Glass-resin composite

Abstract

A glass-resin composite according to the present invention has one or more resin layers on at least one surface of a glass sheet. The thickness of the glass-resin composite is 800 μm or less. When the glass-resin composite is bent at a radius of curvature satisfying formula (1) toward one surface side of the glass-resin composite, the probability of a crack occurring in the glass sheet is 10% or less. (In formula (1), R0 is the radius of curvature [mm] of the inner side of the glass resin-composite; i and k are integers; l is the number of layers [layers], which is the sum of the glass sheet and the resin layers up to the glass sheet when the layers are counted from the inner side of the glass-resin composite; n is the total number of layers [layers]; Ei is the Young's modulus [MPa] of the i-th layer; ti is the thickness [μm] of the i-th resin layer; tk is the thickness [μm] of the k-th resin layer; and tk -1 is the thickness [μm] of the (k-1)-th resin layer.)

Description

Glass Resin Composite

[0001] The present invention relates to a glass resin composite.

[0002] Glass resin laminates in which a resin layer is laminated on an extremely thin, flexible thin glass (hereinafter also referred to as "glass sheet") are used in image display devices such as liquid crystal display elements and organic EL elements, semiconductor elements, solar cells, etc. The glass sheet used in the glass resin laminate is flexible and can be wound into a roll, so that a roll-to-roll process can be used to unwind the rolled glass sheet, apply processing such as laminating or printing a resin layer, and then rewind it into a roll to produce a glass resin laminate.

[0003] As a method for manufacturing a glass resin laminate using a roll-to-roll process, for example, a method has been disclosed in which a roll-to-roll laminating device is used to laminate a flexible glass layer to other material sheets including a PVA layer and a TAC layer in a polarizer structure to form a laminate roll (see, for example, Patent Document 1).

[0004] U.S. Patent No. 8,525,405

[0005] However, Patent Document 1 does not describe how to prevent cracks from occurring within the effective area of ​​the surface of the flexible glass layer when the laminated roll is cut or otherwise formed into chips, and then the chipped laminated roll is attached to a flexible film substrate wound into a roll and transported using a roll-to-roll process.

[0006] When a glass resin composite obtained by chipping a glass resin laminate is attached to a roll-shaped film substrate via an adhesive or the like, and then web-transported (web-handled) using a roll-to-roll process and wound into a roll, there has been a problem in that cracks may occur in the effective area of ​​the surface of the glass sheet.

[0007] From the viewpoint of improving the yield of a glass resin composite wound into a roll on a film substrate, it is important that the glass resin composite can be wound into a roll without cracks occurring in the effective surface area of ​​the glass sheet.

[0008] An object of one aspect of the present invention is to provide a glass resin composite that can suppress the occurrence of cracks in the effective area of ​​the glass surface even when a roll-to-roll process is used.

[0009] One aspect of the present invention is a glass resin composite having one or more resin layers on at least one surface of a glass sheet, wherein the thickness of the glass resin composite is 800 μm or less, and when the glass resin composite is bent toward one surface of the glass resin composite with a curvature radius that satisfies the following formula (1), the probability of cracks occurring in the glass sheet is 10% or less. (In formula (1), R ０ is the inner radius of curvature of the glass resin composite [mm], i and k are integers, l is the number of layers [layers] including the resin layer and the glass sheet when counting from the inside of the glass resin composite, n is the total number of layers [layers], and E ｉ is the Young's modulus [MPa] of the i-th layer, and t ｉ is the thickness [μm] of the i-th resin layer, and t ｋ is the thickness [μm] of the kth resin layer, and t ｋ－１ is the thickness [μm] of the (k-1)th resin layer.

[0010] One aspect of the present invention can suppress the occurrence of cracks in an effective area of ​​the glass surface even when a roll-to-roll process is used.

[0011] It is a schematic cross-sectional view showing the configuration of a glass resin composite according to an embodiment of the present invention. It is an explanatory view showing an example of a method for winding up a glass resin composite using a roll-to-roll transport device. It is a schematic cross-sectional view showing an example of another configuration of a glass resin composite. It is a schematic cross-sectional view showing an example of another configuration of a glass resin composite.

[0012] Hereinafter, embodiments of the present invention will be described in detail. To facilitate understanding of the description, the same components in each drawing are denoted by the same reference numerals, and duplicate descriptions will be omitted. The scale of each component in the drawings may differ from the actual scale. In this specification, unless otherwise specified, the symbol "to" indicating a range of values ​​means that the values ​​before and after it are included as the lower and upper limits.

[0013] <Glass Resin Composite> A glass resin composite according to an embodiment of the present invention will be described. Fig. 1 is a schematic cross-sectional view showing the configuration of a glass resin composite according to this embodiment. As shown in Fig. 1, the glass resin composite 1 according to this embodiment includes a glass sheet 10 and a multilayer resin layer 20 arranged on one main surface (lower surface) 10a of the glass sheet 10. The glass resin composite 1 has a substantially rectangular shape in plan view, and is attached to one main surface of a rolled flexible film substrate via an adhesive or the like using a roll-to-roll process, and then wound into a roll.

[0014] 1 uses a three-dimensional Cartesian coordinate system with three axes (X-axis, Y-axis, and Z-axis), with the width direction of the glass sheet 10 defined as the X-axis, the length direction defined as the Y-axis, and the thickness direction defined as the Z-axis. The direction from the multilayer resin layer 20 of the glass sheet 10 toward the glass sheet 10 (outside) is defined as the +Z-axis direction, and the opposite direction (inside) is defined as the −Z-axis direction. In the following description, the +Z-axis direction may be referred to as up or upward, and the −Z-axis direction may be referred to as down or downward.

[0015] When the glass resin composite 1 is bent on one of its surfaces, the lower surface 1a (the surface on the multilayer resin layer 20 side), with a curvature radius that satisfies the following formula (1) so that the glass sheet 10 side is convex, the probability of cracking occurring in the glass sheet 10 is 10% or less, preferably 9.0% or less, more preferably 5.0% or less, and even more preferably 3.0% or less.

[0016]

[0017] In formula (1), R ０is the inner radius of curvature of the glass resin composite [mm], i and k are integers, l is the number of layers [layers] including the resin layer and the glass sheet when counting from the inside of the glass resin composite, n is the total number of layers [layers], and E ｉ is the Young's modulus [MPa] of the i-th layer, and t ｉ is the thickness [μm] of the i-th resin layer, and t ｋ is the thickness [μm] of the kth resin layer, and t ｋ－１ is the thickness [μm] of the (k-1)th resin layer. The numbers i and k are counted from the inside of the glass resin composite 1. When k is 1, t ｋ－１ is ０ and means the thickness when the resin layer is 0 layer, so t ０ is 0 [μm].

[0018] In addition, the Young's modulus E of the resin layer in formula (1) ｉ can be measured by the resonance method (measurement temperature: 25°C) based on JIS R 1602, or using an autograph under the following Young's modulus measurement conditions: - Young's modulus measurement conditions - Measurement temperature: 25°C Sample size: thickness 50 μm, width 2 cm, length 15 cm Chuck distance: 10 cm Pulling speed: 10 mm / min

[0019] The radius of curvature R in Equation (1) ０ means the radius of an imaginary circle with which the glass resin composite 1 is in contact. As described above, the glass resin composite 1 is wound up by a roll-to-roll process, and therefore the radius of curvature in formula (1) is preferably the radius of a roll with which the glass resin composite 1 is in contact. If the radius of curvature in formula (1) is the radius of the roll, it is possible to confirm the rate of crack occurrence in the glass sheet 10 when the glass resin composite 1 is wound around a roll having a radius of curvature that satisfies formula (1) above.

[0020] The thickness of the glass resin composite 1 is 800 μm or less, preferably 700 μm or less, more preferably 400 μm or less, and even more preferably 350 μm or less.

