Resin composition for forming optical member

Abstract

[PROBLEM]The present invention provides a resin composition suitable for forming an optical member including an optical waveguide that has a low refractive index and exhibits no cracking in a heat cycle test. Further provided are an optical waveguide comprising a cured product of the resin composition, an opto-electric hybrid board comprising the optical waveguide, and a device comprising the opto-electric hybrid board. [SOLUTION]The resin composition for forming an optical member comprises (a) a siloxane polymer having an unsaturated bond-containing group, (b) surface-modified silica nanoparticles, (c) a photopolymerization initiator, and (d) a polyfunctional thiol compound.

Description

Resin composition for forming optical member

[0001] The present invention relates to a resin composition for forming an optical member, which contains a polysiloxane compound, surface-modified silica nanoparticles, and a photopolymerization initiator.

[0002] In recent years, due to the development of cloud computing and the increase in smartphone users, communication traffic has been constantly increasing. Therefore, problems such as a huge amount of power consumption occurring in data servers where transmitted information data is concentrated and the approaching limit of processing capacity have become apparent, and technological progress for improving these problems is urgently needed. Among them, as a technology that can process information at high density and high speed, a technology of an optoelectronic hybrid substrate (also referred to as an optoelectronic composite substrate) that changes some of the electrical wirings in a server board to optical wirings has been intensively studied, and research and development of optical members that control light refraction, transmission, scattering, etc. have been attracting more and more attention.

[0003] An optoelectronic hybrid substrate is a substrate equipped with an optical waveguide, which is an optical transmission path, and an optoelectronic conversion element that converts an electrical signal into an optical signal, enabling an improvement in data transfer speed and a reduction in power consumption, and capable of dramatically improving the communication efficiency of a device.

[0004] An optical waveguide is a structure for transmitting an optical signal along a specific path. The optical waveguide consists of a core where light mainly propagates and a cladding around it. Due to the difference in refractive index between the core and the cladding, incident light is propagated in the core while undergoing total reflection. By using this technology, light can be efficiently guided, and communication and data processing can be performed while minimizing losses.

[0005] Core materials and cladding materials used for optical waveguides are required to have optical properties such as refractive index and stability against heat / light / moisture / temperature changes, etc. Among them, core materials are required to have low propagation loss (transparency and low scattering with respect to the incident wavelength) and patterning properties. Cladding materials are required to have a lower refractive index than the core and mechanical properties. Also, from the perspective of reducing the optical coupling loss between the optical waveguide and peripheral members such as optoelectronic conversion parts, a low refractive index is often required for the optical waveguide.

[0006] Polysiloxane containing inorganic nanoparticles is used as a material for optical waveguides (Patent Documents 1 and 2). Due to their excellent optical properties and heat resistance, inorganic nanoparticles are being investigated as optical waveguide materials when combined with resins.

[0007] Furthermore, several methods have been disclosed for dispersing inorganic fine particles in resins containing siloxanes. For example, one method involves dispersing inorganic fine particles in a resin or solvent using a ball mill, homogenizer, bead mill, etc. (Patent Document 3). Another method involves bonding a polymer to the surface of the fine particles and dispersing them by operations such as heating and stirring (Patent Document 4).

[0008] On the other hand, it is generally known that adding inorganic fine particles to a curable resin composition causes the cured product to become brittle. Furthermore, while optoelectronic composite substrates require resistance to various reliability tests equivalent to those of ordinary electronic substrates, cracking of the optical waveguide during heat cycle tests is a major challenge for optoelectronic composite substrates.

[0009] Japanese Patent Publication No. 2004-102247, Japanese Patent Publication No. 2002-277664, Japanese Patent Publication No. 3901201, Japanese Patent Publication No. 4857496

[0010] The present invention aims to provide a resin composition suitable for forming optical components including optical waveguides that have a low refractive index and do not crack during heat cycle testing.

[0011] The present invention has been made to solve the above problems, and as a first embodiment of the present invention, a resin composition for forming optical components comprising (a) a siloxane polymer having unsaturated bonding groups, (b) surface-modified silica nanoparticles, (c) a photopolymerization initiator, and (d) a polyfunctional thiol compound. As a second embodiment of the present invention, the resin composition for forming optical components according to the first embodiment, wherein the number of thiol groups in the polyfunctional thiol compound (d) is 2 to 6. As a third embodiment of the present invention, the resin composition for forming optical components according to the first or second embodiment, wherein the polyfunctional thiol compound (d) is at least one selected from the group consisting of compounds represented by the following formulas (A2) to (A4). (In formulas (A2) and (A3), Rａ２ each independently represents an organic group having an alkyl group, a halogenated alkyl group, an alkenyl group, an aryl group, a thiol group or a thioureido group, and R ａ３ each independently represents a hydrogen atom, a halogenated alkyl group, or an alkyl group optionally substituted with a hydroxy group, and L １ each independently represents a single bond or an alkylene group, x represents an integer of 2 to 4, and y and z represent integers of 1 to 3. However, at least two R ａ２ are organic groups having a thiol group, and L １ when being an alkylene group, an oxygen atom may be interposed between its carbon atoms, and in formulas (A2) and (A3), the structure of -O-C-O- is not included in the molecule. In formula (A4), R ａ４ to R ａ６ each independently represents an organic group having an alkyl group, a halogenated alkyl group, an alkenyl group, an aryl group, a thiol group or a thioureido group, and L ２ to L ４ represent an alkylene group. However, at least two of R ａ４ to R ａ６ are organic groups having a thiol group.) As the fourth form of the present invention, the optical member-forming resin composition according to any one of the first to third forms, wherein the siloxane polymer having an unsaturated bond group in (a) is a siloxane polymer containing at least a partial structure represented by formula (1). (In formula (1), R １ is an unsaturated bond group, and L ５ is an alkylene group having 1 to 10 carbon atoms or a single bond optionally substituted with a substituent.) As the fifth form of the present invention, the optical member-forming resin composition according to the fourth form, wherein the siloxane polymer having an unsaturated bond group in (a) is a siloxane polymer further containing a partial structure represented by formula (2). (In formula (2), R ２ is an aryl group, an alkyl group having 1 to 20 carbon atoms optionally substituted with a substituent, -O-R ３ , or -L ６ -M-R ４ and R３ L is an alkyl group having 1 to 6 carbon atoms, which may be substituted with substituents. ６ R is an alkylene group having 1 to 10 carbon atoms, which may be substituted with substituents. ４ -R is an alkyl group having 1 to 3 carbon atoms, which may be substituted with substituents. ５ -O-R ６ or H, R ５ R is an alkylene group having 1 to 3 carbon atoms, which may be substituted with substituents. ６ is an alkyl group having 1 to 3 carbon atoms, which may be substituted with substituents, or H, and M is -O-, -N(R ７ )-, or an aryl group, R ７ (This is an alkyl group having 1 to 3 carbon atoms, an aryl group, or H, which may be substituted with substituents.) As a sixth embodiment of the present invention, the above R １ However, the resin composition for forming optical components is the fourth or fifth embodiment, wherein the (meth)acryloyl group, (meth)acryloyloxy group, vinyl group, styryl group, or ethynyl group. As the seventh embodiment of the present invention, the above L ５The present invention relates to a resin composition for forming optical components according to any one of the fourth to sixth forms, wherein the substituent is an unsubstituted alkylene group having 1 to 10 carbon atoms. The present invention relates to a resin composition for forming optical components according to the fourth to seventh forms, wherein the substituent is at least one selected from the group consisting of alkyl groups, alkenyl groups, epoxy groups, isocyanate groups, aryl groups, halogen atoms, hydroxyl groups, nitro groups, sulfone groups, amide groups, amino groups, thiol groups, and ureido groups. The present invention relates to a resin composition for forming optical components according to any one of the fifth to seventh forms, wherein the substituent is at least one selected from the group consisting of alkyl groups, alkenyl groups, epoxy groups, isocyanate groups, aryl groups, halogen atoms, hydroxyl groups, nitro groups, sulfone groups, amide groups, amino groups, thiol groups, and ureido groups. As a tenth embodiment of the present invention, the resin composition for forming optical components according to any one of the first to ninth embodiments is wherein the (b) surface-modified silica nanoparticles are silica nanoparticles surface-modified with at least one silane coupling agent, and at least one of the silane coupling agents contains an ethylenically unsaturated double bond. As an eleventh embodiment of the present invention, the resin composition for forming optical components according to any one of the first to tenth embodiments is wherein the particle size of the (b) surface-modified silica nanoparticles measured by dynamic light scattering (DLS) is 5 to 150 nm. As a twelfth embodiment of the present invention, the resin composition for forming optical components according to any one of the first to eleventh embodiments further comprises a (meth)acrylate compound. As a thirteenth embodiment of the present invention, the resin composition for forming optical components according to any one of the first to twelfth embodiments further comprises a solvent. As a fourteenth embodiment of the present invention, the resin composition for forming optical components according to any one of the first to thirteenth embodiments is wherein the optical component is an optical waveguide. A fifteenth embodiment of the present invention is a resin composition for forming an optical component according to any one of the first to thirteenth embodiments, wherein the optical component is the cladding portion of an optical waveguide. A sixteenth embodiment of the present invention is an optical waveguide containing a cured product of the resin composition for forming an optical component according to any one of the first to thirteenth embodiments. A seventeenth embodiment of the present invention is a photoelectric mixed substrate containing the optical waveguide of the sixteenth embodiment.An eighteenth embodiment of the present invention is an apparatus that includes a photoelectric mixed-signal substrate according to the seventeenth embodiment.

