WO2016140315A1

WO2016140315A1 - Uv-curing optical-material adhesive composition

Info

Publication number: WO2016140315A1
Application number: PCT/JP2016/056623
Authority: WO
Inventors: 影山　裕一; 木村　和資; 成幸三田地
Original assignee: 横浜ゴム株式会社
Priority date: 2015-03-04
Filing date: 2016-03-03
Publication date: 2016-09-09
Also published as: JPWO2016140315A1; JP6834487B2

Abstract

The purpose of the present invention is to provide a UV-curing optical-material adhesive composition having excellent adhesion with respect to glass and moisture/heat resistance. The present invention is a UV-curing optical-material adhesive composition containing: a compound (A) having an aromatic ring and a silicon-containing reactive group; a (meth)acrylic compound (B) having an aromatic ring and a (meth)acryloyloxy group; and a photo-polymerization initiator (C).

Description

UV-curable adhesive composition for optical materials

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 the optical fiber network has been expanded. In this optical communication system, an optical material and an optical element are used. Examples of the material such as the optical material include plastic and glass. Plastic, glass, and the like can be bonded with the adhesive composition.

As an adhesive composition that can be used for plastics, for example, Patent Document 1 discloses (meth) acrylic polymer (A) having a molecular weight of 50,000 to 140,000, urethane (meth) acrylate (B), 1 Polyfunctional monomer (C) having 3 or more (meth) acryloyloxy groups in the molecule, and aliphatic hydrocarbon having a main chain skeleton having 2 (meth) acryloyloxy groups in one molecule A curable resin composition containing a bifunctional monomer (D) and a photopolymerization initiator (E) is described (claim 1).

JP 2008-255228 A

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

As a result of intensive studies to solve the above problems, the present inventors have found that the compound (A) having an aromatic ring and a reactive silicon-containing group, and a (meth) acryl having an aromatic ring and a (meth) acryloyloxy group. The inventors 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 knowledge and the like, and specifically, solves the above problems by the following configuration.

1. 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). , UV-curable optical material adhesive composition.
2. 2. The adhesive composition for an ultraviolet curable optical material according to 1 above, wherein the aromatic ring of 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 material according to 1 or 2 above, wherein the aromatic ring of 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. 4. The adhesive composition for an ultraviolet curable optical material according to any one of 3 above.
5. 5. The adhesive composition for an ultraviolet curable optical material according to any one of the above 1 to 4, further comprising a curing catalyst (G).
6). 6. The ultraviolet curable optical material adhesive composition according to 5 above, wherein the curing catalyst (G) is at least one curing catalyst selected from the group consisting of a tin-based catalyst, a zirconium-based catalyst, and a titanium-based catalyst. .

The adhesive composition for an ultraviolet curable optical material of the present invention is excellent in adhesion to glass and heat and moisture 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 this specification, (meth) acrylate represents acrylate or methacrylate, (meth) acryloyl represents acryloyl or methacryloyl, and (meth) acryl represents acryl or methacryl.
In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
Moreover, in this specification, when a component contains 2 or more types of substance, the content of the said component refers to the sum total of content of 2 or more types of substance.

The adhesive composition for an ultraviolet curable optical material of the present invention (the composition of the present invention)
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). And an adhesive composition for ultraviolet curable optical materials.

Since the composition of this invention takes such a structure, it is thought that a desired effect is acquired. The reason is not clear, but it is presumed that it is as follows.
Since the composition of the present invention contains the (meth) acrylic compound (B), it can be quickly cured by irradiating the composition of the present invention with ultraviolet rays.
Moreover, the composition of this invention can be further hardened | cured by a heating and / or humidity by containing a compound (A). Moreover, since the compound (A) has a reactive silicon-containing group, it has excellent adhesion to glass.
And 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 resulting adhesive layer is increased 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). It is considered to be.

[Composition of the present invention]
Hereinafter, each component contained in the composition of this invention is explained in full 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 a halogen atom such as chlorine or bromine.
Specific examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring, a triphenylene ring, a naphthacene ring, a biphenyl ring, a bisphenol ring, and a terphenyl ring. May be linked). Among 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 connected by any connecting 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 crosslinked by causing a reaction by using a catalyst or the like, if necessary, in the presence of moisture or a crosslinking agent. Examples of the reactive silicon-containing group include a halogenated silicon-containing group, a silicon hydride-containing group, and a hydrolyzable silicon-containing group. Of these, hydrolyzable silicon-containing groups are preferred.

