Glass resin laminate and glass resin laminate substrate

Abstract

Provided is a glass resin laminate in which a glass layer and a resin layer are laminated, wherein the storage modulus of the resin layer at 260°C is 3 MPa or more.

Description

Glass resin laminate and glass resin laminate substrate

[0001] The present invention relates to a glass resin laminate and a glass resin laminate substrate.

[0002] Conventionally, printed circuit boards (PCBs) have been used that incorporate IC chips made of dissimilar materials on an organic substrate. During the manufacturing process of the PCB, the IC chip is mounted onto the organic substrate through a thermal process. However, a problem arises when the IC chip detaches from the organic substrate due to thermal expansion of the substrate. This occurs because there is a large difference between the coefficient of thermal expansion (CTE) of the organic substrate and the coefficient of thermal expansion of the silicon and other materials that make up the IC chip.

[0003] Here, a substrate in which a resin layer is formed on a glass surface is disclosed as a printed circuit board (see, for example, Patent Document 1). However, even with these technologies, the problem of IC chips peeling off from the organic substrate remains unresolved.

[0004] Japanese Patent Application Publication No. 11-329715

[0005] The present invention has been made in view of the above points, and aims to provide a glass resin laminate capable of suppressing the peeling of IC chips from an organic substrate.

[0006] This glass-resin laminate is a glass-resin laminate comprising a glass layer and a resin layer, wherein the storage modulus of the resin layer at 260°C is 3 MPa or higher.

[0007] According to the disclosed technology, it is possible to provide a glass resin laminate that can suppress the peeling of IC chips from organic substrates.

[0008] This is a perspective view illustrating a glass resin laminate according to this embodiment. This is a perspective view illustrating a glass resin laminate according to a modified example 1 of this embodiment. This is a perspective view illustrating a glass resin laminate substrate according to this embodiment. This is a plan view illustrating a glass resin laminate substrate according to this embodiment in which an IC chip (semiconductor chip) is arranged in an opening.

[0009] 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.

[0010] (Glass-resin laminate) Figure 1 is a perspective view illustrating a glass-resin laminate according to this embodiment. As shown in Figure 1, the glass-resin laminate 10 has a structure in which a glass layer 11 and a resin layer 12 are arranged.

[0011] In the glass-resin laminate 10, for example, the glass layer 11 and the resin layer 12 may have the same thickness or they may have different thicknesses. Alternatively, multiple types of unit laminate structures with different thicknesses, in which the glass layer 11 and the resin layer 12 are laminated at arbitrary thicknesses, may be combined.

[0012] Figure 2 is a perspective view illustrating a glass-resin laminate according to Modification 1 of this embodiment. The structure of the glass-resin laminate is such that, as shown in Figure 2, when the glass-resin laminate 10 is viewed from above, openings 13 are provided in the glass layer 11 and the resin layer 12. For example, an IC chip (semiconductor chip) is placed inside the openings 13.

[0013] The opening 13 is not limited to the rectangle shown in Figure 2; it may also be circular, polygonal, or other shapes. Furthermore, there may be one opening, as in the illustrated example, or there may be multiple openings. If there are multiple openings, the shapes of the openings may be a mix of rectangles, circles, polygons, etc.

[0014] In the modified example 1 of this embodiment, the opening 13 in the glass resin laminate preferably has an area of ​​3% or more of the surface area of ​​the glass resin laminate 10. This makes it possible to place many components in one or more openings. If there are multiple openings, it is preferable that the sum of the areas of all openings has an area of ​​3% or more of the surface area of ​​the glass resin laminate 10.

[0015] (Glass-resin laminate substrate) Figure 3 is a perspective view illustrating a glass-resin laminate substrate according to this embodiment. As shown in Figure 3, the glass-resin laminate substrate 20 has a structure comprising a glass-resin laminate 10 having a glass layer 11 and a resin layer 12, and a substrate 14. The glass-resin laminate 10 may be placed on at least one surface of the substrate 14, but it may also be placed on one surface and the other surface of the substrate 14.

