Glass resin laminate

Abstract

This glass resin laminate is obtained by laminating a first protective film, a glass layer, and a second protective film in this order, wherein at least one of the first protective film or the second protective film has through-grooves in the lamination direction.

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 Document 1).

[0004] Patent No. 6146746

[0005] However, in Patent Document 1, since the protective film is formed on only one side of the glass, there is a problem that the thickness of the glass in the desired area on the surface where etching is to be performed becomes smaller.

[0006] The present invention has been made in view of the above points, and aims to provide a glass-resin laminate that can be etched while suppressing a reduction in the thickness of the glass layer.

[0007] This glass resin laminate is a glass resin laminate in which a first protective film, a glass layer, and a second protective film are laminated in this order, wherein at least one of the first protective film and the second protective film has a through groove in the lamination direction.

[0008] According to the disclosed technology, it is possible to provide a glass-resin laminate that can be etched while suppressing a reduction in the thickness of the glass layer.

[0009] This is a cross-sectional view illustrating a glass-resin laminate according to the first embodiment. This is a top 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. This is a cross-sectional view illustrating a glass-resin laminate according to the second embodiment. This is a cross-sectional view illustrating a glass-resin laminate according to a modified example 1 of the second 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 1A is a cross-sectional view illustrating a glass resin laminate according to the first embodiment, and Figure 1B is a top view illustrating a glass resin laminate according to the first embodiment. As shown in Figure 1A, the glass resin laminate 10 has a first protective film 11, a glass layer 12, and a second protective film 13 in this order.

[0012] In the glass resin laminate 10, for example, the first protective film 11, the glass layer 12, and the second protective film 13 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, and the second protective film 13 are laminated at any thickness, may be combined.

[0013] At least one of the first protective film 11 and the second protective film 13 has a groove (hereinafter sometimes referred to as a "through groove") that penetrates in the lamination direction. In Figures 1A and 1B, the first protective film 11 has a through groove, but it is not limited to this; the second protective film 13 may have a through groove 16, or both the first protective film 11 and the second protective film 13 may have a through groove 16. The through groove 16 is formed by irradiating the surface of the protective film with a laser.

[0014] By having through grooves 16 in at least one of the first protective film 11 and the second protective film 13, when etching the glass resin laminate 10, only the desired region where the through grooves 16 are formed can be etched. As a result, the reduction in the thickness of the glass layer outside the desired region can be suppressed.

[0015] The through grooves 16 formed in the protective film 11 form a pattern when the glass-resin laminate 10 is viewed from above. There are no particular restrictions on the pattern, and it can be appropriately selected according to the shape from which the glass is to be removed by etching. For example, the pattern can be a circular or polygonal shape as shown in Figure 1B. In addition, a pattern of an opening may be formed to create a glass opening on the glass-resin laminate 10 that allows an IC chip to be placed. Although multiple patterns are formed in Figure 1B, the pattern is not limited to this, and there may be only one pattern on the glass-resin laminate 10. The pattern of the through grooves 16 is formed by placing the protective film 11 on a movable stage and moving the stage while irradiating the surface of the protective film 11 with a fixed pulsed laser. Alternatively, the protective film 11 may be placed on a fixed stage, and the surface of the protective film 11 may be irradiated with a pulsed laser while moving it.

[0016] [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.

[0017] 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.

[0018] The width w1 of the through groove 16 is preferably, for example, 5 μm or more and 1000 μm or less, and more preferably 30 μm or more and 800 μm or less. Here, the width w1 of the through groove 16 refers to the average distance of the width.

[0019] 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.

[0020] 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.

[0021] 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.

[0022] 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".

[0023] 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.

[0024] [First Protection Film and Second Protection Film] The first protection film 11 and the second protection film 13 protect the surface of the glass layer 12 and suppress the adhesion and contamination of foreign substances and the like on the surface thereof.