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

Of these, an alkoxysilyl group is preferred because it is easy to handle.
Although the alkoxy group couple | bonded with the silicon atom of an alkoxy silyl group is not specifically limited, Since acquisition of a raw material is easy, a methoxy group, an ethoxy group, or a propoxy group is mentioned suitably.
The group other than the alkoxy group bonded to the silicon atom of the alkoxysilyl group is not particularly limited, for example, a hydrogen atom or an alkyl group having 20 or less carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, An alkenyl group or an arylalkyl group is preferable.

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

In the 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 may be mentioned. The hydrocarbon group may have an unsaturated bond.
The hetero atom is not particularly limited. For example, an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen are mentioned. Heteroatoms 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.
More preferably, it includes 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.
The compound (A) can further have a hydroxy group and —NH— in one molecule.

(Preferred embodiment)
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.
One or both of the epoxy compound (d) and the compound (e) may 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), an epoxy group can be bonded to a hydrocarbon group. The hydrocarbon group is as defined above.

The epoxy compound (d) is preferably an aromatic epoxy compound having an aromatic ring or an epoxy silane.
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 novolak, tetrabromobisphenol A, trihydroxybiphenyl, bisresorcinol, bisphenol hexa Glycidyl ether type obtained by reaction of polyphenol such as fluoroacetone, tetramethylbisphenol F, bixylenol, dihydroxynaphthalene and epichlorohydrin; glycerin, neopentyl glycol, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, polyethylene Aliphatic polyhydric alcohols such as glycol and polypropylene glycol Polyglycidyl ether type obtained by reaction with epichlorohydrin; glycidyl ether ester type obtained by reaction of hydroxycarboxylic acid such as p-oxybenzoic acid and β-oxynaphthoic acid with epichlorohydrin; phthalic acid, methylphthalic acid, isophthalic acid, Polyglycidyl ester type derived from polycarboxylic acids such as terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid, endomethylenehexahydrophthalic acid, trimellitic acid, polymerized fatty acid; aminophenol, Glycidylaminoglycidyl ether type derived from aminoalkylphenol, etc .; Glycidylaminoglycidyl ester type derived from aminobenzoic acid; aniline, toluidine, tribromoaniline Glycidylamine type derived from phosphorus, xylylenediamine, diaminocyclohexane, bisaminomethylcyclohexane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, etc .; epoxidized polyolefin, glycidylhydantoin, glycidylalkylhydantoin And triglycidyl cyanurate.

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. An example is glycidyloxyalkylalkoxysilane such as glycidyloxypropyltrimethoxysilane.
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 has 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, and an acid anhydride group. 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 that reacts 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. Silylpropylamine, 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- Aminosilane compounds such as methyl-4-aminobutylmethyldimethoxysilane; (N-cyclohexylaminomethyl) methyldiethoxysilane, (N-cyclohexylaminomethyl) triethoxysilane, (N-phenylaminomethyl) methyldimethoxysilane, (N -Iminosilane compounds such as phenylaminomethyl) trimethyloxysilane, a compound represented by the following formula (1) and 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 Etc.

The polyamine compound having an aromatic ring is a compound having an aromatic ring and at least one selected from the group consisting of an amino group and an imino group, and the number of amino groups and the like is plural per molecule of the polyamine compound.
The aromatic ring has the same meaning as above.
Examples of the polyamine compound include methylene dianiline and diaminobenzene.
A compound (e) may be used independently and may use 2 or more types together.

The reactive group equivalent (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, preferably 0.6 to 0. .8 is more preferable.

As a combination of the epoxy compound (d) and the compound (e), for example, a compound having an aromatic ring having an aromatic ring and at least one functional group selected from the group consisting of an epoxy group, an amino group and an imino group ( 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); an epoxy silane and a polyamine having an aromatic ring The combination (2) with a compound is 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 from 0.1 to 1.0, more preferably from 0.6 to 0.8.

When the combination of the epoxy compound (d) and the compound (e) is (2) above, the epoxy group possessed by the epoxy silane with respect to the amino group and / or imino group (reactive group) possessed by the polyamine compound having an aromatic ring The equivalent of (epoxy 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.
A compound (A) can be used individually or in combination of 2 types or more, respectively.

