WO2011052747A1 - シール部形成用硬化性樹脂組成物、積層体およびその製造方法 - Google Patents
シール部形成用硬化性樹脂組成物、積層体およびその製造方法 Download PDFInfo
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- WO2011052747A1 WO2011052747A1 PCT/JP2010/069355 JP2010069355W WO2011052747A1 WO 2011052747 A1 WO2011052747 A1 WO 2011052747A1 JP 2010069355 W JP2010069355 W JP 2010069355W WO 2011052747 A1 WO2011052747 A1 WO 2011052747A1
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- resin composition
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- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
- B32B17/10706—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer being photo-polymerized
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- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/067—Polyurethanes; Polyureas
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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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
- C09K3/1021—Polyurethanes or derivatives thereof
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- G—PHYSICS
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- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1341—Filling or closing of cells
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- 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
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- H—ELECTRICITY
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- 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
- H01L31/0488—Double glass encapsulation, e.g. photovoltaic cells arranged between front and rear glass sheets
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- 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
- H01L31/049—Protective back sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2003/1034—Materials or components characterised by specific properties
- C09K2003/1062—UV-curable materials
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- 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
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- 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
- Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
- Y10T156/10—Methods of surface bonding and/or assembly therefor
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- 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
- Y10T428/23—Sheet including cover or casing
- Y10T428/239—Complete cover or casing
Definitions
- a curable resin composition for forming a resin layer sandwiched between a first face material and a second face material is cured in a state where the periphery thereof is surrounded by a seal portion (a laminated body (matching) A glass, a display device, a solar cell module, and the like), and a laminate having a seal portion made of the curable resin composition, which is preferably used for forming the seal portion, and It relates to the manufacturing method.
- the following method is proposed as a manufacturing method of transparent laminated bodies, such as a laminated glass, in which the resin layer was pinched
- (C) The other transparent face material is stacked on the curable resin composition for resin layer formation under a reduced pressure atmosphere, and the curable resin composition for resin layer formation is sealed by the two transparent face materials and the seal portion.
- (D) A method for producing a transparent laminate comprising a step of curing a curable resin composition for resin layer formation in a state where the laminate is placed under atmospheric pressure (see Patent Documents 1 and 2).
- the following method is illustrated as a formation method of a seal
- the seal portion can be easily formed, in order to bond the two transparent face materials through the seal portion without any gap, after the other transparent face material is overlaid, that is, in step (c) ) After that, it is necessary to harden the seal part. Therefore, since the curable resin composition for forming a seal part spreads in the width direction of the seal part and the shape of the uncured seal part may be deformed during the step (b), the height of the seal part is sufficient. Cannot be maintained. Therefore, it is difficult to thicken the resin layer forming curable resin composition supplied to the region surrounded by the seal portion and the resin layer formed by curing the resin layer forming curable resin composition.
- the spacer particles need to be enlarged, and the curable resin composition for forming the seal portion containing large spacer particles
- the curable resin composition for forming the seal portion containing large spacer particles
- spacers are likely to be clogged at the application part, and there is a possibility that the application cannot be performed satisfactorily.
- defects such as leakage of the curable resin composition for forming a resin layer from the gap of the seal part due to the curable resin composition for forming the seal part flowing out from between the spacers and the generation of a gap in the seal part. is there.
- a continuous seal portion can be easily formed, and immediately after the uncured seal portion is formed, the liquid material is supplied to the region surrounded by the seal portion and the seal portion is cured.
- a curable resin composition for forming a seal part that can maintain the shape of the part, a laminate that can increase the thickness of the resin layer sandwiched between the first face material and the second face material, and has few defects, And a method for manufacturing the same.
- the curable resin composition for forming a seal portion of the present invention is curable for forming a seal portion surrounding the periphery of a layer made of a liquid material sandwiched between a first face material and a second face material.
- the liquid material is preferably a curable resin composition for resin layer formation.
- the curable resin composition for forming a seal portion of the present invention surrounds the curable resin composition for forming a resin layer sandwiched between a first face material and a second face material with a seal portion. It is preferably used for forming the seal portion when the laminate is produced by curing in an open state.
- the curable resin composition for forming a seal part of the present invention has at least one oligomer (A) having a curable group and having a number average molecular weight of 30,000 to 100,000, a curable group, and a molecular weight.
- the monomer (B) having a molecular weight of 125 to 600 and the proportion of the monomer (B) is 15 to 50% of the total (100% by mass) of the oligomer (A) and the monomer (B) % Is preferred.
- the monomer (B) is a low molecular weight curable compound contained in the curable resin composition for forming a seal portion as a monomer, and the monomer (B) is synthesized with the following oligomer (A1).
- the monomer (B2) reacted with the isocyanate group of the prepolymer is not included, and the monomer (B2) remaining unreacted is included.
- the curable group is preferably at least one group selected from an acryloyloxy group and a methacryloyloxy group.
- the curable group of the oligomer (A) is more preferably an acryloyloxy group, and the curable group of the monomer (B) is more preferably a methacryloyloxy group.
- the oligomer (A) is preferably a urethane oligomer (A1).
- the curable resin composition for forming a seal part of the present invention contains a monomer (B1) having no group that reacts with an isocyanate group as the monomer (B), and the urethane oligomer (A1) is present in the monomer (B1). After the polyol and polyisocyanate are reacted to obtain a prepolymer having an isocyanate group, the isocyanate group of the prepolymer is reacted with a monomer (B2) having a group that reacts with the isocyanate group and a curable group. It is preferable that it is obtained.
- the curable resin composition for forming a seal part of the present invention preferably contains a monomer (B3) having a hydroxyl group as the monomer (B).
- the curable resin composition for forming a seal part of the present invention is preferably a photocurable resin composition containing a photopolymerization initiator (C).
- the curable resin composition for forming a seal part of the present invention may contain two or more photopolymerization initiators having different absorption wavelengths as the photopolymerization initiator (C).
- the laminate of the present invention has a first face material and a second face material, a resin layer sandwiched between the first face material and the second face material, and a seal portion surrounding the periphery of the resin layer.
- the laminate is characterized in that the seal part is made of a cured product of the curable resin composition for forming a seal part of the present invention.
- the width of the seal portion of the laminate of the present invention is preferably 0.3 to 3 mm.
- the thickness of the seal portion of the laminate of the present invention is preferably 10 ⁇ m to 3 mm.
- the laminate of the present invention includes a first face material and a second face material, both of which are transparent face materials, a resin layer sandwiched between the first face material and the second face material, and the periphery of the resin layer It may be a transparent laminate having a seal portion that surrounds.
- the laminated body of the present invention is a resin sandwiched between a first face material and a second face material, one of which is a transparent face material and the other is a display device, and the first face material and the second face material.
- the display device may include a layer and a seal portion surrounding the periphery of the resin layer.
- the laminated body of the present invention includes a first face material and a second face material, at least one of which is a transparent face material, a resin layer sandwiched between the first face material and the second face material, A solar cell module having a thin-film solar cell device formed on the surface of the resin layer side of at least one of the face material and the second face material, and a seal portion surrounding the resin layer Also good.
- the method for manufacturing a laminate of the present invention includes a first face material and a second face material, a resin layer sandwiched between the first face material and the second face material, and a seal portion surrounding the resin layer.
- a method of manufacturing a laminate having the following steps (a) to (d).
- the first face material, the second face material, and the uncured seal portion are laminated on the curable resin composition for forming a resin layer.
- the laminate obtained in the step (c) is a curable resin composition for forming a resin layer sealed with a first face material, a second face material, and an uncured seal portion.
- the product is not yet cured, and this may be referred to as a laminate precursor, but the uncured product is cured through the step (d) above. Also referred to as a laminate.
- the thickness of the curable resin composition for forming a resin layer in the laminate obtained in step (c) is preferably 10 ⁇ m to 3 mm.
- a continuous seal portion can be easily formed, and a liquid material is supplied to an area surrounded by the seal portion immediately after forming an uncured seal portion. Then, the shape of the seal portion can be maintained until the seal portion is cured.
- the laminate of the present invention can increase the thickness of the resin layer sandwiched between the first face material and the second face material, and has few defects. According to the method for manufacturing a laminate of the present invention, it is possible to increase the thickness of the resin layer sandwiched between the first face material and the second face material, and to manufacture a laminate having few defects.
- both face materials are referred to as “surface materials”.
- a transparent surface material serving as a protective plate of the display device is referred to as a “surface material”
- the display device is referred to as a “back material”.
- the face material on the sunlight incident side is referred to as “surface material”
- the other face material is referred to as “back material”.
- the surface material and the back material are collectively referred to as “face material”.
- a face material in which a liquid curable resin composition is supplied to a region where a seal portion is formed at a peripheral portion and surrounded by the seal portion is referred to as “first surface”.
- the face material that is superimposed on the curable resin composition is referred to as a “second face material”.
- a face material having optical transparency is referred to as a “transparent face material”.
- a transparent surface material made of glass is called a “glass plate”.
- the transparent face material made of resin is called “transparent resin plate”.
- a face material on which a thin film solar cell device is formed on the surface is referred to as a “substrate”, and is distinguished from a face material on which no thin film solar cell device is formed on the surface.
- Transparent surface materials with thin-film solar cell devices formed on the surface are called "transparent substrates", including the glass substrates and transparent resin substrates described below, and transparent surface materials with no thin-film solar cell devices formed on the surface. Distinguish.
- a glass plate having a thin-film solar cell device formed on the surface is referred to as a “glass substrate”, and is distinguished from a glass plate having no thin-film solar cell device formed on the surface.
- a transparent resin plate having a thin film solar cell device formed on the surface is referred to as a “transparent resin substrate”, and is distinguished from a transparent resin substrate having no thin film solar cell device formed on the surface.
- a non-transparent face material having a thin-film solar cell device formed on the surface is referred to as a “non-transparent substrate”.
- the curable resin composition for forming a seal portion of the present invention is curable for forming a seal portion surrounding the periphery of a layer made of a liquid material sandwiched between a first face material and a second face material.
- the curable resin composition for forming a resin layer sandwiched between the first face material and the second face material is cured in a state where the periphery is surrounded by a seal portion to produce a laminate. In this case, it is more preferably used for forming the seal portion.
- the viscosity of the curable resin composition for forming a seal part of the present invention is 500 to 3000 Pa ⁇ s at 25 ° C., preferably 800 to 2500 Pa ⁇ s, and more preferably 1000 to 2000 Pa ⁇ s. If the viscosity is 500 Pa ⁇ s or more, the shape of the uncured seal portion can be maintained for a relatively long time, and the height of the seal portion can be sufficiently maintained. If the viscosity is 3000 Pa ⁇ s or less, the seal portion can be formed by coating. The viscosity of the curable resin composition for forming a seal part is measured at 25 ° C. using an E-type viscometer.
- the curable resin composition for forming a seal part of the present invention is a kind of oligomer (A) having a curable group and having a number average molecular weight of 30,000 to 100,000 because the viscosity is easily adjusted to the above range. And a monomer (B) having a curable group and a molecular weight of 125 to 600, the ratio of the monomer (B) being the sum of the oligomer (A) and the monomer (B) Among (100% by mass), those of 15 to 50% by mass are preferable.
- the number average molecular weight of the oligomer (A) is 30,000 to 100,000, preferably 40,000 to 80,000, more preferably 50,000 to 65,000. If the number average molecular weight of an oligomer (A) is this range, it will be easy to adjust the viscosity of the curable resin composition for seal part formation to the said range.
- the number average molecular weight of the oligomer (A) is a number average molecular weight in terms of polystyrene obtained by GPC measurement. In addition, in GPC measurement, when the peak of an unreacted low molecular weight component (monomer etc.) appears, this peak is excluded and a number average molecular weight is calculated
- Examples of the curable group of the oligomer (A) include photopolymerizable addition polymerizable unsaturated groups (acryloyloxy group, methacryloyloxy group, etc.), combinations of unsaturated groups and thiol groups, and the like.
- examples include an epoxy group, and at least one group selected from the group consisting of an acryloyloxy group and a methacryloyloxy group from the viewpoint that a curing rate is high and a highly transparent seal part is obtained. Is preferred.
- the curable group in the relatively high molecular weight oligomer (A) tends to be less reactive than the curable group in the relatively low molecular weight monomer (B)
- the curing of the monomer (B) proceeds first.
- the viscosity of the entire composition suddenly increases and the curing reaction may become inhomogeneous.
- the curable group of the oligomer (A) is changed to a relatively reactive acryloyloxy group and the curable property of the monomer (B). More preferably, the group is a methacryloyloxy group having relatively low reactivity.
- the oligomer (A) those having an average of 1.8 to 4 curable groups per molecule are preferable from the viewpoint of the curability of the curable resin composition for forming a seal part and the mechanical properties of the seal part.
- the oligomer (A) include urethane oligomers having a urethane bond, poly (meth) acrylates of polyoxyalkylene polyols, poly (meth) acrylates of polyester polyols, and the like.
- the urethane oligomer (A1) is preferred because it can adjust a wide range of mechanical properties, adhesion to the face material, and the like.
- the urethane oligomer (A1) having a number average molecular weight of 30,000 to 100,000 has a high viscosity, it is difficult to synthesize by a normal method, and even if synthesized, it is difficult to mix with the monomer (B). Therefore, in this invention, after synthesize
- Method for synthesizing urethane oligomer (A1) As a diluent, a polyol and a polyisocyanate are reacted in the presence of a monomer (B1) that does not have a group that reacts with an isocyanate group, which is one of the monomers (B) described later, to obtain a prepolymer having an isocyanate group. Thereafter, a method of reacting the isocyanate group of the prepolymer with a monomer (B2) having a group that reacts with the isocyanate group and a curable group is mentioned as a method for synthesizing the urethane oligomer (A1).
- polyols and polyisocyanates examples include known compounds such as polyol (i) and diisocyanate described as raw materials for urethane-based oligomers (a) described in WO2009 / 016943 (incorporated into the present application). (Ii) and the like.
- Monomers (B1) having no groups that react with isocyanate groups include alkyl (meth) acrylates having an alkyl group having 8 to 22 carbon atoms (n-dodecyl (meth) acrylate, n-octadecyl (meth) acrylate, n -Behenyl (meth) acrylate and the like) and (meth) acrylate having an alicyclic hydrocarbon group (isobornyl (meth) acrylate, adamantyl (meth) acrylate and the like).
- Examples of the monomer (B2) having a group that reacts with an isocyanate group and a curable group include active hydrogen (hydroxyl group, amino group, etc.) and a monomer having a curable group.
- the monomer has 2 to 6 carbon atoms.
- the molecular weight of the monomer (B) is 125 to 600, preferably 140 to 400, more preferably 150 to 350. If the molecular weight of the monomer (B) is 125 or more, the volatilization of the monomer (B) during production of the laminate by the below-described reduced pressure lamination method can be suppressed. If the molecular weight of the monomer (B) is 600 or less, the solubility of the monomer (B) with respect to the high molecular weight oligomer (A) can be increased, and viscosity adjustment as a seal part-forming curable resin composition is suitably performed. It can be carried out.
- Examples of the curable group of the monomer (B) include photopolymerizable addition polymerizable unsaturated groups (acryloyloxy group, methacryloyloxy group, etc.), combinations of unsaturated groups and thiol groups, and the like.
- examples include an epoxy group, and at least one group selected from the group consisting of an acryloyloxy group and a methacryloyloxy group from the viewpoint that a curing rate is high and a highly transparent seal part is obtained. Is preferred.
- the curing of the monomer (B) proceeds first.
- the viscosity of the entire composition suddenly increases and the curing reaction may become inhomogeneous.
- the curable group of the monomer (B) is a methacryloyloxy group having a relatively low reactivity
- the curable group of the oligomer (A) is a acryloyloxy group having a relatively high reactivity. Is more preferable.
- the monomer (B) those having 1 to 3 curable groups per molecule are preferable from the viewpoint of the curability of the curable resin composition for forming a seal portion and the mechanical properties of the seal portion.
- the curable resin composition for forming a seal part of the present invention may contain a monomer (B1) used as a diluent in the method for synthesizing the urethane oligomer (A1) described above as the monomer (B). Moreover, the unreacted monomer (B2) used for the synthesis
- the monomer (B) preferably contains a monomer (B3) having a hydroxyl group from the viewpoint of the adhesion between the face material and the seal portion and the solubility of various additives described later.
- a monomer (B3) having a hydroxyl group a hydroxy methacrylate having a hydroxyalkyl group having 1 to 2 hydroxyl groups and 3 to 8 carbon atoms (2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 6 -Hydroxyhexyl methacrylate and the like are preferred, and 2-hydroxybutyl methacrylate is particularly preferred.
- the proportion of the monomer (B) is 15 to 50% by mass, preferably 20 to 45% by mass, and preferably 25 to 40% by mass in the total (100% by mass) of the oligomer (A) and the monomer (B). More preferred. If the ratio of a monomer (B) is 15 mass% or more, the sclerosis
- the curable resin composition for forming a seal part of the present invention may be a photocurable resin composition or a thermosetting resin composition.
- a photocurable resin composition containing a photopolymerization initiator (C) is preferable because it can be cured at a low temperature and has a high curing rate.
- Examples of the photopolymerization initiator (C) include acetophenone series, ketal series, benzoin or benzoin ether series, phosphine oxide series, benzophenone series, thioxanthone series, quinone series photopolymerization initiators, and acetophenone series or phosphine series. Oxide-based photopolymerization initiators are preferred. When curing with visible light having a short wavelength, a phosphine oxide-based photopolymerization initiator is more preferable from the viewpoint of the absorption wavelength region. By using two or more types of photopolymerization initiators (C) having different absorption wavelength ranges in combination, the curing time can be further increased and the surface curability at the seal portion can be increased.
