Glass resin laminate

Abstract

This glass resin laminate is obtained by laminating a first protective film, a glass layer, a resin layer, and a second protective film, in that order, and the adhesive force of the first protective film with respect to the glass layer is 1.0 N / 25 mm or greater.

Description

glass resin laminate

[0001] This invention relates to a glass resin laminate.

[0002] In image display devices such as liquid crystal displays and organic EL elements, semiconductor elements, and solar cells, extremely thin, flexible glass sheets (hereinafter also referred to as "glass sheets") are used. Conventionally, a technique is known for forming irregularities on the surface of one or both sides of a thin glass sheet by etching.

[0003] For example, a technique has been proposed in which a protective film is formed on one side of glass, and etching is performed on the side opposite to the side on which the protective film is formed (see, for example, Patent Documents 1 and 2).

[0004] Patent No. 6146746 Patent No. 5955579

[0005] However, in Patent Documents 1 and 2, there were problems with the protective film peeling off from the glass layer or the etching solution seeping into the protective film during the etching process.

[0006] The present invention has been made in view of the above points, and aims to provide a glass resin laminate that suppresses peeling of the protective film and penetration of the etching solution into the protective film during etching.

[0007] This glass-resin laminate is a glass-resin laminate in which a first protective film, a glass layer, a resin layer, and a second protective film are laminated in this order, and the adhesive strength of the first protective film to the glass layer is 1.0 N / 25 mm or more.

[0008] According to the disclosed technology, it is possible to provide a glass resin laminate that suppresses peeling of the protective film and penetration of the etching solution into the protective film during etching.

[0009] This is a cross-sectional view illustrating a glass resin laminate according to the first embodiment. This is a cross-sectional view illustrating a glass resin laminate according to a modified example 1 of the first embodiment.

[0010] The embodiments for carrying out the invention will be described below with reference to the drawings. In each drawing, the same reference numerals are used for identical components, and redundant explanations may be omitted.

[0011] <First Embodiment> (Glass Resin Laminate) Figure 1 is a cross-sectional view illustrating a glass resin laminate according to the first embodiment. As shown in Figure 1, the glass resin laminate 10 is constructed by laminating a first protective film 11, a glass layer 12, a resin layer 13, and a second protective film 14 in this order.

[0012] In the glass-resin laminate 10, for example, the first protective film 11, the glass layer 12, the resin layer 13, and the second protective film 14 may have the same thickness or they may have different thicknesses. Alternatively, multiple types of unit laminate structures with different thicknesses, in which the first protective film 11, the glass layer 12, the resin layer 13, and the second protective film 14 are laminated at any thickness, may be combined.

[0013] [Glass Layer] The glass layer 12 is not particularly limited, and an appropriate one can be used depending on the purpose. Examples of glass layers 12, according to their composition, include soda-lime glass, borate glass, aluminosilicate glass, and quartz glass. Also, according to their alkali content, examples include alkali-free glass and low-alkali glass.

[0014] Alkaline components of glass (e.g., Na ２ O, K ２ O, Li ２ The content of O) is preferably 15% by weight or less, and more preferably 10% by weight or less.

[0015] The thickness t1 of the glass layer 12 is, for example, 10 μm or more and 200 μm or less. Here, a glass layer with a thickness of 10 μm or more and 200 μm or less means a glass layer whose average thickness is 10 μm or more and 200 μm or less.

[0016] The thickness t1 of the glass layer 12 is preferably 10 μm or more, considering the surface hardness, airtightness, and corrosion resistance of the glass. Furthermore, since it is desirable for the single glass layer 12 to have film-like flexibility in order to obtain a curved structure, the thickness t1 of the glass layer 12 is preferably 200 μm or less, and more preferably 50 μm or more and 100 μm or less.

[0017] The light transmittance of the glass layer 12 at a wavelength of 550 nm is preferably 85% or higher. The refractive index of the glass layer 12 at a wavelength of 550 nm is preferably 1.4 to 1.65. The density of the glass layer 12 is preferably 2.3 g / cm³. ３ ~3.0 g / cm ３ And more preferably 2.3 g / cm³ ３ ~2.7 g / cm ３ That is the case.

[0018] The glass layer 12 may be a commercially available product as is, or a commercially available glass layer may be polished to the desired thickness. Examples of commercially available glass layers include Corning's "7059", "1737", or "EAGLE2000", Asahi Glass's "AN100", NH Technoglass's "NA-35", Nippon Electric Glass's "OA-10", and Schott's "D263" or "AF45".

