JP5375290B2 - Adhesive composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesive composition excellent in flame-retardancy, humidity-resistance and heat-resistance. <P>SOLUTION: The adhesive composition includes 100 pts.mass of an alkoxysilyl group-modified polyoxyalkylene polymer, 10-100 pts.mass of an epoxy resin; ketimine obtained by reacting a carbonyl compound represented by formula (I) with polyamine, at least one of flame-retardant fillers selected from the group consisting of aluminum hydroxide, magnesium hydroxide, calcium hydroxide, calcium sulfate hydrates and magnesium sulfate hydrates, and curing catalysts. The amount of the imino group possessed by ketimine is 0.5-1.5 equivalents relative to the epoxy group possessed by the epoxy resin, and the amount of the flame-retardant filler is 30-70 mass% in the whole amount of the composition. In the formula, R<SP>1</SP>is a 1-6C alkyl group, R<SP>2</SP>is a methyl group or an ethyl group, R<SP>3</SP>is a hydrogen atom, a methyl group or an ethyl group, R<SP>4</SP>is a hydrogen atom or an alkyl group, and n is 1 or 2. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to an adhesive composition.

Conventionally, a silicone resin containing a silicone resin in which the silicone reactive group is a methyldimethoxysilyl group, a methyldiethoxysilyl group, a trimethoxysilyl group, or a triethoxysilyl group, and the main chain is substantially a polyoxypropylene structure Compositions have been proposed.
The present applicant has previously contained a specific adhesion-imparting agent, an amine-based latent curing agent, and a urethane prepolymer having an isocyanate group bonded to a tertiary carbon atom, further containing an epoxy resin, and further having an alkoxysilyl at the terminal. A curable resin composition containing a resin having a group has been proposed (Patent Document 1).
In addition, a flame-retardant moisture-curable composition containing a reactive silicon group-containing organic polymer and a metal hydroxide having an average particle size of 0.1 to 200 μm has been proposed (Patent Documents 2 and 3).
In general, a combination of a halogen compound and antimony oxide has been used for a long time in order to impart flame retardancy to a resin composition, but it has not been used in recent years because dioxins are generated during combustion. In addition, red phosphorus and phosphoric acid esters are partly used, but phosphine is generated during combustion, and organic phosphorus compounds are considered to be the main cause of pollution in rivers, etc. .

JP 2003-321665 A JP 2007-84633 A JP 2007-332258 A

Furthermore, a phosphate ester is used as a flame retardant for the purpose of imparting flame retardancy to an alkoxysilyl group-modified polyoxyalkylene polymer having a hydrolyzable silyl group and the main chain being substantially polyoxyalkylene. The inventors have found that when used, poor curing occurs.
Further, a cured product obtained from a composition containing a conventionally known hydrolyzable silyl group-containing alkoxysilyl group-modified polyoxyalkylene polymer whose main chain is substantially polyoxyalkylene and a flame retardant is difficult. There is a problem that flame retardancy does not appear unless a high amount of the flame retardant is filled. Further, when the flame retardant was highly filled, the resin component in the composition was low, so the moisture resistance and water resistance were not at practical levels. Furthermore, the polyoxyalkylene resin does not have sufficient heat resistance and cannot be used for a long period of time at sites exposed to 100 ° C. or higher.
Then, an object of this invention is to provide the adhesive composition excellent in a flame retardance, moisture resistance, and heat resistance.

  As a result of diligent research to solve the above-mentioned problems, the present inventor has found that 100 parts by mass of an alkoxysilyl group-modified polyoxyalkylene polymer having a hydrolyzable silyl group and the main chain being substantially polyoxyalkylene, epoxy 10-100 parts by mass of resin, ketimine obtained by reacting carbonyl compound represented by formula (I) with polyamine, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, calcium sulfate hydrate and sulfuric acid It contains at least one flame retardant filler selected from the group consisting of magnesium hydrate and a curing catalyst, and the amount of imino group possessed by the ketimine is 0.5% relative to the epoxy group possessed by the epoxy resin. -1.5 equivalent, and the amount of the flame retardant filler is 30 to 70% by mass in the total amount of the composition. It found that moisture resistance can be an adhesive composition excellent in heat resistance, and completed the present invention.

That is, this invention provides the following 1-8.
1.
100 parts by mass of an alkoxysilyl group-modified polyoxyalkylene polymer having a hydrolyzable silyl group and the main chain being substantially polyoxyalkylene,
10 to 100 parts by mass of epoxy resin,
A ketimine obtained by reacting a carbonyl compound represented by the following formula (I) with a polyamine;
At least one flame retardant filler selected from the group consisting of aluminum hydroxide, magnesium hydroxide, calcium hydroxide, calcium sulfate hydrate and magnesium sulfate hydrate;
Containing a curing catalyst,
The amount of imino group that the ketimine has is 0.5 to 1.5 equivalents relative to the epoxy group that the epoxy resin has,
The adhesive composition whose quantity of the said flame-retardant filler is 30-70 mass% in the composition whole quantity.

Wherein R ¹ is an alkyl group having 1 to 6 carbon atoms, R ² is a methyl group or an ethyl group, R ³ is a hydrogen atom, a methyl group or an ethyl group, and R ⁴ is a hydrogen atom or An alkyl group, and n is 1 or 2.)
2.
The alkoxysilyl group-modified polyoxyalkylene polymer has at least one selected from the group consisting of a methyldimethoxysilyl group, a methyldiethoxysilyl group, a trimethoxysilyl group, and a triethoxysilyl group as the hydrolyzable silyl group. 2. The adhesive composition according to 1 above.
3.
Furthermore, it contains a polyether having a number average molecular weight of 100 to 5,000 and a terminal hydroxy group blocked, and the amount of the polyether is 5 with respect to 100 parts by mass of the alkoxysilyl group-modified polyoxyalkylene polymer. The adhesive composition according to 1 or 2 above, which is ˜50 parts by mass.
4).
4. The adhesive composition according to any one of 1 to 3 above, comprising 0.2 to 30 parts by weight of an N-silylamide compound represented by the following formula (2) with respect to 100 parts by mass of the alkoxysilyl group-modified polyoxyalkylene polymer. .
(R ¹ -CONH) _4-n -Si-R ² _n (2)
(In the formula, R ¹ is a hydrocarbon group having 5 to 21 carbon atoms which may contain a hetero atom, and when n is 0, 1 or 2, R ¹ may be the same or different. R ² is an alkyl or alkoxy group having 1 to 3 carbon atoms, and n is 0, 1, 2 or 3.)
5.
The said flame-retardant filler is an adhesive composition in any one of said 1-4 whose average particle diameter is 0.5-30 micrometers, and is surface-treated with the fatty acid or the silane compound.
6).
6. The adhesive composition according to any one of 1 to 5 above, which contains aluminum hydroxide as the flame retardant filler.
7).
The adhesive composition according to any one of 1 to 6, wherein the terminal hydroxy group is blocked with an alkyl group, an alkoxy group, or an alkylsilyl group in the polyether.
8).
Furthermore, the adhesive agent in any one of said 1-7 which contains water and the quantity of the said water is 0.5-5 equivalent with respect to the alkoxy group which the said alkoxysilyl group modified polyoxyalkylene polymer has. Composition.

  The adhesive composition of the present invention is excellent in flame retardancy, moisture resistance, and heat resistance.

