CN1914291B - Adhesive composition for optical fiber - Google Patents

Abstract

The purpose of the present invention is to provide an adhesive composition for optical fibers, which is moisture-curable and has excellent adhesion and moist heat resistance. The present invention provides a binder composition containing a compound having a reactive silicon-containing group, the compound comprising a compound (c) formed by reacting an epoxy compound having at least 1 epoxy group with a silane coupling agent (b) having a reactive silicon-containing group and a reactive group reactive with an epoxy group, the compound having a reactive silicon-containing group having a molecular weight per reactive silicon-containing group of 1000 or less; the present invention also provides a binder composition containing an alkylsilyl ester and a compound (B) having a reactive silicon group, which has at least 1 reactive silicon group, other than the above alkylsilyl ester.

Description

Adhesive composition for optical fiber

technical field

The present invention relates to adhesive compositions for optical fibers. More particularly, it relates to adhesive compositions suitable for bonding optical fibers to ferrules.

Background technique

In recent years, due to the spread of the Internet, the importance of techniques for increasing communication capacity has increased, and optical fiber networks have been expanded. Regarding the bonding technology used in the assembly of optical materials and optical components used in the optical communication system, the current mainstream is to use a connector to connect the optical fibers, and the ferrule used to fix the optical fiber in the connector Adhesive composition, requiring high bond strength and reliability. Especially when the optical fiber and the connector are bonded by an adhesive, the optical fiber and the ferrule are often subjected to shearing stress because the optical fiber is often in a state of being crimped by the spring. In addition, there are cases where the optical fiber is stretched in the longitudinal direction of the ferrule and receives a large load. Therefore, the adhesive is required to have high shear strength.

In addition, since optical fibers are sometimes installed outdoors or on roofs, characteristics that maintain sufficient adhesive force even in harsh environments such as high temperature and high humidity are required.

In addition, quartz or glass has been used as the material of optical fiber, but plastic optical fiber (POF) has been developed, which is cheap, easy to process, and has the property of being resistant to bending and extremely difficult to break. It is used in short-distance communication such as home network or digital home appliances. Since the optical fiber adhesive composition has been put into practical use, not only glass but also plastics (mainly acrylic plastics) are required to have adhesive properties.

Conventionally, epoxy resin-based adhesives and the like are used as adhesive compositions for optical fibers. However, studies in recent years have found that epoxy resin-based adhesives have problems in terms of durability. In addition, since the curing of the epoxy resin adhesive requires heating at about 110°C, there is a problem that it is not easy to install at the actual connection site, and when the epoxy resin adhesive is used, it will cause spots. other health damage.

On the other hand, Patent Document 1 discloses an adhesive composition mainly composed of polysiloxane, which is excellent in heat resistance, reduces generation of bubbles during curing, and does not cause cloudiness due to bubbles or the like.

Patent Document 1: JP-A-2002-173661

Contents of the invention

However, since the adhesive composition disclosed in Patent Document 1 contains polysiloxane as the main component, when it is left in a high-humidity environment for a long time, the adhesive force may decrease due to moisture penetration.

Therefore, an object of the present invention is to provide an optical fiber adhesive composition which is moisture-curable and excellent in adhesiveness and heat-and-moisture resistance.

The present inventors conducted intensive studies and found that if a compound having an active silicon-containing group is contained, the compound includes a compound formed by reacting an epoxy compound with a silane coupling agent, and the above-mentioned active silicon-containing group When the molecular weight of each active silicon-containing group of the compound is 1000 or less, it becomes an optical fiber adhesive composition excellent in moisture curing, adhesiveness and heat and humidity resistance. In addition, the present inventors have also found that if a compound having an active silicon-containing group having at least one active silicon-containing group other than the alkyl silyl ester and the above-mentioned alkyl silyl ester, becomes a wettable An optical fiber adhesive composition excellent in curing, adhesiveness, and heat and humidity resistance. The present inventors have completed the present invention based on such findings.

That is, the present invention provides the following (1) to (13).

(1) A binder composition for an optical fiber, containing a compound (A) having an active silicon-containing group, wherein the compound (A) comprises an epoxy compound (a) having at least one epoxy group, Compound (c) formed by reacting with a silane coupling agent (b) having reactive silicon-containing groups and reactive groups reactive with epoxy groups,

The above compound (A) having a reactive silicon-containing group has a molecular weight of 1000 or less per reactive silicon-containing group.

(2) The adhesive composition for an optical fiber according to the above (1), wherein the epoxy compound (a) has at least one aromatic ring.

(3) The adhesive composition for an optical fiber according to (1) or (2) above, wherein the active silicon-containing group of the compound (A) having an active silicon-containing group is a hydrolyzable silicon-containing group.

(4) The optical fiber adhesive composition according to any one of (1) to (3) above, wherein the silane coupling agent (b) is an iminosilane compound.

(5) An optical fiber adhesive composition comprising an alkylsilyl ester and a compound having an active silicon-containing group having at least one active silicon-containing group other than the above-mentioned alkylsilyl ester (B).

(6) The adhesive composition for an optical fiber according to (5) above, wherein the alkylsilyl ester is a monomer and/or oligomer of methylsilyl ester.

(7) The adhesive composition for an optical fiber according to (5) or (6) above, wherein the active silicon-containing group of the compound (B) having an active silicon-containing group is a hydrolyzable silicon-containing group.

(8) The optical fiber adhesive composition according to any one of (5) to (7) above, wherein the compound (B) having an active silicon-containing group contains at least one aromatic ring.

(9) The adhesive composition for an optical fiber as described in any one of the above (5) to (8), wherein the compound (B) having an active silicon-containing group is made to contain at least one epoxy group An epoxy compound (d) formed by reacting a compound (e) having at least one reactive group reactive with an epoxy group.

(10) The adhesive composition for an optical fiber according to (9) above, wherein the epoxy compound (d) is an aromatic epoxy compound, and the compound (e) is an iminosilane compound.

(11) The adhesive composition for an optical fiber according to (9) above, wherein the epoxy compound (d) is an epoxysilane compound, and the compound (e) is an aromatic amine compound.

(12) The adhesive composition for an optical fiber as described in any one of (5) to (11) above, which contains 1 to 300 parts by mass of the above-mentioned Active silicon group-containing compound (B).

(13) The adhesive composition for an optical fiber according to any one of (1) to (12) above, further comprising a curing catalyst.

The adhesive composition for an optical fiber of the present invention is moisture-curable, and has excellent adhesiveness and heat-and-moisture resistance.

Description of drawings

[ Fig. 1] Fig. 1 is a schematic longitudinal sectional view of an example of an optical connector connection portion where an optical fiber and a ferrule are bonded using the composition of the present invention.

Symbol Description

1 fiber

2 The core of the optical fiber

3 Cladding of optical fiber

4 Polymer coating

6 Adhesive layer

7 hoop

8 flange

Detailed ways

The present invention is described in more detail below.