[0019] There are no particular limitations on the method for forming the glass layer 12, and an appropriate method can be adopted depending on the purpose. Typically, the glass layer 12 can be produced by melting a mixture containing main raw materials such as silica and alumina, an antifoaming agent such as Glauber's salt and antimony oxide, and a reducing agent such as carbon at a temperature of about 1400°C to 1600°C, forming it into a thin plate, and then cooling it. Examples of methods for forming the glass layer 12 include the slot-down draw method, the fusion method, and the float method. The glass layer formed into a plate by these methods may be chemically polished with a solvent such as hydrofluoric acid as needed to thin it or improve its smoothness.

[0020] [First protective film and second protective film] The first protective film 11 and the second protective film 14 protect the surface of the glass layer 12 and prevent foreign matter from adhering to and contaminating its surface.

[0021] Examples of materials constituting the first protective film 11 and the second protective film 14 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, silicone resin, and the like.

[0022] The thickness t2 of the first protective film 11 and the second protective film 14 is not particularly limited, but may be, for example, 100 μm or less.

[0023] The adhesive strength of the first protective film 11 to the glass layer is 1.0 N / 25 mm or more, preferably 2.0 N / 25 mm or more, and more preferably 10 N / 25 mm or more. When the adhesive strength of the first protective film 11 to the glass layer is 1.0 N / 25 mm or more, peeling of the protective film and penetration of the etching solution into the protective film during etching can be suppressed. The adhesive strength refers to the adhesive strength of the glass resin laminate before etching.

[0024] The adhesive strength of the first protective film 11 to the glass layer after etching is 2.0 N / 25 mm or less, preferably 1.0 N / 25 mm or less, and more preferably 0.1 N / 25 mm or less. When the adhesive strength of the first protective film 11 to the glass layer after etching is 2.0 N / 25 mm or less, cracking of the glass layer 12 when the protective film is peeled off after etching can be suppressed. Specifically, "after etching" means after ultraviolet irradiation.

[0025] There are no particular limitations on the method used to alter peel strength by ultraviolet irradiation.

[0026] The adhesive strength of the second protective film 14 to the resin layer is 0.2 N / 25 mm or more. When the adhesive strength of the second protective film 14 to the resin layer is 0.2 N / 25 mm or more, peeling of the protective film and penetration of the etching solution into the protective film during etching can be suppressed. The adhesive strength refers to the adhesive strength of the glass resin laminate before etching.

[0027] [Resin Layer] The resin layer 13 is a base layer on which the glass layer 12 is laminated. The resin layer 13 can consist of one or more layers. An adhesive layer or bonding layer may be provided between the resin layer 13 and the glass layer 12. The resin layer 13 may contain additives such as inorganic particles.

[0028] The thickness t2 of the resin layer 13 is, for example, 0.1 μm or more and 2 mm or less. Here, a resin layer with a thickness of 0.1 μm or more and 2 mm or less means a resin layer whose average thickness is 0.1 μm or more and 2 mm or less.

[0029] There are no particular restrictions on the resin components contained in the resin layer, but it may be at least one of a thermosetting resin and a thermoplastic resin, or a mixture of a thermosetting resin and a thermoplastic resin.

[0030] Examples of thermosetting resins include epoxy resins, phenolic resins, amino resins, unsaturated polyester resins, polyurethane resins, silicone resins, and thermosetting polyimide resins. One or more thermosetting resins may be used. Epoxy resins are preferred as thermosetting resins because they contain fewer ionic impurities that can cause corrosion of semiconductor chips. Phenolic resins are preferred as curing agents for epoxy resins.

[0031] Examples of epoxy resins include bisphenol A type, bisphenol F type, bisphenol S type, brominated bisphenol A type, hydrogenated bisphenol A type, bisphenol AF type, biphenyl type, naphthalene type, fluorene type, phenol novolac type, orthocresol novolac type, trishydroxyphenylmethane type, tetraphenyloleethane type, hydantoin type, trisglycidyl isocyanurate type, or glycidylamine type epoxy resins.

[0032] Phenolic resins can act as curing agents for epoxy resins. Examples of phenolic resins include novolac-type phenolic resins, resol-type phenolic resins, and polyoxystyrenes such as polyparaoxystyrene.

[0033] Examples of novolac-type phenolic resins include phenol novolac resin, phenol aralkyl resin, cresol novolac resin, tert-butylphenol novolac resin, and nonylphenol novolac resin. One type of phenolic resin or two or more types may be used.