[0025] Examples of the materials constituting the first protection film 11 and the second protection film 13 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.

[0026] The thickness t2 of the first protection film 11 and the second protection film 13 is not particularly limited, but may be, for example, 100 μm or less.

[0027] <Modification of the First Embodiment> In the modification of the first embodiment, an example of a glass resin laminate having a layer structure different from that of the first embodiment is shown. In the modification of the first embodiment, the description of the same components as those in the already described embodiment may be omitted.

[0028] FIG. 2 is a cross-sectional view illustrating a glass resin laminate according to Modification 1 of the first embodiment. The structure of the glass resin laminate is such that the glass layer 12 has laser processing marks 14 as in the glass resin laminate 10 shown in FIG. 2.

[0029] Specifically, the laser processing marks 14 are formed inside the through grooves 16 in the protection film 11.

[0030] The laser processing marks 14 can be formed by irradiating the surface of the glass layer 12 with a laser.

[0031] A method of forming the laser processing marks 14 on the surface of the glass layer 12 by irradiating laser light will be described. When irradiating laser light, a laser light irradiation device that irradiates arbitrary laser light as appropriate can be used.

[0032] When irradiating the glass resin laminate 10 with laser light, the glass resin laminate is placed on the stage of the laser light irradiation device. The stage is arranged to be movable with respect to the laser light irradiation device, and the laser light source is arranged fixedly. The laser light irradiation device moves the position of the laser light irradiated to the glass layer 12 by moving the stage. Alternatively, while fixing the stage and moving the laser light, the glass layer 12 on the stage may be irradiated with the laser light.

[0033] As the laser light, for example, gas lasers such as CO ２ lasers and excimer lasers; solid lasers such as YAG lasers; semiconductor lasers; ultrashort pulse lasers and the like can be mentioned.

[0034] By irradiating the glass layer 12 with laser light along the planned processing line, laser processing marks 14 may be formed on the glass layer 12. The laser processing marks 14 may be provided intermittently along the planned processing line, or may be provided as a continuous line. The laser processing marks 14 do not penetrate the glass layer 12.

[0035] As the laser light irradiated to the glass layer 12, an ultrashort pulse laser is preferably used. The wavelength of the ultrashort pulse laser oscillated from the ultrashort pulse laser device is preferably 500 nm or more and 2500 nm or less. The pulse width of the ultrashort pulse laser is preferably 100 picoseconds or less, and more preferably 50 picoseconds or less. The oscillation mode of the ultrashort pulse laser may be single pulse oscillation or burst mode multi-pulse oscillation.

[0036] The spot diameter at the irradiation position of the laser light to the glass layer 12 may be set as appropriate, for example, it may be 300 μm or less.

[0037] The stage movement speed when irradiating the glass layer 12 with 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 glass layer 12, and by changing the stage movement speed, different energies can be given to the glass layer 12.

[0038] ]>When the laser processing marks 14 are provided intermittently, the pitch of the laser processing marks 14 is preferably 10 μm or less, and more preferably 5 μm or less.

[0039] Thus, because the glass layer 12 has laser processing marks 14, the laser processing marks 14 function as the starting point for glass etching. Compared to a case where the glass layer 12 does not have laser processing marks 14, this makes it possible to shorten the etching time and process the desired area with high precision.

[0040] <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.

[0041] Figure 3 is a cross-sectional view illustrating a glass-resin laminate according to the second embodiment. The structure of the glass-resin laminate, as shown in Figure 3, has a first protective film 11, a glass layer 12, a resin layer 15, and a second protective film 13 in that order.

[0042] In Figure 3, the glass-resin laminate 10 has a resin layer between the second protective film 13 and the glass layer 12, which do not have through grooves. However, it is not limited to this, and a resin layer may be present in at least one of the spaces between the first protective film and the glass layer, and between the second protective film and the glass layer.

[0043] In the glass resin laminate 10 according to the second embodiment, the glass layer 12 may have laser processing marks.