The adhesive composition for an optical fiber of the first aspect of the present invention (hereinafter also referred to as "the composition of the first aspect") contains a compound (A) having an active silicon-containing group, and the compound (A) A compound (c) formed by reacting an epoxy compound (a) having at least one epoxy group and a silane coupling agent (b) having a reactive silicon-containing group and a reactive group reactive with the epoxy group , and the molecular weight of each active silicon-containing group of the compound (A) having an active silicon-containing group is 1000 or less.

The epoxy compound (a) used for the composition of a 1st aspect is a compound which has at least 1 epoxy group. Specifically, for example, bisphenol A, bisphenol F, bisphenol S, hexahydrobisphenol A, tetramethylbisphenol A, pyrocatechol, resorcinol, cresol novolac, Tetrabromobisphenol A, trihydroxybiphenyl, diresorcinol, bisphenol hexafluoroacetone, tetramethylbisphenol F, bixylenol, dihydroxynaphthalene and other polyphenols react with epichlorohydrin to obtain Glycidyl ether type; obtained by reaction of aliphatic polyols such as glycerin, neopentyl glycol, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, polyethylene glycol, polypropylene glycol, etc., with epichlorohydrin Polyglycidyl ether type; glycidyl ether ester type obtained by the reaction of hydroxycarboxylic acids such as p-hydroxybenzoic acid and β-hydroxynaphthoic acid with epichlorohydrin; from phthalic acid, methyl phthalic acid , Isophthalic acid, Terephthalic acid, Tetrahydrophthalic acid, Hexahydrophthalic acid, Endomethylene tetrahydrophthalic acid, Endomethylene hexahydrophthalic acid, Trimellitic acid Polyglycidyl ester type derived from polycarboxylic acid such as acid, polymerized fatty acid, etc.; glycidylaminoglycidyl ether type derived from aminophenol, aminoalkylphenol, etc.; glycidyl group derived from aminobenzoic acid Amino glycidyl ester type; composed of aniline, benzylidine, tribromoaniline, xylenediamine, diaminocyclohexane, bisaminomethylcyclohexane, 4,4'-diaminodiphenylmethane, Glycidyl amine derived from 4,4′-diaminodiphenyl sulfone, etc.; further epoxidized polyolefin, glycidyl hydantoin, glycidyl alkyl hydantoin, triglycidol cyanurate, etc.; Monoepoxides such as butyl glycidyl ether, phenyl glycidyl ether, alkylphenyl glycidyl ether, glycidyl benzoate, styrene oxide, etc., can be used One or a mixture of two or more of these compounds.

Moreover, it is preferable that the said epoxy compound (a) has at least 1 aromatic ring from a viewpoint of being excellent in the mechanical strength of hardened|cured material, and heat-and-moisture resistance. Bisphenol A type and bisphenol F type epoxy compounds are particularly preferable from the viewpoint of ease of acquisition and excellent balance of properties (performance) of cured products.

In addition, the heat-and-moisture resistance in this specification refers to the characteristic which maintains adhesiveness even if it is left for a long time in high temperature, high humidity, or a high temperature and high humidity environment.

In addition, the epoxy compound (a) preferably has an epoxy equivalent of 50 to 500, more preferably 100 to 400, from the viewpoint of good handleability due to low viscosity and good heat resistance of a cured product.

The said epoxy compound (a) can use a commercial item, and can also prepare it. The preparation conditions are not particularly limited, and can be carried out according to commonly used conditions.

The silane coupling agent (b) used in the composition of the first aspect is not particularly limited as long as it is a compound having an active silicon-containing group and an active group reactive with an epoxy group.

The above-mentioned active silicon-containing group has 1 to 3 active groups bonded to silicon atoms, and is a silicon-containing group that can be reacted and cross-linked by using a catalyst or the like in the presence of moisture or a cross-linking agent as needed group. Specifically, examples thereof include halogenated silicon-containing groups, hydrogenated silicon-containing groups, hydrolyzable silicon-containing groups, and the like. The said silane coupling agent (b) may have 1 type, or 2 or more types of such active silicon-containing groups.

Among the above-mentioned reactive silicon-containing groups, hydrolyzable silicon-containing groups are preferable from the viewpoint of obtaining a moisture-curable composition excellent in storage stability.

The above-mentioned halogenated silicon-containing group has 1 to 3 halogen groups bonded to silicon atoms, specifically, for example, chlorodimethylsilyl, dichloromethylsilyl, trichlorosilyl Base etc.

The above-mentioned hydrogenated silicon-containing group has 1 to 3 hydrogen atoms bonded to a silicon atom, specifically, a hydrogen dimethylsilyl group, a dihydromethylsilyl group, a trihydrosilyl group, etc. .

The above-mentioned halogenated silicon-containing groups may, for example, undergo a dehydrohalogenation reaction with the above-mentioned hydrogenated silicon-containing groups to form a chemical bond for crosslinking. In addition, halogenated silicon-containing groups can undergo displacement reactions with Grignard reagents, and then dehalogenate metals to form silicon-carbon bonds for cross-linking. In addition, halogenated silicon-containing groups, if alkali metals or magnesium are used, undergo reductive silylation reactions with aromatic hydrocarbons, conjugated dienes, aromatic aldehydes, ketones, carboxylic acids, esters, or imines to form silicon - Carbon bonds, for cross-linking.

The aforementioned hydrogenated silicon-containing groups, for example, can undergo a dehydrohalogenation reaction with the aforementioned halogenated silicon-containing groups to form chemical bonds and perform crosslinking. In addition, the hydrogenated silicon-containing group can undergo a hydrosilylation reaction with a compound having an unsaturated carbon bond to form a silicon-carbon bond for crosslinking.

The above-mentioned hydrolyzable silicon-containing group has 1 to 3 hydroxyl groups and/or hydrolyzable groups bonded to silicon atoms, and in the presence of moisture or a crosslinking agent, a condensation reaction can occur by using a catalyst or the like as necessary, Silicon-containing groups that undergo crosslinking through the formation of siloxane bonds. Examples thereof include alkoxysilyl groups, alkenyloxysilyl groups, acyloxysilyl groups, aminosilyl groups, aminooxysilyl groups, oximosilyl groups, and amidosilyl groups. base. Specifically, an alkoxysilyl group, an alkenyloxysilyl group, an acyloxysilyl group, an aminosilyl group, an aminooxysilyl group, and an oximosilyl group as exemplified by the following formula are suitably used. group, amidosilyl group, etc.

[chemical 1]

Among them, an alkoxysilyl group is preferable from the viewpoint of easy handling.

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 are suitably mentioned from the viewpoint of easy availability of raw materials.