[0021] In this specification, the thickness of the glass resin composite 1 refers to the length in a direction perpendicular to the main surface of the glass resin composite 1. The thickness of the glass resin composite 1 may be, for example, the thickness measured at an arbitrary location on the cross section of the glass resin composite 1, or may be the average value of measurements measured at several arbitrary locations. Hereinafter, the definition of thickness is similarly defined for other members.

[0022] When the other surface of the glass resin composite 1, the upper surface 1b (the surface on the glass sheet 10 side), is bent with a curvature radius that satisfies the above formula (1), the probability of cracks occurring in the glass sheet 10 is preferably 10% or less, more preferably 5.0% or less, and even more preferably 3.0% or less.

[0023] [Glass Sheet] The glass sheet 10 has a plate-like (sheet-like) shape and has a substantially rectangular shape in a plan view. The width and length of the glass sheet 10 may be any appropriate size.

[0024] The glass sheet 10 is formed using a long glass ribbon. The glass sheet 10 is obtained by cutting the long glass ribbon, etc. Note that the term "long" refers to an elongated shape in which the length is sufficiently longer than the width, and includes, for example, an elongated rectangular shape in which the length is 10 times or more, preferably 20 times or more, the width.

[0025] The glass sheet 10 can be formed using any suitable glass material. The glass material constituting the glass sheet 10 is preferably inorganic glass. Examples of inorganic glass, classified by composition, include soda-lime glass, borate glass, aluminosilicate glass, and quartz glass. Examples of inorganic glass, classified by alkali component, include alkali-free glass and low-alkali glass. The alkali metal component (e.g., Na) of the above glass is preferably 0.01 to 0.01. ２ O.K. ２ , Li ２ The content of O) is preferably 15% by mass or less, and more preferably 10% by mass or less.

[0026] The thickness of the glass sheet 10 is preferably 20% to 75%, more preferably 25% to 71%, and even more preferably 28% to 65% of the thickness of the glass resin composite 1. When the thickness of the glass sheet 10 relative to the glass resin composite 1 is within the above-mentioned preferred range, the glass sheet 10 becomes easier to bend, and the glass resin composite 1 becomes easier to wind up in a roll-to-roll process. Furthermore, even if a crack occurs on the edge surface of the glass sheet 10, the multilayer resin layer 20 makes it easier to prevent the crack from progressing to the center of the main surface of the glass sheet 10.

[0027] The thickness of the glass sheet 10 can be designed appropriately depending on the thickness of the glass resin composite 1, and is preferably, for example, 30 μm to 300 μm. The thickness of the glass sheet is more preferably 35 μm or more, and even more preferably 40 μm or more. The thickness of the glass sheet is more preferably 250 μm or less, and even more preferably 230 μm or less. If the thickness of the glass sheet 10 is within the above preferred range, the glass sheet 10 becomes easy to bend, and the glass resin composite 1 becomes easy to wind up in a roll-to-roll process.

[0028] The length and width of the glass sheet 10 are not particularly limited and can be appropriately designed depending on the size of the glass resin composite 1, and are, for example, preferably 50 mm to 5000 mm, more preferably 100 mm to 1500 mm. The length and width of the glass sheets 10 may be the same or different.

[0029] The glass sheet 10 is preferably transparent. "Transparent" means that visible light (light with a wavelength of 380 nm to 780 nm) is transmitted through the interior of the glass sheet 10 when irradiated from the outside of the glass sheet 10, and the visible light transmittance of the glass sheet 10 is preferably 85% or more. The light transmittance is measured using "Plastics - Determination of total luminous transmittance and total luminous reflectance" as defined in JIS K 7375:2008.

[0030] The refractive index of the glass sheet 10 at a wavelength of 550 nm may be 1.4 to 1.65.

[0031] The density of the glass sheet 10 is not particularly limited and is, for example, 2.3 g / cm ３ ~3.0 g / cm ３ This can be considered.

[0032] The manufacturing method of the glass sheet 10 is not particularly limited, and a general manufacturing method may be used. The glass sheet 10 is manufactured by melting a mixture containing a main raw material such as silica or alumina, an antifoaming agent such as mirabilite or antimony oxide, and a reducing agent such as carbon at a temperature of 1400°C to 1600°C, forming the mixture into a thin sheet, and then cooling it. The glass sheet 10 may be chemically polished with a solvent such as hydrofluoric acid, as necessary, to thin the glass sheet or to improve its smoothness.

[0033] A common method may be used to form the glass sheet 10. Examples of methods that can be used to form the glass sheet 10 include the slot downdraw method, the fusion method, and the float method. Among these, when the fusion method is used, the surface of the glass sheet is not contaminated with tin or the like as in the float method, so polishing is not necessary, and it is easy to ensure surface smoothness and thinness. Therefore, from these perspectives, the fusion method is preferably used.

[0034] A commercially available glass sheet may be used as is for the glass sheet 10, or a commercially available glass sheet may be polished to a desired thickness and used. Examples of commercially available glass sheets include "7059," "1737," and "EAGLE2000" manufactured by Corning Incorporated, "AN100" manufactured by Asahi Glass Co., Ltd., "NA-35" manufactured by NH Technoglass Co., Ltd., "OA-10" manufactured by Nippon Electric Glass Co., Ltd., and "D263" and "AF45" manufactured by Schott Corporation.

[0035] 1 , the multilayer resin layer 20 is a layer made of resin, and includes one or more resin layers 21N (N is an integer of 1 or more) stacked together. The N resin layers 21N are stacked in the order of resin layers 211...21N from the lower surface 1a side of the glass resin composite 1 toward the glass sheet 10 side. The resin layer 21N can be used as a resin layer, a pressure-sensitive adhesive layer, an adhesive layer, or the like.

[0036] (Resin Layer) The resin layer included in the multilayer resin layer 20 can be made of any appropriate resin depending on the application and the like of the glass resin composite 1. Examples of resins that form the resin layer include polyvinyl alcohol (PVA)-based resins, polyolefin-based resins, cyclic olefin-based resins, polycarbonate-based resins, cellulose-based resins, polyester-based resins, polyamide-based resins, polyimide-based resins, polyether-based resins, polystyrene-based resins, (meth)acrylic-based resins, (meth)acrylic urethane-based resins, polysulfone-based resins, acetate-based resins, epoxy-based resins, silicone-based resins, polyarylate-based resins, polysulfone-based resins, polyetherimide-based resins, epoxy-based resins, urethane-based resins, and silicone-based resins.

[0037] The thickness of the resin layer is not particularly limited, and may be any thickness appropriate depending on the application, type, etc.

[0038] The resin layer can be used as an optical film, a conductive film, a light control film, etc. Examples of optical films include a polarizing plate, a retardation plate, and an isotropic film.

[0039] (Polarizing Plate) The case where the resin layer is used as a polarizing plate will be described.

[0040] The polarizing plate has a film-like polarizer.

[0041] The thickness of the polarizer is not particularly limited and may be set arbitrarily depending on the purpose, for example, from 1 μm to 80 μm.

[0042] The polarizer preferably exhibits absorptive dichroism at any wavelength between 380 nm and 780 nm. The single transmittance of the polarizer is preferably 40.0% or more. The degree of polarization of the polarizer is preferably 99.8% or more.

[0043] The polarizer is preferably an iodine-based polarizer, which can be made of a PVA-based resin containing iodine.

[0044] Any appropriate resin can be used as the PVA-based resin. Examples of PVA-based resins include polyvinyl alcohol and ethylene-vinyl alcohol copolymers. Polyvinyl alcohol is obtained by saponifying polyvinyl acetate. Ethylene-vinyl alcohol copolymers are obtained by saponifying ethylene-vinyl acetate copolymers. The saponification degree of the PVA-based resin is usually 85 mol % to 100 mol %. The saponification degree can be determined in accordance with JIS K 6726-1994. By using a PVA-based resin having such a saponification degree, a polarizer with excellent durability can be obtained.

[0045] The average degree of polymerization of the PVA-based resin may be appropriately selected depending on the purpose, and is usually from 1000 to 10000. The average degree of polymerization can be determined in accordance with JIS K 6726:1994.