The present invention will be described in detail below.
The adhesive composition of the present invention comprises:
100 parts by mass of an alkoxysilyl group-modified polyoxyalkylene polymer having a hydrolyzable silyl group and the main chain being substantially polyoxyalkylene,
10 to 100 parts by mass of epoxy resin,
A ketimine obtained by reacting a carbonyl compound represented by the following formula (I) with a polyamine;
Containing at least one flame retardant filler selected from the group consisting of aluminum hydroxide, magnesium hydroxide, calcium hydroxide, calcium sulfate hydrate and magnesium sulfate hydrate, and a curing catalyst,
The amount of imino group that the ketimine has is 0.5 to 1.5 equivalents relative to the epoxy group that the epoxy resin has,
The amount of the flame retardant filler is 30 to 70% by mass in the total amount of the composition.

Wherein R ¹ is an alkyl group having 1 to 6 carbon atoms, R ² is a methyl group or an ethyl group, R ³ is a hydrogen atom, a methyl group or an ethyl group, and R ⁴ is a hydrogen atom or An alkyl group, and n is 1 or 2.)

The alkoxysilyl group-modified polyoxyalkylene polymer will be described below.
The alkoxysilyl group-modified polyoxyalkylene polymer contained in the adhesive composition of the present invention is a polymer having a hydrolyzable silyl group and the main chain being substantially polyoxyalkylene.

The alkoxysilyl group-modified polyoxyalkylene polymer has a hydrolyzable silyl group as a reactive group. Examples of the hydrolyzable silyl group include an alkyl dialkoxysilyl group and a trialkoxysilyl group. Examples of the alkyl dialkoxysilyl group include a methyldimethoxysilyl group and a methyldiethoxysilyl group.
When the hydrolyzable silyl group is a trialkoxysilyl group, it is excellent in rapid curability, and can be cured at room temperature without foaming (tack-free time: 30 minutes or less is possible). Examples of the trialkoxysilyl group include a trimethoxysilyl group and a triethoxysilyl group.

The number of hydrolyzable silyl groups is superior in terms of flame retardancy, moisture resistance, and heat resistance, and from the viewpoint of excellent balance between heat resistance, fluidity, storage stability, shear strength, viscosity and flexibility, alkoxysilyl groups The number is preferably 1 to 4 per molecule of the modified polyoxyalkylene polymer.
The hydrolyzable silyl group can be bonded to the end of the main chain and / or as a side chain. From the viewpoint of excellent balance between viscosity and flexibility, the hydrolyzable silyl group is preferably bonded to at least both ends of the main chain.
The hydrolyzable silyl group can be bonded to the main chain directly or via an organic group. The organic group is not particularly limited. For example, the hydrocarbon group which may have a hetero atom like an oxygen atom, a nitrogen atom, and a sulfur atom is mentioned.

In the present invention, the main chain of the alkoxysilyl group-modified polyoxyalkylene polymer is substantially polyoxyalkylene. The polyoxyalkylene is not particularly limited. Examples thereof include polyoxyethylene and polyoxypropylene. In the present invention, that the main chain is substantially polyoxyalkylene means that an oxyalkylene group is included as a repeating unit constituting the main chain in an amount of 50% or more of the total number of moles of the repeating unit. The repeating unit other than the oxyalkylene group that can be contained in the polyoxyalkylene is not particularly limited. In the alkoxysilyl group-modified polyoxyalkylene polymer, the main chain may be a homopolymer or a copolymer.
The main chain may be linear or branched. When the main chain is linear, the cured product is excellent in elongation. When the main chain is branched, the shear strength is excellent.

The alkoxysilyl group-modified polyoxyalkylene polymer is preferably a dialkoxysilyl group-modified polyoxyalkylene polymer or a trialkoxysilyl group-modified polyoxyalkylene polymer from the viewpoint of excellent flame retardancy, heat resistance, and moisture resistance.
As the dialkoxysilyl group-modified polyoxyalkylene polymer, for example, a polyoxypropylene polymer having a dimethoxysilyl group or a diethoxysilyl group at the terminal is preferable.

The alkoxysilyl group-modified polyoxyalkylene polymer is preferably a trialkoxysilyl group-modified polyoxyalkylene polymer from the viewpoint of excellent fast curability.
The trialkoxysilyl group-modified polyoxyalkylene polymer is preferably a polyoxypropylene polymer having a trimethoxysilyl group or a triethoxysilyl group at the terminal, and each having one trimethoxysilyl group at two or more terminals. A polyoxypropylene polymer, more preferably a polyoxypropylene polymer having one triethoxysilyl group at each of two or more terminals, a linear polyoxypropylene polymer having a trimethoxysilyl group at both terminals, A linear polyoxypropylene polymer having a triethoxysilyl group at the end, a trifunctional branched polyoxypropylene polymer having a trimethoxysilyl group at both ends and a trimethoxysilyl group at the end of the side chain, Triethoxysilyl groups at both ends and triethoxy Branched polyoxypropylene polymer of trifunctional with Le group is more preferred.

Examples of the trialkoxysilyl group-modified polyoxyalkylene polymer include compounds represented by the following formula (V).

In the formula, R ¹ and R ² are alkylene groups having 1 to 5 carbon atoms, R ³ is a methyl group or an ethyl group, n is an integer of 9 to 900, and m is an integer of 1 to 5. A is a residue of an initiator used as a raw material for producing a polyoxyalkylene monool or a polyoxyalkylene polyol.
When producing a trialkoxysilyl group-modified polyoxyalkylene polymer, polyoxyalkylene monool or polyoxyalkylene polyol can be used as a raw material, but when producing the polyoxyalkylene monool or polyoxyalkylene polyol. The initiator used for is not particularly limited. For example, a conventionally well-known thing is mentioned.
The trialkoxysilyl group-modified polyoxyalkylene polymer is superior in storage stability and fast curability, can suppress thickening, and can have an appropriate viscosity of the composition. ) Is preferred.

The adhesive composition of the present invention has an alkoxysilyl group at one end with respect to a polyoxypropylene polymer having one alkoxysilyl group at each of two or more ends for the purpose of reducing the viscosity of the composition. A polyoxypropylene polymer having one can be mixed. The polyoxypropylene polymer having one alkoxysilyl group at one end may have a hydroxy group without having an alkoxysilyl group at another end.
The amount of the polyoxypropylene polymer having one alkoxysilyl group at one end is 10% by mass or less based on the polyoxypropylene polymer having one alkoxysilyl group at two or more ends. It is preferable from the point that the physical properties (strength and elongation) of the cured product do not extremely decrease.

  The molecular weight of the alkoxysilyl group-modified polyoxyalkylene polymer is superior in terms of flame retardancy, heat resistance, and moisture resistance, and is excellent in quick curing, storage stability, shear strength, and a balance between viscosity and flexibility. It is preferable that it is 10,000-50,000, and it is more preferable that it is 10,000-30,000.

  The alkoxysilyl group-modified polyoxyalkylene polymer is excellent in rapid curability and storage stability, and includes a urethane bond and a urea bond from the viewpoint that the viscosity of the adhesive composition of the present invention can be made appropriate. Preferably not.