<(Meth) acrylic compound (B) having aromatic ring and (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 which a compound (A) has.

The number of (meth) acryloyloxy groups contained in one molecule of (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. A hydrocarbon group and a hetero atom are as defined above.

The (meth) acrylic compound (B) is preferably bisphenol alkyleneoxy-modified poly (meth) acrylate.
Examples of the alkyleneoxy group possessed by 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.

The bisphenol alkyleneoxy modified poly (meth) acrylate is preferably bisphenol A type alkyleneoxy modified poly (meth) acrylate or bisphenol alkyleneoxy modified di (meth) acrylate.

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, and 2 is preferred.
n is preferably 1 to 5, and preferably 1 or 2 to 3.
X is an aromatic ring. The aromatic ring has the same meaning as above.

The production method of the (meth) acrylic compound (B) is not particularly limited. For example, a conventionally well-known thing is mentioned.
The (meth) acrylic compound (B) can be used alone or in combination of two or more.

<Photopolymerization initiator (C)>
The photoinitiator (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, butyroin, toluoin, benzyl, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, α, α-dimethoxy-α-phenylacetophenone Methylphenylglyoxylate, ethylphenylglyoxylate, 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-hydroxycyclohexyl phenyl ketone; Sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide; Azobis Sobuchironitoriru, azo compounds such as azobis-2,4-dimethylvaleronitrile; benzoyl peroxide, peroxide compounds such as di -t- butyl peroxide and the like.

Among them, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl -1-Propan-1-one is preferred.
A photoinitiator can be used individually or in combination of 2 types or more, respectively.

(Content)
The content ratio 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 proportion 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). % By mass is preferable, and 1 to 7% by mass is more preferable.

(Curing catalyst (G))
It is preferable that the composition of this invention contains a curing catalyst (G) further from a viewpoint that it is excellent with a predetermined effect.
The curing catalyst (G) can promote a reaction of a reactive silicon-containing group (for example, hydrolysis or condensation reaction of a 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 metal carboxylate is not particularly limited. Examples include acetic acid, octylic acid, oleic acid, and lauric acid.
The ligand for forming the metal complex is not particularly limited. Examples include acetylacetonate; alkyl acetoacetates such as ethyl acetoacetate.

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. More preferably, the complex is a carboxylate of tin or zirconium.
Examples of the zirconium complex include zirconium acetylacetonate. Examples of zirconium acetylacetonate include zirconium monoacetylacetonate and zirconium tetraacetylacetonate.
Examples of tin carboxylates include dialkyltin dicarboxylates 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 an additive as necessary within the intended range. Examples of the additive include a (meth) acrylic compound having no aromatic ring, an anti-aging agent, an antioxidant, an adhesion imparting agent, a silane coupling agent, a plasticizer, a dispersing agent, and a coloring agent. The content of the additive can be appropriately selected.

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

The content ratio 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 for its production. For example, it can be produced by mixing the above components.

The composition of the present invention can be cured by irradiation with ultraviolet rays. When the composition of the present invention is cured by ultraviolet irradiation, the irradiation amount (integrated light amount) of ultraviolet rays used when curing the composition of the present invention is preferably 300 to 1000 mJ / cm ² . The apparatus used for irradiating ultraviolet rays is not particularly limited. For example, a conventionally well-known thing is mentioned.

Also, the composition of the present invention can be cured by moisture and / or heating. The curing temperature is preferably 23 to 100 ° C. The relative humidity is preferably 50 to 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 for 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.
Especially, it is preferable to adhere | attach a fiber array and an optical waveguide.
The fiber array is not particularly limited.
The optical waveguide is not particularly limited. An example is a PLC (planar optical waveguide circuit). An optical waveguide device can be produced 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 attached drawings.
FIG. 1 is a drawing schematically showing an example of a usage mode of the composition of the present invention.
In FIG. 1, the optical waveguide device 10 includes 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.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.

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

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 referred to as structure)

・ Iminosilane compound e1: Alink-15 (N-ethyl-3-aminoisobutyltrimethoxysilane, manufactured by Momentive Performance Materials) (hereinafter “structure”)

Polyamine compound e2: Methylenedianiline (MDA, manufactured by Kanto Chemical Co.) (hereinafter referred to as structure)

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

In addition, when one molecule of the epoxy compound d1 and one molecule of the iminosilane compound e1 are reacted, the following compounds are obtained.

