Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
• • 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
  • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
  • C09J175/04—Polyurethanes
  • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
  • C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
  • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/44—Polycarbonates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/67—Unsaturated compounds having active hydrogen
  • C08G18/68—Unsaturated polyesters
  • C08G18/683—Unsaturated polyesters containing cyclic groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/81—Unsaturated isocyanates or isothiocyanates
  • C08G18/8108—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group
  • C08G18/8116—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group esters of acrylic or alkylacrylic acid having only one isocyanate or isothiocyanate group
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
  • C08L75/04—Polyurethanes
• • 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
  • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
  • C09J175/04—Polyurethanes
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
  • H10F19/00—Integrated devices, or assemblies of multiple devices, comprising at least one photovoltaic cell covered by group H10F10/00, e.g. photovoltaic modules
  • H10F19/80—Encapsulations or containers for integrated devices, or assemblies of multiple devices, having photovoltaic cells
  • H10F19/85—Protective back sheets
• • 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
• • 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
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31511—Of epoxy ether
  • Y10T428/31515—As intermediate layer
• • 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
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31511—Of epoxy ether
  • Y10T428/31515—As intermediate layer
  • Y10T428/31522—Next to metal
• • 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
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]

Definitions

• the present invention relates to an active energy ray-curable urethane resin suitably used for, for example, adhesives, inks, paints, and the like. Specifically, the present invention relates to an active energy ray-curable urethane resin suitable for an active energy ray-curable adhesive for forming a back surface protection sheet for solar cells.
• the present invention relates to an active energy ray-curable adhesive that makes it possible to produce a solar cell back surface protective sheet excellent in adhesive strength between sheets and wet heat resistance with high yield and productivity and at low cost.
• These solar cells are provided with a back surface protection sheet on the surface opposite to the surface on which sunlight is incident for the purpose of protecting the solar cell elements.
• Performances such as weather resistance, water vapor permeability, electrical insulation, mechanical properties, and mounting workability are required for the back protective sheet for solar cells.
• a laminate of several kinds of sheet-like members is generally used.
• a hydroxyl group-containing resin as a main component and an isocyanate compound as a curing agent are included.
• Use included polyurethane adhesive are included.
• the isocyanate compound as the curing agent not only reacts with the hydroxyl group-containing resin as the main agent, but also reacts with water in the air. Since the addition reaction product of the isocyanate compound and water causes a decarboxylation reaction, bubbles are generated in the adhesive layer after the sheet-like members are laminated. Therefore, the process using the polyurethane-based adhesive also has a problem that appearance defects and delamination occur.
• Japanese Patent Application Laid-Open No. 2008-127475 reacts a polycarbonate diol, a bifunctional epoxy (meth) acrylate having two hydroxyl groups and two ethylenically unsaturated groups in one molecule, and a polyisocyanate.
• An active energy ray-curable resin adhesive obtained by mixing an unsaturated group-containing urethane resin with a photopolymerization initiator is disclosed.
• this was used as an adhesive for a solar cell back surface protective sheet, the adhesive strength between the sheet-like members and the heat and humidity resistance were not sufficient.
• An object of the present invention is to provide an active energy ray-curable composition that can produce a solar cell back surface protection sheet excellent in adhesion between sheet-like members and heat-and-moisture resistance with high yield and productivity and at low cost. There is to do.
• 1st invention is the diol component (A1) which does not have a (meth) acryloyl group, Comprising: Diol (a1) which has a carbonate structure and an alicyclic structure in 1 molecule, An alicyclic structure A combination of a diol (a2) having no carbonate structure and a diol (a3) not having a carbonate structure and having an alicyclic structure, and the diol (a1) And a diol component (A1) selected from the group consisting of a combination of at least one of the diol (a2) and the diol (a3), a (meth) acryloyl group, a carbonate structure, and an alicyclic structure.
• Diol (a1) which has a carbonate structure and an alicyclic structure in 1 molecule
• An alicyclic structure A combination of a diol (a2) having no carbonate structure and a diol (a3) not having a carbonate structure and having an alicycl
• Optional diol component (A2) a polyol component (B) having a (meth) acryloyl group and two or more hydroxyl groups in one molecule, and a polyisocyanate component (C) Made by response to a urethane resin (D) having a (meth) acryloyl groups.
• the second invention relates to the urethane resin (D) according to the invention having a glass transition temperature in the range of ⁇ 60 to ⁇ 10 ° C.
• the third invention relates to the urethane resin (D) according to any one of the inventions having a number average molecular weight in the range of 5000 to 150,000.
• the fourth invention relates to the urethane resin (D) according to any one of the above inventions, wherein the polyol component (B) has two or more (meth) acryloyl groups.
• the fifth invention relates to the urethane resin (D) according to the fourth invention, wherein the polyol component (B) is a compound obtained by adding (meth) acrylic acid to an epoxy group of a compound having two or more epoxy groups.
• the sixth invention relates to the urethane resin (D) according to any one of the above inventions, wherein the (meth) acryloyl group equivalent is in the range of 500 to 40,000.
• the seventh invention relates to an active energy ray-curable adhesive containing the urethane resin (D) according to any of the second to sixth inventions and the epoxy resin (E).
• the eighth invention relates to the active energy ray-curable adhesive according to the invention, wherein the epoxy resin (E) has a number average molecular weight in the range of 500 to 5,000.