[0046] The polarizing plate may have a protective film on at least one surface of the polarizer. The protective film may be formed using any appropriate material, and examples of the material for the protective film include polyester resins such as polyethylene terephthalate (PET), cellulose resins such as triacetyl cellulose (TAC), cycloolefin resins such as norbornene resins, olefin resins such as polyethylene and polypropylene, and (meth)acrylic resins.

[0047] The protective film may have ultraviolet absorbing ability. The protective film can exhibit ultraviolet absorbing ability by appropriately containing any ultraviolet absorber. Examples of ultraviolet absorbers include oxybenzophenone-based compounds, benzotriazole-based compounds, salicylic acid ester-based compounds, benzophenone-based compounds, cyanoacrylate-based compounds, nickel complex salt-based compounds, and triazine-based compounds. The content of the ultraviolet absorber may be any amount that can exhibit sufficient ultraviolet absorbing ability, and is, for example, preferably 0.01 to 30 parts by mass relative to 100 parts by mass of the protective film.

[0048] The protective film can be formed by a general film-forming method, such as melt extrusion, solution casting, calendering, and compression molding.

[0049] The polarizer and the protective film are laminated together via any suitable adhesive layer.

[0050] The thickness of the protective film is not particularly limited and may be, for example, 5 μm to 55 μm.

[0051] (Adhesive Layer) The adhesive layer included in the multilayer resin layer 20 can be formed using any appropriate adhesive. Examples of the adhesive include rubber-based adhesives, acrylic-based adhesives, silicone-based adhesives, urethane-based adhesives, vinyl alkyl ether-based adhesives, polyvinyl alcohol-based adhesives, polyvinylpyrrolidone-based adhesives, polyacrylamide-based adhesives, and cellulose-based adhesives.

[0052] The pressure-sensitive adhesive is preferably an acrylic pressure-sensitive adhesive. The acrylic pressure-sensitive adhesive contains a (meth)acrylic polymer as a base polymer. The content of the (meth)acrylic polymer in the acrylic pressure-sensitive adhesive is preferably 50 parts by mass or more per 100 parts by mass of the total solid content in the acrylic pressure-sensitive adhesive.

[0053] The (meth)acrylic polymer contains a structural unit derived from an alkyl (meth)acrylate. Examples of the alkyl (meth)acrylate include acrylates in which the linear or branched alkyl group has 1 to 18 carbon atoms. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, hexyl, cyclohexyl, heptyl, 2-ethylhexyl, isooctyl, nonyl, decyl, isodecyl, dodecyl, isomyristyl, lauryl, tridecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl groups. These groups may be used alone or in combination. The average carbon number of these alkyl groups is preferably 3 to 9.

[0054] The content of the structural unit derived from alkyl (meth)acrylate is preferably 70 parts by mass or more based on 100 parts by mass of the (meth)acrylic polymer.

[0055] The (meth)acrylic polymer may further contain structural units derived from other monomers such as carboxyl group-containing monomers, hydroxyl group-containing monomers, amide group-containing monomers, and aromatic ring-containing (meth)acrylates. When the pressure-sensitive adhesive contains a crosslinking agent, the carboxyl group-containing monomers, hydroxyl group-containing monomers, amide group-containing monomers, and aromatic ring-containing (meth)acrylates serve as reaction sites with the crosslinking agent. In particular, carboxyl group-containing monomers and hydroxyl group-containing monomers are highly reactive with intermolecular crosslinking agents, and are therefore preferably used to improve the cohesiveness and heat resistance of the pressure-sensitive adhesive layer. In addition, copolymerizable monomers having functional groups containing unsaturated double bonds, such as (meth)acryloyl groups and vinyl groups, may also be used as other monomers.

[0056] The carboxyl group-containing monomer is a compound that contains a carboxyl group in its structure and a polymerizable unsaturated double bond such as a (meth)acryloyl group or a vinyl group, etc. Examples of the carboxyl group-containing monomer include (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid.

[0057] The content of the structural unit derived from the carboxyl group-containing monomer is preferably 0.01 to 10 parts by mass relative to 100 parts by mass of the (meth)acrylic polymer. Within this range, the glass resin composite 1 can exhibit excellent durability and reworkability.

[0058] The hydroxyl group-containing monomer is a compound that contains a hydroxyl group in its structure and a polymerizable unsaturated double bond such as a (meth)acryloyl group or a vinyl group. Specific examples of the hydroxyl group-containing monomer include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, and 12-hydroxylauryl (meth)acrylate, and (4-hydroxymethylcyclohexyl)-methyl acrylate. Among the above hydroxyl group-containing monomers, 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate are preferred, with 4-hydroxybutyl (meth)acrylate being more preferred, from the viewpoint of durability.

[0059] The content of the structural unit derived from the hydroxyl group-containing monomer is preferably 0.01 to 3 parts by mass relative to 100 parts by mass of the (meth)acrylic polymer. Within this range, the glass resin composite 1 can exhibit excellent durability and adhesive properties.

[0060] The amide group-containing monomer is a compound that contains an amide group in its structure and also contains a polymerizable unsaturated double bond such as a (meth)acryloyl group and a vinyl group. Examples of the amide group-containing monomer include acrylamide-based monomers such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropylacrylamide, N-methyl(meth)acrylamide, N-butyl(meth)acrylamide, N-hexyl(meth)acrylamide, N-methylol(meth)acrylamide, N-methylol-N-propane(meth)acrylamide, aminomethyl(meth)acrylamide, aminoethyl(meth)acrylamide, mercaptomethyl(meth)acrylamide, and mercaptoethyl(meth)acrylamide; N-acryloyl heterocyclic monomers such as N-(meth)acryloylmorpholine, N-(meth)acryloylpiperidine, and N-(meth)acryloylpyrrolidine; and N-vinyl group-containing lactam-based monomers such as N-vinylpyrrolidone and N-vinyl-ε-caprolactam.

[0061] The content of the structural unit derived from the amide group-containing monomer is preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the (meth)acrylic polymer. Within this range, the glass resin composite 1 can exhibit excellent durability and adhesive properties.

[0062] The aromatic ring-containing (meth)acrylate is a compound that contains an aromatic ring structure and a (meth)acryloyl group in its structure. Examples of the aromatic ring include a benzene ring, a naphthalene ring, and a biphenyl ring. Specific examples of the aromatic ring-containing (meth)acrylate include benzyl (meth)acrylate, phenyl (meth)acrylate, o-phenylphenol (meth)acrylate, phenoxy (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxypropyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, ethylene oxide-modified nonylphenol (meth)acrylate, ethylene oxide-modified cresol (meth)acrylate, phenol ethylene oxide-modified (meth)acrylate, 2-hydroxybenzoic acid (meth)acrylate, ... Examples of the acrylate include those having a benzene ring, such as hydroxy-3-phenoxypropyl (meth)acrylate, methoxybenzyl (meth)acrylate, chlorobenzyl (meth)acrylate, cresyl (meth)acrylate, and polystyryl (meth)acrylate; those having a naphthalene ring, such as hydroxyethylated β-naphthol acrylate, 2-naphthoethyl (meth)acrylate, 2-naphthoxyethyl acrylate, and 2-(4-methoxy-1-naphthoxy)ethyl (meth)acrylate; and those having a biphenyl ring, such as biphenyl (meth)acrylate.

[0063] The content of the structural unit derived from the aromatic ring-containing (meth)acrylate is preferably 25 parts by mass or less relative to 100 parts by mass of the (meth)acrylic polymer. Within this range, the glass resin composite 1 can exhibit excellent durability.

[0064] The weight-average molecular weight (Mw) of the (meth)acrylic polymer is preferably 1,000,000 to 2,500,000. Within this range, the glass resin composite 1 can exhibit excellent durability and heat resistance. The weight-average molecular weight is measured by GPC (gel permeation chromatography) and calculated in polystyrene equivalent terms.

[0065] The (meth)acrylic polymer can be obtained by polymerization using a general polymerization method.

