WO2021253611A1 - 胶膜、形成其的组合物及电子器件 - Google Patents

胶膜、形成其的组合物及电子器件 Download PDF

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WO2021253611A1
WO2021253611A1 PCT/CN2020/109633 CN2020109633W WO2021253611A1 WO 2021253611 A1 WO2021253611 A1 WO 2021253611A1 CN 2020109633 W CN2020109633 W CN 2020109633W WO 2021253611 A1 WO2021253611 A1 WO 2021253611A1
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group
parts
composition according
ethylene
adhesive film
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PCT/CN2020/109633
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English (en)
French (fr)
Inventor
唐国栋
王龙
桑燕
周光大
侯宏兵
林建华
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杭州福斯特应用材料股份有限公司
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Priority to US17/927,685 priority Critical patent/US20230174827A1/en
Priority to EP20940732.9A priority patent/EP4166618A4/en
Publication of WO2021253611A1 publication Critical patent/WO2021253611A1/zh

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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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/397—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using a single screw
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/14—Monomers containing five or more carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond
    • 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
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/06—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • 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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • 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
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • 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
    • H01L31/04—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 adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/08—Copolymers of ethylene
    • 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
    • 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
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
    • 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
    • C09J2423/00—Presence of polyolefin
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the present invention relates to the field of photoelectric conversion devices, in particular to a glue film, a composition forming the same, and an electronic device.
  • Photoelectric conversion refers to the conversion of solar energy into electrical energy through the photovoltaic effect.
  • electronic devices photoelectric conversion devices
  • solar cells such as crystalline silicon batteries, amorphous silicon batteries, cadmium telluride batteries, copper indium gallium tin batteries, perovskite batteries
  • Liquid crystal panels Liquid crystal panels, electroluminescence devices, plasma display devices, sensors, etc.
  • the sealing material is bonded with the upper and lower substrates to form a complete electronic device module.
  • crystalline silicon solar cell modules are usually laminated according to the front glass substrate, front sealing layer polymer, crystalline silicon battery, rear sealing layer polymer, rear glass substrate or polymer substrate, and then heated and heated by a vacuum laminator. After pressing, a complete solar module is formed.
  • Polymer sealing materials usually need to meet the following conditions: I) Adhesion. The polymer sealing material is chemically bonded to the electronic device and the substrate after being heated and melted, and it is generally expected that no delamination will occur between the sealing material and the electronic device and the substrate during long-term use. II) Softness. It has a low elastic modulus and protects electronic devices from damage caused by external impact; III) Transparency. For example, for solar cells, the sealing material needs to have high light transmittance, so as to maximize the use of sunlight and improve the efficiency of power generation. IV) Insulation. Generally, the polymer sealing material needs high volume resistivity to avoid large leakage current. V) Chemical stability.
  • the sealing material When solar modules are exposed to high temperature, high humidity, and ultraviolet radiation during long-term outdoor use, the sealing material should not be severely deteriorated, resulting in yellowing, decreased mechanical properties, and release of corrosive compounds. VI) Heat resistance. Solar modules are exposed to long-term high temperature outdoors, and the sealing material should not flow or creep. Therefore, the sealing material usually needs to be cross-linked.
  • polymer films especially polyolefin films
  • static electricity is easily accumulated on the surface, which may cause damage to the electronic devices during contact with the electronic devices.
  • a static elimination device is added during the molding process of polymer films to eliminate static electricity on the surface of polymer materials, but the effect of this method is not very complete, and the polymer film will accumulate static electricity again during use.
  • the main purpose of the present invention is to provide an adhesive film, a composition forming the same, and an electronic device, so as to solve the problem that the surface of the existing polymer adhesive film is easy to accumulate static electricity, and the electronic device will be damaged during the contact between the adhesive film and the electronic device. .
  • compositions for forming an adhesive film comprising: a thermoplastic polymer resin and an antistatic agent, wherein the antistatic agent is an amide represented by formula (I) Organic matter,
  • R 1 is H, group A, a substituent formed by the substitution of at least one hydrogen atom in group A by a hydroxy, amino or epoxy group, or a substituent formed by substitution of at least one methylene group in group A by a carbonyl or ether bond ,
  • Group A is linear alkyl, branched alkyl or cycloalkyl, and the number of carbon atoms of group A is ⁇ 10;
  • R 2 is linear alkyl, branched alkyl, cycloalkyl or alkenyl, The number of carbon atoms of R 2 is 2-20.
  • R 2 is selected from the group consisting of vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, decaenyl, undecenyl, dodecenyl, and tetradecenyl Group, hexadecenyl or octadecenyl.
  • the antistatic agent is selected from acrylamide, methacrylamide, N-methacrylamide, N-ethylacrylamide, N-isopropylacrylamide, N-tert-butylacrylamide, dimethylamino Propyl acrylamide, N-(3-dimethylaminopropyl) methacrylamide, N-(butoxymethyl)-acrylamide, N-(3-aminopropyl) methacrylamide, double Acetone acrylamide, 4-acryloylmorpholine, N-methylolacrylamide, N-hydroxyethyl acrylamide, N-(2-hydroxypropyl)acrylamide, N,N'-methylenebisacrylamide , N,N'-diylidene bisacrylamide, maleimide, succinamide, oleic acid amide, 9-hexadecenamide, N-(2-hydroxyethyl)-undec-10- Enamide, 9-tetradecenamide, 9-dodecenamide, 9-de
  • the above composition further includes: 0.005 to 0.3 parts of antistatic agent.
  • the above composition further includes: 0.01 to 0.2 parts of an antistatic agent.
  • the above composition further includes: 0.02 to 0.1 parts of an antistatic agent.
  • thermoplastic polymer resin is selected from ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate, ethylene- ⁇ olefin copolymer, ethylene homopolymer, polyvinyl butyral, silicone resin and polyurethane resin One or more of the group consisting of.
  • the density of the ethylene- ⁇ olefin copolymer is 0.86 to 0.89 g/cm 3
  • the melt index of the ethylene- ⁇ olefin copolymer and the ethylene homopolymer is 1 to 40 g/10 min.
  • the density of the ethylene- ⁇ olefin copolymer is 0.87 to 0.88 g/cm 3 ; the melt index of the ethylene- ⁇ olefin copolymer and the ethylene homopolymer is 3 to 30 g/10 min.
  • melt index of the ethylene- ⁇ olefin copolymer and the ethylene homopolymer is 5-25 g/10 min.
  • the ethylene- ⁇ -olefin copolymer is a copolymer of ethylene and an ⁇ -olefin with carbon atoms ⁇ 10, wherein the ⁇ -olefin with carbon atoms ⁇ 10 is selected from propylene, 1-butene, 1-hexene, One or more of the group consisting of 1-pentene, 1-octene, and 4-methyl-1-pentene.
  • the ⁇ -olefin with carbon number ⁇ 10 is 1-butene and/or 1-octene.
  • the above composition further includes 0.1 to 1 part of initiator and 0.1 to 1.5 parts of crosslinking agent.
  • the above composition further includes 0.2-0.9 parts of initiator and 0.2-1.2 parts of crosslinking agent.
  • the above composition further includes 0.3 to 0.7 parts of initiator and 0.3 to 1 part of crosslinking agent.
  • the above composition further includes 0.1 to 0.8 parts of a tackifier.
  • the tackifier is a silane coupling agent having at least one ethylenically unsaturated group and at least one hydrolyzable group.
  • each ethylenically unsaturated group is independently selected from vinyl group, allyl group or ⁇ -(meth)acryloxy propyl group, and each hydrolyzable group is independently selected from methoxy group or ethyl group.
  • the adhesion promoter is selected from the group consisting of ⁇ -methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane and allyltrimethoxysilane.
  • the above composition also includes one or more of light stabilizers, antioxidants, ultraviolet absorbers, plasticizers, anti-corrosion agents, pigments and fillers.
  • Another aspect of the present application also provides an adhesive film, which is prepared by using the above-mentioned composition through a melt extrusion process.
  • an electronic device including an encapsulating adhesive film, and the encapsulating adhesive film includes the adhesive film provided in the present application.
  • the antistatic agent represented by formula (I) contains a strong polar amide group and optional polar groups (hydroxyl, amino, carbonyl, ether bond or epoxy), and the amide group can Intramolecular hydrogen bonds are formed, and the bond length is short.
  • the positive and negative ions formed after ionization generate a strong dipole electric field, which can offset the strong voltage generated by the external electrostatic field, so it has better antistatic performance.
  • the optional polar groups (hydroxyl, carbonyl or epoxy) can further improve the antistatic properties.
  • the thermoplastic polymer resin has good thermal processing performance, and after being melt-extruded with the antistatic agent represented by formula (I), it can form a film with good antistatic performance and processing performance.
  • the present application provides a composition for forming an adhesive film, the composition comprising: a thermoplastic polymer resin and an antistatic agent, wherein the antistatic agent is an amide organic compound represented by formula (I),
  • R 1 is H, group A, a substituent formed by the substitution of at least one hydrogen atom in group A by a hydroxy, amino or epoxy group, or a substituent formed by substitution of at least one methylene group in group A by a carbonyl or ether bond ,
  • Group A is linear alkyl, branched alkyl or cycloalkyl, and the number of carbon atoms of group A is ⁇ 10;
  • R 2 is linear alkyl, branched alkyl, cycloalkyl or alkenyl, The number of carbon atoms of R 2 is 2-20.
  • the antistatic agent represented by formula (I) contains a strong polar amide group and optional polar groups (hydroxyl, amino, carbonyl, ether bond or epoxy), the amide group can form intramolecular hydrogen bonds, and The bond length is short, and the dipole electric field generated by the positive and negative ions formed after ionization is strong, which can offset the strong voltage generated by the external electrostatic field, so it has better antistatic performance.
  • the optional polar groups (hydroxyl, carbonyl or epoxy) can further improve the antistatic properties.