[0016] The glass resin laminate substrate 20 has an opening 13. An IC chip (semiconductor chip), for example, is placed inside the opening 13.

[0017] Figure 4 is a plan view illustrating a glass-resin laminate substrate in which an IC chip (semiconductor chip) is placed in an opening. The semiconductor chip 15 can be placed, for example, on the upper surface of the substrate 14 that is exposed within the opening 13. The wiring layer constituting the substrate 14 is exposed within the opening 13, and this wiring layer and the electrodes of the semiconductor chip 15 are connected, for example, by solder material. Other electronic components such as capacitors and resistors may be placed in the opening 13 together with the semiconductor chip 15. Alternatively, in addition to the opening 13, other openings may be provided, and other electronic components such as capacitors and resistors may be placed in the other openings. In the glass-resin laminate substrate 20, since the storage modulus of the resin layer 12 constituting the glass-resin laminate substrate 20 is 3 MPa or more at 260°C, peeling of the semiconductor chip 15 from the substrate 14 can be suppressed.

[0018] [Glass Layer] The glass layer 11 is not particularly limited, and an appropriate one can be used depending on the purpose. Examples of glass layers 11, according to their composition, include soda-lime glass, borate glass, aluminosilicate glass, and quartz glass. Examples of glass layers 11, according to their alkali content, include alkali-free glass and low-alkali glass.

[0019] 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.

[0020] The thickness t1 of the glass layer 11 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.

[0021] The thickness t1 of the glass layer 11 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 11 to have film-like flexibility in order to obtain a curved structure, the thickness t1 of the glass layer 11 is preferably 200 μm or less, and more preferably 50 μm or more and 100 μm or less.

[0022] The light transmittance of the glass layer 11 at a wavelength of 550 nm is preferably 85% or higher. The refractive index of the glass layer 11 at a wavelength of 550 nm is preferably 1.4 to 1.65. The density of the glass layer 11 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.

[0023] The glass layer 11 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".

[0024] There are no particular limitations on the method for forming the glass layer 11, and an appropriate method can be adopted depending on the purpose. Typically, the glass layer 11 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 11 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.

[0025] [Resin Layer] The resin layer 12 is a base layer on which the glass layer 11 is laminated. The resin layer 12 can consist of one or more layers. An adhesive layer or bonding layer may be provided between the resin layer 12 and the glass layer 11, or the resin layer 12 may be an adhesive layer or bonding layer. The resin layer 12 may contain additives such as inorganic particles.

[0026] The storage modulus of the resin layer 12 at 260°C is 3 MPa or more, preferably 20 MPa or more, and more preferably 300 MPa or more. A storage modulus of 3 MPa or more at 260°C suppresses peeling of the glass resin laminate from the substrate and suppresses shrinkage of the glass resin laminate due to heat.

[0027] The resin component included in the resin layer is not particularly limited as long as its storage elasticity at 260°C is 3 MPa or higher, 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 inclusion of the above resin component, and can bond the glass layer 11 and the substrate.

[0028] Examples of the thermosetting resin include, for example, epoxy resins, phenolic resins, amino resins, unsaturated polyester resins, polyurethane resins, silicone resins, thermosetting polyimide resins, and the like. As the thermosetting resin, only one type or two or more types may be employed. From the viewpoint of containing less ionic impurities and the like that can cause corrosion of the semiconductor chip, an epoxy resin is preferred as the thermosetting resin. As the curing agent for the epoxy resin, a phenolic resin is preferred.

[0029] Examples of the epoxy resin include, for example, 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 novolak type, ortho-cresol novolak type, trishydroxyphenylmethane type, tetraphenylol ethane type, hydantoin type, tris glycidyl isocyanurate type, or glycidylamine type epoxy resins.