The group other than the alkoxy group bonded to the silicon atom of the alkoxysilyl group is not particularly limited, and for example, a hydrogen atom or a carbon group such as a methyl group, an ethyl group, a propyl group, or an isopropyl group can be mentioned suitably. Alkyl, alkenyl or aralkyl having 20 or less atoms.

The active group which the said silane coupling agent (b) has and reacts with an epoxy group specifically includes an amino group, an imino group, a ureido group, a mercapto group, an acid anhydride group etc., for example.

Specific examples of the above-mentioned silane coupling agent (b) include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethyl Oxysilane, γ-aminopropylethyldiethoxysilane, bistrimethoxysilylpropylamine, bistriethoxysilylpropylamine, bismethoxydimethoxysilylpropylamine, bis Ethoxydiethoxysilylpropylamine, N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldimethoxysilane , N-β(aminoethyl)γ-aminopropyltriethoxysilane, N-β(aminoethyl)γ-aminopropylethyldiethoxysilane, 3,3-dimethyl-4 -Aminosilane compounds such as aminobutyltrimethoxysilane, 3,3-dimethyl-4-aminobutylmethyldimethoxysilane; (N-cyclohexylaminomethyl)methyldiethoxysilane, (N-cyclohexylaminomethyl)triethoxysilane, (N-phenylaminomethyl)methyldimethoxysilane, (N-phenylaminomethyl)trimethyloxysilane, the following Iminosilane compounds such as compounds represented by formula (1) and N-phenyl-3-aminopropyltrimethoxysilane represented by the following formula (2);

[Chem 2]

Ureidosilane compounds such as γ-ureidopropyltrimethoxysilane; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane , mercaptosilane compounds such as γ-mercaptopropylmethyldiethoxysilane, etc.

These compounds may be used alone or in combination of two or more.

The said silane coupling agent (b) can use a commercial item, and can also prepare it. The preparation conditions are not particularly limited, and can be carried out according to known methods and conditions.

The compound (c) used for the composition of a 1st aspect is obtained by making the said epoxy compound (a) and the said silane coupling agent (b) react. The compound (c) has a hydroxyl group derived from an epoxy group by using the above-mentioned epoxy compound (a) as a raw material. Therefore, in the obtained composition of the first form, since intermolecular hydrogen bonds are formed between the hydroxyl group and other hydroxyl groups and/or silanol groups not involved in crosslinking, the mechanical strength such as shear strength is further improved, Excellent adhesion and moisture resistance.

A preferred first embodiment of the compound (c) is a compound obtained by reacting the above-mentioned iminosilane compound with the above-mentioned epoxy compound (aromatic epoxy compound) having at least one aromatic ring. Examples thereof include compounds obtained by reacting 1 equivalent of an iminosilane compound having one imino group in one molecule of an aromatic epoxy compound having two epoxy groups in one molecule, and the like. Specifically, a compound represented by the following formula (3) obtained by reacting 1 equivalent of an iminosilane compound having a structure represented by the above formula (1) with respect to bisphenol A glycidyl ether is mentioned.

[Chem 3]

In addition, as a preferred second aspect of the compound (c), for an aromatic epoxy compound having two epoxy groups in one molecule, reacting 2 equivalents of an iminosilane compound having one imino group in one molecule The resulting compound. Specifically, for example, a compound represented by the following formula (4) obtained by reacting 2 equivalents of the compound having the structure represented by the above formula (1) with respect to bisphenol A glycidyl ether.

[chemical 4]

The compound (A) having an active silicon-containing group used in the composition of the first aspect includes at least the above-mentioned compound (c), and may contain a compound having an active silicon-containing group other than the above-mentioned compound (c).

The reactive silicon-containing group of the compound (A) having the above-mentioned reactive silicon-containing group is preferably a hydrolyzable silicon-containing group from the viewpoint of excellent storage stability and moisture-curable properties.

The number average molecular weight per active silicon-containing group of each active silicon-containing group-containing compound (A) contained in the above-mentioned active silicon-containing group-containing compound is 1,000 or less. Therefore, the composition of the first aspect has a high crosslinking density of a cured product, further improves mechanical strength such as shear strength, and is excellent in adhesiveness and heat-and-moisture resistance. The number average molecular weight per active silicon-containing group of the compound (A) having an active silicon-containing group is preferably 900 or less, more preferably 800 or less, from the viewpoint of the above-mentioned characteristics being more excellent.

In addition, the number average molecular weight per reactive silicon-containing group of the compound (A) having a reactive silicon-containing group is preferably 50 or more, more preferably 70 or more, from the viewpoint of preventing the crosslinking density from becoming too high.

Specific examples of compounds having an active silicon-containing group other than the compound (c) contained in the compound (A) having an active silicon-containing group include silane coupling agents.

The above-mentioned silane coupling agent is not particularly limited, and for example, those exemplified in the above-mentioned silane coupling agent (b); γ-glycidoxypropyltrimethoxysilane, γ-glycidoxy Propyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-epoxy Epoxysilane compounds such as propoxypropylmethyldiethoxysilane and the like.

When the compound (A) having an active silicon-containing group contains a compound having an active silicon-containing group other than the above-mentioned compound (c), it is preferable to contain 5 to 99% by mass of the above compound (c). As long as the content is within this range, the adhesiveness and heat-and-moisture resistance will be excellent. From the viewpoint of being more excellent in these characteristics, it is more preferable to contain 10-90 mass %, and it is more preferable to contain 20-80 mass %.

The composition of the first aspect further preferably contains a curing catalyst.

As the above-mentioned curing catalyst, curing catalysts generally used for compounds having an active silicon-containing group can be used. Specifically, carboxylic acid metal salts such as zinc octoate, iron octoate, manganese octoate, tin octoate, zinc naphthenate, iron naphthenate, tin butyrate, tin octylate, tin oleate, etc.; Dibutyltin, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin dioleate, dioctyltin dilaurate, diphenyltin diacetate, dibutyltin oxide, reaction product of dibutyltin oxide and phthalate Organotin compounds such as dibutyltin dimethoxide, (triethoxysiloxane) dibutyltin, dibutyltin silicate, etc.; tin chelates such as dibutyltin diacetylacetonate; tetraethoxytitanium, Titanium esters of tetrapropoxytitanium, tetrabutoxytitanium, tetra-2-ethylhexyloxytitanium, tetraisopropenyloxytitanium, etc.; diisopropoxytitanium bis(acetylacetonate), diisopropoxytitanium Isopropoxytitanium bis(ethyl acetylacetonate), 1,3-propanedioxytitanium bis(acetylacetonate), 1,3-propanedioxytitanium bis(ethyl acetylacetonate), titanium tris Titanium chelates such as (acetylacetonate); zirconium alkoxides such as tetraisopropoxyzirconium, tetrabutoxyzirconium, tributoxyzirconium stearate, etc.; zirconium chelates such as tetrakis(acetylacetonate)zirconium compound; aluminum alkoxy compounds such as triethoxy aluminum, tripropropoxy aluminum, tributoxy aluminum, etc.; diisopropoxy aluminum (ethyl acetylacetonate), tri (acetyl acetonate) aluminum, tri Aluminum chelates such as (ethyl acetylacetonate) aluminum;