• the ninth invention is an active energy ray curable composition according to any one of the above inventions, which contains 5 to 40 parts by weight of an epoxy resin (E) with respect to 100 parts by weight of a urethane resin (D) having a (meth) acryloyl group. It relates to adhesives.
• the tenth invention is an active energy ray curable adhesive layer formed from the active energy ray curable adhesive according to any of the above inventions, and two or more laminated via an activated energy ray curable adhesive layer It is related with the back surface protection sheet for solar cells which comprised this sheet-like member.
• one of the sheet-like members is a metal foil, or a plastic film with a vapor deposition layer in which a metal oxide or a nonmetal inorganic oxide is vapor-deposited on at least one surface of the plastic film. It is related with the back surface protection sheet for solar cells which concerns on the said invention.
• the twelfth invention relates to the solar cell backsheet according to any one of the above inventions, wherein the glass transition temperature of the active energy ray-curable adhesive layer is in the range of ⁇ 20 to 20 ° C.
• the urethane resin (D) having a (meth) acryloyl group includes a diol component (A1) not having a (meth) acryloyl group, a (meth) acryloyl group, a carbonate structure, and an alicyclic structure.
• the diol component (A1) has a carbonate structure and an alicyclic structure in one molecule.
• the diol (a1) does not have an alicyclic structure but has a carbonate structure.
• a combination of two types of diols that is, a diol (a2) and a diol (a3) that does not have a carbonate structure but has an alicyclic structure, and a diol (a1), a diol (a2), and ( It is selected from a combination with at least one of a3).
• the compound when the notation “(meth) acrylo” is used for a certain compound, the compound is obtained by replacing “(meth) acrylo” with “acrylo”, and “ This means that any compound obtained by replacing “(meth) acrylo” with “methacrylo” may be used.
• the expression “(meth) acryl” when the expression “(meth) acryl” is used for a certain functional group, the functional group is a functional group obtained by replacing “(meth) acryl” with “acryl”, and “( It means that any of the functional groups obtained by replacing “meth) acryl” with “methacryl” may be used.
• the compound is a compound in which “(meth) acrylate” is replaced with “acrylate”, and “(meth) acrylate” "Is replaced with” methacrylate "which means any compound.
• the glass transition temperature of the urethane resin (D) is preferably in the range of ⁇ 60 to ⁇ 10 ° C., and more preferably in the range of ⁇ 50 to ⁇ 20 ° C.
• the glass transition temperature is lower than ⁇ 60 ° C.
• the adhesive force between the sheet-like members tends to be reduced during the moisture and heat resistance test.
• the glass transition temperature is higher than ⁇ 10 ° C.
• the glass transition temperature of the urethane resin (D) was measured using a differential scanning calorimeter (DSC) “RDC220” manufactured by Seiko Instruments Inc. Specifically, first, about 10 mg from a sample obtained by drying the urethane resin solution was weighed in an aluminum pan. Next, this was set in a differential scanning calorimetry (DSC) apparatus and cooled to ⁇ 100 ° C. with liquid nitrogen. Then, this was heated up at 10 degrees C / min, and the glass transition temperature was computed from the DSC chart obtained at that time.
• DSC differential scanning calorimeter
• the number average molecular weight (Mn) of the urethane resin (D) is preferably in the range of 5000 to 150,000, and more preferably in the range of 10,000 to 100,000. When the number average molecular weight is less than 5,000, the cohesive force of the adhesive after curing is low, and the adhesive force between the sheet-like members tends to decrease during the moisture and heat resistance test.
• the active energy ray-curable adhesive becomes highly viscous, the solubility with other components constituting the active energy ray-curable adhesive is low, or the curable adhesive layer or
• the curable adhesive layer or When the sheet-like members are stacked with the cured adhesive layer sandwiched therebetween, the wettability of the adhesive to the sheet-like members is poor, and as a result, the adhesive force between the sheet-like members becomes insufficient. It tends to occur.
• the urethane resin (D) preferably has a (meth) acryloyl group equivalent in the range of 500 to 40,000, and in the range of 1000 to 30000, from the viewpoint of compatibility between the adhesion between the sheet-like members and the heat and humidity resistance. More preferably.
• “(meth) acryloyl group equivalent” means dividing the number average molecular weight of the urethane resin (D) by the average number of (meth) acryloyl groups contained in one molecule of the urethane resin (D). It is a value obtained by this.
• the adhesive force between the sheet-like members tends to be insufficient due to curing shrinkage during active energy ray curing.
• the (meth) acryloyl group equivalent is larger than 40000, the adhesive is not sufficiently cross-linked, and the adhesive force between the sheet-like members tends to be reduced during the wet heat resistance test.
• the urethane resin (D) preferably has a urethane bond equivalent in the range of 200 to 3000, more preferably in the range of 250 to 2000, from the viewpoint of the adhesive strength between the sheet-like members and the heat and humidity resistance.
• the “urethane bond equivalent” referred to here is a value obtained by dividing the number average molecular weight of the urethane resin (D) by the average value of the number of urethane bonds contained in one molecule of the urethane resin (D). is there.
• the urethane bond equivalent When the urethane bond equivalent is less than 200, the cohesive force of the curable adhesive layer or the cured adhesive layer is large. Therefore, the sheet-like members are stacked with the curable adhesive layer or the cured adhesive layer interposed therebetween. At this time, the wettability of the adhesive to the sheet-like member is poor, and the adhesive force between the sheet-like members tends to be insufficient. On the other hand, when the urethane bond equivalent is larger than 3000, there are few urethane bonds having good wet heat resistance, and the adhesive force between the sheet-like members tends to decrease after the wet heat resistance test.