[0034] In the resin layer 13, the hydroxyl groups of the phenolic resin are preferably 0.5 equivalents or more and 2.0 equivalents or less, and more preferably 0.7 equivalents or more and 1.5 equivalents or less, per equivalent of epoxy groups of the epoxy resin. This allows the curing reaction between the epoxy resin and the phenolic resin to proceed sufficiently.

[0035] When the resin layer 13 contains a thermosetting resin, the content of such a thermosetting resin in the resin layer 13 is preferably 5% to 60% by mass, and more preferably 10% to 50% by mass, relative to the total mass of the resin layer 13. This allows the resin layer 13 to appropriately exhibit its function as a thermosetting adhesive.

[0036] Examples of the thermoplastic resin that may be included in the resin layer 13 include natural rubber, butyl rubber, isoprene rubber, chloroprene rubber, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, polybutadiene resin, polycarbonate resin, thermoplastic polyimide resin, polyamide resins such as 6-polyamide resin and 6,6-polyamide resin, phenoxy resin, acrylic resin, saturated polyester resins such as PET and PBT, polyamideimide resin, fluororesin, and the like.

[0037] As the thermoplastic resin, an acrylic resin is preferable in that it has few ionic impurities and high heat resistance, so that the adhesiveness of the resin layer 13 can be more ensured. As the thermoplastic resin, only one kind or two or more kinds may be adopted.

[0038] The acrylic resin is preferably a polymer in which the constituent unit of alkyl (meth)acrylate has the largest mass ratio among the constituent units in the molecule. Examples of the alkyl (meth)acrylate include C2-C4 alkyl (meth)acrylate.

[0039] The acrylic resin may contain a constituent unit derived from another monomer component copolymerizable with the alkyl (meth)acrylate monomer.

[0040] Examples of the other monomer component include functional group-containing monomers such as carboxy group-containing monomer, acid anhydride monomer, hydroxy group (hydroxyl group)-containing monomer, glycidyl group-containing monomer, sulfonic acid group-containing monomer, phosphoric acid group-containing monomer, acrylamide, acrylonitrile, or various other polyfunctional monomers.

[0041] The acrylic resin is preferably a copolymer of an alkyl (meth)acrylate (especially an alkyl (meth)acrylate having 4 or less carbon atoms in the alkyl part), a carboxy group-containing monomer, a nitrogen atom-containing monomer, and a polyfunctional monomer (especially a polyglycidyl-based polyfunctional monomer) in that it can exhibit higher cohesive force in the resin layer 13, and more preferably, it is a copolymer of ethyl acrylate, butyl acrylate, acrylic acid, acrylonitrile, and polyglycidyl (meth)acrylate.

[0042] When the resin layer 13 contains a thermosetting resin and a thermoplastic resin, the content ratio of the thermoplastic resin in the resin layer 13 is preferably 5% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 45% by mass or less, and still more preferably 20% by mass or more and 40% by mass or less with respect to the total mass of the organic components (for example, thermosetting resin, thermoplastic resin, curing catalyst, etc., silane coupling agent, dye) excluding the filler. Note that the elasticity and viscosity of the resin layer 13 can be adjusted by changing the content ratio of the thermosetting resin.

[0043] When the thermoplastic resin of the resin layer 13 has a thermosetting functional group, for example, a thermosetting functional group-containing acrylic resin can be employed as the thermoplastic resin. This thermosetting functional group-containing acrylic resin preferably contains, in the molecule, a structural unit derived from an alkyl (meth)acrylate in the largest mass ratio. Examples of the alkyl (meth)acrylate include the exemplified (meth)alkyl (meth)acrylate. On the other hand, examples of the thermosetting functional group in the thermosetting functional group-containing acrylic resin include a glycidyl group, a carboxy group, a hydroxy group (hydroxyl group), an isocyanate group, etc.

[0044] The resin layer 13 preferably contains a filler. By changing the amount of the filler in the resin layer 13, the elasticity and viscosity of the resin layer 13 can be more easily adjusted. Furthermore, physical properties such as the conductivity, heat conductivity, and elastic modulus of the resin layer 13 can be adjusted.