Primary amines such as butylamine, hexylamine, octylamine, laurylamine, oleylamine, cyclohexylamine, benzylamine, etc.; secondary amines such as dibutylamine; diethylenetriamine, triethylenetetramine, guanidine, diethylene Polyamines such as benzoguanidine and xylenediamine; triethylenediamine, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo[5.4. Cyclic amines such as 0]-7-undecene; aminoalcohol compounds such as monoethanolamine, diethanolamine, and triethanolamine; aminophenol compounds such as 2,4,6-tris(dimethylaminomethyl)phenol amine compounds and their carboxylates; quaternary ammonium salts such as benzyltriethylammonium acetate; low molecular weight amide resins obtained from excess polyamines and polybasic acids; excess polyamines and epoxy compounds reaction products, etc.

These curing catalysts may be used alone or in combination of two or more.

Among them, metal compounds are preferable because they are less volatile during storage and handling, and among them, organotin compounds, tin chelate compounds, and titanates are preferable because they can obtain excellent catalytic performance even when compounded in a small amount.

In addition, the content of the curing catalyst is preferably 1 to 50 parts by mass relative to 100 parts by mass of the compound (A) having an active silicon-containing group. If the content of the curing catalyst is within this range, the effect of the curing catalyst can be fully exhibited, and there is no problem with the compatibility of other components, and local heat generation or foaming does not occur during curing. From the viewpoint of being more excellent in these properties, it is more preferably 1 to 40 parts by mass, and still more preferably 1 to 30 parts by mass.

The composition of the first aspect may contain fillers, reaction retarders, anti-aging agents, antioxidants, pigments (dyes), plasticizers, thixotropy-imparting agents, Various additives such as UV absorbers, flame retardants, solvents, surfactants (including leveling agents), dispersants, dehydrating agents, tackifiers, antistatic agents, etc.

Examples of the filler include organic or inorganic fillers of various shapes. Specifically, for example, fumed silica, calcined silica, precipitated silica, pulverized silica, fused silica; diatomaceous earth; iron oxide, zinc oxide, Titanium oxide, barium oxide, magnesium oxide; calcium carbonate, magnesium carbonate, zinc carbonate; pyrophyllite clay, kaolin clay, calcined clay; carbon black; fatty acid-treated products, resin acid-treated products, urethane compound-treated products, Fatty acid ester treatment. From the viewpoint of the physical properties of the cured product, the content of the filler is preferably 90% by mass or less in the entire composition.

Specific examples of retarders include compounds such as alcohols.

Specific examples of the antiaging agent include compounds such as hindered phenols.

Specific examples of the antioxidant include butylhydroxytoluene (BHT), butylhydroxyanisole (BHA), and the like.

嗪颜料、蒽嘧啶颜料、二苯并芘二酮颜料(anthanthrone)、阴丹酮颜料(indanthrone)、黄烷士酮(flavanthrone)颜料、苝颜料、橘黄(preinone)颜料、二酮吡咯并吡咯颜料(diketopyrrolopyrrole)颜料、喹诺萘酮(quinonaphthalone)颜料、蒽醌颜料、硫靛颜料、苯并咪唑酮颜料、异吲哚满颜料、炭黑等的有机颜料等。Specific examples of pigments include inorganic pigments such as titanium oxide, zinc oxide, ultramarine blue, red iron oxide, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochloride, and sulfate; azo pigments , phthalocyanine pigments, quinacridone pigments, quinacridone quinone pigments, two

Perylene pigments, anthracene pigments, anthanthrone pigments, indanthrone pigments, flavanthrone pigments, perylene pigments, preinone pigments, and diketopyrrolopyrrole pigments (diketopyrrolopyrrole) pigments, quinonaphthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, isoindoline pigments, organic pigments such as carbon black, and the like.

Specifically as the plasticizer, for example, dioctyl phthalate (DOP), dibutyl phthalate (DBP); dioctyl adipate, isodecyl succinate; diethylene glycol Dibenzoate, pentaerythritol ester; butyl oleate, methyl acetyl ricinoleate; tricresyl phosphate, trioctyl phosphate; propylene glycol adipate polyester, butylene adipate polyester, etc. These plasticizers may be used individually or in mixture of 2 or more types. From the viewpoint of handleability, the content of the plasticizer is preferably 50 parts by mass or less with respect to 100 parts by mass of the compound (A) having an active silicon-containing group.

Specific examples of the thixotropy-imparting agent include Aerosil (manufactured by Nippon Aerosil Co., Ltd.), and Disperon (manufactured by Kusumoto Chemical Co., Ltd.).

Specific examples of the tackifier include terpene resins, phenol resins, terpene-phenol resins, rosin resins, and xylene resins.

Specific examples of the flame retardant include chloroalkyl phosphate, dimethyl methyl phosphate, bromine phosphorus compound, ammonium polyphosphate, neopentyl bromide polyether, brominated polyether, and the like.

Examples of the antistatic agent generally include quaternary ammonium salts; hydrophilic compounds such as polyethylene glycol and ethylene oxide derivatives, and the like.

The composition of the first aspect is basically moisture-curable, and may be cured by heating. When used as a moisture-curing type, it does not require heating, so it is easy to handle. On the other hand, when it is used as a heat-curing type, the curing time is short and the deep curing property is excellent. Therefore, a moisture-curable type or a heat-curable type can be appropriately selected according to the use or construction site of the composition of the first embodiment.

In addition, the composition of the first aspect can be used for both one-component and two-component optical fiber adhesive compositions. When used as a one-component, it is excellent in workability because there is no trouble of mixing the main ingredient and curing agent on site. On the other hand, when used as a two-component, the curing time is short and the deep curing property is excellent. Therefore, one-component or two-component can be appropriately selected according to the use or construction site of the composition of the first aspect.

When the composition of the first aspect is used as a two-component, it can be prepared as a two-component adhesive composition comprising a main agent and a curing agent, and the main agent contains the above-mentioned compound (A) having an active silicon-containing group . The curing catalyst and additives added as needed can be combined with one or both of the main agent side and the curing agent side.

As the curing agent, water and other active hydrogen-containing compounds can be used, but water is preferable from the viewpoint of cost and ease of handling.

The production method of the composition of the first form is not particularly limited, for example, by fully kneading each of the above-mentioned components and additives added as needed, preferably under reduced pressure or in an inert atmosphere, using a mixing device such as a ball mill , so that it is uniformly dispersed.

As mentioned above, the composition of the 1st aspect is moisture-curable, and is excellent in adhesiveness and heat-and-moisture resistance.

