JP5359482B2 - Adhesive composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesive composition excellent in a quick curing property, an adhesion property and a depth part curing property and having no odor. <P>SOLUTION: The adhesive composition includes a trialkoxysilyl group-modified polyoxyalkylene polymer having a trimethoxysilyl group and/or a triethoxysilyl group as a reactive group and a main chain substantially comprising a polyoxyalkylene, and a repetition unit represented by formula (1) (wherein X represents at least one kind selected from the group consisting of a 6-20C alkylene groups, cycloalkylene groups and arylene groups), and contains a hydrolyzable silyl group-modified polyester of a number average molecular weight of 300-6,000 having a hydrolyzable silyl group on the terminal group, and a curing catalyst. The mass ratio of the trialkoxysilyl group-modified polyoxyalkylene polymer and the hydrolyzable silyl group-modified polyester is 10:90-90:10. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to an adhesive composition.

Conventionally, the resin component is (a) a silicone-based resin in which the silicone-reactive group is a trimethoxysilyl group and / or triethoxysilyl group and the main chain is substantially a polyoxypropylene structure, and (b) the silicone-reactive group is A methyl resin and / or a methyldiethoxysilyl group, and a silicone resin whose main chain is substantially a polyoxypropylene structure and (c) 0.1 to 20% by weight of a polyalkoxysilyl group in the molecule And an acrylic resin having a silicone-reactive group obtained by polymerizing at least one selected from the group consisting of acrylic acid esters and methacrylic acid esters having an alkyl group having 1 to 20 carbon atoms as a main component. The blending ratio of the silicone resin (a) and the silicone resin (b) is the former: the latter = 10. 90:90 to 10 (weight ratio), and the blending ratio of the acrylic resin (c) is 5 to 200% by weight with respect to the total amount of the silicone resin (a) and the silicone resin (b). A silicone-based resin composition (Patent Document 1) containing a resin is proposed.
A curable composition comprising an organic polymer (a) containing a crosslinkable hydrolyzable trialkoxysilyl group and an organic polymer (b) containing a crosslinkable hydrolyzable silyl group The thing is proposed (patent document 2).

JP-A-10-251552 JP 2006-249250 A

Conventionally, various adhesives using a resin containing a hydrolyzable silyl group as a main polymer have been proposed, but these have relatively good adhesion to a metal but have poor adhesion to the resin. It was a challenge. On the other hand, a method of mixing an acrylic polymer with a hydrolyzable silyl group-containing resin has been proposed, but the adhesion to the resin is improved by the addition of the acrylic polymer. Since the acrylic component is difficult to pass moisture, a new problem has arisen in that the deep curing is remarkably deteriorated.
In addition, it is widely known that acrylic resins are unsuitable for uses sensitive to odors such as air conditioners because of their unique odors.
Then, an object of this invention is to provide the adhesive composition which is excellent in quick-curing property, adhesiveness, and deep part curability, and does not have an odor.

As a result of diligent research to solve the above-mentioned problems, the present inventors have modified a trialkoxysilyl group having a trimethoxysilyl group and / or a triethoxysilyl group as a reactive group and the main chain being substantially polyoxyalkylene. A polyoxyalkylene polymer;
A hydrolyzable silyl group-modified polyester having a number average molecular weight of 300 to 6,000 having a repeating unit represented by the following formula (1) and having a hydrolyzable silyl group at the end;
Containing a curing catalyst,
A composition in which the mass ratio of the trialkoxysilyl group-modified polyoxyalkylene polymer and the hydrolyzable silyl group-modified polyester is 10:90 to 90:10 is excellent in fast curability, adhesiveness, and deep curability. The present inventors have found that an adhesive composition having no odor can be obtained.

（式中、Ｘは炭素原子数６〜２０のアルキレン基、シクロアルキレン基およびアリーレン基からなる群から選ばれる少なくとも１種を表す。）
２．前記Ｘが−（ＣＨ₂）₈−である上記１に記載の接着剤組成物。
３．さらに、分子量が１００〜５，０００であり末端ヒドロキシ基が封鎖されているポリエーテルを含有する上記１または２に記載の接着剤組成物。
４．前記加水分解性シリル基変性ポリエステルが、さらに少なくとも１つのウレタン結合を有する上記１〜３のいずれかに記載の接着剤組成物。
５．さらに、水を含有し、前記水の量が、前記トリアルコキシシリル基変性ポリオキシアルキレン重合体が有するアルコキシ基に対して０．５〜５当量である上記１〜４のいずれかに記載の接着剤組成物。 That is, this invention provides the following 1-5.
1. A trialkoxysilyl group-modified polyoxyalkylene polymer having a trimethoxysilyl group and / or a triethoxysilyl group as a reactive group and the main chain being substantially polyoxyalkylene;
A hydrolyzable silyl group-modified polyester having a number average molecular weight of 300 to 6,000 having a repeating unit represented by the following formula (1) and having a hydrolyzable silyl group at the end;
Containing a curing catalyst,
An adhesive composition in which a mass ratio of the trialkoxysilyl group-modified polyoxyalkylene polymer and the hydrolyzable silyl group-modified polyester is 10:90 to 90:10.