  • the thermoplastic polymer resin has good thermal processing performance, and after being melt-extruded with the antistatic agent represented by formula (I), it can form a film with good antistatic performance and processing performance.
  • the antistatic agent can undergo a grafting reaction with the thermoplastic polymer resin, which can improve the uniformity of the intramolecular hydrogen bond dispersion in the film formed and permanently lock in the polymerization In addition, improve the degree of cross-linking of the film.
  • R 2 includes but is not limited to vinyl, propenyl, butene Alkyl, pentenyl, hexenyl, heptenyl, octenyl, decaenyl, undecenyl, dodecenyl, tetradecenyl, hexadecenyl, or octadecenyl.
  • the antistatic agent represented by formula (I) contains one of the above-mentioned alkenyl groups, it is beneficial to further improve the antistatic effect of the encapsulation film.
  • the antistatic agent includes but is not limited to acrylamide, methacrylamide, N-methacrylamide, N-ethylacrylamide, N-isopropylacrylamide, N-tert-butyl Acrylamide, dimethylaminopropylacrylamide, N-(3-dimethylaminopropyl)methacrylamide, N-(butoxymethyl)-acrylamide, N-(3-aminopropyl) Base) methacrylamide, diacetone acrylamide, 4-acryloylmorpholine, N-methylol acrylamide, N-hydroxyethyl acrylamide, N-(2-hydroxypropyl)acrylamide, N,N '-Methylene bisacrylamide, N,N'-diylidene bisacrylamide, maleimide, succinamide, oleic acid amide, 9-hexadecenamide, N-(2-hydroxyethyl )-Undec-10-enamide, 9-tetradecenamide, 9
  • the above-mentioned antistatic agents have better stability and excellent antistatic properties. More preferably N-methylolacrylamide, N-hydroxyethylacrylamide, N-(2-hydroxypropyl)acrylamide, N,N'-methylenebisacrylamide, maleimide, oil Acid amide, 9-hexadecenamide, N-(2-hydroxyethyl)-undec-10-enamide, 9-tetradecenamide, 9-dodecenamide, 9-decenamide Enamide, octenamide, heptenamide, hexenamide, pentenamide and crotonamide, 4-acryloylmorpholine.
  • the composition further includes: 0.005 to 0.3 parts of antistatic agent, preferably 0.01 to 0.2 parts of antistatic
  • the amount of the antistatic agent is more preferably 0.02 to 0.1 parts.
  • thermoplastic polymer resin in the above composition can be a resin commonly used in the art.
  • the thermoplastic polymer resin includes, but is not limited to, ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate, ethylene- ⁇ olefin copolymer, ethylene homopolymer, polyvinyl butyral One or more of the group consisting of ester, silicone resin and polyurethane resin.
  • the above-mentioned thermoplastic polymer resin is an ethylene- ⁇ olefin copolymer.
  • ethylene- ⁇ olefin copolymer has better water vapor barrier properties, higher insulation properties and higher light transmittance. Therefore, the selection of it as a thermoplastic polymer resin is beneficial to further improve the water vapor barrier of the film. Performance, insulation and light transmittance.
  • the ethylene- ⁇ -olefin copolymer is a copolymer of ethylene and an ⁇ -olefin with carbon atoms ⁇ 10, wherein the ⁇ -olefin with carbon atoms ⁇ 10 is selected from propylene, 1-butene, and 1-hexene One or more of the group consisting of, 1-pentene, 1-octene and 4-methyl-1-pentene; further preferably, the ⁇ -olefin with carbon atoms ⁇ 10 is 1-butene and / Or 1-octene.
  • the density of the ethylene- ⁇ olefin copolymer is 0.86 to 0.89 g/cm 3 , more preferably 0.87 to 0.88 g/cm 3 . If the density of the copolymer is too high, it may affect the light transmittance of the film; if the density is too low, the thermoplastic polymer resin may become sticky and affect the processing performance.
  • the melt index of the ethylene- ⁇ olefin copolymer and the ethylene homopolymer is 1-40 g/10 min, more preferably 3-30 g/10 min, and still more preferably 5-25 g/10 min.
  • melt index of the thermoplastic polymer resin is too low, it will be difficult to form the film, and it will also reduce the wettability with glass and other substrates, thereby reducing the adhesion; if the melt index is too high, the packaging film will be in the production process It is easy to adhere to the film or embossing roller.
  • the polymer has high fluidity after melting, which causes the phenomenon of edge overflow. Limiting the melt index of the ethylene- ⁇ olefin copolymer and the ethylene homopolymer within the above range is beneficial to improve the moldability of the adhesive film, the adhesion to the substrate, and the aesthetics of the adhesive film product.
  • the above composition further includes an initiator and a crosslinking agent. More preferably, based on 100 parts by weight of the thermoplastic polymer resin, the above composition includes 0.1 to 1 part of initiator and 0.1 to 1.5 parts of crosslinking agent. Coupling agent. Under the action of free radical initiator and crosslinking agent, the thermoplastic polymer resin and antistatic agent polymerize, and form intramolecular hydrogen bonds, polar groups are internalized, and the molecular surfaces are mostly non-polar groups, which are not easy to be adsorbed on The inner wall of the container or the surface of the pipe, therefore, the conductivity of the adhesive film prepared with the above composition decays slowly.
  • an initiator and a crosslinking agent More preferably, based on 100 parts by weight of the thermoplastic polymer resin, the above composition includes 0.1 to 1 part of initiator and 0.1 to 1.5 parts of crosslinking agent. Coupling agent. Under the action of free radical initiator and crosslinking agent, the thermoplastic polymer resin and antistatic agent polymerize, and form intramol
  • the adhesive film prepared by limiting the amount of each component in the above composition within the above range not only has better antistatic properties, but also has better insulation properties. More preferably, based on 100 parts by weight of the thermoplastic polymer resin, the above composition further includes 0.2-0.9 parts of initiator and 0.2-1.2 parts of crosslinking agent; further preferably, based on 100 parts by weight of the thermoplastic polymer resin, the composition also Including 0.3 to 0.7 part of initiator and 0.3 to 1 part of crosslinking agent.
  • Free radical initiators are capable of forming active free radicals under the input of energy such as light and heat, thereby initiating the cross-linking reaction of polymers.
  • the free radical initiator includes a photoinitiator and a peroxide. Adding a photoinitiator and a peroxide to the above composition at the same time is beneficial to improve the reactivity of the above composition, thereby further improving the degree of crosslinking, thereby improving the overall performance of the adhesive film.
  • the photoinitiator includes, but is not limited to, benzophenone, benzoanthrone, benzoin, benzoin alkyl ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy 2-phenylacetophenone, p-phenoxydichloroacetophenone, 2-hydroxyisopropyl-phenylketone, 1-phenylpropanedione-2-(ethoxycarbonyl)oxime, ( 2,4,6-Trimethylbenzoyl)diphenylphosphorus oxide Phenyl bis(2,4,6-trimethylbenzoyl) phosphorus oxide 2,2-Dimethoxy-1,2-benzophenone ( 651), 2-ethoxy-1,2-benzophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 2-hydroxy Cyclohexyl phenyl ketone
  • the peroxide includes, but is not limited to, one or more mixtures of diacyl peroxide, dialkyl peroxide, peroxy ester, and peroxy ketal.
  • diacyl peroxide dialkyl peroxide
  • peroxy ester peroxy ester
  • peroxy ketal peroxy ketal
  • tert-butyl peroxybenzoate, tert-amyl peroxybenzoate, tert-butyl peroxyacetate, tert-amyl peroxyacetate, and 3,5,5-triperoxide can be cited.
  • tert-butyl peroxide-2-ethylhexyl carbonate tert-amyl peroxide-2-ethylhexyl carbonate, tert-butyl peroxide-3,5,5-trimethylhexanoate, 1,1 -Bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane.
  • the crosslinking agent is a molecule with multiple ethylenically unsaturated groups, which can promote the crosslinking of the polymer to achieve a higher degree of crosslinking.
  • the crosslinking agent in the above composition can be selected from the types commonly used in the field, preferably triallyl isocyanurate, triallyl cyanurate, triallyl cyanurate, trimethylolpropane Triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, ethoxylated glycerol tripropionate, tetramethylolmethane triacrylate, ethoxylated pentaerythritol tetraacrylate, dihydroxyl Methylpropane tetraacrylate, trimethylolethane trimethacrylate, pentaerythritol tetraacrylate, tetramethylolmethane tetraacrylate, di-trimethylolprop
  • the above composition further includes 0.1-0.8 parts of a tackifier.
  • the amount of the tackifier includes but is not limited to the above range, and limiting it to the above range is beneficial to further improve the adhesion of the adhesive film to the substrate.
  • the above composition includes 0.15 to 0.6 parts of a tackifier.
  • the above composition includes 0.2 to 0.5 part of a tackifier. .
  • the adhesion promoter is a silane coupling agent having at least one ethylenically unsaturated group and at least one hydrolyzable group.
  • the introduction of olefinic groups can chemically bond the tackifier and the polymer, and the introduction of hydrolyzable groups (such as methoxy or ethoxy) allows the tackifier to interact with the substrate or electronic device during heating. Bonding effect.
  • each ethylenically unsaturated group is independently selected from vinyl, allyl or ⁇ -(meth)acryloxypropyl, and each hydrolyzable group is independently selected from methoxy or Ethoxy; adhesion promoter is selected from ⁇ -methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane and allyl One or more of the group consisting of triethoxysilane.
  • the aforementioned additives include one or more of the group consisting of light stabilizers, antioxidants, ultraviolet absorbers, plasticizers, anticorrosive agents, pigments, and fillers.
  • Light stabilizers are used to improve the stability of the packaging film under long-term ultraviolet radiation.
  • the light stabilizer is a hindered amine compound.
