WO2023090317A1 - 硬化性樹脂組成物 - Google Patents

硬化性樹脂組成物 Download PDF

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Publication number
WO2023090317A1
WO2023090317A1 PCT/JP2022/042374 JP2022042374W WO2023090317A1 WO 2023090317 A1 WO2023090317 A1 WO 2023090317A1 JP 2022042374 W JP2022042374 W JP 2022042374W WO 2023090317 A1 WO2023090317 A1 WO 2023090317A1
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Prior art keywords
resin composition
curable resin
curing agent
filler
present
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PCT/JP2022/042374
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English (en)
French (fr)
Japanese (ja)
Inventor
理恵子 永田
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Namics Corp
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Namics Corp
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Application filed by Namics Corp filed Critical Namics Corp
Priority to JP2023561599A priority Critical patent/JPWO2023090317A1/ja
Priority to KR1020247019883A priority patent/KR20240101857A/ko
Priority to CN202280072379.XA priority patent/CN118176231A/zh
Priority to EP22895598.5A priority patent/EP4435030A4/en
Publication of WO2023090317A1 publication Critical patent/WO2023090317A1/ja
Anticipated expiration legal-status Critical
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B7/00—Mountings, adjusting means, or light-tight connections, for optical elements
    • G02B7/02—Mountings, adjusting means, or light-tight connections, for optical elements for lenses
    • G02B7/025—Mountings, adjusting means, or light-tight connections, for optical elements for lenses using glue
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/56—Amines together with other curing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B7/00—Mountings, adjusting means, or light-tight connections, for optical elements
    • G02B7/02—Mountings, adjusting means, or light-tight connections, for optical elements for lenses
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/019—Specific properties of additives the composition being defined by the absence of a certain additive

Definitions

  • the present invention relates to a curable resin composition, a sealing material containing the same, a cured product obtained by curing the same, and a camera module containing the cured product.
  • curable resin compositions especially epoxy resin compositions (hereinafter simply referred to as “sealing (sometimes referred to as “stopping material”) is often used.
  • the epoxy resin composition used for such a sealing material for semiconductor devices generally contains an epoxy resin and a curing agent.
  • curable resin compositions include those disclosed in Patent Document 1. Curing of this curable resin composition can be achieved by heat treatment under appropriate conditions. Hereinafter, the heat treatment for curing the curable resin composition is also referred to as "thermosetting treatment”.
  • Flare is a phenomenon in which light that does not exist originally is reflected in captured images and videos as a result of unintentional reflection of light incident on the camera from the lens surface, lens barrel, and other parts of the camera. That is.
  • Examples of conventional sealing materials include those disclosed in Patent Document 2. Such encapsulants often give a glossy cured product on the surface. For this reason, as described above, while the need to prevent problems such as flare in camera modules is increasing, the characteristics of sealing materials for reducing the glossiness of the surface of the cured product, which was not regarded as a problem in the past, have been developed. improvement is desired.
  • the present invention has been made in view of the above problems, and an object of the present invention is to provide a curable resin composition that uses a new mechanism to give a cured product with reduced surface gloss.
  • An object of the present invention is to provide a sealing material containing
  • Another object of the present invention is to provide a cured product obtained by curing the curable resin composition or sealing material.
  • Still another object of the present invention is to provide a camera module containing the cured product.
  • the present inventors conducted extensive research to develop a curable resin composition that gives a cured product with reduced surface gloss.
  • a curable resin composition that gives a cured product with reduced surface gloss.
  • the present invention includes, but is not limited to, the following inventions.
  • a sealing material comprising the curable resin composition according to any one of the preceding items 1 to 7.
  • a camera module comprising the cured product according to 11 above.
  • the curable resin composition of the present invention contains a black colorant and a specific amount of filler, and also contains a combination of a latent curing agent and a phenolic curing agent as a curing agent for curing the epoxy resin. Therefore, the curable resin composition of the present invention gives a cured product with reduced surface gloss.
  • Such a curable resin composition is extremely useful in the manufacture of various semiconductor devices, particularly camera modules, for which reflection of light on the surface of the cured product is a problem.
  • FIG. 1 is an example of a cross-sectional view of a camera module in which an image sensor is connected to a substrate by wire bonding;
  • FIG. 1 is an example of a cross-sectional view of a camera module in which an image sensor is connected to a substrate by flip-chip bonding;
  • FIG. The curable resin compositions of Examples 1 to 6 and Comparative Examples 1 to 5 were heated from room temperature (25°C) to 120°C at a rate of 3°C/min in accordance with JIS K7244-10. , a frequency of 1.000 Hz, a distance between parallel discs of 0.500 mm, and a strain amount of 0.5.
  • the curable resin composition of the present invention essentially comprises (A) an epoxy resin, (B) a latent curing agent, (C) a phenolic curing agent, (D) a black colorant and (E) a filler. as a component of These (A) to (E) will be described below.
  • resin refers not only to macromolecules (especially synthetic polymers), but also to pre-curing molecules used to produce macromolecules.
  • epoxy resin includes materials such as uncured monomers having epoxy groups.
  • the term “camera” means a device for optically capturing an image, provided with an optical system such as a lens for forming an image, and the imaging wavelength range includes the visible light range, the infrared range, and the ultraviolet range. including. Therefore, the “camera” includes not only cameras that mainly capture the visible light region used in devices such as smartphones, tablet computers and notebook PCs, but also thermal cameras and ToF cameras that measure the distance to an object. Also included are cameras that detect wavelengths in the (near) infrared region, which are used in (Time of Flight) devices. The use of the camera is not particularly limited, and it can be used not only for devices such as smartphones, but also for in-vehicle use, counting and inspection in factories, and monitoring inside and outside buildings. Also, in this specification, a “camera module” is a device obtained by modularizing the main part of the camera.
