Classifications

• • 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
  • 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
  • C08G59/20—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 epoxy compounds used
  • C08G59/22—Di-epoxy compounds
  • C08G59/24—Di-epoxy compounds carbocyclic
• • 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
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
  • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
  • C08G65/16—Cyclic ethers having four or more ring atoms
  • C08G65/18—Oxetanes
• • 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
  • C08K7/00—Use of ingredients characterised by shape
  • C08K7/22—Expanded, porous or hollow particles
• • 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

Definitions

• the present invention relates to a curable composition.
• a curable composition used as an adhesive for fixing members is required to be able to form a cured product with a low coefficient of thermal expansion in order to prevent minute displacement. Furthermore, when used as an adhesive in places where the influence of vibration is a concern, the curable composition is required to be able to form a cured product with a low elastic modulus in order to reduce the influence of vibration (Patent Document 1) .
• the present invention was made in view of the above-mentioned circumstances, and an object of the present invention is to provide a curable composition that can form a cured product that has both a low coefficient of thermal expansion and a low modulus of elasticity.
• the present inventors have discovered a curable composition containing an epoxy compound having two or more alicyclic epoxy groups, an inorganic filler, hollow organic polymer particles, and a cationic polymerization initiator. It was discovered that a cured product having both a low coefficient of thermal expansion and a low modulus of elasticity can be formed, and the present invention was completed.
• the present invention based on such knowledge is as follows.
• a cured product having both a low coefficient of thermal expansion and a low modulus of elasticity can be formed, so the curable composition of the present invention is very useful for adhesion of optical devices. be.
• each component contained in the curable composition of the present invention will be explained in order. Unless otherwise specified, each component may be used alone or in combination of two or more.
• the curable composition of the present invention contains, as component (A), an epoxy compound having two or more alicyclic epoxy groups (herein sometimes referred to as an "alicyclic epoxy compound").
• alicyclic epoxy groups In curing by cationic polymerization, alicyclic epoxy groups have higher reactivity than terminal epoxy groups such as glycidyl ether, so the curable composition of the present invention has good curability.
• epoxy compounds compared to (meth)acrylates and vinyl ethers commonly used in curable compositions, epoxy compounds have a low curing shrinkage rate, so the curable composition of the present invention has low curing shrinkage and precision fixation. Suitable for adhesives.
• alicyclic epoxy group refers to an alicyclic group and an oxirane ring in which two adjacent carbon atoms constituting the alicyclic group form an oxirane ring (epoxy group) with an oxygen atom.
• the alicyclic epoxy compound may have an alicyclic condensed alicyclic structure in which a plurality of alicyclic epoxy groups are condensed at an alicyclic moiety.
• the number of alicyclic epoxy groups in the alicyclic epoxy compound is preferably 2 to 4, particularly preferably 2.
• alicyclic epoxy compounds include formulas (I) to (III):
• L 1 represents a single bond, or a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, a carbonate bond, an amide bond, or a group in which a plurality of these are connected;
• L 2 to L 7 each independently represent a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, a carbonate bond, an amide bond, or a group in which a plurality of these are connected.
• Examples include compounds represented by any of the following.
• the "compound represented by formula (I)” may be abbreviated as “compound (I)”
• the compounds represented by other formulas may also be abbreviated in the same way.
• the divalent hydrocarbon group is preferably an alkylene group having 1 to 18 carbon atoms or a divalent alicyclic hydrocarbon group having 5 to 7 carbon atoms.
• the alkylene group having 1 to 18 carbon atoms may be either linear or branched. Examples of the alkylene group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a trimethylene group, and a propylene group.
• the divalent alicyclic hydrocarbon group having 5 to 7 carbon atoms is preferably a cycloalkylene group having 5 to 7 carbon atoms or a cycloalkylidene group having 5 to 7 carbon atoms.
• Examples of the cycloalkylene group having 5 to 7 carbon atoms include 1,2-cyclopentylene group, 1,3-cyclopentylene group, 1,2-cyclohexylene group, 1,3-cyclohexylene group, 1, A 4-cyclohexylene group is mentioned.
• Examples of the cycloalkylidene group having 5 to 7 carbon atoms include a cyclopentylidene group and a cyclohexylidene group.
• Preferred compounds (I) include, for example, formulas (I-1) to (I-8):
• n1 represents an integer from 1 to 30, n2 represents an integer of 6 to 30, and L 8 represents an alkylene group having 1 to 8 carbon atoms.
• Examples include compounds represented by any of the following.
• Compound (I-6) and compound (I-8) may be a mixture of compounds each having a different number of repeating units.
• n1 in formula (I-6) is preferably an integer of 1 to 6.
• the alkylene group having 1 to 8 carbon atoms in formula (I-8) may be linear or branched.
• Examples of the alkylene group having 1 to 8 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, and an octamethylene group. It will be done.
• Preferred compounds (II) include, for example, formula (II-1):
• n3 and n4 each independently represent an integer of 2 to 30.
• Examples include compounds represented by: Compound (II-1) may be a mixture of compounds having different numbers of repeating units.
• Preferred compounds (III) include, for example, formula (III-1):
• n5 to n8 each independently represent an integer of 2 to 30.
• Examples include compounds represented by: Compound (III-1) may be a mixture of compounds having different numbers of repeating units.
• the alicyclic epoxy compound is preferably selected from compounds (I-1) to (I-8), compound (II-1) and compound (III-1).
• the alicyclic epoxy compound is more preferably selected from compounds (I-1) to (I-7).
• the alicyclic epoxy compound is more preferably selected from compound (I-1) and compound (I-3).
• the molecular weight of the alicyclic epoxy compound is preferably less than 1000, more preferably 900 or less, further preferably 800 or less, even more preferably 700 or less, and even more preferably 600 or less. Particularly preferred. Further, the lower limit of the molecular weight of the alicyclic epoxy compound is not particularly limited, but from the viewpoint of suppressing outgas generation, the molecular weight is preferably 100 or more, more preferably 125 or more, and particularly preferably 150 or more.
• the molecular weight of the alicyclic epoxy compound is the weight average molecular weight (hereinafter referred to as (sometimes abbreviated as "Mw"). This Mw can be calculated, for example, by gel permeation chromatography (GPC) in terms of polystyrene.
• GPC gel permeation chromatography
• the viscosity (25° C.) of the alicyclic epoxy compound is preferably 10 to 3000 mPa ⁇ s, more preferably 25 to 2000 mPa ⁇ s, from the viewpoint of the fluidity of the curable composition at room temperature.
• viscosity (25 degreeC) means the viscosity at 25 degreeC measured using the vibration viscometer.