- the amount of the photopolymerization initiator (C) is preferably 0.01 to 10 parts by weight, and preferably 0.1 to 2.5 parts by weight with respect to 100 parts by weight as the total of the oligomer (A) and the monomer (B). More preferred.
- the curable resin composition for forming a seal part of the present invention includes, as necessary, a polymerization inhibitor, a photocuring accelerator, a chain transfer agent, a light stabilizer (such as an ultraviolet absorber and a radical scavenger), an antioxidant, Various additives such as a flame retardant, an adhesion improver (such as a silane coupling agent), a pigment, and a dye may be included, and a polymerization inhibitor and a light stabilizer are preferably included.
- a polymerization inhibitor in a smaller amount than the polymerization initiator, the stability of the curable resin composition for forming a seal part can be improved, and the molecular weight of the cured resin layer can also be adjusted.
- Polymerization inhibitors include hydroquinone (2,5-di-t-butylhydroquinone, etc.), catechol (pt-butylcatechol, etc.), anthraquinone, phenothiazine, hydroxytoluene and the like. Can be mentioned.
- the light stabilizer include ultraviolet absorbers (benzotriazole series, benzophenone series, salicylate series, etc.), radical scavengers (hindered amine series), and the like.
- the antioxidant include phosphorus-based and sulfur-based compounds.
- the total amount of various additives is preferably 10 parts by mass or less, and more preferably 5 parts by mass or less, with respect to 100 parts by mass in total of the oligomer (A) and the monomer (B).
- the resin layer can be made relatively thick (specifically, about 10 ⁇ m to 3 mm). Moreover, since the viscosity is 3000 Pa ⁇ s or less, a seal part can be formed by coating. Therefore, a continuous seal part can be formed efficiently.
- the laminate of the present invention has a first face material and a second face material, a resin layer sandwiched between the first face material and the second face material, and a seal portion surrounding the periphery of the resin layer.
- the seal portion is made of a cured product of the curable resin composition for forming a seal portion of the present invention.
- Examples of the laminate of the present invention include the following.
- Transparent laminate first and second face materials, both of which are transparent face materials, a resin layer sandwiched between the first face material and the second face material, and a seal surrounding the resin layer Part.
- Display device a first face material and a second face material, one of which is a transparent face material and the other is a display device; a resin layer sandwiched between the first face material and the second face material; And a seal portion surrounding the periphery of the resin layer.
- Solar cell module a first face material and a second face material, at least one of which is a transparent face material, a resin layer sandwiched between the first face material and the second face material, a first face material, and The thin-film solar cell device formed on the surface on the resin layer side of at least one of the second face materials, and a seal portion surrounding the resin layer.
- transparent laminates such as laminated glass and transparent panels, in which two “transparent surface materials” are surface materials (first embodiment).
- Display device in which display device is protected by transparent surface material, wherein “transparent surface material” serving as protective plate of display device is surface material and “display device” is back surface material (second embodiment) .
- the solar cell module include the following three modules.
- Solar cell module having a solar cell device (third embodiment).
- ( ⁇ ) A single-layer thin film in which a “transparent surface material” on which no thin-film solar cell device is formed on the surface is a surface material, and a “substrate” on which a thin-film solar cell device is formed on the surface is a back surface material
- Solar cell module having a solar cell device fourth embodiment.
- a solar cell module having a battery device (fifth embodiment).
- FIG. 1 is a cross-sectional view showing an example of an embodiment of the transparent laminate of the present invention.
- the transparent laminate 1 includes two transparent face materials 10 (first face material and second face material) that are surface materials, a resin layer 40 sandwiched between the two transparent face materials 10, and a resin layer. And a seal portion 42 surrounding the periphery of 40.
- the surface material is a transparent surface material that transmits light.
- the transparent face material include a glass plate or a transparent resin plate. When a glass plate is used, it becomes a laminated glass, and when a transparent resin plate is used, it is called a transparent panel. A glass plate and a transparent resin plate may be used in combination. Also, a part or the whole of the transparent face material may be colored, light may be scattered in the shape of polished glass, or light may be refracted or reflected by fine irregularities on the surface. it can. Moreover, what laminated
- the transparent surface material can also be used as a transparent surface material as an integral thing.
- the material of the glass plate include glass materials such as soda lime glass.
- the material of the transparent resin plate include highly transparent resin materials (such as polycarbonate and polymethyl methacrylate).
- the thickness of the transparent face material is usually preferably 0.3 to 6 mm and more preferably 1 to 6 mm from the viewpoint of mechanical strength and transparency.
- the thickness of the glass plate is preferably 0.3 to 1.5 mm, and more preferably 0.3 to 1 mm.
- the thickness is usually 0.1 to 3 mm.
- a resin layer is a layer which plays the role which joins the laminated
- the thickness of the resin layer is preferably 0.2 to 3 mm. If the thickness of the resin layer is 0.2 mm or more, the mechanical strength of the transparent laminate is good. In particular, the thickness of the resin layer is more preferably 0.2 to 1.5 mm, and still more preferably 0.2 to 0.8 mm. Since the thickness of the resin layer is reduced by curing, the thickness of the resin layer is preferably about 1.2 to 2 times the thickness after curing at the time of application. Examples of a method for adjusting the thickness of the resin layer include a method for adjusting the thickness of a seal portion described later. Spacer particles having a predetermined particle diameter may be disposed on the uncured seal portion.
- the seal part is formed by applying and curing the curable resin composition for forming a seal part of the present invention.
- the width of the seal part is preferably 0.3 to 3 mm, more preferably 0.5 to 2 mm.
- the thickness of the seal portion is preferably 0.3 to 3.2 mm, and more preferably 0.3 to 1.6 mm.
- the size of the transparent laminate is not particularly limited, but it is widely used as a transparent member to be installed in an opening for buildings or vehicles if it is a transparent substrate having at least one side of 300 mm or more, more preferably 600 mm or more. it can. In normal applications, a size of 4 m 2 or less is appropriate.
- FIG. 2 is a cross-sectional view showing an example of an embodiment of the display device of the present invention.
- the display device 2 includes a transparent surface material 10 that is a surface material, a display device 50 that is a back surface material, a resin layer 40 sandwiched between the transparent surface material 10 and the display device 50, and a seal portion that surrounds the periphery of the resin layer 40. 42, a flexible printed wiring board 54 (FPC) on which a driving IC for operating the display device 50 connected to the display device 50 is mounted, and a light-shielding printing portion 55 formed on the peripheral portion of the transparent surface material 10.
- FPC flexible printed wiring board 54
- the display device 50 which is the back surface material is the first face material
- the transparent face material 10 which is the surface material is When it becomes the first face material, the display device 50 that is the back face material becomes the second face material.
- the surface material is a transparent surface material that transmits the display image of the display device.
- a transparent face material a glass plate or a transparent resin plate can be mentioned, and of course, it has high transparency with respect to emitted light and reflected light from a display device, as well as light resistance, low birefringence, high planar accuracy, and resistance to light.
- a glass plate is most preferable from the viewpoint of surface scratch resistance and high mechanical strength.
- a transparent surface material is preferable also in terms of transmitting light for curing the photocurable resin composition.
- the material of the glass plate examples include glass materials such as soda lime glass, and high transmittance glass (white plate glass) having a lower iron content and less bluishness is more preferable. In order to improve safety, tempered glass may be used as a surface material.
- the material of the transparent resin plate include highly transparent resin materials (such as polycarbonate and polymethyl methacrylate).
- the transparent surface material may be subjected to a surface treatment in order to improve the interfacial adhesive force with the resin layer.
- the surface treatment method include a method of treating the surface of the transparent surface material with a silane coupling agent.
- the transparent surface material may be provided with an antireflection layer on the back surface of the joint surface with the resin layer in order to increase the contrast of the display image.
- the antireflection layer can be provided by a method of directly forming an inorganic thin film on the surface of the transparent surface material, or a method of bonding a transparent resin film provided with the antireflection layer to the transparent surface material.
- a part or the whole of the transparent surface material is colored, light is scattered in a frosted glass shape, or the surface is finely uneven. It is also possible to refract or reflect light during transmission.
- stacked the optical film etc. which perform optical modulation, such as an optical film which shows the above aspects, and a polarizing film, etc. on the transparent surface material can also be used as a transparent surface material as an integral thing.
- the thickness of the transparent face material is usually 0.5 to 25 mm in the case of a glass plate from the viewpoint of mechanical strength and transparency.
- 1 to 6 mm is preferable from the viewpoint of reducing the weight of the display device, and for public display applications installed outdoors, 3 to 20 mm is preferable.
- 3 to 20 mm is preferable.
- 2 to 10 mm is preferable.
- the back material is a display device.
- a transparent surface material 52 provided with a color filter and a transparent surface material 53 provided with a TFT are bonded to each other at the periphery of the double-sided material via a liquid crystal layer, and this is bonded to a pair of polarizing plates 51.
- the display device in the present invention is not limited to the illustrated example.
- the display device includes a pair of electrodes, at least one of which is a transparent electrode, sandwiched by a display material whose optical state is changed by an external electric signal.
- a display material whose optical state is changed by an external electric signal.
- the display device has a structure in which a pair of face materials, at least one of which is a transparent face material, is bonded, and is arranged so that the transparent face material side is in contact with the resin layer.
- an optical film such as a polarizing plate or a retardation plate may be provided on the outermost layer side of the transparent surface material in contact with the resin layer.
- the resin layer is in a state of joining the optical film on the display device and the surface material.
- the bonding surface with the resin layer of the display device may be subjected to a surface treatment in order to improve the interfacial adhesive force with the seal portion.
- the surface treatment may be performed only on the peripheral edge or on the entire surface of the face material.
- Examples of the surface treatment method include a treatment method using an adhesion primer or the like which can be processed at a low temperature.
- the thickness of the display device is usually 0.4 to 4 mm in the case of a liquid crystal display device operated by TFT, and is usually 0.2 to 3 mm in the case of an EL display device.
- a resin layer is a layer which plays the role which joins the laminated
- a curable resin composition for forming a resin layer in which the elastic modulus of the cured resin is lower than in other embodiments is preferable.
- the elastic modulus of the resin is large, there is a possibility that stress generated due to curing shrinkage or the like may adversely affect the display performance of the display device when the resin is cured.
- the thickness of the resin layer is preferably 0.03 to 2 mm, and more preferably 0.1 to 0.8 mm. If the thickness of the resin layer is 0.03 mm or more, the resin layer can effectively buffer an impact caused by an external force from the transparent surface material side, and the display device can be protected. Further, in the manufacturing method of the present invention, even if a foreign substance exceeding the thickness of the resin layer is mixed between the transparent surface material and the display device, the thickness of the resin layer does not change greatly, and the light transmission performance is affected. Less is. If the thickness of the resin layer is 2 mm or less, bubbles are unlikely to remain in the resin layer, and the entire thickness of the display device does not increase unnecessarily. As a method of adjusting the thickness of the resin layer, the thickness of the seal portion described later is adjusted, and the supply amount of the liquid resin layer forming curable resin composition supplied to the first face material is adjusted. A method is mentioned.
- the seal part is formed by applying and curing the curable resin composition for forming a seal part of the present invention. Since the area outside the image display area of the display device is relatively narrow, the width of the seal portion is preferably narrowed.
- the width of the seal part is preferably 0.3 to 3 mm, particularly preferably 0.5 to 2 mm. Further, the thickness of the seal portion is preferably 0.1 to 2.2 mm, and more preferably 0.2 to 0.9 mm.
- the light-shielding printing unit hides the wiring member and the like connected to the display device so that areas other than the image display area of the display device cannot be viewed from the transparent surface material side.
- the light-shielding printing part can be provided on the joint surface with the resin layer of the transparent surface material or the back surface thereof, and in terms of reducing the parallax between the light-shielding printing part and the image display area, It is preferable to install on the surface.
- the transparent surface material is a glass plate, it is preferable to use ceramic printing containing a black pigment in the light-shielding printing portion because of high light shielding properties.
- the shape of the display device is usually rectangular.
- the size of the display device is 0.5 m ⁇ 0.4 m or more in the case of a television receiver using a liquid crystal display device because the manufacturing method of the present invention is particularly suitable for manufacturing a display device having a relatively large area. Is suitable, and 0.7 m ⁇ 0.4 m or more is particularly preferable.
- the upper limit of the size of the display device is often determined by the size of the display device. Also, a display device that is too large is likely to be difficult to handle during installation. The upper limit of the size of the display device is usually about 2.5 m ⁇ 1.5 m due to these restrictions.
- the transparent surface material serving as the protective plate and the display device may be substantially equal, the transparent surface material is often slightly larger than the display device because of the relationship with other housings that house the display device. Conversely, depending on the structure of the other casing, the transparent surface material may be slightly smaller than the display device.
- FIG. 3 is a cross-sectional view showing an example of an embodiment of the solar cell module of the present invention.
- the solar cell module 3 includes a glass substrate 16 that is a surface material, a transparent surface material 10 that is a back surface material, a resin layer 40 sandwiched between the glass substrate 16 and the transparent surface material 10, and the resin layer 40 side of the glass substrate 16.
- a thin-film solar cell device 17 formed on the surface, a seal portion 42 surrounding the resin layer 40, and an electric wire 44 connected to the thin-film solar cell device 17 and extending to the outside through the seal portion 42.
- the transparent face material 10 that is the back surface material is the first face material
- the glass substrate 16 that is the surface material is the first face material
- the transparent face material 10 as the back surface material becomes the second face material.
- the surface material is a transparent substrate that transmits sunlight.
- a thin-film solar cell device is formed in a region excluding the peripheral portion of the surface.
- the transparent substrate may be subjected to a surface treatment in order to improve the interfacial adhesive force with the seal portion.
- the surface treatment may be performed only on the peripheral edge or on the entire surface of the face material. Examples of the surface treatment method include a method of treating the surface of the transparent surface material with a silane coupling agent.
- a part or the whole of the transparent surface material is colored, scatters light like a polished glass, or refracts or reflects light during transmission due to fine irregularities on the surface. It can also be made to let you.
- the transparent substrate examples include the glass substrate 16 or the transparent resin substrate in the illustrated example.
- the transparent substrate is not only highly transparent to sunlight but also resistant to the production process of thin-film solar cell devices such as heat resistance and light resistance.
- the glass substrate is most preferable from the viewpoints of heat resistance, weather resistance, corrosion resistance, surface scratch resistance, and high mechanical strength.
- the glass substrate material examples include glass materials such as soda lime glass.
- the material for the transparent resin substrate include highly transparent resin materials (such as polycarbonate and polymethyl methacrylate).
- a transparent resin substrate it is required to form a thin film solar cell device on the substrate surface at a temperature lower than the heat resistant temperature of the transparent resin substrate.
- the thickness of the transparent substrate including the thickness of the thin film solar cell device is usually 0.7 to 6 mm in the case of a glass substrate, and usually 0.1 to 3 mm in the case of a transparent resin substrate. Among them, the thickness of the thin film solar cell device is usually 10 ⁇ m or less.
- a glass substrate having a thin film solar cell device distributed in the market may be obtained and used.
- the thin film solar cell device is formed in a region excluding the peripheral edge of the surface of the transparent substrate. Moreover, the terminal board of the wiring which takes out electric power from a thin film type solar cell device is formed in the peripheral part of the surface of a transparent substrate. A seal portion described later is provided at the peripheral edge of the transparent substrate on which the thin film solar cell device is not formed, and overlaps a part of the surface of the wiring or a part of the surface of the terminal board.
- the thin film solar cell device is formed by patterning each time a transparent electrode layer, a photoelectric conversion layer, and a back electrode layer are formed on the surface of a transparent surface material.
- the material for the transparent electrode layer include indium tin oxide and tin oxide.
- the photoelectric conversion layer is a layer made of a thin film semiconductor.
- the thin film semiconductor include amorphous silicon semiconductors, microcrystalline silicon semiconductors, compound semiconductors (chalcopyrite semiconductors, CdTe semiconductors, etc.), organic semiconductors, and the like.
- Examples of the material for the back electrode layer include materials that do not transmit light (such as silver and aluminum) and materials that transmit light (such as indium tin oxide, tin oxide, and zinc oxide).
- a thin film silicon solar cell device when a photoelectric conversion layer is formed on the transparent electrode layer and power is generated by incident light from the surface material, a thin film silicon solar cell device in which the thin film semiconductor is an amorphous silicon semiconductor is preferable.
- the transparent surface material 10 in the illustrated example is preferable in terms of transmitting light for curing the photo-curable resin composition.
- the thin-film solar cell device is light transmissive (that is, when the material of the back electrode layer is light transmissive indium tin oxide, tin oxide or the like), the light curable resin composition from the surface material side.
- the back material may be a non-transparent surface material (metal plate, ceramic plate, etc.).
- the transparent surface material In the case of transmitting light for curing the photocurable resin composition, the transparent surface material only needs to have sufficient transparency to transmit light. Moreover, the transparent surface material should just have the weather resistance, corrosion resistance, high mechanical strength, etc. which are requested
- the material of the transparent resin plate may be a resin material that transmits light for curing the photocurable resin composition. In addition to the above-described highly transparent resin material, other than ultraviolet rays and visible light of 450 nm or less. A resin material having low transparency to light may be used.
