JP2015096559A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyene-polythiol-based resin composition excellent in heat resistance.SOLUTION: There is provided a resin composition containing (A) a silsesquioxane derivative represented by the general formula [1] having two or more carbon-carbon unsaturated bonds per a molecule and a random type structure, (B) polythiol and (C) photo-radical polymerization initiator. The general formula [1], where Rhas one or more kind of functional group selected from a (meth)acryloyl group, a vinyl group, a vinyl ether group, an allyl group and an allyl ether group and Rmay be same or different, a part of the (meth)acryloyl group, the vinyl group, the vinyl ether group, the allyl group and the ally ether group may be substituted by an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a halogen and m represents a polymerization degree.

Description

The present invention relates to an adhesive comprising, for example, a polyene-polythiol resin composition. The present invention relates to an adhesive body, a cured body, and an optical component that are bonded using the adhesive. Here, “poly” indicates polyfunctionality of bifunctionality or higher.

In recent years, resin compositions that are cured by irradiation with actinic rays such as ultraviolet rays or heat have been used in various fields such as adhesives and coating agents. As one of such resin compositions, a resin composition containing polyene and polythiol as main components is known (Patent Document 1).

The polyene-polythiol-based resin composition has excellent transparency in the visible light region (380 to 780 nm), adhesiveness, and surface curability under air (hereinafter referred to as surface curability). As adhesives and molding materials for transparent plastics and the like, they are used in various fields such as optical parts and electronic parts.

However, the conventional polyene-polythiol-based resin has a problem that the resin composition is yellowed and the transparency is lowered when exposed to a high temperature exceeding 200 ° C. such as solder reflow. Therefore, a resin composition satisfying excellent heat resistance has been desired.

Silsesquioxane derivatives are one of the materials that have recently attracted attention as resin compositions having excellent heat resistance and light resistance. A radical reaction type or addition reaction type silsesquioxane derivative, a copolymer, a resin and a method for producing them are disclosed that react with light or heat (Patent Document 2). A resin composition, a varnish, a molded body, an adhesive, an adhesive sheet, a sealing material, a nanoimprinting composition, and the like using the above-described properties are disclosed (Patent Document 3).

Patent Document 3 shows that a polyene-polythiol-based resin assembly composition using a silsesquioxane derivative has transparency, adhesiveness, and heat resistance. Adhesives utilizing the above characteristics, sealing agents for liquid crystal sealing, cured films, etc. are disclosed.

Japanese Patent Laid-Open No. 03-243626 JP 2004-143449 A JP 2010-168452 A

However, Patent Document 2 does not describe an application such as an adhesive. The silsesquioxane derivative of Patent Document 3 is a cage type. The resin composition using a cage-type silsesquioxane derivative has a problem that it does not dissolve in the polyene-polythiol-based resin composition.

An object of this invention is to provide the polyene-polythiol-type resin composition excellent in heat resistance.

The solution to the above problem is achieved by adopting the following.

（式中、Ｒ_０は、（メタ）アクリロイル基、ビニル基、ビニルエーテル基、アリル基及びアリルエーテル基から選ばれる１種以上の官能基を有する。Ｒ_０は、同一でも異なっても良い。（メタ）アクリロイル基、ビニル基、ビニルエーテル基、アリル基及びアリルエーテル基は、一部が、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、炭素数１〜６のハロゲン化アルキル基、フェニル基、ハロゲンで置換されても良い。ｍは重合度を表す。）
更に、（Ｄ）シルセスキオキサン誘導体以外の、炭素−炭素不飽和結合を有する化合物を含有する該樹脂組成物であり、更に、（Ｅ）酸化防止剤を含有する該樹脂組成物であり、更に、（Ｆ）密着性付与剤を含有する該樹脂組成物であり、該樹脂組成物からなる接着剤であり、該接着剤を用いて接着してなる接着体であり、該樹脂組成物からなる硬化体であり、該硬化体からなる層と、この層より高い屈折率を有する層とを積層してなる光導波路であり、該樹脂組成物を含む光学部品である。 The present invention provides (A) a silsesquioxane derivative represented by the following general formula [1] having two or more carbon-carbon unsaturated bonds per molecule and having a random structure: (B) A resin composition containing polythiol and (C) a photoradical polymerization initiator,
General formula [1]