[0030] The phenolic resin can act as a curing agent for the epoxy resin. Examples of the phenolic resin include, for example, novolak type phenolic resins, resol type phenolic resins, polyoxystyrenes such as polyparaoxystyrene, and the like. [[ID=⑧]]

[0031] [[ID=⑨]]Examples of the novolak type phenolic resin include, for example, phenol novolak resin, phenol aralkyl resin, cresol novolak resin, tert-butylphenol novolak resin, nonylphenol novolak resin, and the like. As the phenolic resin, only one type or two or more types may be employed. [[ID=⑩]] [[ID=⑪]]

[0032] [[ID=⑫]]In the resin layer 12, the hydroxyl group of the phenolic resin is preferably 0.5 equivalents or more and 2.0 equivalents or less, more preferably 0.7 equivalents or more and 1.5 equivalents or less, per equivalent of the epoxy group of the epoxy resin. Thereby, the curing reaction between the epoxy resin and the phenolic resin can proceed sufficiently. [[ID=⑬]] [[ID=⑭]]

[0033] When the resin layer 12 contains a thermosetting resin, the content ratio of such a thermosetting resin in the resin layer 12 is preferably 5% by mass or more and 60% by mass or less, more preferably 10% by mass or more and 50% by mass or less, based on the total mass of the resin layer 12. Thereby, the function as a thermosetting adhesive can be appropriately exhibited in the resin layer 12.

[0034] Examples of the thermoplastic resin that can be included in the resin layer 12 include natural rubber, butyl rubber, isoprene rubber, chloroprene rubber, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic 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.

[0035] As the thermoplastic resin, an acrylic resin is preferable in that the adhesiveness of the resin layer 12 can be more ensured because of less ionic impurities and high heat resistance. As the thermoplastic resin, only one kind or two or more kinds can be adopted.

[0036] 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.

[0037] The acrylic resin may contain a constituent unit derived from another monomer component copolymerizable with the alkyl (meth)acrylate monomer.

[0038] Examples of the other monomer component include functional group-containing monomers such as carboxy group-containing monomer, acid anhydride monomer, hydroxy group-containing monomer, glycidyl group-containing monomer, sulfonic acid group-containing monomer, phosphoric acid group-containing monomer, acrylamide, acrylonitrile, or various other polyfunctional monomers.

[0039] 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 12. More preferably, it is a copolymer of ethyl acrylate, butyl acrylate, acrylic acid, acrylonitrile, and polyglycidyl (meth)acrylate.

[0040] When the resin layer 12 contains both a thermosetting resin and a thermoplastic resin, the content of the thermoplastic resin in the resin layer 12 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 the organic components excluding fillers (e.g., thermosetting resin, thermoplastic resin, curing catalyst, silane coupling agent, dye). The elasticity and viscosity of the resin layer 12 can be adjusted by changing the content of the thermosetting resin.

[0041] If the thermoplastic resin of the resin layer 12 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.

[0042] The resin layer 12 preferably contains a filler. By changing the amount of filler in the resin layer 12, the elasticity and viscosity of the resin layer 12 can be more easily adjusted. Furthermore, the physical properties of the resin layer 12, such as electrical conductivity, thermal conductivity, and elastic modulus, can be adjusted.

[0043] 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.

[0044] 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 12 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.).

[0045] If the resin layer 12 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 12.

[0046] The resin layer 12 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.

[0047] Examples of flame retardants include antimony trioxide, antimony pentoxide, and brominated epoxy resins.

[0048] 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.

[0049] The resin layer 12 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 12, 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.

[0050] The filler content relative to the total mass of the resin layer 12 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.

[0051] The thickness t2 of the resin layer 12 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.

[0052] An adhesive resin film can be used as the resin layer 12. 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 then 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.

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

[0054] [Adhesive layer] An adhesive layer may be provided between the resin layer 12 and the glass layer 11. 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.

[0055] 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.

[0056] 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.