- the transparent surface material may be subjected to a surface treatment in order to improve the interfacial adhesive force with the resin layer.
- a surface treatment method include a method of treating the surface of the glass plate with a silane coupling agent.
- the thickness of the transparent face material is usually 0.7 to 6 mm in the case of a glass plate, and usually 0.1 to 3 mm in the case of a transparent resin plate.
- a resin layer is a layer which plays the role which joins the laminated
- the thickness of the resin layer is preferably from 0.01 to 2 mm, particularly preferably from 0.1 to 0.8 mm. Examples of the method for adjusting the thickness of the resin layer include a method for adjusting the thickness of a seal portion described later.
- the resin layer is preferably excellent in transparency.
- the seal part is formed by applying and curing the curable resin composition for forming a seal part of the present invention.
- the width of the seal portion is preferably 0.3 to 3 mm, and more preferably 0.5 to 2 mm.
- the thickness of the seal portion is preferably 0.1 to 2.2 mm, and more preferably 0.2 to 0.9 mm.
- the shape of the solar cell module is usually rectangular. Since the manufacturing method of the present invention is particularly suitable for manufacturing a large area solar cell module, the size of the solar cell module is appropriately 0.6 m ⁇ 0.6 m, and 0.8 m ⁇ 0.8 m. The above is preferable. In many cases, the upper limit of the size of the solar cell module is determined by the size limitation of a manufacturing device such as a decompression device. In addition, a too large solar cell module tends to be difficult to handle in installation or the like. The upper limit of the size of the solar cell module is usually about 3 m ⁇ 3 m due to these restrictions.
- the shape and size of the surface material and the back material are substantially equal to the shape and size of the solar cell module, and the shape and size of the surface material and the back material may be slightly different.
- FIG. 4 is a cross-sectional view showing another example of the embodiment of the solar cell module of the present invention.
- the solar cell module 4 includes a transparent surface material 10 that is a surface material, a glass substrate 16 that is a back surface material, a resin layer 40 sandwiched between the transparent surface material 10 and the glass substrate 16, and the resin layer 40 side of the glass substrate 16.
- a thin film solar cell device 17 formed on the surface of the thin film solar cell device, a seal portion 42 surrounding the resin layer 40, and an electric wire 44 connected to the thin film solar cell device 17 and extending to the outside through the seal portion 42. .
- the transparent face material 10 as the surface material is the second face material
- the glass substrate 16 as the back surface material is the first face material
- the transparent face material 10 as the surface material is When it becomes the first face material
- the glass substrate 16 as the back face material becomes the second face material.
- the surface material is a transparent surface material that transmits sunlight.
- the transparent face material include a glass plate or a transparent resin plate, and it has not only high transparency to sunlight but also light resistance, weather resistance, corrosion resistance, surface scratch resistance, and high mechanical strength. From the point of view, the glass plate is most preferable.
- a transparent surface material is preferable also in terms of transmitting light for curing the photocurable resin composition.
- the material of the glass plate include glass materials such as soda lime glass, and high transmittance glass (white plate glass) having a lower iron content and less bluishness is more preferable. In order to improve safety, tempered glass may be used as a surface material.
- the material of the transparent resin plate include highly transparent resin materials (such as polycarbonate and polymethyl methacrylate).
- the transparent surface material may be subjected to a surface treatment in order to improve the interfacial adhesive force with the resin layer.
- a surface treatment method include a method of treating the surface of the glass plate with a silane coupling agent.
- the thickness of the transparent face material is usually 1 to 6 mm in the case of a glass plate, and usually 0.1 to 3 mm in the case of a transparent resin plate.
- a glass substrate is more preferable because a thin film solar cell device is preferably formed on the surface.
- the thin film solar cell device can be formed at a temperature lower than the heat resistant temperature of the resin plate, such as by applying an ink containing a compound semiconductor, a resin substrate can be used, and a non-transparent substrate (for example, insulating A solar cell device may be formed on the surface of a metal plate such as stainless steel or a ceramic plate provided with a layer.
- the transparent substrate should just have the weather resistance, corrosion resistance, high mechanical strength, etc. which are requested
- a glass substrate using a glass plate such as soda lime glass is preferable.
- the material for the glass plate of the glass substrate include the same materials as those for the glass plate described above.
- a glass substrate having a thin film solar cell device distributed in the market may be obtained and used.
- a thin-film solar cell device is formed in a region excluding the peripheral portion of the surface.
- the transparent substrate may be subjected to a surface treatment in order to improve the interfacial adhesive force with the seal portion.
- the surface treatment may be performed only on the peripheral edge or on the entire surface of the face material. Examples of the surface treatment method include a method of treating the surface of the transparent surface material with a silane coupling agent.
- the thickness of the transparent substrate including the thickness of the thin film solar cell device is usually 1 to 6 mm in the case of a glass substrate, and is usually in the case of a non-transparent substrate using a transparent resin substrate or a metal plate provided with an insulating layer. 0.1 to 3 mm. Among them, the thickness of the thin film solar cell device is usually 10 ⁇ m or less.
- a thin film solar cell device is formed by patterning each time a back electrode layer, a photoelectric conversion layer, and a transparent electrode layer are formed on the surface of a transparent surface material.
- a buffer layer may be provided between the photoelectric conversion layer and the transparent electrode layer as necessary.
- a compound semiconductor solar cell device such as a chalcopyrite system or a CdTe system is preferable as the thin film system solar cell device that generates power with incident light from the uppermost transparent electrode layer.
- the chalcopyrite semiconductor is CuInGaSe 2 , CdS or ZnO can be used as the buffer layer.
- FIG. 5 is a cross-sectional view showing another example of the embodiment of the solar cell module of the present invention.
- the solar cell module 5 includes a glass substrate 16 as a surface material, a glass substrate 16 as a back material, a resin layer 40 sandwiched between two glass substrates, and a resin layer 40 side surface of each glass substrate 16.
- the glass substrate 16 which is the said surface material turns into a 2nd face material
- the glass substrate 16 which is a back surface material becomes a 1st face material
- the glass substrate 16 which is the said surface material becomes the 1st face material.
- the glass substrate 16 which is the back material is the second face material.
- a glass substrate having a thin film solar cell device distributed in the market may be obtained and used.
- description of the same configurations as those of the third embodiment and the fourth embodiment is omitted.
- the surface material a transparent substrate similar to the surface material of the first embodiment can be used, and the glass substrate 16 of the illustrated example is most preferable.
- the back material the same substrate (transparent substrate or non-transparent substrate) as the back material of the second embodiment can be used, and a transparent substrate is preferable, and the glass substrate 16 in the illustrated example is more preferable.
- the thin film solar cell device on the surface material side is formed by patterning each time the transparent electrode layer, the photoelectric conversion layer, and the back electrode layer are formed on the surface of the transparent surface material.
- a material for the back electrode layer it is necessary to use a light-transmitting material (indium tin oxide, tin oxide, etc.) in order to transmit at least part of sunlight to the thin film solar cell device on the back material side.
- the thin film semiconductor is preferably a thin film silicon solar cell device which is an amorphous silicon semiconductor.
- the thin film solar cell device on the back material side is formed by patterning each time the back electrode layer, the photoelectric conversion layer, and the transparent electrode layer are formed on the surface of the transparent surface material.
- a compound semiconductor solar cell device such as a chalcopyrite system or a CdTe system is preferable as a thin film semiconductor.
- a light-transmitting material indium tin oxide, tin oxide, etc.
- the transparent substrate similar to a surface material can also be used for a back surface material. In this case, incident light from the front surface material and the back surface material can be used for power generation.
- a seal part consists of hardened
- the height of a seal part is fully maintained. Therefore, the thickness of the resin layer sandwiched between the first face material and the second face material can be increased. Specifically, the thickness can be 10 ⁇ m to 3 mm.
- a seal part consists of hardened
- the method for producing a laminate of the present invention is a method having the following steps (a) to (d).
- (A) A step of applying the curable resin composition for forming a seal portion of the present invention to the peripheral portion of the surface of the first face material to form an uncured seal portion (however, the surface of the first face material)
- an uncured seal portion (however, the surface of the first face material)
- the first face material described above may be a back surface material or a surface material.
- (B) A step of supplying a liquid curable resin composition for forming a resin layer to a region surrounded by an uncured seal portion.
- (C) In a reduced pressure atmosphere of 100 Pa or less, the first face material, the second face material, and the uncured seal portion are laminated on the curable resin composition for forming a resin layer.
- the step of obtaining a laminate in which the curable resin composition for forming a resin layer is sealed (however, when a thin film solar cell device is formed on the surface of the second face material, a thin film solar cell device is formed)
- the antireflection film is provided on the surface on the side where the surface is formed and on the surface of the second face material, the surface on the back side is overlaid so as to be in contact with the curable resin composition for resin layer formation.
- the second face material is a display device, the image display side is overlapped so as to be in contact with the curable resin composition for forming a resin layer).
- the second face material described above may be a front surface material or a back surface material.
- the production method of the present invention encloses a liquid resin layer-forming curable resin composition between a first face material and a second face material under a reduced pressure atmosphere, and then a high pressure atmosphere such as an atmospheric pressure atmosphere.
- This is a method of forming a resin layer by curing a curable resin composition for forming a resin layer contained underneath.
- the containment of the curable resin composition for resin layer formation under reduced pressure is not a method of injecting the curable resin for resin layer formation into a narrow and wide space between the first face material and the second face material.
- a curable resin composition for forming a resin layer is supplied to almost the entire surface of the first face material, and then the second face material is stacked to form a resin layer between the first face material and the second face material. This is a method of containing a curable resin composition.
- Examples of methods for producing a laminate by containing a curable resin composition for forming a liquid resin layer under reduced pressure and curing the curable resin composition for forming a resin layer under atmospheric pressure include, for example, International Publication No. 2008/81838.
- No. pamphlet and International Publication No. 2009/16943 pamphlet (incorporated in the present application) can refer to a method for producing a transparent laminate and a photocurable resin composition used in the production method.
- an uncured seal portion is formed along the peripheral portion of one surface of the first face member.
- the back material or the front material is used as the first face material is arbitrary.
- the surface that forms the uncured seal portion is: Either of the two surfaces is optional. If the properties of the two surfaces are different, one of the necessary surfaces is selected. For example, when a surface treatment for improving the interfacial adhesive force with the resin layer is performed on one surface, an uncured seal portion is formed on the surface.
- an uncured seal portion is formed on the back surface.
- the surface on which the uncured seal portion is formed is the surface on the side where the thin film solar cell device is formed.
- the surface forming the uncured seal portion is the surface on the image display side.
- the uncured seal portion is a liquid resin layer from the interface between the uncured seal portion and the first face material and the interface between the uncured seal portion and the second face material in step (c) described later. It is preferable to form the resin so that the forming curable resin composition has such an interface adhesive strength as to prevent leakage and a hardness sufficient to maintain the shape.
- the uncured seal portion is formed by applying the curable resin composition for forming a seal portion of the present invention by printing, dispensing, or the like. Moreover, in order to maintain the space
- a liquid curable resin composition for forming a resin layer is supplied to a region surrounded by an uncured seal portion.
- the supply amount of the curable resin composition for resin layer formation is such that the space formed by the seal portion, the first face material, and the second face material is filled with the curable resin composition for resin layer formation, and
- the amount is set in advance so as to have a predetermined distance between the face material and the second face material (that is, the resin layer has a predetermined thickness). At this time, it is preferable to consider in advance volume reduction due to curing shrinkage of the resin layer forming curable resin composition.
- the amount is preferably such that the thickness of the curable resin composition for forming a resin layer is slightly larger than the predetermined thickness of the resin layer.
- the supply method include a method in which the first face material is placed flat and supplied in a dot shape, a linear shape, or a planar shape by a supply means such as a dispenser or a die coater.
- the viscosity of the curable resin composition for forming a resin layer is preferably 0.05 to 50 Pa ⁇ s, more preferably 1 to 20 Pa ⁇ s. If the viscosity is 0.05 Pa ⁇ s or more, the proportion of the monomer (B ′) described later can be suppressed, and the deterioration of the physical properties of the resin layer can be suppressed. Moreover, since the component having a low boiling point is reduced, it is suitable for the reduced pressure laminating method described later. If the viscosity is 50 Pa ⁇ s or less, bubbles are unlikely to remain in the resin layer.
- the viscosity of the curable resin composition for resin layer formation is measured using an E-type viscometer at 25 ° C.
- one or more oligomers (A ′) having a curable group and having a number average molecular weight of 1,000 to 100,000 are preferable because the viscosity is easily adjusted to the above range.
- One or more monomers (B ′) having a curable group and a molecular weight of 125 to 600, and the proportion of the monomer (B ′) is such that the oligomer (A ′) and the monomer (B ′) Of the total (100% by mass), it is preferably 40 to 80% by mass.
- the number average molecular weight of the oligomer (A ′) is preferably from 1,000 to 100,000, more preferably from 10,000 to 70,000. When the number average molecular weight of the oligomer (A ′) is within this range, it is easy to adjust the viscosity of the curable resin composition for resin layer formation within the above range.
- the number average molecular weight of the oligomer (A ′) is a polystyrene-equivalent number average molecular weight obtained by GPC measurement. In addition, in GPC measurement, when the peak of an unreacted low molecular weight component (monomer etc.) appears, this peak is excluded and a number average molecular weight is calculated
- Examples of the curable group of the oligomer (A ′) include photopolymerizable addition polymerizable unsaturated groups (acryloyloxy group, methacryloyloxy group, etc.), combinations of unsaturated groups and thiol groups, and the like.
- photopolymerizable addition polymerizable unsaturated groups acryloyloxy group, methacryloyloxy group, etc.
- combinations of unsaturated groups and thiol groups and the like.
- thermosetting an epoxy group and the like are mentioned, and at least one selected from the group consisting of an acryloyloxy group and a methacryloyloxy group from the viewpoint of obtaining a fast curing rate and a highly transparent resin layer. Groups are preferred.
- the curable group in the relatively high molecular weight oligomer (A ′) tends to be less reactive than the curable group in the relatively low molecular weight monomer (B ′), the monomer (B ′) is cured. There is a possibility that the viscosity of the whole composition increases suddenly and the curing reaction becomes inhomogeneous.
- the curable group of the oligomer (A ′) is an acryloyloxy group having a relatively high reactivity
- the curable group of the monomer (B ′) is a methacryloyloxy group having a relatively low reactivity. More preferably.
- the oligomer (A ′) preferably has an average of 1.8 to 4 curable groups per molecule from the viewpoint of the curability of the resin layer-forming curable resin composition and the mechanical properties of the resin layer.
- examples of the oligomer (A ′) include urethane oligomers having urethane bonds, poly (meth) acrylates of polyoxyalkylene polyols, poly (meth) acrylates of polyester polyols, etc., and resins after curing by molecular design of urethane chains Of these, urethane oligomers are preferred because they can be widely adjusted in terms of their mechanical properties, adhesion to face materials, and the like.
- the proportion of the oligomer (A ′) is preferably 20 to 60% by mass and more preferably 30 to 50% by mass in the total (100% by mass) of the oligomer (A ′) and the monomer (B ′).
- the proportion of the oligomer (A ′) is 20% by mass or more, the heat resistance of the resin layer is good.
- the proportion of the oligomer (A ′) is 60% by mass or less, the curability of the curable resin composition for forming a resin layer and the adhesion between the face material and the resin layer are good.
- the molecular weight of the monomer (B ′) is preferably 125 to 600, more preferably 140 to 400. If the molecular weight of the monomer (B ′) is 125 or more, volatilization of the monomer during production of the laminate by the below-described reduced pressure lamination method can be suppressed. When the molecular weight of the monomer (B ′) is 600 or less, the adhesion between the face material and the resin layer becomes good.
- Examples of the curable group of the monomer (B ′) include, in the case of photocuring, addition polymerizable unsaturated groups (acryloyloxy group, methacryloyloxy group, etc.), combinations of unsaturated groups and thiol groups, and the like.
- addition polymerizable unsaturated groups acryloyloxy group, methacryloyloxy group, etc.
- combinations of unsaturated groups and thiol groups and the like.
- thermosetting an epoxy group and the like are exemplified, and a group selected from an acryloyloxy group and a methacryloyloxy group is preferable from the viewpoint that a curing rate is high and a highly transparent resin layer is obtained.
- the curable group in the relatively low molecular weight monomer (B ′) tends to be more reactive than the curable group in the relatively high molecular weight oligomer (A ′), the monomer (B ′) is cured. There is a possibility that the viscosity of the whole composition increases suddenly and the curing reaction becomes inhomogeneous.
- the curable group of the monomer (B ′) is a methacryloyloxy group having a relatively low reactivity
- the curable group of the oligomer (A ′) is a acryloyloxy group having a relatively high reactivity. More preferably.
- the monomer (B ′) those having 1 to 3 curable groups per molecule are preferable from the viewpoint of the curability of the resin layer forming curable resin composition and the mechanical properties of the resin layer.
- a monomer (B ') contains the monomer (B3) which has a hydroxyl group from the point of the adhesiveness of a face material and a resin layer.
- the monomer (B3) having a hydroxyl group include those similar to the monomer (B3) in the curable resin composition for forming a seal portion, and 2-hydroxybutyl methacrylate is particularly preferable.
- the proportion of the monomer (B3) is preferably 15 to 70% by mass and more preferably 20 to 50% by mass in the total (100% by mass) of the oligomer (A ′) and the monomer (B ′). If the ratio of a monomer (B3) is 15 mass% or more, the sclerosis
- the monomer (B ′) preferably contains the following monomer (B4) from the viewpoint of the mechanical properties of the resin layer.