  • the aforementioned light stabilizers include, but are not limited to, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(1-octyloxy-2,2,6 ,6-Tetramethyl-4-piperidinyl) sebacate, 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine and ⁇ -olefin monomer polymerization
  • the obtained graft copolymer, 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol, 3,5-di-tert-butyl-4-hydroxy-benzoic acid cetyl ester One of the group consisting of bis-2,2,6,6-tetramethylpiperidinol and tris(1,2,2,6,6-pentamethyl-4-piperidinyl) phos
  • the light stabilizer is used in the above composition in an amount of 0.02-0.8 parts, preferably 0.05-0.6 parts, more preferably 0.1- 0.5 copies.
  • Antioxidants are used to improve the stability of the polymer extrusion process and the long-term use process, and delay the degradation due to the action of hot oxygen.
  • the antioxidant is a hindered phenol compound and/or a phosphite compound. Compared with other antioxidants, the above-mentioned antioxidants have better stability and antioxidant properties.
  • hindered phenol compounds include but are not limited to 2,6-di-tert-butyl-4-ethylphenol, 2,2'-methylene-bis-(4-methyl-6-tert-butyl Phenol), 2,2'-methylene-bis-(4-ethyl-6-tert-butylphenol), 4,4'-butylene-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-hydroxyl Phenyl) propionate), 7-octadecyl-3-(4'-hydroxy-3',5'-di-tert-butylphenyl) propionate, tetra-(methylene-3- (3',5'-di-tert-butyl
  • the amount of the antioxidant in the above composition is 0.005 to 0.5 parts, more preferably 0.01 to 0.4 parts, and still more preferably 0.02 ⁇ 0.3 parts, more preferably 0.03 to 0.2 parts.
  • Ultraviolet absorber refers to a substance that can absorb most of the ultraviolet energy and convert it into heat, thereby protecting certain electronic devices from being damaged by ultraviolet rays.
  • the aforementioned ultraviolet light absorber is selected from benzophenones and/or benzotriazoles.
  • the ultraviolet light absorber includes but is not limited to 2-hydroxy-4-positive Octyloxybenzophenone, 2,2-tetramethylenebis(3,1-benzoxazin-4-one), 2-(2'-hydroxy-5-methylphenyl)benzotris Azole, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-(2'-hydroxy-3',5'-bis[1,1-dimethylphenyl] Phenyl)-benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3 ',5'di-tert-butylphenyl)-5-chlorobenzotriazole and 2-(2'-hydroxy-3',5'di-tert-amylphenyl)-benzotriazole One or more.
  • the amount of the ultraviolet absorber in the above composition is 0.05 to 0.5 parts, more preferably It is 0.1 to 0.4 parts, more preferably 0.2 to 0.3 parts.
  • Plasticizers can reduce the force between polymer molecules and the metal surface during processing, and reduce the friction between the polymer melt and the metal surface, so that the plasticity of the polymer is enhanced and processing is facilitated.
  • the plasticizer includes, but is not limited to, phthalate organics, aliphatic dibasic acid ester organics, phosphate ester organics, polyethylene wax organics, and stearic acid organics.
  • the plasticizer includes but not limited to polyethylene wax, trialkyl phosphate, triaryl phosphate, dioctyl sebacate, dioctyl adipate , One or more of the group consisting of dodecane dicarboxylate, dioctyl phthalate, dibutyl phthalate, stearic acid, zinc stearate and calcium stearate, and The number average molecular weight of the plasticizer is 2,000 to 10,000.
  • the amount of the plasticizer in the above composition is 0.01-5 parts, more preferably 0.05-4 parts , More preferably 0.1 to 3 parts, still more preferably 0.3 to 2 parts.
  • Anti-corrosion agents refer to substances that can absorb free acid in the film, including metal oxides and metal hydroxides.
  • the metal oxide is preferably one or more of the group consisting of magnesium oxide, zinc oxide and calcium oxide;
  • the hydroxide is preferably magnesium hydroxide and/or calcium hydroxide.
  • the anti-corrosion agent is used in the above composition in an amount of 0.05-0.3 parts, preferably 0.08-0.2 parts.
  • the pigment can color the encapsulation film and has light permeability, so the encapsulated electronic device can become beautiful.
  • Pigments include inorganic pigments and organic pigments, which can be selected from iron nickel yellow, titanium chrome brown, cobalt green, iron red, iron yellow, cobalt blue, copper chrome black, ultramarine blue, indigo, cinnabar, realgar, cadmium red, cadmium yellow, Any one or a mixture of iron blue, lithopone powder, iron oxide red, and iron oxide yellow.
  • the amount of the pigment in the above composition is 0.1-10 parts, more preferably 0.5-8 parts, still more preferably 1-7 parts, and further Preferably it is 2-6 parts.
  • the filler is an inorganic substance that can give the encapsulation film a light-reflecting or light-absorbing property, preferably titanium dioxide, calcium carbonate, lithopone, aluminum oxide, aluminum-doped zinc oxide, indium tin oxide, antimony oxide, barium sulfate, One or more of the group consisting of montmorillonite, kaolin, talc, feldspar, and carbon black.
  • the amount of filler is 1-40 parts, preferably 2-30 parts, more preferably 3-20 parts, and even more preferably 4-15 parts. share.
  • Another aspect of the present application also provides an adhesive film, which is prepared by using the above-mentioned composition provided in the present application through a melt extrusion process.
  • the antistatic agent represented by formula (I) contains a strong polar amide group.
  • the amide group can form intramolecular hydrogen bonds with a shorter bond length.
  • the positive and negative ions formed after ionization produce a strong dipole electric field that can offset the external electrostatic field.
  • the generated voltage is strong, so it has better antistatic performance.
  • the thermoplastic polymer resin has good thermal processing performance, and after being melt-extruded with the antistatic agent represented by the formula (I), a film with good antistatic performance can be formed.
  • the electronic device packaging adhesive film provided by the present invention has a thickness between 0.1 mm and 0.8 mm, has low surface resistance, can prevent the accumulation of static electricity, and is suitable for packaging various electronic devices, especially solar cell modules.
  • Another aspect of the present application also provides an electronic device, including an encapsulating adhesive film, and the encapsulating adhesive film includes the adhesive film provided in the present application.
  • the above-mentioned adhesive film provided by the present application not only has a good antistatic effect, but also can ensure good insulation of the adhesive film. Selection and use as a packaging film can greatly improve the overall performance of electronic devices.
  • thermoplastic polymer resin particles are continuously sprayed into the thermoplastic polymer resin particles in liquid form (liquid additives or solid additives are dissolved in a solvent to form a solution), while stirring for several hours or keeping the mixture in mixed motion, Until the liquid is completely absorbed by the polymer particles. It is also possible to granulate the solid or liquid additives and the polymer particles to form a masterbatch through a granulator, and then add the masterbatch to the polymer particles.
  • the mixed materials are added to the screw extruder, and the mixed composition is melted and meshed through the screw extruder to make the reaction raw materials uniformly mixed.
  • the melt is extruded through a wide slot nozzle.
  • surface embossing is carried out by means of an embossing roller and a rubber roller, and the cooling roller is cooled and then wound to form a roll-shaped rubber film, thereby completing the present invention.
  • the dry POE particles are added to a single-screw extruder, and a uniform POE melt is formed through the melting and shearing action of the screw, which is extruded into a film through a wide-slit nozzle, and is squeezed by the embossing roller and the rubber roller.
  • the surface of the film forms a texture structure, which is then cooled by several cooling rolls, and finally rewinded by a winding roll to obtain a transparent film.
  • the thickness of the film is 0.5 mm.
  • the granules form orange transparent granulated particles; the pre-prepared solution is evenly sprayed into the pre-prepared granulated particles and stirred until the ethanol evaporates and the surface of the POE particles is dry.
  • the dry POE particles are added to a single-screw extruder, and a uniform POE melt is formed through the melting and shearing action of the screw, which is extruded into a film through a wide-slit nozzle, and is squeezed by the embossing roller and the rubber roller.
  • the surface of the film forms a texture structure, which is then cooled by several cooling rollers, and finally rewinded by a winding roller to obtain an orange transparent film.
  • the thickness of the film is 0.5 mm.
  • maleimide 0.5 part of tert-butyl peroxide 2-ethylhexyl carbonate (TBEC), 0.5 part of triallyl isocyanurate (TAIC), 0.5 part of trimethylolpropane Acrylate (TMPTA), 0.25 parts of ⁇ -methacryloxypropyltrimethoxysilane (KH570), 0.07 parts of sebacic acid bis-2,2,6,6-tetramethylpiperidinol ester (Tinuvin 770), dissolve with an appropriate amount of absolute ethanol to form a solution; mix 7 parts of titanium dioxide and 100 parts of POE particles (DOW Engage 8669) through a twin-screw granulator to form white granulated particles; prepare them in advance Evenly spray the solution into the pre-prepared granulated particles and stir until the ethanol evaporates and the surface of the POE particles is dry.
  • TBEC tert-butyl peroxide 2-ethylhexyl carbonate
  • TAIC trial
  • the dry POE particles are added to a single-screw extruder, and a uniform POE melt is formed through the melting and shearing action of the screw, which is extruded into a film through a wide-slit nozzle, and is squeezed by the embossing roller and the rubber roller.
  • the surface of the film forms a texture structure, which is then cooled by several cooling rollers, and finally rewinded by a winding roller to obtain a white film.
  • the thickness of the film is 0.5 mm.
  • Example 3 The difference from Example 3 is that the antistatic agent is acrylamide.
  • Example 3 The difference from Example 3 is: the antistatic agent is dimethylaminopropyl acrylamide.
  • Example 3 The difference from Example 3 is that the antistatic agent is diacetone acrylamide.
  • Example 3 The difference from Example 3 is that the antistatic agent is 4-acryloylmorpholine.
  • Example 3 The difference from Example 3 is that the antistatic agent is oleic acid amide.
  • thermoplastic polymer resin is an ethylene-propylene hydrocarbon copolymer with a density of 0.88 g/cm 3 and a melt index of 30 g/10 min.
  • thermoplastic resin is ethylene-methyl methacrylate.