[0045] Examples of fillers include inorganic fillers and organic fillers. Inorganic fillers are preferred. Examples of inorganic fillers include aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, boron nitride, silica such as crystalline silica and amorphous silica, etc. Examples of materials for inorganic fillers include elemental metals such as aluminum, gold, silver, copper, and nickel, as well as alloys. Fillers such as aluminum borate whiskers, amorphous carbon black, and graphite may also be used. The shape of the filler may be spherical, needle-shaped, flake-shaped, or various other shapes. Only one type of filler or two or more types may be used.

[0046] The average particle size of the filler is preferably 0.005 μm or more and 10 μm or less, and more preferably 0.005 μm or more and 1 μm or less. An average particle size of 0.005 μm or more improves wettability and adhesion to the substrate such as a semiconductor wafer. An average particle size of 10 μm or less allows the properties of the added filler to be fully exhibited, and also allows the heat resistance of the resin layer 13 to be fully exhibited. The average particle size of the filler can be determined, for example, using a photometric particle size distribution analyzer (for example, product name "LA-910", manufactured by Horiba, Ltd.).

[0047] If the resin layer 13 contains a filler, the filler content is preferably 30% to 70% by mass, more preferably 40% to 60% by mass, and even more preferably 42% to 55% by mass, based on the total mass of the resin layer 13.

[0048] The resin layer 13 may contain other components as needed. Examples of other components include curing catalysts, flame retardants, silane coupling agents, ion trapping agents, dyes, and the like.

[0049] Examples of flame retardants include antimony trioxide, antimony pentoxide, and brominated epoxy resins.

[0050] Examples of silane coupling agents include β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropylmethyldiethoxysilane. Examples of ion trapping agents include hydrotalcites, bismuth hydroxide, and benzotriazole. Other additives may be used individually or in combination of two or more.

[0051] The resin layer 13 preferably includes a thermoplastic resin (particularly an acrylic resin), a thermosetting resin, and a filler, as these properties allow for easy adjustment of elasticity and viscosity. In the resin layer 13, the content ratio of the thermoplastic resin, such as an acrylic resin, to the total mass of organic components excluding the filler is preferably 70% by mass or less, and more preferably 50% by mass or less.

[0052] The filler content relative to the total mass of the resin layer 13 is preferably 30% by mass or more and 70% by mass or less, more preferably 40% by mass or more and 60% by mass or less, and even more preferably 42% by mass or more and 55% by mass or less.

[0053] The thickness t3 of the resin layer 13 is preferably 25 μm or more and 1 mm or less, and more preferably 50 μm or more and 500 μm or less.

[0054] <Second Embodiment> The second embodiment shows an example of a glass resin laminate with a different layer structure from the first embodiment. In the first embodiment, descriptions of components that are the same as those described in the previously described embodiment may be omitted.

[0055] Figure 2 is a cross-sectional view illustrating a glass-resin laminate according to the second embodiment. The structure of the glass-resin laminate is as shown in Figure 2, with a first protective film 11, a first adhesive layer 16, a glass layer 12, a resin layer 13, a second adhesive layer 17, and a second protective film 14 laminated in this order.

[0056] [First Adhesive Layer and Second Adhesive Layer] In order to change the peel strength of the first protective film 11 and the second protective film 14 before and after irradiation with ultraviolet light, it is preferable to use a first adhesive layer 16 between the first protective film 11 and the glass layer 12, and a second adhesive layer 17 between the second protective film 14 and the resin layer 13.

[0057] The first adhesive layer 16 is provided between the first protective film 11 and the glass layer 12. The second adhesive layer 17 is provided between the resin layer 13 and the second protective film 14. Examples of materials for the first adhesive layer 16 and the second adhesive layer 17 include acrylic adhesives, silicone adhesives, rubber adhesives, and the like.

[0058] The adhesive layer contains an adhesive polymer component. Examples of polymer components include acrylic polymers, olefin polymers, or silicone polymers. Among these, acrylic polymers are preferred.

[0059] Acrylic polymers are polymers that contain (meth)acrylate monomers as constituent units. (Meth)acrylate is a concept that includes methacrylate and acrylate. Acrylic polymers may also contain monomers other than (meth)acrylate monomers as constituent units.

[0060] The adhesive layer contains an ultraviolet-curable polymeric polymer having polymerizable unsaturated bonds as an adhesive polymer.

[0061] Examples of polymerizable polymers include polymers containing polymerizable vinyl groups (H2C=CH-) or ethynyl groups (HC≡C-) at the ends of the main chain or side chains.

[0062] In this embodiment, the adhesive layer contains an ultraviolet-curable polymerizable acrylic polymer having polymerizable unsaturated bonds as the polymerizable polymer.