- Monomer (B4) alkyl methacrylate having an alkyl group having 8 to 22 carbon atoms.
- Examples of the monomer (B4) include n-dodecyl methacrylate, n-octadecyl methacrylate, n-behenyl methacrylate and the like, and n-dodecyl methacrylate and n-octadecyl methacrylate are preferable.
- the proportion of the monomer (B4) is preferably 5 to 50% by mass and more preferably 15 to 40% by mass in the total (100% by mass) of the oligomer (A ′) and the monomer (B ′).
- the proportion of the monomer (B4) is 5% by mass or more, the flexibility of the resin layer is improved.
- the curable resin composition for forming a resin layer may be a photocurable resin composition or a thermosetting resin composition.
- the curable resin composition for forming a resin layer is preferably a photocurable resin composition containing a photopolymerization initiator (C) because it can be cured at a low temperature and has a high curing rate.
- a photoinitiator (C) the thing similar to the photoinitiator (C) in the curable resin composition for seal part formation is mentioned.
- the amount of the photopolymerization initiator (C) is preferably 0.01 to 10 parts by weight, and preferably 0.1 to 2.5 parts by weight with respect to 100 parts by weight as a total of the oligomer (A ′) and the monomer (B ′). Part is more preferred.
- the curable resin composition for forming the resin layer can be prepared by using a polymerization inhibitor, a photocuring accelerator, a chain transfer agent, a light stabilizer (such as an ultraviolet absorber or a radical scavenger), an antioxidant, and a flame retardant as necessary.
- a polymerization inhibitor such as an ultraviolet absorber or a radical scavenger
- a light stabilizer such as an ultraviolet absorber or a radical scavenger
- an antioxidant such as an ultraviolet absorber or a radical scavenger
- a flame retardant such as an agent, an adhesion improver (such as a silane coupling agent), a pigment, and a dye may be included, and a polymerization inhibitor and a light stabilizer are preferably included.
- a polymerization inhibitor in a smaller amount than the polymerization initiator, the stability of the curable resin composition for resin layer formation can be improved, and the molecular weight of the cured resin layer can also be adjusted.
- the first face material supplied with the resin layer forming curable resin composition is put in a decompression device, and the surface of the curable resin composition is placed on the fixed support plate in the decompression device.
- Lay the first face material flat so that A movement support mechanism that can move in the vertical direction is provided in an upper portion of the decompression device, and a second face material is attached to the movement support mechanism.
- the thin film solar cell device is formed on the surface of the second face material, the surface on the side on which the thin film solar cell device is formed is displayed.
- the second face material is a display device, an image is displayed. Turn the side surface down.
- the surface on which the antireflection layer is not formed is directed downward.
- the second face material is placed at a position above the first face material and not in contact with the curable resin composition for resin layer formation. That is, the resin layer forming curable resin composition on the first face material and the second face material (in the case where a thin film solar cell device is formed) are brought into contact with each other. Make them face each other.
- a moving support mechanism that can move in the vertical direction may be provided in the lower part of the decompression device, and the first face material supplied with the curable resin composition may be placed on the moving support mechanism.
- the second face material is attached to a fixed support board provided at the upper part in the decompression device, and the first face material and the second face material are opposed to each other.
- you may support both the 1st face material and the 2nd face material with the movement support mechanism provided in the upper and lower sides in a decompression device.
- the inside of the pressure reducing device is depressurized to form a predetermined reduced pressure atmosphere.
- the first face material and the second face material may be positioned at predetermined positions in the decompression device during the decompression operation or after a predetermined decompressed atmosphere.
- the second face material supported by the moving support mechanism is moved downward, and the curable resin composition for resin layer formation on the first face material is removed.
- a second face material is overlaid on top.
- the surface of the first face material if a thin film solar cell device is formed on the first face material, the surface of the thin film solar cell device; in the case of a display device, the first face material Surface of the image display side
- the surface of the second face material if a thin film solar cell device is formed on the second face material, the surface of the thin film solar cell device, in the case of a display device
- the curable resin composition for resin layer formation is sealed in the space surrounded by the second face material on the image display side) and the uncured seal portion.
- the curable resin composition for resin layer formation is spread by the weight of the second face material, the pressure from the moving support mechanism, etc., and the curable resin composition for resin layer formation is expanded in the space.
- a layer of a curable resin composition for forming a resin layer with few or no bubbles is formed.
- the laminate is also referred to as “lamination precursor”.
- the reduced pressure atmosphere at the time of superposition is 100 Pa or less, preferably 10 Pa or more. If the reduced-pressure atmosphere is too low, each component (curable compound, photopolymerization initiator, polymerization inhibitor, light stabilizer, etc.) contained in the curable resin composition for resin layer formation may be adversely affected. For example, if the reduced-pressure atmosphere is too low, each component may be vaporized, and it may take time to provide the reduced-pressure atmosphere.
- the pressure in the reduced pressure atmosphere is more preferably 15 to 40 Pa.
- the time from when the first face material and the second face material are overlapped to the release of the reduced-pressure atmosphere is not particularly limited, and immediately after sealing the curable resin composition for resin layer formation, the reduced-pressure atmosphere is immediately reduced. You may cancel
- the time for maintaining the reduced pressure state may be several hours or longer, but is preferably within 1 hour, more preferably within 10 minutes from the viewpoint of production efficiency.
- the uncured seal portion is formed by applying the curable resin composition for forming a seal portion of the present invention
- the resin layer in the laminated precursor obtained in the step (c) The thickness of the curable resin composition for formation can be made relatively thick, from 10 ⁇ m to 3 mm.
- the lamination precursor After releasing the reduced pressure atmosphere in the step (c), the lamination precursor is placed in a pressure atmosphere having an atmospheric pressure of 50 kPa or more.
- a pressure atmosphere of 50 kPa or more bubbles are present in the sealed space in the layered precursor because it is pressed in the direction in which the first and second face materials are in close contact with each other due to the increased pressure.
- the resin layer forming curable resin composition flows into the bubbles, and the entire sealed space is uniformly filled with the resin layer forming curable resin composition.
- the pressure atmosphere is usually 80 to 120 kPa.
- the pressure atmosphere may be an atmospheric pressure atmosphere or a higher pressure.
- An atmospheric pressure atmosphere is most preferable because operations such as curing of the curable resin composition for forming a resin layer can be performed without requiring special equipment.
- the time from when the lamination precursor is placed in a pressure atmosphere of 50 kPa or more to the start of curing of the curable resin composition for forming a resin layer (hereinafter referred to as high pressure holding time) is not particularly limited.
- the time required for the process becomes the high pressure holding time. Therefore, when there is no bubble in the sealed space of the laminated precursor already when placed in an atmospheric pressure atmosphere, or when the bubble disappears during the process, the curable resin composition for resin layer formation is immediately Can be cured.
- the lamination precursor When it takes time for the bubbles to disappear, the lamination precursor is held in an atmosphere at a pressure of 50 kPa or more until the bubbles disappear.
- the high pressure holding time since there is usually no problem even if the high pressure holding time is increased, the high pressure holding time may be increased due to other necessity in the process.
- the high-pressure holding time may be a long time of one day or longer, but is preferably within 6 hours from the viewpoint of production efficiency, more preferably within 1 hour, and particularly within 10 minutes from the viewpoint of further increasing production efficiency. preferable.
- the uncured seal portion formed from the curable resin composition for forming the seal portion may be cured simultaneously with the curing of the curable resin composition for forming the resin layer, or the curable resin composition for forming the resin layer. You may harden beforehand before hardening of a thing.
- the photocurable resin composition in the laminated precursor is irradiated with light and cured.
- the photocurable resin composition is cured by irradiating ultraviolet light or short wavelength visible light from a light source (ultraviolet lamp, high pressure mercury lamp, etc.).
- the light has a first face material (including a thin film solar cell device when a thin film solar cell device is formed) and a second face material (when a thin film solar cell device is formed).
- a thin film solar cell device is also included.
- light transmission can be obtained by operating a transmissive display device, but since there are many that do not have light transmission in the state where it is not operated, from a transparent surface material serving as a protective plate Irradiate the light to be cured.
- a transmission-scattering type display device that exhibits a transparent state when not operating is used, light from the display device side can also be used.
- the light is preferably ultraviolet light or visible light of 450 nm or less.
- a transparent surface material is provided with an antireflection layer and the antireflection layer or the transparent resin film on which the antireflection layer is formed does not transmit ultraviolet rays, curing with visible light is required.
- a light shielding part is provided in the periphery of the transparent surface material, and an uncured seal part or a curable resin composition for resin layer formation exists in a region sandwiched between the printing light shielding part and the display device The light from the opening other than the printing light-shielding portion of the transparent surface material may not be sufficiently cured.
- the uncured seal portion and the curable resin composition for resin layer formation by irradiating ultraviolet rays or visible light of 450 nm or less from the side surface of the display device.
- a light source for light irradiation from the side surface a light source used for light irradiation from the transparent surface material side may be used, but using an LED that emits ultraviolet light or visible light of 450 nm or less from the viewpoint of the arrangement space of the light source. preferable.
- the light irradiation step after the light irradiation from the transparent surface material, the light may be irradiated from the side surface of the display device, or vice versa, or the light irradiation may be performed simultaneously.
- the pressure reducing device in which the step (c) has been performed, the pressure reduction in the pressure reducing chamber of the pressure reducing device is released, the pressure reducing chamber is adjusted to a pressure of 80 k to 120 kPa, for example, atmospheric pressure, A treatment for curing the uncured seal portion of the laminated precursor and the curable resin composition for forming a resin layer in a pressure atmosphere may be performed, or may be performed separately from the decompression apparatus in which the step (c) is performed.
- the curing treatment apparatus is adjusted to a pressure of 80 to 120 kPa, and the uncured seal portion of the laminated precursor and the curable resin composition for forming a resin layer in this pressure atmosphere You may perform the process which hardens.
- ( ⁇ -1) A method in which a display device (back surface material) is used as the first surface material, and a transparent surface material 10 (surface material) serving as a protective plate is used as the second surface material.
- ( ⁇ -2) A method of using a transparent surface material 10 (surface material) serving as a protective plate as the first surface material and a display device (back surface material) as the second surface material.
- ( ⁇ -1) A method in which the transparent face material 10 (back surface material) is used as the first face material, and the glass substrate 16 (surface material) is used as the second face material.
- ( ⁇ -2) A method in which the glass substrate 16 (surface material) is used as the first face material, and the transparent face material 10 (back surface material) is used as the second face material.
- ( ⁇ -1) A method in which the glass substrate 16 (back surface material) is used as the first face material and the transparent face material 10 (surface material) is used as the second face material.
- ( ⁇ -2) A method in which the transparent face material 10 (surface material) is used as the first face material, and the glass substrate 16 (back surface material) is used as the second face material.
- ( ⁇ -1) A method in which the glass substrate 16 (back surface material) is used as the first face material and the glass substrate 16 (surface material) is used as the second face material.
- ( ⁇ -2) A method of using the glass substrate 16 (front surface material) as the first face material and using the glass substrate 16 (back surface material) as the second face material.
- the photocurable resin composition for forming a seal portion of the present invention is applied along the peripheral portion of the display device 50 (first face material) by a dispenser (not shown) or the like.
- An uncured seal portion 12 is formed.
- a wiring member such as an FPC that transmits an electrical signal for operating the display device may be installed on the outer periphery of the display device.
- the resin layer forming photocurable resin composition 14 is supplied to the rectangular region 13 surrounded by the uncured seal portion 12 of the display device 50.
- the supply amount of the resin layer forming photocurable resin composition 14 is such that the space sealed by the uncured seal portion 12, the display device 50, and the transparent surface material 10 (see FIG. 9) is photocurable for resin layer formation.
- the amount is set in advance so as to be filled with the resin composition 14.
- the resin layer forming photocurable resin composition 14 is supplied by placing the display device 50 flat on the lower surface plate 18 and moving the resin layer forming light horizontally by the dispenser 20. It is carried out by supplying the curable resin composition 14 in a linear shape, a strip shape or a dot shape.
- the dispenser 20 is horizontally movable over the entire range of the region 13 by a known horizontal movement mechanism including a pair of feed screws 22 and a feed screw 24 orthogonal to the feed screws 22.
- a die coater may be used instead of the dispenser 20.
- the display device 50 first face material
- the transparent face material 10 second face material
- An upper surface plate 30 having a plurality of suction pads 32 is disposed in the upper portion of the decompression device 26, and a lower surface plate 31 is disposed in the lower portion.
- the upper surface plate 30 can be moved in the vertical direction by an air cylinder 34.
- the transparent face material 10 is attached to the suction pad 32.
- the display device 50 is fixed on the lower surface plate 31 with the surface to which the photocurable resin composition 14 for resin layer formation is supplied facing up.
- the air in the decompression device 26 is sucked by the vacuum pump 28.
- the display device 50 stands by below in a state where the transparent surface material 10 is sucked and held by the suction pad 32 of the upper surface plate 30.
- the air cylinder 34 is operated and moved downward.
- the display device 50 and the transparent surface material 10 are overlapped with each other via the uncured seal portion 12 to form a lamination precursor, and the lamination precursor is held for a predetermined time in a reduced pressure atmosphere.
- the mounting position of the display device 50 with respect to the lower surface plate 31, the number of suction pads 32, the mounting position of the transparent surface material 10 with respect to the upper surface plate 30, and the like depend on the size, shape, etc. of the display device 50 and the transparent surface material 10. Adjust as appropriate.
- the device 2 is manufactured.
- the method for producing the laminate of the present invention has been specifically described by taking the case of the method ( ⁇ -1) as an example, but other methods ( ⁇ -2, ⁇ -1, ⁇ -2, ⁇ -1, In the case of ⁇ -2, ⁇ -1, ⁇ -2) and in the case of the transparent laminate ( ⁇ ) of Embodiment 1, a laminate can be produced in the same manner.
- the height of the uncured seal portion is formed by applying the curable resin composition for forming a seal portion of the present invention to form an uncured seal portion. Is well maintained. Therefore, the thickness of the curable resin composition for forming the resin layer sandwiched between the first face material and the second face material can be increased. Specifically, this thickness can be 10 ⁇ m to 3 mm. Moreover, since the curable resin composition for forming a seal portion of the present invention is applied to form an uncured seal portion, the uncured seal portion is continuous and has no gap. Therefore, defects such as leakage of the curable resin composition for forming a resin layer, which is a raw material for the resin layer, at the time of production are unlikely to occur.
- a relatively large area solar cell module and a display device can be manufactured without generating bubbles in the resin layer. Even if bubbles remain in the curable resin composition for resin layer formation sealed under reduced pressure, the pressure is also applied to the curable resin composition for resin layer formation sealed under a high pressure atmosphere before curing. , The volume of the bubbles decreases and the bubbles disappear easily.
- the volume of gas in the bubbles in the curable resin composition for forming a resin layer sealed under 100 Pa is considered to be 1/1000 under 100 kPa. Since the gas may be dissolved in the curable resin composition for forming a resin layer, the gas in a small volume of bubbles quickly dissolves and disappears in the curable resin composition for forming a resin layer.
- the liquid curable resin composition for forming a resin layer is a fluid composition.
- the pressure is uniformly distributed on the surface of the battery device, and no further stress is applied to a part of the surface of the thin film solar cell device in contact with the curable resin composition for resin layer formation.
- the high temperature is not required for hardening when the curable resin composition for resin layer formation is a photocurable composition, there is also little possibility of damage to the thin film type solar cell device or display device by high temperature.
- the interfacial adhesive force between the resin layer and the thin-film solar cell device or face material, or display device or transparent face material due to the curing of the resin layer forming curable resin composition is Higher than adhesive strength.
- the curable resin composition for forming a fluid resin layer is pressurized and adhered to the surface of the thin film solar cell device or the face material, or the surface of the display device or the transparent face material, and cured in that state, High interfacial adhesive strength is obtained, and uniform adhesion to the surface of thin-film solar cell devices and face materials, or display devices and transparent face materials is obtained. . Therefore, there is a low possibility that peeling will occur on the surface of the resin layer, and there is little possibility that moisture or corrosive gas will enter from a portion where the interfacial adhesive force is insufficient.
- a curable resin composition for forming a high-viscosity resin layer containing a relatively high molecular weight curable compound capable of increasing the strength of the resin layer can be used.
- Example 1 is an example
- Examples 2 and 3 are comparative examples.
- the number average molecular weight of the oligomer was determined using a GPC apparatus (manufactured by TOSOH, HLC-8020).
- the viscosity of the photocurable resin composition was measured with an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., RE-85U).
- the haze value was determined by measurement according to ASTM D1003 using a haze guard II manufactured by Toyo Seiki Seisakusho.
- Example 1 (Display device) The liquid crystal display device was taken out from a commercially available 32-type liquid crystal television receiver (HDV-32WX2D-V manufactured by PC DEPOT CORPORATION). The liquid crystal display device had a length of 712 mm, a width of 412 mm, and a thickness of about 2 mm. Polarizing plates were bonded to both surfaces of the liquid crystal display device, and six driving FPCs were bonded to one side of the long side, and a printed wiring board was bonded to the end of the FPC. The image display area was 696 mm long and 390 mm wide. The liquid crystal display device was designated as display device A.
- Glass plate Printed on a peripheral edge of one surface of soda lime glass having a length of 794 mm, a width of 479 mm, and a thickness of 3 mm, in a frame shape by ceramic printing containing black pigment so that the opening has a length of 698 mm and a width of 392 mm Formed.