  • Example 3 The difference from Example 3 is that no tackifier is added.
  • Example 3 The difference from Example 3 is that the adhesion promoter is propenyltriethoxysilane.
  • the material forming the adhesive film only contains POE particles, and the preparation method is the same as that of Example 1, to obtain an adhesive film with a pattern on the surface, and the thickness of the film is 0.5 mm.
  • Example 3 The difference from Example 3 is: no antistatic agent is added, and the preparation method of Example 3 is the same to obtain an adhesive film with a pattern on the surface, and the thickness of the film is 0.5 mm.
  • Example 4 The difference from Example 4 is: no antistatic agent is added, and the preparation method of Example 3 is the same to obtain an adhesive film with a pattern on the surface, and the thickness of the film is 0.5 mm.
  • the obtained sheet was cut into a size of 10cm ⁇ 10cm, and laminated at 150°C, vacuum for 5 minutes, and pressure for 13 minutes, using a laminating device to remove the pattern on the surface of the film to obtain a flat surface film.
  • a cross-linking reaction occurs in the adhesive film (if a cross-linking agent is added).
  • the adhesive films of Example 4 and Comparative Example 3 were irradiated with ultraviolet light with an irradiation dose of 5 J/cm 2 ; the adhesive films of Example 5 were irradiated with an electron beam with an irradiation dose of 5 kGy.
  • the obtained sheet was cut into a size of 10cm ⁇ 10cm, and laminated at 150°C, vacuum for 5 minutes, and pressure for 13 minutes, using a laminating device to remove the pattern on the surface of the film to obtain a flat surface film.
  • a cross-linking reaction occurs in the adhesive film (if a cross-linking agent is added).
  • the adhesive films of Example 4 and Comparative Example 3 were irradiated with ultraviolet light with an irradiation dose of 5 J/cm 2 ; the adhesive films of Example 5 were irradiated with an electron beam with an irradiation dose of 5 kGy.
  • the obtained sheet was cut into a size of 10cm ⁇ 10cm, and laminated at 150°C, vacuum for 5 minutes, and pressure for 13 minutes, using a laminating device to remove the pattern on the surface of the film to obtain a flat surface film.
  • a cross-linking reaction occurs in the adhesive film (if a cross-linking agent is added).
  • the adhesive films of Example 4 and Comparative Example 3 were irradiated with ultraviolet light with an irradiation dose of 5 J/cm 2 ; the adhesive films of Example 5 were irradiated with an electron beam with an irradiation dose of 5 kGy.
  • thermoplastic resin is beneficial to improve the overall performance of the adhesive film.

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Abstract

本发明提供了一种胶膜、形成其的组合物及电子器件。该组合物包括：热塑性聚合树脂和抗静电剂，其中抗静电剂为式(Ⅰ)所示的酰胺类有机物。上述抗静电剂含有强极性酰胺基以及可选的极性基团，酰胺基团能够形成分子内氢键，且键长较短，电离后形成的正负离子产生的偶极电场强，能够抵消外静电场产生的电压强，因而具有较好的抗静电性能。可选的极性基团能够进一步提高上述抗静电性能。热塑性聚合树脂具有良好的热加工性能，将其与式(Ⅰ)所示的抗静电剂进行熔融挤出后能够形成具有较好的抗静电性能和加工性能的胶膜。

Description

胶膜、形成其的组合物及电子器件 技术领域
本发明涉及光电转化器件领域，具体而言，涉及一种胶膜、形成其的组合物及电子器件。
背景技术
光电转化是指通过光伏效应将太阳能转化为电能。常用的能够实现上述光电转化过程的电子器件(光电转化器件)，包括但不限于太阳能电池(如晶硅电池、非晶硅电池、碲化镉电池、铜铟镓锡电池、钙钛矿电池)、液晶面板、场致发光器件、等离子显示器件、传感器等，通常需要经过一层或多层聚合物材料的密封，然后密封材料再和上下两个基板相粘接从而形成一个完整电子器件模块。例如晶硅太阳能电池组件，通常是按照前层玻璃基板、前密封层聚合物、晶硅电池、后密封层聚合物、后层玻璃基板或聚合物基板层叠好后，通过真空层压机加热加压后形成一个完整的太阳能组件。
聚合物密封材料通常需要满足以下条件：Ⅰ)粘接性。聚合物密封材料在受热融化后通过化学作用和电子器件以及基板进行粘接，并通常期望在长期的使用过程中，密封材料和电子器件以及和基板之间不会发生分层。Ⅱ)柔软性。具有较低的弹性模量，保护电子器件以免受到外力冲击而损坏；Ⅲ)透明性。例如太阳能电池，需要密封材料具有高的透光率，从而最大化的利用太阳光，提高发电效率。Ⅳ)绝缘性。通常该聚合物密封材需要较高的体积电阻率，从而避免产生较大漏电流。Ⅴ)化学稳定性。太阳能组件在长期户外使用时所经受高温、高湿气、紫外光辐射等，密封材料不应该发生严重的劣化，从而造成黄变，机械性能下降，释放腐蚀性化合物等。Ⅵ)耐热性。太阳能组件在户外经受长期高温作用，密封材料不应该发生流动或蠕变，因此密封材料通常需要进行交联处理。
通常，聚合物薄膜尤其是聚烯烃薄膜具有较高的绝缘电阻，其在生产成型过程中，尤其是和金属滚筒摩擦过程中表面容易积累静电，从而在和电子器件接触过程中造成电子器件的损坏。一般在聚合物薄膜成型过程中会添加静电消除这一装置来消除聚合物材料表面的静电，但这种方法效果并不是很彻底，且聚合物薄膜在使用过程中会再次累积产生静电。
发明内容
本发明的主要目的在于提供一种胶膜、形成其的组合物及电子器件，以解决现有的聚合胶膜表面容易积累静电，在胶膜与电子器件接触过程中会造成电子器件损坏的问题。