  • Epoxy resin The curable resin composition of the present invention contains an epoxy resin. Epoxy resins are roughly classified into monofunctional epoxy resins and polyfunctional epoxy resins. In the present invention, the epoxy resin preferably contains a polyfunctional epoxy resin. In some aspects of the invention, epoxy resins include multifunctional epoxy resins and monofunctional epoxy resins.
  • a monofunctional epoxy resin is an epoxy resin containing one epoxy group.
  • monofunctional epoxy resins include n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, p-s-butylphenyl glycidyl ether, styrene oxide, ⁇ -pinene oxide, 4-tert.
  • a polyfunctional epoxy resin is an epoxy resin containing two or more epoxy groups. Polyfunctional epoxy resins are roughly classified into aliphatic polyfunctional epoxy resins and aromatic polyfunctional epoxy resins. Aliphatic polyfunctional epoxy resins are polyfunctional epoxy resins having structures that do not contain aromatic rings.
  • aliphatic polyfunctional epoxy resins include: - (poly)ethylene glycol diglycidyl ether, (poly)propylene glycol diglycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, poly Tetramethylene ether glycol diglycidyl ether, glycerin diglycidyl ether, neopentyl glycol diglycidyl ether, 1,2-epoxy-4-(2-methyloxiranyl)-1-methylcyclohexane, cyclohexane type diglycidyl ether, dicyclo diepoxy resins such as pentadiene-type diglycidyl ethers; - triepoxy resins such as trimethylolpropane triglycidyl ether,
  • aromatic polyfunctional epoxy resin is a polyfunctional epoxy resin having a structure containing an aromatic ring.
  • Many conventional epoxy resins such as bisphenol A type epoxy resin, are of this type.
  • aromatic polyfunctional epoxy resins include: - bisphenol A type epoxy resin; - branched polyfunctional bisphenol A type epoxy resins such as p-glycidyloxyphenyldimethyltrisbisphenol A diglycidyl ether; - bisphenol F type epoxy resin; - novolac type epoxy resins; - tetrabromobisphenol A type epoxy resin; - a fluorene-type epoxy resin; - biphenyl aralkyl epoxy resins; - diepoxy resins such as 1,4-phenyldimethanol diglycidyl ether; of tris(4-hydroxyphenyl)methane triglycidyl ether, 4,4′-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]e
  • the epoxy equivalent of the epoxy resin is preferably 80 to 500 g/eq, more preferably 80 to 450 g/eq, even more preferably 80 to 300 g/eq.
  • a silane coupling agent having a reactive functional group such as an epoxy group is not included in the thermosetting resin.
  • the thermosetting resin does not contain silicon atoms.
  • the curable resin composition of the present invention contains a latent curing agent.
  • a latent curing agent is a curing agent for the above epoxy resin, and its curing action is restored by appropriate physical or chemical stimuli (heat, reaction with moisture, electromagnetic waves, ultrasonic waves, mechanical shear, etc.). refers to something that is blocked so that it can be Therefore, in the mixture obtained by mixing the epoxy resin and the latent curing agent, the curing reaction hardly or does not proceed at room temperature, but when the mixture is given an appropriate stimulus, the curing action of the latent curing agent is restored. The curing reaction proceeds.
  • latent curing agents those that are solid and liquid at room temperature (for example, 25° C.) are known.
  • the latent curing agent used in the present invention is preferably solid at 25°C.
  • the curing action of the latent curing agent is substantially not exhibited before heating and can be restored by heating.
  • a latent curing agent whose curing action can be restored by heating is hereinafter referred to as a "thermally activated curing agent". It is particularly preferred that the curing action of the heat-activated latent curing agent can be restored by heating to temperatures above 25°C. In one aspect of the invention, the curing action of the heat-activated latent curing agent is restored even by heating to temperatures of 40 degrees or less.
  • the latent hardener is a heat-activated latent hardener.
  • examples of means for reversibly blocking the hardening action so that it can be restored by heating include modification to substances having a softening point, microencapsulation (encapsulation in microcapsules ) etc. can be mentioned.
  • the heat-activated latent curing agent is a modified amine or microcapsule-type latent curing agent with a softening point.
  • the modified amine having a softening point used in the present invention is solid at 25°C and contains an amine compound.
  • Amine compounds include, for example, aliphatic primary amines, cycloaliphatic primary amines, aromatic primary amines, aliphatic secondary amines, cycloaliphatic secondary amines, aromatic secondary amines, aliphatic tertiary amines, tertiary cycloaliphatic amines, tertiary aromatic amines, imidazole compounds and imidazoline compounds.
  • the amine compound is preferably selected from aliphatic tertiary amines, cycloaliphatic tertiary amines, aromatic tertiary amines, imidazole compounds and imidazoline compounds.
  • Amine compounds may also be used in the form of reaction products with carboxylic acids, sulfonic acids, isocyanates, epoxides and the like. These compounds may be used alone or in combination of two or more.
  • the amine compounds described above can be used in combination with their reaction products with carboxylic acids, sulfonic acids, isocyanates, or epoxides.
  • modified amines with softening points include imidazole compounds and/or tertiary amine compounds.
  • Modified amines with softening points are commercially available, but can also be prepared by known methods. Known methods include the method described in JP-A-2005-206744. Typical examples of commercially available modified amines having a softening point include "Fujicure FXR-1121”, “Fujicure FXR-1020”, “Fujicure FXR-1030", “Fujicure FXR-1081”, and “Fujicure FXR-1032”. ”, “Fujicure FXR-1131” and the like, but are not limited to these.