• the epoxy equivalent of the alicyclic epoxy compound is preferably 50 to 500 g/eq, more preferably 75 to 450 g/eq, particularly preferably 90 to 400 g/eq.
• the "epoxy equivalent" of an epoxy compound means the number of grams of the epoxy compound containing 1 gram equivalent of epoxy groups. This epoxy equivalent value can be determined according to the method specified in JIS K 7236. Moreover, the epoxy equivalent can be theoretically calculated by dividing the molecular weight of the epoxy compound by the number of epoxy groups that the epoxy compound has.
• the content of component (A) is preferably 20.0% by mass or more, and 30% by mass, based on the resin content of the curable composition, from the viewpoint of good curability of the curable composition and low coefficient of thermal expansion of the cured product.
• the content is more preferably 40% by mass or more, particularly preferably 40% by mass or more.
• the content of component (A) is preferably 99.99% by mass or less, more preferably 99.9% by mass or less, particularly preferably 99.8% by mass or less, based on the resin content of the curable composition.
• the "resin component of the curable composition” refers to the "alicyclic epoxy compound” of component (A), which is an essential component, and the “two or more oxetanyl groups described below, which is an optional component. It means the total amount of “oxetane compound” and “polyester polyol”.
• the content of component (A) is preferably 3% by mass or more, and 5% by mass or more based on the solid content of the curable composition, from the viewpoint of good curability of the curable composition and a low coefficient of thermal expansion of the cured product.
• the content is more preferably 10% by mass or more, particularly preferably 10% by mass or more.
• the content of component (A) is 80% by mass per solid content of the curable composition. % or less, more preferably 70% by mass or less, particularly preferably 60% by mass or less.
• the curable composition of the present invention contains an inorganic filler as component (B).
• the inorganic filler contributes to a low coefficient of thermal expansion of the cured product and improves the filling property of hollow organic polymer particles (component (C) described later) into the curable composition.
• component (C) hollow organic polymer particles
• the filling properties of the hollow organic polymer particles are low, and without the use of the filler itself, the hollow styrene particles cannot be sufficiently dispersed and a uniform composition cannot be obtained.
• the curable composition of the present invention by blending an inorganic filler, it becomes possible to fill the curable composition with a sufficient amount of hollow organic polymer. Therefore, the curable composition of the present invention can form a cured product that has both a low coefficient of thermal expansion and a low modulus of elasticity due to the inclusion of the hollow organic polymer.
• inorganic fillers examples include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, and magnesium hydroxide.
• inorganic filler examples include barium, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate.
• the inorganic filler is preferably selected from silica and cordierite, more preferably silica. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Further, as the silica, spherical silica is preferable.
• the particle diameter of the inorganic filler is preferably 20 ⁇ m or less, more preferably 15 ⁇ m or less, particularly preferably 10 ⁇ m or less, from the viewpoint of reducing the practical adhesive thickness and reducing positional displacement due to thermal expansion or the like.
• the lower limit of the particle size of the inorganic filler is not particularly limited, but is preferably 0.01 ⁇ m or more, more preferably 0.05 ⁇ m or more, even more preferably 0.1 ⁇ m or more, particularly preferably 0.2 ⁇ m or more. be.
• the "particle diameter" of the inorganic filler means the median diameter that can be calculated by a laser diffraction/scattering method based on Mie scattering theory.
• the particle size distribution of the inorganic filler can be created on a volume basis using a laser diffraction scattering type particle size distribution measuring device, and the median diameter can be calculated. More specifically, as a measurement sample, 100 mg of the inorganic filler and 10 g of the dispersion medium were weighed into a vial and dispersed for 10 minutes using sound waves, and a laser diffraction particle size distribution measuring device was used. Then, the volume-based particle size distribution of the inorganic filler is measured using a flow cell method using blue and red light source wavelengths, and the median diameter can be calculated from the obtained particle size distribution. Examples of the laser diffraction particle size distribution measuring device include "LA-960" manufactured by Horiba, Ltd.
• the specific surface area of the inorganic filler is preferably 0.1 m 2 /g or more, more preferably 0.5 m 2 /g or more, particularly preferably 1 m 2 /g or more, from the viewpoint of improving the filling properties of the hollow organic polymer particles.
• the upper limit of the specific surface area of the inorganic filler is not particularly limited, but is preferably 100 m 2 /g or less, more preferably 70 m 2 /g or less, particularly preferably 50 m 2 /g or less.
• the specific surface area of the inorganic filler can be obtained by adsorbing nitrogen gas onto the surface of the sample using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountec) according to the BET multi-point method.
• the inorganic filler may be surface-treated with an appropriate surface treatment agent.
• Surface treatment can improve the moisture resistance and dispersibility of the inorganic filler.
• surface treatment agents include vinyl silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane; 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and 3-glycidoxypropylmethyldimethoxysilane.
• surface treatment agents include, for example, “KBM-1003”, “KBE-1003” (vinyl silane coupling agent); “KBM-303", “KBM-402”, and “KBE-1003” manufactured by Shin-Etsu Chemical Co., Ltd.
• KBM-403 "KBM-4803", “KBE-402”, “KBE-403” (epoxy silane coupling agent); "KBM-1403” (styryl silane coupling agent); "KBM-502” , “KBM-503”, “KBE-502”, “KBE-503” (methacrylic silane coupling agent); “KBM-5103” (acrylic silane coupling agent); "KBM-602”, “KBM- 603", “KBM-903”, “KBE-903”, “KBE-9103P”, "KBM-573", "KBM-575" (amino-based silane coupling agent); “KBM-9659” (isocyanurate-based silane coupling agent); "KBE-585" (ureide silane coupling agent); "KBM-802", “KBM-803” (mercapto silane coupling agent); “KBE-9007N” (isocyanate silane coupling agent); ring agent); "X-12-967C” (acid anhydride silane
• the degree of surface treatment with the surface treatment agent is preferably within a predetermined range from the viewpoint of improving the dispersibility of the inorganic filler.
• the inorganic filler is preferably surface-treated with 0.2 parts by mass to 5 parts by mass of a surface treatment agent, and 0.2 parts by mass to 3 parts by mass, based on 100 parts by mass of the inorganic filler. More preferably, the surface is treated with a surface treatment agent of 0.3 parts by mass to 2 parts by mass, and even more preferably with a surface treatment agent of 0.3 parts by mass to 2 parts by mass.
• the degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler.
• the amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m 2 or more, more preferably 0.1 mg/m 2 or more, and 0.2 mg/m 2 from the viewpoint of improving the dispersibility of the inorganic filler. The above is more preferable.
• it is preferably 1.0 mg/m 2 or less, more preferably 0.8 mg/m 2 or less, and even more preferably 0.5 mg/m 2 or less.