[0044] [Resin Layer] The resin layer 15 is a base layer on which the glass layer 12 is laminated. The resin layer 15 can consist of one or more layers. An adhesive layer or bonding layer may be provided between the resin layer 15 and the glass layer 12, or the resin layer 15 may be an adhesive layer or bonding layer. The resin layer 15 may contain additives such as inorganic particles.

[0045] The thickness t2 of the resin layer 15 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.

[0046] There are no particular restrictions on the resin components contained in the resin layer 15, 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. The resin layer has adhesive properties due to the presence of the above resin components, and can bond the glass layer 12 and the substrate.

[0047] 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.

[0048] 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.

[0049] 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.

[0050] 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.

[0051] In the resin layer 15, 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.

[0052] When the resin layer 15 contains a thermosetting resin, the content of such a thermosetting resin in the resin layer 15 is preferably 5% by mass or more and 60% by mass or less, and more preferably 10% by mass or more and 50% by mass or less, based on the total mass of the resin layer 15. This allows the resin layer 15 to appropriately exhibit its function as a thermosetting adhesive.

[0053] Examples of thermoplastic resins that may be included in the resin layer 15 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, polyamide-imide resin, and fluororesin.

[0054] Acrylic resin is preferred as the thermoplastic resin because it has fewer ionic impurities and high heat resistance, which allows for better adhesion of the resin layer 15. One type of thermoplastic resin or two or more types may be used.

[0055] The acrylic resin is preferably a polymer in which alkyl (meth)acrylate units constitute the largest proportion by mass among the constituent units of the molecule. Examples of alkyl (meth)acrylates include C2 to C4 alkyl (meth)acrylates.

[0056] The acrylic resin may contain constituent units derived from other monomer components copolymerizable with alkyl (meth)acrylate monomers.

[0057] Other monomer components include, for example, carboxyl group-containing monomers, acid anhydride monomers, hydroxyl group-containing monomers, glycidyl group-containing monomers, sulfonic acid group-containing monomers, phosphate group-containing monomers, acrylamide, acrylonitrile and other functional group-containing monomers, or various other polyfunctional monomers.

[0058] The acrylic resin is preferably a copolymer of alkyl (meth)acrylate (particularly alkyl (meth)acrylate with four or fewer carbon atoms in the alkyl portion), a carboxyl group-containing monomer, a nitrogen atom-containing monomer, and a polyfunctional monomer (particularly polyglycidyl polyfunctional monomer), in that it can exhibit higher cohesive force in the resin layer 15. More preferably, it is a copolymer of ethyl acrylate, butyl acrylate, acrylic acid, acrylonitrile, and polyglycidyl (meth)acrylate.

[0059] When the resin layer 15 contains both a thermosetting resin and a thermoplastic resin, the proportion of thermoplastic resin in the resin layer 15 is preferably 5% to 50% by mass, more preferably 10% to 45% by mass, and even more preferably 20% to 40% by mass, based on the total mass of organic components excluding fillers (e.g., thermosetting resin, thermoplastic resin, curing catalyst, silane coupling agent, dye). The elasticity and viscosity of the resin layer 15 can be adjusted by changing the proportion of thermosetting resin.

[0060] If the thermoplastic resin of the resin layer 15 has thermosetting functional groups, for example, a thermosetting functional group-containing acrylic resin can be used as the thermoplastic resin. Preferably, this thermosetting functional group-containing acrylic resin contains alkyl (meth)acrylate-derived structural units in the molecule in the largest mass proportion. Examples of alkyl (meth)acrylate include the exemplified (meth)alkyl (meth)acrylate. On the other hand, examples of thermosetting functional groups in the thermosetting functional group-containing acrylic resin include glycidyl groups, carboxyl groups, hydroxyl groups, isocyanate groups, and the like.