  • the heat-activated latent hardener is a microencapsulated latent hardener.
  • Microencapsulated latent hardeners are hardeners for epoxy resins whose curing action is reversibly blocked by microencapsulation. In this microcapsule-type latent hardener, the hardening action can optionally be restored by other suitable physical or chemical stimuli (such as mechanical shear) in addition to heating.
  • the curing agent contained in the microcapsule-type latent curing agent is not particularly limited as long as it can cure the epoxy resin. Examples of curing agents contained in microcapsule-type latent curing agents include amine compounds (including imidazole compounds).
  • the microcapsule-type latent curing agent preferably contains an amine compound.
  • Amine compounds include, for example, aliphatic primary amines, cycloaliphatic primary amines, aromatic primary amines, aliphatic secondary amines, cycloaliphatic secondary amines, aromatic secondary amines, aliphatic tertiary amines, tertiary cycloaliphatic amines, tertiary aromatic amines, imidazole compounds and imidazoline compounds.
  • the amine compound is preferably selected from aliphatic tertiary amines, cycloaliphatic tertiary amines, aromatic tertiary amines, imidazole compounds and imidazoline compounds.
  • Amine compounds may also be used in the form of reaction products with carboxylic acids, sulfonic acids, isocyanates, epoxides and the like. These compounds may be used alone or in combination of two or more.
  • the amine compounds described above can be used in combination with their reaction products with carboxylic acids, sulfonic acids, isocyanates, or epoxides.
  • the microencapsulated latent curing agent comprises an imidazole compound.
  • imidazole compounds include imidazole, 2-methylimidazole, 2-ethylimidazole, 1-isobutyl-2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole.
  • 2-phenyl-4-methyl-5-hydroxymethylimidazole 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole, 1 -2-substituted imidazole compounds such as cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole; 1-cyanoethyl-2-undecylimidazolium trimellie Trimellitates such as Tate, 1-cyanoethyl-2-phenylimidazolium trimellitate; 2,4-diamino-6-[(2-methyl-1-imidazolyl)ethyl]s-triazine, 2,4-diamino -Triazine rings such as 6-[(2-undecyl-1
  • imidazole compounds include adducts of imidazole to epoxy resins.
  • imidazole compounds 2-phenyl-4-methylimidazole, 2,4-diamino-6-[(2-methyl-1-imidazolyl)ethyl]s-triazine, 2-phenyl-4-methyl-5- Hydroxymethylimidazole (including isocyanuric acid adducts thereof) and the like are preferred.
  • microcapsule-type latent curing agent used in the present invention is commercially available, but can also be prepared by a known method of microencapsulating the curing agent.
  • Known microencapsulation methods include a method of forming a film with an isocyanate compound on the surface of fine powder particles of a curing agent (WO2004/037885, WO2005/095486). Further, for example, there is a method of coating the surface of fine powder particles of the curing agent with a material capable of forming a film (JP-A-5-247179, JP-A-6-73163, etc.).
  • Typical examples of commercially available microcapsule-type latent curing agents include "Novacure HXA9322HP” (trade name, manufactured by Asahi Kasei Corporation), “Novacure HXA3922HP” (trade name, manufactured by Asahi Kasei Corporation), and “Novacure HXA3932HP”.
  • HP grade curing agents are preferred for electronic materials due to their low chlorine content.
  • the microcapsule-type latent curing agent is provided in the form of a dispersion containing a liquid epoxy resin and a microcapsulated curing agent dispersed therein, such as a powder made of an amine compound. be.
  • a liquid epoxy resin such as a powder made of an amine compound.
  • a microcapsulated curing agent dispersed therein, such as a powder made of an amine compound.
  • the amount of this liquid epoxy resin is also included in the amount of the above (A) epoxy resin in the curable resin composition of the present invention.
  • the latent curing agent or heat-activated latent curing agent contains an amine compound.
  • examples of usable amine compounds are the same as those for the microcapsule-type latent curing agent.
  • the curable resin composition of the present invention may contain the latent curing agent singly or in combination of two or more. Moreover, the curable resin composition of the present invention may contain a latent curing agent in combination with other forms of curing agents within a range that does not impair the effects of the present invention. In some embodiments, the latent curing agent does not contain phenolic compounds.
  • the curable resin composition of the present invention preferably contains a latent curing agent in an amount of 0.1 to 50% by weight with respect to the total of (A) the epoxy resin and (C) the phenolic curing agent, and 1 to 30% by weight. % by weight is more preferred, and 1 to 20% by weight is particularly preferred.
  • the curable resin composition of the present invention contains a latent curing agent.
  • a curable resin composition containing a non-latent curing agent has a high temperature at which the viscosity becomes the lowest when heated for curing.
  • the temperature at which the viscosity is lowest is typically 75° C. or higher.
  • the imidazole compound dissolves in the epoxy resin and then immediately diffuses, it forms a salt with the phenolic curing agent, making it difficult for the reaction between the epoxy resin or between the epoxy resin and the phenolic curing agent to proceed. Therefore, it is inferred that the temperature at which the minimum viscosity is reached increases.
  • the curable resin composition of the present invention containing a latent curing agent has a minimum viscosity temperature of 70° C. or lower, preferably 60° C. or lower. Even if such a resin composition is heated for curing, the curing action of the latent curing agent is not instantly restored, so it is thought that it is difficult to form a salt with the phenolic curing agent. For this reason, it is difficult for the composition to reach a low-viscosity state before it loses fluidity, and curing of the composition is completed before a glossy and smooth surface is formed.