[0066] The pressure-sensitive adhesive may further contain a silane coupling agent. By using a pressure-sensitive adhesive containing a silane coupling agent, a pressure-sensitive adhesive layer with excellent durability can be formed. As the silane coupling agent, a silane coupling agent having any appropriate functional group can be used. Examples of the functional group include a vinyl group, an epoxy group, an amino group, a mercapto group, a (meth)acryloxy group, an acetoacetyl group, an isocyanate group, a styryl group, and a polysulfide group. Specific examples of the silane coupling agent include vinyl group-containing silane coupling agents such as vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, and vinyltributoxysilane; epoxy group-containing silane coupling agents such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)3-aminopropylmethyldimethoxysilane, γ-triethoxysilyl-N- Examples of suitable silane coupling agents include amino group-containing silane coupling agents such as (1,3-dimethylbutylidene)propylamine and N-phenyl-γ-aminopropyltrimethoxysilane; mercapto group-containing silane coupling agents such as γ-mercaptopropylmethyldimethoxysilane; styryl group-containing silane coupling agents such as p-styryltrimethoxysilane; (meth)acrylic group-containing silane coupling agents such as γ-acryloxypropyltrimethoxysilane and γ-methacryloxypropyltriethoxysilane; isocyanate group-containing silane coupling agents such as 3-isocyanatepropyltriethoxysilane; and polysulfide group-containing silane coupling agents such as bis(triethoxysilylpropyl)tetrasulfide.

[0067] The silane coupling agent may be a silane coupling agent having multiple alkoxysilyl groups in the molecule, such as X-41-1053, X-41-1059A, X-41-1056, X-41-1805, X-41-1818, X-41-1810, and X-40-2651 manufactured by Shin-Etsu Chemical Co., Ltd.

[0068] The content of the silane coupling agent is preferably 0.001 to 5 parts by mass relative to 100 parts by mass of the base polymer in the pressure-sensitive adhesive.

[0069] The silane coupling agent may be a thiol group-containing silane coupling agent. Use of a thiol group-containing silane coupling agent allows the formation of a pressure-sensitive adhesive layer that is excellent in durability and reworkability.

[0070] As the thiol group-containing silane coupling agent, an oligomeric thiol group-containing silane coupling agent is used. Use of an oligomeric thiol group-containing silane coupling agent allows for the formation of a pressure-sensitive adhesive layer with superior durability and reworkability. Here, "oligomeric" refers to a polymer of a dimer or more but less than 100 of a monomer, and the weight-average molecular weight (Mw) of the oligomeric silane coupling agent is preferably 300 to 30,000. As the oligomeric thiol group-containing silane coupling agent, an oligomeric thiol group-containing silane coupling agent having two or more alkoxysilyl groups in the molecule is preferred. Examples of such silane coupling agents include X-41-1805, X-41-1810, and X-41-1818 manufactured by Shin-Etsu Chemical Co., Ltd.

[0071] The number of alkoxysilyl groups in the thiol group-containing silane coupling agent is not particularly limited, but it is preferable that there are two or more alkoxysilyl groups in the molecule.

[0072] The content of the alkoxy group in the thiol group-containing silane coupling agent is preferably 10% by mass to 60% by mass in the silane coupling agent.

[0073] The type of alkoxy group is not particularly limited, but examples include alkoxy groups having 1 to 6 carbon atoms, such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, and hexyloxy. Among these, methoxy and ethoxy are preferred, and methoxy is more preferred. It is preferred that both methoxy and ethoxy are contained in one molecule.

[0074] The thiol equivalent (mercapto equivalent) of the thiol group-containing silane coupling agent is preferably 200 g / mol to 1000 g / mol.

[0075] The pressure-sensitive adhesive may further contain a crosslinking agent. Examples of the crosslinking agent that can be used include organic crosslinking agents and polyfunctional metal chelates. Examples of organic crosslinking agents include isocyanate crosslinking agents, peroxide crosslinking agents, epoxy crosslinking agents, and imine crosslinking agents. Polyfunctional metal chelates are those in which a polyvalent metal is covalently or coordinately bonded to an organic compound. The crosslinking agent is preferably at least one of an isocyanate crosslinking agent and a peroxide crosslinking agent, and more preferably a combination of an isocyanate crosslinking agent and a peroxide crosslinking agent.

[0076] The isocyanate crosslinking agent may be a compound having at least two isocyanate groups, such as an aliphatic diisocyanate, an alicyclic diisocyanate, or an aromatic diisocyanate, which are generally used in urethane reactions.

[0077] Examples of the aliphatic diisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate.

[0078] Examples of alicyclic diisocyanates include 1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated tetramethylxylylene diisocyanate.

[0079] Examples of aromatic diisocyanates include phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, and xylylene diisocyanate.

[0080] Examples of the isocyanate-based crosslinking agent include urethane-modified products, urea-modified products, biuret-modified products, alphanate-modified products, isocyanurate-modified products, and carbodiimide-modified products obtained by reacting a multimer (dimer, trimer, pentamer, etc.) of a diisocyanate such as the above-mentioned aliphatic diisocyanate, alicyclic diisocyanate, and aromatic diisocyanate with a polyhydric alcohol such as trimethylolpropane.

[0081] Commercially available isocyanate crosslinking agents include, for example, "Millionate MT", "Millionate MTL", "Millionate MR-200", "Millionate MR-400", "Coronate L", "Coronate HL" and "Coronate HX" manufactured by Nippon Polyurethane Industry Co., Ltd., and "Takenate D-110N", "Takenate D-120N", "Takenate D-140N", "Takenate D-160N", "Takenate D-165N", "Takenate D-170HN", "Takenate D-178N", "Takenate 500" and "Takenate 600" manufactured by Mitsui Chemicals, Inc. These compounds may be used alone or in combination of two or more.

[0082] As the isocyanate-based crosslinking agent, aliphatic polyisocyanates and their modified aliphatic polyisocyanate-based compounds are preferred. The use of aliphatic polyisocyanate-based compounds results in a highly flexible crosslinked structure, which easily relieves stress associated with the expansion / contraction of the pressure-sensitive adhesive layer, making it possible to form a pressure-sensitive adhesive layer with excellent durability and adhesive properties. As the aliphatic polyisocyanate-based compound, hexamethylene diisocyanate or its modified product is particularly preferred.

[0083] As the peroxide-based crosslinking agent, it is preferable to use a peroxide having a one-minute half-life temperature of 80° C. to 160° C. Examples of the peroxide-based crosslinking agent include di(2-ethylhexyl)peroxydicarbonate (one-minute half-life temperature: 90.6° C.), di(4-t-butylcyclohexyl)peroxydicarbonate (one-minute half-life temperature: 92.1° C.), di-sec-butylperoxydicarbonate (one-minute half-life temperature: 92.4° C.), t-butylperoxyneodecanoate (one-minute half-life temperature: 103.5° C.), t-hexylperoxypivalate (one-minute half-life temperature: 109.1° C.), t-butylperoxypivalate (one-minute half-life temperature: 110.3° C.), dilauroyl peroxide ( 1-minute half-life temperature: 116.4°C), di-n-octanoyl peroxide (1-minute half-life temperature: 117.4°C), 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (1-minute half-life temperature: 124.3°C), di(4-methylbenzoyl)peroxide (1-minute half-life temperature: 128.2°C), dibenzoyl peroxide (1-minute half-life temperature: 130.0°C), t-butylperoxyisobutyrate (1-minute half-life temperature: 136.1°C), and 1,1-di(t-hexylperoxy)cyclohexane (1-minute half-life temperature: 149.2°C). Among these, di(4-t-butylcyclohexyl)peroxydicarbonate (1-minute half-life temperature: 92.1°C), dilauroyl peroxide (1-minute half-life temperature: 116.4°C), and dibenzoyl peroxide (1-minute half-life temperature: 130.0°C) are preferably used because of their particularly excellent crosslinking reaction efficiency. The half-life of a peroxide is an index representing the decomposition rate of the peroxide, and refers to the time until the remaining amount of peroxide is reduced to half. The decomposition temperature for obtaining the half-life at any time and the half-life time at any temperature are described in manufacturer catalogs, for example, in "Organic Peroxide Catalog, 9th Edition (May 2003)" manufactured by NOF Corporation.