- an antireflection film manufactured by Nippon Oil & Fats Co., Ltd., Realak X4001
- a glass plate B serving as a protective plate was produced.
- oligomer (A) a urethane acrylate oligomer (hereinafter referred to as UC-1) solution diluted with 30% by mass of isobornyl acrylate was obtained.
- the number of curable groups of UC-1 was 2, and the number average molecular weight was about 55000.
- the viscosity of the UC-1 solution at 60 ° C. was about 580 Pa ⁇ s.
- Defoaming treatment was performed by placing the photocurable resin composition C for forming a seal part in a decompression device in an open state while being placed in a container, and reducing the pressure in the decompression device to about 20 Pa and holding for 10 minutes. .
- the viscosity at 25 ° C. of the photocurable resin composition C for forming a seal part was measured and found to be about 1400 Pa ⁇ s.
- a photocurable resin composition C for forming a seal portion is sandwiched between a pair of soda lime glasses (100 ⁇ 100 mm, thickness 2 mm) so that the thickness is about 1 mm, and light intensity of 365 nm from a chemical lamp is obtained.
- a bifunctional polypropylene glycol having a molecular end modified with ethylene oxide (number average molecular weight calculated from hydroxyl value: 4000) and isophorone diisocyanate were mixed at a molar ratio of 4 to 5, and 70 in the presence of a tin compound catalyst.
- a urethane acrylate oligomer (hereinafter referred to as UA-2) is obtained by adding 2-hydroxyethyl acrylate in a molar ratio of about 1: 2 to the prepolymer obtained by reacting at a temperature of 70 ° C. and reacting at 70 ° C. Got.
- the number of curable groups of UA-2 was 2, the number average molecular weight was about 24,000, and the viscosity at 25 ° C. was about 830 Pa ⁇ s.
- Defoaming treatment was performed by placing the photocurable resin composition D for resin layer formation in a decompression device in an open state while being placed in a container, and reducing the pressure in the decompression device to about 20 Pa and holding for 10 minutes. . It was 1.7 Pa.s when the viscosity at 25 degrees C of the photocurable resin composition D for resin layer formation was measured.
- the display device A was placed flat on the upper surface of the lower surface plate in the decompression device in which a pair of surface plate lifting devices were installed so that the surface of the photocurable resin composition D for resin layer formation was on top.
- An electrostatic chuck is used on the lower surface of the upper surface plate of the lifting device in the decompression device so that the glass plate B as the first face material faces the display device A on the side where the printing light-shielding portion is formed. And held it.
- the holding position is the same as that of the display device A in the vertical direction so that the opening without the light-shielding portion of the glass plate B and the image display area of the display device A are at the same position with a margin of about 1 mm.
- the distance was set to 30 mm.
- the decompression device was sealed and evacuated until the pressure in the decompression device reached about 15 Pa.
- the upper and lower surface plates are brought close to each other by the lifting device in the decompression device, and the display device A and the glass plate B are pressure-bonded at a pressure of 2 kPa through the photocurable resin composition D for resin layer formation and held for 1 minute. It was. Static electricity is removed from the electrostatic chuck, the glass plate H is separated from the upper surface plate, the pressure reducing device is returned to atmospheric pressure in about 15 seconds, and light for forming a resin layer is formed by the display device A, the glass plate B, and the uncured seal portion A lamination precursor E in which the curable resin composition D was sealed was obtained. In the laminated precursor E, the shape of the uncured seal portion was maintained in an almost initial state.
- a light emitting dominant wavelength is about 390 nm from the side of the display device A on an uncured seal portion (photocurable resin composition C for forming a seal portion) provided on the peripheral portion of the display device A of the laminated precursor E.
- an ultraviolet light source in which ultraviolet LEDs are linearly arranged, light is irradiated for about 10 minutes over the entire circumference of the uncured seal portion, the seal portion is cured, and the laminated precursor E is kept horizontal for about 10 minutes. I put it.
- the resin layer had a target thickness (about 0.4 mm) and width (about 1 mm).
- a transparent laminate was prepared in the same manner using a glass plate of almost the same size in place of the display device A, and the haze value in a portion without the printing light-shielding portion was measured. Met.
- the display device F was returned to the housing of the liquid crystal television receiver from which the liquid crystal display device was taken out, the wiring was rejoined and the power was turned on, an image with a high display contrast was obtained from the beginning. Even if the image display surface was strongly pressed with a finger, the image was not disturbed, and the glass plate B effectively protected the display device A.
- Example 2 (Photo-curable resin composition for forming a seal part)
- Bifunctional polypropylene glycol having a molecular end modified with ethylene oxide (number average molecular weight calculated from hydroxyl value: 4000) and hexamethylene diisocyanate were mixed at a molar ratio of 6 to 7, and then diluted with n-dodecyl methacrylate. Thereafter, 2-hydroxyethyl acrylate was added to the prepolymer obtained by reacting at 70 ° C. in the presence of a tin compound catalyst at a molar ratio of approximately 1: 2, and reacted at 70 ° C. to obtain 10% by mass.
- a urethane acrylate oligomer (hereinafter referred to as UC-3) solution diluted with n-dodecyl methacrylate was obtained.
- the number of curable groups of UC-3 was 2, and the number average molecular weight was about 45,000.
- the viscosity of the UC-3 solution at 60 ° C. was about 650 Pa ⁇ s.
- the defoaming treatment was performed by placing the photocurable resin composition G for forming a seal part in a decompression device in an open state while being placed in a container, and reducing the pressure in the decompression device to about 20 Pa and holding it for 10 minutes. . It was about 1300 Pa.s when the viscosity at 25 degrees C of the photocurable resin composition G for seal part formation was measured.
- a photocurable resin composition G for forming a seal portion is sandwiched between a pair of soda lime glasses (100 ⁇ 100 mm, thickness 2 mm) so as to have a thickness of about 1 mm.
- a pair of soda lime glasses 100 ⁇ 100 mm, thickness 2 mm
- Example 3 (Photo-curable resin composition for forming a seal part) 80 parts by mass of UA-2 used in Example 1, 10 parts by mass of 2-hydroxybutyl methacrylate (Kyoeisha Chemical Co., Ltd., light ester HOB) and 10 parts by mass of n-dodecyl methacrylate were uniformly mixed.
- the defoaming treatment was performed by placing the photocurable resin composition H for forming a seal part in a decompression device in an open state while being placed in a container, and reducing the pressure in the decompression device to about 20 Pa and holding for 10 minutes. .
- the viscosity at 25 ° C. of the photocurable resin composition H for forming a seal part was measured, it was 400 Pa ⁇ s, which was lower than the preferred viscosity.
- the photocurable resin composition H for forming a seal portion is applied with a dispenser so as to have a width of about 1 mm and a coating thickness of about 0.6 mm over the entire circumference at a position of about 5 mm outside the image display area of the display device A. Then, an uncured seal portion was formed. However, after only 2 minutes, the photocurable resin composition H for forming a seal portion began to spread in the width direction of the seal portion, and the shape of the uncured seal portion could not be maintained. Further, with another photocurable resin composition for forming a seal part (viscosity at 25 ° C .: 3200 Pa ⁇ s), the seal part cannot be applied uniformly.
- the curable resin composition for forming a seal portion of the present invention surrounds the curable resin composition for forming a resin layer sandwiched between a first face material and a second face material with a seal portion. It is useful as a material for forming the seal portion when a laminated body (laminated glass, display device, solar cell module, etc.) is produced by curing in the open state.
- a laminated body laminated glass, display device, solar cell module, etc.