• the diol component (A1) having no (meth) acryloyl group used for forming the urethane resin (D) is a diol (a1) having a carbonate structure and an alicyclic structure in one molecule; A combination of a diol (a2) having no alicyclic structure and having a carbonate structure and a diol (a3) not having a carbonate structure and having an alicyclic structure; and It is selected from the group consisting of a combination of diol (a1) and at least one of diols (a2) and (a3).
• the carbonate structure is a structure containing a carbonate group (—O—CO—O— group).
• the urethane resin (D) contains a carbonate group derived from the diol component (A1).
• the concentration is preferably in the range of 2 mmol / g to 8 mmol / g, and more preferably in the range of 3 mmol / g to 7 mmol / g.
• the concentration of the carbonate group mentioned here is 1 g of the total solid content of the diol component (A1), the diol component (A2) that can be used as necessary, the polyol component (B), and the polyisocyanate component (C). It is the amount of carbonate group contained in the inside.
• this concentration is less than 2 mmol / g, the solubility of the urethane resin in the solvent tends to be poor, or sufficient wet heat resistance tends not to be obtained. Moreover, when this concentration is larger than 8 mmol / g, there is a tendency that sufficient adhesive force cannot be obtained.
• the alicyclic structure is a structure containing a carbocyclic ring having no aromaticity.
• the urethane resin (D) contains a carbocycle derived from the diol component (A1).
• the carbocycle a cyclohexane skeleton that is a 6-membered ring is preferable.
• the diol component (A1), the diol component (A2) that can be used as necessary, the polyol component (B), and the diol component relative to the total solid content of the polyisocyanate component (C) (The concentration of the alicyclic skeleton derived from A1) is preferably in the range of 0.05 mmol / g to 5 mmol / g, and more preferably in the range of 0.1 mmol / g to 4.5 mmol / g.
• the concentration of the alicyclic skeleton derived from the diol component (A1) here refers to the diol component (A1), the diol component (A2) that can be used as necessary, the polyol component (B), and the polyisocyanate component (C ) And the alicyclic skeleton derived from the diol component (A1) contained in 1 g of the total solid content.
• this concentration is less than 0.05 mmol / g, sufficient wet heat resistance tends not to be obtained.
• this concentration is larger than 5 mmol / g, there is a tendency that sufficient adhesive force cannot be obtained.
• the diol (a1) having a carbonate structure and an alicyclic structure in one molecule is, for example, at least one kind of diol having no alicyclic structure and a carbonate ester. Is used as a raw material to cause a transesterification reaction.
• diols that do not have a carbonate structure but have an alicyclic structure include 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 2-bis (4 -Hydroxycyclohexyl) -propane, hydrogenated bisphenol A, hydrogenated bisphenol F, or a combination of two or more thereof can be used.
• a diol that does not have a carbonate structure and has an alicyclic structure and a diol that does not have a carbonate structure and an alicyclic structure may be used in combination.
• the diol having no carbonate structure and alicyclic structure include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1, 7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,5-hexanediol, 2-methyl-1,8-octanediol, neopentyl glycol, 2- Isopropyl-1,4-butanediol, 2-ethyl-1,6-hexanediol, 3-methyl-1,5-
• a polycarbonate diol having an alicyclic structure for example, a diol that does not have a carbonate structure and is obtained by copolymerization of a diol having an alicyclic structure and caprolactone may be used.
• examples of such a diol component include ETERNACOLL UC-100, ETERNCOLL UM-90 (3/1), ETERNACOLL UM-90 (1/1), and ETERNACOLL UM-90 (1/3) manufactured by Ube Industries, Ltd. Can be mentioned. These may be used alone or in combination of two or more.
• the diol component (a2) which does not have an alicyclic structure but has a carbonate structure uses, for example, at least one kind of diol not having a carbonate structure and an alicyclic structure and a carbonate as a raw material. It is obtained by causing a transesterification reaction.
• diol having no carbonate structure and alicyclic structure examples include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1, 7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,5-hexanediol, 2-methyl-1,8-octanediol, neopentyl glycol, 2- Isopropyl-1,4-butanediol, 2-ethyl-1,6-hexanediol, 3-methyl-1,5-pentanediol, 2,4-dimethyl-1,5-pentanediol, 2,4-diethyl- 1,5-pentanediol, 1,3-butanediol, 2-
• the polycarbonate diol which does not have an alicyclic structure for example, the diol obtained by copolymerization of the diol which does not have a carbonate structure and an alicyclic structure, and caprolactone.
• diol components include C-1090, C-2050, C-2090, C-3090 manufactured by Kuraray Co., Ltd., ETERNACOLL UH-50, ETERNACOLL UH-100, ETERNACOLL UH-200 manufactured by Ube Industries, Ltd., ETERNACOLL UH-300, ETERNACOLL UH-50-200, ETERNACOLL UH-50-100, T6002, T6001, T5652 manufactured by Asahi Kasei Chemicals Corporation.
• Examples include T4672, Plaxel CD CD205, Plaxel CD CD205PL, Plaxel CD CD210, Plaxel CD CD210PL, Plaxel CD CD220, Plaxel CD CD220PL manufactured by Daicel Chemical Industries, Ltd. These may be used alone or in combination of two or more.