[0061] The resin layer 15 preferably contains a filler. By changing the amount of filler in the resin layer 15, the elasticity and viscosity of the resin layer 15 can be more easily adjusted. Furthermore, the physical properties of the resin layer 15, such as electrical conductivity, thermal conductivity, and elastic modulus, can be adjusted.

[0062] 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.

[0063] 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 15 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.).

[0064] If the resin layer 15 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 15.

[0065] The resin layer 15 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.

[0066] Examples of flame retardants include antimony trioxide, antimony pentoxide, and brominated epoxy resins.

[0067] 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.

[0068] The resin layer 15 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 15, 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.

[0069] The filler content relative to the total mass of the resin layer 15 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.

[0070] An adhesive resin film can be used as the resin layer 15. The adhesive resin film can be obtained, for example, by blending acrylic rubber, phenolic resin, epoxy resin, filler, catalyst, silane coupling agent, and methyl ethyl ketone, stirring the resulting varnish, applying it to a separator (a PET film treated with silicone release agent), and heating and drying it in an oven (see, for example, Japanese Patent Application Publication Nos. 2016-219720 and 2007-129016). A commercially available die-attach film can be used as the adhesive resin film.

[0071] The thickness t3 of the resin layer 15 is preferably 25 μm or more and 1 mm or less, and more preferably 50 μm or more and 500 μm or less.

[0072] [Adhesive layer] An adhesive layer may be provided between the resin layer 15 and the glass layer 12. Any suitable adhesive can be used as the adhesive layer. Examples of materials for the adhesive layer include acrylic adhesives, silicone adhesives, and rubber adhesives. The thickness of the adhesive layer is not particularly limited, but for example, it is about 10 μm to 500 μm.

[0073] Depending on the requirements, an adhesive layer may be used instead of the tack layer. Examples of materials for the adhesive layer used instead of 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.

[0074] 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.

[0075] In this way, by having a resin layer 15 between the glass layer 12 and the second protective film 13, the effect of protecting the glass surface by the resin layer can be obtained even when the second protective film having an adhesive layer is peeled off.

[0076] <Modification of the Second Embodiment> The modification of the second embodiment shows an example of a glass resin laminate with a different layer structure from that of the second embodiment. In the first and second embodiments, descriptions of components that are the same as those described in the embodiments already described may be omitted.

[0077] Figure 4 is a cross-sectional view illustrating a glass-resin laminate according to the second embodiment. The structure of the glass-resin laminate, as shown in Figure 4, has a first protective film 11, a resin layer 15, a glass layer 12, and a second protective film 13 in that order.

[0078] A modified glass-resin laminate according to the second embodiment has a through groove 16 through which the first protective film 11 and the resin layer 15 penetrate to the surface of the glass layer 12.

[0079] Since the first protective film 11 and the resin layer 15 have through grooves 16, when etching the glass resin laminate 10, only the desired area where the through grooves 16 are formed can be etched.

[0080] Thus, a resin layer 15 may be provided between the first protective film 11 and the glass layer 12. In this case as well, the same effects as when the resin layer 15 is provided between the glass layer 12 and the second protective film 13 can be obtained.

[0081] In the modified glass-resin laminate 10 of the second embodiment, the glass layer 12 may have laser processing marks. This makes it possible to process a desired area with even greater precision.

[0082] [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 via an adhesive 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.

[0083] 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.

[0084] 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.

[0085] 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.

[0086] 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.

[0087] 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.

[0088] 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.

[0089] 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.

[0090] 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.

[0091] 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.

[0092] 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.

[0093] 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.

[0094] 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.

[0095] 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. Examples of the irradiation conditions for ultraviolet light irradiation typically include an integrated irradiation light amount of 100 mJ / cm ２ to 2,000 mJ / cm ２ and an irradiation time of 5 minutes to 30 minutes. Examples of the conditions for heat treatment typically include a heating temperature of 100°C to 200°C and a heating time of 5 minutes to 30 minutes. In addition, after applying a thermosetting resin or an active energy ray-curable resin on the surface of the glass layer or the 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.

