JP6834487B2 - Adhesive composition for UV curable optical materials - Google Patents

Description

The present invention relates to an adhesive composition for an ultraviolet curable optical material.

In recent years, with the spread of the Internet, the importance of technology for increasing communication capacity has increased, and optical fiber networks have been expanded. Optical materials and optical elements are used in this optical communication system, and examples of the materials such as the optical materials include plastic and glass. Plastic, glass and the like can be adhered with an adhesive composition.

Examples of the adhesive composition that can be used for plastics include, in Patent Document 1, a (meth) acrylic polymer (A) having a molecular weight of 50,000 to 140,000, a urethane (meth) acrylate (B), and 1 A polyfunctional monomer (C) having three or more (meth) acryloyloxy groups in a molecule and an aliphatic hydrocarbon having two (meth) acryloyloxy groups in one molecule and a main chain skeleton. A curable resin composition containing the bifunctional monomer (D) and the photopolymerization initiator (E) is described (claim 1).

Japanese Unexamined Patent Publication No. 2008-255228

Under such circumstances, in order to bond the fiber array as an optical material and the optical waveguide, a composition containing a compound having a (meth) acryloyloxy group was prepared based on the above-mentioned Patent Document 1, and this was prepared as described above. When used for adhesion, the present inventors have clarified that such a composition has a problem of low adhesiveness to glass and low moisture and heat resistance (Comparative Examples 1 to 3).
Therefore, an object of the present invention is to provide an adhesive composition for an ultraviolet curable optical material, which has excellent adhesiveness to glass and moisture and heat resistance.

As a result of diligent research to solve the above problems, the present inventors have made a compound (A) having an aromatic ring and a reactive silicon-containing group, and a (meth) acrylic having an aromatic ring and a (meth) acryloyloxy group. We have found that a predetermined effect can be obtained by using a composition containing the compound (B) and the photopolymerization initiator (C), and have reached the present invention.
The present invention is based on the above findings and the like, and specifically solves the above problems by the following configurations.

1. 1. It contains a compound (A) having an aromatic ring and a reactive silicon-containing group, a (meth) acrylic compound (B) having an aromatic ring and a (meth) acryloyloxy group, and a photopolymerization initiator (C). , Adhesive composition for UV curable optical materials.
2. 2. The adhesive composition for an ultraviolet curable optical material according to 1 above, wherein the aromatic ring contained in the compound (A) is at least one selected from the group consisting of a bisphenol ring, a biphenyl ring, a naphthalene ring and a fluorene ring. ..
3. 3. The ultraviolet curable optical according to 1 or 2 above, wherein the aromatic ring contained in the (meth) acrylic compound (B) is at least one selected from the group consisting of a bisphenol ring, a biphenyl ring, a naphthalene ring and a fluorene ring. Adhesive composition for materials.
4. The ratio of the content of the compound (A) to the total content of the compound (A), the (meth) acrylic compound (B) and the photopolymerization initiator (C) is 10 to 50% by mass. The content ratio of the (meth) acrylic compound (B) is 30 to 90% by mass, and the content ratio of the photopolymerization initiator (C) is 0.5 to 10% by mass. The adhesive composition for an ultraviolet curable optical material according to any one of 3.
5. The adhesive composition for an ultraviolet curable optical material according to any one of 1 to 4 above, which further contains a curing catalyst (G).
6. The adhesive composition for an ultraviolet curable optical material according to 5 above, wherein the curing catalyst (G) is at least one curing catalyst selected from the group consisting of a tin catalyst, a zirconium catalyst, and a titanium catalyst. ..

The adhesive composition for an ultraviolet curable optical material of the present invention is excellent in adhesiveness to glass and moisture and heat resistance.

FIG. 1 is a drawing schematically showing an example of a usage mode of the composition of the present invention.

The present invention will be described in detail below.
In addition, in this specification, (meth) acrylate represents acrylate or methacrylate, (meth) acryloyl represents acryloyl or methacryloyl, and (meth) acrylic represents acrylic or methacrylic.
In addition, the numerical range represented by using "~" in the present specification means a range including the numerical values before and after "~" as the lower limit value and the upper limit value.
Further, in the present specification, when the component contains two or more kinds of substances, the content of the above component means the total content of the two or more kinds of substances.