[0012] The resin composition for forming optical components of the present invention improves the flexibility of the cured product through the use of a polyfunctional thiol compound. As a result, crack resistance can be imparted to the optical waveguide. Furthermore, by introducing a portion that interacts with the silica surface into the siloxane resin, silica nanoparticles can be uniformly dispersed in the siloxane resin. As a result, the cured film produced from this resin composition for forming optical components has low turbidity and refractive index, thus enabling the formation of a cured film that achieves high light transmittance and low transmission loss in the optical waveguide.

[0013] The resin composition for forming optical components of the present invention comprises (a) a siloxane polymer having unsaturated bonding groups, (b) surface-modified silica nanoparticles, (c) a photopolymerization initiator, and (d) a polyfunctional thiol compound.

[0014] <Component (a)> Component (a) of the resin composition for forming optical components of the present invention is a siloxane polymer having an unsaturated bonding group. Preferably, the siloxane polymer is a siloxane polymer containing at least a substructure represented by formula (1). In formula (1), R １ L is an unsaturated bonding group. ５ This is an alkylene group having 1 to 10 carbon atoms, which may be substituted with substituents, or a single bond.

[0015] Furthermore, the siloxane polymer having an unsaturated bonding group of component (a) has a substructure represented by formula (2) in addition to the substructure represented by formula (1). In formula (2), R ２ This includes an aryl group, an alkyl group having 1 to 20 carbon atoms which may be substituted with substituents, and -O-R ３ , or -L ６ -M-R ４ And R ３ L is an alkyl group having 1 to 6 carbon atoms, which may be substituted with substituents. ６ R is an alkylene group having 1 to 10 carbon atoms, which may be substituted with substituents. ４-R is an alkyl group having 1 to 3 carbon atoms, which may be substituted with substituents. ５ -O-R ６ or H, R ５ R is an alkylene group having 1 to 3 carbon atoms, which may be substituted with substituents. ６ is an alkyl group having 1 to 3 carbon atoms, which may be substituted with substituents, or H, and M is -O-, -N(R ７ )-, or an aryl group, R ７ This is an alkyl group having 1 to 3 carbon atoms, an aryl group, or H, which may be substituted with substituents.

[0016] In the substructure represented by equation (1), R １ However, these are unsaturated bonding groups. For example, (meth)acryloyl group, (meth)acryloyloxy group, vinyl group, styryl group, or ethynyl group.

[0017] L in formula (1) ５ This is an alkylene group having 1 to 10 carbon atoms, or a single bond, which may be substituted with substituents.

[0018] Furthermore, L included in formula (2) ６This is an alkylene group having 1 to 10 carbon atoms, which may be substituted with substituents. Examples of alkylene groups having 1 to 10 carbon atoms include methylene, ethylene, n-propylene, isopropylene, cyclopropylene, n-butylene, isobutylene, s-butylene, t-butylene, cyclobutylene, 1-methylcyclopropylene, 2-methylcyclopropylene, n-pentylene, 1-methyl-n-butylene, 2-methyl-n-butylene, 3-methyl-n-butylene, 1,1-dimethyl-n-propylene, 1,2-dimethyl-n-propylene, and 2,2-dimethyl-n-propylene. Len, 1-ethyl-n-propylene group, cyclopentylene group, 1-methyl-cyclobutylene group, 2-methyl-cyclobutylene group, 3-methyl-cyclobutylene group, 1,2-dimethyl-cyclopropylene group, 2,3-dimethyl-cyclopropylene group, 1-ethyl-cyclopropylene group, 2-ethyl-cyclopropylene group, n-hexylene group, 1-methyl-n-pentylene group, 2-methyl-n-pentylene group, 3-methyl-n-pentylene group, 4-methyl-n-pentylene group, 1,1-dimethyl-n-butylene group, 1,2-dimethyl-n -Butylene group, 1,3-dimethyl-n-butylene group, 2,2-dimethyl-n-butylene group, 2,3-dimethyl-n-butylene group, 3,3-dimethyl-n-butylene group, 1-ethyl-n-butylene group, 2-ethyl-n-butylene group, 1,1,2-trimethyl-n-propylene group, 1,2,2-trimethyl-n-propylene group, 1-ethyl-1-methyl-n-propylene group, 1-ethyl-2-methyl-n-propylene group, cyclohexylene group, 1-methyl-cyclopentylene group, 2-methyl-cyclopentylene group, 3-methyl-cyclopentylene group ethylene group, 1-ethyl-cyclobutylene group, 2-ethyl-cyclobutylene group, 3-ethyl-cyclobutylene group, 1,2-dimethyl-cyclobutylene group, 1,3-dimethyl-cyclobutylene group, 2,2-dimethyl-cyclobutylene group, 2,3-dimethyl-cyclobutylene group, 2,4-dimethyl-cyclobutylene group, 3,3-dimethyl-cyclobutylene group, 1-n-propyl-cyclopropylene group, 2-n-propyl-cyclopropylene group, 1-isopropyl-cyclopropylene group, 2-isopropyl-cyclopropylene group, 1,2,Examples include 2-trimethylcyclopropylene group, 1,2,3-trimethylcyclopropylene group, 2,2,3-trimethylcyclopropylene group, 1-ethyl-2-methylcyclopropylene group, 2-ethyl-1-methylcyclopropylene group, 2-ethyl-2-methylcyclopropylene group, 2-ethyl-3-methylcyclopropylene group, n-heptylene group, n-octylene group, n-nonylene group, or n-decanylene group.

[0019] The alkylene group having 1 to 10 carbon atoms may be substituted with alkyl groups, alkenyl groups, epoxy groups, isocyanate groups, aryl groups, halogen atoms, hydroxyl groups, nitro groups, sulfone groups, amide groups, amino groups, thiol groups, and ureido groups, etc.

[0020] L ５ and L ６ Preferably, it is an unsubstituted alkylene group having 1 to 10 carbon atoms. More preferably, it is an unsubstituted alkylene group having 1 to 8 carbon atoms. Particularly preferably, it is an unsubstituted alkylene group having 1 to 4 carbon atoms.