(In the formula, X represents at least one selected from the group consisting of an alkylene group having 6 to 20 carbon atoms, a cycloalkylene group, and an arylene group.)
2. _2. The adhesive composition according to 1 above, wherein X is — (CH ₂ ) ₈ —.
3. 3. The adhesive composition according to the above 1 or 2, further comprising a polyether having a molecular weight of 100 to 5,000 and having a terminal hydroxy group blocked.
4). 4. The adhesive composition according to any one of 1 to 3, wherein the hydrolyzable silyl group-modified polyester further has at least one urethane bond.
5. Further, the adhesive according to any one of the above 1 to 4, further comprising water, wherein the amount of the water is 0.5 to 5 equivalents relative to the alkoxy group of the trialkoxysilyl group-modified polyoxyalkylene polymer. Agent composition.

  The adhesive composition of the present invention is excellent in fast curability, adhesiveness and deep part curability and has no odor.

（式中、Ｘは炭素原子数６〜２０のアルキレン基、シクロアルキレン基およびアリーレン基からなる群から選ばれる少なくとも１種を表す。） The present invention will be described in detail below.
The adhesive composition of the present invention comprises:
A trialkoxysilyl group-modified polyoxyalkylene polymer having a trimethoxysilyl group and / or a triethoxysilyl group as a reactive group and the main chain being substantially polyoxyalkylene;
A hydrolyzable silyl group-modified polyester having a number average molecular weight of 300 to 6,000 having a repeating unit represented by the following formula (1) and having a hydrolyzable silyl group at the end;
Containing a curing catalyst,
The mass ratio of the trialkoxysilyl group-modified polyoxyalkylene polymer and the hydrolyzable silyl group-modified polyester is 10:90 to 90:10.

(In the formula, X represents at least one selected from the group consisting of an alkylene group having 6 to 20 carbon atoms, a cycloalkylene group, and an arylene group.)

The trialkoxysilyl group-modified polyoxyalkylene polymer will be described below.
The trialkoxysilyl group-modified polyoxyalkylene polymer contained in the adhesive composition of the present invention has a trimethoxysilyl group and / or a triethoxysilyl group as a reactive group, and the main chain is substantially polyoxyalkylene. Is a polymer.
The adhesive composition of the present invention contains a trialkoxysilyl group-modified polyoxyalkylene polymer, so that it has excellent fast curing properties and accelerates curing at room temperature without foaming (tack-free time: 30 minutes or less is possible) .)be able to.

In the present invention, the main chain of the trialkoxysilyl 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 trialkoxysilyl 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 superior.

In the present invention, the trialkoxysilyl group-modified polyoxyalkylene polymer has a trimethoxysilyl group and / or a triethoxysilyl group as a reactive group. The number of reactive groups is superior in fast curability, adhesion, and deep curability, has no odor, and has excellent balance between shear strength, viscosity and flexibility, trialkoxysilyl group-modified polyoxyalkylene polymer It is preferable that it is 1-4 per molecule.
The reactive group can be attached to the end of the main chain and / or as a side chain. The reactive groups are preferably bonded to at least both ends of the main chain from the viewpoints of being excellent in quick curing property, adhesive property and deep portion curing property, having no odor, and excellent in balance between shear strength, viscosity and flexibility.
The reactive 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.

  The trialkoxysilyl group-modified polyoxyalkylene polymer has two or more terminal groups from the viewpoint that it is excellent in quick curing, adhesiveness, and deep curability, has no odor, and has an excellent balance of shear strength, viscosity, and flexibility. A polyoxypropylene polymer having one trimethoxysilyl group at each end, a polyoxypropylene polymer having one triethoxysilyl group at two or more terminals is preferred, and a straight chain having trimethoxysilyl groups at both ends Polyoxypropylene polymer, linear polyoxypropylene polymer having triethoxysilyl groups at both ends, trifunctional having trimethoxysilyl groups at both ends and trimethoxysilyl groups at the ends of side chains Branched polyoxypropylene polymer having triethoxysilyl groups at both ends and triethoxysilyl at the end of the side chain Branched polyoxypropylene polymer of trifunctional having group is more preferable.