• Examples of the diol component (a3) not having a carbonate structure and having an alicyclic structure include 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, -Bis (4-hydroxycyclohexyl) -propane, hydrogenated bisphenol A, hydrogenated bisphenol F. These may be used alone or in combination of two or more.
• the diol component (A1) may be used in combination with the diol component (A2) that does not have any (meth) acryloyl group, carbonate structure, or alicyclic structure.
• the diol component (A2) can be omitted, but the diol component (A2) can be used for adjusting the glass transition temperature of the urethane resin (D).
• diol component (A2) examples include so-called prepolymers such as polyester diol, polyethylene glycol, and polypropylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,6-hexanediol, and neopentyl. And glycol, 1,4-butylene glycol, 1,9-nanonediol, and 3-methyl-1,5-pentanediol. These may be used alone or in combination of two or more.
• the proportion of the diol component (A2) in the total amount thereof is preferably 20% by weight or less, and more preferably 10% by weight or less.
• this ratio is large, the effects of the polycarbonate skeleton and the alicyclic skeleton on the heat and moisture resistance and the adhesive strength tend to be small, and it is difficult to achieve both excellent heat and heat resistance and excellent adhesive strength.
• the polyol component (B) having a (meth) acryloyl group used as a raw material for the urethane resin (D) has two or more hydroxyl groups.
• a (meth) acryloyl group can be introduced not only into the terminal of the main chain of the urethane resin (D) but also into the side chain.
• the amount of (meth) acryloyl group introduced can be controlled by controlling the composition of the diol components (A1) and (A2) and the polyol component (B).
• polyol component (B) having a (meth) acryloyl group and two or more hydroxyl groups in one molecule for example, (meth) acrylic acid is added to the epoxy group of a compound having two or more epoxy groups.
• Examples of the compound (B1) obtained by adding (meth) acrylic acid to an epoxy group of a compound having two or more epoxy groups include, for example, a (meth) acrylic acid adduct of propylene glycol diglycidyl ether, 1,6-hexanediol (Meth) acrylic acid adduct of diglycidyl ether, (meth) acrylic acid adduct of ethylene glycol diglycidyl ether, (meth) acrylic acid adduct of 1,4-butanediol diglycidyl ether, 1,5-pentanediol (Meth) acrylic acid adduct of diglycidyl ether, (meth) acrylic acid adduct of 1,6-hexanediol diglycidyl ether, (meth) acrylic acid adduct of 1,9-nonanediol diglycidyl ether, neopentyl (Meth) acrylic acid adduct of glycol digly
• Examples of the polyisocyanate component (C) used as a raw material for the urethane resin (D) include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, 1, And diisocyanates such as 5-naphthalene diisocyanate, hexamethylene diisocyanate, and hydrogenated diphenylmethane diisocyanate. These may be used alone or in combination of two or more. From the viewpoint of weather resistance, the diisocyanate is preferably an alicyclic diisocyanate.
• This urethane resin (D) may be produced by reacting raw materials in the absence of a solvent, or may be produced by reacting in an organic solvent.
• organic solvent examples include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, and methoxyethyl acetate; ethers such as diethyl ether and ethylene glycol dimethyl ether.
• Aromatic compounds such as toluene and xylene; Aliphatic compounds such as pentane and hexane;
• solvents such as halogenated hydrocarbons such as methylene chloride, chlorobenzene and chloroform can be used.
• a catalyst can be added to the organic solvent as necessary.
• the catalyst include metal catalysts such as dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, and dibutyltin dimaleate; 1,8-diaza-bicyclo (5,4,0) undecene-7, 1,5-diazabicyclo Tertiary amines such as (4,3,0) nonene-5,6-dibutylamino-1,8-diazabicyclo (5,4,0) undecene-7; reactive tertiary amines such as triethanolamine It is done. These may be used alone or in combination of two or more.
• An active energy ray-curable adhesive according to an aspect of the present invention includes an urethane resin (D) having a glass transition temperature in the range of ⁇ 60 to ⁇ 10 ° C. and an epoxy resin (E). It contains.
• D urethane resin
• E epoxy resin
• Examples of the epoxy resin (E) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, brominated bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, biphenol type epoxy resin, and biphenol type epoxy resin.
• Glycidyl ether compounds such as skeleton-containing phenol novolac epoxy resins and dicyclopentadiene skeleton-containing phenol novolac epoxy resins
• Glycidyl ester compounds such as diglycidyl ester
• Alicyclic epoxy resins such as EHPE-3150 manufactured by Daicel Chemical Industries
• heterocyclic epoxy resins such as triglycidyl isocyan
• the functional group generated by the decomposition of the urethane resin during the wet heat resistance test can be reacted with the epoxy group. Accordingly, a decrease in molecular weight of the adhesive layer can be suppressed, and a decrease in adhesive force can be suppressed.
• the epoxy resin (E) is preferably a bisphenol type epoxy resin having a number average molecular weight in the range of 500 to 5,000.
• the number average molecular weight of the epoxy resin is smaller than 500, the adhesive layer is soft and sufficient moisture and heat resistance tends not to be obtained. If the number average molecular weight of the epoxy resin is greater than 5000, the compatibility with other components of the active energy ray-curable adhesive is low, and the adhesive tends to become cloudy.
• This active energy ray-curable adhesive can contain an aziridine compound (F).