The adhesive composition for an ultraviolet curable optical material of the present invention (the composition of the present invention) is
It contains a compound (A) having an aromatic ring and a reactive silicon-containing group, a (meth) acrylic compound (B) having an aromatic ring and a (meth) acryloyloxy group, and a photopolymerization initiator (C). , An adhesive composition for an ultraviolet curable optical material.

Since the composition of the present invention has such a structure, it is considered that a desired effect can be obtained. The reason is not clear, but it is presumed to be as follows.
Since the composition of the present invention contains the (meth) acrylic compound (B), it can be rapidly cured by irradiating the composition of the present invention with ultraviolet rays.
Further, the composition of the present invention can be further cured by heating and / or humidity by containing the compound (A). Further, since the compound (A) has a reactive silicon-containing group, it has excellent adhesiveness to glass.
The compound (A) and the (meth) acrylic compound (B) contained in the composition of the present invention each have an aromatic ring. The shearing force of the adhesive layer obtained by the π-π interaction (π-π stacking interaction) between the aromatic ring of the compound (A) and the aromatic ring of the (meth) acrylic compound (B) is high. It is considered to be.

[Composition of the present invention]
Hereinafter, each component contained in the composition of the present invention will be described in detail.
<Compound (A) having an aromatic ring and a reactive silicon-containing group>
The compound (A) contained in the composition of the present invention is not particularly limited as long as it is a compound having at least one aromatic ring and at least one reactive silicon-containing group in one molecule.

The aromatic ring is not particularly limited, but is preferably an aromatic ring having 6 to 20 carbon atoms. The aromatic ring may have halogen atoms such as chlorine and bromine, for example.
Specific examples of the aromatic ring include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring, triphenylene ring, naphthalene ring, biphenyl ring, bisphenol ring, and terphenyl ring (three benzene rings can be connected in any manner. May be connected) and the like. Of these, a bisphenol ring, a biphenyl ring, a naphthalene ring, and a fluorene ring are preferable, and a bisphenol ring is more preferable.

In the bisphenol ring, the two benzene rings may be linked by any linking group. Examples of the linking group include −C (CH ₃ ) ₂ −, −CH ₂ −, −SO ₂ −, and −C (CF ₃ ) ₂ −.

Examples of the bisphenol ring include bisphenol A type, bisphenol F type, halogenated bisphenol A type, bisphenol S type, and bisphenol AF type.
Of these, bisphenol A type and bisphenol F type are preferable.

The reactive silicon-containing group has 1 to 3 reactive groups bonded to a silicon atom. The reactive silicon-containing group can be cross-linked by causing a reaction in the presence of humidity, a cross-linking agent or the like, if necessary, by using a catalyst or the like. Examples of the reactive silicon-containing group include a silicon halide-containing group, a silicon hydride-containing group, and a hydrolyzable silicon-containing group. Of these, a hydrolyzable silicon-containing group is preferable.

The hydrolyzable silicon-containing group has 1 to 3 hydroxy groups and / or hydrolyzable groups bonded to a silicon atom. Examples of the hydrolyzable silicon-containing group include hydrolyzable silyl groups such as alkoxysilyl group, alkenyloxysilyl group, asyloxysilyl group, aminosilyl group, aminooxysilyl group, oximesilyl group and amidesilyl group. .. Specifically, an alkoxysilyl group, an alkenyloxysilyl group, an asyloxysilyl group, an aminosilyl group, an aminooxysilyl group, an oximesilyl group, an amidesilyl group and the like, which are exemplified by the following formulas, are preferably used.

Of these, an alkoxysilyl group is preferable because it is easy to handle.
The alkoxy group bonded to the silicon atom of the alkoxysilyl group is not particularly limited, but a methoxy group, an ethoxy group or a propoxy group is preferably used because a raw material is easily available.
The group other than the alkoxy group bonded to the silicon atom of the alkoxysilyl group is not particularly limited, and for example, an alkyl group having 20 or less carbon atoms such as a hydrogen atom or a methyl group, an ethyl group, a propyl group and an isopropyl group. Alkoxy groups or arylalkyl groups are preferably used.