[0021] The partial structures of the siloxane polymer represented by formula (1) include, for example, allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, triethoxyvinylsilane, trimethoxyvinylsilane, vinyltris(2-ethoxy)silane, vinyltris(2-methoxy)silane, m-styryltriethoxysilane, m-styryltrimethoxysilane, p-styryltriethoxysilane, p-styryltrimethoxysilane, 3-(N-styrylmethyl-2-aminoethylamino)propyltrimethoxysilane, and 3-(triethoxysilyl)propyl It is derived from methacrylate, 3-(trimethoxysilyl)propyl methacrylate, 3-(triethoxysilyl)propyl acrylate, 3-(trimethoxysilyl)propyl acrylate, 2-(triethoxysilyl)ethyl methacrylate, 2-(trimethoxysilyl)ethyl methacrylate, 2-(triethoxysilyl)ethyl acrylate, 2-(trimethoxysilyl)ethyl acrylate, (triethoxysilyl)methyl methacrylate, (trimethoxysilyl)methyl methacrylate, (triethoxysilyl)methyl acrylate, or (trimethoxysilyl)methyl acrylate.

[0022] In the substructure represented by formula (2) above, R ２ This includes an aryl group, an alkyl group having 1 to 20 carbon atoms which may be substituted with substituents, and -O-R ３ , or -L ６ -M-R ４ The above R ３ is an alkyl group having 1 to 6 carbon atoms, which may be substituted with substituents, and preferably an unsubstituted alkyl group having 1 to 6 carbon atoms.

[0023] R ４ -R is an alkyl group having 1 to 3 carbon atoms, which may be substituted with substituents. ５ -O-R ６ Or H, preferably an unsubstituted alkyl group having 1 to 3 carbon atoms, -R ５ -O-R ６ Or it is H.

[0024] R ５R is an alkylene group having 1 to 3 carbon atoms, which may be substituted with substituents. ６ is an alkyl group having 1 to 3 carbon atoms, which may be substituted with substituents, or H. Preferably, R ５ is an unsubstituted alkylene group having 1 to 3 carbon atoms. Preferably, R ６ This is an unsubstituted alkyl group having 1 to 3 carbon atoms.

[0025] And M is -O-, -N(R ７ ) - or an aryl group. R ７ This is an alkyl group having 1 to 3 carbon atoms, an aryl group, or H, which may be substituted with substituents. Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, or a cyclopropyl group.

[0026] Preferably, R ７ This is an unsubstituted alkyl group, aryl group, or H with 1 to 3 carbon atoms.

[0027] In formulas (1) and (2), the alkylene group having 1 to 10 carbon atoms that may be substituted with the substituent, the alkyl group having 1 to 20 carbon atoms that may be substituted with the substituent, the alkyl group having 1 to 6 carbon atoms that may be substituted with the substituent, the alkyl group having 1 to 3 carbon atoms that may be substituted with the substituent, and the alkylene group having 1 to 3 carbon atoms that may be substituted with the substituent can be substituted with substituents such as alkyl groups, alkenyl groups, epoxy groups, isocyanate groups, aryl groups, halogen atoms, hydroxyl groups, nitro groups, sulfone groups, amide groups, amino groups, thiol groups, and ureido groups.

[0028] The partial structures of the siloxane polymer represented by formula (2) include, for example, diethoxy(3-glycidyloxypropyl)methylsilane, 3-glycidyloxypropyl(dimethoxy)methylsilane, 3-glycidyloxypropyl(diethoxy)methylsilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, and 3-(2-aminoethyl)propyl Dimethoxylan, 3-(2-aminoethyl)propyldiethoxylan, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, trimethoxy[3-(phenylamino)propyl]silane, 3-mercaptopropyl(dimethoxy)methylsilane, (3-mercaptopropyl)triethoxysilane, (3-mercaptopropyl)trimethoxysilane, 3-(triethoxysilyl ) Propyl isocyanate, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltripropoxysilane, (R)-N-1-phenylethyl-N'-triethoxysilylpropylurea, (R)-N-1-phenylethyl-N'-trimethoxysilylpropylurea, 1-[3-(trimethoxysilyl)propyl]urea, tetramethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltri Alkyltrialkoxysilanes such as methoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane;It is derived from trialkoxysilanes having aromatic groups such as phenyltrimethoxysilane, phenyltriethoxysilane, benzyltrimethoxysilane, and benzyltriethoxysilane, dialkoxysilanes such as dimethyldimethoxysilane and dimethyldiethoxysilane, cyclohexyltriethoxysilane, or cyclohexyltrimethoxysilane.

[0029] The content of component (a) in the resin composition for forming optical components of the present invention is 5% to 97% by mass, based on 100% by mass of the total solid content in the composition. Preferably, it is 10% to 95% by mass. The total solid content in the composition refers to the sum of the masses of components (a), (b), (c), and (d).

[0030] <Component (b)> The surface-modified silica nanoparticles, which are component (b) of the resin composition for forming optical components of the present invention, are silica nanoparticles whose surfaces have been modified with a silane coupling agent.

[0031] The above-mentioned silica nanoparticles can be solid silica nanoparticles, mesoporous silica nanoparticles, or hollow silica nanoparticles. There are no particular limitations.

[0032] Hollow silica nanoparticles are particles that have an outer shell layer made of silica, with a hollow interior surrounded by the outer shell layer, containing air within the cavity. Hollow silica nanoparticles have excellent low refractive index and heat insulating properties. Solid silica nanoparticles are particles that do not have a hollow interior like hollow silica nanoparticles. Furthermore, there are no particular limitations on the shape of hollow silica nanoparticles and solid silica nanoparticles, and they may be spherical, ellipsoidal, or approximately spherical, such as polyhedral shapes that can approximate a sphere. Hollow and solid silica nanoparticles may be synthesized or commercially available. Examples of commercially available solid silica nanoparticles include organosilica sol (Nissan Chemical Corporation) and high-purity organosol (Fuso Chemical Co., Ltd.). Examples of commercially available hollow silica nanoparticles include Thruria (JGC Catalysts & Chemicals Corporation) and HighPresica (Ube Eximo Corporation).

[0033] The average primary particle diameter of hollow silica particles, as observed by transmission electron microscopy, can be in the range of 20 nm to 150 nm, 40 nm to 150 nm, or 40 nm to 100 nm. By setting the average primary particle diameter of hollow silica particles to 20 nm to 150 nm, the refractive index of the cladding material can be lowered while maintaining transparency.

[0034] The average particle diameter (DLS average particle diameter) of hollow silica particles measured by dynamic light scattering (DLS) can be in the range of 5 nm to 150 nm, 40 nm to 150 nm, or 40 nm to 100 nm. By setting the average particle diameter of hollow silica particles measured by dynamic light scattering to 5 nm to 150 nm, the refractive index of the cladding material can be lowered while maintaining transparency.

[0035] The outer shell thickness of hollow silica particles, as observed by transmission electron microscopy, can be in the range of 3.0 to 15.0 nm, or 3.0 to 12.0 nm, preferably 3.0 to 8.0 nm. By setting the outer shell thickness of hollow silica particles to 3.0 to 15.0 nm, damage to the hollow silica particles is prevented, and the cladding material can be made to have a low refractive index.

[0036] Furthermore, hollow silica particles may contain aluminum atoms, and the amount of aluminum atoms present in the entire hollow silica particle (i.e., the entire particle including the surface and interior) (in short, the aluminum atom content in the hollow silica particle) is Al ２ O ３ The amount of aluminum atoms present in the entire hollow silica particle can be calculated as Al 120 to 50,000 ppm, 500 to 20,000 ppm, or 500 to 5,000 ppm relative to the mass of the hollow silica particle. ２ O ３ By converting the surface charge to 120 to 50,000 ppm relative to the mass of the hollow silica particles, the surface charge of the hollow silica particles increases, causing electrical repulsion between the particles and improving the dispersion stability in the cladding material.