The production of the alkoxysilyl group-modified polyoxyalkylene polymer is not particularly limited. For example, a polyoxyalkylene monool and / or a polyoxyalkylene polyol (for example, a compound represented by A-[(OR ¹ ) _n —OH] _m is mentioned. R ¹ , n and m are the same as the above formula. And a halogenated unsaturated hydrocarbon group (for example, a compound represented by R ² —X, where R ² has an unsaturated bond having 1 to 10 carbon atoms). And a polyoxyalkylene compound having an unsaturated bond (for example, A-[(OR ¹ ) _n ), which is a hydrocarbon group, and X is a halogen atom such as a chlorine atom, a bromine atom or an iodine atom. -O-R < ² >] _m .

Next, a polyoxyalkylene compound having an unsaturated bond is converted to a hydrotrialkoxysilane (for example, HSi (OR ³ ) ₃ in the presence of a platinum catalyst such as a platinum vinylsiloxane complex. R ³ represents the above formula. (It is synonymous with (V).) Or an alkoxysilyl group modified polyoxyalkylene polymer can be manufactured by making it react with hydrodialkoxyalkylsilane.
The platinum catalyst is not particularly limited as long as it can be used for the reaction between the hydrosilane compound and the unsaturated hydrocarbon group.
The alkoxysilyl group-modified polyoxyalkylene polymer can be used alone or in combination of two or more.

The epoxy resin will be described below.
The adhesive composition of this invention is excellent in a flame retardance, moisture resistance, and heat resistance by containing an epoxy resin and ketimine.
The epoxy resin contained in the adhesive composition of the present invention is not particularly limited as long as it is a compound having two or more epoxy groups in one molecule. For example, bisphenol A, bisphenol F, bisphenol S, hexahydrobisphenol A, tetramethylbisphenol A, pyrocatechol, resorcinol, cresol novolac, tetrabromobisphenol A, trihydroxybiphenyl, bisresorcinol, bisphenol hexafluoroacetone, tetramethylbisphenol F Glycidyl ether type obtained by reaction of polyphenols such as bixylenol and epichlorohydrin; glycerin, neopentyl glycol, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, polyethylene glycol, polypropylene glycol, etc. Polyglycidyl obtained by reaction of monohydric alcohol with epichlorohydrin Ether type; 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, terephthalic acid, tetrahydrophthalic acid, hexa Polyglycidyl ester type derived from polycarboxylic acid such as hydrophthalic acid, endomethylenetetrahydrophthalic acid, endomethylenehexahydrophthalic acid, trimellitic acid, polymerized fatty acid; glycidylamino derived from aminophenol, aminoalkylphenol, etc. Glycidyl ether type; glycidyl aminoglycidyl ester type derived from aminobenzoic acid; aniline, toluidine, tribromoaniline, xylylenediamine, diaminocyclohexane, bisamido Glycidylamine type derived from nomethylcyclohexane, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, and the like; and epoxidized polyolefin, glycidylhydantoin, glycidylalkylhydantoin, and triglycidylcyanurate.

Among them, bisphenol A type epoxy resin and bisphenol F type epoxy resin are superior in terms of moisture resistance, flame retardancy, heat resistance, fluidity, storage stability, shear strength, and excellent balance between viscosity and flexibility. preferable.
The epoxy resins can be used alone or in combination of two or more.

  In the present invention, the amount of the epoxy resin is 10 to 100 parts by mass with respect to 100 parts by mass of the alkoxysilyl group-modified polyoxyalkylene polymer. From the viewpoint of excellent flame retardancy, moisture resistance, heat resistance, fluidity, storage stability, shear strength, excellent balance between viscosity and flexibility, the amount of epoxy resin is an alkoxysilyl group-modified polyoxyalkylene polymer. It is preferable that it is 10-50 mass parts with respect to 100 mass parts.

Ketimine is described below.
The ketimine contained in the adhesive composition of the present invention is a compound obtained by reacting a carbonyl compound represented by the following formula (I) with a polyamine.

In the formula, R ¹ is an alkyl group having 1 to 6 carbon atoms, R ² is a methyl group or an ethyl group, R ³ is a hydrogen atom, a methyl group or an ethyl group, and R ⁴ is a hydrogen atom or an alkyl group. And n is 1 or 2.
R ¹ and R ² can be bonded to each other to form a ring structure. R ¹ and R ⁴ can be bonded to each other to form a ring structure.
One imino group (—N═) of ketimine reacts with moisture to hydrolyze to become a primary amine, and can react with one or two epoxy groups.

The carbonyl compound will be described below.
The carbonyl compound used in the production of the ketimine contained in the adhesive composition of the present invention is represented by the formula (I).
In the formula (I), the alkyl group having 1 to 6 carbon atoms may be linear or branched. Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 1,2-dimethylpropyl group, hexyl group, isohexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 1,1 -Dimethylbutyl group, 1,2-dimethylbutyl group, 2,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1,1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group, 1-ethyl-1-methyl Propyl group, and a 1-ethyl-2-methylpropyl group.
The alkyl group as R ⁴ is not particularly limited. For example, it is synonymous with said C1-C6 alkyl group.

Examples of the carbonyl compound include ketones in which n is 1 in formula (I) and R ⁴ is an alkyl group, such as methyl isopropyl ketone (MIPK), methyl t-butyl ketone (MTBK), methyl cyclohexyl ketone, and methylcyclohexanone. A ketone in which n in formula (I) is 2: an aldehyde compound in which n in formula (I) is 1 and R ⁴ is a hydrogen atom.
Among these, from the viewpoint of being excellent in rapid curability and storage stability, a ketone in which n in the formula (I) is 1 and R ⁴ is an alkyl group is preferable, and methyl isopropyl ketone (MIPK), methyl t-butyl ketone ( MTBK), methyl cyclohexyl ketone, and methyl cyclohexanone are more preferable.

The polyamine used in the production of ketimine is described below.
The polyamine is not particularly limited as long as it is a compound having two or more amino groups. For example, the compound represented by Formula (II) is mentioned.
R— (CH ₂ —NH ₂ ) _n (II)
In the formula, R is a hydrocarbon group that may have a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom, and n is an integer of 2 or more.
R preferably has 1 to 10 carbon atoms from the viewpoint of excellent fast curability and storage stability.
n is preferably 1 to 4 which are easily available.

  Examples of polyamines include aliphatic polyamines such as ethylenediamine, propylenediamine, butylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenediamine, trimethylhexamethylenediamine, and 1,2-diaminopropane. A diamine having a polyether skeleton such as Jeffamine EDR148 manufactured by Sun Techno Chemical Co., Ltd .; 1,3-bisaminomethylcyclohexane, 1-cyclohexylamino-3-aminopropane, 3-aminomethyl-3,3,5-trimethyl- Cyclohexylamine, norbornane skeleton typified by NBDA (norbornanediamine) manufactured by Mitsui Toatsu Chemicals, Ltd., alicyclic hydrocarbon such as N-aminoethylpiperazine A polyamine having a group; an aromatic polyamine; a polyamine having an aliphatic hydrocarbon group bonded to an aromatic hydrocarbon group such as metaxylylenediamine and tetramethylxylylenediamine; a polyamidoamine having an amino group at the molecular end of the polyamide Is mentioned.

  Of these, hexamethylenediamine (HMDA) and NBDA are preferred from the viewpoint of rapid curing and excellent storage stability with an epoxy resin.