  • the curable resin composition of the present invention contains a phenolic curing agent.
  • Phenolic hardeners are not latent.
  • the phenolic curing agent is not particularly limited as long as it contains a phenolic compound that has a free phenolic hydroxyl group and is capable of curing the (A) epoxy resin.
  • a phenolic resin particularly a novolac resin obtained by condensing phenols or naphthols (eg, phenol, cresol, naphthol, alkylphenol, bisphenol, terpenephenol, etc.) with formaldehyde is preferably used.
  • novolak resins examples include phenol novolak resin, o-cresol novolak resin, p-cresol novolak resin, ⁇ -naphthol novolak resin, ⁇ -naphthol novolak resin, t-butylphenol novolak resin, bisphenol A type novolak resin, and xylylene-modified novolak resin. resins, decalin-modified novolak resins, allylated phenol novolak resins, and the like.
  • phenolic resins examples include dicyclopentadiene cresol resin, polyparavinylphenol, poly(di-o-hydroxyphenyl)methane, poly(di-m-hydroxyphenyl)methane and poly(di-p-hydroxyphenyl ) methane and the like. These phenol compounds may be used alone or in combination of two or more. From the viewpoint of workability, the phenolic curing agent is preferably liquid at 25°C. Moreover, from the viewpoint of suppressing the surface gloss of the cured product, an allylated phenol novolac resin is preferable.
  • the curable resin composition of the present invention contains an excessive amount of phenolic curing agent, curing may be delayed. As a result, the time for which the composition exhibits fluidity (leveling property) to some extent or more is extended, and the surface gloss of the cured product produced by curing may not be reduced. Therefore, in the present invention, [(C) the total number of hydroxyl groups in the phenolic curing agent]/[(A) the total number of epoxy groups in the epoxy resin] is preferably 0.01 to 0.5. .
  • [(C) the total number of hydroxyl groups in the phenolic curing agent]/[(A) the total number of epoxy groups in the epoxy resin] is more preferably 0.3 or less, more preferably 0.1 or less. is more preferable.
  • [(C) the total number of hydroxyl groups in the phenolic curing agent]/[(A) the total number of epoxy groups in the epoxy resin] is more preferably 0.01 to 0.3, and still more preferably 0.01. 0.2, particularly preferably 0.01 to 0.1.
  • the total number of epoxy groups for an epoxy resin is the quotient of the mass (g) of the epoxy resin divided by the epoxy equivalent weight of that epoxy resin (if more than one type of epoxy resin is involved, such a quotient for each epoxy resin). ).
  • the epoxy equivalent can be determined by the method described in JIS K7236. If the epoxy equivalent cannot be obtained by this method, it may be calculated as a quotient obtained by dividing the molecular weight of the epoxy resin by the number of epoxy groups in one molecule of the epoxy resin.
  • the total number of hydroxyl groups for a phenolic curing agent is the quotient of the weight (g) of the phenolic curing agent divided by the hydroxyl equivalent weight of the phenolic curing agent (if more than one type of phenolic curing agent is included, each is the sum of such quotients for phenolic hardeners).
  • the hydroxyl equivalent can be determined by the method described in JIS K0070. This method of obtaining is also described in JP-A-2017-210613, WO2019/189023, and the like. If the hydroxyl equivalent cannot be obtained by this method, it may be calculated as a quotient obtained by dividing the molecular weight of the phenolic curing agent by the number of hydroxyl groups in one molecule of the phenolic curing agent.
  • the curable resin composition of the present invention contains (D) a black colorant.
  • a black colorant is a compound that colors black by absorbing light with a wavelength of visible light (380 to 780 nm). Specific examples include pigments and dyes. If the light transmittance of the cured product of the curable resin composition that seals the metal wiring in the camera module is high, the light reflected by the gold bumps, gold wires, and other wiring causes problems such as flare phenomenon. may cause Since the curable resin composition of the present invention contains a black colorant, the influence of unintended light on the image sensor (imaging device) in the camera module is further reduced.
  • the black colorant is not particularly limited, but black pigments such as black organic pigments, mixed color organic pigments, inorganic black pigments (carbon black, titanium black, etc.), black organic dyes, and the like can be used.
  • black organic pigments include perylene black, and examples of black organic dyes include aniline black.
  • mixed-color organic pigments include pseudo-blackened pigments obtained by mixing at least two kinds of pigments selected from red, blue, green, purple, yellow, magenta, cyan, and the like.
  • inorganic black pigments include fine particles of graphite, metals and their oxides (including composite oxides), sulfides, and nitrides.
  • the metals include titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver and the like.
  • the black pigment may be used alone or in combination of two or more. Black pigments may also be used in combination with other colorants such as dyes.
  • the black colorant preferably contains a black pigment from the viewpoint of concealability.
  • the black pigment preferably contains an inorganic black pigment, and more preferably contains carbon black and/or titanium black.
  • the black colorant is preferably a dye.
  • the average particle size of the primary particles of the black pigment is preferably 20-200 nm, more preferably 50-150 nm.
  • the average particle diameter of the primary particles of the black pigment refers to the volume-based median diameter (d50) measured by the laser diffraction method according to ISO-13320 (2009). If the measurement by the laser diffraction method is difficult (for example, if the object to be measured contains fine particles to which the laser diffraction method is difficult to apply), the average particle size of the primary particles to be measured may be measured by another measurement method. good. Examples of other measuring methods include measurement by observation with a scanning electron microscope (SEM), dynamic light scattering method, calculation from specific surface area, and the like.
  • SEM scanning electron microscope
  • the black colorant is preferably 0.01 to 10 mass % of the curable resin composition.