• the amount of carbon per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler whose surface has been treated with a surface treatment agent, and the mixture is subjected to ultrasonic cleaning at 25° C. for 5 minutes. After removing the supernatant liquid and drying the solid content, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd., etc. can be used.
• EMIA-320V manufactured by Horiba, Ltd., etc.
• the content of component (B) is preferably 30 parts by mass or more, and 40 parts by mass, based on 120 parts by mass of the resin content of the curable composition, from the viewpoint of the filling property of component (C) and the low coefficient of thermal expansion of the cured product.
• the amount above is more preferable, and 50 parts by mass or more is particularly preferable.
• the content of component (B) is preferably 500 parts by mass or less, more preferably 400 parts by mass or less, and 300 parts by mass or less, based on 120 parts by mass of the resin content of the curable composition. Parts by mass or less are particularly preferred.
• the content of component (B) is preferably 5% by mass or more, and 10% by mass or more based on the solid content of the curable composition, from the viewpoint of the filling property of component (C) and the low coefficient of thermal expansion of the cured product. More preferably, 20% by mass or more is particularly preferred.
• the content of component (B) is preferably 80% by mass or less, more preferably 70% by mass or less, and 60% by mass or less based on the solid content of the curable composition. Particularly preferred.
• the curable composition of the present invention contains hollow organic polymer particles as component (C).
• Hollow organic polymer particles are organic polymer-containing particles that have pores inside the particles.
• the hollow organic polymer particles are present in particulate form in the composition.
• the hollow organic polymer particles contribute to low elastic modulus and low coefficient of thermal expansion of the cured product, and low curing shrinkage of the curable composition.
• general non-hollow organic polymer particles are blended into a curable composition, the curing shrinkage rate of the curable composition and the elastic modulus of the cured product decrease, but the thermal expansion coefficient of the cured product increases. It is assumed that by blending hollow organic polymer particles, the volume increase due to thermal expansion of the cured product is absorbed by compression of the hollow part of the hollow organic polymer particles, and as a result, the coefficient of thermal expansion of the cured product is reduced. .
• the form of pore formation in the hollow organic polymer particles is not particularly limited, and even if the particle is in the form of a single hollow particle having one pore inside the particle, it may be in the form of a single hollow particle having a plurality of pores inside the particle.
• the particles may be in the form of hollow particles (including hollow porous particles whose interior is porous), but are preferably in the form of single hollow particles.
• the hollow organic polymer particles may be spherical particles or non-spherical particles, but are preferably spherical particles.
• the hollow organic polymer particles have a shell consisting of at least one or more layers.
• the shell may consist of one layer or two or more layers.
• the hollow organic polymer particles may have a form in which the pores are covered with a shell.
• the organic polymer contained in the hollow organic polymer particles is an organic polymer composed of a monomer including an ethylenically unsaturated monomer.
• the ethylenically unsaturated monomer has at least one ethylenically unsaturated group.
• the ethylenically unsaturated group is not particularly limited as long as it is radically polymerizable, but it may be any ethylenically unsaturated group that has a carbon-carbon double bond at the end or inside, and specifically, an allyl group.
• unsaturated aliphatic groups such as 3-cyclohexenyl group; aromatic groups containing unsaturated aliphatic groups such as p-vinylphenyl group, m-vinylphenyl group, styryl group; acryloyl group, methacryloyl group, maleoyl group, fumaroyl group It may be an ⁇ , ⁇ -unsaturated carbonyl group such as a group.
• ethylenically unsaturated monomers include monofunctional ethylenically unsaturated monomers, polyfunctional ethylenically unsaturated monomers, silyl group-containing ethylenically unsaturated monomers, and epoxy group-containing ethylenically unsaturated monomers. Examples include monomers.
• a monofunctional ethylenically unsaturated monomer is a compound having one ethylenically unsaturated group.
• monofunctional ethylenically unsaturated monomers include, but are not limited to, styrene, ⁇ -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-ethylstyrene, Monofunctional aromatic vinyl compounds such as m-ethylstyrene, p-ethylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, monofunctional aromatic allyl compounds such as allylbenzene, 1-allyl-4-methylbenzene, etc.
• Monofunctional aromatic olefin compounds such as vinyl acetate, vinyl propionate, allyl acetate, allyl propionate, vinyl butyrate, vinyl benzoate; monofunctional olefin ether compounds such as allyl ethyl ether; Methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, norbornyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, lau
• Aromatic (meth)acrylic ester compounds such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate ) acrylate and other halogen-containing (meth)acrylic ester compounds, cyano group-containing (meth)acrylic esters such as methyl cyano (meth)acrylate, ethyl cyano (meth)acrylate, propyl cyano (meth)acrylate, isopropyl cyano (meth)acrylate, etc.
• Monofunctional ethylenically unsaturated carboxylic acid ester compounds such as compounds; monofunctional ethylenically unsaturated carboxylic acid amide compounds such as (meth)acrylamide, maleimide, N-methylmaleimide, N-phenylmaleimide; (meth)acrylic acid , monofunctional ethylenically unsaturated carboxylic acid compounds such as maleic acid, fumaric acid, and itaconic acid; monofunctional ethylenically unsaturated nitrile compounds such as (meth)acrylonitrile; "(Meth)acrylate” includes acrylate and methacrylate.
• a polyfunctional ethylenically unsaturated monomer is a compound having multiple ethylenically unsaturated groups.
• polyfunctional ethylenically unsaturated monomers include, but are not limited to, conjugated diolefin compounds such as butadiene and isoprene; polyfunctional aromatic vinyl compounds such as p-divinylbenzene and m-divinylbenzene; Polyfunctional aromatic olefin compounds such as compounds; polyfunctional olefin ester compounds such as diallyl phthalate, triallyl isocyanurate, triallyl cyanurate, diallyl maleate, divinyl adipate, divinyl glutarate; tetraallyloxyethane, diallyl ether Polyfunctional olefin ether compounds such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 1,6-hexanediol di(
• Examples include polyfunctional ethylenically unsaturated carboxylic acid amide compounds such as N,N'-ethylenebis(meth)acrylamide.
• polyfunctional ethylenically unsaturated monomer may be used, or two or more types may be used in combination.
• the silyl group-containing ethylenically unsaturated monomer is a compound having at least one ethylenically unsaturated group and a silyl group such as a trialkoxysilyl group or an alkyldialkoxysilyl group.
• Silyl group-containing ethylenically unsaturated monomers are not particularly limited, but include, for example, vinyl silane compounds such as vinyltrimethoxysilane and vinyltriethoxysilane; aromatic olefins such as p-vinylphenyltrimethoxysilane.