(In the formula, R ₀ has one or more functional groups selected from a (meth) acryloyl group, a vinyl group, a vinyl ether group, an allyl group, and an allyl ether group. R ₀ may be the same or different. Some of the (meth) acryloyl group, vinyl group, vinyl ether group, allyl group and allyl ether group are alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, and alkyl halides having 1 to 6 carbon atoms. And may be substituted with a group, a phenyl group or a halogen, m represents the degree of polymerization.)
Further, (D) the resin composition containing a compound having a carbon-carbon unsaturated bond other than the silsesquioxane derivative, and (E) the resin composition containing an antioxidant, Further, (F) the resin composition containing an adhesion-imparting agent, an adhesive comprising the resin composition, and an adhesive bonded with the adhesive, the resin composition comprising A cured body, an optical waveguide formed by laminating a layer composed of the cured body and a layer having a higher refractive index than the layer, and an optical component including the resin composition.

The present invention has heat resistance.

Hereinafter, the present invention will be described in detail.

The (A) polyene of the present invention is a silsesquioxane represented by the following general formula [1] having (A) two or more carbon-carbon unsaturated bonds per molecule and a random structure. Is a derivative. (A) polyene of this invention is used as a main component with the polythiol mentioned later.

（式中Ｒ_０は、（メタ）アクリロイル基、ビニル基、ビニルエーテル基、アリル基及びアリルエーテル基から選ばれる１種以上の官能基を有する。Ｒ_０は、同一でも異なっても良い。（メタ）アクリロイル基、ビニル基、ビニルエーテル基、アリル基及びアリルエーテル基は、一部が、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、炭素数１〜６のハロゲン化アルキル基、フェニル基、ハロゲンで置換されても良い。ｍは重合度を表す。） General formula [1]

(In the formula, R ₀ has one or more functional groups selected from (meth) acryloyl group, vinyl group, vinyl ether group, allyl group and allyl ether group. R ₀ may be the same or different. ) The acryloyl group, vinyl group, vinyl ether group, allyl group, and allyl ether group are partially alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, and halogenated alkyl groups having 1 to 6 carbon atoms. , Phenyl group or halogen may be substituted, m represents the degree of polymerization.)

In the present invention, a silsesquioxane derivative that is preferably used is a silsesquioxane derivative having a functional group having a carbon-carbon unsaturated bond such as a (meth) acryloyl group, a vinyl group, a vinyl ether group, an allyl group, or an allyl ether group. It is a sesquioxane compound. 2-50 are preferable and, as for the average number of the functional groups in 1 molecule, 3-10 are more preferable.

The silsesquioxane derivative of the present invention is known to be able to obtain a ladder-type or random-type structure depending on the conditions of co-hydrolysis and co-condensation of alkoxysilane. Has a structure represented by the following general formula [2], for example.

（式中Ｒ_０は、（メタ）アクリロイル基、ビニル基、ビニルエーテル基、アリル基及びアリルエーテル基から選ばれる１種以上の官能基を有する。Ｒ_０は、同一でも異なっても良い。（メタ）アクリロイル基、ビニル基、ビニルエーテル基、アリル基及びアリルエーテル基は、一部が、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、炭素数１〜６のハロゲン化アルキル基、フェニル基、ハロゲンで置換されても良い。ｍは重合度を表す。） General formula [2]

(In the formula, R ₀ has one or more functional groups selected from (meth) acryloyl group, vinyl group, vinyl ether group, allyl group and allyl ether group. R ₀ may be the same or different. ) The acryloyl group, vinyl group, vinyl ether group, allyl group, and allyl ether group are partially alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, and halogenated alkyl groups having 1 to 6 carbon atoms. , Phenyl group or halogen may be substituted, m represents the degree of polymerization.)

The silsesquioxane derivative of the present invention is mainly composed of a silsesquioxane derivative having a random structure, but has a cage-type (cage-type) silsesquioxane as long as the object of the present invention is not impaired. A derivative or a silsesquioxane derivative having a ladder structure may be contained.