  • the black colorant is carbon black, it is preferably 0.01 to 5% by mass, more preferably 0.05 to 4% by mass of the curable resin composition.
  • the black colorant is titanium black, it is preferably 0.1 to 10% by mass, more preferably 0.1 to 8% by mass of the curable resin composition.
  • the curable resin composition of the present invention contains a filler.
  • a filler in the curable resin composition of the present invention, the gloss of the cured product is further suppressed, and as a result, flare can be effectively prevented.
  • the reason why the gloss of the cured product is suppressed is that the filler gives an irregular structure to the surface of the cured product, so that specular reflection is further reduced when the cured product is irradiated with light.
  • the filler is not particularly limited, and various known fillers can be used. Specific examples of fillers include inorganic fillers such as silica fillers, alumina fillers, talc fillers and calcium carbonate fillers, and organic fillers such as polytetrafluoroethylene (PTFE) fillers, acrylic polymer fillers and silicone fillers. .
  • the filler comprises silica filler or silicone filler, preferably silica filler.
  • the filler may be surface-treated with a surface-treating agent such as a silane coupling agent (which may have a substituent such as a phenyl group, a vinyl group, an acryloyl group, or a methacryloyl group).
  • the filler is surface-treated from the viewpoint of easy maintenance of fluidity even when the filler is highly filled. In another aspect, it is preferable that the filler is not surface-treated so as not to excessively reduce the minimum viscosity of the curable resin composition during heating.
  • the particle size distribution, average particle size, etc. of the filler are not particularly limited, it is preferable to use a filler having an average particle size of 20.0 ⁇ m or less.
  • the average particle size of the filler is preferably 15.0 ⁇ m or less, more preferably 10.0 ⁇ m or less. If the average grain size exceeds 20.0 ⁇ m, it may become difficult to inject into narrow gaps.
  • the lower limit of the average particle size of the filler is not particularly limited. It is preferable to use a fine filler having an average particle size of about 0.005 to 0.05 ⁇ m because the minimum viscosity during heating does not become too low.
  • the average particle diameter of the filler used in the present invention is preferably 0.005 ⁇ m or more and 10.0 ⁇ m or less, more preferably 0.005 ⁇ m or more and 5.0 ⁇ m or less, still more preferably 0.005 ⁇ m or more, It is 3.0 ⁇ m or less.
  • the average particle diameter of the filler refers to the volume-based median diameter (d50) measured by the laser diffraction method according to ISO-13320 (2009).
  • the filler used in the present invention preferably has a spherical shape from the viewpoint of dischargeability from a dispenser.
  • the amount of (E) filler is 20 to 60% by volume relative to the entire curable resin composition.
  • the amount of filler is the sum of the amounts of all fillers. If the amount of the filler is less than 20% by volume relative to the entire curable resin composition, the resin component is relatively increased, and the surface of the cured product tends to be glossy.
  • the amount of the filler is preferably 25% by volume or more, more preferably 30% by volume or more, and particularly preferably 35% by volume or more, relative to the entire curable resin composition.
  • the amount of filler exceeds 60% by volume, the amount of the resin component is relatively small, so there is concern about deterioration of the fluidity of the curable resin composition and deterioration of the mechanical properties of the cured product.
  • the amount of filler is preferably 57% by volume or less, more preferably 55% by volume or less, relative to the entire curable resin composition. In one aspect, the amount of the filler is preferably 25 to 60% by volume, more preferably 25 to 57% by volume, and particularly preferably 25 to 55% by volume, based on the total curable resin composition. .
  • the ratio (% by volume) of the volume of the filler to the volume of the entire curable resin composition is obtained by, for example, obtaining cross-sectional image data of the cured product of the curable resin composition at a magnification of 3000 times, using appropriate image processing software, It can be obtained by subjecting it to appropriate image processing including binarization processing and the like. Image data can be acquired, for example, using a scanning electron microscope (SEM). Also, this volume ratio (% by volume) may be obtained by calculation from the mass and specific gravity of the entire curable resin composition and the filler.
  • Patent Document 3 discloses the use of a black coloring agent and/or a filler to suppress flare during imaging with a camera.
  • the invention of Patent Document 3 relates to an antireflection layer provided on a flexible printed circuit board or an antireflection film attached to the same circuit board in order to suppress reflection of light from the flexible printed circuit board inside the camera. It does not relate to curable resin compositions or encapsulants.
  • the curable resin composition of the present invention may optionally contain optional components other than the above (A) to (E), such as those described below, if desired.
  • the curable resin composition of the present invention may contain a stabilizer, if desired.
  • a stabilizer can be added to the curable resin composition of the present invention in order to improve its storage stability and prolong its pot life.
  • Various known stabilizers can be used as stabilizers for one-liquid type adhesives, but they are selected from the group consisting of boric acid ester compounds, aluminum chelates and organic acids because of their high effect of improving storage stability. are preferred, and at least one selected from the group consisting of liquid borate compounds and aluminum chelates is more preferred.
  • borate ester compounds include 2,2′-oxybis(5,5′-dimethyl-1,3,2-oxaborinane), trimethylborate, triethylborate, tri-n-propylborate, triisopropylborate, tri - n-butylborate, tripentylborate, triallylborate, trihexylborate, tricyclohexylborate, trioctylborate, trinonylborate, tridecylborate, tridodecylborate, trihexadecylborate, trioctadecylborate, tris(2 -ethylhexyloxy)borane, bis(1,4,7,10-tetraoxaundecyl)(1,4,7,10,13-pentaoxatetradecyl)(1,4,7-trioxaundecyl) Borane, tribenzylborate, triphenyl
  • liquid borate ester compound is liquid at room temperature (25° C.), it is preferable because the viscosity of the formulation can be kept low.