• Silane compound 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 8-methacryloxyoctyltriethoxysilane, 3 - Ethylenically unsaturated carboxylic acid ester silane compounds such as acryloxypropyltrimethoxysilane and the like.
• the silyl group-containing ethylenically unsaturated monomers may be used alone or in combination of two or more.
• the epoxy group-containing ethylenically unsaturated monomer is a compound having at least one ethylenically unsaturated group and an epoxy group.
• the epoxy group-containing ethylenically unsaturated monomer is not particularly limited, but includes, for example, epoxy group-containing aromatic olefin compounds such as styrene-4-glycidyl ether and 4-glycidyl styrene; allyl glycidyl ether, etc.
• Epoxy group-containing olefin ether compounds epoxy group-containing ethylenically unsaturated carboxylic acid ester compounds such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, 3,4-epoxycyclohexylmethyl (meth)acrylate, etc. Can be mentioned.
• the epoxy group-containing ethylenically unsaturated monomers may be used alone or in combination of two or more.
• the monomer constituting the organic polymer contained in the hollow organic polymer particles contains an epoxy group-containing ethylenically unsaturated monomer
• the monomer further contains a crosslinkable monomer.
• the crosslinkable monomer include ethylenediaminediethylenetriamine, dipropylenetriamine, triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, N-(2-aminoethyl)piperazine, 1,4-bis(3-aminopropyl) ) Piperazine, 2,4,4-trimethylhexamethylenediamine, 2,2,4-trimethylhexamethylenediamine, bis(hexamethylene)triamine, poly(propylene glycol)diamine, 4,4'-diamino-3,3' - Aliphatics such as dimethyldicyclohexylmethane, 3-amino-1-(cyclohexylamino)propane, 4,4'-diamino
• Polyamine compounds 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfone, m-phenylenediamine, p-phenylenediamine, 2,3-tolylenediamine, 2,4- Examples include aromatic amine compounds such as tolylene diamine and 2,5-tolylene diamine.
• One type of crosslinkable monomer may be used, or two or more types may be used in combination.
• the organic polymer contained in the hollow organic polymer particles is preferably an aromatic olefin compound (e.g., a monofunctional aromatic olefin compound, a polyfunctional aromatic olefin compound, an aromatic olefin silane compound, an epoxy group-containing (aromatic olefin compounds, etc.), ethylenically unsaturated carboxylic acid ester compounds (e.g., a monofunctional aromatic olefin compound, a polyfunctional aromatic olefin compound, an aromatic olefin silane compound, an epoxy group-containing (aromatic olefin compounds, etc.), ethylenically unsaturated carboxylic acid ester compounds (e.g.
• an aromatic olefin compound e.g., a monofunctional aromatic olefin compound, a polyfunctional aromatic olefin compound, an aromatic olefin silane compound, an epoxy group-containing (aromatic olefin compounds, etc.
• the organic polymer contained in the hollow organic polymer particles is more preferably an organic polymer composed of a monomer containing one or more monomers selected from aromatic olefin compounds, and an ethylenically unsaturated carboxylic acid ester compound.
• An organic polymer composed of a monomer containing one or more selected monomers, or an organic polymer composed of a monomer containing one or more monomers selected from ethylenically unsaturated nitrile compounds. be.
• the organic polymer contained in the hollow organic polymer particles is more preferably an organic polymer composed of a monomer containing styrene, an organic polymer composed of a monomer containing a (meth)acrylic acid ester, or an organic polymer composed of a monomer containing a (meth)acrylic acid ester. It is an organic polymer composed of monomers containing acrylamide.
• the organic polymer contained in the hollow organic polymer particles is a thermosetting polymer (cured product), for example, a monomer containing an isocyanate compound, a compound having an amino group, and a compound having a hydroxy group.
• a thermosetting polymer for example, a monomer containing an isocyanate compound, a compound having an amino group, and a compound having a hydroxy group.
• organic polymers with urea bonds and/or It is an organic polymer with urethane bonds.
• the hollow organic polymer particles may be treated with a surface treatment agent.
• surface treatment agents for hollow organic polymer particles include inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid; carboxylic acids such as acetic acid, propionic acid, butyric acid, and acrylic acid; p-toluenesulfonic acid, ethylsulfonic acid, and dodecyl acid; Sulfonic acids such as benzenesulfonic acid, phosphoric acids such as polyoxyethylene alkyl ether phosphoric acid, organic acids such as phosphonic acids, phosphinic acids; tetraethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, 3-(meth)acrylic Examples include silane coupling agents such as roxypropyltrimethoxysilane and 8-(meth)acryloxyoctyltrimethoxysilane; and isocyanate compounds such as
• the porosity of the hollow organic polymer particles is preferably 20% by volume or more, more preferably 30% by volume or more, and particularly preferably 40% by volume or more.
• the upper limit of the porosity of the hollow organic polymer particles is preferably 95% by volume or less, more preferably 90% by volume or less, and particularly preferably 85% by volume or less.
• the porosity is the ratio (%) of the volume of pores inside the particle to the total volume of the hollow organic polymer particle.
• the particle diameter of the hollow organic polymer particles is preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less, and particularly preferably 30 ⁇ m or less, from the viewpoint of reducing the practical adhesive thickness and reducing misalignment due to thermal expansion or the like.
• the lower limit of the particle size of the hollow organic polymer particles is preferably 0.05 ⁇ m or more, more preferably 0.1 ⁇ m or more, and particularly preferably 0.3 ⁇ m or more from the viewpoint of particle filling properties.
• the "particle diameter" of the hollow organic polymer particles can be calculated by the laser diffraction/scattering method based on Mie scattering theory, as in the case of the "particle diameter" of the inorganic filler. Means the median diameter that can be achieved.
• the particle size distribution of hollow organic polymer particles can be created on a volume basis using a laser diffraction scattering type particle size distribution measurement device, and the median diameter can be calculated.
• the hollow organic polymer particles may be commercially available or may be produced by a known method.
• Commercially available products include, for example, "XX-6214Z”, “XX-6368Z”, “XX-5598Z” manufactured by Sekisui Plastics Co., Ltd.; "NC-751C” manufactured by Sansui Co., Ltd.; "MFL-80GCA” manufactured by Matsumoto Fine Chemicals; etc. can be mentioned.
• Known methods include, for example, WO 2018/051794, JP 2017-119843, JP 2017-119843, JP 2016-119230, JP 4-68324, and JP 63-135409. Examples include methods described in Japanese Patent Application Publication No. 2002-241448 and the like.