The molecular weight of the silsesquioxane derivative is preferably 100 to 100,000, and more preferably 500 to 60,000. When the molecular weight is 100 or more, excellent heat resistance can be obtained, and when the molecular weight is 100,000 or less, the viscosity of the adhesive does not become too high, and the workability and moldability are not impaired and stored. There is no problem with stability.

The molecular weight of the oligomer refers to the weight average molecular weight calculated as the average molecular weight per molecule. In the Example of this invention, the weight average molecular weight of polystyrene conversion measured by GPC (gel permeation chromatography) is used.
In the silsesquioxane derivative of the present invention, the gram number of the silsesquioxane derivative per equivalent of the ethylenically unsaturated group is preferably 50 to 300 g / eq, and more preferably 100 to 200 g / eq. The ethylenically unsaturated group refers to one or more functional groups selected from a (meth) acryloyl group, a vinyl group, a vinyl ether group, an allyl group, and an allyl ether group.

The (B) polythiol of the present invention has two or more thiol groups per molecule. The average molecular weight of the polythiol of the present invention is preferably 50 to 15,000. The polythiol of the present invention is used as a main component together with the aforementioned polyene. Preferred polythiols include mercapto group-substituted alkyl compounds such as dimercaptobutane and trimercaptohexane, mercapto group-substituted allyl compounds such as dimercaptobenzene, polyhydric alcohol esters such as thioglycolic acid and thiopropionic acid, and alkylenes of polyhydric alcohols. Examples include a reaction product of an oxide adduct and hydrogen sulfide.

Examples of the polythiol of the present invention include tris [(3-mercaptopropionyloxy) -ethyl] isocyanurate, trimethylolpropane-tris- (β-thiopropinate), tris-2-hydroxyethyl-isocyanurate-tris-β. -Mercaptopropionate, pentaerythritol tetrakis (β-thiopropionate), 1,8-dimercapto-3,6-dioxaoctane, 1,8-dimercapto-3,6-disulfide octane, triazine thiol, and more Examples thereof include polythiols of silsesquioxane derivatives. The polythiol of the present invention is not particularly limited, and may be a single or a mixture of two or more.

The mass ratio of the silsesquioxane derivative (A) of the present invention to the polythiol (B) is preferably from 5 to 95:95 to 5 when the total of (A) and (B) is 100. 90: 85-10 is more preferable, and 35-85: 65-15 is most preferable.

Furthermore, it is preferable that the resin composition of this invention contains (C) radical photopolymerization initiator.

The (C) photoradical polymerization initiator of the present invention is not particularly limited as long as it is a compound that absorbs light and generates a radical capable of initiating polymerization. Examples of the photo radical polymerization initiator of the present invention include benzoin derivatives such as benzyl, benzoin, benzoin benzoic acid, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether, benzophenone derivatives such as benzophenone and 4-phenylbenzophenone, 2,2- Alkylacetophenone derivatives such as dimethoxy-1,2-diphenylethane-1-one, 2,2-diethoxyacetophenone, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 1- (4-isopropylphenyl) -2-hydroxy- 2-methylpropan-1-one, 1- (4- (2-hydroxyethoxy) -phenyl) -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-2-methyl-1- Fe Α-hydroxyacetophenone derivatives such as rupropan-1-one, bisdiethylaminobenzophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino Α-Aminoalkylacetophenone derivatives such as -1- (4-morpholinophenyl) -1-butanone-1, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenyl And acylphosphine oxide derivatives such as phosphine oxide and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide. The radical photopolymerization initiator of the present invention is not particularly limited, and may be a single one or a mixture of two or more.

The radical photopolymerization initiator of the present invention can be mixed with polyene or polythiol in advance.

The amount of the (C) radical photopolymerization initiator used in the present invention is 0.01 to 100 parts by mass with respect to a total of 100 parts by mass of the component (A), the component (B), and the component (D) used as necessary. 10 mass parts is preferable and 0.05-5 mass parts is more preferable. If it is 0.01 mass part or more, sufficient sclerosis | hardenability can be obtained, and if it is 10 mass parts or less, visible light transparency will not be impaired.

The resin composition of the present invention can further contain a compound having a carbon-carbon unsaturated bond other than (D) a silsesquioxane derivative.

(D) The compound having a carbon-carbon unsaturated bond other than the silsesquioxane derivative is not particularly defined, but even if it is a monofunctional compound having one carbon-carbon unsaturated bond, carbon -It may be a bifunctional or higher functional compound having two or more carbon unsaturated bonds.