[0037] The surface charge of hollow silica particles can be in the range of 20 to 250 μeq / g, 20 to 100 μeq / g, or 20 to 45 μeq / g, when calculated as the surface charge amount (negative charge amount) per gram of hollow silica particles.

[0038] By setting the surface charge of hollow silica particles to 20 to 250 μeq / g (negative charge amount per gram of hollow silica particles), electrical repulsion occurs between the hollow silica particles, thereby improving dispersion stability in the cladding material. The surface charge of hollow silica particles changes depending on the amount of aluminum atoms (aluminosilicate) present in the hollow silica particles, which is one of the contributing factors.

[0039] The refractive index of the hollow silica particles can be in the range of 1.20 to 1.45, or 1.25 to 1.40. By setting the refractive index of the hollow silica particles to 1.20 to 1.45, the refractive index of the cladding material can be reduced.

[0040] The above-mentioned silane coupling agents can be used individually or in combination, and at least one of the silane coupling agents used for surface modification contains an ethylenically unsaturated double bond. Examples of silane coupling agents containing an ethylenically unsaturated double bond include silane coupling agents having a vinyl group, a methacrylic group, or an acrylic group, with silane coupling agents having a methacrylic group or an acrylic group being preferred.

[0041] Examples of silane coupling agents having a vinyl group include vinyltrimethoxysilane, vinyltriethoxysilane, 4-vinylphenyltrimethoxysilane, dimethylvinylethoxysilane, allyltrimethoxysilane, and 1,3-diallyl-5-(3-trimethoxysilyl)propyl)triazinan-2,4,6-trione.

[0042] Silane coupling agents having a methacrylic group or acrylic group include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloxypropylmethyldiethoxysilane, methacryloxymethyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxypropyltris(methoxyethoxy)silane, and [8-(methacryloyloxy)octyl]trimethoxy Examples include sisilane, [8-(methacryloyloxy)octyl]methyldimethoxysilane, [8-(methacryloyloxy)octyl]triethoxysilane, [8-(methacryloyloxy)octyl]methyldiethoxysilane, 2-allyloxy3-methacryloxypropyltrimethoxysilane, 2-allyloxy3-methacryloxypropylmethyldimethoxysilane, 2-allyloxy3-methacryloxypropyltriethoxysilane, 2-allyloxy3-methacryloxypropylmethyldiethoxysilane, 4-vinylphenyltrimethoxysilane, 4-vinylphenylmethyldimethoxysilane, 4-vinylphenyltriethoxysilane, and 4-vinylphenylmethyldiethoxysilane.

[0043] Furthermore, to improve dispersibility and performance in resins, silica nanoparticles can be surface-modified using other silane coupling agents. Examples of other silane coupling agents include silazane compounds, siloxane compounds, or alkoxysilanes.

[0044] Examples of silazane compounds include hexamethyldisilazane and hexaethyldisilazane.

[0045] Examples of siloxane compounds include hexamethyldisiloxane, 1,3-dibutyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, 1,3-divinyltetramethyldisiloxane, and hexaethyldisiloxane.

[0046] Examples of alkoxysilanes include trimethylmethoxysilane, trimethylethoxysilane, trimethylpropoxysilane, phenyldimethylmethoxysilane, chloropropyldimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, ethyltrimethoxysilane, dimethyldiethoxysilane, propyltriethoxysilane, n-butyltrimethoxysilane, n-hexyltrimethoxysilane, n-octyltriethoxysilane, n-octylmethyldiethoxysilane, n-octadecyltrimethoxysilane, phenyltrimethoxysilane, phenylmethyldimethoxysilane, phenethyltrimethoxysilane, dodecyltrimethoxysilane, n-octadecyltriethoxysilane, phenyldimethylethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, vinyltrimethoxysilane, vinyltris(β-methoxy) Ethoxy)silane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, N-β(aminoethyl)γ-(aminopropyl)methyldimethoxysilane, N-β(aminoethyl)γ-(aminopropyl)trimethoxysilane, N-β(aminoethyl)γ-(aminopropyl)triethoxysilane Examples include lanes, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, 3-isocyanatetopropyltriethoxysilane, trifluoropropyltrimethoxysilane, heptadecatrifluoropropyltrimethoxysilane, n-decyltrimethoxysilane, dimethoxydiethoxysilane, bis(triethoxysilyl)ethane, and hexaethoxydisiloxane. The silane coupling agent may be the same as the compound constituting the siloxane polymer of component (a).

[0047] The particle size of the surface-modified silica nanoparticles is preferably 5 to 150 nm, more preferably 10 to 130 nm, more preferably 15 to 120 nm, and particularly preferably 20 to 110 nm, depending on the balance between the transparency and dispersibility of the composition. In this invention, the particle size of the surface-modified silica nanoparticles refers to the average particle size measured by dynamic light scattering (DLS) method.

[0048] The content of component (b) in the resin composition for forming optical components of the present invention is preferably in the range of 3% to 60% by mass based on 100% by mass of the total solid content in the composition. More preferably, it is in the range of 5% to 50% by mass.

[0049] In the resin composition for forming optical components of the present invention, the content of component (b) is preferably in the range of 2 to 60 parts by mass, when the total mass of components (a) and (d) in the composition is 100 parts by mass. More preferably, it is in the range of 5 to 50 parts by mass.

[0050] <Component (c)> Component (c) in the resin composition for forming optical components of the present invention is at least one photopolymerization initiator. The photopolymerization initiator of component (c) is not particularly limited as long as it has absorption into the light source used during photocuring.

[0051] Examples of the photopolymerization initiators include tert-butylperoxy-iso-butyrate, 2,5-dimethyl-2,5-bis(benzoyldioxy)hexane, 1,4-bis[α-(tert-butyldioxy)-iso-propoxy]benzene, di-tert-butylperoxide, 2,5-dimethyl-2,5-bis(tert-butyldioxy)hexenehydroperoxide, α-(iso-propylphenyl)-iso-propylhydroperoxide, tert-butylhydroperoxide, 1,1-bis(tert-butyldioxy)-3,3,5-trimethylcyclohexane, butyl-4,4-bis(tert-butyldioxy)valerate, cyclohexanone peroxide, 2,2',5,5'-tetra(tert-butylperoxycarbonyl)benzophenone, 3 Organic peroxides such as ,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(tert-amylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(tert-hexylperoxycarbonyl)benzophenone, 3,3'-bis(tert-butylperoxycarbonyl)-4,4'-dicarboxybenzophenone, tert-butylperoxybenzoate, di-tert-butyldiperoxyisophthalate, etc.; quinones such as 9,10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, etc.; benzoin derivatives such as benzoin methyl, benzoin ethyl ether, α-methylbenzoin, α-phenylbenzoin, etc.2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-[4-{4-(2-hydroxy-2-methylpropionyl)benzyl}phenyl]-2-methylpropan-1-one, phenylglyoxylic acid methyl ester, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl Examples include alkylphenone compounds such as nyl)-1-butanone and 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholine-4-ylphenyl)-butan-1-one; acylphosphine oxide compounds such as phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide and diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide; and oxime ester compounds such as 2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione and 1-(O-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone.