• an aziridine compound (F) in the active energy ray-curable adhesive, a covalent bond can be formed between the sheet-like member and the aziridine compound, and the adhesive force between the sheet-like members can be improved.
• aziridine compound (F) examples include 2,2-bishydroxymethylbutanol-tris [3- (1-aziridinyl) propionate] and 4,4-bis (ethyleneiminocarbonylamino) diphenylmethane. These may be used alone or in combination of two or more.
• the back surface protection sheet to be used can be appropriately selected depending on the product or application on which the solar cell module is mounted.
• the active energy ray-curable adhesive may not contain the aziridine-based compound (F).
• This active energy ray-curable adhesive can further contain a compound having a (meth) acryloyl group other than the urethane resin (D).
• a compound having a (meth) acryloyl group other than the urethane resin (D) include relatively low molecular weight (meth) acrylate monomers and so-called prepolymers and polymers having a relatively high molecular weight.
• Examples of relatively low molecular weight (meth) acrylate monomers include monofunctional (meth) acrylate monomers such as 4-hydroxybutyl (meth) acrylate, isobornyl (meth) acrylate, lauryl (meth) acrylate, and acryloylmorpholine; 1,9-nonanediol di (meth) acrylate, bisphenol A di (meth) acrylate, pentaerythritol tri (meth) acrylate, tris ((meth) acryloxyethyl) isocyanurate, and dipentaerythritol hexa (meth)
• a polyfunctional (meth) acrylate monomer such as acrylate can be exemplified.
• prepolymer and polymer examples include radically polymerizable prepolymers having (meth) acryloyl groups such as polyester (meth) acrylate, polyurethane (meth) acrylate, epoxy (meth) acrylate, and (meth) acrylated maleic acid-modified polybutadiene. Mention may be made of polymers or polymers. These may be used alone or in combination of two or more.
• This active energy ray-curable adhesive can contain a photopolymerization initiator and a compound that does not have active energy ray curability.
• photopolymerization initiator a known photopolymerization initiator can be used.
• photopolymerization initiators include benzophenone, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-benzyl -2-dimethylamino-1- (4-morpholinophenyl) butanone-1,2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-1- (4-methylthiophenyl) -2 -Morpholinopropan-1-one, benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, benzoin isopropyl ether, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2-hydroxy-2-methyl- (4- (1-Methylvini ) Pheny
• an aliphatic amine such as n-butylamine, triethylamine, ethyl p-dimethylaminobenzoate, or an aromatic amine may be used in combination as a sensitizer.
• This active energy ray-curable adhesive can further contain other compounds not having active energy ray curability.
• compounds that do not have active energy ray curability include curing agents such as acrylic resins, polyester resins, amino resins, xylene resins, petroleum resins, isocyanate compounds, aluminum chelate compounds, and silane coupling agents.
• curing agents such as acrylic resins, polyester resins, amino resins, xylene resins, petroleum resins, isocyanate compounds, aluminum chelate compounds, and silane coupling agents.
• UV absorbers, antioxidants, leveling agents, antifoaming agents, adhesion aids, dispersants, drying regulators, antifriction agents, or combinations of two or more thereof can be used.
• This active energy ray-curable adhesive is based on the solid content of the active energy ray-curable adhesive, 50 to 85% by weight of the urethane resin (D), 2.5 to 34% by weight of the epoxy resin (E), It is preferable to contain 0 to 10% by weight of the aziridine compound (F) and 0 to 30% by weight of a compound having a (meth) acryloyl group other than the urethane resin (D), and 60 to 85% by weight of the urethane resin (D).
• the amount of the urethane resin (D) is less than 50% by weight, the cohesive force of the adhesive layer is reduced, and the adhesive force and the heat and humidity resistance tend to be insufficient.
• the amount of the urethane resin (D) is more than 85% by weight, the heat and humidity resistance tends to be lowered.
• the amount of the epoxy resin (E) is less than 2.5% by weight, the effect of improving the heat and moisture resistance tends to be hardly obtained.
• the amount of the epoxy resin (E) is more than 34% by weight, the heat and humidity resistance tends to be lowered because the crosslinking density of the adhesive layer is lowered.
• the amount of the aziridine compound (F) is more than 10% by weight, the heat and moisture resistance tends to be lowered.
• the adhesive force tends to be insufficient due to shrinkage during curing.
• the active energy ray-curable adhesive layer constituting the solar cell back surface protective sheet according to one embodiment of the present invention preferably has a glass transition temperature in the range of ⁇ 20 ° C. to 20 ° C.
• the active energy ray-curable adhesive can form an adhesive layer having a glass transition temperature in the range of ⁇ 20 ° C. to 20 ° C. when cured by irradiation with active energy rays. Is preferred.
• the glass transition temperature exceeds 20 ° C.
• the wettability of the adhesive to the sheet-like member tends to be poor when the sheet-like member is stacked with the curable adhesive layer or the cured adhesive layer interposed therebetween. .
• the adhesive force between the sheet-like members tends to be insufficient.
• the glass transition temperature is lower than ⁇ 20 ° C.
• the cohesive strength of the adhesive layer is small, and the adhesive strength and heat-and-moisture resistance tend to be insufficient.
• the back surface protection sheet for solar cells includes two or more sheet-like members laminated via an active energy ray-curable adhesive layer formed from the above-described active energy ray-curable adhesive. It will be.