The viscosity of the compound having a carbon-carbon unsaturated bond other than the (D) silsesquioxane derivative of the present invention is preferably 1000 mPa · s or less and 500 mPa · s or less in terms of adjusting the viscosity of the composition. More preferred is 100 mPa · s or less.

The molecular weight of the compound having a carbon-carbon unsaturated bond other than the (D) silsesquioxane derivative of the present invention is preferably 1000 or less, more preferably 100 to 800, in terms of adjusting the viscosity of the composition. -500 is most preferred. The carbon-carbon unsaturated bond particularly refers to a carbon-carbon double bond.

Although it does not specifically limit as a compound which has a carbon-carbon unsaturated bond other than the (D) silsesquioxane derivative of this invention, 2-ethylhexyl (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, 2 -Hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, benzyl (meth) acrylate, butanediol mono (meth) acrylate, butyl (Meth) acrylate, ethylene oxide modified (hereinafter referred to as “EO”) cresol (meth) acrylate, dipropylene glycol (meth) acrylate, ethoxylated phenyl (meth) acrylate, ethyl (meth) acrylate, isobuty (Meth) acrylate, isooctyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclohentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, lauryl (meth) acrylate, nonyl Phenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate, octyl (meth) acrylate, phenoxyethyl (meth) acrylate, 1,9-nonanediol di (meth) acrylate, propylene oxide (hereinafter referred to as “PO”) .) Neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) a Lilate, tris ((meth) acryloxyethyl) isocyanurate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol hydroxypenta (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate , Pentaerythritol tetra (meth) acrylate trimethylolethane trivinyl ether, hexanediol divinyl ether, tetraethylene glycol divinyl ether, pentaerythritol divinyl ether, triethylene glycol diethylene vinyl ether, ethylene glycol dipropylene vinyl ether, triethylene glycol diethylene vinyl ether, diallyl phthalate , Diallyl maleate, Examples include arylaryl cyanurate, triallyl isocyanurate, triallyl trimellitate, tetraallyloxyethane, trimethylolpropane diallyl, and trimethylolpropane triallyl. Of these, allyl compounds are preferred. Examples of the allyl compound include diallyl phthalate, diallyl maleate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, tetraallyloxyethane, trimethylolpropane diallyl, trimethylolpropane triallyl and the like.

The amount of the compound having a carbon-carbon unsaturated bond other than the (D) silsesquioxane derivative of the present invention is low in viscosity, so that the workability is improved and the adhesiveness is improved. ), Component (B), and component (D) in a total of 100 parts by mass, 2 to 50 parts by mass are preferred, 5 to 30 parts by mass are more preferred, and 7 to 15 parts by mass are most preferred.

It is preferable that the resin composition of the present invention further contains (E) an antioxidant because excellent heat resistance and storage stability can be obtained.

(E) Antioxidant is an antioxidant substance added in order to suppress the oxidation of the component in a product. The antioxidant is not particularly limited, but is triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- ( 3,5-di-t-butyl-4-hydroxyphenyl) propionate], pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2′- Methylenebis (6-tert-butyl-p-cresol), isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2′-methylenebis (4-methyl-6-tert- Butylphenol), 2,2,4,4 tetramethyl-21-oxo-7-oxa-3.20-diazadispiro 5.111.2] -Henicosane-20-propionic acid dodecyl ester and 2,2,4,4 tetramethyl-21-oxo-7-oxa-3.20-diazadispiro [5.1.1.12] A mixture of henicosane-20-propionic acid tetradecyl ester, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, bis (2,2,6,6) Hindered amines such as -tetramethyl-4-piperidyl) sebacate, 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra- Phosphorus compounds such as tert-butyldibenz [d, f] [1,3,2] dioxaphosphine, dilauryl 3,3′-thiodipropionate, di Sulfur compounds such as listyl 3,3′-thiodipropionate, distearyl 3,3′-thiodipropionate, pentaerythrityltetrakis (3-laurylthiopropionate), 2-mercaptobenzimidazole, etc. . In these, a phenol type compound and / or a hindered amine compound are preferable.