  • aluminum chelate for example, aluminum chelate A (manufactured by Kawaken Fine Chemicals Co., Ltd.) can be used.
  • organic acid for example, barbituric acid can be used.
  • the amount of the stabilizer is 0.01 to 20 parts by mass with respect to 100 parts by mass of the total amount of components (A) to (C). It is preferably from 0.05 to 10 parts by mass, and even more preferably from 0.1 to 5 parts by mass.
  • the curable resin composition of the present invention may contain a coupling agent, if desired.
  • Addition of a coupling agent, particularly a silane coupling agent, is preferable from the viewpoint of improving adhesive strength.
  • a silane coupling agent is an organosilicon compound having two or more different functional groups in its molecule, including a functional group that can chemically bond with an inorganic material and a functional group that can chemically bond with an organic material.
  • a functional group capable of chemically bonding with an inorganic material is a hydrolyzable silyl group, and an alkoxy group, especially a silyl group containing a methoxy group and/or an ethoxy group is used as this functional group.
  • silane coupling agents As functional groups capable of chemically bonding with organic materials, vinyl groups, epoxy groups, (meth)acrylic groups, styryl groups, unsubstituted or substituted amino groups, mercapto groups, ureido groups, isocyanate groups and the like are used.
  • the coupling agent various silane coupling agents having the above functional groups can be used. Specific examples of silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, vinyltrimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene).
  • silane coupling agents may be used alone or in combination of two or more.
  • the amount of the coupling agent is 0.1 to 10 parts by mass with respect to 100 parts by mass of the total amount of components (A) to (C) from the viewpoint of improving adhesive strength. is preferred, and 0.3 to 5 parts by mass is more preferred.
  • the curable resin composition of the present invention may contain other additives, such as ion trapping agents, leveling agents, antioxidants, antifoaming agents, if desired, within the scope of the present invention. , flame retardants, solvents, and the like.
  • the type and amount of each additive are as per conventional methods.
  • the curable resin composition of the present invention does not contain a thiol compound. This is because the thiol compound may cause metal corrosion when the curable resin composition of the present invention is used to seal wiring.
  • the curable resin composition is substantially free of thiol compounds.
  • the method for producing the curable resin composition of the present invention is not particularly limited.
  • components (A) to (E) and, if desired, other additives are simultaneously or separately introduced into a suitable mixer and mixed by stirring while melting by heating if necessary, By forming a uniform composition, the curable resin composition of the present invention can be obtained.
  • the mixer is not particularly limited, but a Raikai machine equipped with a stirring device and a heating device, a Henschel mixer, a three-roll mill, a ball mill, a planetary mixer, a bead mill, or the like can be used. Also, these devices may be used in combination as appropriate.
  • the curable resin composition thus obtained can be converted into a final cured product by subjecting it to a heat curing treatment, as described above.
  • a heat curing treatment can be performed by heating the curable resin composition of the present invention under appropriate conditions. This heating is preferably carried out at 80 to 250°C, more preferably at 90 to 180°C, particularly preferably at 90 to 150°C. This heating is preferably carried out for 1 second to 120 minutes, more preferably for 10 seconds to 90 minutes, particularly preferably for 15 seconds to 70 minutes.
  • the curable resin composition of the present invention When the curable resin composition of the present invention is subjected to the above heat curing treatment, it gives a cured product with reduced surface gloss.
  • the reason why the gloss is reduced is that there is a structure with fine bumps on the surface of this cured product, and when it is irradiated with light, the reflection is mainly diffuse reflection, and the specular reflection is reduced. is.
  • This fine protrusion structure is produced by reflecting the shape of the (E) filler contained in the composition on the surface of the cured product.
  • a curable resin composition when a curable resin composition is subjected to heat curing treatment, its viscosity decreases as the temperature rises, and its fluidity (leveling property) increases.
  • the curable resin composition before curing remains in such a state for a certain amount of time or more, curing occurs while a smooth resin layer is formed on the surface of the curable resin composition due to its fluidity.
  • the surface of the cured product becomes smooth, making it difficult to reduce the glossiness of the surface of the cured product.
  • the curable resin composition of the present invention does not significantly decrease its viscosity and does not significantly increase its fluidity (leveling property) even when heated for curing.
  • the curable resin composition of the present invention has a temperature increase rate of 3° C./min, a temperature range of 25° C. to 120° C., a frequency of 1.000 Hz, and a distance between parallel discs of 0 in accordance with JIS K7244-10.
  • the minimum absolute value of the complex shear viscosity in the above temperature range is 1.5 Pa ⁇ s or more when the dynamic viscoelasticity measurement is performed under the conditions of 0.5 mm and 0.5 strain.
  • complex shear viscosity may be simply referred to as "complex shear viscosity".
  • minimum value of such complex shear viscosity observed in dynamic viscoelasticity measurement is sometimes referred to as “minimum viscosity”.
  • the same composition initiates the curing reaction and accompanying thickening at relatively low temperatures. This is suggested by the relatively low temperature at which the complex shear viscosity is minimized in dynamic viscoelasticity measurements of the same composition.
  • the time for which the composition exhibits fluidity (leveling property) to a certain extent is limited, curing is completed before a smooth resin layer is formed on the surface of the curable resin composition, and the glossiness of the surface is reduced. A reduced cured product is produced.
  • the curable resin composition of the present invention has a temperature increase rate of 3° C./min, a temperature range of 25° C. to 120° C., a frequency of 1.000 Hz, and a distance between parallel discs of 0 in accordance with JIS K7244-10.