Further, when one molecule of the epoxy compound d2 and one molecule of the iminosilane compound e1 are reacted, the following compounds are obtained.

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

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

<Evaluation>
-Preparation of test body Two glass plates (length 30 mm x width 25 mm x thickness 5 mm) were prepared, and the adhesive composition prepared as described above was applied to one glass plate, and another sheet was applied thereto. Glass plates were stacked and pressure bonded 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 conditions of 23 ° C. and 60% RH. The test piece was prepared by curing the adhesive composition. The thickness of the adhesive layer after curing was 0.03 mm.

-Initial shear strength Using the specimen 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 wet heat deterioration Moreover, the test body produced as mentioned above was put in 80 degreeC and 95% RH environment for 10 days, and the test body was wet-heat deteriorated.
The shear strength after wet heat deterioration was measured in the same manner as the initial shear strength using the test body after wet heat deterioration. The results are shown in Table 2.

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

・ (Meth) acrylic compound B1: Aronix M-211B (bisphenol A ethyleneoxy-modified diacrylate, manufactured by Toagosei Co., Ltd.)

In the formula, m≈2 and n≈2.

・ (Meth) acrylic compound B2: Light acrylate BP-4PA (bisphenol A propyleneoxy-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)

・ (Meth) acrylic compound F1: Biscoat # 300 (manufactured by Osaka Organic Chemical Industry Co., Ltd.) (hereinafter referred to as structure)

Curing catalyst G1: ORGATICS ZC-150 (zirconium tetraacetylacetonate, manufactured by Matsumoto Fine Chemical Co.)

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

From the results shown in Table 2, Comparative Examples 1 and 2 not containing the predetermined compound (A) had low adhesion to glass and moist heat resistance.
Comparative Example 3 containing a (meth) acrylic compound not containing the predetermined (meth) acrylic compound (B) and having no aromatic ring instead had low adhesion to glass and heat and moisture resistance.

In contrast, Examples 1 to 9 were excellent in adhesion to glass and heat and humidity resistance.
When Example 1 and Example 4 were compared regarding the reactive group / epoxy group, Example 4 was superior to Example 1 in adhesion to glass and heat-and-moisture resistance.
Similar results were obtained for Examples 2 and 5.
From this, when the 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 became clear that the larger the group, the better the adhesion to glass and the heat and moisture resistance.

When Examples 3 and 6 are compared, the equivalent of the epoxy group of epoxysilane (epoxy group / reactive group. Epoxy group / reactive group) with respect to the amino group and / or imino group (reactive group) of the polyamine compound having an aromatic ring. It became clear that the larger the reactive group (reciprocal of reactive group / epoxy group) shown in Table 1 is, the better the adhesion to glass and heat-and-moisture resistance are.

When comparing Example 4 and Example 7, Example 7 further containing a curing catalyst (G) was superior to Example 4 in adhesion.

When comparing Example 4 and Example 8, Example 4 was more excellent in adhesiveness after wet heat degradation than Example 8. From this, when it further contains the (meth) acryl compound which does not have an aromatic ring, it became clear that the one where the quantity of the (meth) acryl compound which does not have an aromatic ring is smaller is superior to the adhesiveness after wet heat deterioration. .

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

DESCRIPTION OF SYMBOLS 1 Optical fiber 2 Fiber array 3 Optical waveguide 4 Adhesive layer (adhesive composition)
10 Optical waveguide devices

Claims

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). , UV-curable optical material adhesive composition.
The adhesive composition for an ultraviolet curable optical material according to claim 1, wherein the aromatic ring of 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. object.
The ultraviolet curable type according to claim 1 or 2, wherein the aromatic ring of 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 optical materials.
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. 4. The adhesive composition for an ultraviolet curable optical material according to any one of items 1 to 3.
The adhesive composition for an ultraviolet curable optical material according to any one of claims 1 to 4, further comprising a curing catalyst (G).
The adhesive composition for an ultraviolet curable optical material according to claim 5, wherein the curing catalyst (G) is at least one curing catalyst selected from the group consisting of a tin-based catalyst, a zirconium-based catalyst, and a titanium-based catalyst. object.