyl) [1, 1-biphenylyl ] -4, 4' -diyl bisphosphite, and bis (2, 4-di-t-butylphenyl) pentaerythritol diphosphite.

Ultraviolet light absorbers are substances that absorb most of the ultraviolet energy and convert it into heat, thereby protecting certain electronic devices from ultraviolet light. In a preferred embodiment, the above-mentioned ultraviolet light absorbers include, but are not limited to, benzophenone and/or benzotriazole species, and more preferably, the ultraviolet light absorbers include, but are not limited to, one or more of the group consisting of 2-hydroxy-4-n-octoxybenzophenone, 2-tetramethylene bis (3, 1-benzoxazin-4-one), 2- (2 ' -hydroxy-5-methylphenyl) benzotriazole, 2 ' -dihydroxy-4, 4 ' -dimethoxybenzophenone.

The light stabilizer is used for improving the stability of the packaging adhesive film under long-term ultraviolet irradiation. Preferably, the light stabilizer is a hindered amine-based compound. In a preferred embodiment, the light stabilizer includes, but is not limited to, bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate, bis (1-octyloxy-2, 2,6, 6-tetramethyl-4-piperidyl) sebacate, graft copolymers obtained by polymerizing 4- (meth) acryloyloxy-2, 2,6, 6-tetramethylpiperidine with an α -olefinic monomer, 4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidinol, 3, 5-di-tert-butyl-4-hydroxy-benzoic acid hexadecyl ester, sebacic acid bis-2, 2,6, 6-tetramethylpiperidinol and tris (1,2,2,6, 6-pentamethyl-4-piperidyl) phosphite.

The tackifier is added to improve the adhesive performance of the adhesive film. In a preferred embodiment, the adhesion promoter includes, but is not limited to, one or more of the group consisting of gamma-aminopropyltriethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma- (2, 3-glycidoxy) propyltrimethoxysilane, vinyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, gamma-glycidoxypropyltrimethylsilane, 3-aminopropyltrimethylsilane.

The addition of the pigment can meet different application scenes according to the requirements of customers. In a preferred embodiment, the pigment includes, but is not limited to, one or more of the following materials mixed according to any proportion: calcium carbonate, barium sulfate, talcum powder, titanium dioxide, zinc oxide, carbon black, graphene oxide, copper-chromium black, magnesium hydroxide, aluminum oxide, magnesium oxide, boron nitride, silicon carbide, ammonium phosphate, ammonium polyphosphate, pentaerythritol, dipentaerythritol, polypentaerythritol ester and melamine polyphosphate borate.

The second aspect of the present application also provides a master batch comprising a matrix resin comprising the above resin composition provided herein. Because the resin composition provided by the application forms the adhesive film, the adhesive film can simultaneously meet the advantages of good yellowing resistance, high light transmittance, corrosion resistance and the like, and the effect can be realized after the adhesive film is prepared into master batches. Meanwhile, in the industrial application process, the steps of material proportioning, material mixing and the like can be omitted after the resin composition is prepared into master batches, so that the production efficiency is improved.

The third aspect of the present application also provides a glue film, wherein the glue film comprises at least one single-layer film, and the single-layer film is prepared from raw materials comprising the resin composition or the master batch provided by the present application.

When the guanidine compound is added in a specific amount, the light transmittance of a film formed from the resin composition can be improved, and the yellowing rate of the film can be reduced. Meanwhile, because the guanidine compound has stronger alkalinity, the guanidine compound can react with acetic acid generated by Norrish type II deacetylation reaction of ethylene-vinyl acetate copolymer (EVA) in the application process, thereby improving the corrosion resistance of the adhesive film formed by the resin combination. In conclusion, the adhesive film formed by the resin composition can simultaneously meet the advantages of good yellowing resistance, high light transmittance, corrosion resistance and the like.

By adopting the adhesive film, the advantages of good yellowing resistance, high light transmittance, corrosion resistance and the like can be simultaneously met, so that the adhesive film can be used as a packaging adhesive film of a photovoltaic module or a part close to a battery piece in the packaging adhesive film, and the photoelectric property of the photovoltaic module can be greatly improved.