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Abstract
Description
(a)一方の透明面材の表面の周縁部にシール部を形成する工程と、
(b)シール部で囲まれた領域に液状の樹脂層形成用硬化性樹脂組成物を供給する工程と、
(c)減圧雰囲気下にて樹脂層形成用硬化性樹脂組成物の上に他方の透明面材を重ねて、2枚の透明面材およびシール部で樹脂層形成用硬化性樹脂組成物が密封された積層物を得る工程と、
(d)大気圧下に積層物を置いた状態にて、樹脂層形成用硬化性樹脂組成物を硬化させる工程と
を有する透明積層体の製造方法(特許文献1、2参照)。
(1)一方の透明面材の周縁部に沿って両面接着テープを貼着する方法。
(2)一方の透明面材の周縁部に沿って両面接着テープを貼着し、その上面にシール部形成用硬化性樹脂組成物を塗布する方法。
(3)一方の透明面材の周縁部に沿ってシール部形成用硬化性樹脂組成物を塗布する方法。
(4)一方の透明面材の周縁部に沿ってスペーサー粒子を混合したシール部形成用硬化性樹脂組成物を塗布する方法。
また、(2)の方法では、シール部の形成に複数の工程が必要となり、煩雑である。
本発明のシール部形成用硬化性樹脂組成物は、第1の面材と第2の面材との間に挟持された樹脂層形成用硬化性樹脂組成物を、その周囲をシール部で囲んだ状態で硬化させて積層体を製造する際に、該シール部を形成するために用いられることが好ましい。
なお、ここでモノマー(B)とは、モノマーとしてシール部形成用硬化性樹脂組成物に含まれる低分子量の硬化性化合物であり、該モノマー(B)には、下記のオリゴマー(A1)の合成に用いてプレポリマーのイソシアネート基と反応したモノマー(B2)は含まれず、未反応で残存するモノマー(B2)は含まれる。
オリゴマー(A)の硬化性基は、アクリロイルオキシ基であることがより好ましく、モノマー(B)の硬化性基は、メタクリロイルオキシ基であることがより好ましい。
本発明のシール部形成用硬化性樹脂組成物は、モノマー(B)として、イソシアネート基と反応する基を有さないモノマー(B1)を含み、ウレタンオリゴマー(A1)が、モノマー(B1)の存在下、ポリオールとポリイソシアネートとを反応させてイソシアネート基を有するプレポリマーを得た後、該プレポリマーのイソシアネート基に、イソシアネート基と反応する基および硬化性基を有するモノマー(B2)を反応させて得られたものであることが好ましい。
本発明のシール部形成用硬化性樹脂組成物は、光重合開始剤(C)を含む光硬化性樹脂組成物であることが好ましい。
本発明のシール部形成用硬化性樹脂組成物は、光重合開始剤(C)として、吸収波長の異なる2種以上の光重合開始剤を含んでいてもよい。
本発明の積層体のシール部の幅は、0.3~3mmであることが好ましい。
本発明の積層体のシール部の厚さは、10μm~3mmであることが好ましい。
本発明の積層体は、両方が透明面材である第1の面材および第2の面材と、第1の面材および第2の面材に挟まれた樹脂層と、樹脂層の周囲を囲むシール部とを有する透明積層体であってもよい。
本発明の積層体は、少なくとも一方が透明面材である第1の面材および第2の面材と、第1の面材および第2の面材に挟まれた樹脂層と、第1の面材および第2の面材のうちの少なくとも一方の面材の樹脂層側の表面に形成された薄膜系太陽電池デバイスと、樹脂層の周囲を囲むシール部とを有する太陽電池モジュールであってもよい。
(a)第1の面材の表面の周縁部に、本発明のシール部形成用硬化性樹脂組成物を塗布して未硬化のシール部を形成する工程。
(b)未硬化のシール部で囲まれた領域に液状の樹脂層形成用硬化性樹脂組成物を供給する工程。
(c)100Pa以下の減圧雰囲気下にて、樹脂層形成用硬化性樹脂組成物の上に第2の面材を重ねて、第1の面材、第2の面材および未硬化のシール部で樹脂層形成用硬化性樹脂組成物が密封された積層物を得る工程。
(d)50kPa以上の圧力雰囲気下に積層物を置いた状態にて、未硬化のシール部および樹脂層形成用硬化性樹脂組成物を硬化させる工程。
なお、本明細書において、前記(c)工程にて得られた積層物は、第1の面材、第2の面材および未硬化のシール部により密封された樹脂層形成用硬化性樹脂組成物がまだ硬化されていないものであり、これを積層体前駆体と称することもあるが、この硬化されていない状態のもの、上記(d)工程を経て、樹脂層形成用組成物が硬化されたものも含め、積層物とも称する。
本発明の積層体は、第1の面材および第2の面材に挟まれた樹脂層の厚さを厚くすることができ、かつ欠陥が少ない。
本発明の積層体の製造方法によれば、第1の面材および第2の面材に挟まれた樹脂層を肉厚にでき、かつ欠陥が少ない積層体を製造できる。
合わせガラス等の透明積層体においては、両方の面材を「表面材」という。
表示装置においては、表示デバイスの保護板となる透明面材を「表面材」、表示デバイスを「裏面材」という。
太陽電池モジュールにおいては、太陽光入射側の面材を「表面材」、他の面材を「裏面材」という。
表面材および裏面材を総称して「面材」という。
該面材のうち、本発明の製造方法において、周縁部にシール部が形成され、かつシール部で囲まれた領域に液状の硬化性樹脂組成物が供給される面材を「第1の面材」といい、該硬化性樹脂組成物の上に重ねられる面材を「第2の面材」という。
光透過性を有する面材を「透明面材」という。
ガラスからなる透明面材を「ガラス板」という。
樹脂からなる透明面材を「透明樹脂板」という。
表面に薄膜系太陽電池デバイスが形成された面材を「基板」といい、表面に薄膜系太陽電池デバイスが形成されていない面材と区別する。
表面に薄膜系太陽電池デバイスが形成された透明面材を、下記するガラス基板、透明樹脂基板を含め、「透明基板」といい、表面に薄膜系太陽電池デバイスが形成されていない透明面材と区別する。
表面に薄膜系太陽電池デバイスが形成されたガラス板を「ガラス基板」といい、表面に薄膜系太陽電池デバイスが形成されていないガラス板と区別する。
表面に薄膜系太陽電池デバイスが形成された透明樹脂板を「透明樹脂基板」といい、表面に薄膜系太陽電池デバイスが形成されていない透明樹脂基板と区別する。
表面に薄膜系太陽電池デバイスが形成された非透明な面材を「非透明基板」という。
本発明のシール部形成用硬化性樹脂組成物は、第1の面材と第2の面材との間に挟持される液状物からなる層の周囲を囲むシール部を形成するための硬化性樹脂組成物であり、また第1の面材と第2の面材との間に挟持される液状の樹脂層形成用硬化性樹脂組成物の周囲を囲むシール部を形成するために好適なものであり、また第1の面材と第2の面材との間に挟持された樹脂層形成用硬化性樹脂組成物を、その周囲をシール部で囲んだ状態で硬化させて積層体を製造する際に、該シール部を形成するためにより好適に用いられる。
シール部形成用硬化性樹脂組成物の粘度は、25℃においてE型粘度計を用いて測定する。
オリゴマー(A)の数平均分子量は、30000~100000であり、40000~80000が好ましく、50000~65000がより好ましい。オリゴマー(A)の数平均分子量が該範囲であれば、シール部形成用硬化性樹脂組成物の粘度を前記範囲に調整しやすい。
オリゴマー(A)の数平均分子量は、GPC測定によって得られた、ポリスチレン換算の数平均分子量である。なお、GPC測定において、未反応の低分子量成分(モノマー等)のピークが現れる場合は、該ピークを除外して数平均分子量を求める。
オリゴマー(A)としては、ウレタン結合を有するウレタンオリゴマー、ポリオキシアルキレンポリオールのポリ(メタ)アクリレート、ポリエステルポリオールのポリ(メタ)アクリレート等が挙げられ、ウレタン鎖の分子設計等によって硬化後の樹脂の機械的特性、面材との密着性等を幅広く調整できる点から、ウレタンオリゴマー(A1)が好ましい。
希釈剤として、後述するモノマー(B)の1種であるイソシアネート基と反応する基を有さないモノマー(B1)の存在下、ポリオールとポリイソシアネートとを反応させてイソシアネート基を有するプレポリマーを得た後、該プレポリマーのイソシアネート基に、イソシアネート基と反応する基および硬化性基を有するモノマー(B2)を反応させる方法がウレタンオリゴマー(A1)の合成方法として挙げられる。
モノマー(B)の分子量は、125~600であり、140~400が好ましく、150~350がより好ましい。モノマー(B)の分子量が125以上であれば、後述の減圧積層方法によって積層体を製造する際のモノマー(B)の揮発が抑えられる。モノマー(B)の分子量が600以下であれば、高分子量のオリゴマー(A)に対するモノマー(B)の溶解性を高めることができ、シール部形成用硬化性樹脂組成物としての粘度調整を好適に行うことができる。
モノマー(B)としては、シール部形成用硬化性樹脂組成物の硬化性、シール部の機械的特性の点から、硬化性基を1分子あたり1~3個有するものが好ましい。
水酸基を有するモノマー(B3)としては、水酸基数1~2、炭素数3~8のヒドロキシアルキル基を有するヒドロキシメタアクリレート(2-ヒドロキシプロピルメタクリレート、2-ヒドロキシブチルメタクリレート、4-ヒドロキシブチルメタクリレート、6-ヒドロキシヘキシルメタクリレート等)が好ましく、2-ヒドロキシブチルメタクリレートが特に好ましい。
本発明のシール部形成用硬化性樹脂組成物は、光硬化性樹脂組成物であってもよく、熱硬化性樹脂組成物であってもよい。本発明のシール部形成用硬化性樹脂組成物としては、低温で硬化でき、かつ硬化速度が速い点から、光重合開始剤(C)を含む光硬化性樹脂組成物が好ましい。
本発明のシール部形成用硬化性樹脂組成物は、必要に応じて、重合禁止剤、光硬化促進剤、連鎖移動剤、光安定剤(紫外線吸収剤、ラジカル捕獲剤等)、酸化防止剤、難燃化剤、接着性向上剤(シランカップリング剤等)、顔料、染料等の各種添加剤を含んでいてもよく、重合禁止剤、光安定剤を含むことが好ましい。特に、重合禁止剤を重合開始剤より少ない量含むことによって、シール部形成用硬化性樹脂組成物の安定性を改善でき、硬化後の樹脂層の分子量も調整できる。
光安定剤としては、紫外線吸収剤(ベンゾトリアゾール系、ベンゾフェノン系、サリチレート系等)、ラジカル捕獲剤(ヒンダードアミン系)等が挙げられる。
酸化防止剤としては、リン系、イオウ系の化合物が挙げられる。
以上説明した本発明のシール部形成用硬化性樹脂組成物にあっては、粘度が500Pa・s以上であるため、未硬化のシール部を形成した直後から、シール部で囲まれた領域内に液状物を供給し、シール部を硬化させるまでの一定時間ずっと、シール部の形状を維持できる。そのため、シール部の高さを充分に維持でき、シール部で囲まれた領域に供給される樹脂層形成用硬化性樹脂組成物の量およびこれを硬化させてなる樹脂層の厚さを、一定値にできる。また、シール部は、液状物が供給され硬化されるまでの一定時間、該液晶物の堰の役割を果たすことができる。また、樹脂層の厚さを比較的厚く(具体的には10μm~3mm程度)にすることも可能である。
また、粘度が3000Pa・s以下であるため、塗布によるシール部の形成が可能である。そのため、連続したシール部を効率的に形成できる。
本発明の積層体は、第1の面材および第2の面材と、第1の面材および第2の面材に挟まれた樹脂層と、樹脂層の周囲を囲むシール部とを有する積層体であって、シール部が、本発明のシール部形成用硬化性樹脂組成物の硬化物からなるものである。
透明積層体:両方が透明面材である第1の面材および第2の面材と、第1の面材および第2の面材に挟まれた樹脂層と、樹脂層の周囲を囲むシール部とを有する。
表示装置:一方が透明面材であり、他方が表示デバイスである、第1の面材および第2の面材と、第1の面材および第2の面材に挟まれた樹脂層と、樹脂層の周囲を囲むシール部とを有する。
太陽電池モジュール:少なくとも一方が透明面材である第1の面材および第2の面材と、第1の面材および第2の面材に挟まれた樹脂層と、第1の面材および第2の面材のうちの少なくとも一方の面材の樹脂層側の表面に形成された薄膜系太陽電池デバイスと、樹脂層の周囲を囲むシール部とを有する。
(α)2枚の「透明面材」が表面材である、合わせガラス、透明パネル等の透明積層体(第1の実施形態)。
(β)表示デバイスの保護板となる「透明面材」が表面材であり、「表示デバイス」が裏面材である、透明面材によって表示デバイスが保護された表示装置(第2の実施形態)。
(γ)表面に薄膜系太陽電池デバイスが形成された「透明基板」が表面材であり、表面に薄膜系太陽電池デバイスが形成されていない「面材」が裏面材である、1層の薄膜系太陽電池デバイスを有する太陽電池モジュール(第3の実施形態)。
(δ)表面に薄膜系太陽電池デバイスが形成されていない「透明面材」が表面材であり、表面に薄膜系太陽電池デバイスが形成された「基板」が裏面材である、1層の薄膜系太陽電池デバイスを有する太陽電池モジュール(第4の実施形態)。
(ε)表面に薄膜系太陽電池デバイスが形成された「透明基板」が表面材であり、表面に薄膜系太陽電池デバイスが形成された「基板」が裏面材である、2層の薄膜系太陽電池デバイスを有する太陽電池モジュール(第5の実施形態)。
図1は、本発明の透明積層体の実施形態の一例を示す断面図である。
透明積層体1は、表面材である2枚の透明面材10(第1の面材および第2の面材)と、2枚の透明面材10に挟まれた樹脂層40と、樹脂層40の周囲を囲むシール部42とを有する。
表面材は、光を透過する透明面材である。
透明面材としては、ガラス板、または透明樹脂板が挙げられる。ガラス板を用いた場合、合わせガラスとなり、透明樹脂板を用いた場合、透明パネルと称する。ガラス板と透明樹脂板とを組み合わせて用いてもよい。
また、透明面材の一部または全体が、着色していたり、磨りガラス状に光を散乱、あるいは表面の微細な凹凸等によって透過時の光を屈折させたり、反射させるようにしておくこともできる。また、上記のような様態を示す光学フィルム、偏光フィルム等の光学変調を行う光学フィルム等を透明面材に貼合したものを一体物として透明面材として用いることもできる。
ガラス板の材料としては、ソーダライムガラス等のガラス材料が挙げられる。
透明樹脂板の材料としては、透明性の高い樹脂材料(ポリカーボネート、ポリメチルメタクリレート等)が挙げられる。
透明面材の厚さは、機械的強度、透明性の点から、ガラス板の場合は通常0.3~6mmが好ましく、1~6mmがより好ましい。特に、厚さの薄い透明積層体が要求される場合には、ガラス板の厚さは、0.3~1.5mmが好ましく、0.3~1mmが好ましい。また、透明樹脂板の場合の厚さは通常0.1~3mmである。
樹脂層は、積層された表面材と裏面材とを接合する役目をする層であり、後述する液状の樹脂層形成用硬化性樹脂組成物を硬化してなる層である。
樹脂層の厚さは、0.2~3mmが好ましい。樹脂層の厚さが0.2mm以上であれば、透明積層体の機械的強度が良好となる。特に、樹脂層の厚さは、0.2~1.5mmがより好ましく、0.2~0.8mmであることが更に好ましい。なお、硬化により樹脂層の厚さはうすくなるため、塗布時には、樹脂層の厚さは、硬化後の厚さの1.2~2倍程度であることが好ましい。
樹脂層の厚さを調整する方法としては、後述のシール部の厚さを調整する方法が挙げられる。未硬化のシール部に所定の粒子径のスペーサ粒子を配置しておいてもよい。
シール部は、本発明のシール部形成用硬化性樹脂組成物を塗布し、硬化してなるものである。透明積層体の場合、シール部の幅は、0.3~3mmが好ましく、特に0.5~2mmがより好ましい。また、シール部の厚さは、0.3~3.2mmが好ましく、特に0.3~1.6mmがより好ましい。
透明積層体の大きさは、特に限定されないが、300mm以上、より好ましくは600mm以上の辺を少なくとも1つ有する透明基板であれば、建築用や車両用の開口部に設置する透明部材として広く利用できる。通常の用途においては、4m2以下の大きさが適当である。
図2は、本発明の表示装置の実施形態の一例を示す断面図である。
表示装置2は、表面材である透明面材10と、裏面材である表示デバイス50と、透明面材10および表示デバイス50に挟まれた樹脂層40と、樹脂層40の周囲を囲むシール部42と、表示デバイス50に接続された表示デバイス50を動作させる駆動ICを搭載したフレキシブルプリント配線板54(FPC)と、透明面材10の周縁部に形成された遮光印刷部55とを有する。なお、上記表面材である透明面材10が、第2の面材となる場合は、裏面材である表示デバイス50が第1の面材となり、また上記表面材である透明面材10が、第1の面材となる場合は、裏面材である表示デバイス50が第2の面材となる。
表面材は、表示デバイスの表示画像を透過する透明面材である。
透明面材としては、ガラス板、または透明樹脂板が挙げられ、表示デバイスからの出射光や反射光に対して透明性が高い点はもちろん、耐光性、低複屈折性、高い平面精度、耐表面傷付性、高い機械的強度を有する点からも、ガラス板が最も好ましい。光硬化性樹脂組成物の硬化のための光を透過させる点でも透明面材が好ましい。
透明樹脂板の材料としては、透明性の高い樹脂材料(ポリカーボネート、ポリメチルメタクリレート等)が挙げられる。
透明面材には、表示画像のコントラスを高めるために、樹脂層との接合面の裏面に反射防止層を設けてもよい。反射防止層は、透明面材の表面に無機薄膜を直接形成する方法、反射防止層を設けた透明樹脂フィルムを透明面材に貼合する方法によって設けることができる。
また、画像表示の目的に応じて、第1の実施形態と同様に、透明面材の一部または全体が、着色していたり、磨りガラス状に光を散乱、あるいは表面の微細な凹凸等により透過時の光を屈折させたり、反射させるようにしておくこともできる。また、上記のような様態を示す光学フィルム、偏光フィルム等の光学変調を行う光学フィルム等を透明面材に貼合したものを一体物として透明面材として用いることもできる。
裏面材は、表示デバイスである。
図示例の表示デバイス50は、カラーフィルタを設けた透明面材52とTFTを設けた透明面材53とを液晶層を介して両面材の周辺部において貼合し、これを一対の偏光板51で挟んだ構成の液晶表示デバイスの一例であるが、本発明における表示デバイスは、図示例のものに限定されない。
表示デバイスの厚さは、TFTによって動作させる液晶表示デバイスの場合は通常0.4~4mmであり、EL表示デバイスの場合は通常0.2~3mmである。
樹脂層は、積層された表面材と裏面材とを接合する役目をする層であり、後述する液状の樹脂層形成用硬化性樹脂組成物を硬化してなる層である。表示装置においては、他の実施形態に比べ、硬化後の樹脂の弾性率が低くなる樹脂層形成用硬化性樹脂組成物が好ましい。樹脂の弾性率が大きいと、樹脂の硬化に際して、硬化収縮等で発生する応力が表示デバイスの表示性能への悪影響を与えるおそれがある。
樹脂層の厚さを調整する方法としては、後述するシール部の厚さを調節するとともに、第1の面材に供給される液状の樹脂層形成用硬化性樹脂組成物の供給量を調節する方法が挙げられる。
シール部は、本発明のシール部形成用硬化性樹脂組成物を塗布し、硬化してなるものである。表示デバイスの画像表示領域の外側の領域が比較的狭いため、シール部の幅は狭くすることが好ましい。シール部の幅は、0.3~3mm、特に0.5~2mmが好ましい。また、シール部の厚さは、0.1~2.2mmが好ましく、特に0.2~0.9mmがより好ましい。
遮光印刷部は、表示デバイスの画像表示領域以外が透明面材側から視認できないようにして、表示デバイスに接続されている配線部材等を隠蔽するものである。遮光印刷部は、透明面材の樹脂層との接合面、またはその裏面に設けることができ、遮光印刷部と画像表示領域との視差を低減する点では、透明面材の樹脂層との接合面に設置するのが好ましい。透明面材がガラス板の場合、遮光印刷部に黒色顔料を含むセラミック印刷を用いると遮光性が高く好ましい。
表示装置の形状は、通常矩形である。
表示装置の大きさは、本発明の製造方法が比較的大面積の表示装置の製造に特に適していることから、液晶表示デバイスを用いたテレビ受像機の場合、0.5m×0.4m以上が適当であり、0.7m×0.4m以上が特に好ましい。表示装置の大きさの上限は、表示デバイスの大きさで決まることが多い。また、あまりに大きい表示装置は、設置等における取り扱いが困難となりやすい。表示装置の大きさの上限は、これらの制約から、通常2.5m×1.5m程度である。