为了实现上述目的，根据本发明的一个方面，提供了一种形成胶膜的组合物，该组合物包括：热塑性聚合树脂和抗静电剂，其中抗静电剂为式(Ⅰ)所示的酰胺类有机物，
Figure PCTCN2020109633-appb-000001
R 1为H、基团A、基团A中至少一个氢原子被羟基、氨基或环氧基取代形成的取代基或基团A中至少一个亚甲基被羰基或醚键取代形成的取代基，基团A为直链烷基、支链烷基或环烷基，且基团A的碳原子数≤10；R 2为直链烷基、支链烷基、环烷基或烯基，且R 2的碳原子数为2～20。
进一步地，R 2选自乙烯基、丙烯基、丁烯基、戊烯基、己烯基、庚烯基、辛烯基、十烯基、十一烯基、十二烯基、十四烯基、十六烯基或十八烯基。
进一步地，抗静电剂选自丙烯酰胺、甲基丙烯酰胺、N-甲基丙烯酰胺、N-乙基丙烯酰胺、N-异丙基丙烯酰胺、N-叔丁基丙烯酰胺、二甲胺基丙基丙烯酰胺、N-(3-二甲胺基丙基)甲基丙烯酰胺、N-(丁氧基甲基)-丙烯酰胺、N-(3-氨丙基)甲基丙烯酰胺、双丙酮丙烯酰胺、4-丙烯酰吗啉、N-羟甲基丙烯酰胺、N-羟乙基丙烯酰胺、N-(2-羟基丙基)丙烯酰胺、N,N’-亚甲基双丙烯酰胺、N，N’-二亚基双丙烯酰胺、马来酰亚胺、琥珀酰胺、油酸酰胺、9-十六碳烯酰胺、N-(2-羟基乙基)-十一碳-10-烯酰胺、9-十四碳烯酰胺、9-十二碳烯酰胺、9-十碳烯酰胺、辛烯酰胺、庚烯酰胺、己烯酰胺、戊烯酰胺和丁烯酰胺组成的组中的一种或多种。
进一步地，以100重量份热塑性聚合树脂计，上述组合物还包括：0.005～0.3份抗静电剂。
进一步地，以100重量份热塑性聚合树脂计，上述组合物还包括：0.01～0.2份抗静电剂。
进一步地，以100重量份热塑性聚合树脂计，上述组合物还包括：0.02～0.1份抗静电剂。
进一步地，热塑性聚合树脂选自乙烯-醋酸乙烯酯共聚物、乙烯-甲基丙烯酸甲酯、乙烯-α烯烃共聚物、乙烯均聚物、聚乙烯醇缩丁醛酯、有机硅树脂和聚氨酯树脂组成的组中的一种或多种。
进一步地，乙烯-α烯烃共聚物的密度为0.86～0.89g/cm 3，乙烯-α烯烃共聚物和所述乙烯均聚物的熔融指数为1～40g/10min。
进一步地，乙烯-α烯烃共聚物的密度为0.87～0.88g/cm 3；所述乙烯-α烯烃共聚物和所述乙烯均聚物的熔融指数为3～30g/10min。
进一步地，乙烯-α烯烃共聚物和所述乙烯均聚物的熔融指数为5～25g/10min。
进一步地，乙烯-α-烯烃共聚物为乙烯与碳原子数≤10的α-烯烃的共聚物，其中碳原子数≤10的α-烯烃选自丙烯、1-丁烯、1-己烯、1-戊烯、1-辛烯和4-甲基-1-戊烯组成的组中的一种或多种。
进一步地，碳原子数≤10的α-烯烃为1-丁烯和/或1-辛烯。
进一步地，以100重量份热塑性聚合树脂计，上述组合物还包括0.1～1份引发剂和0.1～1.5份交联剂。
进一步地，以100重量份热塑性聚合树脂计，上述组合物还包括0.2～0.9份引发剂和0.2～1.2份交联剂。
进一步地，以100重量份热塑性聚合树脂计，上述组合物还包括0.3～0.7份引发剂和0.3～1份交联剂。
进一步地，以100重量份热塑性聚合树脂计，上述组合物还包括0.1～0.8份增粘剂。
进一步地，增粘剂为具有至少一个烯属不饱和基团和至少一个可水解基团的硅烷偶联剂。
进一步地，各烯属不饱和基团分别独立地选自乙烯基、烯丙基或γ-(甲基)丙烯酰氧基丙基，各可水解基团分别独立地选自甲氧基或乙氧基。
进一步地，增粘剂选自γ-甲基丙烯酰氧基丙基三甲氧基硅烷、乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、烯丙基三甲氧基硅烷和烯丙基三乙氧基硅烷组成的组中的一种或多种。
进一步地，上述组合物还包括光稳定剂、抗氧剂、紫外线吸收剂、增塑剂、抗腐蚀剂、颜料和填料中的一种或多种。
本申请的另一方面还提供了一种胶膜，胶膜采用上述组合物经熔融挤出工艺制得。
本申请的又一方面还提供了一种电子器件，包括封装胶膜，该封装胶膜包括本申请提供的胶膜。
应用本发明的技术方案，式(Ⅰ)所示的抗静电剂含有强极性酰胺基以及可选的极性基团(羟基、氨基、羰基、醚键或环氧基)，酰胺基团能够形成分子内氢键，且键长较短，电离后形成的正负离子产生的偶极电场强，能够抵消外静电场产生的电压强，因而具有较好的抗静电性能。而可选的极性基团(羟基、羰基或环氧基)能够进一步提高上述抗静电性能。热塑性聚合树脂具有良好的热加工性能，将其与式(Ⅰ)所示的抗静电剂进行熔融挤出后能够形成具有较好的抗静电性能和加工性能的胶膜。
具体实施方式
需要说明的是，在不冲突的情况下，本申请中的实施例及实施例中的特征可以相互组合。下面将结合实施例来详细说明本发明。
正如背景技术所描述的，现有的聚合胶膜表面容易积累静电，在胶膜与电子器件接触过程中会造成电子器件损坏的问题。为了解决上述技术问题，本申请提供了一种形成胶膜的组合物，该组合物包括：热塑性聚合树脂和抗静电剂，其中抗静电剂为式(Ⅰ)所示的酰胺类有机物，
Figure PCTCN2020109633-appb-000002
R 1为H、基团A、基团A中至少一个氢原子被羟基、氨基或环氧基取代形成的取代基或基团A中至少一个亚甲基被羰基或醚键取代形成的取代基，基团A为直链烷基、支链烷基或环烷基，且基团A的碳原子数≤10；R 2为直链烷基、支链烷基、环烷基或烯基，且R 2的碳原子数为2～20。
式(Ⅰ)所示的抗静电剂含有强极性酰胺基以及可选的极性基团(羟基、氨基、羰基、醚键或环氧基)，酰胺基团能够形成分子内氢键，且键长较短，电离后形成的正负离子产生的偶极电场强，能够抵消外静电场产生的电压强，因而具有较好的抗静电性能。而可选的极性基团(羟基、羰基或环氧基)能够进一步提高上述抗静电性能。热塑性聚合树脂具有良好的热加工性能，将其与式(Ⅰ)所示的抗静电剂进行熔融挤出后能够形成具有较好的抗静电性能和加工性能的胶膜。
相比于烷基，当R 2为烯基时，抗静电剂能够与热塑性聚合树脂一起进行接枝反应，从而能够提高其形成胶膜中分子内氢键分散的均匀性，并永久锁定于聚合物中，以及提升胶膜的交联度。为了进一步降低抗静电剂和聚合树脂的接枝难度，减少副产物的生成，并提高其交联度，在一种优选的实施例中，R 2包括但不限于乙烯基、丙烯基、丁烯基、戊烯基、己烯基、庚烯基、辛烯基、十烯基、十一烯基、十二烯基、十四烯基、十六烯基或十八烯基。当式(Ⅰ)所示的抗静电剂含有上述几种烯基中的一种时，有利于进一步提高封装胶膜的抗静电效果。
在一种优选的实施例中，抗静电剂包括但不限于丙烯酰胺、甲基丙烯酰胺、N-甲基丙烯酰胺、N-乙基丙烯酰胺、N-异丙基丙烯酰胺、N-叔丁基丙烯酰胺、二甲胺基丙基丙烯酰胺、N-(3-二甲胺基丙基)甲基丙烯酰胺、N-(丁氧基甲基)-丙烯酰胺、N-(3-氨丙基)甲基丙烯酰胺、双丙酮丙烯酰胺、4-丙烯酰吗啉、N-羟甲基丙烯酰胺、N-羟乙基丙烯酰胺、N-(2-羟基丙基)丙烯酰胺、N,N’-亚甲基双丙烯酰胺、N，N’-二亚基双丙烯酰胺、马来酰亚胺、琥珀酰胺、油酸酰胺、9-十六碳烯酰胺、N-(2-羟基乙基)-十一碳-10-烯酰胺、9-十四碳烯酰胺、9-十二碳烯酰胺、9-十碳烯酰胺、辛烯酰胺、庚烯酰胺、己烯酰胺、戊烯酰胺和丁烯酰胺组成的组中的一种或多种。相比于其它种类的抗静电剂，上述几种抗静电剂具有较好的稳定性，同时抗静电性更加优异。更优选为N-羟甲基丙烯酰胺、N-羟乙基丙烯酰胺、N-(2-羟基丙基)丙烯酰胺、N,N’-亚甲基双丙烯酰胺、马来酰亚胺、油酸酰胺、9-十六碳烯酰胺、N-(2-羟基乙基)-十一碳-10-烯酰胺、9-十四碳烯酰胺、9-十二碳烯酰胺、9-十碳烯酰胺、辛烯酰胺、庚烯酰胺、己烯酰胺、戊烯酰胺和丁烯酰胺、4-丙烯酰吗啉。
为了进一步提高胶膜的抗静电性能，在一种优选的实施例中，以100重量份热塑性聚合树脂计，该组合物还包括：0.005～0.3份抗静电剂，优选为0.01～0.2份抗静电剂，更优选为0.02～0.1份抗静电剂。
上述组合物中热塑性聚合树脂可以选用本领域常用的树脂。在一种优选的实施例中，热塑性聚合树脂包括但不限于乙烯-醋酸乙烯酯共聚物、乙烯-甲基丙烯酸甲酯、乙烯-α烯烃共聚物、乙烯均聚物、聚乙烯醇缩丁醛酯、有机硅树脂和聚氨酯树脂组成的组中的一种或多种。
优选地，上述热塑性聚合树脂为乙烯-α烯烃共聚物。相比于其它聚合物，乙烯-α烯烃共聚物具有更优异的水汽阻隔性能，较高的绝缘性能和较高的透光性，因而选用其作为热塑性聚合树脂有利于进一步提高胶膜的水汽阻隔性能、绝缘性和透光率。更优选地，乙烯-α-烯烃共聚物为乙烯与碳原子数≤10的α-烯烃的共聚物，其中碳原子数≤10的α-烯烃选自丙烯、1-丁烯、1-己烯、1-戊烯、1-辛烯和4-甲基-1-戊烯组成的组中的一种或多种；进一步优选地，碳原子数≤10的α-烯烃为1-丁烯和/或1-辛烯。
在一种优选的实施例中，乙烯-α烯烃共聚物的密度为0.86～0.89g/cm 3，更优选为0.87～0.88g/cm 3。若共聚物的密度过高，则有可能影响胶膜的透光率；若密度过低，则有可能热塑性聚合树脂发粘，影响加工性能。在一种优选的实施例中，乙烯-α烯烃共聚物和乙烯均聚物的熔融指数为1～40g/10min，更优选为3～30g/10min，进一步优选为5～25g/10min。若热塑性聚合树脂的熔融指数过低则会造成胶膜成型困难，也会造成和玻璃等基材的浸润性降低，从而使粘接力降低；若熔融指数过高，封装胶膜在生产过程中容易和胶膜或压花辊粘连，另外电子器件在压合过程中，聚合物因熔融后流动性高而产生边缘溢胶的现象。将乙烯-α烯烃共聚物和乙烯均聚物的熔融指数限定在上述范围，有利于提高胶膜的成型性、与基材的粘合力以及胶膜产品的美观性。