The number of reactive silicon-containing groups contained in one molecule of the compound (A) is one or more, and preferably one or two.

In compound (A), the aromatic ring and the reactive silicon-containing group can be bonded to a hydrocarbon group. The above hydrocarbon groups can have heteroatoms.
The hydrocarbon group is not particularly limited. For example, an aliphatic hydrocarbon group (which may be linear, branched, or cyclic), an aromatic hydrocarbon group, or a combination thereof can be mentioned. The hydrocarbon group may have an unsaturated bond.
The heteroatom is not particularly limited. For example, oxygen atom, nitrogen atom, sulfur atom, halogen can be mentioned. Heteroatoms may be combined, or heteroatoms and carbon atoms and / or hydrogen atoms may be combined to form a functional group. Examples of the functional group include a hydroxy group and an epoxy group.

The compound (A) preferably contains at least a compound having an aromatic ring, a reactive silicon-containing group and an epoxy group in one molecule.
It is more preferable to contain a compound having an aromatic ring, one reactive silicon-containing group and one or more epoxy groups, and a compound having an aromatic ring and two reactive silicon-containing groups.
Compound (A) can further have a hydroxy group, −NH−, in one molecule.

(Preferable aspect)
The compound (A) is preferably a compound obtained by reacting the epoxy compound (d) with the compound (e) having a reactive group that reacts with the epoxy group of the epoxy compound (d). ..
One or both of the epoxy compound (d) and the compound (e) may have an aromatic ring.
It is sufficient that one or both of the epoxy compound (d) and the compound (e) have a reactive silicon-containing group.

The epoxy compound (d) is not particularly limited as long as it is a compound having at least one epoxy group. The epoxy compound (d) preferably has 2 or more and 10 or less epoxy groups in one molecule.
In the epoxy compound (d), the epoxy group can be bonded to the hydrocarbon group. Hydrocarbon groups are synonymous with the above.

The epoxy compound (d) is preferably an aromatic epoxy compound or epoxysilane having an aromatic ring.
The aromatic epoxy compound is not particularly limited as long as it is an epoxy compound having an aromatic ring and an epoxy group. The aromatic epoxy compound is preferably an aromatic epoxy resin having a plurality of epoxy groups.

Examples of the aromatic epoxy compound include bisphenol A, bisphenol F, bisphenol S, hexahydrobisphenol A, tetramethylbisphenol A, pyrocatechol, resorcinol, cresol novolac, tetrabromobisphenol A, trihydroxybiphenyl, bisresolsinol, and bisphenol hexa. Glysidyl ether type obtained by reaction of polyvalent phenols such as fluoroacetone, tetramethylbisphenol F, bixylenol, dihydroxynaphthalene with epichlorohydrin; glycerin, neopentyl glycol, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, polyethylene. Polyglycidyl ether type obtained by reaction of aliphatic polyhydric alcohols such as glycol and polypropylene glycol with epichlorohydrin; glycidyl ether obtained by reaction of hydroxycarboxylic acids such as p-oxybenzoic acid and β-oxynaphthoic acid with epichlorohydrin. Ester type: Polycarboxylic acids such as phthalic acid, methylphthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid, endomethylenehexahydrophthalic acid, trimellitic acid, polymerized fatty acids, etc. Polyglycidyl ester type derived from; glycidyl aminoglycidyl ether type derived from aminophenol, aminoalkylphenol, etc .; glycidyl aminoglycidyl ester type derived from aminobenzoic acid; aniline, toluidine, tribromaniline, xylylene diamine, Glysidylamine type derived from diaminocyclohexane, bisaminomethylcyclohexane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, etc .; Can be mentioned.

The epoxy silane is not particularly limited as long as it is a silane coupling agent having an epoxy group and a reactive silicon-containing group. For example, glycidyloxyalkylalkoxysilanes such as glycidyloxypropyltrimethoxysilane can be mentioned.
The epoxy compound (d) can be used alone or in combination of two or more.