保護板となる透明面材と表示デバイスの寸法は、ほぼ等しくてもよいが、表示装置を収納する他の筺体との関係から、透明面材が表示デバイスより一回り大きくなる場合も多い。また逆に、他の筺体の構造によっては、透明面材を表示デバイスより若干小さくしてもよい。
図3は、本発明の太陽電池モジュールの実施形態の一例を示す断面図である。
太陽電池モジュール3は、表面材であるガラス基板16と、裏面材である透明面材10と、ガラス基板16および透明面材10に挟まれた樹脂層40と、ガラス基板16の樹脂層40側の表面に形成されている薄膜系太陽電池デバイス17と、樹脂層40の周囲を囲むシール部42と、薄膜系太陽電池デバイス17に接続し、シール部42を通って外部に延びる電線44とを有する。なお、上記表面材であるガラス基板16が、第2の面材となる場合は、裏面材である透明面材10が第1の面材となり、また上記表面材であるガラス基板16が、第1の面材となる場合は、裏面材である透明面材10が第2の面材となる。
表面材は、太陽光を透過する透明基板である。
透明基板には、表面の周縁部を除く領域に薄膜系太陽電池デバイスが形成されている。
透明基板には、シール部との界面接着力を向上させるために、表面処理を施してもよい。表面処理は、周縁部だけであってもよく、面材の表面全体であってもよい。表面処理の方法としては、透明面材の表面をシランカップリング剤で処理する方法等が挙げられる。
第1の実施形態と同様に、透明面材の一部または全体が、着色していたり、磨りガラス状に光を散乱、あるいは表面の微細な凹凸等により透過時の光を屈折させたり、反射させるようにしておくこともできる。また、上記のような様態を示す光学フィルム、波長変換フィルム等の光学変調を行う光学フィルム等を透明面材に貼合したものを一体物として透明面材として用いることもできる。
透明基板としては、図示例のガラス基板16、または透明樹脂基板が挙げられ、太陽光に対して透明性が高い点はもちろん、耐熱性等の薄膜系太陽電池デバイスの生産プロセスへの耐性、耐光性、耐候性、耐食性、耐表面傷付性、高い機械的強度を有する点からも、ガラス基板が最も好ましい。
透明樹脂基板の材料としては、透明性の高い樹脂材料(ポリカーボネート、ポリメチルメタクリレート等)が挙げられる。透明樹脂基板を用いた場合には、透明樹脂基板の耐熱温度以下で薄膜系太陽電池デバイスを基板面に形成することが求められる。
薄膜系太陽電池デバイスの厚さを含む透明基板の厚さは、ガラス基板の場合は通常0.7~6mmであり、透明樹脂基板の場合は通常0.1~3mmである。そのうち薄膜系太陽電池デバイスの厚さは、通常10μm以下である。
本発明におけるガラス基板としては、市場で流通する薄膜系太陽電池デバイスを有するガラス基板を入手して用いてもよい。
薄膜系太陽電池デバイスは、透明基板の表面の周縁部を除く領域に形成されている。また、薄膜系太陽電池デバイスから電力を取り出す配線の端子盤が、透明基板の表面の周縁部に形成されている。後述するシール部は、薄膜系太陽電池デバイスが形成されていない透明基板の周縁部に設けられ、配線の表面の一部または端子盤の表面の一部と重なる。
透明電極層の材料としては、酸化インジウム錫、酸化錫等が挙げられる。
光電変換層は、薄膜半導体からなる層である。薄膜半導体としては、アモルファスシリコン系半導体、微結晶シリコン系半導体、化合物半導体(カルコパイライト系半導体、CdTe系半導体等)、有機系半導体等が挙げられる。
裏面電極層の材料としては、光透過性を有さない材料(銀、アルミニウム等)、光透過性を有する材料(酸化インジウム錫、酸化錫、酸化亜鉛等)が挙げられる。
薄膜系太陽電池デバイスとしては、光電変換層を透明電極層の上に形成して表面材からの入射光で発電させる場合は、薄膜半導体がアモルファスシリコン系半導体である薄膜シリコン太陽電池デバイスが好ましい。
裏面材としては、光硬化性樹脂組成物の硬化のための光を透過させる点から、図示例の透明面材10が好ましい。ただし、薄膜系太陽電池デバイスが光透過性を有する場合(すなわち、裏面電極層の材料が光透過性を有する酸化インジウム錫、酸化錫等である場合)、表面材側から光硬化性樹脂組成物の硬化のための光を透過できるため、裏面材は、非透明面材(金属板、セラミックス板等)であってもよい。
ガラス板の材料としては、上述のガラス基板の材料と同じものが挙げられる。
透明樹脂板の材料は、光硬化性樹脂組成物の硬化のための光を透過する樹脂材料であればよく、上述の透明性の高い樹脂材料のほかに、紫外線および450nm以下の可視光以外の光に対して透明性の低い樹脂材料であってもよい。
透明面材の厚さは、機械的強度、透明性の点から、ガラス板の場合は通常0.7~6mmであり、透明樹脂板の場合は通常0.1~3mmである。
樹脂層は、積層された表面材と裏面材とを接合する役目をする層であり後述する液状の樹脂層形成用硬化性樹脂組成物を硬化してなる層である。
樹脂層の厚さは、0.01~2mmが好ましく、0.1~0.8mmが特に好ましい。
樹脂層の厚さを調整する方法としては、後述するシール部の厚さを調整する方法が挙げられる。樹脂層は、透明性に優れることが好ましい。
シール部は、本発明のシール部形成用硬化性樹脂組成物を塗布し、硬化してなるものである。上記した太陽電池モジュールの場合、シール部の幅は、0.3~3mmが好ましく、特に0.5~2mmがより好ましい。また、シール部の厚さは、0.1~2.2mmが好ましく、特に0.2~0.9mmがより好ましい。
太陽電池モジュールの形状は、通常矩形である。
太陽電池モジュールの大きさは、本発明の製造方法が大面積の太陽電池モジュールの製造に特に適していることから、0.6m×0.6m以上が適当であり、0.8m×0.8m以上が好ましい。太陽電池モジュールの大きさの上限は、減圧装置等の製造装置の大きさの制約で決まることが多い。また、あまりに大きい太陽電池モジュールは、設置等における取り扱いが困難となりやすい。太陽電池モジュールの大きさの上限は、これらの制約から、通常3m×3m程度である。
表面材および裏面材の形状や大きさは、太陽電池モジュールの形状や大きさにほぼ等しく、表面材および裏面材の形状や大きさは、多少異なっていてもよい。
図4は、本発明の太陽電池モジュールの実施形態の他の例を示す断面図である。
太陽電池モジュール4は、表面材である透明面材10と、裏面材であるガラス基板16と、透明面材10およびガラス基板16に挟まれた樹脂層40と、ガラス基板16の樹脂層40側の表面に形成された薄膜系太陽電池デバイス17と、樹脂層40の周囲を囲むシール部42と、薄膜系太陽電池デバイス17に接続し、シール部42を通って外部に延びる電線44とを有する。なお、上記表面材である透明面材10が、第2の面材となる場合は、裏面材であるガラス基板16が第1の面材となり、また上記表面材である透明面材10が、第1の面材となる場合は、裏面材であるガラス基板16が第2の面材となる。
第4の実施形態において、第3の実施形態と同じ構成については説明を省略する。
表面材は、太陽光を透過する透明面材である。
透明面材としては、ガラス板、または透明樹脂板が挙げられ、太陽光に対して透明性が高い点はもちろん、耐光性、耐候性、耐食性、耐表面傷付性、高い機械的強度を有する点からも、ガラス板が最も好ましい。光硬化性樹脂組成物の硬化のための光を透過させる点でも透明面材が好ましい。
ガラス板の材料としては、ソーダライムガラス等のガラス材料が挙げられ、鉄分がより低く、青みの小さい高透過ガラス(白板ガラス)がより好ましい。安全性を高めるために表面材として強化ガラスを用いてもよい。
透明樹脂板の材料としては、透明性の高い樹脂材料(ポリカーボネート、ポリメチルメタクリレート等)が挙げられる。
透明面材の厚さは、機械的強度、透明性の点から、ガラス板の場合は通常1~6mmであり、透明樹脂板の場合は通常0.1~3mmである。
裏面材としては、その表面に薄膜系太陽電池デバイスが形成されたものが好ましい点から、ガラス基板がより好ましい。ただし、化合物半導体を含むインクを塗布する等、薄膜系太陽電池デバイスを樹脂板の耐熱温度よりも低い温度で形成できる場合には、樹脂基板を用いることもでき、また非透明基板(たとえば、絶縁層を設けたステンレス等の金属板、セラミックス板等の表面に太陽電池デバイスが形成され基板)であってもよい。
ガラス基板のガラス板の材料としては、上述のガラス板の材料と同じものが挙げられる。
本発明におけるガラス基板としては、市場で流通する薄膜系太陽電池デバイスを有するガラス基板を入手して用いてもよい。
透明基板には、シール部との界面接着力を向上させるために、表面処理を施してもよい。表面処理は、周縁部だけであってもよく、面材の表面全体であってもよい。表面処理の方法としては、透明面材の表面をシランカップリング剤で処理する方法等が挙げられる。
薄膜系太陽電池デバイスは、透明面材の表面に裏面電極層、光電変換層、透明電極層の各層を成膜する毎にパターニングすることで形成される。必要に応じて光電変換層と透明電極層の間にバッファー層を設けてもよい。最上層の透明電極層からの入射光で発電する薄膜系太陽電池デバイスとして、カルコパイライト系やCdTe系等の化合物半導体太陽電池デバイスが好ましい。カルコパイライト系半導体が、CuInGaSe2の場合には、バッファー層としてCdSやZnOを用いることができる。
図5は、本発明の太陽電池モジュールの実施形態の他の例を示す断面図である。
太陽電池モジュール5は、表面材であるガラス基板16と、裏面材であるガラス基板16と、2枚のガラス基板に挟まれた樹脂層40と、各ガラス基板16の樹脂層40側の表面に形成された合計で2層の薄膜系太陽電池デバイス17と、樹脂層40の周囲を囲むシール部42と、薄膜系太陽電池デバイス17に接続し、シール部42を通って外部に延びる電線44とを有する。なお、上記表面材であるガラス基板16が、第2の面材となる場合は、裏面材であるガラス基板16が第1の面材となり、また上記表面材であるガラス基板16が、第1の面材となる場合は、裏面材であるガラス基板16が第2の面材となる。
本発明におけるガラス基板としては、市場で流通する薄膜系太陽電池デバイスを有するガラス基板を入手して用いてもよい。
第5の実施形態において、第3の実施形態および第4の実施形態と同じ構成については説明を省略する。
表面材としては、第1の実施形態の表面材と同様の透明基板を用いることができ、図示例のガラス基板16が最も好ましい。
裏面材としては、第2の実施形態の裏面材と同様の基板(透明基板または非透明基板)を用いることができ、透明基板が好ましく、図示例のガラス基板16がより好ましい。
表面材側の薄膜系太陽電池デバイスは、透明面材の表面に透明電極層、光電変換層、裏面電極層の各層を成膜する毎にパターニングすることで形成される。
裏面電極層の材料としては、裏面材側の薄膜系太陽電池デバイスまで少なくとも一部の太陽光を透過させるために、光透過性を有する材料(酸化インジウム錫、酸化錫等)を用いる必要がある。この場合、薄膜半導体はアモルファスシリコン系半導体である薄膜シリコン太陽電池デバイスが好ましい。
裏面電極層の材料としては、裏面材側から光硬化性樹脂組成物の硬化のための光を透過させる場合は、光透過性を有する材料(酸化インジウム錫、酸化錫等)を用いる。
また、裏面材に表面材と同様の透明基板を用いることもできる。この場合には、表面材および裏面材からの入射光を発電に利用できる。
以上説明した本発明の積層体にあっては、シール部が本発明のシール部形成用硬化性樹脂組成物の硬化物からなるため、シール部の高さが充分に維持されている。そのため、第1の面材および第2の面材に挟まれた樹脂層の厚さを厚くすることができる。具体的には10μm~3mmの厚さにすることができる。また、シール部が本発明のシール部形成用硬化性樹脂組成物の硬化物からなるため、シール部が連続して隙間がない。そのため、樹脂層の原料である樹脂層形成用硬化性樹脂組成物が製造時に漏れ出す等の欠陥が生じにくい。
本発明の積層体の製造方法は、下記の工程(a)~(d)を有する方法である。
(a)第1の面材の表面の周縁部に、本発明のシール部形成用硬化性樹脂組成物を塗布して未硬化のシール部を形成する工程(ただし、第1の面材の表面に薄膜系太陽電池デバイスが形成されている場合は、薄膜系太陽電池デバイスが形成されている側の表面に、また第1の面材が表示デバイスである場合は、画像表示される側の表面にシール部を形成する)。なお、上記した第1の面材は、裏面材となる場合もあり、または表面材となる場合もある。
(b)未硬化のシール部で囲まれた領域に液状の樹脂層形成用硬化性樹脂組成物を供給する工程。
(c)100Pa以下の減圧雰囲気下にて、樹脂層形成用硬化性樹脂組成物の上に第2の面材を重ねて、第1の面材、第2の面材および未硬化のシール部で樹脂層形成用硬化性樹脂組成物が密封された積層物を得る工程(ただし、第2の面材の表面に薄膜系太陽電池デバイスが形成されている場合は、薄膜系太陽電池デバイスが形成されている側の表面が、また第2の面材の表面に反射防止膜が設けられている場合は、その裏面側の表面が、樹脂層形成用硬化性樹脂組成物に接するように重ねる。また、第2の面材が表示デバイスである場合は、画像表示される側が、樹脂層形成用硬化性樹脂組成物に接するように重ねる)。なお、上記した第2の面材は、表面材となる場合もあり、または裏面材となる場合もある。
(d)50kPa以上の圧力雰囲気下に積層物を置いた状態にて、未硬化のシール部および樹脂層形成用硬化性樹脂組成物を硬化させる工程。
まず、第1の面材の一方の表面の周辺部に沿って未硬化のシール部を形成する。第1の面材として裏面材を用いるか表面材を用いるかは任意である。
第1の面材が、薄膜系太陽電池デバイスが形成されていない「面材」や、表示デバイスの保護板となる「透明面材」である場合、未硬化のシール部を形成する面は、2つ表面のいずれか任意である。2つの表面の性状が異なる場合等では必要な一方の表面を選択する。たとえば、一方の表面に樹脂層との界面接着力を向上させる表面処理を施した場合、該表面に未硬化のシール部を形成する。また、一方の表面に反射防止層が設けられている場合、その裏面に未硬化のシール部を形成する。
第1の面材が、薄膜系太陽電池デバイスが形成された「基板」である場合、未硬化のシール部を形成する面は、薄膜系太陽電池デバイスが形成されている側の表面である。第1の面材が表示デバイスである場合、未硬化のシール部を形成する面は、画像表示される側の表面である。
また、第1の面材と第2の面材との間隔を保持するために、所定の粒子径のスペーサ粒子をシール部形成用硬化性樹脂組成物に配合してもよい。
工程(a)の後、未硬化のシール部で囲まれた領域に液状の樹脂層形成用硬化性樹脂組成物を供給する。
樹脂層形成用硬化性樹脂組成物の供給量は、シール部、第1の面材および第2の面材によって形成される空間が樹脂層形成用硬化性樹脂組成物によって充填され、かつ第1の面材と第2の面材との間を所定の間隔とする(すなわち樹脂層を所定の厚さとする)だけの分量にあらかじめ設定する。この際、樹脂層形成用硬化性樹脂組成物の硬化収縮による体積減少をあらかじめ考慮することが好ましい。よって、該分量は、樹脂層の所定厚さよりも樹脂層形成用硬化性樹脂組成物の厚さが若干厚くなる量が好ましい。
供給方法としては、第1の面材を平置きにし、ディスペンサ、ダイコータ等の供給手段によって、点状、線状または面状に供給する方法が挙げられる。
樹脂層形成用硬化性樹脂組成物の粘度は、25℃においてE型粘度計を用いて測定する。
オリゴマー(A’)の数平均分子量は、GPC測定によって得られた、ポリスチレン換算の数平均分子量である。なお、GPC測定において、未反応の低分子量成分(モノマー等)のピークが現れる場合は、該ピークを除外して数平均分子量を求める。
オリゴマー(A’)としては、ウレタン結合を有するウレタンオリゴマー、ポリオキシアルキレンポリオールのポリ(メタ)アクリレート、ポリエステルポリオールのポリ(メタ)アクリレート等が挙げられ、ウレタン鎖の分子設計等によって硬化後の樹脂の機械的特性、面材との密着性等を幅広く調整できる点から、ウレタンオリゴマーが好ましい。
モノマー(B’)としては、樹脂層形成用硬化性樹脂組成物の硬化性、樹脂層の機械的特性の点から、硬化性基を1分子あたり1~3個有するものが好ましい。
水酸基を有するモノマー(B3)としては、シール部形成用硬化性樹脂組成物におけるモノマー(B3)と同様のものが挙げられ、2-ヒドロキシブチルメタクリレートが特に好ましい。
モノマー(B4):炭素数8~22のアルキル基を有するアルキルメタクリレート。
モノマー(B4)としては、n-ドデシルメタクリレート、n-オクタデシルメタクリレート、n-ベヘニルメタクリレート等が挙げられ、n-ドデシルメタクリレート、n-オクタデシルメタクリレートが好ましい。
光重合開始剤(C)としては、シール部形成用硬化性樹脂組成物における光重合開始剤(C)と同様のものが挙げられる。
光重合開始剤(C)の量は、オリゴマー(A’)とモノマー(B’)との合計100質量部に対して、0.01~10質量部が好ましく、0.1~2.5質量部がより好ましい。
工程(b)の後、樹脂層形成用硬化性樹脂組成物が供給された第1の面材を減圧装置に入れ、減圧装置内の固定支持盤の上に硬化性樹脂組成物の面が上になるように第1の面材を平置きする。
減圧装置内の上部には、上下方向に移動可能な移動支持機構が設けられ、移動支持機構に第2の面材が取り付けられる。第2の面材の表面に薄膜系太陽電池デバイスが形成されている場合、薄膜系太陽電池デバイスが形成された側の表面を、また第2の面材が表示デバイスの場合、画像を表示する側の表面を下に向ける。第2の面材の表面に反射防止層が設けられている場合、反射防止層が形成されていない側の表面を下に向ける。
第2の面材は、第1の面材の上方かつ樹脂層形成用硬化性樹脂組成物と接しない位置に置く。すなわち、第1の面材の上の樹脂層形成用硬化性樹脂組成物と第2の面材(薄膜系太陽電池デバイスが形成されている場合は、薄膜系太陽電池デバイス)とを接触させることなく対向させる。
また、第1の面材および第2の面材の両方を、減圧装置内の上下に設けた移動支持機構で支持してもよい。
減圧装置の内部が所定の減圧雰囲気となった後、移動支持機構で支持された第2の面材を下方に移動し、第1の面材の上の樹脂層形成用硬化性樹脂組成物の上に第2の面材を重ね合わせる。
重ね合わせの際、第2の面材の自重、移動支持機構からの押圧等によって、樹脂層形成用硬化性樹脂組成物が押し広げられ、前記空間内に樹脂層形成用硬化性樹脂組成物が充満し、その後、工程(d)において高い圧力雰囲気に曝した際に、気泡の少ないまたは気泡のない樹脂層形成用硬化性樹脂組成物の層が形成される。以下、積層物を「積層前駆体」とも記す。
工程(c)において減圧雰囲気を解除した後、積層前駆体を雰囲気圧力が50kPa以上の圧力雰囲気下に置く。
積層前駆体を50kPa以上の圧力雰囲気下に置くと、上昇した圧力によって第1の面材と第2の面材とが密着する方向に押圧されるため、積層前駆体内の密閉空間に気泡が存在すると、気泡に樹脂層形成用硬化性樹脂組成物が流動していき、密閉空間全体が樹脂層形成用硬化性樹脂組成物によって均一に充填される。
表示装置の場合は、透過型の表示デバイスを動作させることで光透過性を得ることはできるが、動作させない状態では光透過性を有さないものが多いため、保護板となる透明面材から硬化させる光を照射する。非動作時に透明状態を呈する透過-散乱型の表示デバイスを用いる場合は、表示デバイス側からの光を利用することもできる。
透明面材の周辺部に印刷遮光部が設けられていて、印刷遮光部と表示デバイスに挟持される領域に、未硬化のシール部や樹脂層形成用硬化性樹脂組成物が存在する場合には、透明面材の印刷遮光部以外の開口部からの光だけでは充分に硬化できないおそれがある。この場合、表示デバイスの側面から紫外線または450nm以下の可視光を照射して、未硬化のシール部および樹脂層形成用硬化性樹脂組成物を硬化させることが好ましい。側面からの光照射の光源としては、透明面材側からの光照射に用いる光源を用いてもよいが、紫外線または450nm以下の可視光を発光するLEDを用いることが光源の配置スペースの点から好ましい。光照射のステップとしては、透明面材からの光照射の後に表示デバイスの側面から光照射してもよいし、その逆、あるいは同時に光照射してもよいが、印刷遮光部における未硬化のシール部や樹脂層形成用硬化性樹脂組成物の光硬化をより促進するためには、先に側面から光を照射するか、側面と同時に透明面材側から光照射することが好ましい。