[0052] The aforementioned photopolymerization initiators are commercially available, for example, OMNIRAD® 651, 184, 500, 2959, 127, 754, 907, 369, 379, 379EG, 819, 819DW, 1700, 1870, 784, 1173, MBF, 4265, and TPO (all IGM) Resins Inc.) [formerly IRGACURE® 651, 184, 500, 2959, 127, 754, 907, 369, 379, 379EG, 819, 819DW, 1700, 1870, 784, 1173, MBF, 4265, TPO (all manufactured by BASF Japan Ltd.)], IRGACURE® 1800, OXE01, OXE02 (all manufactured by BASF Japan Ltd.), KAYACURE® DETX, MBP, DMBI, EPA, OA (all manufactured by Nippon Kayaku Co., Ltd.), VICURE-10, 55 (all manufactured by STAUFFER Examples include ESACURE® KIP150, TZT, 1001, KTO46, KB1, KL200, KS300, EB3, Triazine-PMS, Triazine A, Triazine B (all manufactured by DKSH Japan Co., Ltd.), ADEKA optomer N-1717, N-1414, N-1606 (manufactured by ADEKA Corporation).

[0053] (c) The photopolymerization initiator of component (c) can be used alone or in combination of two or more types.

[0054] The content of component (c) in the resin composition for forming optical components of the present invention is 0.1% to 15% by mass, based on 100% by mass of the total solid content in the composition. Preferably, it is 0.3% to 10% by mass.

[0055] The content of component (c) in the resin composition for forming optical components of the present invention is preferably in the range of 0.05 parts by mass to 15 parts by mass, when the total mass of components (a) and (d) in the composition is 100 parts by mass. More preferably, it is in the range of 0.2 parts by mass to 10 parts by mass.

[0056] <Component (d)> The polyfunctional thiol compound that can be used as component (d) of the present invention is not particularly limited, but the polyfunctional thiol compound preferably has 2 to 6 thiol groups, and more preferably 2 to 4. Furthermore, as the above polyfunctional thiol compound, compounds represented by the following formulas (A1) to (A4) are preferred, and compounds represented by the following formulas (A2) to (A4) are more preferred.

[0057] In formula (A1), R ａ１ R represents an organic group having a thiol group. However, the thiol group described in formula (A1) is R ａ１ It is bonded to the carbon atom.

[0058] In equations (A2) and (A3), R ａ２ Each of these independently represents an organic group having an alkyl group, a halogenated alkyl group, an alkenyl group, an aryl group, a thiol group, or a thioureid group, and R ａ３ Each of these independently represents a hydrogen atom, a halogenated alkyl group, or an alkyl group which may be substituted with a hydroxyl group, L １ Each of the following independently represents a single bond or an alkylene group, x represents an integer from 2 to 4, and y and z represent integers from 1 to 3. However, at least two R ａ４ L is an organic group having a thiol group. １ When is an alkylene group, oxygen atoms may be interposed between its carbon atoms, and formulas (A2) and (A3) do not contain a structure in which -O-C-O- is formed within the molecule.

[0059] In formula (A4), R ａ４ ~R ａ６ Each of these independently represents an organic group having an alkyl group, a halogenated alkyl group, an alkenyl group, an aryl group, a thiol group, or a thioureid group, L ２ ~L ４ R represents an alkylene group. ａ４ ~R ａ６ At least two of them are organic groups containing a thiol group.

[0060] In formulas (A1) to (A4), alkyl groups having 1 to 18 carbon atoms are preferred, alkyl groups having 1 to 10 carbon atoms are more preferred, and alkyl groups having 1 to 8 carbon atoms are even more preferred. Specific examples of the alkyl groups include methyl group, ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, and 1-ethyl-n-propyl group. 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n- Butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,Examples include 3-trimethylcyclopropyl group, 2,2,3-trimethylcyclopropyl group, 1-ethyl-2-methylcyclopropyl group, 2-ethyl-1-methylcyclopropyl group, 2-ethyl-2-methylcyclopropyl group and 2-ethyl-3-methylcyclopropyl group, 2-ethyl-n-hexyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, etc.

[0061] Examples of alkyl halides include groups in which at least one carbon atom of the alkyl group is substituted with a halogen atom. Halogenated alkyl groups having 1 to 18 carbon atoms are preferred, halogenated alkyl groups having 1 to 10 carbon atoms are more preferred, and halogenated alkyl groups having 1 to 8 carbon atoms are even more preferred. Specific examples of the above-mentioned halogenated alkyl groups include fluoromethyl group, difluoromethyl group, trifluoromethyl group, bromodifluoromethyl group, 2-chloroethyl group, 2-bromoethyl group, 1,1-difluoroethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, 2-chloro-1,1,2-trifluoroethyl group, pentafluoroethyl group, 3-bromopropyl group, 2,2,3,3-tetrafluoropropyl group, 1,1,2,3,3,3-hexafluoropropyl group, 1,1,1,3,3,3-hexafluoroisopropyl group, 3-bromo-2-methylpropyl group, 4-bromobutyl group, perfluoropentyl group, and 2-(perfluorohexyl)ethyl group.

[0062] As the alkenyl group, an alkenyl group having 2 to 10 carbon atoms is preferred, and an alkenyl group having 2 to 8 carbon atoms is more preferred. Specific examples of the above alkenyl groups include ethenyl group, 1-propenyl group, 2-propenyl group, 1-methyl-1-ethenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-n-propylethenyl group, 1-methyl-1-butenyl group, 1-methyl-2-butenyl group, 1-methyl-3-butenyl group, 2-ethyl-2-propenyl group, 2-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2-methyl-3-butenyl group, 3 Examples include methyl-1-butenyl group, 3-methyl-2-butenyl group, 3-methyl-3-butenyl group, 1,1-dimethyl-2-propenyl group, 1-i-propylethenyl group, 1,2-dimethyl-1-propenyl group, 1,2-dimethyl-2-propenyl group, 1-cyclopentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 1-methyl-1-pentenyl group, 1-methyl-2-pentenyl group, 1-methyl-3-pentenyl group, 1-methyl-4-pentenyl group, 1-n-butylethenyl group, 2-methyl-1-pentenyl group, and 2-methyl-2-pentenyl group.

[0063] The aryl group is preferably one having 6 to 30 carbon atoms, and more preferably one having 6 to 10 carbon atoms. Specific examples of the above aryl group include phenyl, naphthyl, anthracenyl, and pyrenyl groups.

[0064] Examples of alkylene groups include alkylene groups derived from the alkyl groups mentioned above, with alkylene groups having 1 to 18 carbon atoms being preferred, and alkylene groups having 1 to 8 carbon atoms being more preferred. Specific examples of the alkylene groups include methylene group, methylmethylene group, dimethylmethylene group, ethylene group, 1,2-dimethylethylene group, tetramethylethylene group, trimethylene group, propylene group, tetramethylene group, pentamethylene group, hexamethylene group, 1,2-cyclohexylene group, 1,3-cyclohexylene group, and 1,4-cyclohexylene group.

[0065] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0066] Examples of alkyl groups that may be substituted with a hydroxyl group include hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl, hydroxyheptyl, and hydroxyoctyl groups.

[0067] Examples of organic groups having a thiol group include mercaptomethyl group, 2-mercaptoethyl group, 2-mercaptopropyl group, 3-mercaptopropyl group, 4-mercaptobutyl group, 5-mercaptopentyl group, 6-mercaptohexyl group, 8-mercaptooctyl group, 10-mercaptodecyl group, 3,5-dimercaptophenyl group, 4-mercaptophenyl group, 3-mercaptophenyl group, 5-mercaptonaphthyl group, and groups represented by the following formula.

[0068] (In the equation, dashed lines represent connections.)

[0069] Examples of organic groups having a thioureido group include 3-thioureidopropyl.

[0070] Specific examples of compounds represented by formula (A1) include, but are not limited to, the compounds represented by formulas (A1-16) to (A1-33) below.

[0071]

[0072] Specific examples of compounds represented by formula (A2) include, but are not limited to, the compounds represented by formulas (A2-1) to (A2-10) below.