[0096] (Glass processing method) The glass processing method according to the present embodiment forms through grooves in the glass layer by immersing the glass resin laminate according to the present embodiment in an etching solution. Since at least one of the first protective film and the second protective film in the glass resin laminate according to the present embodiment has through grooves in the stacking direction, the region where the surface of the glass layer is exposed by the through holes is etched. Thereby, a desired region along the pattern of the through holes can be etched.

[0097] The etching solution is not particularly limited and can be appropriately selected according to the purpose. For example, it can contain 6% hydrogen fluoride and may contain other components such as a solvent as necessary.

[0098] The time for immersing the glass resin laminate in the etching solution is not particularly limited and can be appropriately selected according to the purpose.

[0099] [Applications] The glass resin laminate according to this embodiment can be suitably used, for example, in display elements or solar cells. Examples of display elements include semiconductor packages, liquid crystal displays, plasma displays, organic EL displays, and the like.

[0100] (Example 1) Both sides of a glass layer (OA-10G, manufactured by NEG) and the adhesive layer surface of a protective film (SPV-362X-2K2, manufactured by Nitto Denko Corporation) were bonded together using a hand roller under a pressure of 2 kg to obtain a glass-resin laminate. Next, the glass-resin laminate was placed on a stage with the first protective film facing upwards, and CO ２ Using a laser device (250 kHz, 10 W output), CO ２ CO emitted from a laser light source ２ While irradiating only the first protective film with a laser, the stage was moved to form a square through-groove 16 with sides of approximately 25 mm in the center of the protective film when viewed from above. ２ The laser is focused to a spot diameter of 100 μm using a focusing lens, and the stage movement speed is set to 350 mm / s, and CO2 is applied to the glass resin laminate. ２ The relative movement speed (processing speed) of the laser was set. This resulted in obtaining a through groove 16 that was approximately the same diameter as the spot.

[0101] (Example 2) One side of a glass layer (OA-10G, manufactured by NEG) and the adhesive layer surface of a protective film with an adhesive layer (SPV-362X-2K2, manufactured by Nitto Denko Corporation, first protective film) were bonded together using a hand roller under a pressure of 2 kg. Next, the dicing tape was peeled off the die-attach film with dicing tape (EM-350, manufactured by Nitto Denko Corporation) to prepare an adhesive die-attach film as the resin layer. The temperature was raised to 60°C on a hot plate, and the other side of the glass and one side of the die-attach film were bonded together using a hand roller under a pressure of 2 kg. Next, the other side of the die-attach film and the adhesive layer surface of a protective film with an adhesive layer (EMASK RP207, manufactured by Nitto Denko Corporation, second protective film) were bonded together to obtain a glass-resin laminate. Next, the glass laminate was placed on a stage with the second protective film side facing upwards, and CO ２ Using a laser device (250 kHz, 10 W output), CO ２ CO emitted from a laser light source ２ While irradiating only the second protective film and the die attach film with a laser, the stage was moved to form a square through groove 16 with sides of approximately 25 mm in the center of the second protective film. ２ The laser is focused to a spot diameter of 100 μm using a focusing lens, and the stage movement speed is set to 350 mm / s, and CO2 is applied to the glass resin laminate. ２ The relative movement speed (processing speed) of the laser was set.