在一种优选的实施例中，上述组合物还包括引发剂和交联剂，更优选地，以100重量份热塑性聚合树脂计，上述组合物包括0.1～1份引发剂和0.1～1.5份交联剂。在自由基引发剂和交联剂的作用下，热塑性聚合树脂和抗静电剂发生聚合，并形成分子内氢键，极性基团内收，分子表面多为非极性基团，不易吸附在容器内壁或管道表面，因此采用上述组合物制得的胶膜的电导率衰减较慢。因而将上述组合物中各组分的用量限定在上述范围内制得的胶膜不仅具有较好的抗静电性能，还具有较好的绝缘性能。更优选地，以100重量份热塑性聚合树脂计，上述组合物还包括0.2～0.9份引发剂和0.2～1.2份交联剂；进一步优选地，以100重量份热塑性聚合树脂计，该组合物还包括0.3～0.7份引发剂和0.3～1份交联剂。
自由基引发剂是指能够在光、热等能量输入下形成活性自由基，从而引发聚合物的交联反应。本申请提供的上述形成胶膜的组合物中，自由基引发剂包括光引发剂和过氧化物。在上述组合物中同时加入光引发剂和过氧化物，有利于提高上述组合物的反应活性，从而有利于进一步提高其交联度，进而提高胶膜的综合性能。
上述光引发剂和过氧化物可以选用本申请常用的种类。优选地，光引发剂包括但不限于二苯甲酮、苯并蒽酮、苯偶姻、苯偶姻烷基醚、2,2-二乙氧基苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、对苯氧基二氯苯乙酮、2-羟基异丙基-苯基酮、1-苯基丙二酮-2-(乙氧基羰基)肟、(2,4,6-三甲基苯甲酰基)二苯基氧化磷
Figure PCTCN2020109633-appb-000003
苯基双(2,4,6-三甲基苯甲酰基)氧化磷
Figure PCTCN2020109633-appb-000004
2,2-二甲氧基-1,2-二苯乙酮(
Figure PCTCN2020109633-appb-000005
651)、2-乙氧基-1,2-二苯 乙酮、2,2-二乙氧基-2-苯基苯乙酮、2,2-二乙氧基苯乙酮、2-羟基环己基苯基酮
Figure PCTCN2020109633-appb-000006
2-羟基异丙基苯基酮
Figure PCTCN2020109633-appb-000007
2-羟基-1-[4-(2-羟基乙氧基)苯基]-2-甲基-1-丙酮
Figure PCTCN2020109633-appb-000008
2-甲基-1-(4-甲巯基苯基)-吗啉-1-丙酮
Figure PCTCN2020109633-appb-000009
和2-苯基-2,2-二甲氨基-1-(4-吗啉苯基)-1-丁酮(
Figure PCTCN2020109633-appb-000010
369)组成的组中的一种或多种。优选地，过氧化物包括但不限于过氧化二酰、二烷基过氧化物、过氧化酯、过氧化缩酮中的一种或多种混合物。在这些有机过氧化物中可以列举出过氧化苯甲酸叔丁酯、过氧化苯甲酸叔戊酯、过氧化醋酸叔丁酯、过氧化醋酸叔戊酯、过氧化-3，5，5-三甲基己酸叔丁酯、过氧化-3，5，5-三甲基己酸叔戊酯、2，5-二甲基-2，5-双(苯甲酰过氧)-己烷、过氧化异丙基碳酸叔丁酯、过氧化物-2-乙基己基碳酸叔丁酯、过氧化-2-乙基己基碳酸叔戊酯、过氧化异丁酸叔戊酯、3，3-双(叔丁基过氧)丁酸乙酯、3，3-双(叔戊基过氧)丁酸乙酯、4，4-双(叔丁基过氧)戊酸正丁酯、2，2-双(叔丁基过氧)丁烷、1，1-双(叔丁基过氧)环己烷、1，1-双(叔丁基过氧)-3，3，5-三甲基环己烷、1，1-双(叔戊基过氧)环己烷、1，1-双(叔戊基过氧)-3，3，5-三甲基环己烷。其中，优选过氧化-2-乙基己基碳酸叔丁酯、过氧化-2-乙基己基碳酸叔戊酯、过氧化-3，5，5-三甲基己酸叔丁酯、1，1-双(叔丁基过氧)-3，3，5-三甲基环己烷。
交联剂是具有多个烯属不饱和基团的分子，可以促进聚合物交联，达到更高的交联度。上述组合物中交联剂可以选用本领域常用的种类，优选为三烯丙基异氰脲酸酯、三烯丙基氰脲酸酯、三聚氰酸三烯丙酯、三羟甲基丙烷三丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯、季戊四醇三丙烯酸酯、乙氧基化甘油三丙酸酯、四羟甲基甲烷三丙烯酸酯、乙氧基化季戊四醇四丙烯酸酯、二羟甲基丙烷四丙烯酸酯、三羟甲基乙烷三甲基丙烯酸酯、季戊四醇四丙烯酸酯、四羟甲基甲烷四丙烯酸酯、二-三羟甲基丙烷四丙烯酸酯、季戊四醇四甲基丙烯酸酯、四羟甲基甲烷四甲基丙烯酸酯、二-三羟甲基丙烷四甲基丙烯酸酯、二季戊四醇聚丙烯酸酯、二季戊四醇六丙烯酸酯、二季戊四醇聚甲基丙烯酸酯、二季戊四醇六甲基丙烯酸酯、二乙二醇二甲基丙烯酸酯、1,6-己二醇二丙烯酸酯组成的组中的一种或多种，更优选为三烯丙基异氰脲酸酯。
在一种优选的实施例中，以100重量份热塑性聚合树脂计，上述组合物还包括0.1～0.8份增粘剂。增粘剂的用量包括但不限上述范围，而将其限定在上述范围内有利于进一步提高胶膜与基材的附着力。更优选地，以100重量份热塑性聚合树脂计，上述组合物包括为0.15～0.6份增粘剂，进一步优选地，以100重量份热塑性聚合树脂计，上述组合物包括0.2～0.5份增粘剂。
上述增粘剂可以选用本领域常用的种类。在一种优选的实施例中，增粘剂为具有至少一个烯属不饱和基团和至少一个可水解基团的硅烷偶联剂。烯属基团的引入可以使增粘剂和聚合物发生化学结合，可水解基团(比如甲氧基或乙氧基)的引入，使得增粘剂在加热过程中可以和基板或电子器件发生粘接作用。更优选地，各烯属不饱和基团分别独立地选自乙烯基、烯丙基或γ-(甲基)丙烯酰氧基丙基，各可水解基团分别独立地选自甲氧基或乙氧基；增粘 剂选自γ-甲基丙烯酰氧基丙基三甲氧基硅烷、乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、烯丙基三甲氧基硅烷和烯丙基三乙氧基硅烷组成的组中的一种或多种。
为了进一步提高胶膜的综合性能，还可以在上述组合物中加入一些助剂。在一种优选的实施例中，上述助剂包括光稳定剂、抗氧剂、紫外线吸收剂、增塑剂、抗腐蚀剂、颜料和填料组成的组中的一种或多种。
光稳定剂是用来提高封装胶膜在长期紫外线辐照下的稳定性。优选地，光稳定剂为受阻胺系化合物。更优选地，上述光稳定剂包括但不限于双(2,2,6,6-四甲基-4-哌啶基)癸二酸酯、双(1-辛氧基-2,2,6,6-四甲基-4-哌啶基)癸二酸酯、4-(甲基)丙烯酰氧基-2,2,6,6-四甲基哌啶与α-烯类单体聚合得到的接枝共聚物、4-羟基-2,2,6,6-四甲基-1-哌啶醇、3,5-二叔丁基-4-羟基-苯甲酸十六烷基酯、葵二酸双-2,2,6,6-四甲基哌啶醇和三(1,2,2,6,6-五甲基-4-哌啶基)亚磷酸酯组成的组中的一种或多种。为了进一步提高胶膜的光稳定性，优选地，以100重量份热塑性聚合树脂计，上述组合物中，光稳定剂的用量为0.02～0.8份，优选为0.05～0.6份，更优选为0.1～0.5份。
抗氧剂用来提高聚合物挤出加工过程，以及长期使用过程中的稳定性，延缓因为热氧的作用下而发生降解。在一种优选的实施例中，抗氧剂为受阻酚系化合物和/或亚磷酸酯系化合物。相比于其它抗氧剂，上述抗氧剂具有较好的稳定性和抗氧化性能。更优选地，受阻酚系化合物包括但不限于2,6-二-叔丁基-4-乙基苯酚、2,2’-亚甲基-双-(4-甲基-6-叔丁基苯酚)、2,2’-亚甲基-双-(4-乙基-6-叔丁基苯酚)、4,4’-亚丁基-双-(3-甲基-6-叔丁基苯酚)、十八烷基-3-(3,5-二-叔丁基-4-羟基苯基)丙酸酯、季戊四醇-四[3-(3,5-二-叔丁基-4-羟基苯基)丙酸酯]、7-十八烷基-3-(4’-羟基-3’,5’-二-叔丁基苯基)丙酸酯、四-[亚甲基-3-(3’,5’-二-叔丁基-4’-羟基苯基)丙酸酯]甲烷组成的组中的一种或多种；亚磷酸酯系化合物包括但不限于三(2,4-二-叔丁基苯基)亚磷酸酯、双[2,4-双(1,1-二甲基乙基)-6-甲基苯基]乙基酯亚磷酸、四(2,4-二-叔丁基苯基)[1,1-连苯基]-4,4’-二基双亚磷酸酯和双(2,4-二-叔丁基苯基)季戊四醇二亚磷酸酯组成的组中的一种或多种。为了进一步提高胶膜的抗氧化性能，优选地，以100重量份热塑性聚合树脂计，上述组合物中，抗氧剂的用量为0.005～0.5份，更优选为0.01～0.4份，进一步优选为0.02～0.3份，更进一步优选为0.03～0.2份。