[0063] Furthermore, in this embodiment, the adhesive layer includes, for example, the polymerizable acrylic polymer, an isocyanate compound, and a polymerization initiator.

[0064] This allows the adhesive strength of the adhesive layer to be adjusted to the desired strength, and by irradiating the adhesive layer with ultraviolet light, the UV-curable polymerizable polymers in the adhesive layer can be radically polymerized, thereby reducing the adhesive strength of the adhesive layer.

[0065] The thicknesses of the first adhesive layer 16 and the second adhesive layer 17 are not particularly limited, but are, for example, approximately 10 μm to 500 μm.

[0066] Depending on the requirements, an adhesive layer may be used instead of the tack layer. Any suitable adhesive can be used as the adhesive layer in place of the tack layer. Examples of materials for the tack layer include UV-curable acrylic adhesives, UV-curable epoxy adhesives, thermosetting epoxy adhesives, thermosetting melamine adhesives, thermosetting phenolic adhesives, ethylene vinyl acetate (EVA) interlayers, and polyvinyl butyral (PVB) interlayers. The thickness of the adhesive layer is not particularly limited, but for example, it is about 10 μm to 500 μm.

[0067] In this specification, an adhesive layer refers to a layer that is adhesive at room temperature and adheres to an object with light pressure. Therefore, even when an object attached to the adhesive layer is peeled off, the adhesive layer retains practical adhesive strength. On the other hand, an adhesive layer refers to a layer that can bond substances together by being interposed between them. Therefore, when an object attached to an adhesive layer is peeled off, the adhesive layer does not have practical adhesive strength.

[0068] In this way, by having a resin layer 13 between the glass layer 12 and the second protective film 14, the effect of protecting the glass surface by the resin layer can be obtained even when the first adhesive layer, the second adhesive layer, and the second protective film having an adhesive layer are peeled off.

[0069] [Method for Manufacturing Glass-Resin Laminates] Examples of methods for manufacturing glass-resin laminates include a method of forming a resin layer on a glass layer by solution coating to obtain a glass-resin laminate, and a method of forming a resin layer by attaching a resin film to a glass layer to obtain a glass-resin laminate. Preferably, the method of forming a resin layer on a glass layer by solution coating to obtain a glass-resin laminate is preferred. With such a method, the resin layer formed by solution coating is directly constrained by the glass layer, so a glass-resin laminate with excellent dimensional stability can be obtained.

[0070] A method for obtaining a glass-resin laminate by forming a resin layer on a glass layer by solution coating preferably includes a coating step of applying a resin solution to one or both sides of the glass layer to form a coating layer, a drying step of drying the coating layer, and a heat treatment step of heat-treating the dried coating layer to form a resin layer.

[0071] Examples of coating solvents used in the coating process include halogenated solvents such as methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, and trichloroethane; aromatic solvents such as toluene, benzene, and phenol; cellosolve solvents such as methyl cellosolve and ethyl cellosolve; ether solvents such as propylene glycol monomethyl ether and ethylene glycol monoisopropyl ether; and ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone. Among these, halogenated solvents, aromatic solvents, cellosolve solvents, or ether solvents are preferred. By using such solvents as coating solvents, it is possible to obtain a glass-resin laminate with excellent durability and reliability by maintaining sufficient adhesion between the resin layer and the glass layer even under high temperature and high humidity conditions.

[0072] Coating methods for resin solutions 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, calender coating, electrodeposition coating, dip coating, and die coating; and printing methods such as relief printing methods like flexographic printing, intaglio printing methods like direct gravure printing and offset gravure printing, lithographic printing methods like offset printing, and stencil printing methods like screen printing.

[0073] Any suitable drying method (e.g., natural drying, forced-air drying, or heat drying) can be used for the drying process. For example, in the case of heat drying, the drying temperature is typically 100°C to 200°C, and the drying time is typically 1 to 10 minutes.

[0074] Any suitable heat treatment method can be used as the heat treatment process. Typically, the heat treatment temperature is 100°C to 300°C, and the heat treatment time is 5 to 45 minutes. If the glass resin laminate has a coupling agent layer, the heat treatment can cause the coupling agent to chemically bond or interact with the resin contained in the resin layer.

[0075] Preferably, the process includes a coupling treatment of the surface of the glass layer before the coating process. By performing the coupling treatment and forming a coupling agent layer, the resin layer can adhere firmly to the glass layer via the coupling agent layer.