The composition of the first form can be easily connected, for example, between ceramic materials, glass materials, plastic materials, metal materials, organic-inorganic composite materials, semiconductor materials, dielectric materials, etc., or any combination of these different materials, and is particularly suitable for use Adhesion of materials in high temperature and humidity environment. The composition of the first aspect is suitable for bonding an optical fiber to a ferrule because of the excellent characteristics as described above.

The adhesive composition for an optical fiber of the second aspect of the present invention (hereinafter also referred to as "the composition of the second aspect") contains an alkylsilyl ester and an active compound other than the above-mentioned alkylsilyl ester. A silicon group-containing compound (B), the compound (B) having at least one active silicon-containing group.

The alkylsilyl ester used in the composition of the second aspect is a compound represented by the following formula (5) and/or an oligomer thereof. In the composition of the second aspect, by using the above-mentioned alkylsilyl ester as the resin component, the crosslinking density becomes high, the mechanical strength of the cured product is improved, and a composition excellent in adhesiveness and heat-and-moisture resistance can be obtained. .

[chemical 5]

In the formula, R ¹ represents an alkyl group having 1 to 6 carbon atoms, preferably a methyl group, an ethyl group, an n-propyl group, or an isopropyl group, and more preferably a methyl group or an ethyl group. R ² represents an alkyl group having 1 to 3 carbon atoms, preferably a methyl group, an ethyl group, an n-propyl group, or an isopropyl group, more preferably a methyl group or an ethyl group.

As said alkyl silyl ester, the methyl silyl ester represented by following formula (6) and its oligomer are mentioned suitably.

These substances may be used alone or in combination of two or more.

[chemical 6]

When the said alkylsilyl ester is an oligomer of the compound represented by Formula (5), it is preferable that the number average molecular weight is 90-3000. If the molecular weight is within this range, it will have low viscosity, excellent handleability, and high reactivity. It is more preferable that the number average molecular weight of the said oligomer is 90-2000 from a viewpoint which is more excellent in these characteristics.

In particular, when the above-mentioned alkylsilyl ester is an oligomer of methyl silyl ester represented by formula (6), it is preferable that the number average molecular weight 90-3000. The number average molecular weight of the oligomer of methylsilyl ester is more preferably 90-2000, and still more preferably 90-1500 from the viewpoint of these characteristics being more excellent.

The above-mentioned alkylsilyl esters can be prepared using commercially available ones. The preparation conditions are not particularly limited, and can be carried out according to known methods and conditions.

The compound (B) having an active silicon-containing group used in the composition of the second aspect is not particularly limited as long as it is a compound having at least one active silicon-containing group other than the above-mentioned alkylsilyl ester. .

The reactive silicon-containing group of the compound (B) having the above-mentioned reactive silicon-containing group is the same as the reactive silicon-containing group of the above-mentioned silane coupling agent (b).

From the viewpoint of excellent mechanical strength and heat-and-moisture resistance of a cured product, the compound (B) having an active silicon-containing group preferably has at least one aromatic ring.

As the above-mentioned compound (B) having an active silicon-containing group, specifically, for example, an epoxy compound (d) containing at least one epoxy group, and an epoxy compound (d) containing at least one epoxy group reacted with A compound obtained by reacting a compound (e) of an active group (hereinafter referred to as "compound (f)"), a condensate of an alkoxysilane, a silane coupling agent, and the like.

These substances may be used alone or in combination of two or more.

Among them, the above-mentioned compound (f) is preferably used from the viewpoint of obtaining a composition excellent in adhesiveness and moisture resistance.

A preferred first aspect of the compound (f) is a compound obtained by reacting an iminosilane compound and an aromatic epoxy compound.

The above-mentioned iminosilane compound is not particularly limited as long as it is a compound having at least one active silicon-containing group and at least one imino group. Specifically, for example, (N-cyclohexylaminomethyl)methyldiethoxysilane, (N-cyclohexylaminomethyl)triethoxysilane, N-phenylaminomethyl)methoxysilane, Dimethoxysilane, (N-phenylaminomethyl)trimethyloxysilane, the compound represented by the above formula (3) and the N-phenyl-3-aminopropane represented by the above formula (4) Trimethoxysilane, etc.

The above-mentioned aromatic epoxy compound is a compound having at least one epoxy group and at least one aromatic ring. Specifically, for example, glycidyl ether type epoxy compounds obtained by reacting polyhydric phenols such as bisphenol A and bisphenol F with epichlorohydrin; compounds derived from aminophenols, aminoalkylphenols, etc. Glycidylaminoglycidyl ether-type epoxy compounds; glycidylaminoglycidyl ester-type epoxy compounds derived from aminobenzoic acid; derived from aniline, toluidine, tribromoaniline, xylenediamine, 4,4 Glycidylamine-type epoxy compounds derived from '-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, etc.

As a specific example of the first embodiment of the above-mentioned preferable compound (f), for an aromatic epoxy compound having two epoxy groups in one molecule, an imino group having one imino group in one molecule of one equivalent A compound obtained by reacting an aminosilane compound. More specifically, for example, a compound represented by the above formula (3) obtained by reacting 1 equivalent of an iminosilane compound having a structure represented by the above formula (1) with respect to bisphenol A glycidyl ether.

In addition, as another specific example of the preferred first form of the compound (f), an aromatic epoxy compound having two epoxy groups in one molecule having one imino group in two equivalents per molecule can be mentioned. The compound obtained by reacting the iminosilane compound. More specifically, for example, a compound represented by the above formula (4) obtained by reacting 2 equivalents of an iminosilane compound having a structure represented by the above formula (1) with respect to bisphenol A glycidyl ether.

A preferred second embodiment of the compound (f) is a compound obtained by reacting an epoxysilane compound and an aromatic amine compound.

The above-mentioned epoxy silane compound is not particularly limited as long as it is a compound containing at least one active silicon-containing group and at least one epoxy group. Specifically, for example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, Methoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and the like.

The above-mentioned aromatic amine compound is a compound having at least one amino group and/or imino group, and at least one aromatic ring. Specifically, for example, diphenylaminomethane (MDA), diaminodiphenylsulfone, diaminodiphenyl ether, diaminobenzophenone, phenylenediamine, xylylenediamine, 2,2 - Bis(4-aminophenyl)propane and the like.

As a specific example of the second embodiment of the above-mentioned preferred compound (f), for an aromatic amine compound having two amino groups in one molecule, 4 equivalents of an epoxy group having one epoxy group in one molecule A compound obtained by reacting a silane compound. More specifically, for example, a compound represented by the following formula (7) obtained by reacting 4 equivalents of 3-glycidoxypropyltrimethoxysilane with respect to diphenylaminomethane (MDA) .