The usage-amount of (E) antioxidant of this invention is 0.001-3 mass with respect to a total of 100 mass parts of a component (A), a component (B), and the component (D) used as needed. Part is preferable, and 0.01 to 2 parts by mass is more preferable. If it is 0.001 part by mass or more, durability and storage stability are sufficient, and if it is 3 parts by mass or less, reliable adhesiveness is obtained, and there is no possibility of becoming uncured.

The mass ratio of the polyene and the polythiol of the present invention is preferably 49: 1 to 1:49, more preferably 45: 5 to 5:45, from the viewpoint of obtaining good heat resistance and adhesiveness. In particular, it is most preferable when the double bond in the polyene and the thiol group in the polythiol have a chemical equivalent. The chemical equivalent here means that (number of moles of polyene / number of double bonds of polyene molecule) and (number of moles of polythiol / number of SH groups of polythiol molecule) are equal. Here, polyene refers to component (A) and component (D), and polythiol refers to component (B).

In the present invention, (F) an adhesion-imparting agent may be used to improve adhesion. As the adhesion-imparting agent, 3-glycidoxypropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyl-tris (β-methoxyethoxy) silane, γ- (meth) acryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltri Ethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-ureidopropyltriethoxysilane, hydroxyethyl (meta Acrylate Phosphate esters, (2-hydroxyethyl) (meth) acrylic acid phosphate, (meth) acrylate Roxio carboxyethyl acid phosphate, and (meth) acrylate Roxio carboxyethyl acid phosphate Tomono ethylamine half salt and the like.

(F) The usage-amount of an adhesive imparting agent is 0.001-10 mass parts with respect to a total of 100 mass parts of a component (A), a component (B), and the component (D) used as needed. Preferably, 0.01-5 mass parts is more preferable. If it is 0.001 part by mass or more, the adhesiveness is sufficient, and if it is 10 parts by mass or less, reliable adhesiveness is obtained.

The resin composition of the present invention includes a thermal radical polymerization initiator, a curing accelerator, a filler, a colorant, a thixotropy imparting agent, a plasticizer, a surfactant, and a lubricant as long as the desired effects are not impaired. Additives such as antistatic agents can be added.

The resin composition of the present invention can be used as an adhesive. Examples of the substrate to be bonded with the adhesive of the present invention and the substrate to form a molded body with the adhesive of the present invention include glass materials such as quartz, quartz glass, borosilicate glass and soda glass, potassium bromide, and calcium fluoride. Halogenated minerals such as sapphire, single crystal ceramics such as sapphire, acrylic resin, polycarbonate resin, polystyrene resin, polyester resin, polyethylene resin, polypropylene resin, fluororesin, cellulose resin, styrene-butadiene copolymer, methyl methacrylate-styrene copolymer Polymer, silicon resin, polycycloolefin resin, acrylonitrile-butadiene-styrene copolymer resin, polyphenyl sulfide resin, liquid crystal polymer, epoxy resin, resin reinforced with glass fiber or carbon fiber, silicon, resin Semiconductor materials such as manium, gallium, indium, zinc oxide and titanium oxide, the above-mentioned semiconductor materials deposited, plated and sputtered with metal layers, resin layers and ceramic layers, as well as iron, stainless steel, aluminum, zinc, magnesium and copper , Metal materials such as brass, phosphor bronze, silver, gold and platinum.

The resin composition of the present invention can be cured by active energy rays such as light and ultraviolet rays. An optical member using an adhesive made of the resin composition of the present invention can also be bonded by active energy rays.

For curing or bonding with active energy rays, halogen lamps, metal halide lamps, high power metal halide lamps (containing indium, etc.), low pressure mercury lamps, high pressure mercury lamps, ultra high pressure mercury lamps, xenon lamps, xenon excimer lamps, xenon flashes. An irradiation device using a lamp or the like as a light source can be applied, and further, laser light, electron beam (EUV), or the like can be applied.

The above apparatus can irradiate condensed light by a direct irradiation, a reflecting mirror, or the like, and collect and irradiate with a fiber.

The present invention uses, for example, a polyene which is a silsesquioxane derivative and a polyene-polythiol resin composition containing polythiol as a main component, thereby providing heat resistance, light resistance, transparency, fast curing, adhesion It has the effect that it is excellent in property and storage stability. The present invention can provide an adhesive body, a cured body, a molded body, an optical component, and an optical waveguide.