[0084] The content of the crosslinking agent is preferably 0.01 to 3 parts by mass relative to 100 parts by mass of the base polymer. Within this range, a pressure-sensitive adhesive layer having appropriate creep characteristics, elastic modulus, etc. can be formed.

[0085] The PSA may further contain any suitable ionic compound. Examples of the ionic compound include (perfluoroalkylsulfonyl)imide lithium salt and bis(trifluoromethanesulfonylimide)lithium. The content of the ionic compound is preferably 10 parts by mass or less per 100 parts by mass of the base polymer.

[0086] The pressure-sensitive adhesive layer may further contain any other appropriate additives, such as polyether compounds of polyalkylene glycols such as polypropylene glycol, colorants, powders such as pigments, dyes, surfactants, plasticizers, tackifiers, surface lubricants, leveling agents, softeners, antioxidants, antiaging agents, light stabilizers, ultraviolet absorbers, polymerization inhibitors, inorganic or organic fillers, etc.

[0087] The thickness of the pressure-sensitive adhesive layer is not particularly limited, and may be, for example, 10 μm to 200 μm.

[0088] (Adhesive Layer) The adhesive layer included in the multilayer resin layer 20 can be formed using any suitable adhesive. Examples of adhesives that can be used include photocurable and thermosetting adhesives. Examples of adhesives include epoxy adhesives, rubber adhesives, acrylic adhesives, silicone adhesives, urethane adhesives, and mixtures thereof. Examples of adhesive materials that can be used for the adhesive include mixtures of polyurethane, polyvinyl chloride, polyvinyl acetate, vinyl alcohol, and the like; epoxy resins, polyvinyl butyral, polymethacrylate esters, cyclized rubbers, ethyl cellulose, vinyl copolymers, and the like. Epoxy resins, polyvinyl butyral, polymethacrylate esters, cyclized rubbers, ethyl cellulose, and vinyl copolymers are preferred because they have good adhesion to the glass sheet 10.

[0089] The adhesive layer is preferably optically transparent in the visible wavelength range. The adhesive layer may be formed by curing the adhesive with light, heat, or a combination of these.

[0090] The thickness of the adhesive layer is not particularly limited and may be, for example, 1 μm to 50 μm.

[0091] (Transparent Conductive Layer) The multilayer resin layer 20 may have a transparent conductive layer. Examples of the transparent conductive layer include a metal oxide layer, a metal layer, a layer containing a conductive polymer, a layer containing metal nanowires, and a layer composed of a metal mesh.

[0092] [Protective Layer] The glass resin composite 1 may be temporarily provided with a protective layer on the surface of the glass sheet 10 opposite to the multilayer resin layer 20. The protective film temporarily protects the surface of the glass sheet 10 and prevents contamination of the surface due to adhesion of foreign matter or the like.

[0093] Examples of materials that can be used to form the protective film include polyethylene, polyvinyl chloride, polyethylene terephthalate, polyvinylidene chloride, polypropylene, polyvinyl alcohol, polyester, polycarbonate, polystyrene, polyacrylonitrile, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-methacrylic acid copolymer, nylon, cellophane, and silicone resin.

[0094] The thickness of the protective layer is not particularly limited, but may be, for example, 100 μm or less.

[0095] The glass resin composite 1 may optionally include a functional layer, such as a transparent electrode, an anti-reflection layer, or an anti-fouling layer, on the surface of the glass sheet 10 opposite to the multilayer resin layer 20. The thickness of the functional layer is not particularly limited, but may be, for example, 1 μm or less.

[0096] <Method for Manufacturing Glass Resin Composite> (Formation of Laminate) The glass sheet 10 and the multilayer resin layer 20 are laminated together using a roll-to-roll process to form a laminate.

[0097] The length of the glass sheet 10 before cutting is a long glass ribbon. Therefore, the length of the glass sheet 10 before cutting is, for example, preferably 50 m or more, more preferably 100 m or more, and even more preferably 500 m or more. The upper limit of the length of the glass sheet 10 before cutting is not particularly limited and may be, for example, 1000 m.

[0098] When the multilayer resin layer 20 includes an adhesive layer as a resin layer, the laminate can be formed by laminating the remaining resin layers of the multilayer resin layer 20 to the glass sheet 10 via the adhesive layer, which is one of the resin layers of the multilayer resin layer 20.

[0099] The laminate can also be formed by applying a resin solution to form a resin layer to one main surface of the glass sheet 10 or to a main surface of one of the resin layers of the multilayer resin layer 20 that is different from the glass sheet 10 side to form a resin layer.

[0100] Examples of methods for applying the resin solution used to form the resin layer include coating methods such as air doctor coating, blade coating, knife coating, reverse coating, transfer roll coating, gravure roll coating, kiss coating, cast coating, spray coating, slot orifice coating, calendar coating, electrodeposition coating, dip coating, and die coating; and printing methods such as relief printing methods such as flexographic printing, intaglio printing methods such as direct gravure printing and offset gravure printing, lithographic printing methods such as offset printing, and stencil printing methods such as screen printing.

[0101] When one of the resin layers constituting the multilayer resin layer 20 is a curable resin layer such as an adhesive layer, the resin solution constituting the resin layer may be cured using any appropriate curing method depending on the type of resin layer. Examples of the curing method include a method of curing the resin solution by ultraviolet irradiation or heat treatment.

[0102] (Cutting of Laminate) Next, the laminate formed by laminating the glass sheet 10 and the multilayer resin layer 20 is cut to a predetermined size to obtain a glass resin composite 1. For example, as shown in Fig. 2 , the obtained plurality of glass resin composites 1 are attached to one main surface of a rolled flexible film substrate 101 at predetermined intervals by a nip mechanism 120 via an adhesive or the like while the film substrate 101 is being transported from a payout roller 110 using a roll-to-roll transport device 100, and then taken up into a roll by a take-up roller 130.

[0103] The laminate may be cut by any suitable method, for example, by mechanically cutting the laminate, by providing a scratch (scribe) on the surface of the laminate and then causing a crack to grow (break) by heat or bending stress, by irradiating the laminate with laser light, or by using a full back mill, a water jet, an end mill, or the like to cut the laminate.

[0104] The laminate may be cut into individual glass sheets 10 or individual multilayer resin layers 20 using any of the cutting methods described above.

[0105] Of the above-mentioned cutting methods, the method of cutting the laminate by irradiating laser light to divide the laminate is preferred from the viewpoints of ease of cutting the laminate and ease of adjusting the Young's modulus of at least one of the glass sheet 10 and the multilayer resin layer 20 of the laminate.

[0106] A method of dividing a laminate by irradiating with laser light will be described. When using a method of dividing a laminate by irradiating with laser light, the laminate may be divided using a laser light irradiating device that irradiates any suitable laser light.

[0107] The laminate is placed on the stage of a laser beam irradiation device. The stage is movably arranged in the laser beam irradiation device, and the laser light source is fixedly arranged. The laser beam irradiation device moves the stage to move the position of the laser beam irradiated onto the laminate.

[0108] The laser light is, for example, CO ２ Examples of such lasers include gas lasers such as lasers and excimer lasers; solid-state lasers such as YAG lasers; semiconductor lasers; and ultrashort pulse lasers.

[0109] The laminate may be cut by forming processing marks along the planned cutting line in the laminate with a laser beam. The processing marks may be formed in the form of perforations along the planned cutting line, or may be formed as a continuous line. The processing marks may be through holes that penetrate each layer, or may be blind holes.

[0110] It is preferable to use different laser beams for irradiating the surface of the multilayer resin layer 20 and the surface of the glass sheet 10. That is, it is preferable to divide the laminate by irradiating the surfaces of the glass sheet 10 and the multilayer resin layer 20 with different laser beams. In each of the steps of irradiating the surface of the glass sheet 10 with a laser and irradiating the surface of the multilayer resin layer 20 with a laser beam, the laser beam leaves processing marks on each layer, making it easier to cut the laminate.