As a combination of a carbonyl compound and a polyamine, a combination of methyl isopropyl ketone (MIPK) and hexamethylene diamine (HMDA), methyl isopropyl ketone (MIPK), and NBDA are used from the viewpoint of an excellent balance between fast curability and storage stability. The combination with is preferable.
Ketimines can be used alone or in combination of two or more.

In this invention, the quantity of the imino group which the said ketimine has is 0.5-1.5 equivalent with respect to the epoxy group which the said epoxy resin has.
The amount of the imino group possessed by the ketimine is preferably 0.7 to 1.0 equivalent with respect to the epoxy group possessed by the epoxy resin, from the viewpoint of superior heat resistance, storage stability, and shear strength.

The flame retardant filler will be described below.
The flame retardant filler contained in the adhesive composition of the present invention is at least one inorganic substance selected from the group consisting of aluminum hydroxide, magnesium hydroxide, calcium hydroxide, calcium sulfate hydrate and magnesium sulfate hydrate. Filler flame retardant.
Inorganic filler flame retardants have the property of thermally decomposing at high temperatures to generate water.
When the flame retardant filler contains at least one inorganic filler flame retardant selected from the group consisting of aluminum hydroxide, magnesium hydroxide, calcium hydroxide, calcium sulfate hydrate and magnesium sulfate hydrate, dioxin and phosphine No toxic substances such as the above are generated, and there is no curing delay as in the case of phosphate esters, which is excellent in fast curability, a large endothermic amount, a low thermal decomposition temperature, and excellent flame retardancy.
Of these, aluminum hydroxide is preferred from the viewpoint of superior flame retardancy.

  The flame retardant filler may be surface-treated. Examples of the surface treatment agent include fatty acids, silane compounds, and resin acids. Of these, fatty acids and silane compounds are preferred from the viewpoint of superior flame retardancy.

Examples of the silane compound as the surface treatment agent include organic titanate compounds, organic aluminum compounds, organic zirconium compounds, and alkoxysilanes.
Examples of the organic titanate compound include tetrapropoxy titanium, tetrabutoxy titanium, tetrakis (2-ethylhexyloxy) titanium, tetrastearyloxy titanium, diproxy bis (acetylacetonato) titanium, titanium propoxyoctylene glycolate, titanium stearate, Isopropyltriisostearoyl titanate, isopropyltridodecylbenzenesulfonyl titanate, isopropyltris (dioctylpyrophosphate) titanate, tetraisopropylbis (dioctylphosphite) titanate, tetraoctylbis (ditridecylphosphite) titanate, tetra (2,2-diallyl) Oxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpi) Phosphate) oxyacetate titanate, tris (dioctyl pyrophosphate) ethylene titanate.

Examples of the organoaluminum compound include acetoalkoxyaluminum diisopropylate.
Examples of the organic zirconium compound include zirconium butyrate, zirconium acetylacetonate, acetylacetone zirconium butyrate, zirconium lactate, and zirconium stearate butyrate.

  Examples of the alkoxysilane include vinyltrimethoxysilane, vinyltriethoxysilane, bistris (2-methoxyethoxy) silane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, and N- (2-aminoethyl). 3-aminopropylmethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, hex Mechirujishirazan and the like.

Examples of fatty acids as the surface treatment agent include saturated fatty acids such as caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, and alginic acid, unsaturated fatty acids such as oleic acid, elaidic acid, linoleic acid, and ricinoleic acid, And alicyclic carboxylic acids such as naphthenic acid.
Examples of the resin acid as the surface treatment agent include abitienic acid, pimaric acid, parastrinic acid, neoabietic acid, and the like.

The average particle diameter of the flame retardant is preferably 0.5 to 30 μm, more preferably 0.5 to 10 μm, from the viewpoint of excellent flame retardancy.
A flame-retardant filler can be used individually or in combination of 2 types or more, respectively.
The flame retardant filler is not particularly limited for its production. For example, a conventionally well-known thing is mentioned.

In this invention, the quantity of a flame retardant filler is 30-70 mass% among the total weight of an adhesive composition from a viewpoint that it is excellent in a flame retardance. When the amount of the flame retardant filler is 30% by mass or more, the flame retardancy is excellent. When the amount of the flame retardant filler is 70% by mass or less, the viscosity of the composition becomes appropriate, and the physical properties (for example, elongation and strength) are excellent.
The amount of the flame retardant filler is indispensable to be 30% by mass or more from the viewpoint of expressing flame retardancy, and from the viewpoint of excellent workability (low viscosity), moisture resistance, and physical properties (elongation) of a cured product, It is preferable that it is 40-60 mass%.

The curing catalyst will be described below.
The curing catalyst contained in the adhesive composition of the present invention is not particularly limited as long as it is used as a silanol condensation catalyst. Examples thereof include titanium-based esters, tin compounds, organoaluminum compounds, organozirconium compounds, bismuth compounds, and amine compounds.
Of these, tin compounds are preferred and tetravalent tin compounds are more preferred from the viewpoints of fast curability and relatively difficult discoloration of the cured product.
Examples of tetravalent tin compounds include carboxylates such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate, tin naphthenate, tin laurate; reaction of dibutyltin oxide and phthalate Dialkylstannoxane dicarboxylates; dialkyltin alcoholates such as dibutyltin dimethoxide; (dialkylstannoxane) disilicate compounds; chelates such as dibutyltin diacetylacetonate.

Examples of the (dialkylstannoxane) disilicate compound include compounds represented by the following formula (IV).

In the formula, R ⁵ is a hydrocarbon group having 1 to 10 carbon atoms, R ⁶ is a hydrocarbon group having 1 to 10 carbon atoms, and R ⁵ and R ⁶ may be the same or different. m is an integer of 0-3.
Examples of the hydrocarbon group having 1 to 10 carbon atoms (R ⁵ ) include a methyl group, an ethyl group, a propyl group, and an isopropyl group.
Examples of the hydrocarbon group having 1 to 10 carbon atoms (R ^6), for example, butyl group.
Examples of the (dialkylstannoxane) disilicate compound include a reaction product of dibutyltin salt (for example, dibutyltin acetate) and normal ethyl silicate.

Of these, dialkyltin alcoholates, chelates, and (dialkylstannoxane) disilicate compounds are preferred from the viewpoints of being excellent in fast curability and storage stability and being stable against polyethers, and include dibutyltin salts and orthoethyl silicates. The reaction product is more preferred.
The curing catalysts can be used alone or in combination of two or more.

  The amount of the curing catalyst is from 0.1 to 100 parts by mass with respect to 100 parts by mass of the alkoxysilyl group-modified polyoxyalkylene polymer, from the viewpoints of excellent rapid curing, excellent heat resistance, excellent fluidity, storage stability, and shear strength. It is more preferably 1 to 3.0 parts by mass.

The adhesive composition of the present invention can further contain a polyether having a terminal hydroxy group blocked.
Examples of the polyether that can be further contained in the adhesive composition of the present invention include compounds having a number average molecular weight of 100 to 5,000 and a terminal hydroxy group blocked.
The polyether that the adhesive composition of the present invention can further contain is inert to the alkoxysilyl group-modified polyoxyalkylene polymer and the curing catalyst contained in the adhesive composition of the present invention, The curing catalyst is not deactivated.
The inventors of the present application have found that a polyether having a number average molecular weight of 100 to 5,000 and having a terminal hydroxy group blocked has stability to an alkoxysilyl group-modified polyoxyalkylene polymer and a curing catalyst. It was.
The adhesive composition of the present invention contains a polyether having a number average molecular weight of 100 to 5,000 and a terminal hydroxy group blocked as a plasticizer, as compared with the case of containing an ester plasticizer. Stable to alkoxysilyl group-modified polyoxyalkylene polymer and curing catalyst, fast curing, excellent storage stability to alkoxysilyl group-modified polyoxyalkylene polymer, hard to thicken, workability and curing speed Does not change over time.