The compound (e) is not particularly limited as long as it is a compound having a reactive group that reacts with an epoxy group.
Specific examples of the reactive group that reacts with the epoxy group include an amino group (-NH ₂ ), an imino group (= NH, -NH-), a ureido group, a mercapto group, an acid anhydride group and the like. Of these, an amino group and an imino group are preferable.
Examples of the compound (e) include a silane coupling agent having a reactive group reacting with an epoxy group and a reactive silicon-containing group, and an amine compound having an aromatic ring. The amine compound having an aromatic ring is preferably a polyamine compound having a plurality of at least one selected from the group consisting of an amino group and an imino group.

Examples of the silane coupling agent include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylethyldiethoxysilane, bistrimethoxysilylpropylamine, and bistriethoxy. Cyrilpropylamine, bismethoxydimethoxysilylpropylamine, bisethoxydiethoxysilylpropylamine, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N −β (aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylethyldiethoxysilane, 3,3-dimethyl-4-aminobutyltrimethoxysilane, 3,3-dimethyl- Aminosilane compounds such as 4-aminobutylmethyldimethoxysilane; (N-cyclohexylaminomethyl) methyldiethoxysilane, (N-cyclohexylaminomethyl) triethoxysilane, (N-phenylaminomethyl) methyldimethoxysilane, (N-phenyl) Aminomethyl) trimethyloxysilane, a compound represented by the following formula (1), and an iminosilane compound such as N-phenyl-3-aminopropyltrimethoxysilane represented by the following formula (2);

Ureidosilane compounds such as γ-ureidopropyltrimethoxysilane; mercaptosilane compounds such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane And so on.

The polyamine compound having an aromatic ring is a compound having at least one selected from the group consisting of an aromatic ring and an amino group and an imino group, and the number of the amino groups and the like is plural per molecule of the polyamine compound.
Aromatic rings are synonymous with the above.
Examples of the polyamine compound include methylene dianiline and diaminobenzene.
Compound (e) may be used alone or in combination of two or more.

The equivalent of the reactive group (reactive group / epoxy group) of the compound (e) with respect to the epoxy group of the epoxy compound (d) is preferably 0.1 to 1.0, and is 0.6 to 0. It is more preferably 8.8.

As a combination of the epoxy compound (d) and the compound (e), for example, a compound having an aromatic ring and an aromatic ring having at least one functional group selected from the group consisting of an epoxy group, an amino group and an imino group ( Examples thereof include a combination of a compound having an aromatic ring and a functional group) and a silane coupling agent (silane coupling agent) having a reactive group capable of reacting with the functional group and a reactive silicon-containing group. Specifically, for example, a combination of an aromatic epoxy resin and a silane coupling agent having a reactive group capable of reacting with an epoxy group and a reactive silicon-containing group (1); epoxy silane and a polyamine having an aromatic ring. The combination with the compound (2) can be mentioned.

When the combination of the epoxy compound (d) and the compound (e) is the above (1), the equivalent of the reactive group of the silane coupling agent to the epoxy group of the aromatic epoxy resin (reactive group / epoxy). The group) is preferably 0.1 to 1.0, and more preferably 0.6 to 0.8.

When the combination of the epoxy compound (d) and the compound (e) is the above (2), the epoxy group of the epoxy silane with respect to the amino group and / or the imino group (reactive group) of the polyamine compound having an aromatic ring. The equivalent of (epoxide group / reactive group) is preferably 0.1 to 2.0, more preferably 0.6 to 1.6.

Examples of the method for producing the compound (A) include a method in which the epoxy compound (d) and the compound (e) are stirred at 100 to 140 ° C. in an inert gas atmosphere such as nitrogen gas.
Compound (A) can be used alone or in combination of two or more.

<A (meth) acrylic compound (B) having an aromatic ring and a (meth) acryloyloxy group>
The (meth) acrylic compound (B) contained in the composition of the present invention is not particularly limited as long as it is a compound having at least one aromatic ring and at least one (meth) acryloyloxy group in one molecule.

The aromatic ring is not particularly limited. It is synonymous with the aromatic ring of compound (A).

The number of (meth) acryloyloxy groups contained in one molecule of the (meth) acrylic compound (B) is one or more, and preferably one or two.