[0111] An ultrashort pulse laser is preferably used as the laser light irradiated onto the surface of the glass sheet 10. The wavelength of the ultrashort pulse laser emitted from the ultrashort pulse laser device is preferably 500 nm to 2500 nm. The pulse width of the ultrashort pulse laser is preferably 100 picoseconds or less, more preferably 50 picoseconds or less. The oscillation mode of the ultrashort pulse laser may be single pulse oscillation or birth mode multi-pulse oscillation.

[0112] The laser light irradiated onto the surface of the multilayer resin layer 20 is, for example, CO ２ Examples of such lasers include lasers, CO lasers, visible light pulse lasers, and ultraviolet pulse lasers. Examples of visible light pulse lasers and ultraviolet pulse lasers include lasers emitting laser light with wavelengths of 532 nm, 355 nm, 349 nm, or 266 nm (high-order harmonics of solid-state laser light sources using Nd:YAG, Nd:YLF, or YVO4 as a medium), excimer lasers emitting laser light with wavelengths of 351 nm, 248 nm, 222 nm, 193 nm, or 157 nm, and F2 lasers emitting laser light with wavelengths of 157 nm. Furthermore, as the laser light, a pulsed laser emitting laser light with a wavelength outside the ultraviolet range and a pulse width on the order of femtoseconds or picoseconds may be used. The oscillation mode of the laser light irradiated onto the multilayer resin layer 20 may be pulsed or continuous. The spatial intensity distribution of the laser light may be a Gaussian distribution or a flat-top distribution.

[0113] The spot diameter at the irradiation position of the laser light on the multilayer resin layer 20 may be set appropriately, and may be, for example, 300 μm or less.

[0114] The stage movement speed during irradiation of the laminate with the laser light may be set arbitrarily as appropriate. The stage movement speed corresponds to the relative movement speed of the laser light with respect to the laminate, and by changing the stage movement speed, different energies can be applied to the laminate.

[0115] When different laser beams are irradiated onto the surfaces of the glass sheet 10 and the multilayer resin layer 20, the stage movement speed may be different when irradiating the glass sheet 10 with laser beam and when irradiating the glass sheet 10 of the laminate with laser beam.

[0116] When an ultrashort pulse laser is irradiated onto the surface of the glass sheet 10 as laser light, the stage movement speed can be adjusted to make it easier to cut the laminate while preventing damage such as cracks from occurring to the glass sheet 10.

[0117] The surface of the multilayer resin layer 20 is exposed to CO ２ When irradiating the laser, the stage movement speed is adjusted to prevent the multilayer resin layer 20 from being exposed to CO ２ The degree of thermal degradation can be adjusted by using a laser. ２ When thermally deteriorated by the laser, the flexibility of the multilayer resin layer 20 decreases, and the Young's modulus tends to decrease. ２ The faster the stage moving speed during laser irradiation, the more CO ２ Since thermal degradation caused by the laser is suppressed, the multilayer resin layer 20 maintains its flexibility, and the decrease in the Young's modulus of the multilayer resin layer 20 is suppressed. ２ The slower the stage moving speed during laser irradiation, the more the CO ２ Since thermal degradation due to the laser is likely to occur, the flexibility of the multilayer resin layer 20 decreases, and the Young's modulus of the multilayer resin layer 20 decreases.

[0118] When different laser beams are irradiated onto the surfaces of the glass sheet 10 and the multilayer resin layer 20, cutting the glass sheet 10 using an ultrashort pulse laser can prevent damage such as cracks from being caused to the glass sheet 10 and make it easier to cut the laminate. ２ By using a laser or the like, it is possible to suppress thermal deterioration of the multilayer resin layer 20. Therefore, when the multilayer resin layer 20 is exposed to CO ２ After the laser irradiation, the glass sheet 10 is irradiated with ultrashort pulse laser light as the laser light, whereby the laminate can be cut while more effectively preventing thermal deterioration of the multilayer resin layer 20 .

[0119] When the processing marks such as through holes or through-holes are provided in the form of perforations, the pitch of the processing marks is preferably 10 μm or less, and more preferably 5 μm or less. Within this range, the laminate can be divided well.

[0120] After irradiation with the laser light, the laminate may be divided by, for example, applying an external force to fold the laminate, heating the area near the processing marks with infrared light, applying vibration with an ultrasonic roller, or sucking a part of the laminate onto a suction cup and lifting it up.

[0121] As described above, by cutting the laminate, a plurality of glass resin composites 1 are obtained. As described above, the obtained plurality of glass resin composites 1 can be attached at predetermined intervals to one main surface of a film substrate via an adhesive or the like by a roll-to-roll process and wound into a roll.

[0122] Thus, the glass resin composite 1 includes a glass sheet 10 and a multilayer resin layer 20 composed of one or more resin layers 21N. The thickness of the glass resin composite is 800 μm or less. When the glass resin composite 1 is bent toward its lower surface 1a with a radius of curvature that satisfies the above formula (1), the probability of cracking in the glass sheet 10 can be reduced to 10% or less. The elastic modulus and thickness of the multilayer resin layer 20 are the sum of the elastic modulus and thickness of all the resin layers 21N that constitute the multilayer resin layer 20. If the relationship between the elastic modulus and thickness of all the resin layers 21N that constitute the multilayer resin layer 20 is equal to or less than a value that satisfies the above formula (1), the bending durability of the glass sheet 10 can be enhanced. Therefore, even if a crack occurs at the edge of the glass sheet 10 when the relationship between the elastic modulus and thickness of the resin layers 21N that constitute the multilayer resin layer 20 is equal to or less than a value that satisfies the above formula (1), the propagation of the crack can be suppressed, and cracking in the effective surface area can be suppressed. Therefore, if the glass resin composite 1 is bent so that the glass sheet 10 side is convex with a curvature radius that is equal to or less than the value that satisfies the above formula (1), it is possible to prevent cracks from occurring in the effective area of ​​the surface of the glass sheet 10 even when a roll-to-roll process is used.

[0123] The effective region is the region in the glass resin composite 1 where the glass sheet 10 will ultimately be used or where it is planned to be put to practical use later. The effective region is the remaining region excluding the region within 1 / 6 of the outer periphery of the surface of the glass sheet 10 from the outer periphery of the surface, preferably the remaining region excluding the region within 1 / 10 of the outer periphery of the surface, and more preferably the remaining region excluding the region within 1 / 15 of the outer periphery of the surface. For example, when one side of the outer periphery of the surface of the glass sheet 10 is 300 mm, the effective region is the remaining region excluding the region within 50 mm from the outer periphery 300 mm.

[0124] When the glass resin composite 1 is bent toward its upper surface 1b with a radius of curvature that satisfies the above formula (1), the probability of cracking in the glass sheet 10 can be reduced to 10% or less. As described above, if the relationship between the elastic modulus and thickness of the resin layer 21N is equal to or less than a value that satisfies the above formula (1), the glass sheet 10 can have improved bending durability. Therefore, even if a crack occurs at the edge of the glass sheet 10 when the relationship between the elastic modulus and thickness of the resin layer 21N that constitutes the multilayer resin layer 20 is equal to or less than a value that satisfies the above formula (1) and the glass resin composite 1 is bent so that the multilayer resin layer 20 side is convex, the progression of the crack can be suppressed, and cracking in the effective surface area can be suppressed. Therefore, even if the glass resin composite 1 is bent with a radius of curvature that is equal to or less than a value that satisfies the above formula (1) so that the multilayer resin layer 20 side is convex, cracking in the effective surface area of ​​the glass sheet 10 can be suppressed when using a roll-to-roll process.