[chemical 7]

Moreover, although it does not specifically limit as a condensate of the said alkoxysilane, For example, the condensate of tetraalkoxysilane, its epoxy-modified thing, its amino-modified thing etc. are used suitably. It is preferable that the number average molecular weight of the condensate of the said alkoxysilane is about 200-3000.

The silane coupling agent is not particularly limited, and known silane coupling agents can be used. Specifically, in addition to the above-mentioned iminosilane compound and the above-mentioned epoxy silane compound, for example, ureidosilane compounds such as γ-ureidopropyltrimethoxysilane; γ-aminopropyltrimethoxysilane; Silane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylethyldiethoxysilane, bistrimethoxysilylpropylamine, bistrimethoxy Ethoxysilylpropylamine, Bismethoxydimethoxysilylpropylamine, Bisethoxydiethoxysilylpropylamine, N-β(aminoethyl)γ-aminopropyltrimethoxy Silane, N-β(aminoethyl)γ-aminopropylmethyldimethoxysilane, N-β(aminoethyl)π-aminopropyltriethoxysilane, N-β(aminoethyl) γ-aminopropylethyldiethoxysilane, 3,3-dimethyl-4-aminobutyltrimethoxysilane, 3,3-dimethyl-4-aminobutylmethyldimethoxysilane, etc. Aminosilane compounds; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxy Mercaptosilane compounds such as silane; (poly)sulfide silane compounds such as bis(triethoxysilylpropyl)tetrasulfide and bis(triethoxysilylpropyl)disulfide; vinyl Vinylsilane compounds such as trichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(β-methoxyethoxy)silane; γ-methacryloxypropyl Methyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyl Methacryloxysilane compounds such as triethoxysilane;

β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis(2-methoxyethoxy)silane, N-β-(carboxymethyl)aminoethyl-γ-aminopropyltrimethyl Carboxysilane compounds such as oxysilane; Dimethoxysilane, γ-isocyanateethyltrimethoxysilane, γ-isocyanateethyltriethoxysilane, γ-isocyanateethylmethyldiethoxysilane, γ-isocyanateethylmethyldimethoxysilane Isocyanate silane compounds such as base silane; halogen silane compounds such as γ-chloropropyltrimethoxysilane, etc.

These compounds may be used alone or in combination of two or more.

When the compound (B) having an active silicon-containing group contains a compound having an active silicon-containing group other than the above-mentioned compound (f), it preferably contains 5 to 99% by mass of the above compound (f). As long as the content is within this range, the adhesiveness and heat-and-moisture resistance will be excellent. From the viewpoint of being more excellent in these characteristics, it is more preferable to contain 10-90 mass %, and it is more preferable to contain 20-80 mass %.

It is preferable that content of the compound (B) which has the said active silicon-containing group is 1-300 mass parts with respect to 100 mass parts of said alkylsilyl esters. If the content is within this range, the composition of the second aspect will be excellent in adhesiveness and heat-and-moisture resistance. From the viewpoint of these properties being more excellent, the content of the above-mentioned active silicon-containing group-containing compound (B) is more preferably 50 to 300 parts by mass with respect to 100 parts by mass of the above-mentioned alkylsilyl ester, and further preferably contains 100 parts by mass. ~300 parts by mass.

The composition of the second aspect further preferably contains a curing catalyst. The curing catalyst is the same as the curing catalyst used in the composition of the above-mentioned first aspect.

Moreover, it is preferable that content of a curing catalyst is 1-50 mass parts with respect to a total of 100 mass parts of the said alkylsilyl ester, and the said compound (B) which has an active silicon-containing group. If the content of the curing catalyst is within this range, the effect of the curing catalyst can be fully exhibited, and there is no problem with the compatibility of other components, and local heat generation or foaming does not occur during curing. From the viewpoint of being more excellent in these properties, it is more preferably 1 to 40 parts by mass, and still more preferably 1 to 30 parts by mass.

The composition of the second aspect may contain fillers, reaction retardants, antiaging agents, antioxidants, pigments (dyes), plasticizers, thixotropy imparting agents, ultraviolet ray Various additives such as absorbents, flame retardants, solvents, surfactants (including leveling agents), dispersants, dehydrating agents, tackifiers, antistatic agents, etc.

The composition of the second aspect is basically moisture-curable, and may be cured by heating. When used as a moisture-curing type, since heating is not required, the workability is good. On the other hand, when used as a heat curing type, the curing time is short and the deep curability is excellent. Therefore, a moisture-curable type or a heat-curable type can be appropriately selected according to the use or construction site of the composition of the second aspect.

In addition, the composition of the second aspect can be used for both one-component and two-component optical fiber adhesive compositions. When used as a one-component, it is excellent in workability because there is no trouble of mixing the main ingredient and curing agent on site. On the other hand, when used as a two-component, the curing time is short and the deep curability is excellent. Therefore, one-component or two-component can be appropriately selected according to the use or construction site of the composition of the second aspect.

When the composition of the second form is used as a two-component, it can be made into a two-component adhesive composition comprising a main agent and a curing agent. The main agent contains an alkyl silyl ester and the above-mentioned active silicon-containing Group compound (B). The curing catalyst and additives added according to the needs can be combined with one or both of the main agent side and the curing agent side.

As the curing agent, water and other active hydrogen-containing compounds can be used, but water is preferable from the viewpoint of cost and ease of handling.

The production method of the composition of the second form is not particularly limited, for example, by fully kneading each of the above-mentioned components and additives added as needed, preferably under reduced pressure or in an inert atmosphere, using a mixing device such as a ball mill , so that it is uniformly dispersed.

As mentioned above, the composition of the 2nd aspect is moisture-curable, and is excellent in adhesiveness and heat-and-moisture resistance.

The composition of the second form can easily connect, for example, ceramic materials, glass materials, plastic materials, metal materials, organic-inorganic composite materials, semiconductor materials, dielectric materials, etc., or any combination of such different materials, especially Suitable for bonding materials under high temperature and humidity environment. Since it has excellent characteristics as described above, the composition of the second aspect is suitable for bonding an optical fiber and a ferrule.

Example

Next, the present invention will be described concretely by showing examples. However, the present invention is not limited thereto.

<Synthesis of compound (c)>

(Synthesis Examples 1-6)

Each component shown in the following Table 1 was mixed according to the composition (parts by mass) shown in Table 1, and after stirring at 80° C. for 8 hours under an inert gas atmosphere, each compound corresponding to the above compound (c) was obtained .

The silylation rate shown in Table 1 is a percentage (theoretical value) showing the ratio of the number of reactions of the silane coupling agent (b) to the total number of active groups of the epoxy compound (a). For example, in Synthesis Example 2, since one silane coupling agent (b) is reacted with respect to the compound (a) having two epoxy groups, the silylation rate is 50%.