The main chain of the polyether is not particularly limited as long as it is a polymer having an oxyalkylene group as a repeating unit. Examples thereof include polyoxyethylene, polyoxypropylene, and copolymers thereof.
The main chain of the polyether is preferably a polyoxypropylene polymer from the viewpoint of excellent wet heat resistance.

In the present invention, the hydroxy group bonded to the end of the polyether is blocked. The group for blocking the terminal hydroxy group is not particularly limited. For example, an alkyl group, an alkoxy group, an alkenyloxy group, and an alkylsilyl group can be mentioned.
Among these, when blocked with an alkyl group, an alkoxy group, or an alkylsilyl group, it is easy to handle from the viewpoint that the curing rate and the physical properties after curing do not change depending on the amount added.
Examples of the alkyl group include those having 1 to 3 carbon atoms. For example, a methyl group, an ethyl group, and a propyl group are mentioned.
Examples of the alkoxy group include those having 1 to 3 carbon atoms. For example, a methoxy group, an ethoxy group, and a propoxy group are mentioned.
Examples of the alkylsilyl group include those having 1 to 3 carbon atoms in the alkyl group portion. An oxygen atom can be bonded to the silicon atom of the alkylsilyl group. For example, the following trialkylsilyl groups can be mentioned.

Examples of the polyether include compounds represented by the following formulas (VI) and (III).
B—R ⁴ — (OR ⁴ ) _n —B (VI)
In Formula (VI), R ⁴ is an alkylene group having 1 to 5 carbon atoms, n is an integer of 1 to 120, and B is a group that blocks the terminal hydroxy group. The group for blocking the terminal hydroxy group is as defined above. In the formula (VI), the polymerization initiator used when producing the polyoxyalkylene diol as a raw material is omitted.
_{^{D- (OR 4) n -B (}} III)
In formula (III), R ⁴ is an alkylene group having 1 to 5 carbon atoms, n is an integer of 1 to 120, B is a group that blocks the terminal hydroxy group, and D is used as a polymerization initiator. Monool residue. The group for blocking the terminal hydroxy group is as defined above.

In the present invention, the number average molecular weight of the polyether is preferably 100 to 5,000. When the number average molecular weight of the polyether is in such a range, the polyether is less likely to volatilize and the adhesive composition of the present invention can be made solvent-free.
The number average molecular weight of the polyether is more preferably 500 to 3,000 from the viewpoint that the composition has no volatile component and can be reduced in viscosity.
Polyethers can be used alone or in combination of two or more.
The polyether is not particularly limited for its production. For example, a conventionally well-known thing is mentioned. The polyether having a hydroxy group as a raw material used in the production of the polyether includes a polyether having one or more hydroxy groups (for example, a polyoxyalkylene having one or more hydroxy groups). Are not particularly limited as long as they include polyoxyalkylene monools and polyoxyalkylene polyols.

In the present invention, the amount of the polyether is preferably 5 to 50 parts by mass with respect to 100 parts by mass of the alkoxysilyl group-modified polyoxyalkylene polymer from the viewpoint that the viscosity can be lowered while maintaining the shear strength. .
The amount of the polyether is more preferably 5 to 20 parts by mass with respect to 100 parts by mass of the trialkoxysilyl group-modified polyoxyalkylene polymer from the viewpoint that the viscosity can be lowered while maintaining the shear strength.

The adhesive composition of the present invention may further contain an N-silylamide compound in order to enhance storage stability.
Examples of the N-silylamide compound used in the present invention include those represented by the following formula (2).
(R ¹ -CONH) _4-n -Si-R ² _n (2)
(In the formula, R ¹ is a hydrocarbon group having 5 to 21 carbon atoms which may contain a hetero atom, and when n is 0, 1 or 2, R ¹ may be the same or different. R ² is an alkyl or alkoxy group having 1 to 3 carbon atoms, and n is 0, 1, 2 or 3.)
More specifically, the N-silylamide compound used in the present invention includes a compound represented by the above formula (2) and a partial hydrolysis condensate thereof. Since these N-silylamide compounds are easily hydrolyzed to form an amide compound (R ¹ —CONH ₂ group-containing compound) and a silanol compound (HO—Si≡ group-containing compound), the moisture curable resin composition Moisture can be easily removed. Therefore, it contributes to the improvement of storage stability. The produced amide compound plays a role of improving thixotropy.

Specific examples of R ¹ include phenyl, benzyl, hexyl, heptyl, octyl, nonyl, decyl, pentadecyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, and other alkyl groups, oleic acid Examples thereof include acid residues such as a residue, linoleic acid residue, and linolenic acid residue, and among them, phenyl, pentadecyl, heptadecyl group and oleic acid residue are preferable.

R ² is specifically methyl, ethyl, propyl, methoxy, ethoxy, or propoxy, and methyl, ethyl, methoxy, or ethoxy is particularly preferable.

The method for synthesizing the N-silylamide compound is not particularly limited. For example, a carboxylic acid amide containing R ¹ group (R ¹ is the same as formula (2)) and a formula Si—R ² _n X ₄₋ It can be synthesized from a halogenated silane compound represented by _n (R ² and n are the same as in formula (2), X is a halogen).
Examples of carboxylic acid amides include caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, montanic acid, and melicic acid. Chain saturated fatty acids; unsaturated fatty acids such as caproleic acid, oleic acid, celetic acid, sorbic acid, linoleic acid, linolenic acid; amide derivatives of carboxylic acids selected from aromatic carboxylic acids such as benzoic acid and phenylacetic acid, or the like, or A combination of two or more of these may be mentioned. In particular, amide compounds of palmitic acid, stearic acid and oleic acid are preferred.

  Examples of halogenated silane compounds include tetrachlorosilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, vinyltrichlorosilane, 2-chloroethyltrichlorosilane, ethyltrichlorosilane, 2-cyanoethyltrichlorosilane, allyltrichlorosilane, and 3-bromopropyl. Trichlorosilane, methylvinyltrichlorosilane, ethylmethyldichlorosilane, trimethylbromosilane, divinyldichlorosilane, methyl-3,3,3-trifluoropropyldichlorosilane, isobutyltrichlorosilane, pentyltrichlorosilane, phenyltrichlorosilane, methylphenyldi Chlorosilane, dimethylphenylchlorosilane, cyclohexyltrichlorosilane, benzyltrichlorosilane, p-to Rutrichlorosilane, 6-trichlorosilyl-2-norbornene, 2-trichlorosilylnorbornane, 2- (4-cyclohexylnylethyl) trichlorosilane, dodecyltrichlorosilane, tetradecyltrichlorosilane, 1,2-bis (trichlorosilyl) ethane, 1,2-bis (dimethylchlorosilyl) ethane, chlorosilane compounds such as 1,4-bis (dimethylchlorosilyl) benzene, 1,1,3,3-tetramethyl-1,3-dichlorosiloxane or two of these The above can be used in combination.