[0102] (Example 3) One side of a glass layer (OA-10G, manufactured by NEG) and the adhesive side of a protective film having an adhesive layer (SPV-362X-2K2, manufactured by Nitto Denko Corporation, the first protective film) were bonded together using a hand roller under a pressure of 2 kg to obtain a glass-resin laminate. Next, the glass-resin laminate was placed on a stage with the first protective film facing upwards, and CO ２ Using a laser device (250 kHz, 10 W output), CO ２ CO emitted from a laser light source ２While irradiating only the first protective film with a laser, the stage was moved to form a square through-groove 16 with sides of approximately 25 mm in the center of the first protective film. ２ The laser is focused to a spot diameter of 100 μm using a focusing lens, and the stage movement speed is set to 350 mm / s, and CO2 is applied to the glass resin laminate. ２ The relative movement speed (processing speed) of the laser was set. Next, the glass layer of the glass-resin laminate, in which the through groove 16 was formed in the first protective film, was placed on the stage with the glass layer facing upwards. Using an ultrashort pulse laser device (oscillation wavelength 1064 nm, pulse width of ultrashort pulse laser 10 psec, pulse repetition frequency 125 kHz, pulse energy 80 uJ), the stage was moved while irradiating the ultrashort pulse laser emitted from the ultrashort pulse laser light source through the optical system along the region in which the through groove 16 was formed, from the surface on the glass layer side. The stage movement speed was set to 125 mm / s to determine the relative movement speed (processing speed) of the ultrashort pulse laser relative to the glass-resin laminate, and the ultrashort pulse laser was scanned to form laser-processed marks with a pitch of 1 μm. Next, the adhesive side of a protective film having an adhesive layer (SPV-362X-2K2, manufactured by Nitto Denko Corporation, second protective film) was bonded to the glass side of the glass resin laminate on which laser processing marks had been formed, using a hand roller under a pressure of 2 kg, thereby obtaining a glass resin laminate with protective films bonded to both sides.

[0103] (Example 4) 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 was prepared as the resin layer. The temperature was raised to 60°C on a hot plate, and one side of the glass (OA-10G NEG, manufactured as the glass layer) and one side of the die-attach film were bonded together using a hand roller under a pressure of 2 kg. Next, the other side of the die-attach film was bonded to the adhesive layer surface of a protective film with an adhesive layer (EMASK RP207, manufactured by Nitto Denko Corporation, second protective film) to obtain a glass-resin laminate. Next, the glass laminate was placed on a stage with the second protective film side facing upwards, and CO ２Using a laser device (250 kHz, 10 W output), CO ２ CO emitted from a laser light source ２ While irradiating only the second protective film and the die attach film with a laser, the stage was moved to form a square through groove 16 with sides of approximately 25 mm in the center of the second protective film. ２ The laser is focused to a spot diameter of 100 μm using a focusing lens, and the stage movement speed is set to 350 mm / s, and CO2 is applied to the glass resin laminate. ２ The relative movement speed (processing speed) of the laser was set. Next, the glass-resin laminate, in which through grooves 16 were formed in the second protective film, was placed on the stage with the glass layer side facing upwards. Using an ultrashort pulse laser device (oscillation wavelength 1064 nm, pulse width of ultrashort pulse laser 10 psec, pulse repetition frequency 125 kHz, pulse energy 80 uJ), the stage was moved while irradiating the glass-layer side surface along the region where the through grooves 16 were formed, via the optical system, with the ultrashort pulse laser emitted from the ultrashort pulse laser light source. The stage movement speed was set to 125 mm / s to determine the relative movement speed (processing speed) of the ultrashort pulse laser relative to the glass-resin laminate, and the ultrashort pulse laser was scanned along the outer circumference of the resin layer to form laser-processed marks with a pitch of 1 μm. Next, the adhesive side 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 side of the glass resin laminate on which laser processing marks had been formed, using a hand roller under a pressure of 2 kg, thereby obtaining a glass resin laminate with protective films bonded to both sides.