The compound obtained, presumably synthesis example 1 is the mixture of the compound shown in above-mentioned formula (3) and unreacted epoxy compound 1, and synthesis example 2 is the compound shown in above-mentioned formula (3), and synthesis example 3 is the compound shown in above-mentioned formula (3) (3) and a mixture of the compound represented by the above formula (4), Synthesis Example 4 is a compound represented by the above formula (4). In addition, Synthesis Example 5 is estimated to be a compound represented by the following formula (8), and Synthesis Example 6 is estimated to be a compound represented by the following formula (9).

[chemical 8]

[Table 1]

Each component shown in Table 1 is as follows.

・Epoxy compound 1 (bisphenol A glycidyl ether): EPOT-YD-128, manufactured by Tohto Chemical Co., Ltd.

・Epoxy compound 2 (bisphenol F glycidyl ether): EPOT-YDF-170, manufactured by Tohto Chemical Co., Ltd.

・Imidosilane compound (the compound represented by the above-mentioned formula (1)): Alink-15, manufactured by Japan Unicar Co., Ltd.

<Preparation and evaluation of two-component adhesive composition>

(Examples 1 to 6 and Comparative Examples 1 and 2)

Mix the components of liquid A shown in the following Table 2 according to the composition (parts by mass) shown in Table 2, and use a mixer to fully disperse them, then add the entire amount of liquid B components, and make them fully dispersed to obtain the following: Each composition shown in 2. In addition, in Comparative Example 2, a conventional epoxy resin-based adhesive composition (trade name Epotec 353ND, manufactured by Muromachi Technologies Co., Ltd. was used.

Using each of the obtained compositions, the curing speed (moisture curability), adhesiveness, moisture and heat resistance, and cure shrinkage were evaluated as follows. The results are shown in Table 2.

(Evaluation of curing speed (moisture curability))

Each of the obtained compositions was placed in an environment of 20° C. and 65% RH according to the method of JIS A5758-2004, and the tack-free time (tack-free time) was measured immediately after the composition was prepared. In addition, since the composition of Comparative Example 2 is a heat-curable type, it was not cured at room temperature.

(Evaluation of adhesion and heat and humidity resistance)

Prepare 2 glass plates (length 30mm×width 25mm×thickness 5mm), laminate one end 3mm×width 25mm of each composition obtained, heat and cure at 110°C for 1 hour to prepare a test object . Using the prepared test piece, the shear strength (initial stage) was measured according to JIS K6852-1994.

In addition, the test object produced in the same manner as above was left to deteriorate for 10 days in an environment of 80° C. and 95% RH. Using this test piece, the shear strength (after damp heat deterioration) was measured in the same manner as above.

Table 2

Each component shown in said Table 2 is as follows.

・Epoxysilane compound (3-glycidoxypropyltrimethoxysilane): A-187, manufactured by Japan Unica Co., Ltd.

・Curing catalyst (dibutyltin diacetylacetonate): U-220, manufactured by Nitto Kasei Co., Ltd.

It can be clearly seen from the above Table 2 that the compositions containing at least one compound obtained in Synthesis Examples 1 to 6 (Examples 1 to 6) can be cured in 10 to 60 minutes even at room temperature. The composition of the compounds obtained in Examples 1 to 6 (Comparative Example 1) has excellent adhesiveness compared with the conventional epoxy resin-based adhesive (Comparative Example 2). In particular, the difference in the shear strength after the heat-and-moisture deterioration was remarkable, so it was proved that the compositions of Examples 1 to 6 were very excellent in heat-and-moisture resistance.

<Preparation of One-Component Binder Composition>

(Examples 7-11 and Comparative Example 3)

Each component shown in the following Table 3 was mixed according to the composition (parts by mass) shown in Table 3, and it was fully dispersed using the mixer, and each composition shown in Table 3 was obtained.

Using each of the obtained compositions, the curing rate (moisture curability) was evaluated in the same manner as above, and the adhesiveness and heat-and-moisture resistance were evaluated by the following methods. Table 3 shows the results.

(Evaluation of adhesion and heat and humidity resistance)

Except having changed curing conditions to 20 degreeC, 65%RH, and 3 days, the test object was produced similarly to the above, and the shear strength (initial stage) was measured.

In addition, this test object was left to deteriorate for 10 days under the environment of 80 degreeC and 95%RH. Using this test piece, the shear strength (after damp heat deterioration) was measured in the same manner as above.

table 3

Each component shown in Table 3 is the same as each component shown in Table 2.

It can be clearly seen from Table 3 that the one-component adhesive composition (Example 7-11) containing the compound of Synthesis Examples 2-6, and the two-component adhesive composition of Examples 1-6 shown in Table 2 The same agent composition has excellent adhesion and heat and humidity resistance. In particular, although the shear strength (initial stage) when moisture-cured at room temperature tends to be slightly lower than the shear strength (initial stage) when heat-cured (refer to Table 2), compared with conventional Compared with the two-component epoxy resin adhesive (comparative example 2) or the cured product of epoxy silane (comparative example 3), it is very excellent. That is, it was proved that the one-component adhesive compositions of Examples 7 to 11 can be sufficiently used even as moisture-curable adhesive compositions.

<Bonding of optical fiber and ferrule>

Fig. 1 is a schematic longitudinal sectional view of an example of an optical connector connection portion where an optical fiber and a ferrule are bonded using the composition of the present invention.

As shown in FIG. 1 , at the end of a single-mode glass optical fiber (about 1 m in length) 1 having a polymer coating 4, a core 2, and a cladding 3, a part of the polymer coating 4 is removed at a length of 2 cm, The compositions of Example 2 and Comparative Example 2 were applied, inserted into the cavity of the ferrule 7 made of zirconia fixed to the flange 8, heated and left at 110°C for 1 hour, and the optical fiber 1 was bonded through the adhesive layer 6. with hoop7. Thereafter the end faces of the hoop are precision ground.

Next, grasp the ferrule 7 or the optical fiber with respect to the product (initial stage) bonded to the optical fiber 1 and the ferrule 7, and the product (after damp heat deterioration) left in an environment of 80° C. and 95% RH for 10 days. 1 Gently stretch. As a result, in the product bonded by the composition of Comparative Example 2 using the conventional epoxy resin adhesive, although the initial bonded part was not destroyed, the bonded part 6 and the optical fiber 1 were damaged in the product after moisture and heat deterioration. The interface peeled off. On the other hand, in the product bonded using the composition of Example 2, none of the bonded parts were damaged. This is considered to be because the composition of Example 2 is excellent in adhesiveness and heat-and-moisture resistance.

<Synthesis of Compound (B) Having Active Silicon-Containing Group>

(Synthesis Examples 7-10)

The components shown in the following Table 4 were mixed according to the composition (parts by mass) shown in Table 4, and stirred at 80° C. for 8 hours under an inert gas atmosphere to obtain the corresponding active silicon-containing group. Each compound of the compound (B) (the above-mentioned compound (f)).