[0125] In the glass resin composite 1, the thickness of the glass sheet 10 can be 20% to 75% of the thickness of the glass resin composite 1. This makes it easier to set the configuration of each resin layer 21N of the multilayer resin layer 20 so that the relationship between the elastic modulus and thickness of the resin layer 21N is equal to or less than the value that satisfies the above formula (1). Therefore, even if the glass resin composite 1 is bent to a value that satisfies the above formula (1), it is possible to suppress the occurrence of cracks in the effective area of ​​the surface of the glass sheet 10.

[0126] The glass resin composite 1 can have a thickness of the glass sheet 10 of 30 μm to 300 μm. This makes it easier to set the configuration of each resin layer 21N of the multilayer resin layer 20 so that the relationship between the elastic modulus and thickness of the resin layer 21N is equal to or less than the value that satisfies the above formula (1). Therefore, even if the glass resin composite 1 is bent to a value that satisfies the above formula (1), it is possible to suppress the occurrence of cracks in the effective area of ​​the surface of the glass sheet 10.

[0127] As described above, even when the glass resin composite 1 is transported and rolled up in a roll-to-roll process, it is possible to prevent cracks from occurring in the effective area of ​​the surface of the glass sheet 10, and therefore it can be effectively used in image display devices such as liquid crystal display elements and organic EL elements, semiconductor elements, solar cells, etc.

[0128] In this embodiment, the glass resin composite 1 may have a multilayer resin layer 20 on the upper surface 10b of the glass sheet 10, as shown in Figure 3, or may have a multilayer resin layer 20 on both the lower surface 10a and the upper surface 10b of the glass sheet 10, as shown in Figure 4.

[0129] Although the embodiments have been described above, they are presented as examples and the present invention is not limited to the above embodiments. The above embodiments can be embodied in various other forms, and various combinations, omissions, substitutions, modifications, etc. can be made without departing from the spirit of the invention. The above embodiments and their modifications are included within the scope and spirit of the invention, and are also included in the scope of the invention and its equivalents as set forth in the claims.

[0130] Hereinafter, the embodiment will be described in more detail with reference to examples and comparative examples, but the embodiment is not limited to these examples and comparative examples.

[0131] <Preparation of Glass Resin Composite> [Example 1] (Preparation of Laminate) An adhesive (epoxy resin (Celloxide 2021P, manufactured by Daicel Chemical Industries, Ltd., thickness: 10 μm)) was applied to one main surface of a 300 mm square glass sheet (OA-10, manufactured by Nippon Electric Glass Co., Ltd., thickness: 100 μm), and a PET layer (A4360, manufactured by Toyobo Co., Ltd., thickness: 100 μm) was laminated thereon. Thereafter, ultraviolet light (wavelength: 365 nm, intensity: 1000 mJ / cm) was applied from a high-pressure mercury lamp. ２ The adhesive was cured by irradiating the adhesive with the above-mentioned light. In this way, a laminate 1 was produced in which a multilayer resin layer 1 composed of an adhesive layer and a PET layer was laminated on a glass sheet.

[0132] (Removal of the multilayer resin layer) The laminate 1 was placed on a stage with the adhesive layer side facing up.２ Using a laser device (250 kHz, output 10 W), CO ２ CO emitted from a laser light source ２ The laser was focused to a spot diameter of 100 μm using a focusing lens and irradiated onto the multilayer resin layer 1. The stage movement speed was set to 350 mm / s, and the CO ２ The relative movement speed (processing speed) of the laser was set so that the in-plane dimensions of the laminate were 300 mm x 300 mm. ２ The multilayer resin layer 1 was irradiated with a laser to remove the multilayer resin layer 1, thereby cutting the laminate 1 in half.

[0133] In addition, CO ２ The stage moving speed during laser irradiation is set to the CO ２ The glass sheet and the multilayer resin layer 1 are moved in accordance with the relative moving speed of the laser. ２ This indicates the degree of thermal degradation caused by the laser, and therefore the flexibility of the glass sheet and the multilayer resin layer 1 tends to decrease, and the Young's modulus tends to decrease. ２ By increasing the stage movement speed during laser irradiation, the CO ２ Since thermal degradation caused by the laser is suppressed, the decrease in the Young's modulus of the glass sheet and the multilayer resin layer 1 is suppressed. ２ By slowing down the stage movement speed during laser irradiation, the CO ２ Since thermal degradation due to the laser becomes more likely to occur, the glass sheet and the multilayer resin layer 1 become hard, and the Young's modulus of the glass sheet and the multilayer resin layer 1 decreases.

[0134] (Removal of glass sheet) Next, the glass sheet was placed on the stage with the glass sheet side facing up, and an ultrashort pulse laser device (oscillation wavelength 1064 nm, ultrashort pulse laser pulse width 10 psec, pulse repetition frequency 125 kHz, pulse energy 80 uJ) was used. The ultrashort pulse laser emitted from the ultrashort pulse laser light source was irradiated through an optical system onto the surface opposite the resin film side of the glass sheet. The stage movement speed was set to 125 mm / s, and the relative movement speed (processing speed) of the ultrashort pulse laser with respect to the laminate 1 was set, and the ultrashort pulse laser was scanned along the periphery of the adhesive layer and the resin layer to form perforated through holes with a pitch of 1 μm as processing marks. The laminate 1 was pulled horizontally and divided into multiple pieces (4 pieces), to prepare a glass resin composite test piece (composite chip).

[0135] (Calculation of Radius of Curvature) The radius of curvature R is calculated using the following formula (1): ０ was calculated.

[0136] (In formula (1), R ０ is the inner radius of curvature of the glass resin composite [mm], i and k are integers, l is the number of layers [layers] including the resin layer and the glass sheet when counting from the inside of the glass resin composite, n is the total number of layers [layers], and E ｉ is the Young's modulus [MPa] of the i-th layer, and t ｉ is the thickness [μm] of the i-th resin layer, and t ｋ is the thickness [μm] of the kth resin layer, and t ｋ－１ is the thickness [μm] of the (k-1)th resin layer.

[0137] In the formula (1), l represents 3 layers and n represents 2 layers. The Young's modulus of the resin layer was measured using an autograph under the following Young's modulus measurement conditions: Measurement temperature: 25°C Sample size: Thickness 50 μm, width 2 cm, length 15 cm Distance between chucks: 10 cm Pulling speed: 10 mm / min

[0138] Example 2 The same glass-resin composite test piece as in Example 1 was used.

[0139] [Example 3] In Example 1, the multilayer resin layer 1 formed on one main surface of the glass sheet was changed to a multilayer resin layer 2 in which a triacetyl cellulose (TAC) layer (thickness: 40 μm), a polyvinyl alcohol (PVA) layer (thickness: 18 μm), a TAC layer (thickness: 40 μm), a pressure-sensitive adhesive (PSA) layer (thickness: 20 μm), and a PET layer (thickness: 100 μm) were laminated in this order on an adhesive (epoxy resin ("Celloxide 2021P" manufactured by Daicel Chemical Industries, Ltd., thickness: 10 μm). Except for this, the same procedure as in Example 1 was carried out to prepare a glass resin composite test piece.

[0140] The PSA layer was prepared as follows: A four-neck flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube, and a condenser was charged with 90.7 parts by mass of butyl acrylate, 3 parts by mass of acrylic acid, 0.3 parts by mass of 2-hydroxybutyl acrylate, and 0.1 parts by mass of 2,2'-azobisisobutyronitrile as a polymerization initiator, along with 100 g of ethyl acetate, to prepare a mixture. Nitrogen gas was introduced into the mixture while gently stirring to replace the atmosphere with nitrogen, and the liquid temperature in the flask was maintained at around 55°C while the polymerization reaction was carried out for 8 hours to prepare an acrylic polymer solution. An acrylic pressure-sensitive adhesive solution was prepared by blending 0.2 parts by mass of an isocyanate crosslinking agent (Coronate L manufactured by Nippon Polyurethane Industry Co., Ltd., an adduct of trimethylolpropane and tolylene diisocyanate), 0.3 parts by mass of benzoyl peroxide (Niper BMT manufactured by NOF Corporation), and 0.2 parts by mass of γ-glycidoxypropyl methoxysilane (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.) per 100 parts by mass of the solids content of the obtained acrylic polymer solution. Next, the acrylic pressure-sensitive adhesive solution was applied to one side of a silicone-treated PET film so that the thickness of the PSA layer after drying would be 20 μm, and the coating was dried at 150° C. for 3 minutes to form a PSA layer.