An optical waveguide confines light by creating a part with a slightly higher refractive index than the surroundings on the surface of the substrate or just below the substrate surface, and controls light propagation, branching, reflection, refraction, amplification, attenuation, etc. Electronic components that perform multiplexing / demultiplexing and switching. This invention can provide an optical waveguide by laminating | stacking the layer which consists of a hardening body of the resin composition of this invention, and the layer which has a higher refractive index than this layer.

Specific examples of specific components of the optical waveguide include optical multiplexing circuits, frequency filters, optical switches, and optical interconnection components used in the fields of communication and optical information processing.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

<Examples 1 to 10 and Comparative Examples 1 to 3>
Each component of the kind shown in Tables 1-2 was mixed with the composition shown in the table to prepare a resin composition. The following compounds were selected for each component described in Tables 1-2.
(A) Silsesquioxane derivative having two or more carbon-carbon unsaturated bonds per molecule and having a random structure (a-1) manufactured by Toagosei Co., Ltd .: polyacryloyloxypropyl polyorganosilsesqui Oxan (AC-SQ TA-100) (polystyrene equivalent weight average molecular weight 1,200 to 4,000 by GPC, acrylic group equivalent 165 g / eq
(A-2) manufactured by Toagosei Co., Ltd .: polymethacryloyloxypropyl polyorganosilsesquioxane (MAC-SQ TM-100) (weight average molecular weight in terms of polystyrene by GPC 1,000 to 2,500, methacryl group equivalent 179 g) / Eq
(B) Polythiol (b-1) manufactured by Sakai Chemical Industry Co., Ltd .: trimethylolpropane-tris- (β-thiopropionate) (TP)
(B-2) SC Organic Chemical Company: Tris [(3-mercaptopropionyloxy) -ethyl] isocyanurate (TEMPIC)
(D) Compound having carbon-carbon unsaturated bond other than silsesquioxane derivative (d-1) Nippon Kasei Co., Ltd .: triallyl isocyanurate (TAIC)
(D-2) Kurokin Kasei Co., Ltd .: diallyl maleate (DAM)
(C) Photoradical polymerization initiator (c-1) manufactured by BASF: 2,2-dimethoxy-1,2-diphenylethane-1-one (IRGACURE651)
(C-2) manufactured by BASF: 2-hydroxy-2-methyl-1-phenyl-propan-1-one (DAROCUR1173)
(E) Antioxidant (e-1) manufactured by BASF: isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (IRGANOX1135)
I would like the above contents.
(E-2) manufactured by Sumitomo Chemical Co., Ltd .: 2,2′-methylenebis (4-methyl-6-tert-butylphenol) (Sumilyzer MDP-S)
(F) Adhesion imparting agent (f-1) manufactured by Momentive: γ-methacryloxypropyltrimethoxysilane (A-174)
(F-2) Shin-Etsu Chemical Co., Ltd .: 3-glycidoxypropyltrimethoxysilane (KBM-403)
(G) Silsesquioxane derivative polyene having a cage structure (g-1) manufactured by Toagosei Co., Ltd .: Octa [(3-methacryloxypropyl) dimethylsiloxy] silsesquioxane] (Q-8) (molecular weight 2027)

The following performance evaluation was performed about the composition obtained by the said Example and comparative example, and the result is shown to Tables 1-2.

(Adhesive curing conditions)
For the evaluation, an adhesion test specimen was prepared according to the procedure described below.

Curing method Curing was performed under the condition of an integrated light amount of 3000 mJ / cm ² at a wavelength of 365 nm by a curing apparatus manufactured by HOYA using an ultra-high pressure mercury lamp.

(1) Viscosity of the viscosity composition was measured using an E-type viscometer under conditions of a temperature of 25 ° C. and a rotation speed of 20 rpm.

(2) Light transmittance (transparency evaluation, after UV curing)
As a test piece, a test piece was prepared by curing a resin composition having a shape of 20 mmφ × 200 μmt on a BK7 glass (borosilicate glass, 30 mmφ × 3 mmt) substrate under the curing conditions described above. The light transmittance was measured with a spectrophotometer (manufactured by Shimadzu Corporation, UV-2550), and the transmittance at wavelengths of 400 nm and 600 nm was measured. The evaluation results are shown in Tables 1-2.