[0073]

[0074] Of the compounds represented by formula (A2), (A2-1) and (A2-2) are preferred.

[0075] Specific examples of compounds represented by formula (A3) include, but are not limited to, the compounds represented by formulas (A3-1) and (A3-2) below.

[0076]

[0077] Specific examples of compounds represented by formula (A4) include, but are not limited to, the compounds represented by the following formulas (A4-1) to (A4-3).

[0078]

[0079] As the polyfunctional thiol compound, commercially available products such as Karenz MT® PE1, NR1, BD1, TPMB, TEMB (all manufactured by Resonac Co., Ltd.), and TMMP, TEMPIC, PEMP, EGMP-4, DPMP, PEPT (all manufactured by Sakai Chemical Industry Co., Ltd.) can be used.

[0080] The content of component (d) of the present invention is 2 to 100 parts by mass, preferably 3 to 50 parts by mass, per 100 parts by mass of component (a). If the content of component (d) is less than 2 parts by mass, the crack resistance of the cured product and molded article obtained from the resin composition for forming optical components will be insufficient, and cracks may occur, especially during thermal shock tests. If the content of component (d) is more than 100 parts by mass, the curing of the resin composition for forming optical components will be uneven, and there is a risk of phase separation and clouding when exposed to harsh environments such as high temperature and high humidity, or a decrease in storage stability.

[0081] The polyfunctional thiol compounds of component (d) described above can be used individually or in combination of two or more.

[0082] <(Meth)acrylate Compounds> The resin composition for forming optical components of the present invention may further contain (meth)acrylate compounds. In the present invention, (meth)acrylate compounds include both acrylate compounds and methacrylate compounds, and for example, (meth)acrylic acid includes acrylic acid and methacrylic acid.

[0083] Specifically, the above (meth)acrylate compounds include, for example, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, glycerin tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, ethoxylated glycerin tri(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, 1,3-propanediol di(meth)acrylate, and 1,3-but Dianediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 2-methyl-1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, bis(2-hydroxyethyl) isocyanurate di(meth)acrylate, tris(2-hydroxyethyl) isocyanurate tri(meth)acrylate, tricyclo[5.2.1.0 ２，６Examples include decanedimethanol di(meth)acrylate, dioxane glycol di(meth)acrylate, 2-hydroxy-1-acryloyloxy-3-methacryloyloxypropane, 2-hydroxy-1,3-di(meth)acryloyloxypropane, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, bis[4-(meth)acryloylthiophenyl]sulfide, bis[2-(meth)acryloylthioethyl]sulfide, 1,3-adamantanediol di(meth)acrylate, 1,3-adamantanedimethanol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and polypropylene glycol di(meth)acrylate. Among these, preferred (meth)acrylate compounds include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, and tris(2-hydroxyethyl) isocyanurate tri(meth)acrylate.

[0084] In the resin composition for forming optical components of the present invention, if a (meth)acrylate compound is included, its content is 5% to 100% by mass based on 100% by mass of the total solid content in the composition. Preferably, it is 10% to 70% by mass.

[0085] <Solvent> The resin composition for forming optical components of the present invention may further contain a solvent. The solvent is not particularly limited as long as it dissolves components (a), (b), (c), and (d).

[0086] Examples of the aforementioned solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol monobutyl ether, propylene glycol monobutyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyethyl acetate, ethyl hydroxyethyl acetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, 2-heptanone, and γ-butyrolactone. The solvent can be used alone or in combination of two or more.

[0087] If a solvent is included, the amount used is preferably 3% to 50% by mass, and particularly preferably 5% to 40% by mass, relative to the total amount of solids in the composition.

[0088] Furthermore, the resin composition for forming optical components of the present invention may optionally contain additives such as antioxidants, reactive diluents, curing agents, curing aids, sensitizers, plasticizers, light stabilizers (HALS), and adhesion treatment agents, as long as they do not impair the effects of the present invention.

[0089] The use of the resin composition for forming optical components of the present invention will be described below.

[0090] <Optical Waveguides> Optical components, which are optical waveguides, can be formed from the resin composition for forming optical components of the present invention. The resin composition for forming optical components of the present invention is applicable to both cladding materials that form the cladding portion of an optical waveguide and core materials that form the core portion, but is particularly suitable for cladding materials where a lower refractive index than that of the core is required. Furthermore, the resin composition for forming optical components of the present invention can be used in combination with various materials that have been conventionally used to form the cladding portion and core portion of optical waveguides to form optical waveguides. That is, materials that harden by light irradiation or heat treatment, such as materials mainly composed of silicone resin, acrylic resin, vinyl resin, epoxy resin, polyimide resin, polyolefin resin, polynorbornene resin, etc., can be appropriately selected and used as cladding materials and core materials.

[0091] The method for manufacturing an optical waveguide formed using the resin composition for forming optical components of the present invention is not particularly limited. For example, an optical waveguide containing a cured product of the resin composition for forming optical components of the present invention can be formed by applying the resin composition for forming optical components of the present invention or the above-mentioned conventional materials to a desired substrate using a coating device such as a spin coater, removing the solvent by heating or the like if the composition contains a solvent, and curing by exposure (photocuring) or heating (thermocuring). As a typical example, an optical waveguide containing a cured product of the resin composition for forming optical components of the present invention can be formed using lithography technology with a photomask, through etching and developing steps. Examples of light used for lithography include far ultraviolet light (wavelength: e.g., 193 nm, 253 nm), i-line (wavelength: 365 nm), g-line (wavelength: 436 nm), h-line (wavelength: 405 nm), and other ultraviolet rays.

[0092] <Optoelectric Mixed-Platform Substrate> An optoelectric mixed-platform substrate includes the optical waveguide described above. Typically, an optoelectric mixed-platform substrate includes an optical waveguide and an electrical circuit board. The electrical circuit board may include electronic components and wiring connected to the electronic components. Examples of electronic components include passive components such as capacitors, inductors, and resistors; active components such as semiconductor chips; and so on. The optical waveguide and the wiring of the electrical circuit board may be connected via a photoelectric conversion element. The photoelectric conversion element may include a combination of a light-emitting element capable of converting electricity into light (e.g., a surface-emitting light-emitting diode) and a light-receiving element capable of converting light into electricity (e.g., a photodiode). Furthermore, the optoelectric mixed-platform substrate may include optical elements such as mirrors for adjusting the optical path.

[0093] A preferred example of an optoelectronic hybrid substrate is one that includes a chip formed on a silicon wafer with an optical integrated circuit. This chip is expected to be put into practical use early on using silicon photonics, and is anticipated to be mounted on semiconductor packages, for example. An optoelectronic hybrid substrate containing this chip includes, for example, an electrical circuit board, a chip mounted on the electrical circuit board, and an optical waveguide. The optical waveguide can be used to connect the wiring of the electrical circuit board to the chip, or to connect multiple chips.

[0094] <Devices including optical-electric mixed-signal substrates> Examples of devices including optical-electric mixed-signal substrates include supercomputers, personal computers, mobile devices such as mobile phones, video equipment, measuring instruments, router devices, WDM devices, automobiles, game consoles, televisions, server devices, etc.

[0095] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples. The apparatus and conditions used for sample preparation and analysis of physical properties in the examples are as follows.