[0057] [Substrate] The substrate 14 is an organic substrate having, for example, a base material containing an organic material such as glass epoxy material, and a wiring layer made of Cu or the like disposed on the base material. The substrate 14 may also be a build-up substrate in which the wiring layer and insulating layer are alternately laminated on a base material containing an organic material such as glass epoxy material. The wiring layer and insulating layer may be laminated on only one side of the base material, or on both sides of the base material.

[0058] [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.

[0059] 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.

[0060] 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.

[0061] 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.

[0062] 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.

[0063] 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.

[0064] 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.

[0065] 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.

[0066] 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.

[0067] 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.

[0068] 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.

[0069] 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.

[0070] 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.

[0071] As a method for forming the adhesive layer, for example, after applying a thermosetting resin or an active energy ray-curable resin to the surface of a glass layer or a resin film, the glass layer and the resin film are adhered, 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. 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. After applying a thermosetting resin or an active energy ray-curable resin to 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.

[0072] [Use] The glass resin laminate according to the present embodiment can be suitably used, for example, for display elements or solar cells. Examples of display elements include semiconductor packages, liquid crystal displays, plasma displays, organic EL displays, and the like.

[0073] (Example 1) [Fabrication of Substrate] A glass epoxy material with Cu (FR-4, thickness 18 μm) was laminated with the Ajinomoto Build-up Film (registered trademark) (hereinafter sometimes referred to as "ABF") by vacuum lamination under the conditions of a temperature of 100°C, a bonding pressure of 0.39 MPa, and an air pressure of 100 Pa. Next, the ABF was heated at 180°C for 90 minutes. Next, electroless plating was performed on the surface of the ABF to plate copper, and then electroplating was performed to plate copper with a thickness of 18 μm. A solder resist (AUS703) was coated on the surface of the copper after electroplating with a roll coater and dried at 70°C. Next, exposure was performed through a photomask with a predetermined pattern, heat-cured at 180°C, and then 1000 mJ / cm ２UV treatment was performed under the specified conditions. Next, a pre-solder film was deposited on the openings of the solder resist (hereinafter sometimes referred to as "chip mounts") by screen printing to obtain a substrate (45 mm).

[0074] [Fabrication of Glass-Resin Laminates] <Lamination of Glass and Resin Layers> Glass was placed on a hot plate and heated to 60°C. A die-attach film, which served as the resin layer, was then bonded to the glass-resin laminate using a 2 kg hand roller. The size of the laminate was 43 mm. As for the die-attach film, only die-attach film with dicing tape (EM-350, manufactured by Nitto Denko Corporation) was used, with the dicing tape removed.

[0075] <Formation of openings in the glass-resin laminate> The glass-resin laminate is placed on the stage with the resin layer side facing upwards, CO ２ Using a laser device (250 kHz, 10 W output), CO ２ CO emitted from a laser light source ２ The laser is focused to a spot diameter of 100 μm using a focusing lens, and CO is emitted while moving the stage (stage speed at 350 mm / s). ２ A laser beam was shone onto the resin layer. This created a line in which the resin at the focusing area was removed in a groove shape. The shape of the line drawn was a square with sides of approximately 25 mm in the center of the glass-resin laminate.

[0076] Next, with the glass side of the glass-resin laminate facing upwards, 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-resin laminate from the glass layer side surface along the grooves where the resin had been removed, via an optical system. At this time, the stage was moved (stage speed 125 mm / s) while irradiating with the ultrashort pulse laser to form laser-processed marks with a pitch of 1 μm along the grooves in the resin, resulting in a glass-resin laminate with a square glass processing mark with sides of approximately 25 mm in the center of the glass-resin laminate. The obtained glass-resin laminate was immersed in an etching solution containing 6% hydrogen fluoride to perform glass etching, removing the glass-resin laminate in the center along the glass processing mark, resulting in a glass-resin laminate with a square opening with sides of approximately 25 mm in the center.