The N-silylamide compound is a mixture of the above-mentioned carboxylic acid amide and the halogenated silane compound with hexane, heptane, benzene, toluene, xylene, methylene chloride, chloroform, etc. having no active hydrogen as a solvent, and triethylamine, pyridine, etc. It is synthesized by reacting a tertiary amine as a dehydrochlorinating agent at a temperature from room temperature to 100 ° C.
Further, the N-silylamide compound can be synthesized while heating the above carboxylic acid amide and the chlorosilane compound to 120 to 180 ° C. without using a dehydrochlorinating agent and removing the generated hydrogen chloride gas. . As the catalyst, triethylamine, pyridine and the like can be used.

  Further, among N-silylamide compounds, for example, an amide compound to which a trimethylsilyl group is bonded is reacted with hexamethyldisilazane and an amide compound at 80 to 150 ° C. in the presence of saccharin while distilling off the produced ammonia. Can also be synthesized.

From the viewpoint of excellent storage stability, the N-silylamide compound is preferably a compound represented by the formula (2), more preferably N-trimethylsilyloleic acid amide or N-trimethylsilylstearic acid amide.
N-silylamide compounds can be used alone or in combination of two or more.
The amount of the N-silylamide compound is preferably 0.2 to 30 parts by mass with respect to 100 parts by mass of the alkoxysilyl group-modified polyoxyalkylene polymer from the viewpoint of excellent storage stability. More preferably, it is part.

The adhesive composition of the present invention can further contain fumed silica.
When the adhesive composition of the present invention further contains fumed silica, high shear strength can be obtained.
Fumed silica is not particularly limited. For example, a conventionally well-known thing is mentioned.
The fumed silica is preferably hydrophobic fumed silica from the viewpoint that higher shear strength can be obtained.
The average particle size of fumed silica is preferably 0.005 to 0.5 μm because the reinforcing effect is large.
In order to improve the storage stability, fumed silica having a surface silanol group treated with an organosilicon compound such as organoalkoxysilane, organohalosilane, or organosilazane can be used.
Fumed silica can be used alone or in combination of two or more.
Fumed silica is not particularly limited for its production. For example, a conventionally well-known thing is mentioned.

  The amount of fumed silica is 1 to 10 parts by mass with respect to 100 parts by mass of the alkoxysilyl group-modified polyoxyalkylene polymer from the viewpoint of excellent shear strength and excellent balance between the shear strength and the viscosity of the composition. Is preferred.

The adhesive composition of the present invention can further contain surface-treated calcium carbonate. When the adhesive composition of the present invention further contains surface-treated calcium carbonate, particularly colloidal calcium carbonate, it has an effect on reinforcing properties and consequently has excellent shear strength.
The surface-treated calcium carbonate is not particularly limited. For example, a conventionally well-known thing is mentioned.
The surface treatment agent is not particularly limited. Examples include fatty acids, various silane coupling agents, and waxes such as urethane resins and paraffins. Among these, it is preferable to treat with a urethane resin that is well dispersed in the resin and has a large reinforcing effect.
The average particle diameter of the surface-treated calcium carbonate is preferably 0.01 to 0.5 μm from the viewpoint of excellent heat resistance, storage stability, and shear strength.
The surface-treated calcium carbonate can be used alone or in combination of two or more.
The surface-treated calcium carbonate is not particularly limited for its production. For example, a conventionally well-known thing is mentioned.

  The amount of the surface-treated calcium carbonate is preferably 10 to 100 parts by mass with respect to 100 parts by mass of the alkoxysilyl group-modified polyoxyalkylene polymer from the balance of the shear strength and the viscosity of the composition.

The adhesive composition of the present invention can further contain water.
When the adhesive composition of the present invention contains water, the adhesive composition of the present invention can be excellent in initial strength. In particular, it can be used under conditions where moisture is difficult to enter, such as when the adherend is made of metal.
The amount of water is preferably 0.5 to 5 equivalents relative to the alkoxy group of the alkoxysilyl group-modified polyoxyalkylene polymer in that the initial strength is exhibited and unnecessary residual moisture is negligible. .

  The adhesive composition of the present invention can further contain additives in addition to the above components as long as the object of the present invention is not impaired as required. Examples of additives include carbon black, fused silica, silica sand, calcium silicate, etc., mica, talc, alumina, montmorillonite filler, aluminum nitride, boron nitride, and other thermally conductive fillers, glass balloons, and various resin balloons. Such as hollow fillers, various resin fillers made by refining polymethacrylic acid, etc., plasticizers other than polyethers contained in the adhesive composition of the present invention, vinylsilane, dehydrating agents such as silicate compounds, epoxysilanes, aminosilanes, Silane coupling agents such as methacrylic silane, thixotropy imparting agents such as fatty acid polyamide waxes, pigments such as titanium oxide, dyes, anti-aging agents, antioxidants, antistatic agents, adhesion imparting agents, dispersants, solvents, A curing agent is mentioned.

The adhesive composition of the present invention is not particularly limited for its production. For example, the above-mentioned components are decompressed and sufficiently kneaded using a stirring device such as a mixing mixer in a nitrogen atmosphere and uniformly dispersed.
The adhesive composition of the present invention can be produced as a one-pack type or a two-pack type.
When the adhesive composition of the present invention further contains water, it contains an alkoxysilyl group-modified polyoxyalkylene polymer, an epoxy resin, a ketimine, a polyether, a flame retardant filler, and a curing catalyst from the viewpoint of excellent storage stability. One of the preferred embodiments is a two-component type having a main agent to be treated and a curing agent containing at least water. Fumed silica, surface-treated calcium carbonate, and additives can be added to the main agent and / or the curing agent, respectively.

The adhesive composition of the present invention can be cured at room temperature (5-35 ° C.).
Moreover, the adhesive composition of the present invention can be cured by moisture contained in components such as moisture in the atmosphere and a filler that can be contained in the composition.

The adherend to which the adhesive composition of the present invention can be applied is not particularly limited. For example, metal, plastic, rubber, glass, and ceramic are mentioned.
The method for applying the adhesive composition of the present invention to an adherend is not particularly limited. For example, a conventionally well-known thing is mentioned.