• the sheet-like member that constitutes the solar cell back surface protective sheet is not particularly limited.
• Examples of the sheet-like member include a plastic film, a metal foil, or a material obtained by evaporating a metal oxide or a non-metal oxide on a plastic film.
• plastic film examples include polyester resin films made of polyester such as polyethylene terephthalate and polynaphthalene terephthalate; polyethylene resin films; polypropylene resin films; polyvinyl chloride resin films; polycarbonate resin films; Poly (meth) acrylic resin film; polyvinyl fluoride, polyvinylidene fluoride, polychlorotrifluoroethylene, polyethylene tetrafluoroethylene, polytetrafluoroethylene, tetrafluoroethylene perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoro Examples thereof include a fluorine resin film made of a fluorine resin such as a propylene copolymer.
• a multilayer plastic film may be used.
• a film formed by coating the above-described plastic film with an acrylic or fluorine-based paint, or a multilayer film obtained by laminating polyvinylidene fluoride and an acrylic resin by coextrusion may be used.
• Examples of the metal foil include aluminum foil.
• metal oxide or non-metallic inorganic oxide to be deposited examples include oxides such as silicon, aluminum, magnesium, calcium, potassium, tin, sodium, boron, titanium, lead, zirconium, and yttrium.
• polyester resins such as polyethylene terephthalate and polynaphthalene terephthalate that have resistance to temperature in terms of weather resistance, water vapor permeability, electrical insulation, mechanical properties, mounting workability, etc. when used as solar cell modules It is preferable to use a film or a polycarbonate resin film.
• a metal foil such as a plastic film or an aluminum foil on which a metal oxide or non-metal inorganic oxide having a water vapor barrier property is deposited. preferable.
• the solar cell back surface protection sheet according to an aspect of the present invention can be obtained by any of the following methods [1] to [3], for example.
• An active energy ray-curable adhesive is applied to a certain sheet-like member, and another sheet-like member is overlaid on the formed active energy ray-curable adhesive layer. Next, active energy rays are irradiated to this laminate from one sheet-like member side or both sheet-like member sides, and an active energy ray-curing adhesive layer is formed between these sheet-like members.
• An active energy ray-curable adhesive is applied to a certain sheet-like member to form an active energy ray-curable adhesive layer.
• the active energy ray-curable adhesive layer is formed by irradiating active energy rays from the active energy ray-curable adhesive layer side and / or from the sheet-like member side. Thereafter, another sheet-like member is laminated on the active energy ray-curable adhesive layer.
• An active energy ray-curable adhesive is applied to a certain sheet-like member to form an active energy ray-curable adhesive layer.
• the active energy ray-curable adhesive layer is formed by irradiating active energy rays from the active energy ray-curable adhesive layer side and / or from the sheet-like member side.
• another coating material for forming a sheet-like member is applied to the active energy ray-curable adhesive layer, and another sheet-like member is formed by heat or active energy rays.
• Examples of the other sheet-like member forming coating solution used in the method [3] include, for example, a polyester resin solution, a polyethylene resin solution, a polypropylene resin solution, and a polyvinyl chloride resin that can be used for forming a plastic film.
• Examples thereof include a solution, a polycarbonate resin solution, a polysulfone resin solution, a poly (meth) acrylic resin solution, and a fluorine resin solution.
• the method [1] has an advantage that when the active energy ray-curable adhesive is radically polymerizable, it is less susceptible to oxygen inhibition during curing.
• the active energy ray-curable adhesive layer is irradiated with the active energy ray-curable adhesive layer through the sheet-like member, regardless of whether the active energy ray-curable adhesive is radically polymerizable or not. It is important to use a sheet-like member that can transmit the active energy rays without being attenuated as much as possible.
• Method [2] has different characteristics from Method [1]. That is, in the method [2], the active energy ray is irradiated in a situation where oxygen inhibition is likely to occur. However, on the other hand, the method [2] has an advantage that there are wide choices of sheet-like members that can be used.
• another sheet-like member can be superposed on the curable adhesive layer or on the cured adhesive layer under heating and / or pressure conditions.
• a solvent may be contained within a range that does not affect the sheet-like member in the drying step.
• the active energy ray-curable adhesive contains a solvent, after the solvent is volatilized, the active energy ray-curable adhesive can be cured by irradiation with active energy rays.
• Examples of the solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, and methoxyethyl acetate; ethers such as diethyl ether and ethylene glycol dimethyl ether.
• ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone
• esters such as methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, and methoxyethyl acetate
• ethers such as diethyl ether and ethylene glycol dimethyl ether.
• Aromatic compounds such as toluene and xylene; aliphatic compounds such as pentane and hexane; halogenated hydrocarbon compounds such as methylene chloride, chlorobenzene and chloroform; alcohols such as ethanol, isopropyl alcohol and normal butanol; and water. These solvents may be used alone or in combination of two or more.
• Examples of apparatuses that apply the active energy ray-curable adhesive to a sheet-like member include a comma coater, a dry laminator, a roll knife coater, a die coater, a roll coater, a bar coater, a gravure roll coater, a reverse roll coater, a blade coater, and a gravure coater And a micro gravure coater.
• the amount of adhesive applied to the sheet-like member is preferably about 0.1 to 50 g / m 2 in terms of dry film thickness.
• Examples of active energy rays irradiated for curing the active energy ray-curable adhesive include ultraviolet rays, electron beams, ⁇ rays, infrared rays, and visible rays.