  • the temperature at which the complex shear viscosity becomes minimum is 55° C. or less. Therefore, in an assembly in which the parts are joined using the curable resin composition of the present invention, the problem caused by specular reflection of light can be solved. For example, in a camera module manufactured using the curable resin composition of the present invention, flare during imaging is greatly suppressed.
  • the curable resin composition of the present invention preferably exhibits a certain degree of thixotropy. This is because when the composition is heated for curing, convection due to the heating is suppressed, and the dispersed state of the filler in the composition is maintained. Thus, when the thixotropic index of the same composition is large, the dispersed state of the filler is maintained even during heating, so that the dispersed filler hardly settles. Since the filler is dispersed in the composition without sedimentation, the shape of the filler is easily reflected on the surface of the cured product, and the glossiness of the surface of the cured product is easily reduced.
  • the curable resin composition of the present invention preferably has a thixotropic index of 1.0 to 5.5, more preferably 1.1 to 5.5, still more preferably 1.2 to 5.0. is.
  • the thixotropic index is obtained by measuring the curable resin composition at 25 ° C ⁇ 2 ° C and 50% RH ⁇ 10% RH with an E-type viscometer (TVE-25H: manufactured by Toki Sangyo Co., Ltd., rotor name: 3 ° ⁇ R9 .7), measured at 1 rpm and 10 rpm in the appropriate preset range (H, R, or U), and calculated as a value of 1 rpm/10 rpm.
  • E-type viscometer TVE-25H: manufactured by Toki Sangyo Co., Ltd., rotor name: 3 ° ⁇ R9 .7
  • the curable resin composition of the present invention since the curable resin composition of the present invention has a specific structure, it is possible to secure a certain degree of viscosity or higher even at room temperature. This is because, if the viscosity is above a certain level at room temperature, the minimum viscosity during heating is less likely to decrease.
  • the epoxy resin composition of the present invention has a viscosity at 25° C. that is not too low, typically 5 Pa ⁇ s or more.
  • the epoxy resin composition of the present invention preferably has a viscosity at 25° C. of 3 Pa ⁇ s or more, more preferably 5 Pa ⁇ s or more, and even more preferably 8 Pa ⁇ s or more.
  • the viscosity at 25° C. is preferably 100 Pa ⁇ s or less.
  • the viscosity is expressed as a value measured according to Japanese Industrial Standard JIS K6833. Specifically, it can be obtained by measuring with an E-type viscometer at a rotation speed of 10 rpm. There are no particular restrictions on the equipment, rotors, or measurement range to be used.
  • the glossiness of the surface of an object can be evaluated by specular glossiness measured at an incident angle of 20° in accordance with JIS Z 8741.
  • the specular gloss of the cured product provided by the curable resin composition of the present invention is preferably 10% or less, more preferably 5% or less when the film thickness of the cured product is 100 ⁇ m or more.
  • the curable resin composition of the present invention can be used as an adhesive or sealing material.
  • the curable resin composition of the present invention can be used for manufacturing camera modules. More specifically, the resin composition of the present invention can be used for bonding and sealing camera module parts, particularly for sealing wiring connecting an image sensor and a substrate in a camera module.
  • the present invention also provides a sealing material containing the curable resin composition of the present invention.
  • the sealing material of the present invention is suitable, for example, for sealing wiring that connects an image sensor and a substrate in a camera module.
  • the image sensor and the substrate are connected by wire bonding.
  • the wiring that connects the image sensor and the substrate is a bonding wire.
  • FIG. 1 shows an example of a cross-sectional view of a camera module in which an image sensor is connected to a substrate by wire bonding.
  • wiring (bonding wires) connecting the image sensor and the substrate is sealed with a cured adhesive 10 .
  • the adhesive may be an encapsulant.
  • the image sensor and substrate are connected by flip-chip bonding.
  • FIG. 2 shows an example of a cross-sectional view of a camera module in which an image sensor is connected to a substrate by flip-chip bonding.
  • wiring (bumps) connecting the image sensor and the substrate are sealed with a cured adhesive 102 .
  • the adhesive may be an encapsulant.
  • the curable resin composition or sealing material of the present invention is for flare prevention in imaging.
  • the curable resin composition or encapsulating material of the present invention for providing a cured product having a fine projection structure on its surface is also provided.
  • the curable resin composition of the present invention is, for example, a semiconductor device containing various electronic components (especially those in which it is important to suppress reflection of light inside), and parts that constitute electronic components. It can be used as an adhesive or a raw material thereof.
  • the present invention also provides a cured product obtained by curing the curable resin composition or sealing material of the present invention.
  • the present invention further provides a camera module containing the cured product of the present invention.
  • Examples 1-6, Comparative Examples 1-6 A curable resin composition was prepared according to the formulation shown in Table 1 by mixing predetermined amounts of each component using a three-roll mill. In Table 1, the amount of each component is expressed in parts by mass (unit: g).
  • (A) Epoxy resin In the examples and comparative examples, the compounds used as (A) the epoxy resin are as follows.
  • (A-3) Bisphenol F type epoxy resin/bisphenol A type epoxy resin mixture (trade name: EXA-835LV, manufactured by DIC Corporation, epoxy equivalent: 165)
  • (B) Latent Curing Agent The compounds used as the (B) latent curing agent in Examples and Comparative Examples are as follows.
  • (B-1) Latent curing agent 1 (trade name: Novacure HXA3932HP, manufactured by Asahi Kasei Corporation)
  • Latent curing agent 2 (trade name: Novacure HXA9322HP, manufactured by Asahi Kasei Corporation)
  • Latent curing agent 3 (trade name: Novacure HXA5945HP, manufactured by Asahi Kasei Corporation)
  • Latent curing agent 4 (trade name: Fujicure FXR1121, manufactured by T&K TOKA Co., Ltd.)