The silylation rate shown in Table 4 represents the reaction rate of the iminosilane compound or epoxysilane compound with respect to the number of epoxy groups of the aromatic epoxy compound or the number of active hydrogens of the aromatic amine compound. The percentage of the proportion of the number (theoretical value). For example, in Synthesis Example 12, since one iminosilane compound reacts with respect to an aromatic epoxy compound having two epoxy groups, the silylation rate is 50%. Also in Synthesis Example 15, since four epoxysilane compounds reacted with respect to the aromatic amine compound having two amino groups (having four active hydrogens), the silylation rate was 100%.

The compound that obtains, presumably synthesis example 7 is the compound shown in above-mentioned formula (3), and synthesis example 8 is the mixture of the compound shown in above-mentioned formula (3) and above-mentioned formula (4), and synthesis example 9 is the compound shown in above-mentioned formula (4). Among the compounds shown, Synthesis Example 10 is a compound represented by the above formula (7).

[Table 4]

Each component shown in Table 4 is as follows.

・Aromatic epoxy compound (bisphenol A glycidyl ether): EPOT-YD-128, manufactured by Tohto Chemical Co., Ltd.

・Aromatic amine compound (diphenylaminomethane): MDA, manufactured by Kanto Chemical Co., Ltd.

・Imidosilane compound (the compound represented by the above-mentioned formula (1)): Alink-15, manufactured by Japan Unicar Co., Ltd.

・Epoxysilane compound (3-glycidoxypropyltrimethoxysilane): A-187, manufactured by Japan Unica Co., Ltd.

<Preparation and evaluation of two-component adhesive composition>

(Examples 12 to 15 and Comparative Examples 4 and 5)

Mix the components of A liquid shown in Table 5 below according to the composition (parts by mass) shown in Table 5, and use a mixer to make it fully dispersed, then add the full amount of B liquid components, and make it fully dispersed to obtain the following: Each composition shown in 5. In addition, in Comparative Example 5, a conventional epoxy resin-based adhesive composition (trade name Epotec 353ND, manufactured by Muromachi Technologies Co., Ltd. was used.

Using each of the obtained compositions, the curing rate (moisture curability), adhesiveness, and heat-and-moisture resistance were evaluated in the same manner as above.

The results are shown in Table 5. In addition, since the composition of Comparative Example 5 is a heat-curable type, it was not cured at room temperature.

table 5

Each component shown in the said Table 5 is as follows. In addition, as the epoxy silane compound, the same compounds as those shown in Table 4 were used.

・Methylsilyl ester: MSE-100, manufactured by Asahi Kasei Watsuka Co., Ltd.

・Curing catalyst (dibutyltin diacetylacetonate): U-220, manufactured by Nitto Kasei Co., Ltd.

It can be clearly seen from Table 5 that the compositions containing at least one compound obtained in Synthesis Examples 7 to 10 (Examples 12 to 15) solidify in a few minutes at room temperature, and the compositions that do not contain the compounds obtained in Synthesis Examples 7 to 10 (Comparative Example 4) and the conventional epoxy resin-based adhesive (Comparative Example 5) have excellent adhesiveness. In particular, the difference in the shear strength after the heat-and-moisture deterioration was remarkable, so it was proved that the compositions of Examples 12 to 15 were very excellent in heat-and-moisture resistance.

<Preparation of One-Component Binder Composition>

(Examples 16-19 and Comparative Example 6)

Each component shown in the following Table 6 was mixed according to the composition (parts by mass) shown in Table 6, and it was fully dispersed using the mixer, and each composition shown in Table 6 was obtained.

Using each of the obtained compositions, the curing rate (moisture curability), adhesiveness, and heat-and-moisture resistance were evaluated in the same manner as above. The results are shown in Table 6.

[Table 6]

Each component shown in Table 6 is the same as each component shown in Table 5.

It can be clearly seen from Table 6 that the one-component adhesive composition (Examples 16-19) containing the compounds of Synthesis Examples 7-10 is bonded with the two-component adhesives of Examples 12-15 shown in Table 5. The same agent composition has excellent adhesion and heat and humidity resistance. In particular, although the shear strength (initial stage) when it is moisture-cured at room temperature tends to be slightly lower than the shear strength (initial stage) when heat-cured (see Table 5), but compared with conventional Compared with the two-component epoxy resin adhesive (comparative example 5) or the cured product of epoxy silane (comparative example 6), it is very excellent. That is, it was demonstrated that the one-component adhesive compositions of Examples 16 to 19 can be sufficiently used even as moisture-curable adhesive compositions.

<Bonding of optical fiber and ferrule>

Fig. 1 is a schematic longitudinal sectional view of an example of a connection portion between an optical fiber and a ferrule bonded using the composition of the present invention.

As shown in FIG. 1 , at the end of a single-mode glass optical fiber (about 1 m in length) 1 having a polymer coating 4, a core 2, and a cladding 3, a part of the polymer coating 4 is removed at a length of 2 cm, The composition of Example 12 and Comparative Example 5 was applied, inserted into the cavity of the ferrule 7 made of zirconia fixed to the flange 8, heated at 110°C, and left to stand for 1 hour to bond the optical fiber through the adhesive layer 6 1 with hoop 7 . Thereafter the end faces of the hoop are precision ground.

Next, grasp the ferrule 7 or the optical fiber with respect to the product (initial stage) bonded to the optical fiber 1 and the ferrule 7, and the product (after damp heat deterioration) left in an environment of 80° C. and 95% RH for 10 days. 1 Gently stretch. As a result, in the product bonded with the composition of Comparative Example 5 of the conventional epoxy resin adhesive, although the initial bonded part was not destroyed, the bonded part 6 and the optical fiber were damaged in the product after moisture and heat deterioration. The interface of 1 peeled off. On the other hand, in the product bonded using the composition of Example 12, none of the bonded parts were damaged. This is considered to be because the composition of Example 12 was excellent in adhesiveness and heat-and-moisture resistance.

Claims (4)

1. adhesive compositions for optical fibers, it contains the compound (A) with active silicon-containing group, described compound (A) comprise make epoxy compounds (a) with at least 1 epoxy group(ing), with the compound (c) that has active silicon-containing group and form with silane coupling agent (b) reaction of the active group of epoxy reaction

Above-mentioned silane coupling agent (b) is the imino-silane compound,

The molecular weight of each active silicon-containing group of above-mentioned compound (A) with active silicon-containing group is below 1000.

2. adhesive compositions for optical fibers as claimed in claim 1, above-mentioned epoxy compounds (a) contains at least 1 aromatic nucleus.

3. adhesive compositions for optical fibers as claimed in claim 1 or 2, above-mentioned active silicon-containing group with compound (A) of active silicon-containing group is water-disintegrable silicon-containing group.

4. adhesive compositions for optical fibers as claimed in claim 1 further contains curing catalysts.

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