[0076] Any suitable method can be used for the coupling treatment. Specifically, for example, a method can be used in which a coupling agent solution is applied to the surface of the glass layer, followed by heat treatment.

[0077] Any suitable solvent can be used when preparing a coupling agent solution, as long as it does not react with the coupling agent. Examples of solvents include aliphatic hydrocarbon solvents such as hexane and hexadecane; aromatic solvents such as benzene, toluene, and xylene; halogenated hydrocarbon solvents such as methylene chloride and 1,1,2-trichloroethane; ether solvents such as tetrahydrofuran and 1,4-dioxane; alcohol solvents such as methanol and propanol; ketone solvents such as acetone and 2-butanone; and water.

[0078] Any suitable heat treatment method can be used during the coupling process. Typically, the heat treatment temperature is 50°C to 150°C, and the heat treatment time is 1 to 10 minutes. Through heat treatment, the coupling agent and the glass layer surface can be chemically bonded together.

[0079] In a method for obtaining a glass-resin laminate by forming a resin layer by attaching a resin film to a glass layer, a resin solution may be applied to any suitable substrate to form a resin film, and then the resin film may be transferred to the surface of the glass layer to bond the glass layer and the resin film together, thereby forming the resin layer. Alternatively, the glass layer may be subjected to a coupling treatment before attaching the resin film. The above-described method may be used as the coupling treatment method.

[0080] The resin film may be annealed before or after being attached to the glass layer. Annealing efficiently removes impurities such as residual solvent and unreacted monomer components. The annealing temperature is preferably 100°C to 200°C. The annealing time is preferably 5 to 20 minutes.

[0081] The resin film is preferably attached to the surface of the glass layer via an adhesive layer. The adhesive layer may be formed on the resin film and then attached to the surface of the glass layer, or the adhesive layer may be formed on the glass layer and then the resin film may be attached.

[0082] As a method for forming the adhesive layer, for example, after applying a thermosetting resin or an active energy ray-curable resin on the surface of a glass layer or a resin film, the glass layer and the resin film are adhered to each other, and then the thermosetting resin or the active energy ray-curable resin is cured by ultraviolet light irradiation or heat treatment. The irradiation conditions for ultraviolet light irradiation are typically such that the integrated irradiation light amount is 100 mJ / cm ２ to 2,000 mJ / cm ２ and the irradiation time is 5 minutes to 30 minutes. The conditions for heat treatment are typically such that the heating temperature is 100°C to 200°C and the heating time is 5 minutes to 30 minutes. Incidentally, after applying a thermosetting resin or an active energy ray-curable resin on the surface of a glass layer or a resin film, the thermosetting resin or the active energy ray-curable resin may be semi-cured before adhering the glass layer and the resin film. The semi-curing can be performed, for example, by irradiating ultraviolet light of 1 mJ / cm ２ to 10 mJ / cm ２ for 1 second to 60 seconds.

[0083] [Use] The glass resin laminate according to the present embodiment can be suitably used, for example, for a display element or a solar cell. Examples of the display element include a semiconductor package, a liquid crystal display, a plasma display, an organic EL display, and the like.

[0084] (Example 1) The dicing tape was peeled off a die-attach film with dicing tape (EM-350, manufactured by Nitto Denko Corporation), and an adhesive die-attach film with a release liner was prepared as the resin layer. Glass (OA-10G, manufactured by NEG) as the glass layer was placed on a hot plate and heated to 60°C, and the adhesive surface of the die-attach film with a release liner and the glass surface were bonded together using a hand roller at a pressure of 2 kg. Next, the adhesive layer surface of a protective film having an adhesive layer (ELP BM-03, manufactured by Nitto Denko Corporation, first protective film) was bonded to the glass layer surface on the side where the die-attach film was not bonded, using a hand roller at a pressure of 2 kg. Next, the release liner was peeled off, and the adhesive layer surface of a protective film (E-MASK RP207, manufactured by Nitto Denko Corporation, second protective film) and the adhesive surface of the die-attach film were bonded together using a hand roller at a pressure of 2 kg to obtain a glass-resin laminate.