[0077] [Bonding of glass-resin laminate and substrate] The chip-mount side of the substrate and the resin layer side of the glass-resin laminate having an opening were bonded by vacuum lamination under the conditions of a temperature of 100°C, a bonding pressure of 0.15 MPa, and an atmospheric pressure of 100 Pa. Subsequently, the resin layer side of the glass-resin laminate having an opening was similarly bonded to the opposite side of the chip-mount side of the substrate by vacuum lamination to obtain a glass-resin laminate substrate.

[0078] (Example 2) A glass resin laminate substrate was obtained in the same manner as in Example 1, except that the resin film (EM-350, manufactured by Nitto Denko Corporation) used as the resin layer was changed to a resin film (EM-430, manufactured by Nitto Denko Corporation).

[0079] (Example 3) A glass resin laminate substrate was obtained in the same manner as in Example 1, except that the resin film (EM-350, manufactured by Nitto Denko Corporation) used as the resin layer was changed to a resin film (EM-710, manufactured by Nitto Denko Corporation).

[0080] (Comparative Example 1) [Preparation of Adhesive Composition Solution] First, an acrylic polymer was prepared. In a four-necked flask equipped with a stirring blade, thermometer, nitrogen gas inlet tube, and condenser, 62.9 parts by mass of n-butyl acrylate (BA), 33.9 parts by mass of 4-acryloylmorpholine (ACMO), 2.9 parts by mass of acrylic acid (AA), 0.3 parts by mass of 4-hydroxybutyl acrylate (4HBA), and 0.1 parts by mass of 2,2'-azobisisobutyronitrile as a polymerization initiator were placed in the flask together with ethyl acetate so that the total monomer content was 50% by mass. Nitrogen gas was introduced while gently stirring, and the flask was purged with nitrogen for 1 hour. Then, the temperature of the liquid in the flask was maintained at around 58°C and the polymerization reaction was carried out for 8 hours to obtain an acrylic polymer. Two hours after the start of the polymerization reaction, ethyl acetate was added dropwise over 3 hours until the solid content became 35% by mass. That is, the acrylic polymer was obtained as an acrylic polymer solution with a solid content of 35% by mass.

[0081] Next, to the obtained acrylic polymer solution, an adhesive composition solution was prepared by adding 7 parts by mass of UV-curable urethane acrylate resin A (weight-average molecular weight Mw: 5,500) per 100 parts by mass of polymer, 0.7 parts by mass of 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name "Omnirad 651", manufactured by IGM Japan LLC) as a photopolymerization initiator, and 0.1 parts by mass of 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane (trade name "TETRAD-C", manufactured by Mitsubishi Gas Chemical Company, Ltd.) as a crosslinking agent.

[0082] [Preparation of Adhesive Sheet] An adhesive composition solution was applied to one side of a 38 μm thick polyethylene terephthalate (PET) film (product name "MRF38", manufactured by Mitsubishi Chemical Corporation) that had been silicone-released to form an adhesive composition solution layer. At this time, the thickness of the adhesive composition solution layer was applied so that the thickness after drying (i.e., the thickness of the adhesive composition layer) was 1 μm. By drying the adhesive composition solution layer at 150°C for 3 minutes, the solvent of the adhesive composition solution layer was removed and the acrylic polymer was crosslinked with a crosslinking agent to obtain an adhesive composition layer having a first crosslinked structure. Next, the release-treated side of a 38 μm thick polyethylene terephthalate (PET) film (product name "MRE38", manufactured by Mitsubishi Chemical Corporation) that had been silicone-released was bonded to the adhesive composition layer to produce an adhesive sheet (first laminate) having a laminated structure of PET film / adhesive composition layer / PET film.

[0083] [Fabrication of Optical Laminate] The PET film on one side of the obtained first laminate was peeled off and bonded with a 2 kg hand roller to obtain a glass resin laminate. Then, an opening was formed in the glass resin laminate using the same method as in Example 1.