• the content of component (C) is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and 30 parts by mass based on 120 parts by mass of the resin content of the curable composition. The above is particularly preferable. Further, from the viewpoint of the viscosity of the curable composition (viscosity that can be used as an adhesive), the content of component (C) is preferably 300 parts by mass or less with respect to 120 parts by mass of the resin content of the curable composition. It is more preferably 250 parts by mass or less, particularly preferably 200 parts by mass or less.
• the content of component (C) is preferably 3% by mass or more, more preferably 5% by mass or more, and 10% by mass or more based on the solid content of the curable composition. Particularly preferred.
• the content of component (C) is preferably 70% by mass or less, and 60% by mass or less, based on the solid content of the curable composition. is more preferable, and 50% by mass or less is particularly preferable.
• the mass ratio of component (B):component (C) is preferably 1:10 to 20:1, and 1:5 from the viewpoint of filling properties of component (C) and low elastic modulus and low coefficient of thermal expansion of the cured product. ⁇ 15:1 is more preferable, and 1:3 ⁇ 10:1 is particularly preferable.
• the present invention includes a cationic polymerization initiator as component (D) in order to cure the curable composition.
• a cationic polymerization initiator as component (D) in order to cure the curable composition.
• the curing shrinkage rate of the curable composition is lower and the resulting cured product has higher heat resistance than in curing by photoradical polymerization or thermal anionic polymerization.
• the cationic polymerization initiator of component (D) acts on the alicyclic epoxy group in the alicyclic epoxy compound of component (A) and the oxetanyl group in the oxetane compound having two or more oxetanyl groups described below to initiate a cationic polymerization reaction. It may be a photo cationic polymerization initiator or a thermal cationic polymerization initiator as long as it can initiate .
• the photocationic polymerization initiator is preferably a photoacid generator, which generates protons or Lewis acids upon irradiation with light.
• Typical photoacid generators include triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, p-(phenylthio)phenyldiphenylsulfonium hexafluoroantimonate, and p-(phenylthio) described in WO2019/146736.
• the photoacid generator described in WO2018/110297 the photoacid generator described in WO2020/171186 (for example, p-(phenylthio)phenyldiphenylsulfonium tris(pentafluoroethyl)trifluoro phosphate) can also be mentioned.
• examples of the photoacid generator include other known salts containing sulfonium cations and commercially available salts containing sulfonium cations. Only one type of photoacid generator may be used, or two or more types may be used in combination.
• the thermal cationic polymerization initiator is preferably a thermal acid generator, which generates protons or Lewis acids upon heating.
• Typical thermal acid generators include organic onium salt compounds in which a cation component and an anion component are paired, as described in WO2019/146736.
• examples of the cationic component include organic sulfonium, organic oxonium, organic ammonium, organic phosphonium, and organic iodonium.
• examples of anion components include BF 4 ⁇ , B(C 6 F 5 ) 4 ⁇ , SbF 4 ⁇ , Sb(C 6 F 5 ) 4 ⁇ , AsF 6 ⁇ , PF 6 ⁇ , PF 6 ⁇ , CF 3 SO 3 - , C 4 F 9 SO 3 - , (CF 3 SO 2 ) 3 C - , and the like.
• thermal acid generator the thermal acid generator described in WO2018/110297 is also mentioned.
• examples of the thermal acid generator include other known salts containing quaternary ammonium cations and commercially available salts containing quaternary ammonium cations.
• the thermal acid generator may be used alone or in combination of two or more.
• a commercially available product can be used as the thermal acid generator.
• Commercially available products include, for example, "K-PURE TAG-2678,” “K-PURE TAG-2681,” “K-PURE TAG-2689,” “K-PURE TAG-2690,” and “K-PURE TAG-2678” manufactured by King Industries.
• the content of component (D) is preferably 0.01% by mass or more, based on the amount of the curable composition excluding components (B) and (C), and 0.
• the content is more preferably 0.1% by mass or more, and particularly preferably 0.2% by mass or more.
• the content of component (D) is preferably 15% by mass or less, and 10% by mass or less, based on the amount of the curable composition excluding component (B) and component (C). % or less is more preferable, and 5 mass % or less is particularly preferable.
• the content of component (D) is preferably 0.005% by mass or more, and 0.01% by mass or more based on the solid content of the curable composition. More preferably, 0.1% by mass or more is particularly preferred.
• the content of component (D) is preferably 15% by mass or less, more preferably 10% by mass or less, and 5% by mass, based on the solid content of the curable composition. The following are particularly preferred.
• the curable composition of the present invention may further contain components other than components (A) to (D) (herein sometimes referred to as "other components") as optional components.
• other components include oxetane compounds having two or more oxetanyl groups, polyester polyols, photosensitizers, and the like.
• oxetane compound having two or more oxetanyl groups contributes to low curing shrinkage of the curable composition.
• the number of oxetanyl groups in the oxetane compound is preferably 2 to 4, particularly preferably 2.
• R 1 to R 4 each independently have a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, or a carbon number optionally substituted with an alkyl group having 1 to 6 carbon atoms.
• L 9 is a polyoxyalkylene group, an alkylene group having 1 to 6 carbon atoms, a cycloalkylene group having 5 to 7 carbon atoms, an arylene group having 6 to 10 carbon atoms, an alkylene group having 1 to 6 carbon atoms, and an alkylene group having 6 to 6 carbon atoms;
• L 10 - represents -O-, -S-, -CH 2 -, -NH-, -SO-, -SO 2 -, -C(CF 3 ) 2 - or -C(CH 3 ) 2 - and L 11 represents an alkylene group having 1 to 6 carbon atoms, a cycloalkylene group having 5 to 7 carbon atoms, or an arylene group having 6 to 10 carbon atoms.
• m1 represents an integer of 1 to 3.
• Examples include compounds represented by any of the following.
• Compound (V) may be a mixture of compounds having different numbers of repeating units.
• the alkyl group having 1 to 6 carbon atoms in formulas (IV) and (V) may be linear or branched.
• Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, and hexyl group.
• Examples of the cycloalkyl group having 5 to 7 carbon atoms in formulas (IV) and (V) include a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.
• Examples of the aryl group having 6 to 10 carbon atoms which may be substituted with an alkyl group having 1 to 6 carbon atoms in formulas (IV) and (V) include phenyl group, naphthyl group, tolyl group, and xylyl group. can be mentioned.
• Examples of the aralkyl group having 6 to 16 carbon atoms in formulas (IV) and (V) include benzyl group and phenethyl group.
• the number of carbon atoms in the alkylene group in the polyoxyalkylene group in formula (V) is preferably 1 to 4.
• the repeating number of oxyalkylene groups in the polyoxyalkylene group is preferably 2 to 30.
• the alkylene group having 1 to 6 carbon atoms in formulas (VI) and (VII) may be linear or branched.