Applications of the adhesive composition of the present invention include, for example, sealing materials, adhesives, coating materials, primers, paints, and potting materials.
The adhesive composition of the present invention can be used for various electric / electronic fields, buildings, automobiles, civil engineering and the like.
The adhesive composition of the present invention can be used for an air conditioner, a fan heater, a blower, a dehumidifier, and a humidifier.
Moreover, the adhesive composition of this invention can be used for the components adhesion | attachment of a flame-retardant product. Examples of flame retardant products include speakers, video cassette players, televisions, radios, vending machines, refrigerators, personal computers, card-type batteries, video cameras, cameras, automobile parts, precision equipment, and the like.
In addition, the adhesive composition of the present invention can be applied to high-voltage parts, adhesion of circuits that can be high voltage and parts used in the vicinity thereof, and adhesion in electrical appliances that are operated continuously for a long time. Specific examples of these parts include connectors, switches, relays, electric cables, flyback transformers, and deflection yokes.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.
<Production of trialkoxysilyl group-modified polyoxyalkylene polymer>
(1) Trialkoxysilyl group-modified polyoxyalkylene polymer Polymerization of propylene oxide using a dehydrated polyoxypropylene diol (linear, number average molecular weight of about 3,000, number of hydroxy groups per molecule: 2) as an initiator And a hydroxyl group-terminated polypropylene oxide having a number average molecular weight of about 20,000 was obtained. Subsequently, an allyl chloride is further added to the hydroxyl group of the hydroxyl group-terminated polypropylene oxide to convert the terminal hydroxyl group into an allyl group, and the bifunctional allyl polypropylene having a number average molecular weight of about 20,000 whose terminal is an allyl group. The oxide was obtained.
With respect to 100 parts by weight of the obtained bifunctional allyl polypropylene oxide, 150 ppm of an isopropanol solution containing 3 wt% of platinum in a platinum vinylsiloxane complex as a catalyst, the following chemical formula: HSi (OCH ₃ ) ₃
And 90 ° C. for 2 hours to obtain a polymer having a trimethoxysilyl group (terminal silyl linear polyether resin).
The obtained polymer was analyzed by ¹ H-NMR and confirmed to be a trialkoxysilyl group-modified polyoxyethylene polymer having an average of two trimethoxysilyl groups per molecule at the molecular end.
The obtained trialkoxysilyl group-modified polyoxypropylene polymer is referred to as trialkoxysilyl group-modified polyoxyalkoxylene polymer.

<Manufacture of ketimine>
Hexamethylenediamine (reagent, manufactured by Wako Pure Chemical Industries, Ltd.) 580 g, methyl isopropyl ketone (reagent, manufactured by Wako Pure Chemical Industries, Ltd.) 860 g, toluene (reagent, manufactured by Wako Pure Chemical Industries, Ltd., hereinafter the same) 710 g, and acetic acid (reagent) 1.65 g (manufactured by Wako Pure Chemical Industries, Ltd., the same shall apply hereinafter) was put in a flask, and the reaction was continued at 120 ° C. for 15 hours while removing generated water by azeotropic distillation. Next, distillation under reduced pressure at 150 ° C. and 5 mmHg was performed to remove toluene, residual ketone and the like.

<Production of end-capped polyether>
Hydroxyl terminal of dried polyoxypropylene monool having a number average molecular weight of 800 (Asahi Glass: XS-1003P) is alcoholated with sodium hydroxide, and then reacted with methyl chloride to convert the terminal hydroxy group with methyl ether (methoxy group). Blocked. The complete disappearance of the hydroxyl group was confirmed by IR spectrum.

<Production of silylamide (N-trimethylsilyloleic acid amide as N-silylamide compound)>
To 800 g of oleic acid amide, 400 g of toluene and 0.5 g of saccharin were added and dissolved by heating at 100 ° C. To this, 260 g of hexamethyldisilazane was added dropwise, and after completion of the addition, the mixture was heated at 130 ° C. for 4 hours. Thereafter, unreacted hexamethyldisilazane and toluene were distilled off under reduced pressure to obtain 1003 g of N-trimethylsilyloleic acid amide. The synthesis of N-trimethylsilyloleic acid amide was confirmed by IR spectrum, ¹ H-NMR spectrum and MS spectrum.

<Evaluation>
The adhesive composition obtained as described below was evaluated for viscosity, tack free time, shear strength, heat resistance, and flame retardancy by the following methods. The results are shown in Tables 1 and 2.
(1) Viscosity (fluidity)
Initial viscosity: A TV20 viscometer (rotor # 7, 1 rpm) was used, and the initial viscosity (unit: Pa · s) of the adhesive composition obtained as described below was measured at 20 ° C. .

(2) Tack free time (TFT, fast curability, storage stability)
-Initial: The adhesive composition obtained as described below was placed under conditions of 20 ° C. and 55% RH, a polyethylene film was pressed against the surface of the adhesive composition, and the adhesive composition adhered to the film. The time until disappearance was measured.
-After storage promotion: The adhesive composition obtained as described below was placed under conditions of 70 ° C for 24 hours, and the tack-free time after storage promotion of the adhesive composition was the same as the initial tack-free time. It was measured.
Change rate: [Change rate] = ([After storage promotion]-[Initial]) / [Initial]

(3) Shear strength Using two steel plates having a length of 150 mm, a width of 15 mm, and a thickness of 1 mm, the adhesive composition is one steel plate so that the adhesive area is 10 mm × 25 mm and the adhesive layer thickness is 0.3 mm. Then, the two pieces were immediately overlapped and brought into close contact with each other, and cured for 7 days under conditions of 20 ° C. and 55% RH to obtain a test specimen.
After curing, the initial shear strength (normal state, 20 ° C.) of the test specimen was measured using a tensile tester (AGS-10 kNG, manufactured by Shimadzu Corporation) under the condition of a tensile speed of 10 mm / min. The obtained specimen was placed under conditions of 60 ° C. and 90% RH for 1000 hours and then placed under conditions of 60 ° C. and 90% RH for 1000 hours under the same conditions as the initial shear strength. The shear strength was measured (Table 1).
Further, after the steel plates were superposed and brought into close contact with each other, after curing for 1 hour under the conditions of 20 ° C. and 55% RH, the initial shear strength of the obtained test specimen was measured in the same manner as described above. Further, the steel plates were overlapped and brought into close contact with each other, and after being cured for 14 days under the conditions of 20 ° C. and 55% RH, the shear strength after 14 days was measured in the same manner as above for the obtained test specimen (Table 2). .

(4) Heat resistance Using a test specimen similar to the above-mentioned shear strength, the shear strength after placing the test specimen under a condition of 120 ° C. for 4 weeks and the normal shear strength are the same as described above. Measured with
As an evaluation standard of heat resistance,
Retention rate [%] = (120 ° C. × shear strength after 4 weeks) / (normal shear strength)
As a result, a retention rate of 60% or more was evaluated as ◯, and a retention rate of less than 60% as ×.

(5) Flame retardancy The adhesive composition obtained as described below was made into a sheet using a silicone release paper and a 1.5 mm spacer, cured at 20 ° C. for 7 days, and then peeled off from the release paper. A cured sheet having a length of 1.5 mm, a width of 13 mm, and a length of 130 mm was produced. The obtained cured sheet was subjected to a vertical combustion test based on the UL94 standard, and the flame retardancy was evaluated by measuring the afterflame time of the sample (cured sheet) by flame contact.

<Production of Adhesive Composition (Example I)>
The components shown in Table 1 were used in the amounts (parts by mass) shown in the same table, and they were mixed using a stirrer to obtain an adhesive composition.