The adhesive film is not limited to being used as a packaging adhesive film, and another application is that the adhesive film is used as a sealing component in a display device to seal a light-emitting unit. Because the adhesive film can simultaneously meet the advantages of good yellowing resistance, high light transmittance, corrosion resistance and the like, the display device adopting the adhesive film as the sealing assembly can greatly prolong the service life and improve the display performance of the display device.

The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.

Example 1

Raw materials for forming the resin composition: 100 parts by weight of a base resin ethylene-vinyl acetate resin (DuPont), 0.05 part by weight of an organic base compound (7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene, pKa 14.27), 0.2 part by weight of a crosslinking agent (isopropyl t-butylperoxycarbonate), 0.3 part by weight of a co-crosslinking agent (trimethylolpropane trimethacrylate).

The preparation method comprises the following steps: the raw materials are uniformly mixed, and a single-layer packaging adhesive film is prepared through the processes of premixing, melt extrusion, film casting, cooling, slitting and rolling.

Example 2

The differences from example 1 are: the organic base compound is 2-vinyl-4, 6-diamino-triazine (PKa 14.2).

Example 3

The differences from example 1 are: the organic base compound is 1,5, 7-triazabicyclo [4.4.0] dec-5-ene (pKa 14.47).

Example 4

The differences from example 1 are: the organic base compound was 0.03 parts by weight of 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene (PKa of 14.27) and 0.02 parts by weight of 2-vinyl-4, 6-diamino-triazine (PKa of 14.2).

Example 5

The differences from example 1 are: the organic base compound was 0.05 part by weight of hexamethylenetetramine (PKa of 8.4).

Example 6

The differences from example 1 are: the organic base compound was 0.5 part by weight of cyclohexylamine (PKa 10.66).

Example 7

The differences from example 1 are: the organic base compound was 1 part by weight of cyclohexylamine (PKa 10.66).

Example 8

The differences from example 1 are: the organic base compound was 0.05 part by weight of triethanolamine (PKa 7.82).

Example 9

The differences from example 1 are: the organic base compound was 1 part by weight of diisopropanolamine (PKa 14.54).

Example 10

The differences from example 1 are: the organic base compound was 3 parts by weight of diisopropanolamine (PKa 14.54).

Example 11

The differences from example 1 are: the organic base compound was 0.1 parts by weight of hexamethylenetetramine (PKa of 8.4) and 0.5 parts by weight of 2-vinyl-4, 6-diamino-triazine (PKa of 14.2).

Example 12

The differences from example 1 are: the organic base compound was 0.01 part by weight of 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene (pKa: 14.27).

Example 13

The differences from example 1 are: the organic base compound was 2 parts by weight of 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene (pKa: 14.27).

Example 14

The differences from example 1 are: the resin composition also included 0.01 parts by weight of magnesium oxide.

Example 15

The differences from example 1 are: the resin composition further includes 0.1 parts by weight of magnesium hydroxide.

Example 16

The differences from example 1 are: the resin composition also included 1.5 parts by weight of calcia.

Example 17

The differences from example 1 are: the adhesive film is two layers, wherein the formula of one layer of adhesive film is the same as that of the adhesive film in example 1. The other adhesive film layer is as follows: 100 parts of matrix resin polyolefin (Dow), 0.2 part by weight of crosslinking agent (isopropyl t-butylperoxycarbonate), 0.3 part by weight of co-crosslinking agent (trimethylolpropane trimethacrylate).

The preparation method comprises the following steps: and respectively mixing the raw materials of each layer uniformly, and adding the mixture into different extruders. And respectively melting and plasticizing the extruded materials of each layer, injecting the melted and plasticized extruded materials into the same die head, combining the extruded materials in the T die head to form a melt flow, and preparing the double-layer photovoltaic co-extrusion film through the processes of melting extrusion, casting film forming, cooling, slitting, rolling and the like.

Example 18

The differences from example 1 are: the resin composition also comprises 5 parts by weight of titanium dioxide.