In the (meth) acrylic compound (B), the aromatic ring and the (meth) acryloyloxy group can be bonded to a hydrocarbon group. The above hydrocarbon groups can have heteroatoms. Hydrocarbon groups and heteroatoms are synonymous with the above.

The (meth) acrylic compound (B) is preferably a bisphenol alkyleneoxy-modified poly (meth) acrylate.
Examples of the alkyleneoxy group contained in the bisphenol alkyleneoxy-modified poly (meth) acrylate include an alkyleneoxy group having 1 to 10 carbon atoms. The alkyleneoxy group may be linear or branched. Examples of the alkyleneoxy group include a methyleneoxy group, an ethyleneoxy group, and a propyleneoxy group.

As the bisphenol alkyleneoxy-modified poly (meth) acrylate, bisphenol A type alkyleneoxy-modified poly (meth) acrylate and bisphenol alkyleneoxy-modified di (meth) acrylate are preferable.

Examples of the bisphenol alkyleneoxy-modified poly (meth) acrylate include [CH ₂ = CHR ^1- COO- (R ² O) _n ] _m- X.
In the formula, R ¹ is a hydrogen atom or a methyl group.
R ² O is an oxyalkylene group. The oxyalkylene group preferably has 1 to 10 carbon atoms. Examples of the oxyalkylene group include an oxyethylene group and an oxypropylene group.
m is preferably 1 to 3, preferably 2.
n is preferably 1 to 5, preferably 1 or 2 to 3.
X is an aromatic ring. Aromatic rings are synonymous with the above.

The method for producing the (meth) acrylic compound (B) is not particularly limited. For example, conventionally known ones can be mentioned.
The (meth) acrylic compound (B) can be used alone or in combination of two or more.

<Photopolymerization initiator (C)>
The photopolymerization initiator (C) contained in the composition of the present invention is not particularly limited.
Examples of the photopolymerization initiator (C) include acetophenone compounds, benzoin ether compounds, benzophenone compounds, sulfur compounds, azo compounds, peroxide compounds, phosphine oxide compounds and the like.
Specifically, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, acetoin, butyroine, toluoin, benzyl, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, α, α-dimethoxy-α-phenylacetophenone. , Methylphenyl glyoxylate, ethylphenyl glyoxylate, 4,4'-bis (dimethylaminobenzophenone), 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy-1, Carbonyl compounds such as 2-diphenylethane-1-one and 1-hydroxycyclohexylphenylketone; sulfur compounds such as tetramethylthium monosulfide and tetramethylthiuram disulfide; azobisisobutyronitrile, azobis-2,4-dimethylvalero Azo compounds such as benzoyl peroxide, peroxide compounds such as di-t-butyl peroxide and the like.

Among them, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl -1-Propane-1-one is preferred.
The photopolymerization initiators can be used alone or in combination of two or more.

(Content)
The ratio of the content of the compound (A) is preferably 10 to 50% by mass with respect to the total content of the compound (A), the (meth) acrylic compound (B) and the photopolymerization initiator (C). More preferably, it is 20 to 40% by mass.
The ratio of the content of the (meth) acrylic compound (B) is 30 to 90 mass with respect to the total content of the compound (A), the (meth) acrylic compound (B) and the photopolymerization initiator (C). % Is preferable, 30 to 89.5% by mass is more preferable, and 50 to 80% by mass is further preferable.
The ratio of the content of the photopolymerization initiator (C) is 0.5 to 10 with respect to the total content of the compound (A), the (meth) acrylic compound (B) and the photopolymerization initiator (C). It is preferably by mass, more preferably 1 to 7% by mass.

(Curing catalyst (G))
The composition of the present invention preferably further contains a curing catalyst (G) from the viewpoint of being superior to a predetermined effect.
The curing catalyst (G) can be capable of accelerating the reaction of the reactive silicon-containing group (for example, the hydrolysis or condensation reaction of the hydrolyzable silicon-containing group).

Examples of the curing catalyst (G) include oxides, hydroxides, carboxylates, and complexes of at least one metal selected from the group consisting of tin, zirconium, and titanium.
The carboxylic acid that forms the carboxylic acid salt of the metal is not particularly limited. For example, acetic acid, octyl acid, oleic acid, lauric acid can be mentioned.
The ligand that forms the metal complex is not particularly limited. For example, acetylacetone; alkylacetate such as ethylacetacetate can be mentioned.