• Examples of the alkylene group having 1 to 6 carbon atoms include methylene group, ethylene group, trimethylene group, propylene group, tetramethylene group, pentamethylene group, and hexamethylene group.
• Examples of the cycloalkylene group having 5 to 7 carbon atoms in formulas (VI) and (VII) include 1,2-cyclopentylene group, 1,3-cyclopentylene group, 1,2-cyclohexylene group, 1, Examples include 3-cyclohexylene group, 1,4-cyclohexylene group, 1,2-cycloheptylene group, 1,3-cycloheptylene group, and 1,4-cycloheptylene group.
• Examples of the arylene group having 6 to 10 carbon atoms in formulas (VI) and (VII) include benzenediyl group and biphenyldiyl group.
• an alkylene group having 1 to 6 carbon atoms and an arylene group having 6 to 10 carbon atoms are connected in formulas (VI) and (VII)
• an alkylene group having 1 to 6 carbon atoms and an arylene group having 6 to 6 carbon atoms are connected.
• ⁇ 10 arylene groups may be one or two or more, for example, benzene-4,4-diylbismethylene group (-CH 2 -Ph-CH 2 -), biphenyl-4,4'- Diylbismethylene (-CH 2 -Ph-Ph-CH 2 -) group is mentioned.
• the oxetane compound is preferably selected from a compound represented by the following formula (IV-1) and a compound represented by the following formula (V-1).
• Compound (V-1) may be a mixture of compounds having different numbers of repeating units.
• oxetane compound Only one type of oxetane compound may be used, or two or more types may be used in combination.
• oxetane compound commercially available products can be used. Examples of commercially available products include “OXT-121" and “OXT-221" manufactured by Toagosei Co., Ltd.; “OXBP” and “OXIPA” manufactured by Ube Industries, Ltd.; and the like.
• the molecular weight of the oxetane compound is preferably 180 or more, more preferably 190 or more, and even more preferably 200 or more.
• the upper limit of the molecular weight of the oxetane compound is appropriately selected depending on the viscosity of the curable composition, but is preferably 400 or less.
• the molecular weight of the oxetane compound is 180 or more, the oxetane compound becomes difficult to volatilize from the curable composition. As a result, when applying the composition by an inkjet method, the composition of the composition is unlikely to change, and furthermore, the working environment is unlikely to deteriorate.
• the molecular weight of the oxetane compound means the weight average molecular weight (Mw). This Mw can be calculated, for example, by gel permeation chromatography (GPC) in terms of polystyrene.
• the viscosity (25° C.) of the oxetane compound is preferably 1 to 10,000 mPa ⁇ s, more preferably 2 to 5,000 mPa ⁇ s, from the viewpoint of the fluidity of the curable composition at room temperature.
• viscosity (25°C) means “viscosity at 25°C measured using a vibratory viscometer.”
• the oxetanyl equivalent of the oxetane compound is preferably 30 to 5,000 g/eq, more preferably 50 to 2,000 g/eq, and particularly preferably 100 to 1,000 g/eq.
• the "oxetanyl equivalent" of an oxetane compound means the number of grams of the oxetane compound containing 1 gram equivalent of oxetanyl group. This value of oxetanyl equivalent can be determined according to the method specified in JIS K 7236.
• the oxetanyl equivalent can be theoretically calculated by dividing the molecular weight of the oxetane compound by the number of oxetanyl groups that the oxetane compound has.
• the content of the oxetane compound is preferably 1% by mass or more, more preferably 2% by mass or more, particularly preferably 3% by mass or more, based on the resin content of the curable composition.
• the content of oxetane is preferably 65% by mass or less, more preferably 55% by mass or less, particularly preferably 45% by mass or less, based on the resin content of the curable composition. .
• the content of the oxetane compound is preferably 0.5% by mass or more, more preferably 1% by mass or more, and 2% by mass, based on the solid content of the curable composition. The above is particularly preferable.
• the content of the oxetane compound is preferably 30% by mass or less, more preferably 25% by mass or less, particularly 20% by mass or less, based on the solid content of the curable composition. preferable.
• polyester polyol By using a polyester polyol, the moisture and heat resistant adhesive properties of the curable composition can be improved.
• polyester polyols include polyester polyols obtained by condensation polymerization of dicarboxylic acids and diols.
• dicarboxylic acids include aliphatic carboxylic acids such as adipic acid, azelaic acid, sebacic acid, and dodecanedioic acid; aromatic carboxylic acids such as terephthalic acid and isophthalic acid.
• diols examples include linear diols such as ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, and diethylene glycol; 1,2-propylene glycol, 1,3- Butylene glycol, 2-methyl-1,3-propanediol, neopentyl glycol, 3-methyl-1,5-pentadiol, 2,2-dimethyl-1,3-propanediol, 2-methyl-1,8- Examples include octanediol. Only one type of polyester polyol may be used, or two or more types may be used in combination.
• the number average molecular weight of the polyester polyol is preferably from 500 to 20,000, more preferably from 1,000 to 15,000, from the viewpoint of obtaining good adhesion.
• the number average molecular weight can be calculated in terms of polystyrene by gel permeation chromatography (GPC).
• the hydroxyl value of the polyester polyol is preferably 5 to 500 mgKOH/g, more preferably 10 to 400 mgKOH/g, and particularly preferably 20 to 300 mgKOH/g.
• hydroxyl value refers to the number of mg of potassium hydroxide corresponding to hydroxyl groups in 1 g of sample. The hydroxyl value can be measured according to the method specified in JIS K 1557-1.
• polyester polyols can be used. Examples of such commercial products include “OD-X-102”, “OD-X-668", “OD-X-2068", and “OD-X-3100” manufactured by DIC; “P -1010”, “P-2010”, “P-3010”, “P-2050”; ADEKA “NS-2400”, “YT-101”, “F7-67”, “#50”, “F1212” -29'', ⁇ YG-108'', ⁇ V14-90'', ⁇ Y65-55'', and the like.
• the content of the polyester polyol is preferably 1% by mass or more, more preferably 2% by mass or more, particularly 3% by mass or more, based on the resin content of the curable composition, from the viewpoint of moisture-heat-resistant adhesive properties of the curable composition. preferable.
• the content of the polyester polyol is preferably 40% by mass or less, more preferably 30% by mass or less, and 20% by mass or less, based on the resin content of the curable composition. Particularly preferably less than % by mass.
• the content of the polyester polyol is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, based on the solid content of the curable composition, from the viewpoint of heat-and-moisture resistant adhesiveness of the curable composition. Particularly preferred is 1% by mass or more.
• its content is preferably 30% by mass or less, and 20% by mass or less, based on the solid content of the curable composition, from the viewpoint of obtaining a cured product with high Tg and high heat resistance stability. The following is more preferable, and 10% by mass or less is particularly preferable.