[0085] (Example 2) The dicing tape was peeled off a die-attach film with dicing tape (EM-350, manufactured by Nitto Denko Corporation), and an adhesive die-attach film with a release liner was prepared as the resin layer. Glass (OA-10G, manufactured by NEG) as the glass layer was placed on a hot plate and heated to 60°C, and the adhesive surface of the die-attach film with a release liner and the glass surface were bonded together using a hand roller at a pressure of 2 kg. Next, the adhesive layer surface of a protective film having an adhesive layer (SPV-362X-2K2, manufactured by Nitto Denko Corporation, first protective film) was bonded to the glass layer surface on the side where the die-attach film was not bonded, using a hand roller at a pressure of 2 kg. Next, the release liner was peeled off, and the adhesive layer surface of the protective film (E-MASK RP207, manufactured by Nitto Denko Corporation, second protective film) and the adhesive surface of the die-attach film were bonded together using a hand roller at a pressure of 2 kg to obtain a glass-resin laminate.

[0086] (Example 3) The dicing tape was peeled off a die-attach film with dicing tape (EM-350, manufactured by Nitto Denko Corporation), and an adhesive die-attach film with a release liner was prepared as the resin layer. Glass (OA-10G, manufactured by NEG) as the glass layer was placed on a hot plate and heated to 60°C, and the adhesive surface of the die-attach film with a release liner and the glass surface were bonded together using a hand roller at a pressure of 2 kg. Next, the adhesive layer surface of a protective film having an adhesive layer (SPV-3620K, manufactured by Nitto Denko Corporation, first protective film) was bonded to the glass layer surface on the side where the die-attach film was not bonded, using a hand roller at a pressure of 2 kg. Next, the release liner was peeled off, and the adhesive layer surface of a protective film (E-MASK RP207, manufactured by Nitto Denko Corporation, second protective film) and the adhesive surface of the die-attach film were bonded together using a hand roller at a pressure of 2 kg to obtain a glass-resin laminate.

[0087] (Comparative Example 1) The dicing tape was peeled off a die-attach film with dicing tape (EM-350, manufactured by Nitto Denko Corporation), and an adhesive die-attach film with a release liner was prepared as the resin layer. Glass (OA-10G, manufactured by NEG) as the glass layer was placed on a hot plate and heated to 60°C, and the adhesive surface of the die-attach film with a release liner and the glass surface were bonded together using a hand roller at a pressure of 2 kg. Next, the adhesive layer surface of a protective film having an adhesive layer (E-MASK RP207, manufactured by Nitto Denko Corporation, first protective film) was bonded to the glass layer surface on the side where the die-attach film was not bonded, using a hand roller at a pressure of 2 kg. Next, the release liner was peeled off, and the adhesive layer surface of the protective film (E-MASK RP207, manufactured by Nitto Denko Corporation, second protective film) and the adhesive surface of the die-attach film were bonded together using a hand roller at a pressure of 2 kg to obtain a glass-resin laminate.

[0088] (Comparative Example 2) The dicing tape was peeled off a die-attach film with dicing tape (EM-350, manufactured by Nitto Denko Corporation), and an adhesive die-attach film with a release liner was prepared as the resin layer. Glass (OA-10G, manufactured by NEG) as the glass layer was placed on a hot plate and heated to 60°C, and the adhesive surface of the die-attach film with a release liner and the glass surface were bonded together using a hand roller at a pressure of 2 kg. Next, the adhesive layer surface of a protective film having an adhesive layer (E-MASK AW700, manufactured by Nitto Denko Corporation, first protective film) was bonded to the glass layer surface on the side where the die-attach film was not bonded, using a hand roller at a pressure of 2 kg. Next, the release liner was peeled off, and the adhesive layer surface of the protective film (E-MASK RP207, manufactured by Nitto Denko Corporation, second protective film) and the adhesive surface of the die-attach film were bonded together using a hand roller at a pressure of 2 kg to obtain a glass-resin laminate.

[0089] (Comparative Example 3) The dicing tape was peeled off a die attach film with dicing tape (EM-350, manufactured by Nitto Denko Corporation) and an adhesive die attach film with a release liner was prepared as the resin layer. Glass (OA-10G, manufactured by NEG) as the glass layer was placed on a hot plate and heated to 60°C, and the adhesive surface of the die attach film with a release liner and the glass surface were bonded together using a hand roller under a pressure of 2 kg. Next, the adhesive layer surface of a protective film having an adhesive layer (SPV-362X-2K2, manufactured by Nitto Denko Corporation, the first protective film) was bonded to the glass layer surface on the side where the die attach film was not bonded, using a hand roller under a pressure of 2 kg to obtain a glass-resin laminate.