[0141] [Example 4] In Example 1, the multilayer resin layer 1 formed on one main surface of the glass sheet was also formed on the other main surface of the glass sheet, and the multilayer resin layer 1 was laminated on both the top and bottom surfaces of the glass sheet. ２ Removed with laser and CO ２The multilayer resin layer 1 was removed twice by laser. Except for this, the same procedure as in Example 1 was carried out to prepare a glass resin composite test piece.

[0142] [Example 5] In Example 1, the multilayer resin layer 1 formed on one main surface of the glass sheet was changed to a multilayer resin layer 3 in which a PSA layer (thickness: 200 μm) and a PET layer (thickness: 150 μm) were laminated in this order, and a multilayer resin layer 3 was formed on the other main surface of the glass sheet. Except for this, the same procedure as in Example 1 was carried out to prepare a glass resin composite test piece.

[0143] Comparative Examples 1 and 2 In Comparative Example 1, the same glass resin composite test piece as in Example 1 was used, and in Comparative Example 2, the same glass resin composite test piece as in Example 3 was used.

[0144] The layer structure and total thickness of the laminate of each Example and Comparative Example, and the CO ２ Stage movement speed and curvature radius R during laser irradiation ０ is shown in Table 1.

[0145] <Evaluation> The glass resin composite test pieces of each of the Examples and Comparative Examples were evaluated for the occurrence of cracks in the glass sheet and whether web transport (web handling) was possible.

[0146] [Evaluation of cracks in the effective area of ​​the surface of the glass sheet] Next, a cylinder (SUS) with a curvature radius satisfying the above formula (1) was prepared, and the glass resin composite test piece was wrapped around the cylinder to check whether cracks occurred in the effective area (250 mm x 250 mm) of the surface of the glass sheet. The test was conducted using 30 glass resin composite test pieces. The crack occurrence rate in the effective area of ​​the surface of the glass sheet for the 30 glass resin composite test pieces was calculated based on the following formula (i). The calculation results of the crack occurrence rate in the effective area of ​​the surface of the glass sheet are shown in Table 1. Crack occurrence rate in the effective area of ​​the surface of the glass sheet [%] = number of glass resin composite test pieces in which cracks occurred in the effective area of ​​the surface of the glass sheet / 30 x 100 ... (i)

[0147] [Web Handling Possibility] Using a roll-to-roll transport device equipped with a payout mechanism, a nip mechanism, and a winding mechanism, the multilayer resin layer side of the glass resin composite test piece was bonded to the surface of a PET carrier (100 μm) conveyed from the roll of the payout mechanism via an acrylic adhesive (25 μm thick). The PET carrier to which the glass resin composite test piece was bonded was transported to the roll of the winding mechanism and wound up. After winding, the glass resin composite test piece bonded to the PET carrier was sampled, and the presence or absence of cracks was confirmed in the effective area (250 mm × 250 mm) of the surface of the glass sheet relative to the overall size (300 mm × 300 mm) of the main surface of the glass sheet of the glass resin composite test piece. The test was conducted using 30 glass resin composite test pieces. The crack occurrence rate in the effective area of ​​the surface of the glass sheet of the 30 glass resin composite test pieces was calculated based on the following formula (i), and the web handling possibility was evaluated based on the following evaluation criteria. The evaluation results for web handling possibility are shown in Table 1. Rate of crack occurrence in effective area of ​​surface of glass sheet [%] = number of glass resin composite test pieces in which cracks occurred in the effective area of ​​the surface of the glass sheet / 30 × 100 ... (i) (Evaluation criteria) A: The rate of glass resin composite test pieces in which cracks occurred in the effective area of ​​the surface of the glass sheet is 10% or less. B: The rate of glass resin composite test pieces in which cracks occurred in the effective area of ​​the surface of the glass sheet is more than 10%.

[0148]

[0149] As can be seen from Table 1, in each Example, the crack occurrence rate in the effective area of ​​the surface of the glass sheet was 10% or less, and web handling was good. On the other hand, in each Comparative Example, the crack occurrence rate in the effective area of ​​the surface of the glass sheet was 20% or more, and web handling was poor.

[0150] Therefore, if the glass resin composite according to this embodiment satisfies the above formula (1), even when the glass resin composite is transported and wound up in a roll-to-roll process, the occurrence of cracks in the effective area of ​​the surface of the glass sheet can be suppressed, and therefore the glass resin composite can be effectively used in the roll-to-roll process.

[0151] The present invention provides, for example, the following embodiments: <1> A glass resin composite having one or more resin layers on at least one surface of a glass sheet, wherein the thickness of the glass resin composite is 800 μm or less, and when the glass resin composite is bent toward one surface of the glass resin composite with a curvature radius that satisfies the following formula (1), the probability of cracking occurring in the glass sheet is 10% or less. (In formula (1), R ０ is the inner radius of curvature of the glass resin composite [mm], i and k are integers, l is the number of layers [layers] including the resin layer and the glass sheet when counting from the inside of the glass resin composite, n is the total number of layers [layers], and E ｉ is the Young's modulus [MPa] of the i-th layer, and t ｉ is the thickness [μm] of the i-th resin layer, and t ｋ is the thickness [μm] of the kth resin layer, and t ｋ－１ is the thickness [μm] of the (k-1)th resin layer.) <2> The glass resin composite according to <1>, wherein when the glass resin composite is bent toward the other surface of the glass resin composite with a radius of curvature that satisfies the following formula (1), the probability of cracking occurring in the glass sheet is 10% or less. <3> The glass resin composite according to <1> or <2>, wherein the thickness of the glass sheet is 20% to 75% of the thickness of the glass resin composite. <4> The glass resin composite according to any one of <1> to <3>, wherein the thickness of the glass sheet is 30 μm to 300 μm. <5> The glass resin composite according to any one of <1> to <4>, wherein the radius of curvature is the radius of a roll with which the glass resin composite comes into contact.

[0152] This application claims priority based on Japanese Patent Application No. 2023-166771, filed with the Japan Patent Office on September 28, 2023, and incorporates the entire contents of said application by reference.

[0153] 1 Glass-resin composite 1a, 10a Lower surface 1b, 10b Upper surface 10 Glass sheet 20 Multi-layer resin layer 211, 21N Resin layer

Claims

1. A glass resin composite having one or more resin layers on at least one surface of a glass sheet, wherein the thickness of the glass resin composite is 800 μm or less, and when the glass resin composite is bent toward one surface of the glass resin composite with a curvature radius that satisfies the following formula (1), the probability of cracking occurring in the glass sheet is 10% or less. (In formula (1), R ０ is the inner radius of curvature of the glass resin composite [mm], i and k are integers, l is the number of layers [layers] including the resin layer and the glass sheet when counting from the inside of the glass resin composite, n is the total number of layers [layers], E ｉ is the Young's modulus [MPa] of the i-th layer, and t ｉ is the thickness [μm] of the i-th resin layer, and t ｋ is the thickness [μm] of the kth resin layer, and t ｋ－１ is the thickness [μm] of the (k-1)th resin layer.

2. A glass resin composite as described in claim 1, wherein when the glass resin composite is bent toward the other surface of the glass resin composite with a radius of curvature that satisfies the following formula (1), the probability of cracks occurring in the glass sheet is 10% or less.

3. The glass resin composite according to claim 1, wherein the thickness of the glass sheet is 20% to 75% of the thickness of the glass resin composite.

4. The glass resin composite according to claim 1, wherein the glass sheet has a thickness of 30 μm to 300 μm.

5. A glass resin composite according to claim 1, wherein the radius of curvature is the radius of a roll with which the glass resin composite comes into contact.

Images