(3) Heat resistance test (after light transmittance, heat resistance test)
A test piece was prepared by curing a resin composition having a shape of 20 mmφ × 200 μmt on a BK7 glass (30 mmφ × 3 mmt) substrate as a test piece under the curing conditions described above. This test piece was exposed to an atmosphere of 260 ° C. for 40 seconds. Using a spectrophotometer (manufactured by Shimadzu Corporation, UV-2550), the transmittance of the test piece after the exposure was measured at wavelengths of 400 nm and 600 nm, and those with 90% or more were evaluated as good. The evaluation results are shown in Tables 1-2.

(4) Light resistance test (after light transmittance, light resistance test)
A test piece was prepared by curing a resin composition having a shape of 20 mmφ × 200 μmt on a BK7 glass (30 mmφ × 3 mmt) substrate as a test piece under the curing conditions described above. This test piece was exposed for 80 hours under the light of illuminance 7 mW / cm < ² > of 365 nm light using the high pressure mercury lamp (The Toshiba Corporation make, Toscure 400 HC-0411 type | mold). Using a spectrophotometer (manufactured by Shimadzu Corporation, UV-2550), the transmittance of the test piece after the exposure was measured at wavelengths of 400 nm and 600 nm, and those with 90% or more were evaluated as good. The evaluation results are shown in Tables 1-2.

(5) Tensile bond shear strength (adhesiveness)
It measured according to JIS K 6850. Specifically, (Tempax glass) (trademark) (25 mm × 25 mm × 2.0 mm) as an adherend was used, and the bonded portion was 8 mm in diameter. Bonding and the adhesive were cured under the curing conditions described above to produce a tensile shear bond strength test piece. The produced test piece was measured for tensile shear bond strength at a tensile rate of 10 mm / min in an environment of a temperature of 23 ° C. and a humidity of 50% using a tensile tester. The evaluation results are shown in Tables 1-2.

The following was confirmed from Tables 1-2. The resin composition of the present invention is excellent in heat resistance, light resistance, transparency and adhesiveness. When the (A) silsesquioxane derivative of the present invention is not used, heat resistance, light resistance and adhesion cannot be obtained (Comparative Example 1). When a cage-type silsesquioxane derivative is used, it does not dissolve in the resin composition and the effect of the present invention cannot be obtained (Comparative Example 2). When the (B) polythiol of the present invention is not used, heat resistance and adhesiveness cannot be obtained (Comparative Example 3).

The present invention provides a polyene-polythiol-based resin composition excellent in heat resistance, light resistance, transparency, fast curability, adhesion, and storage stability. The adhesive of the present invention exhibits remarkable effects in various fields such as optical waveguide layers, optical components, and electronic components.

Claims (9)

(A) Silsesquioxane derivative represented by the following general formula [1] having two or more carbon-carbon unsaturated bonds per molecule and having a random structure, (B) polythiol, (C ) A resin composition containing a photo radical polymerization initiator.
General formula [1]

(In the formula, R ₀ has one or more functional groups selected from a (meth) acryloyl group, a vinyl group, a vinyl ether group, an allyl group, and an allyl ether group. R ₀ may be the same or different. Some of the (meth) acryloyl group, vinyl group, vinyl ether group, allyl group and allyl ether group are alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, and alkyl halides having 1 to 6 carbon atoms. And may be substituted with a group, a phenyl group or a halogen, m represents the degree of polymerization.) Furthermore, the resin composition of Claim 1 containing the compound which has a carbon-carbon unsaturated bond other than (D) silsesquioxane derivative. Furthermore, the resin composition of Claims 1-2 containing (E) antioxidant. The resin composition according to claim 1, further comprising (F) an adhesion-imparting agent. An adhesive comprising the resin composition according to claim 1. The adhesive body formed by adhere | attaching using the adhesive agent of Claim 5. A cured product comprising the resin composition according to claim 1. An optical waveguide formed by laminating a layer made of the cured body according to claim 7 and a layer having a higher refractive index than this layer. An optical component comprising the resin composition according to claim 1.