• Example 1 In a polymerization tank of a polymerization reactor equipped with a polymerization tank, a stirrer, a thermometer, a reflux condenser, a nitrogen introduction pipe, and a dropping tank, 716.6 parts of methyl ethyl ketone (MEK) and Kuraray polyol C-1090 (manufactured by Kuraray Co., Ltd.) 607.8 parts, 89.2 parts of cyclohexanedimethanol (CHDM), and 19.6 parts of epoxy ester 70PA (manufactured by Kyoeisha Chemical Co., Ltd.), which is a compound obtained by adding 2 mol of acrylic acid to propylene glycol diglycidyl ether.
• MEK methyl ethyl ketone
• Kuraray polyol C-1090 manufactured by Kuraray Co., Ltd. 607.8 parts
• CHDM cyclohexanedimethanol
• epoxy ester 70PA manufactured by Kyoeisha Chemical Co.,
• the temperature in the polymerization tank was increased to 80 ° C. while stirring the mixture under a nitrogen stream. When the temperature reached 80 ° C., 0.5 part of dibutyltin dilaurate (DBTDL) was added to the polymerization tank.
• DBTDL dibutyltin dilaurate
• urethane resin solutions (D-2) to (D-22) were obtained in the same manner as in Example 1. Properties of these urethane resin solutions are shown in Tables 1 to 4.
• Comparative Example 1 869.4 parts of methyl ethyl ketone (MEK) and Kuraray polyol C-3090 (manufactured by Kuraray Co., Ltd.) were added to the polymerization tank of a polymerization reactor equipped with a polymerization tank, a stirrer, a thermometer, a reflux condenser, a nitrogen inlet tube, and a dropping tank. 834.1 parts and 41.7 parts of cyclohexanedimethanol (CHDM) were charged. The temperature in the polymerization tank was increased to 80 ° C. while stirring the mixed solution under a nitrogen stream. When the temperature reached 80 ° C., 0.5 part of dibutyltin dilaurate (DBTDL) was added to the polymerization tank.
• DBTDL dibutyltin dilaurate
• the temperature of the polymerization tank was lowered to 60 ° C., and 6.4 parts of 2-acryloyloxyethyl isocyanate having one isocyanate group and one acryloyl group (Karenz AOI, Showa Denko) and MEK were added. A mixture with 6.4 parts was added to the polymerization vessel. The reaction was performed at 60 ° C., and the reaction was continued until the infrared absorption peak of the isocyanate group completely disappeared with an infrared spectrophotometer. Thereafter, the temperature of the polymerization tank was lowered to 40 ° C., and 500.0 parts of MEK was added to the polymerization tank to obtain a urethane resin solution (D-23) having a solid content of 40%. Table 5 shows the properties of the urethane resin solution (D-23).
• Comparative Example 2 862.5 parts of methyl ethyl ketone (MEK) and Kuraray polyol C-3090 (manufactured by Kuraray Co., Ltd.) were added to the polymerization tank of a polymerization reactor equipped with a polymerization tank, a stirrer, a thermometer, a reflux condenser, a nitrogen inlet tube, and a dropping tank. 826.7 parts and 41.3 parts of cyclohexanedimethanol (CHDM) were charged. The temperature in the polymerization tank was increased to 80 ° C. while stirring the mixed solution under a nitrogen stream.
• CHDM cyclohexanedimethanol
• DBTDL dibutyltin dilaurate
• IPDI isophorone diisocyanate
• MEK MEK
• the temperature of the polymerization tank was lowered to 60 ° C., and a mixture of 5.5 parts of hydroxyethyl acrylate (HEA) and 5.5 parts of MEK was added to the polymerization tank.
• the reaction was performed at 60 ° C., and the reaction was continued until the infrared absorption peak of the isocyanate group completely disappeared with an infrared spectrophotometer.
• the temperature of the polymerization tank was lowered to 40 ° C., and 500.0 parts of MEK was added to the polymerization tank to obtain a urethane resin solution (D-24) having a solid content of 40%.
• Table 5 shows the properties of the urethane resin solution (D-24).
• ⁇ Glass transition temperature (Tg)> The glass transition temperature was measured using DSC “RDC220” manufactured by Seiko Instruments Inc. Specifically, about 10 mg of a sample obtained by drying the urethane resin solutions (D-1) to (D-27) was weighed into an aluminum pan. This was set in a DSC apparatus, cooled to ⁇ 100 ° C. with liquid nitrogen, and then heated at 10 ° C./min. The glass transition temperature was calculated from the DSC chart obtained at this time.
• Epicoat 828 Epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd.) Number average molecular weight 370
• Epicoat 1001 Epoxy resin (Japan Epoxy Resin Co., Ltd.) Number average molecular weight 900
• Epicoat 1002 Epoxy resin (Japan Epoxy Resin Co., Ltd.) Number average molecular weight 1200
• Epicoat 1009 Epoxy resin (Japan Epoxy Resin Co., Ltd.) Number average molecular weight 3800
• IBXA Isobornyl acrylate (manufactured by Osaka Organic Chemical Co., Ltd.)
• M-210 EO-modified bisphenol A diacrylate (manufactured by Toagosei Co., Ltd.)
• M305 Pentaerythritol triacrylate (manufactured by Toagosei Co., Ltd.)