The curing catalyst (G) is preferably at least one curing catalyst selected from the group consisting of a tin-based catalyst, a zirconium-based catalyst, and a titanium-based catalyst, more preferably a tin-based or zirconium-based catalyst, and tin or zirconium. The complex, tin or zirconium carboxylate, is more preferred.
Examples of the zirconium complex include zirconium acetylacetonate. Examples of the zirconium acetylacetoneate include zirconium monoacetylacetoneate and zirconium tetraacetylacetoneate.
Examples of tin carboxylates include dialkyltin dicarboxylic acid salts such as dibutyltin dilaurate and dioctyltin dilaurate.
The curing catalyst (G) can be used alone or in combination of two or more.

The content of the curing catalyst (G) is 0.05 to 1.0% by mass with respect to the total content of the compound (A), the (meth) acrylic compound (B) and the photopolymerization initiator (C). Preferably, 0.1 to 0.7% by mass is more preferable.

The composition of the present invention may further contain additives within the desired range, if necessary. Examples of the additive include (meth) acrylic compounds having no aromatic ring, antioxidants, antioxidants, adhesion-imparting agents, silane coupling agents, plasticizers, dispersants, and colorants. The content of the additive can be appropriately selected.

When the composition of the present invention further contains a (meth) acrylic compound having no aromatic ring, examples of the (meth) acrylic compound having no aromatic ring include an aliphatic hydrocarbon group and (meth) acryloyloxy. Examples include compounds having a group. Examples of the above compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol tetra (meth) acrylate. Examples thereof include compounds having a plurality of (meth) acryloyloxy groups, such as tripentaerythritol tetra (meth) acrylate.

The ratio of the content of the (meth) acrylic compound having no aromatic ring is 0 to 30% by mass with respect to the total amount of the (meth) acrylic compound and the (meth) acrylic compound having no aromatic ring. preferable.

The composition of the present invention is not particularly limited in its production. For example, it can be produced by mixing the above components.

The composition of the present invention can be cured by irradiating with ultraviolet rays. When the composition of the present invention is cured by ultraviolet irradiation, the irradiation amount (integrated light amount) of the ultraviolet rays used when curing the composition of the present invention is preferably ^{300 to 1000 mJ / cm 2.} The device used to irradiate the ultraviolet rays is not particularly limited. For example, conventionally known ones can be mentioned.

In addition, the composition of the present invention can be cured by moisture and / or heating. The temperature at the time of curing is preferably 23 to 100 ° C. The relative humidity is preferably 50-98% RH.

The thickness of the adhesive layer obtained by curing the composition of the present invention is preferably 0.01 to 0.05 mm.

The material of the adherend to which the composition of the present invention can be applied is not particularly limited. For example, plastic, rubber, glass, metal, ceramic and the like can be mentioned.
The method of applying the composition of the present invention to an adherend is not particularly limited.

The composition of the present invention can be used as an adhesive for adhering optical materials.
Examples of the optical material include an optical fiber, a fiber array, an optical waveguide, a lens, a filter, a diffraction grating, and an optical active element.
Of these, it is preferable to bond the fiber array and the optical waveguide.
The fiber array is not particularly limited.
The optical waveguide is not particularly limited. For example, PLC (plane optical waveguide circuit) can be mentioned. An optical waveguide device can be manufactured by adhering an optical waveguide with the composition of the present invention.

[Optical waveguide device]
An example of the usage mode of the composition of the present invention will be described with reference to the accompanying drawings. The present invention is not limited to the accompanying drawings.
FIG. 1 is a drawing schematically showing an example of how to use the composition of the present invention.
In FIG. 1, the optical waveguide device 10 has a fiber array 2 and an optical waveguide 3. The fiber array 2 has an optical fiber 1. The fiber array 2 and the optical waveguide 3 are bonded and connected via an adhesive layer 4.
The composition of the present invention is used for the adhesive layer 4.

The present invention will be specifically described below with reference to examples. However, the present invention is not limited to these. In addition, in this specification, Example 3 and Example 6 shall be read as Reference Example 3 and Reference Example 6, respectively.