[0096] (1) Gel Permeation Chromatography (GPC) Apparatus: Prominence® GPC system manufactured by Shimadzu Corporation Column: Shodex® GPC KF-804L and GPC KF-803L manufactured by Resonaq Corporation Column temperature: 40°C Solvent: Tetrahydrofuran Detector: RI Calibration curve: Standard polystyrene (2) UV exposure apparatus: Batch-type UV irradiation apparatus manufactured by iGraphics Co., Ltd. (High-pressure mercury lamp 2kW x 1 lamp) (3) Haze apparatus: Haze meter NDH8000 manufactured by Nippon Denshoku Industries, Ltd. (4) Refractive index apparatus: Model 2010 / M prism coupler manufactured by Metricon Inc. (5) Spin coater apparatus: Cee200X manufactured by Brewer Science Inc. (6) Heat cycle testing equipment: Hitachi constant temperature bath EC-25EXHH manufactured by Hitachi Global Life Solutions, Ltd.

[0097] Furthermore, the abbreviations represent the following meanings. TEAH: 35% by mass aqueous solution of tetraethylammonium hydroxide [manufactured by Aldrich] MATMS: 3-(trimethoxysilyl)propyl methacrylate [manufactured by Shin-Etsu Chemical Co., Ltd.] MPTMS: Trimethoxy(3-methoxypropyl)silane [manufactured by Gelest] PGMEA: Propylene glycol monomethyl ether acetate THF: Tetrahydrofuran MEK: Methyl ethyl ketone DBU: 1,8-Diazabicyclo[5.4.0]-7-Undecene [manufactured by Tokyo Chemical Industry Co., Ltd.] X-40-2761: Polysiloxane polymer with undisclosed structure [manufactured by Shin-Etsu Chemical Co., Ltd.] M-350: Trimethylolpropane EO-modified triacrylate [manufactured by Toagosei Co., Ltd.] A-9300S: Tris-(2-acryloxyethyl) isocyanurate [manufactured by Shin-Nakamura Chemical Industry Co., Ltd.] A-TMPT-9EO: Ethoxylated trimethylolpropane triacrylate [manufactured by Shin-Nakamura Chemical Industry Co., Ltd.] Karenz MT-PE1: Pentaerythritol tetrakis(3-mercaptobutyrate) [manufactured by Resonac Co., Ltd.] Karenz MT-BD1: 1,4-bis(3-mercaptobutyryloxy)butane [manufactured by Resonac Co., Ltd.] Omnirad819: Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide [manufactured by IGM Resins B.V.] Omnirad2959: 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxymethylpropanone [manufactured by IGM Resins B.V.] [Manufactured by BASF] Irganox 1010: Pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) [Manufactured by BASF] KBM-503: 3-Methacryloxypropyltrimethoxysilane [Manufactured by Shin-Etsu Chemical Co., Ltd.]

[0098] [1] Synthesis of Polysiloxane [Synthesis Example 1] Synthesis of Polysiloxane A In a 300 mL reaction flask equipped with a condenser, 2.17 g (5.15 mmol) of TEAH, 6.95 g (386 mmol) of deionized water, and 6.7 g of THF were charged. The air in the flask was replaced with nitrogen using a nitrogen balloon, and the mixture was stirred at 40°C. A mixture of 19.17 g (77.2 mmol) of MATMS and 35.0 g (180 mmol) of MPTMS was added dropwise to this reaction flask over 30 minutes, and the mixture was stirred at 40°C for 6 hours. After stirring was complete, the resulting reaction mixture was cooled to room temperature (approximately 25°C). Then, 5.42 g of cation exchange resin [Amberlist® 15JWET, manufactured by Dow Chemical Company, hereinafter the same], which had been pre-washed with THF, and 0.5 g of powdered cellulose KC Floc® W-100GK (manufactured by Nippon Paper Industries Co., Ltd., hereinafter the same) were added to the reaction mixture, and the mixture was stirred for 2 hours to stop the reaction. After that, the mixture was filtered through a PTFE membrane filter with a pore size of 1.0 μm, and the filtrate was washed with THF. 2.5 mg of Q-1301 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., hereinafter the same) was added to the obtained filtrate as a polymerization inhibitor, and after dissolving by stirring, the solvent was removed under reduced pressure using an evaporator to obtain the target polysiloxane A. The weight-average molecular weight (Mw) of polysiloxane A, measured in polystyrene equivalent by GPC, was 2,300, and the dispersion ratio (Mw: weight-average molecular weight / Mn: number-average molecular weight) was 1.2.

[0099] [Synthesis Example 2] Polysiloxane B synthesis: 0.66 g (4.35 mmol) of DBU, 11.75 g (65.2 mmol) of deionized water, and 146.8 g of THF were charged into a 500 mL reaction flask equipped with a condenser. The air in the flask was replaced with nitrogen using a nitrogen balloon, and the mixture was stirred at 40°C. A mixture of 32.40 g (130 mmol) of MATMS and 59.15 g (304 mmol) of MPTMS was added dropwise to this reaction flask over 30 minutes, and the mixture was stirred at 40°C for 2.5 hours. After stirring was complete, the resulting reaction mixture was cooled to room temperature (approximately 25°C). Then, 13.6 g of cation exchange resin [Amberlist® 15JWET, manufactured by Dow Chemical Company, hereinafter the same], which had been pre-washed with THF, and 1.87 g of powdered cellulose KC Floc® W-100GK (manufactured by Nippon Paper Industries Co., Ltd., hereinafter the same) were added to the reaction mixture, and the mixture was stirred for 2 hours to stop the reaction. After that, the mixture was filtered through a PTFE membrane filter with a pore size of 1.0 μm, and the filtrate was washed with THF. 6.1 mg of Q-1301 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., hereinafter the same) was added to the obtained filtrate as a polymerization inhibitor, and after dissolving by stirring, the solvent was removed under reduced pressure using an evaporator to obtain the target polysiloxane B. The weight-average molecular weight (Mw) of polysiloxane B, measured in polystyrene equivalents by GPC, was 3,200, and the dispersion ratio (Mw: weight-average molecular weight / Mn: number-average molecular weight) was 1.3.

[0100] [2] Synthesis of hollow silica sol A surface-modified with a silane coupling agent having a methacrylic group Hollow silica sol A surface-modified with a silane coupling agent having a methacrylic group was obtained according to the methods described in Examples 7, 8 and 13 of WO2024 / 096130. Its physical properties were: total aluminum content of 1400 ppm, average primary particle diameter of 47 nm as measured by transmission electron microscopy, particle refractive index of 1.27, outer shell thickness of 6.2 nm, pH 6.0, average particle diameter of 77 nm as measured by DLS, SiO ２ Concentration 14.9% by mass, SiO2 of hollow silica particles ２ The surface charge, calculated per gram, was 51 μeq / g.

[0101] [3] Preparation of varnish composition Various acrylic compounds, photopolymerization initiators, antioxidants, adhesion treatment agents, and MEK 50phr were placed in a flask in the proportions shown in Tables 1 and 2 so that the total amount of acrylic compounds and thiol compounds was 5 g, and the solid components were completely dissolved by stirring. Then, MEK-dispersed hollow silica A was added and mixed in the proportions shown in Tables 1 and 2, and the MEK was removed by vacuum distillation using an evaporator. After that, the thiol compounds were added and stirred at room temperature to prepare the varnish composition.

[0102]

[0103]

[0104] [4] Preparation of cured film and Haze measurement A 40 mm x 40 mm x 1 mm thick quartz glass substrate was fitted with 50 μm thick Kapton tape as spacers at both ends, and the prepared varnish composition (1 ml) was dropped onto the center of the substrate. Next, a 40 mm x 40 mm x 1 mm thick quartz glass substrate was placed on top of the varnish-coated substrate, and a substrate was prepared in which various varnish compositions were sandwiched between glass substrates to a thickness of 50 μm. Then, using a batch-type UV exposure irradiation device manufactured by I-Graphics Co., Ltd., the exposure was performed at 2 J / cm² with ghhi interference. ２ The film was exposed to light for 100 seconds at 20 mW. Afterward, the resulting cured film was subjected to haze measurement while still sandwiched between glass substrates. The haze measurement was performed in accordance with JIS standards (JIS K7136).