上記した工程(d)は、工程(c)が行なわれた減圧装置において、減圧装置の減圧室の減圧を解除し、当該減圧室を80k~120kPaの圧力に調整し、たとえば大気圧とし、この圧力雰囲気下において前記積層前駆体の未硬化のシール部および前記樹脂層形成用硬化性樹脂組成物を硬化させる処理を施しても良いし、あるいはまた工程(c)が行なわれた減圧装置から別の硬化処理装置に移して、この硬化処理装置内を80k~120kPaの圧力に調整して、この圧力雰囲気下において前記積層前駆体の未硬化のシール部および前記樹脂層形成用硬化性樹脂組成物を硬化させる処理を施しても良い。
本発明の製造方法において、第1の面材として裏面材を用いるか表面材を用いるかは任意である。よって、第2の実施形態の表示装置、および第3~5の実施形態の太陽電池モジュール(図示例)の場合は、第1の面材の選択に応じて、それぞれ以下の2種類の方法によって製造できる。
(β-1)第1の面材として表示デバイス(裏面材)を用い、第2の面材として保護板となる透明面材10(表面材)を用いる方法。
(β-2)第1の面材として保護板となる透明面材10(表面材)を用い、第2の面材として表示デバイス(裏面材)を用いる方法。
(γ-1)第1の面材として透明面材10(裏面材)を用い、第2の面材としてガラス基板16(表面材)を用いる方法。
(γ-2)第1の面材としてガラス基板16(表面材)を用い、第2の面材として透明面材10(裏面材)を用いる方法。
(δ-1)第1の面材としてガラス基板16(裏面材)を用い、第2の面材として透明面材10(表面材)を用いる方法。
(δ-2)第1の面材として透明面材10(表面材)を用い、第2の面材としてガラス基板16(裏面材)を用いる方法。
(ε-1)第1の面材としてガラス基板16(裏面材)を用い、第2の面材としてガラス基板16(表面材)を用いる方法。
(ε-2)第1の面材としてガラス基板16(表面材)を用い、第2の面材としてガラス基板16(裏面材)を用いる方法。
図6および図7に示すように、表示デバイス50(第1の面材)の周縁部に沿ってディスペンサ(図示略)等によって本発明のシール部形成用光硬化性樹脂組成物を塗布して未硬化のシール部12を形成する。
表示デバイスの外周部には、表示デバイスを動作させるための電気信号を伝達するFPC等の配線部材が設置されていることがある。本発明の製造方法において各面材を保持する際に、配線部材の配置を容易にする点では、表示デバイスを第1の面材として下側に配置することが好ましい。
ついで、図8、図9に示すように、表示デバイス50の未硬化のシール部12に囲まれた矩形状の領域13に樹脂層形成用光硬化性樹脂組成物14を供給する。樹脂層形成用光硬化性樹脂組成物14の供給量は、未硬化のシール部12と表示デバイス50と透明面材10(図9参照)とによって密閉される空間が樹脂層形成用光硬化性樹脂組成物14によって充填されるだけの量にあらかじめ設定されている。
ディスペンサ20は、一対の送りねじ22と、送りねじ22に直交する送りねじ24とからなる公知の水平移動機構によって、領域13の全範囲において水平移動可能となっている。なお、ディスペンサ20の代わりに、ダイコータを用いてもよい。
ついで、図10に示すように、表示デバイス50(第1の面材)と透明面材10(第2の面材)とを減圧装置26内に搬入する。減圧装置26内の上部には、複数の吸着パッド32を有する上定盤30が配置され、下部には、下定盤31が設けられている。上定盤30は、エアシリンダ34によって上下方向に移動可能とされている。
透明面材10は、吸着パッド32に取り付けられる。表示デバイス50は、樹脂層形成用光硬化性樹脂組成物14が供給された面を上にして下定盤31の上に固定される。
ついで、減圧装置26の内部をたとえば大気圧にした後、積層前駆体を減圧装置26から取り出す。積層前駆体を大気圧雰囲気下に置くと、積層前駆体の表示デバイス50側の表面と透明面材10側の表面とが大気圧によって押圧され、密閉空間内の樹脂層形成用光硬化性樹脂組成物14が表示デバイス50と透明面材10とで加圧される。この圧力によって、密閉空間内の樹脂層形成用光硬化性樹脂組成物14が流動して、密閉空間全体が樹脂層形成用光硬化性樹脂組成物14によって均一に充填される。この後、積層前駆体の側面および透明面材10側から紫外線を照射し、積層前駆体内部の未硬化のシール部12および樹脂層形成用光硬化性樹脂組成物14を硬化させることによって、表示装置2が製造される。
以上説明した本発明の積層体の製造方法にあっては、本発明のシール部形成用硬化性樹脂組成物を塗布して未硬化のシール部を形成するため、未硬化のシール部の高さが充分に維持されている。そのため、第1の面材および第2の面材に挟まれた樹脂層を形成用硬化性樹脂組成物の厚さを厚くすることができる。具体的には、この厚さを10μm~3mmにすることができる。また、本発明のシール部形成用硬化性樹脂組成物を塗布して未硬化のシール部を形成するため、未硬化のシール部が連続して隙間がない。そのため、樹脂層の原料である樹脂層形成用硬化性樹脂組成物が製造時に漏れ出す等の欠陥が生じにくい。
オリゴマーの数平均分子量は、GPC装置(TOSOH社製、HLC-8020)を用いて求めた。
光硬化性樹脂組成物の粘度は、E型粘度計(東機産業社製、RE-85U)にて測定した。
硬化物の硬化度合の指標として、下記の方法でゲル分率を求めた。
硬化物の0.4gを採取し、100mLのトルエンに25℃で24時間浸漬した後、トルエンを濾別して、残留固形分を100℃で1時間乾燥させ、乾燥質量を測定し、下式からゲル分率を算出した。
ゲル分率(%)=浸漬後の乾燥質量(g)/0.4(g)×100。
ヘイズ値は、東洋精機製作所社製のヘイズガードIIを用い、ASTM D1003に準じた測定によって求めた。
(表示デバイス)
市販の32型液晶テレビ受像機(ピーシーデポコーポレーション社製、HDV-32WX2D-V)から液晶表示デバイスを取り出した。液晶表示デバイスは、長さ712mm、幅412mm、厚さ約2mmであった。液晶表示デバイスの両面には偏光板が貼合されており、長辺の片側に駆動用のFPCが6枚接合されていてFPCの端部にはプリント配線板が接合されていた。画像表示領域は、長さ696mm、幅390mmであった。該液晶表示デバイスを表示デバイスAとした。
長さ794mm、幅479mm、厚さ3mmのソーダライムガラスの一方の表面の周縁部に、開口部が長さ698mm、幅392mmとなるように黒色顔料を含むセラミック印刷にて額縁状に印刷遮光部を形成した。ついで、印刷遮光部の裏面の全面に反射防止フィルム(日本油脂社製、リアルックX4001)を、保護フィルムを介してつけた状態で貼合して、保護板となるガラス板Bを作製した。
分子末端をエチレンオキシドで変性した2官能のポリプロピレングリコール(水酸基価より算出した数平均分子量:4000)と、ヘキサメチレンジイソシアネートとを、6対7となるモル比で混合し、ついでイソボルニルアクリレート(大阪有機化学工業社製、IBXA)で希釈した後、錫化合物の触媒存在下70℃で反応させて得られたプレポリマーに、2-ヒドロキシエチルアクリレートをほぼ1対2となるモル比で加えて70℃で反応させることによって、30質量%のイソボルニルアクリレートで希釈されたウレタンアクリレートオリゴマー(以下、オリゴマー(A)。UC-1と記す。)溶液を得た。UC-1の硬化性基数は2であり、数平均分子量は約55000であった。UC-1溶液の60℃における粘度は約580Pa・sであった。
ついで、一対のソーダライムガラス(100×100mm、厚さ2mm)に、厚さが約1mmとなるようにシール部形成用光硬化性樹脂組成物Cを挟持して、ケミカルランプから365nmの光強度が2mW/cm2の紫外線を照射して硬化物を得た。硬化物のゲル分率を求めたところ、91%であり、硬化性は良好であった。
分子末端をエチレンオキシドで変性した2官能のポリプロピレングリコール(水酸基価より算出した数平均分子量:4000)と、イソホロンジイソシアネートとを、4対5となるモル比で混合し、錫化合物の触媒存在下で70℃で反応させて得られたプレポリマーに、2-ヒドロキシエチルアクリレートをほぼ1対2となるモル比で加えて70℃で反応させることによって、ウレタンアクリレートオリゴマー(以下、UA-2と記す。)を得た。UA-2の硬化性基数は2であり、数平均分子量は約24000であり、25℃における粘度は約830Pa・sであった。
第2の面材としての表示デバイスAの画像表示領域の外側の約5mmの位置の全周にわたって、幅約1mm、塗布厚さ約0.6mmとなるようにシール部形成用光硬化性樹脂組成物Cをディスペンサにて塗布し、未硬化のシール部を形成した。
表示デバイスAの画像表示領域の外周に塗布された未硬化のシール部の内側の領域に、樹脂層形成用光硬化性樹脂組成物Dを、ディスペンサを用いて総質量が125gとなるように複数個所に供給した。
樹脂層形成用光硬化性樹脂組成物Dを供給する間、未硬化のシール部の形状は維持されていた。
表示デバイスAを、一対の定盤の昇降装置が設置されている減圧装置内の下定盤の上面に、樹脂層形成用光硬化性樹脂組成物Dの面が上になるように平置した。
第1の面材としてのガラス板Bを、印刷遮光部が形成された側の表面が表示デバイスAに対向するように、減圧装置内の昇降装置の上定盤の下面に静電チャックを用いて、保持させた。保持位置は、上面から見た場合にガラス板Bの印刷遮光部のない開口部と表示デバイスAの画像表示領域とが約1mmのマージンをもって同位置となるように、垂直方向では表示デバイスAとの距離が30mmとなるようにした。
積層前駆体Eにおいて未硬化のシール部の形状は、ほぼ初期の状態のまま維持されていた。
積層前駆体Eの表示デバイスAの周縁部に設けられた未硬化のシール部(シール部形成用光硬化性樹脂組成物C)に、表示デバイスAの側方から、発光主波長が約390nmの紫外線LEDを線状に配した紫外線光源を用いて、未硬化のシール部の全周にわたって約10分間光を照射し、シール部を硬化させ、積層前駆体Eを水平に保って約10分静置した。
表示装置Fを液晶表示デバイスを取り出した液晶テレビ受像機の筺体に戻し、配線を再接合して電源を入れたところ、当初より表示コントラストの高い画像が得られた。画像表示面を指で強く押しても画像が乱れることはなく、ガラス板Bが表示デバイスAを効果的に保護していた。
(シール部形成用光硬化性樹脂組成物)
分子末端をエチレンオキシドで変性した2官能ポリプロピレングリコール(水酸基価より算出した数平均分子量:4000)と、ヘキサメチレンジイソシアネートとを、6対7となるモル比で混合し、ついでn-ドデシルメタクリレートで希釈した後、錫化合物の触媒存在下で70℃で反応させて得られたプレポリマーに、2-ヒドロキシエチルアクリレートをほぼ1対2となるモル比で加えて70℃で反応させることによって、10質量%のn-ドデシルメタクリレートで希釈されたウレタンアクリレートオリゴマー(以下、UC-3と記す。)溶液を得た。UC-3の硬化性基数は2であり、数平均分子量は約45000であった。UC-3溶液の60℃における粘度は約650Pa・sであった。
ついで、一対のソーダライムガラス(100×100mm、厚さ2mm)に、厚さが約1mmとなるようにシール部形成用光硬化性樹脂組成物Gを挟持して、ケミカルランプから365nmの光強度が2mW/cm2の紫外線を照射して硬化物を得た。硬化物のゲル分率を求めたところ、66%であり、硬化性は充分ではなかった。
(シール部形成用光硬化性樹脂組成物)
例1で用いたUA-2の80質量部、2-ヒドロキシブチルメタクリレート(共栄社化学社製、ライトエステル HOB)の10質量部、n-ドデシルメタクリレートの10質量部を均一に混合し、該混合物の100質量部に、ビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド(光重合開始剤、チバ・スペシャルティ・ケミカルズ社製、IRGACURE 819)の0.2質量部、2,5-ジ-t-ブチルハイドロキノン(重合禁止剤)の0.04質量部、紫外線吸収剤(チバ・スペシャリティ・ケミカルズ社製、TINUVIN 109)の0.3質量部を均一に溶解させて、シール部形成用光硬化性樹脂組成物Hを得た。
表示デバイスAの画像表示領域の外側の約5mmの位置の全周にわたって、幅約1mm、塗布厚さ約0.6mmとなるようにシール部形成用光硬化性樹脂組成物Hをディスペンサにて塗布し、未硬化のシール部を形成した。
しかし、わずか2分後にシール部形成用光硬化性樹脂組成物Hがシール部の幅方向に広がり始め、未硬化のシール部の形状を維持することができなかった。
また、別のシール部形成用光硬化性樹脂組成物(25℃における粘度:3200Pa・s)では、シール部を均一に塗布することができない。
なお、2009年10月30日に出願された日本特許出願2009-250335号の明細書、特許請求の範囲、図面及び要約書の全内容をここに引用し、本発明の開示として取り入れるものである。
2 表示装置
3 太陽電池モジュール
4 太陽電池モジュール
5 太陽電池モジュール
10 透明面材
12 未硬化のシール部
13 領域
14 樹脂層形成用光硬化性樹脂組成物
16 ガラス基板
17 薄膜系太陽電池デバイス
40 樹脂層
42 シール部
50 表示デバイス
Claims (20)
- 第1の面材と第2の面材との間に挟持される液状物からなる層の周囲を囲むシール部を形成するための硬化性樹脂組成物であって、
25℃における粘度が、500~3000Pa・sである、シール部形成用硬化性樹脂組成物。 - 液状物が、樹脂層形成用硬化性樹脂組成物である、請求項1に記載のシール部形成用硬化性樹脂組成物。
- 第1の面材と第2の面材との間に挟持された樹脂層形成用硬化性樹脂組成物を、その周囲をシール部で囲んだ状態で硬化させて積層体を製造する際に、該シール部を形成するために用いられる、請求項1または2に記載のシール部形成用硬化性樹脂組成物。
- 硬化性基を有し、かつ数平均分子量が30000~100000であるオリゴマー(A)の1種以上と、
硬化性基を有し、かつ分子量が125~600であるモノマー(B)の1種以上とを含み、
モノマー(B)の割合が、オリゴマー(A)とモノマー(B)との合計(100質量%)のうち、15~50質量%である、請求項1~3のいずれか1項に記載のシール部形成用硬化性樹脂組成物。 - 硬化性基が、アクリロイルオキシ基およびメタクリロイルオキシ基からなる群から選ばれる少なくとも1種の基である、請求項4に記載のシール部形成用硬化性樹脂組成物。
- オリゴマー(A)の硬化性基が、アクリロイルオキシ基であり、
モノマー(B)の硬化性基が、メタクリロイルオキシ基である、請求項4または5に記載のシール部形成用硬化性樹脂組成物。 - オリゴマー(A)が、ウレタンオリゴマー(A1)である、請求項4~6のいずれか1項に記載のシール部形成用硬化性樹脂組成物。
- モノマー(B)として、イソシアネート基と反応する基を有さないモノマー(B1)を含み、
ウレタンオリゴマー(A1)が、モノマー(B1)の存在下、ポリオールとポリイソシアネートとを反応させてイソシアネート基を有するプレポリマーを得た後、該プレポリマーのイソシアネート基に、イソシアネート基と反応する基および硬化性基を有するモノマー(B2)を反応させて得られたものである、請求項7に記載のシール部形成用硬化性樹脂組成物。 - モノマー(B)として、水酸基を有するモノマー(B3)を含む、請求項4~8のいずれか1項に記載のシール部形成用硬化性樹脂組成物。
- 光重合開始剤(C)を含む光硬化性樹脂組成物である、請求項4~9のいずれか1項に記載のシール部形成用硬化性樹脂組成物。
- 光重合開始剤(C)として、吸収波長域の異なる2種以上の光重合開始剤を含む、請求項10に記載のシール部形成用硬化性樹脂組成物。
- 第1の面材および第2の面材と、
前記第1の面材および前記第2の面材に挟まれた樹脂層と、
前記樹脂層の周囲を囲むシール部とを、有する積層体であって、
前記シール部が、25℃における粘度が500~3000Pa・sであるシール部形成用硬化性樹脂組成物の硬化物からなる、積層体。 - 前記シール部の幅が0.3~3mmであるシール部形成用硬化性樹脂組成物の硬化物からなる、請求項12に記載の積層体。
- 前記シール部の厚さが10μm~3mmであるシール部形成用硬化性樹脂組成物の硬化物からなる、請求項12に記載の積層体。
- 両方が透明面材である第1の面材および第2の面材と、第1の面材および第2の面材に挟まれた樹脂層と、樹脂層の周囲を囲むシール部とを有する透明積層体である、請求項12に記載の積層体。
- 一方が透明面材であり、他方が表示デバイスである第1の面材および第2の面材と、第1の面材および第2の面材に挟まれた樹脂層と、樹脂層の周囲を囲むシール部とを有する表示装置である、請求項12に記載の積層体。
- 少なくとも一方が透明面材である第1の面材および第2の面材と、第1の面材および第2の面材に挟まれた樹脂層と、第1の面材および第2の面材のうちの少なくとも一方の面材の樹脂層側の表面に形成された薄膜系太陽電池デバイスと、樹脂層の周囲を囲むシール部とを有する太陽電池モジュールである、請求項12に記載の積層体。
- 少なくとも一方が透明面材である第1の面材および第2の面材と、第1の面材および第2の面材に挟まれた樹脂層と、第1の面材および第2の面材のうちの少なくとも一方の面材の樹脂層側の表面に形成された表示デバイスと、樹脂層の周囲を囲むシール部とを有する表示装置である、請求項12に記載の積層体。
- (a)第1の面材の表面の周縁部に、25℃における粘度が500~3000Pa・sであるシール部形成用硬化性樹脂組成物を塗布して未硬化のシール部を形成し、
(b)前期未硬化のシール部で囲まれた領域に液状の樹脂層形成用硬化性樹脂組成物を供給し、
(c)100Pa以下の減圧雰囲気下にて、前記樹脂層形成用硬化性樹脂組成物の上に第2の面材を重ねて、前記第1の面材、前記第2の面材および前記未硬化のシール部で前記樹脂層形成用硬化性樹脂組成物が密封された積層物を得て、
(d)50kPa以上の圧力雰囲気下に前記積層物を置いた状態にて、前記未硬化のシール部および前記樹脂層形成用硬化性樹脂組成物を硬化させることにより、
前記第1の面材および前記第2の面材と、前記第1の面材および前記前記第2の面材に挟まれた樹脂層と、前記樹脂層の周囲を囲むシール部と、を有する積層体を製造する方法。 - 工程(c)で得られた積層物における樹脂層形成用硬化性樹脂組成物の厚さが、10μm~3mmである、請求項19に記載の積層体の製造方法。
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Also Published As
Publication number | Publication date |
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KR20120091126A (ko) | 2012-08-17 |
TW201122055A (en) | 2011-07-01 |
US20120211080A1 (en) | 2012-08-23 |
JPWO2011052747A1 (ja) | 2013-03-21 |
US20130306236A1 (en) | 2013-11-21 |
EP2495298A1 (en) | 2012-09-05 |
EP2495298A4 (en) | 2013-09-18 |
CN102597155A (zh) | 2012-07-18 |
US8748505B2 (en) | 2014-06-10 |
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