[0090] [Method for Measuring the Adhesion of Protective Film Before Etching] The adhesive strength of the protective film in the glass resin laminates of Examples 1-3 and Comparative Examples 1-3 was measured using the following procedure. Specifically, an alkali-free glass plate with a thickness of 0.7 mm (Corning, product name: EG-XG) and a 150 mm x 25 mm glass sheet were prepared. The protective films used in Examples 1-3 and Comparative Examples 1-3 were attached to only one side of the glass sheet, and the glass surface of the glass sheet without the protective film was fixed to the alkali-free glass using epoxy adhesive (Araldite) to obtain evaluation samples. Two types of evaluation samples were prepared so that each protective film was the top surface for measurement. Next, using a tensile testing machine (Autograph Shimazu AG-1 10KN), a 25 mm wide edge was chucked to the protective film under the conditions of 23°C / 55% humidity, peel angle of 90°, and peel speed of 300 mm / min, and the protective film was peeled off the glass sheet to measure the adhesive strength of the protective film.

[0091] The glass resin laminates of Examples 1-3 and Comparative Examples 1-3 were etched using an etching solution containing 6% hydrogen fluoride. The peeling of the protective film and the penetration of the etching solution into the protective film after etching were evaluated. Furthermore, the adhesive strength of the protective film after etching was measured in the same manner as the adhesive strength of the protective film before etching. The evaluation results are shown in Table 1.

[0092] To evaluate penetration, we examined the reflection image of the protective film using an optical microscope, and determined that penetration was present if the area within 500 μm from the edge of the protective film was discolored.

[0093] [evaluation]

[0094]

[0095] As described above, the glass-resin laminate according to this embodiment is a glass-resin laminate in which a first protective film, a glass layer, a resin layer, and a second protective film are laminated in this order, and the adhesive strength of the first protective film to the glass layer is 1.0 N / 25 mm or more. This makes it possible to suppress peeling of the protective film and penetration of the etching solution into the protective film during etching.

[0096] Although preferred embodiments have been described in detail above, the invention is not limited to the embodiments described above, and various modifications and substitutions can be made to the embodiments described above without departing from the scope of the claims.

[0097] In addition to the embodiments described above, the following further notes are disclosed. (Note 1) A glass-resin laminate comprising a first protective film, a glass layer, a resin layer, and a second protective film laminated in this order, characterized in that the adhesive force of the first protective film to the glass layer is 1.0 N / 25 mm or more. (Note 2) The glass-resin laminate according to Note 1, wherein the adhesive force of the second protective film to the resin layer is 0.2 N / 25 mm or more. (Note 3) The glass-resin laminate according to Note 1 or 2, wherein the adhesive force of the first protective film to the glass layer after irradiation of the glass-resin laminate with ultraviolet light is less than 2.0 N / 25 mm. (Note 4) The glass-resin laminate according to Note 1 or 2, further comprising a first adhesive layer between the first protective film and the glass layer. (Note 5) The glass-resin laminate according to Note 1 or 2, further comprising a second adhesive layer between the resin layer and the second protective film. (Note 6) The glass resin laminate according to Note 4, wherein the first adhesive layer contains an ultraviolet-curable polymer having an adhesive polymer and a polymerizable unsaturated bond.

[0098] This application claims priority based on Japanese Patent Application No. 2025-019456, filed with the Japan Patent Office on 7 February 2025, and includes the entire contents of that Japanese Patent Application.

[0099] 10 Glass resin laminate 11 First protective film 12 Glass layer 13 Resin layer 14 Second protective film 16 First adhesive layer 17 Second adhesive layer

Claims

1. A glass-resin laminate comprising a first protective film, a glass layer, a resin layer, and a second protective film, laminated in this order, characterized in that the adhesive strength of the first protective film to the glass layer is 1.0 N / 25 mm or more.

2. The glass resin laminate according to claim 1, wherein the adhesive strength of the second protective film to the resin layer is 0.2 N / 25 mm or more.

3. The glass resin laminate according to claim 1 or 2, wherein the adhesive strength of the first protective film to the glass layer after irradiation of the glass resin laminate with ultraviolet light is less than 2.0 N / 25 mm.

4. The glass resin laminate according to claim 1 or 2, further comprising a first adhesive layer between the first protective film and the glass layer.

5. The glass resin laminate according to claim 1 or 2, further comprising a second adhesive layer between the resin layer and the second protective film.

6. The glass resin laminate according to claim 4, wherein the first adhesive layer contains an ultraviolet-curable polymer having an adhesive polymer and a polymerizable unsaturated bond.

Images