<Synthesis of compound (A)>
Each component shown in Table 1 below is mixed with the composition (parts by mass) shown in the same table, stirred at 120 ° C. for 8 hours in an inert gas atmosphere, and has an aromatic ring and a reactive silicon-containing group. Compounds A1, A2, A3, A4, A5 and A6, which are compounds (A), were obtained.

The details of each component in Table 1 are as follows.
-Epoxy compound d1: Epototo YD-128 (bisphenol A diglycidyl ether, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) (hereinafter structure)
-Epoxy compound d2: Epototo YDF-170 (bisphenol F diglycidyl ether, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) (hereinafter structure)
-Epoxy compound d3: 3-glycidoxypropyltrimethoxysilane (A-187, manufactured by Momentive Performance Materials) (hereinafter, structure)
-Iminosilane compound e1: Alink-15 (N-ethyl-3-aminoisobutyltrimethoxysilane, manufactured by Momentive Performance Materials) (hereinafter, structure)
-Polyamine compound e2: Methylene dianiline (MDA, manufactured by Kanto Chemical Co., Inc.) (hereinafter structure)

In Table 1, “reactive group / epoxy group” refers to the molar ratio of amino group or imino group of iminosilane compound e1 or amine compound e2 to the epoxy group of epoxy compounds d1 to d3 [(amino group or imino group). ) / Epoxide group].

When one molecule of the epoxy compound d1 and one molecule of the iminosilane compound e1 react, the following compounds are obtained.

When one molecule of the epoxy compound d2 and one molecule of the iminosilane compound e1 react, the following compounds are obtained.

When two molecules of the epoxy compound d3 and one molecule of the polyamine compound e2 react, the following compounds are obtained.

<Preparation of adhesive composition>
Each component shown in Table 2 below was mixed with the composition (part by mass) shown in the same table and stirred using a stirrer to prepare an adhesive composition of Examples and Comparative Examples.

<Evaluation>
-Preparation of test piece Prepare two glass plates (length 30 mm x width 25 mm x thickness 5 mm), apply the adhesive composition prepared as described above to one glass plate, and apply another one. Glass plates were overlapped and crimped to obtain a laminate.

-Curing with ultraviolet rays Using an ultraviolet irradiation device (trade name CSOT-40A, manufactured by GS Yuasa), the laminate obtained as described above was subjected to 700 to 900 mJ / cm ^{2 under the conditions of 23 ° C. and 60% RH.} The adhesive composition was cured by irradiating with the ultraviolet rays of No. The thickness of the adhesive layer after curing was 0.03 mm.

-Initial Shear Strength Using the test piece prepared as described above, the initial shear strength was measured under the conditions of a tensile speed of 3 mm / min and 23 ° C. in accordance with JIS K6852-1994. The results are shown in Table 2.

-Shear strength after moist heat deterioration Further, the test body prepared as described above was placed in an environment of 80 ° C. and 95% RH for 10 days to deteriorate the test body by moist heat.
Using the test piece after moist heat deterioration, the shear strength after moist heat deterioration was measured in the same manner as the initial shear strength. The results are shown in Table 2.

The details of each component in Table 2 are as follows.
-Compound A1: Compound A1 synthesized as described above.
-Compound A2: Compound A2 synthesized as described above.
-Compound A3: Compound A3 synthesized as described above.
-Compound A4: Compound A4 synthesized as described above.
-Compound A5: Compound A5 synthesized as described above.
-Compound A6: Compound A6 synthesized as described above.

(Meta) Acrylic Compound B1: Aronix M-211B (bisphenol A ethyleneoxy-modified diacrylate, manufactured by Toagosei Co., Ltd.) (hereinafter structure)
In the formula, m≈2 and n≈2.

(Meta) acrylic compound B2: light acrylate BP-4PA (bisphenol A propylene oxy-modified diacrylate, manufactured by Kyoeisha Chemical Co., Ltd.) (hereinafter structure)
In the formula, m + n≈4.