紫外光吸收剂是指能够在吸收大部分的紫外线能量，转换成热量的物质，从而保护某些电子器件不被紫外线所破坏。在一种优选的实施例中，上述紫外光吸收剂选自二苯甲酮类和/或苯并三唑类物质，更优选地，紫外光吸收剂包括但不限于2-羟基-4-正辛氧基二苯甲酮、2,2-四亚甲基双(3,1-苯并噁嗪-4-酮)、2-(2’-羟基-5-甲基苯基)苯并三唑、2,2’-二羟基-4,4’-二甲氧基二苯甲酮、2-(2’-羟基-3’,5’-二[1,1-二甲基苯基]苯基)-苯并三唑、2-(2’-羟基-3’-叔丁基-5’-甲基苯基)-5-氯苯并三唑、2-(2’-羟基-3’，5’二叔丁基苯基)-5-氯苯并三唑和2-(2’-羟基-3’，5’二叔戊基苯基)-苯并三唑组成的组中的一种或多种。为了进一步提高其形成的胶膜的抗紫外线性能，在一种优选的实施例中，以100重量份热塑性聚合树脂计，上述组合物中，紫外光吸收剂的用量为0.05～0.5份，更优选为0.1～0.4份，进一步优选为0.2～0.3份。
增塑剂是在加工过程中，能够减小聚合物分子与分子之间的作用力，以及减少聚合物熔体与金属表面的摩擦力，使得聚合物塑性增强，便于加工。在一种优选的实施例中，增塑剂包括但不限于邻苯二甲酸酯类有机物、脂肪族二元酸酯类有机物、磷酸酯类有机物、聚乙烯蜡类有机物和硬脂酸酸类有机物组成的组中的一种或多种；更优选地，增塑剂包括但不限于聚乙烯蜡、磷酸三烷基酯、磷酸三芳基酯、癸二酸二辛酯、己二酸二辛酯、十二烷二羧酸酯、邻苯二甲酸二辛酯、邻苯二甲酸二丁酯、硬脂酸、硬脂酸锌和硬脂酸钙组成的组中的一种或多种，且增塑剂的数均分子量为2000～10000。为了进一步提高胶膜的加工性能，在一种优选的实施例中，以100重量份热塑性聚合树脂计，上述组合物中，增塑剂的用量为0.01～5份，更优选为0.05～4份，进一步优选为0.1～3份，更进一步优选为0.3～2份。
抗腐蚀剂指可以吸收胶膜中游离酸的物质，包括金属氧化物和金属氢氧化物。金属氧化物优选为氧化镁、氧化锌和氧化钙组成的组中的一种或多种；氢氧化物优选为氢氧化镁和/或氢氧化钙。在一种优选的实施例中，以100重量份热塑性聚合树脂计，上述组合物中，抗腐蚀剂的用量为0.05～0.3份，优选为0.08～0.2份。
颜料是能够使封装胶膜着色，而又具有透光性，因此可以使得封装的电子器件变得美观。颜料包含无机颜料和有机颜料，可选自铁镍黄、钛铬棕、钴绿、铁红、铁黄、钴蓝、铜铬黑、群青蓝、靛蓝、朱砂、雄黄、镉红、镉黄、铁蓝、立德粉、氧化铁红、氧化铁黄中的任意一种或多种混合物。
在一种优选的实施例中，以100重量份热塑性聚合树脂计，上述组合物中，颜料的用量为0.1～10份，更优选为0.5～8份，进一步优选为1～7份，更进一步优选为2～6份。
填料是能够赋予封装胶膜具有反光性能或吸光性能的无机物，优选为钛白粉、碳酸钙、锌钡白、三氧化二铝、掺铝氧化锌、氧化铟锡、氧化二锑、硫酸钡、蒙脱土、高岭土、滑石粉、长石粉、炭黑组成的组中的一种或多种。为了进一步提高胶膜的反射率，从而提高电子器件的功率，更优选地，填料的用量为1～40份，优选为2～30份，更优选为3～20份，再优选为4～15份。
本申请的另一方面还提供了一种胶膜，胶膜采用本申请提供的上述组合物经熔融挤出工艺制得。式(Ⅰ)所示的抗静电剂含有强极性酰胺基，酰胺基团能够形成分子内氢键的键长较短，电离后形成的正负离子产生的偶极电场强，能够抵消外静电场产生的电压强，因而具有较好的抗静电性能。热塑性聚合树脂具有良好的热加工性能，将其与式(Ⅰ)所示的抗静电剂进行熔融挤出后能够形成较好的抗静电性能的胶膜。
优选地，本发明所提供的电子器件封装胶膜的厚度在0.1～0.8mm之间，具有低的表面电阻，可防止静电的积累，适用于多种电子器件，尤其是太阳能电池模块的封装。
本申请的又一方面还提供了一种电子器件，包括封装胶膜，封装胶膜包括本申请提供的胶膜。
本申请提供的上述胶膜不仅具有较好的抗静电作用，同时还能保证胶膜的良好的绝缘性。选用及作为封装胶膜能够大大提高电子器件的综合性能。
本发明提供的再一方面还提供了一种电子器件封装胶膜的制备方法，包括：
(1)混料。在混合器中，将除热塑性聚合树脂颗粒之外的原料以液体形式(液体添加剂或固体添加剂溶解于溶剂中形成溶液)连续喷射入热塑性聚合树脂颗粒，同时搅拌数小时或使混合物保持混合运动，直至该液体完全被聚合物粒子吸收。也可以通过造粒机将固体或者液体助剂与聚合物粒子进行造粒形成母粒，再以母粒的形式添加到聚合物颗粒中。
(2)将混好的物料加入到螺杆挤出机中，通过螺杆挤出机将该混合好的组合物熔融、啮合使反应原料混合均匀。在挤出机的末端，使熔体经过宽缝式喷嘴压出。在喷嘴之后借助压花滚和胶辊进行表面压花，再经过冷却辊冷却后收卷，形成卷状的胶膜，从而完成本发明。
以下结合具体实施例对本申请作进一步详细描述，这些实施例不能理解为限制本申请所要求保护的范围。
以下结合具体实施例对本申请作进一步详细描述，这些实施例不能理解为限制本申请所要求保护的范围。
实施例1
称取0.005份丙烯酰胺，用适量的无水乙醇溶解，形成溶液；将溶液均匀的喷洒入100份POE粒子(DOW Engage 8669，熔融指数14g/10min，密度0.873g/cc)中并进行搅拌，直至乙醇挥发，POE粒子表面干燥。将干燥的POE粒子加入单螺杆挤出机，通过螺杆的熔融剪切作用形成均匀的POE熔体，在通过一个宽缝式喷嘴挤出成膜，通过压花辊和胶辊的挤压作用在膜的表面形成纹理结构，然后经过数个冷却辊进行冷却，最后通过收卷辊进行收卷。膜的厚度为0.5mm。
实施例2
称取0.3份油酸酰胺，用适量的无水乙醇溶解，形成溶液；将溶液均匀的喷洒入100份POE粒子(DOW Engage 8669)中并进行搅拌，直至乙醇挥发，POE粒子表面干燥。将干燥的POE粒子加入单螺杆挤出机，通过螺杆的熔融剪切作用形成均匀的POE熔体，在通过一个宽缝式喷嘴挤出成膜，通过压花辊和胶辊的挤压作用在膜的表面形成纹理结构，然后经过数个冷却辊进行冷却，最后通过收卷辊进行收卷。膜的厚度为0.5mm。
实施例3
称取0.05份N-羟甲基丙烯酰胺、0.6份过氧化2-乙基己基碳酸叔丁酯(TBEC)、0.5份三烯丙基异氰脲酸酯(TAIC)、0.25份γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH570)、0.1份癸二酸双-2,2,6,6-四甲基哌啶醇酯(Tinuvin 770)、0.2份2-羟基-4-正辛氧基二苯甲酮(Cyasorb 531)用适量的无水乙醇溶解，形成溶液；将溶液均匀的喷洒入100份POE粒子(DOW Engage  8669)中并进行搅拌，直至乙醇挥发，POE粒子表面干燥。将干燥的POE粒子加入单螺杆挤出机，通过螺杆的熔融剪切作用形成均匀的POE熔体，在通过一个宽缝式喷嘴挤出成膜，通过压花辊和胶辊的挤压作用在膜的表面形成纹理结构，然后经过数个冷却辊进行冷却，最后通过收卷辊进行收卷得到透明的胶膜。膜的厚度为0.5mm。
实施例4
称取0.02份N,N’-亚甲基双丙烯酰胺、0.7份二苯甲酮(BP)、0.4份三烯丙基异氰脲酸酯(TAIC)、0.4份三羟甲基丙烷三丙烯酸酯(TMPTA)、0.25份γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH570)、0.1份癸二酸双-2,2,6,6-四甲基哌啶醇酯(Tinuvin 770)，用适量的无水乙醇溶解，形成溶液；将1份氧化铁红、1份氧化铁黄、0.5份聚乙烯蜡和100份POE粒子(DOW Engage 8669)通过双螺杆造粒机进行混合造粒形成橙色透明的造粒粒子；将预先制备好的溶液均匀的喷洒入预先制备好的造粒粒子中并进行搅拌，直至乙醇挥发，POE粒子表面干燥。将干燥的POE粒子加入单螺杆挤出机，通过螺杆的熔融剪切作用形成均匀的POE熔体，在通过一个宽缝式喷嘴挤出成膜，通过压花辊和胶辊的挤压作用在膜的表面形成纹理结构，然后经过数个冷却辊进行冷却，最后通过收卷辊进行收卷得到橙色透明的胶膜。膜的厚度为0.5mm。
实施例5
称取0.1份马来酰亚胺、0.5份过氧化2-乙基己基碳酸叔丁酯(TBEC)、0.5份三烯丙基异氰脲酸酯(TAIC)、0.5份三羟甲基丙烷三丙烯酸酯(TMPTA)、0.25份γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH570)、0.07份癸二酸双-2,2,6,6-四甲基哌啶醇酯(Tinuvin 770)，用适量的无水乙醇溶解，形成溶液；将7份钛白粉和100份POE粒子(DOW Engage 8669)通过双螺杆造粒机进行混合造粒形成白色的造粒粒子；将预先制备好的溶液均匀的喷洒入预先制备好的造粒粒子中并进行搅拌，直至乙醇挥发，POE粒子表面干燥。将干燥的POE粒子加入单螺杆挤出机，通过螺杆的熔融剪切作用形成均匀的POE熔体，在通过一个宽缝式喷嘴挤出成膜，通过压花辊和胶辊的挤压作用在膜的表面形成纹理结构，然后经过数个冷却辊进行冷却，最后通过收卷辊进行收卷得到白色的胶膜。膜的厚度为0.5mm。
实施例6
与实施例3的区别为：抗静电剂为丙烯酰胺。
实施例7
与实施例3的区别为：抗静电剂为二甲胺基丙基丙烯酰胺。
实施例8
与实施例3的区别为：抗静电剂为双丙酮丙烯酰胺。
实施例9
与实施例3的区别为：抗静电剂为4-丙烯酰吗啉。
实施例10
与实施例3的区别为：抗静电剂为油酸酰胺。
实施例12
与实施例3的区别为：热塑性聚合树脂为乙烯-丙烯烃共聚物，密度为0.88g/cm 3,熔融指数为30g/10min。
实施例13
与实施例3的区别为：热塑性树脂为乙烯-甲基丙烯酸甲酯。
实施例14
与实施例3的区别为：不加入增粘剂。