Example 19

The differences from example 1 are: the resin composition further includes 1 part by weight of carbon black.

Comparative example 1

Raw materials for forming the resin composition: 100 parts of matrix resin ethylene-vinyl acetate resin (DuPont), 0.05 part of magnesium hydroxide, 0.2 part of crosslinking agent tert-butyl peroxyisopropyl carbonate and 0.3 part of auxiliary crosslinking agent trimethylolpropane trimethacrylate.

The preparation method comprises the following steps: the raw materials are uniformly mixed, and a single-layer packaging adhesive film is prepared through the processes of premixing, melt extrusion, film casting, cooling, slitting and rolling.

Comparative example 2

Raw materials for forming the resin composition: 100 parts of matrix resin ethylene-vinyl acetate resin (DuPont), 0.05 part of magnesium oxide, 0.2 part of crosslinking agent tert-butyl peroxyisopropyl carbonate and 0.3 part of auxiliary crosslinking agent trimethylolpropane trimethacrylate.

The preparation method comprises the following steps: the raw materials are uniformly mixed, and a single-layer packaging adhesive film is prepared through the processes of premixing, melt extrusion, film casting, cooling, slitting and rolling.

Comparative example 3

The differences from example 1 are: the organic base compound is methylguanamine (PKa 4.19).

Comparative example 4

The differences from example 1 are: the organic base compound is pyridine (PKa of 5.25).

And (3) performance detection:

(1) light transmittance.

Light transmittance test of the light receiving side adhesive film: the sealant materials of examples 1-19 and comparative examples 1-4 were laminated and then subjected to a transmittance test, wherein the thickness of the adhesive films of the examples and comparative examples after lamination was 0.45mm, the transmittance test was performed according to GB/T2410-2008, and the transmittance of the adhesive films was measured by an ultraviolet-visible spectrophotometer at 700-400 nm.

(2) And (6) yellowing test.

Taking the packaging adhesive films of examples 1 to 19 and comparative examples 1 to 4, putting the sample with the structure of glass/packaging adhesive film/back plate into an ultraviolet aging test box, and irradiating the sample with ultraviolet light at 120kWh/m²And (6) sampling. Before and after the experiment, the yellow index of the test sample is tested according to ASTM E313-2010, and each test sampleMeasuring not less than 3 points, taking an average value, and taking the difference value of the yellow indexes before and after the ultraviolet accelerated aging test as the yellowing index delta YI.

(3) And evaluating the lamination appearance of the assembly.

The solar cell modules were packaged by the same process using the packaging adhesive films obtained in the above examples and comparative examples. The solar cell module is prepared by stacking glass/adhesive film/cell piece/adhesive film/glass according to the stacking sequence, stacking the glass/adhesive film/flexible back plate of 300mm multiplied by 150mm in sequence in a vacuum laminating machine, pressing the glass/adhesive film/flexible back plate at 145 ℃ for 16min, and preparing a standard double-glass solar cell module, wherein the specification of the module is 60 (6 multiplied by 10) cell pieces (the module is a type of the same manufacturer, the same batch, the same grade and the size of 156 mm). And manufacturing the assembly according to different adhesive films. The above modules were subjected to PCT aging (121 ℃, 100% RH) and DH aging (85 ℃, 85% RH), and appearance corrosion of the module cells was observed by EL tracking.

(4) And testing the photoelectric conversion efficiency.

According to the specification in IEC61215, testing the power attenuation condition of the double-glass photovoltaic module after the double-glass photovoltaic module is aged for 1000 hours under the conditions of 85 ℃ and 85% of humidity, wherein the power attenuation rate of the photovoltaic module is (initial power of the module-power after PID (proportion integration differentiation) ageing)/initial power of the module, and the power attenuation is required to be less than or equal to 5%.

TABLE 1

From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects: the adhesive film formed by adopting the resin composition can simultaneously meet the advantages of good yellowing resistance, high light transmittance, corrosion resistance and the like.

It is noted that the terms first, second and the like in the description and in the claims of the present application are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances such that the embodiments of the application described herein are, for example, capable of operation in sequences other than those described or illustrated herein.

The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.