• a photosensitizer When using a photocationic polymerization initiator (particularly a photoacid generator) as component (D), a photosensitizer is added to increase the activity of the photocationic polymerization initiator and increase the curability of the curable composition. It is preferable to use A sensitizer has an absorption band in a wavelength range longer than that of a photocationic polymerization initiator, and after being excited by light absorption, electrons or energy are transferred, and the photoacid generator is decomposed and the polymerization initiation species is activated. It is a compound that contributes to development.
• the sensitizer can be appropriately blended depending on the wavelength of the light source used for photocuring.
• sensitizers include anthracene compounds such as dimethylanthracene, 9,10-diethoxyanthracene, and 9,10-dibutoxyanthracene, thioxanthone compounds such as 2-isopropylthioxanthone and diethylthioxanthone, 2-ethylanthraquinone, ( Examples include quinone compounds such as ⁇ )-camphorquinone, naphthalene compounds such as dialkoxynaphthalene, and aromatic diketone compounds such as benzyl and curcumin. Only one type of photosensitizer may be used, or two or more types may be used in combination.
• photosensitizers include anthracene compounds (such as 9, 10-dibutoxyanthracene), thioxanthone compounds, and quinone compounds, the absorbance in the long wavelength range is at a suitable level, poor dispersion in the composition is less likely to occur, and curability is improved. It is preferable from the viewpoint of improving the curing rate and improving the curing speed during curing.
• photosensitizers include, for example, “AnthraCure UVS-1331", “AnthraCure UVS-1101”, “AnthraCure UVS-581”, and “AnthraCure UVS-2171” manufactured by Air Water Performance Chemical; Examples include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, and 2-ethylanthraquinone manufactured by Tokyo Kasei Kogyo Co., Ltd.
• the content of the photosensitizer is preferably 0.01% or more, more preferably 0.03% or more, based on the resin content of the curable composition. Particularly preferred is 0.05% or more.
• the content of the photosensitizer is preferably 5% or less, more preferably 4% or less, particularly preferably 3% or less, based on the resin content of the curable composition.
• the curable composition of the present invention comprises essential components (components (A) to (D)) and optional components (for example, an oxetane compound having two or more oxetanyl groups, a polyester polyol, a photosensitizer, etc.). ) using a known stirrer or disperser.
• the stirrer and dispersion machine include a dissolver, a planetary mixer, a roll mill, a sand mill, a ball mill, a bead mill, a homogenizer, a high-pressure homogenizer, an ajihomo mixer, an autorotation/revolution mixer, and the like.
• the curable composition of the present invention is liquid at 25°C, and preferably has a viscosity (at 25°C) of less than 300,000 mPa ⁇ s, more preferably 250,000 mPa ⁇ s or less.
• the lower limit is not particularly limited, it is preferably 10 mPa ⁇ s or more, and preferably 20 mPa ⁇ s or more.
• a cured product having both a low coefficient of thermal expansion and a low modulus of elasticity can be formed from the curable composition of the present invention. That is, it is possible to obtain an optical device having a cured layer formed from a curable composition that has both a low coefficient of thermal expansion and a low modulus of elasticity. Therefore, the curable composition of the present invention can be suitably used for adhesion of optical devices (specifically, for adhesion of members in optical devices). Specifically, it is used as an adhesive for fiber arrays and ball lenses, for example. Since the curable composition of the present invention has excellent fluidity at room temperature, it can be directly applied to an object to be sealed, and a composition layer (coating layer) with uniform properties can be easily formed.
• composition layer As a coating method, bar coating, comma coating, die coating, blade coating, dispenser coating, inkjet coating, etc. can be used alone or in combination.
• a cured layer having a low coefficient of thermal expansion and a low modulus of elasticity can be formed.
• the curable composition of the present invention can be cured by light or heat.
• light irradiation of 300 mJ/cm 2 or more can be performed using, for example, a mercury lamp, UV-LED, or the like.
• it can be cured by heating, for example, at a temperature of 60 to 150°C.
• Component (B): Inorganic filler 40SE-C3: Silica manufactured by Admatex, particle size (median diameter): 3.0 ⁇ m, specific surface area: 3.3 m 2 /g SS-1000: Cordierite manufactured by Marusu Glaze Co., Ltd., particle size (median diameter): 1.7 ⁇ m
• XX-6214Z Hollow styrene particles manufactured by Sekisui Plastics Co., Ltd., organic polymer: styrene polymer, number of pores in one particle: 1, porosity: 50%, particle size (median diameter): 0.42 ⁇ m
• XX-6368Z Hollow acrylic particles manufactured by Sekisui Plastics Co., Ltd., number of pores in one particle: 1, porosity: 60%, particle diameter (median diameter): 4 ⁇ m
• NC-751C Hollow thermosetting resin particles manufactured by Sansuisha, number of pores in one particle: 1, porosity: 69%, particle size (median diameter): 4.4 ⁇ m
• MFL-80GCA hollow acrylonitrile particles manufactured by Matsumoto Fine Chemicals, organic polymer: acrylonitrile-based polymer, number of pores in one particle: 1, porosity: 80%, particle size (median diameter): 20 ⁇ m
• OXT-221 3-ethyl-3 ⁇ [(3-ethyloxetan-3-yl)methoxy]methyl ⁇ oxetane (compound IV-1) manufactured by Toagosei Co., Ltd., molecular weight: 214, number of oxetanyl groups in one molecule :2
• ARX-805 Acrylic particles manufactured by Sekisui Plastics, organic polymer: (meth)acrylate polymer, particle size (median diameter): 8 ⁇ m
• Example 1 50 parts of an alicyclic epoxy compound ("Celoxide 2021P” manufactured by Daicel Corporation), 50 parts of an oxetane compound ("OXT-221" manufactured by Toagosei Co., Ltd.), and 20 parts of polyester polyol ("OD-X-3100” manufactured by DIC Corporation). were mixed uniformly using a high-speed rotating mixer to obtain a mixture. 100 parts of silica (“40SE-C3" manufactured by Admatex) and 40 parts of hollow styrene particles (“XX-6214Z” manufactured by Sekisui Plastics Co., Ltd.) were added to the resulting mixture, and the resulting mixture was rotated at high speed. Uniformly dispersed with a mixer.
• a photoacid generator (“CPI-210S” manufactured by Sun-Apro Corporation) and 1 part of a photosensitizer (“UVS-1331” manufactured by Air Water Performance Chemical Company) were uniformly added to the obtained mixture using a high-speed rotating mixer. The mixture was mixed to obtain a curable composition.