实施例15
与实施例3的区别为：增粘剂为丙烯基三乙氧基硅烷。
对比例1
形成胶膜的材料只包含POE颗粒，和实施例1的制备方法相同，得到表面带有花纹的胶膜，且膜的厚度均为0.5mm。
对比例2
与实施例3的区别为：不加入抗静电剂，实施例3的制备方法相同，得到表面带有花纹的胶膜，且膜的厚度均为0.5mm。
对比例3
与实施例4的区别为：不加入抗静电剂，实施例3的制备方法相同，得到表面带有花纹的胶膜，且膜的厚度均为0.5mm。
测定方法
(1)体积电阻率
将所得的片裁切成10cm×10cm的尺寸，以150℃、真空5分钟、加压13分钟，使用层压装置进行层压，以使得胶膜表面花纹除去，得到表面平整的胶膜，另一方面使得胶膜发生交联反应，(如果添加有交联剂)。另一方面，实施例4和对比例3的胶膜再通过紫外光辐照，辐照剂量5J/cm 2；实施例5的胶膜通过电子束的辐照，辐照剂量为5kGy。
依照IEC62788-1-2 method A，在施加电压1000V，极化1小时下测定所制得的胶片的体积电阻率(Ω·cm)，结果在表1；
(2)表面电阻率
将所得的片裁切成10cm×10cm的尺寸，以150℃、真空5分钟、加压13分钟，使用层压装置进行层压，以使得胶膜表面花纹除去，得到表面平整的胶膜，另一方面使得胶膜发生交联反应，(如果添加有交联剂)。另一方面，实施例4和对比例3的胶膜再通过紫外光辐照，辐照剂量5J/cm 2；实施例5的胶膜通过电子束的辐照，辐照剂量为5kGy。
依照GB/T 1410-2006，在施加电压1000V，极化10分钟下测定所制得的胶片的表面电阻率Ω，结果在表1；
(3)交联度
将所得的片裁切成10cm×10cm的尺寸，以150℃、真空5分钟、加压13分钟，使用层压装置进行层压，以使得胶膜表面花纹除去，得到表面平整的胶膜，另一方面使得胶膜发生交联反应，(如果添加有交联剂)。另一方面，实施例4和对比例3的胶膜再通过紫外光辐照，辐照剂量5J/cm 2；实施例5的胶膜通过电子束的辐照，辐照剂量为5kGy。
称取所制得的胶片约1g(记称量值为A(g)),利用沸腾的二甲苯进行索氏提取5小时，用30目的不锈钢过滤网过滤后，将网在145℃进行3小时减压干燥，算出网上的残存量B(g)，使用下述式计算出交联度。交联度(重量％)＝B/A×100％。实施例1至15及对比例1至3中形成的胶膜的测试结果见表1。
表1
  交联度％ 体积电阻率，10 16[Ω.cm] 表面电阻率，10 15Ω
实施例1 0 6.9 7.3
实施例2 0 74 5.1
实施例3 75 23 9.2
实施例4 70 18 4.9
实施例5 74 12 21
实施例6 75 11 10.6
实施例7 76 21 8.5
实施例8 76 20 9.2
实施例9 76 19 10.4
实施例10 75 17 11
实施例11 74 22 21
实施例12 69 21 15
实施例13 68 1.5 14
实施例14 71 20 15.5
实施例15 78 26 15
对比例1 0 7.1 66
对比例2 76 38 45
对比例3 71 27 52
从以上的描述中，可以看出，本发明上述的实施例实现了如下技术效果：
比较实施例1至15及对比例1至3可知，采用本申请提供的组合物制得的胶膜具有较高的交联度和抗静电性能。
比较实施例1至11可知，采用本申请优选的抗静电剂有利于提高胶膜的抗静电性能。
比较实施例3和12及13可知，选用特定的热塑性树脂有利于提高胶膜的综合性能。
比较实施例3、14和15可知，选用本申请优选的增粘剂有利于提高胶膜的综合性能。
需要说明的是，本申请的说明书和权利要求书中的术语“第一”、“第二”等是用于区别类似的对象，而不必用于描述特定的顺序或先后次序。应该理解这样使用的术语在适当情况下可以互换，以便这里描述的本申请的实施方式例如能够以除了在这里描述的那些以外的顺序实施。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (21)

  1. 一种形成胶膜的组合物，其特征在于，所述组合物包括：热塑性聚合树脂和抗静电剂，其中所述抗静电剂为式(Ⅰ)所示的酰胺类有机物，
    Figure PCTCN2020109633-appb-100001
    所述R 1为H、基团A、基团A中至少一个氢原子被羟基、氨基或环氧基取代形成的取代基或基团A中至少一个亚甲基被羰基或醚键取代形成的取代基，所述基团A为直链烷基、支链烷基或环烷基，且所述基团A的碳原子数≤10；
    所述R 2为直链烷基、支链烷基、环烷基或烯基，且所述R 2的碳原子数为2～20。
  2. 根据权利要求1所述的组合物，其特征在于，所述R 2选自乙烯基、丙烯基、丁烯基、戊烯基、己烯基、庚烯基、辛烯基、十烯基、十一烯基、十二烯基、十四烯基、十六烯基或十八烯基。
  3. 根据权利要求2所述的组合物，其特征在于，所述抗静电剂选自丙烯酰胺、甲基丙烯酰胺、N-甲基丙烯酰胺、N-乙基丙烯酰胺、N-异丙基丙烯酰胺、N-叔丁基丙烯酰胺、二甲胺基丙基丙烯酰胺、N-(3-二甲胺基丙基)甲基丙烯酰胺、N-(丁氧基甲基)-丙烯酰胺、N-(3-氨丙基)甲基丙烯酰胺、双丙酮丙烯酰胺、4-丙烯酰吗啉、N-羟甲基丙烯酰胺、N-羟乙基丙烯酰胺、N-(2-羟基丙基)丙烯酰胺、N,N’-亚甲基双丙烯酰胺、N，N’-二亚基双丙烯酰胺、马来酰亚胺、琥珀酰胺、油酸酰胺、9-十六碳烯酰胺、N-(2-羟基乙基)-十一碳-10-烯酰胺、9-十四碳烯酰胺、9-十二碳烯酰胺、9-十碳烯酰胺、辛烯酰胺、庚烯酰胺、己烯酰胺、戊烯酰胺和丁烯酰胺组成的组中的一种或多种。
  4. 根据权利要求1至3中任一项所述的组合物，其特征在于，以100重量份所述热塑性聚合树脂计，所述组合物还包括：0.005～0.3份所述抗静电剂。
  5. 根据权利要求4所述的组合物，其特征在于，以100重量份所述热塑性聚合树脂计，所述组合物还包括：0.01～0.2份所述抗静电剂。
  6. 根据权利要求5所述的组合物，其特征在于，以100重量份所述热塑性聚合树脂计，所述组合物还包括：0.02～0.1份所述抗静电剂。
  7. 根据权利要求4所述的组合物，其特征在于，所述热塑性聚合树脂选自乙烯-醋酸乙烯酯共聚物、乙烯-甲基丙烯酸甲酯、乙烯-α烯烃共聚物、乙烯均聚物、聚乙烯醇缩丁醛酯、有机硅树脂和聚氨酯树脂组成的组中的一种或多种。
  8. 根据权利要求7所述的组合物，其特征在于，所述乙烯-α烯烃共聚物的密度为0.86～0.89g/cm 3，所述乙烯-α烯烃共聚物和所述乙烯均聚物的熔融指数为1～40g/10min。
  9. 根据权利要求8所述的组合物，其特征在于，所述乙烯-α烯烃共聚物的密度为0.87～0.88g/cm 3；所述乙烯-α烯烃共聚物和所述乙烯均聚物的熔融指数为3～30g/10min。
  10. 根据权利要求9所述的组合物，其特征在于，所述乙烯-α烯烃共聚物和所述乙烯均聚物的熔融指数为5～25g/10min。
  11. 根据权利要求7所述的组合物，其特征在于，所述乙烯-α-烯烃共聚物为乙烯与碳原子数≤10的α-烯烃的共聚物，其中所述碳原子数≤10的α-烯烃选自丙烯、1-丁烯、1-己烯、1-戊烯、1-辛烯和4-甲基-1-戊烯组成的组中的一种或多种。
  12. 根据权利要求5至11中任一项所述的组合物，其特征在于，以100重量份所述热塑性聚合树脂计，所述组合物还包括0.1～1份引发剂和0.1～1.5份交联剂。
  13. 根据权利要求12所述的组合物，其特征在于，以100重量份所述热塑性聚合树脂计，所述组合物还包括0.2～0.9份所述引发剂和0.2～1.2份所述交联剂。
  14. 根据权利要求13所述的组合物，其特征在于，以100重量份所述热塑性聚合树脂计，所述组合物还包括0.3～0.7份所述引发剂和0.3～1份所述交联剂。
  15. 根据权利要求12所述的组合物，其特征在于，以100重量份所述热塑性聚合树脂计，所述组合物还包括0.1～0.8份增粘剂。
  16. 根据权利要求15所述的组合物，其特征在于，所述增粘剂为具有至少一个烯属不饱和基团和至少一个可水解基团的硅烷偶联剂。
  17. 根据权利要求16所述的组合物，其特征在于，各所述烯属不饱和基团分别独立地选自乙烯基、烯丙基或γ-(甲基)丙烯酰氧基丙基，各所述可水解基团分别独立地选自甲氧基或乙氧基。
  18. 根据权利要求17所述的组合物，其特征在于，所述增粘剂选自γ-甲基丙烯酰氧基丙基三甲氧基硅烷、乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、烯丙基三甲氧基硅烷和烯丙基三乙氧基硅烷组成的组中的一种或多种。
  19. 根据权利要求12所述的组合物，其特征在于，所述组合物还包括光稳定剂、抗氧剂、紫外线吸收剂、增塑剂、抗腐蚀剂、颜料和填料中的一种或多种。
  20. 一种胶膜，其特征在于，所述胶膜采用权利要求1至19中任一项所述的组合物经熔融挤出工艺制得。
  21. 一种电子器件，包括封装胶膜，其特征在于，所述封装胶膜包括权利要求20所述的胶膜。
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