[0104] (Comparative Example 1) One side of a glass layer (OA-10G, manufactured by NEG) and the adhesive side of a protective film having an adhesive layer (SPV-362X-2K2, manufactured by Nitto Denko Corporation, the first protective film) were bonded together using a hand roller under a load of 2 kg. Next, the glass-resin laminate was placed on a stage, and the stage was moved while irradiating the glass layer with an ultrashort pulse laser emitted from an ultrashort pulse laser light source via an optical system using an ultrashort pulse laser device (oscillation wavelength 1064 nm, pulse width of ultrashort pulse laser 10 psec, pulse repetition frequency 125 kHz, pulse energy 80 uJ). 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 glass-resin laminate was set, and the ultrashort pulse laser was scanned to form laser processing marks with a pitch of 1 μm.

[0105] (Comparative Example 2) A glass layer (OA-10G NEG) was placed on a stage, and an ultrashort pulse laser device (oscillation wavelength 1064 nm, pulse width 10 psec, pulse repetition frequency 125 kHz, pulse energy 80 uJ) was used to irradiate the glass layer with an ultrashort pulse laser emitted from the ultrashort pulse laser light source via the optical system while the stage was moved. The stage movement speed was set to 125 mm / s to determine the relative movement speed (processing speed) of the ultrashort pulse laser with respect to the glass resin laminate, and the ultrashort pulse laser was scanned to form laser processing marks with a pitch of 1 μm.

[0106] The glass resin laminates of Examples 1-4 and Comparative Examples 1-2 were etched by immersion in an etching solution containing 6% hydrogen fluoride to form openings in the glass layer. The etching time until the openings were formed, the thickness of the glass layer after etching compared to the thickness of the glass layer before etching, and the amount of thickness reduction after etching were evaluated. The thickness of the glass after etching was measured at a position 10 mm away from the opening. The evaluation results are shown in Table 1.

[0107] [evaluation]

[0108]

[0109] Thus, the glass resin laminate according to this embodiment is a glass resin laminate having a first protective film, a glass layer, and a second protective film in this order, wherein at least one of the first protective film and the second protective film has a through groove that penetrates to the surface of the glass layer. As a result, the glass resin laminate according to this embodiment can be etched while suppressing a reduction in the thickness of the glass layer.

[0110] 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.

[0111] 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, and a second protective film laminated in this order, wherein at least one of the first protective film and the second protective film has through grooves in the lamination direction. (Note 2) The glass-resin laminate according to Note 1, wherein the through grooves form a pattern when the glass-resin laminate is viewed from above. (Note 3) The glass-resin laminate according to any one of Notes 1 to 2, wherein the glass layer has laser processing marks. (Note 4) The glass-resin laminate according to any one of Notes 1 to 3, wherein a resin layer is provided in at least one of the spaces between the first protective film and the glass layer, and between the second protective film and the glass layer. (Note 5) The glass-resin laminate according to Note 4, wherein the resin layer has through grooves in the lamination direction. (Note 6) A glass processing method for forming through grooves in the glass layer by immersing the glass-resin laminate according to Note 1 in an etching solution.

[0112] This application claims priority based on Japanese Patent Application No. 2025-019455, filed with the Japan Patent Office on 7 February 2025, and includes the entire contents of that Japanese Patent Application.

[0113] 10 Glass resin laminate 11 First protective film 12 Glass layer 13 Second protective film 14 Laser processing marks 15 Resin layer

Claims

1. A glass resin laminate comprising a first protective film, a glass layer, and a second protective film laminated in this order, characterized in that at least one of the first protective film and the second protective film has a through groove in the lamination direction.

2. The glass resin laminate according to claim 1, wherein the through grooves form a pattern when the glass resin laminate is viewed in plan view.

3. The glass resin laminate according to claim 1 or 2, wherein the glass layer has laser processing marks.

4. The glass resin laminate according to claim 1 or 2, wherein a resin layer is provided in at least one of the spaces between the first protective film and the glass layer, and between the second protective film and the glass layer.

5. The glass resin laminate according to claim 4, wherein the resin layer has through grooves in the lamination direction.

6. A glass processing method comprising immersing the glass resin laminate described in claim 1 in an etching solution to form through grooves in the glass layer.

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