Details of the components shown in Table 1 are as follows.
Trialkoxysilyl group-modified polyoxyalkylene polymer: trialkoxysilyl group-modified polyoxyalkylene polymer produced as described above dialkoxysilyl group-modified polyoxyalkylene polymer: methyldimethoxysilyl group-modified polyoxypropylene polymer, Trade name MS polymer S-303, manufactured by Kaneka Corporation ・ BPA type epoxy resin: bisphenol A type epoxy resin, trade name YD-128, Tohto Kasei Co., Ltd., epoxy equivalent 190 g / equivalent ・ Aluminum hydroxide (no treatment, 8 μ): Aluminum hydroxide, surface untreated, average particle size 8 μm, B103, Nippon Light Metal Co., Ltd. Aluminum hydroxide (no treatment, 2 μm): aluminum hydroxide, surface untreated, average particle size 2 μm, B703, Nippon Light Metal Co., Ltd. Colloidal aluminum hydroxide (no treatment, 1μ): colloidal Aluminum hydroxide, surface untreated, average particle size 1 μm, BF013, Nippon Light Metal Co., Ltd. Aluminum hydroxide (fatty acid treatment, 2 μm): aluminum hydroxide, surface fatty acid treatment, average particle size 2 μm, B703S, Nippon Light Metal Co., Ltd. Aluminum hydroxide (silane treatment, 2μ): Aluminum hydroxide, surface silane compound treatment, average particle size 2 μm, B703ST, Nippon Light Metal Co., Ltd. Aluminum hydroxide (fatty acid treatment, 1μ): Aluminum hydroxide, surface fatty acid treatment, average Particle size 1 μm, BF013S, Nippon Light Metal Co., Ltd. ・ Colloidal calcium carbonate: Viscolite MBP (calcium carbonate surface-treated with a reaction product of tolylene diisocyanate and stearyl alcohol), manufactured by Shiraishi Calcium Co., Ltd. ・ Heavy calcium carbonate: Super S, Maruo Calcium Co., Ltd. Mudoshirika: hydrophobic fumed silica, R-972, manufactured by Nippon Aerosil Co., Ltd., particle size 0.016μm
End-capped polyether: manufactured as described above Vinyl silane: KBM 1003, Shin-Etsu Chemical Co., Ltd. Epoxy silane: KBM 403, Shin-Etsu Chemical Co., Ltd. Silyl amide: manufactured as described above
· Ketimine: above as manufacturing the one-tin catalyst: tetravalent tin compound (reaction product of dibutyltin salt and ethyl orthosilicate, structural _{formula: (C 4 H 9) 2} Sn [OSi (OC 2 H 5) ₃ ] ₂ )
For each flame retardant filler, the surface treatment state and average particle diameter are shown in parentheses.

As is apparent from the results shown in Table 1, Comparative Example 1 in which the amount of the flame retardant filler was less than 30% by mass in the total amount of the composition was inferior in flame retardancy. Comparative Example 2 containing no flame retardant filler was inferior in flame retardancy. Moreover, the comparative example 3 which does not contain an epoxy resin was clearly inferior to the flame retardance with respect to Example 7 containing the same weight% flame-retardant filler in a composition.
On the other hand, Examples I-1 to 9 are excellent in flame retardancy, moisture resistance, and heat resistance. In Examples I-4 and 5 which were surface-treated with a fatty acid / silane, the viscosity of the composition could be lowered as compared with the case of no treatment.

<Production of Adhesive Composition (Example II)>
The components shown in Table 2 were used in the amounts (parts by mass) shown in the same table, and they were mixed using a stirrer to prepare a two-component type (Example II-1) and a one-component type (Example II-2). An adhesive composition was obtained.

Details of the components shown in Table 2 are as follows.
Trialkoxysilyl group-modified polyoxyalkylene polymer: trialkoxysilyl group-modified polyoxyalkylene polymer produced as described above BPA type epoxy resin: bisphenol A type epoxy resin, trade name YD-128, Toto Kasei Co., Ltd. Epoxy equivalent 190 g / equivalent ・ Aluminum hydroxide (untreated, 2 μ): Aluminum hydroxide, surface untreated, average particle size 2 μm, B703, Nippon Light Metal Co., Ltd. ・ Fumed silica: hydrophobic fumed silica, R-972, Nippon Aerosil Co., Ltd., particle size 0.016μm
End-capped polyether: as in Table 1 Vinyl silane: KBM 1003, Shin-Etsu Chemical Co., Ltd. Epoxy silane: KBM 403, Shin-Etsu Chemical Co., Ltd. Ketimine: manufactured as described above Tin catalyst: Tetravalent tin Compound (Reaction product of dibutyltin salt and normal ethyl silicate, structural formula: (C ₄ H ₉ ) ₂ Sn [OSi (OC ₂ H ₅ ) ₃ ] ₂ )
In Table 2, the amount of water is 1.3 equivalents relative to the alkoxy group of the alkoxysilyl group-modified polyoxyalkylene polymer (trialkoxysilyl group-modified polyoxyalkylene polymer).
Tin catalyst: tetravalent tin compound (reaction product of dibutyltin salt and normal ethyl silicate)

  As is apparent from the results shown in Table 2, the two-component adhesive composition is superior in initial shear strength in bonding between metals than the one-component adhesive composition.

Claims (7)

100 parts by mass of an alkoxysilyl group-modified polyoxyalkylene polymer having a hydrolyzable silyl group and the main chain being substantially polyoxyalkylene,
10 to 100 parts by mass of epoxy resin,
A ketimine obtained by reacting a carbonyl compound represented by the following formula (I) with a polyamine;
At least one flame retardant filler selected from the group consisting of aluminum hydroxide, magnesium hydroxide, calcium hydroxide, calcium sulfate hydrate and magnesium sulfate hydrate;
A curing catalyst ;
A polyether having a number average molecular weight of 100 to 5,000 and a terminal hydroxy group blocked ;
The amount of imino group that the ketimine has is 0.5 to 1.5 equivalents relative to the epoxy group that the epoxy resin has,
The amount of the flame retardant filler, Ri 30-70% by mass in the total composition,
The adhesive composition whose quantity of the said polyether is 5-50 mass parts with respect to 100 mass parts of said alkoxy silyl group modified polyoxyalkylene polymers .
Wherein R ¹ is an alkyl group having 1 to 6 carbon atoms, R ² is a methyl group or an ethyl group, R ³ is a hydrogen atom, a methyl group or an ethyl group, and R ⁴ is a hydrogen atom or An alkyl group, and n is 1 or 2.)   The alkoxysilyl group-modified polyoxyalkylene polymer has at least one selected from the group consisting of a methyldimethoxysilyl group, a methyldiethoxysilyl group, a trimethoxysilyl group, and a triethoxysilyl group as the hydrolyzable silyl group. The adhesive composition according to claim 1. The adhesive composition according to claim 1 or 2, comprising 0.2 to 30 parts by mass of an N-silylamide compound represented by the following formula (2) with respect to 100 parts by mass of the alkoxysilyl group-modified polyoxyalkylene polymer. .
(R ¹ -CONH) _4-n -Si-R ² _n (2)
(In the formula, R ¹ is a hydrocarbon group having 5 to 21 carbon atoms which may contain a hetero atom, and when n is 0, 1 or 2, R ¹ may be the same or different. R ² is an alkyl or alkoxy group having 1 to 3 carbon atoms, and n is 0, 1, 2 or 3.) The adhesive composition according to any one of claims 1 to 3 , wherein the flame retardant filler has an average particle size of 0.5 to 30 µm and is surface-treated with a fatty acid or a silane compound. The adhesive composition according to any one of claims 1 to 4 , comprising aluminum hydroxide as the flame retardant filler. The adhesive composition according to any one of claims 1 to 5 , wherein in the polyether, the terminal hydroxy group is blocked with an alkyl group, an alkoxy group or an alkylsilyl group. Furthermore, it contains water and the quantity of the said water is 0.5-5 equivalent with respect to the alkoxy group which the said alkoxy silyl group modification | denaturation polyoxyalkylene polymer has, Adhesion in any one of Claims 1-6. Agent composition.