  • the epoxy resin that constitutes this dispersion is treated as part of (A). Therefore, in Table 1, the amount of only the latent curing agent in (B-1) to (B-3) is shown in column (B), and the amount of epoxy resin in (B-1) to (B-3) is shown. Amounts are given in column (A).
  • (C) Phenolic Curing Agent Compounds used as (C) phenolic curing agent in Examples and Comparative Examples are as follows.
  • (C') Curing Agents Other than (B) or (C) above Compounds used as curing agents other than (B) or (C) above in Examples and Comparative Examples are as follows.
  • (D) Black Coloring Agent The compound used as the (D) black coloring agent in Examples and Comparative Examples is as follows.
  • (E) Filler Compounds used as (E) filler in Examples and Comparative Examples are as follows.
  • (E-3) Silica filler 3 (trade name: Seahoster (registered trademark) KE-S30HG, average particle size 0.3 ⁇ m, manufactured by Nippon Shokubai Co., Ltd.)
  • Surface-treated silica filler (trade name: Aerosil (registered trademark) R805, manufactured by Nippon Aerosil Co., Ltd., average particle size 12 nm, surface-treated with oc
  • the specific gravity of (A), (B), (C) and (C'-1) is 1.1 g/ cm3
  • the specific gravity of (C'-2) is 1.2 g/ cm3
  • the specific gravity of (D) is The specific gravity is 1.9 g/cm 3
  • the specific gravity of (E-1) to (E-3) and (E-5) is 2.2 g/cm 3
  • the specific gravity of (E-4) is 0.99 g/cm 3 cm 3 and the volume ratio (% by volume) of the (E) filler to the entire curable resin composition was determined from the mass of each component.
  • the results are shown in Table 1 as "(E) amount of filler (% by volume)".
  • the complex shear viscosity (Pa s) of the curable resin composition was measured using a rheometer (MARS II, manufactured by HAAKE) according to JIS K7244-10, and the temperature was raised from room temperature (25 ° C.) to 120 ° C. Measurement was performed under the conditions of a frequency of 1.000 Hz, a distance between parallel discs of 0.500 mm, and a strain amount of 0.5 while increasing the temperature at a rate of 3° C./min.
  • Table 1 shows the temperature at which the complex shear viscosity becomes minimum in the above temperature range and the complex shear viscosity (minimum viscosity) at that time for each curable resin composition.
  • FIG. 3 shows changes in complex shear viscosity with temperature for the curable resin compositions of Examples 1 to 6 and Comparative Examples 1 to 5 during the dynamic viscoelasticity measurement.
  • Viscosity at 25°C The viscosity (unit: Pa s) of the curable resin composition was measured using a Brookfield E-type rotational viscometer (TVE-25H: manufactured by Toki Sangyo Co., Ltd., rotor name: 3 ° ⁇ R9.7). Measured under conditions of 25° C. and 10 rpm. Table 1 shows the results.
  • the viscosity (unit: Pa ⁇ s) of the curable resin composition was measured under the same conditions as the above "viscosity at 25°C” except that the rotation speed was 1 rpm.
  • the thixotropic index (TI) of the curable resin composition was calculated as a value obtained by dividing the "viscosity at 25°C” by this viscosity. Table 1 shows the results.
  • a curable resin composition coated on a 40 mm ⁇ 60 mm ⁇ 3 mm SUS plate is heated at 120 ° C. for 1 hour in a precision thermostat DH412 manufactured by Yamato Scientific Co., Ltd. to obtain a cured product having a thickness of 300 ⁇ 20 ⁇ m. Formed on a plate. The obtained cured product on the SUS plate was used as a test piece.
  • the specular glossiness (%) of the surface of this test piece was measured using a gloss checker IG-331 (light source: LED (wavelength 890 nm)) manufactured by Horiba, Ltd., according to the provisions of JIS Z 8741, incident angle 20 °, light receiving Measured under the condition of an angle of 20°. Table 1 shows the results.
  • the curable resin composition of the present invention which contains a black colorant and a specific amount of filler, and contains a combination of a latent curing agent and a phenolic curing agent, gives a cured product with significantly reduced surface gloss ( Examples 1-6). This is because even when this composition is heated for curing, it exhibits fluidity (leveling) to a certain extent or more for a limited time only, so that a smooth resin layer is formed on the surface of this composition. This is because curing is completed before the
  • curable resin compositions containing no fillers or containing curing agents other than the above combinations give cured products with unreduced surface gloss (Comparative Examples 1 to 5). This is because the leveling time of the composition when heated for curing is long enough to form a smooth resin layer on the surface of the composition prior to curing. Moreover, a curable resin composition containing no black colorant gives a cured product with high light transmittance. If the cured product is a thin film formed on a metal plate, it is difficult to measure the specular glossiness of the surface of the cured product because of the light reflected by the metal plate and transmitted through the cured product (Comparative Example 6). When such a composition is used to seal metal wiring in a semiconductor device, the light reflected by the wiring may cause problems such as a flare phenomenon.
  • the curable resin composition of the present invention contains a black colorant and a specific amount of filler, and also contains a combination of a latent curing agent and a phenolic curing agent as a curing agent for curing the epoxy resin. Therefore, the curable resin composition of the present invention gives a cured product with reduced surface gloss.
  • Such a curable resin composition is extremely useful in the manufacture of various semiconductor devices, particularly camera modules, for which reflection of light on the surface of the cured product is a problem.

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