[0084] The other PET film was peeled off the obtained layer, and the glass resin laminate and the substrate were laminated from the peeled-off side using the same substrate as in Example 1. Then, ultraviolet light was irradiated from the glass layer side to cure the curable resin of the adhesive composition layer, thereby forming an adhesive layer having a second crosslinking structure in addition to the first crosslinking structure, and a laminated structure was obtained in the order of glass layer, adhesive composition layer, and substrate. The ultraviolet irradiation was performed using an LED lamp (manufactured by Quark Technology Co., Ltd., peak illuminance: 200 mW / cm²). ２ , cumulative light intensity 1500 mJ / cm ２ (Wavelength 345-365 nm) was used, and the irradiance of ultraviolet light was measured using a UV Power Puck (manufactured by Fusion UV Systems Japan Co., Ltd.).

[0085] Next, a first laminate was also provided on the opposite side of the substrate from the chip-mount side, and ultraviolet light was irradiated from the glass layer side to obtain a glass-resin laminate substrate.

[0086] (Comparative Example 2) A die attach film similar to the die attach film used in Example 1 was placed on the stage, CO ２ Using a laser device (250 kHz, 10 W output), a CO2 spot with a diameter of 100 μm was generated. ２ A laser was shone onto the die attach film at a stage movement speed of 350 mm / s to obtain a die attach film (resin layer) having an opening (25 mm) in the center.

[0087] A resin layer was bonded to the chip-mount side of a substrate similar to the one used in Example 1 by vacuum lamination under the conditions of a temperature of 100°C, a bonding pressure of 0.39 MPa, and an atmospheric pressure of 100 Pa. Subsequently, the resin layer was similarly bonded to the opposite side of the substrate from the chip-mount side by vacuum lamination to obtain a resin substrate.

[0088] The glass resin laminate substrates of Examples 1-3 and Comparative Examples 1-2 were evaluated as follows. The evaluation results are shown in Table 1.

[0089] [Evaluation] <Storage modulus at 260°C> Strip-shaped resin samples were prepared by cutting the die-attach films used in Examples 1 to 3 and Comparative Example 2, and the adhesive sheet used in Comparative Example 1, into strips with a thickness of 20 μm, a width of 10 mm, and a length of 40 mm. The tensile storage modulus of each prepared strip-shaped resin sample was measured under the following measurement conditions.

[0090] Measurement device: Solid viscoelasticity analyzer (e.g., "RSA III" manufactured by TA Instruments) Sample size: Initial length 40 mm, width 10 mm, thickness 20 μm (If the thickness is less than 20 μm, multiple sheets are stacked to form a laminate) Measurement environment: Nitrogen gas atmosphere Heating rate: 10 °C / min Measurement temperature: Temperature range of -40 °C to 280 °C (The value of the tensile storage modulus at 260 °C is read) Initial distance between chucks: 22.5 mm Frequency: 10 Hz Strain: 0.005%

[0091] <ΔCTE> A single substrate was placed on a ceramic heater with a built-in thermocouple, with the analysis surface facing upwards. The temperature was increased using the ceramic heater in the order of 50°C, 100°C, 150°C, 200°C, and 250°C while measuring the temperature with the thermocouple. After reaching each temperature, the temperature was maintained for 5 minutes, and images were obtained using two cameras with an image scale of 18 μm / px. From the obtained images, the strain of the substrate at each temperature was calculated by image processing. The CTE was calculated as the difference between the strain of the substrate at 50°C and the strain of the substrate at 250°C (hereinafter referred to as "CTE"). Ａ (It is sometimes referred to as "...").

[0092] The above procedure was carried out similarly for the glass resin laminate substrates of Examples 1 to 3 and Comparative Example 1, and the CTE was calculated as the difference between the substrate strain at 50°C and the substrate strain at 250°C (hereinafter referred to as "CTE"). Ｂ (This is sometimes referred to as "..."). Regarding substrate distortion, the distortion of the substrate at the opening where the glass resin laminate was not mixed was calculated. Note that for Comparative Example 2, no measurement was performed because no glass layer was provided.