• the obtained curable composition was placed on the release-treated surface of a polyethylene terephthalate (PET) film (“NS-80A” manufactured by Toray Industries, Ltd., PET film thickness: 38 ⁇ m) that had been treated with an alkyd-based mold release agent. It was applied uniformly with a glass rod and irradiated with 365 nm ultraviolet rays at 30 mW for 100 seconds to obtain a cured product with a thickness of 100 ⁇ m.
• PET polyethylene terephthalate
• Example 2 Example 1 except that 40 parts of hollow acrylic particles ("XX-6368Z” manufactured by Sekisui Plastics Co., Ltd.) were used instead of 40 parts of hollow styrene particles ("XX-6214Z” manufactured by Sekisui Plastics Co., Ltd.) A curable composition and a cured product were produced in the same manner.
• Example 3 Example 1 except that 90 parts of hollow thermosetting resin particles ("NC-751C” made by Sansui Co., Ltd.) were used instead of 40 parts of hollow styrene particles ("XX-6214Z” made by Sekisui Plastics Co., Ltd.). A curable composition and a cured product were produced in the same manner.
• Example 4 Same as Example 1 except that 50 parts of hollow acrylonitrile particles ("MFL-80GCA” manufactured by Matsumoto Fine Chemical Co., Ltd.) were used instead of 40 parts of hollow styrene particles ("XX-6214Z” manufactured by Sekisui Plastics Co., Ltd.) A curable composition and a cured product were produced.
• MFL-80GCA hollow acrylonitrile particles
• XX-6214Z hollow styrene particles
• Example 5 Except for adding 5 parts of hollow styrene particles ("XX-6214Z” manufactured by Sekisui Plastics Co., Ltd.) and changing the amount of silica ("40SE-C3" manufactured by Admatex Co., Ltd.) from 100 parts to 200 parts. A curable composition and a cured product were produced in the same manner as in Example 4.
• Example 6 The amount of alicyclic epoxy compound (“Celoxide 2021P” manufactured by Daicel Corporation) was changed from 50 parts to 60 parts, and the amount of oxetane compound (“OXT-221” manufactured by Toagosei Co., Ltd.) was changed from 50 parts to 60 parts.
• a curable composition and a cured product were produced in the same manner as in Example 4, except that the polyester polyol ("OD-X-3100" manufactured by DIC Corporation) was not used.
• Example 7 Instead of 2 parts of photoacid generator (CPI-210S manufactured by Sun-Apro) and 1 part of photosensitizer (UVS-1331 manufactured by Air Water Performance Chemical), A curable composition and a cured product were produced in the same manner as in Example 4, except that 5 parts of "Irgacure 290") were used.
• Example 8 Curing was carried out in the same manner as in Example 4, except that 100 parts of cordierite ("SS-1000", manufactured by Marusu Glaze Co., Ltd.) was used in place of 100 parts of silica ("40SE-C3", manufactured by Admatex). A composition and a cured product were produced.
• Example 9 Except that the amount of the alicyclic epoxy compound (“Celoxide 2021P” manufactured by Daicel Corporation) was changed from 50 parts to 100 parts, and the oxetane compound (“OXT-221” manufactured by Toagosei Co., Ltd.) was not used. A curable composition and a cured product were produced in the same manner as in Example 4.
• the amount of the alicyclic epoxy compound (“Celoxide 2021P” manufactured by Daicel Corporation) was changed from 50 parts to 100 parts, and the oxetane compound (“OXT-221” manufactured by Toagosei Co., Ltd.) was not used.
• a curable composition and a cured product were produced in the same manner as in Example 4.
• Example 10 The same procedure as in Example 4 was carried out, except that 50 parts of an alicyclic epoxy compound ("Celoxide 8000" manufactured by Daicel) was used instead of 50 parts of the alicyclic epoxy compound (“Celoxide 2021P” manufactured by Daicel). , a curable composition and a cured product were produced.
• an alicyclic epoxy compound (“Celoxide 8000" manufactured by Daicel)
• 50 parts of the alicyclic epoxy compound (“Celoxide 2021P” manufactured by Daicel).
• Example 11 Curing was carried out in the same manner as in Example 4, except that 50 parts of the oxetane compound ("OXT-121", manufactured by Toagosei Co., Ltd.) was used instead of 50 parts of the oxetane compound ("OXT-221", manufactured by Toagosei Co., Ltd.). A composition and a cured product were produced.
• OXT-121 manufactured by Toagosei Co., Ltd.
• OXT-221 manufactured by Toagosei Co., Ltd.
• Example 12 In place of 2 parts of a photoacid generator ("CPI-210S” manufactured by Sun-Apro) and 1 part of a photosensitizer ("UVS-1331” manufactured by Air Water Performance Chemicals), a thermal acid generator (King Industries) was used. Using 1 part of hollow acrylonitrile particles ("MFL-80GCA”, manufactured by Matsumoto Fine Chemical Co., Ltd.), hollow acrylic particles (“XX-6368Z”, manufactured by Sekisui Plastics Co., Ltd.) were used. A curable composition and a cured product were produced in the same manner as in Example 11, except that 50 parts were used. Further, a cured product with a thickness of 100 ⁇ m was obtained in the same manner as in Example 11, except that instead of photocuring by ultraviolet irradiation, thermal curing was performed by heating in an oven at 120° C. for 30 minutes.
• a thermal acid generator King Industries
• MFL-80GCA hollow acrylonitrile particles
• XX-6368Z manufactured by Sekis
• Example 1 except that 50 parts of acrylic particles ("ARX-805", manufactured by Sekisui Plastics Co., Ltd.) were used instead of 40 parts of hollow styrene particles ("XX-6214Z", manufactured by Sekisui Plastics Co., Ltd.). A curable composition and a cured product were produced in the same manner.
• a sheet-shaped cured product was obtained by peeling off the PET film from the cured product obtained in Examples and Comparative Examples.
• the cured product was cut into test pieces with a width of about 4 mm and a length of about 15 mm, and thermomechanical analysis was performed using a thermomechanical analyzer TMA-SS6100 (manufactured by Seiko Instruments Inc.) using a tensile loading method. .
• TMA-SS6100 manufactured by Seiko Instruments Inc.
• the average coefficient of thermal expansion (ppm/°C) from 30°C to 80°C in the second measurement was calculated.
• (Evaluation criteria) ⁇ : Average coefficient of thermal expansion (30°C to 80°C) ⁇ 100ppm/°C
• ⁇ Average coefficient of thermal expansion (30°C to 80°C)>100ppm/°C
• a cured product having both a low coefficient of thermal expansion and a low modulus of elasticity can be formed, so the curable composition of the present invention is very useful for adhesion of optical devices. be.

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