• M315 isocyanuric acid EO-modified triacrylate (manufactured
• a cured adhesive sheet having a thickness of about 200 ⁇ m is prepared and measured using a dynamic viscoelasticity measuring device DVA-200 (manufactured by IT Measurement & Control Co., Ltd.). did.
• the cured adhesive sheet was prepared by applying an adhesive to a polyester film having a silicone release layer with a blade coater, drying the solvent, and then ultraviolet rays (120 W metal halide lamp, integrated light quantity of UV-A region 500 mJ). / Cm 2 ) to form an active energy ray-curable adhesive layer, and the polyester film was peeled from the adhesive layer.
• ultraviolet rays 120 W metal halide lamp, integrated light quantity of UV-A region 500 mJ). / Cm 2
• the solar cell back surface protection sheet was obtained as described above.
• the amount of the adhesive layer was 8 to 10 g / m 2 .
• the active energy ray-curable adhesive was applied to the sheet-like member (S1), and the solvent was volatilized from the coating film. Next, this coating film was irradiated with ultraviolet rays (120 W high-pressure mercury lamp, accumulated light quantity of UV-A region 200 mJ / cm 2 ) from the surface side to form an active energy ray-cured adhesive layer. Thereafter, the upper sheet member (S1) and the other sheet member (S2) were stacked with the active energy ray-curing adhesive layer interposed therebetween, and this laminate was passed between two rolls set at 60 ° C. .
• ultraviolet rays 120 W high-pressure mercury lamp, accumulated light quantity of UV-A region 200 mJ / cm 2
• the solar cell back surface protection sheet was obtained as described above.
• the amount of the adhesive layer was 8 to 10 g / m 2 .
• the active energy ray-curable adhesive was applied to the sheet-like member (S1), and the solvent was volatilized from the coating film. Next, this coating film was irradiated with ultraviolet rays (120 W high-pressure mercury lamp, accumulated light quantity of UV-A region 200 mJ / cm 2 ) from the surface side to form an active energy ray-cured adhesive layer. Thereafter, the sheet-like member (S1) and the other sheet-like member (S2) were stacked with the active energy ray-curing adhesive layer interposed therebetween, and this laminate was passed between two rolls set at 60 ° C. .
• ultraviolet rays 120 W high-pressure mercury lamp, accumulated light quantity of UV-A region 200 mJ / cm 2
• an active energy ray-curable adhesive was applied to one main surface of the laminate, and the solvent was volatilized from the coating film.
• this coating film was irradiated with ultraviolet rays (120 W high-pressure mercury lamp, accumulated light quantity of UV-A region 200 mJ / cm 2 ) from the surface side to form an active energy ray-cured adhesive layer.
• the previous laminate and another sheet-like member (S3) were stacked with this active energy ray-curing adhesive layer interposed therebetween, and this was passed between two rolls set at 60 ° C.
• the solar cell back surface protection sheet was obtained as described above.
• the amount of the two adhesive layers was 8 to 10 g / m 2 .
• PET (1) colorless and transparent polyethylene terephthalate film (thickness: 188 ⁇ m) -Vapor-deposited PET: A film obtained by depositing a mixture of silicon oxide and magnesium fluoride at a ratio of 90/10 to a thickness of 500 mm on one side of a polyethylene terephthalate film (thickness 12 ⁇ m).
• AL (1) Aluminum foil (thickness 30 ⁇ m) provided with a 10 ⁇ m weathering resin layer * on one side Weathering resin layer *: Obligato PS2012 (white)
• Main agent Curing agent (13: 1) (manufactured by AGC Co-Tech)
• White PET White polyethylene terephthalate film (thickness 50 ⁇ m)
• Black PET Black polyethylene terephthalate film (thickness 50 ⁇ m)
• PVF DuPont polyvinyl fluoride film “Tedlar” (thickness 38 ⁇ m) ⁇
• KFC Kureha Extec Multi-layer Film “FT-50Y” (50 ⁇ m thickness)
• EVA Ethylene / vinyl acetate copolymer resin film (thickness 100 ⁇ m)
• Tables 9 to 13 The evaluation methods and the evaluation criteria shown in Tables 9 to 13 are as follows.
• the back surface protection sheet for solar cells was stored at 85 ° C. in an 85% RH atmosphere for 1000 and 2000 hours.
• the stored back surface protection sheet for solar cells was cut into a size of 200 mm ⁇ 15 mm to obtain a test piece.
• a T-type peel test was performed on the test piece at a load rate of 300 mm / min using a tensile tester in accordance with the test method of ASTM D1876-61.
• the peel strength (N / 15 mm width) between the sheet-like members was shown as an average value of five test pieces.
• a high-yield high-yield protective sheet for solar cells which is excellent in adhesive strength and heat-and-moisture resistance between sheet-like members and does not cause appearance defects and delamination due to generation of bubbles in the adhesive layer. And in productivity and at low cost.
• the cured product obtained by curing the composition containing the urethane resin (D) described here is excellent in adhesiveness to various substrates such as plastic films and metal films, and deteriorates under conditions of high temperature and high humidity. hard. Therefore, the above composition is suitably used for the production of a back surface protection sheet for solar cells, and for other uses, for example, optical members such as plastic lenses, prisms and optical fibers, and flexible printed wiring boards. It can also be used as an electrical / electronic member such as a solder resist, an interlayer insulating film for multilayer printed wiring boards, a coating agent for paper or plastic film, and an adhesive for food packaging.

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• 2010
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