-Photopolymerization initiator C1: Irgacure 184 (1-hydroxy-cyclohexyl-phenyl-ketone, manufactured by BASF)

・ (Meta) acrylic compound F1: Viscote # 300 (manufactured by Osaka Organic Chemical Industry Co., Ltd.) (hereinafter structure)

-Curing catalyst G1: Organix ZC-150 (zirconium tetraacetylacetoneate, manufactured by Matsumoto Fine Chemicals)

-Silane coupling agent: A-187 (3-glycidoxypropyltrimethoxysilane, manufactured by Momentive Performance Materials) (hereinafter, structure)

From the results shown in Table 2, Comparative Examples 1 and 2 containing no predetermined compound (A) had low adhesiveness to glass and low moisture and heat resistance.
Comparative Example 3 containing the predetermined (meth) acrylic compound (B) and instead containing the (meth) acrylic compound having no aromatic ring had low adhesiveness to glass and low moisture and heat resistance.

On the other hand, Examples 1 to 9 were excellent in adhesiveness to glass and moisture heat resistance.
Comparing Example 1 and Example 4 with respect to the reactive group / epoxy group, Example 4 was superior to Example 1 in adhesiveness to glass and moisture and heat resistance.
Similar results were obtained for Examples 2 and 5.
From this, when compound (A) is obtained by a combination of an aromatic epoxy resin and a silane coupling agent having a reactive group capable of reacting with an epoxy group and a reactive silicon-containing group, the reactive group / epoxy It was clarified that the larger the group, the better the adhesiveness to the glass and the moisture heat resistance.

Comparing Examples 3 and 6, the equivalent of the epoxy group of the epoxysilane (epoxide group / reactive group; epoxy group /) to the amino group and / or imino group (reactive group) of the polyamine compound having an aromatic ring. It was clarified that the larger the reactive group (the inverse number of the reactive group / epoxy group shown in Table 1), the better the adhesiveness to the glass and the moisture heat resistance.

Comparing Example 4 and Example 7, Example 7 further containing the curing catalyst (G) was superior in adhesiveness to Example 4.

Comparing Example 4 and Example 8, Example 4 was more excellent in adhesiveness after moist heat deterioration than Example 8. From this, it was clarified that when the (meth) acrylic compound having no aromatic ring is further contained, the smaller the amount of the (meth) acrylic compound having no aromatic ring, the better the adhesiveness after moist heat deterioration. ..

Comparing Example 4 and Example 9, the alkyleneoxy group of the (meth) acrylic compound (B) is more excellent in adhesiveness and moisture heat resistance when it is an ethyleneoxy group than when it is a propyleneoxy group. Became clear.

1 Optical fiber 2 Fiber array 3 Optical waveguide 4 Adhesive layer (adhesive composition)
10 Optical waveguide device

Claims (6)

Containing compound having a reactive silicon-containing groups and aromatic ring (A), and a bisphenol ring and (meth) acryloyloxy group-containing (meth) acrylic compound (B), and a photopolymerization initiator and (C) ,
An adhesive composition for an ultraviolet curable optical material, wherein the compound (A) contains at least a compound (AA) having a bisphenol ring and one reactive silicon-containing group. The ratio of the content of the compound (A) to the total content of the compound (A), the (meth) acrylic compound (B) and the photopolymerization initiator (C) is 10 to 50% by mass. the content ratio of (meth) acrylic compound (B) is 30 to 90 wt%, the proportion of the content of the photopolymerization initiator (C) is 0.5 to 10 mass%, claim 1 The adhesive composition for an ultraviolet curable optical material according to. The adhesive composition for an ultraviolet curable optical material according to claim 1 or 2 , further comprising a curing catalyst (G). The adhesive composition for an ultraviolet curable optical material according to claim 3 , wherein the curing catalyst (G) is at least one curing catalyst selected from the group consisting of a tin catalyst, a zirconium catalyst, and a titanium catalyst. Stuff. The adhesive composition for an ultraviolet curable optical material according to any one of claims 1 to 4, wherein the compound (AA) further has an epoxy group and / or a hydroxy group. Any of claims 1 to 5, wherein the compound (AA) further comprises an epoxy group, and the compound (A) further comprises a compound having an aromatic ring and two reactive silicon-containing groups. The adhesive composition for an ultraviolet curable optical material according to item 1.