[0105] The results of the haze measurements performed are shown in Table 3.

[0106]

[0107] [5] Measurement of the refractive index of the cured film by UV / O ３ After washing, the prepared varnish composition was applied dropwise and coated by spin coating (650 rpm x 60 seconds). Next, it was heated on a hot plate at 130°C for 1 minute, and then exposed to UV light at 2 J / cm² with ghi interference using a batch-type UV exposure device manufactured by I-Graphics Co., Ltd. ２The sample was exposed to light for 100 seconds at 20 mW. Then, a cured film approximately 50 μm thick was obtained by heating it on a hot plate at 180°C for 20 minutes. The refractive index of the obtained cured film at a wavelength of 1310 nm was measured using a prism coupler.

[0108] The results of the refractive index measurements performed above are shown in Tables 4 and 5.

[0109]

[0110]

[0111] From the refractive index measurement results in Tables 4 and 5, the cured films made from the compositions of Examples 1-8 and Comparative Examples 1-4, which contain silica nanoparticles, had a lower refractive index than the cured film made from the composition of Comparative Example 5, which does not contain silica nanoparticles. This indicates that including silica nanoparticles in the composition lowers the refractive index of the cured film compared to the case of resin alone.

[0112] [6] Heat cycle test The silicon wafer substrate was cleaned with an ultraviolet ozone cleaning device (Technovision, UV-208). KBM-503 (Shin-Etsu Chemical) was applied to the silicon wafer substrate and heated at 130°C for 15 minutes to produce an adhesion-treated silicon wafer substrate. Next, a spin coat was performed using a spin coater at 650 rpm for 60 seconds, followed by heating on a hot plate at 100°C for 2 minutes, and exposure was performed using a batch-type UV exposure irradiation device manufactured by I-Graphics, Inc. with ghi mixed light at 2 J (20 mW x 100 seconds). After that, heating was performed at 180°C for 20 minutes to obtain a cured film with a thickness of approximately 50 μm. The heat cycle test consisted of holding the temperature at -65°C for 15 minutes, raising it to 150°C at a rate of 15°C / min, holding it for 15 minutes, and then lowering it back down to -65°C at a rate of 15°C / min. One cycle was defined as 70 cycles, and the results were evaluated as A if no cracks or peeling were observed, and B if cracks or peeling were observed.

[0113] The results of the heat cycle tests conducted are shown in Table 6.

[0114]

[0115] The results from Examples 1 to 8 showed that the samples with added thiol compounds did not show any cracking or peeling even after 70 cycles, demonstrating good crack resistance. On the other hand, Comparative Examples 1 to 4 showed cracking and peeling within 70 cycles or less. This confirmed that the addition of thiol compounds improved crack resistance, thus confirming the superiority of the present invention.

Claims

1. A resin composition for forming optical components comprising (a) a siloxane polymer having unsaturated bonding groups, (b) surface-modified silica nanoparticles, (c) a photopolymerization initiator, and (d) a polyfunctional thiol compound.

2. The resin composition for forming optical components according to claim 1, wherein the polyfunctional thiol compound (d) has 2 to 6 thiol groups.

3. The resin composition for forming an optical member according to claim 1, wherein the above-mentioned (d) polyfunctional thiol compound is at least one selected from the group consisting of compounds represented by the following formulas (A2) to (A4). (In formulas (A2) and (A3), R ａ２ each independently represents an organic group having an alkyl group, a halogenated alkyl group, an alkenyl group, an aryl group, a thiol group or a thioureido group, and R ａ３ each independently represents a hydrogen atom, a halogenated alkyl group, or an alkyl group optionally substituted with a hydroxy group, and L １ each independently represents a single bond or an alkylene group, x represents an integer of 2 to 4, and y and z represent integers of 1 to 3. However, at least two R ａ２ are organic groups having a thiol group, and when L １ is an alkylene group, an oxygen atom may be interposed between its carbon atoms, and in formulas (A2) and (A3), the structure of -O-C-O- is not included in the molecule. In formula (A4), R ａ４ to R ａ６ each independently represents an organic group having an alkyl group, a halogenated alkyl group, an alkenyl group, an aryl group, a thiol group or a thioureido group, and L ２ to L ４ represent an alkylene group. However, at least two of R ａ４ to R ａ６ are organic groups having a thiol group.) 4. The resin composition for forming optical components according to claim 1, wherein the siloxane polymer having an unsaturated bonding group (a) is a siloxane polymer comprising at least a substructure represented by formula (1). (In formula (1), R １ L is an unsaturated bonding group. ５ (This is an alkylene group having 1 to 10 carbon atoms, or a single bond, which may be substituted with substituents.) 5. The resin composition for forming optical components according to claim 4, wherein the siloxane polymer having an unsaturated bonding group (a) is a siloxane polymer further comprising a substructure represented by formula (2). (In formula (2), R ２ This includes an aryl group, an alkyl group having 1 to 20 carbon atoms which may be substituted with substituents, and -O-R ３ , or -L ６ -M-R ４ And R ３ L is an alkyl group having 1 to 6 carbon atoms, which may be substituted with substituents. ６ R is an alkylene group having 1 to 10 carbon atoms, which may be substituted with substituents. ４ -R is an alkyl group having 1 to 3 carbon atoms, which may be substituted with substituents. ５ -O-R ６ or H, R ５ R is an alkylene group having 1 to 3 carbon atoms, which may be substituted with substituents. ６ is an alkyl group having 1 to 3 carbon atoms, which may be substituted with substituents, or H, and M is -O-, -N(R ７ )-, or an aryl group, R ７ (This is an alkyl group, aryl group, or H group having 1 to 3 carbon atoms, which may be substituted with substituents.) 6. The above R １ The resin composition for forming optical components according to claim 4, wherein the group is a (meth)acryloyl group, a (meth)acryloyloxy group, a vinyl group, a styryl group, or an ethynyl group.

7. The above L ５ The resin composition for forming optical components according to claim 4, wherein the group is an unsubstituted alkylene group having 1 to 10 carbon atoms.

8. The resin composition for forming optical components according to claim 4, wherein the substituent is at least one selected from the group consisting of alkyl groups, alkenyl groups, epoxy groups, isocyanate groups, aryl groups, halogen atoms, hydroxyl groups, nitro groups, sulfone groups, amide groups, amino groups, thiol groups, and ureido groups.

9. The resin composition for forming optical components according to claim 5, wherein the substituent is at least one selected from the group consisting of alkyl groups, alkenyl groups, epoxy groups, isocyanate groups, aryl groups, halogen atoms, hydroxyl groups, nitro groups, sulfone groups, amide groups, amino groups, thiol groups, and ureido groups.

10. The resin composition for forming optical components according to claim 1, wherein the (b) surface-modified silica nanoparticles are silica nanoparticles surface-modified with at least one silane coupling agent, and at least one of the silane coupling agents contains an ethylenically unsaturated double bond.

11. The resin composition for forming optical components according to claim 1, wherein the particle size of the surface-modified silica nanoparticles (b) measured by dynamic light scattering (DLS) is 5 to 150 nm.

12. The resin composition for forming optical components according to claim 1, further comprising a (meth)acrylate compound.

13. The resin composition for forming optical components according to claim 1, further comprising a solvent.

14. The resin composition for forming an optical component according to any one of claims 1 to 13, wherein the optical component is an optical waveguide.

15. The resin composition for forming an optical component according to any one of claims 1 to 13, wherein the optical component is the cladding portion of an optical waveguide.

16. An optical waveguide comprising a cured product of the resin composition for forming optical components according to any one of claims 1 to 13.

17. A photoelectric mixed-signal substrate including the optical waveguide of claim 16.

18. Apparatus comprising the photoelectric mixed-signal substrate of claim 17.

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