[0093] Based on the following formula 1, the ΔCTE of the glass resin laminate substrates of Examples 1 to 3 and Comparative Example 1 was calculated.

[0094] [Equation 1] ΔCTE = CTE Ａ - CTE Ｂ

[0095] <IC Chip Detachment from Substrate> To test for detachment of IC chips due to reflow soldering, a simulated IC chip was created by applying a 25 μm thick solder layer to one side of a 10 mm square silicon substrate (75 μm thick).

[0096] With the solder layer side of the obtained pseudo-IC chip facing downwards, four pseudo-IC chips were placed in the openings (pre-solder areas) of the substrates of the example and comparative example, and the solder layers of the pseudo-IC chips were fused to the substrates of the example and comparative example in a reflow oven at 260°C.

[0097] The presence or absence of lifting and peeling at the joint between the substrate and the pseudo-IC chip after welding, and the presence or absence of package cracks were evaluated using a scanning ultrasonic flaw detection device (Hye-Focus, manufactured by Hitachi Construction Machinery Fine Tech Co., Ltd.) and cross-sectional observation. The substrate / semiconductor chip joint had an area of ​​0.25 mm². ２ If the above-mentioned delamination was observed, it was determined that delamination had occurred.

[0098]

[0099] Thus, the glass-resin laminate according to this embodiment is a glass-resin laminate having a glass layer and a resin layer, wherein the storage modulus of the resin layer at 260°C is 3 MPa or more. As a result, the glass-resin laminate according to this embodiment can suppress the peeling of IC chips from the organic substrate.

[0100] 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.

[0101] In addition to the embodiments described above, the following further notes are disclosed: (Note 1) A glass-resin laminate comprising a glass layer and a resin layer, wherein the storage modulus of the resin layer at 260°C is 3 MPa or more. (Note 2) The glass-resin laminate according to Note 1, wherein the glass layer has an opening when viewed from above. (Note 3) The glass-resin laminate according to Note 2, wherein the opening has an area of ​​3% or more of the surface area of ​​the glass-resin laminate. (Note 4) The glass-resin laminate according to any one of Notes 1 to 3, wherein the resin layer consists of at least one of a thermosetting resin and a thermoplastic resin. (Note 5) A glass-resin laminate substrate comprising a substrate and a glass-resin laminate according to any one of Notes 1 to 4 on at least one surface of the substrate. (Note 6) The glass-resin laminate substrate according to Note 5, wherein a semiconductor chip is disposed on the substrate. (Note 7) The glass resin laminate substrate according to (Note 6), wherein the semiconductor chip is arranged within the opening of the glass layer.

[0102] This application claims priority based on Japanese Patent Application No. 2025-019454, filed with the Japan Patent Office on 7 February 2025, and includes the entire contents of that Japanese Patent Application.

[0103] 10 Glass-resin laminate 11 Glass layer 12 Resin layer 13 Aperture 14 Substrate 15 Semiconductor chip 20 Glass-resin laminate substrate

Claims

1. A glass-resin laminate comprising a glass layer and a resin layer, characterized in that the storage modulus of the resin layer at 260°C is 3 MPa or more.

2. The glass resin laminate according to claim 1, wherein the glass layer has an opening when viewed from above.

3. The glass resin laminate according to claim 2, wherein the opening has an area of ​​3% or more of the surface area of ​​the glass resin laminate.

4. The glass resin laminate according to claim 1, wherein the resin layer comprises at least one of a thermosetting resin and a thermoplastic resin.

5. A glass resin laminate substrate comprising a substrate and a glass resin laminate according to claim 1 or 2 on at least one surface of the substrate.

6. The glass resin laminate substrate according to claim 5, wherein a semiconductor chip is arranged on the substrate.

7. The glass resin laminate substrate according to claim 6, wherein the semiconductor chip is disposed within the opening of the glass layer.

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