式中、Ｒ¹、Ｒ²は炭素原子数１〜５のアルキレン基であり、Ｒ³はメチル基またはエチル基であり、ｎは９〜９００の整数であり、ｍは１〜５の整数であり、Ａは原料として使用される、ポリオキシアルキレンモノオールまたはポリオキシアルキレンポリオールを製造する際に用いられる開始剤の残基である。
トリアルコキシシリル基変性ポリオキシアルキレン重合体を製造する際、原料としてポリオキシアルキレンモノオールまたはポリオキシアルキレンポリオールを使用することができるが、そのポリオキシアルキレンモノオールまたはポリオキシアルキレンポリオールを製造する際に用いられる開始剤は特に制限されない。例えば、従来公知のものが挙げられる。
トリアルコキシシリル基変性ポリオキシアルキレン重合体は、貯蔵安定性、速硬化性により優れ、増粘を抑制することができ組成物の粘度を適正なものとすることができるという観点から、式（Ｖ）で表されるものが好ましい。 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 is a polyoxypropylene polymer having one trimethoxysilyl group at two or more terminals and / or two or more terminals for the purpose of reducing the viscosity of the composition. A polyoxypropylene polymer having one triethoxysilyl group and / or a polyoxypropylene polymer having one trimethoxysilyl group at one end and / or a polyoxypropylene polymer having one triethoxysilyl group at one end. Propylene polymers can be mixed. A polyoxypropylene polymer having one trimethoxysilyl group at one end or a polyoxypropylene polymer having one triethoxysilyl group at one end has a trimethoxysilyl group or a triethoxysilyl group at the other end. It may have a hydroxy group.
The amount of the polyoxypropylene polymer having one trimethoxysilyl group at one end and / or the polyoxypropylene polymer having one triethoxysilyl group at one end is such that the trimethoxysilyl group is present at two or more ends. The physical property (strength) of the cured product is 10% by mass or less with respect to the polyoxypropylene polymer having one each and / or the polyoxypropylene polymer having one triethoxysilyl group at two or more terminals. And elongation) are preferable from the viewpoint that they do not extremely decrease.

  The molecular weight of the trialkoxysilyl group-modified polyoxyalkylene polymer is 3,000 from the viewpoint that it is excellent in quick curing, adhesiveness and deep curability, has no odor, and has excellent balance of shear strength, viscosity and flexibility. It is preferably ˜50,000, more preferably 1,000 to 30,000.

  The trialkoxysilyl group-modified polyoxyalkylene polymer is excellent in fast curability and storage stability, and from the viewpoint that the viscosity of the adhesive composition of the present invention can be made appropriate, urethane bonds and urea bonds. It is preferably not included.

The trialkoxysilyl group-modified polyoxyalkylene polymer is not particularly limited for its production. 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).) And a trialkoxysilyl group-modified polyoxyalkylene polymer can be produced.
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 trialkoxysilyl group-modified polyoxyalkylene polymer can be used alone or in combination of two or more.

（式中、Ｘは炭素原子数６〜２０のアルキレン基、シクロアルキレン基およびアリーレン基からなる群から選ばれる少なくとも１種を表す。） The hydrolyzable silyl group-modified polyester will be described below.
The hydrolyzable silyl group-modified polyester contained in the adhesive composition of the present invention contains a repeating unit represented by the following formula (1), and has a number average molecular weight of 300 to 6, having a hydrolyzable silyl group at the terminal. 000 compounds.

(In the formula, X represents at least one selected from the group consisting of an alkylene group having 6 to 20 carbon atoms, a cycloalkylene group, and an arylene group.)

X in Formula (1) represents at least one selected from the group consisting of an alkylene group having 6 to 20 carbon atoms, a cycloalkylene group, and an arylene group.
The alkylene group having 6 to 20 carbon atoms may be linear or branched. For example, — (CH ₂ ) ₆ —, — (CH ₂ ) ₇ —, — (CH ₂ ) ₈ —, — (CH ₂ ) ₉ —, — (CH ₂ ) ₁₀ —, — (CH ₂ ) ₁₁ —, _{- (CH 2) 12 -,} - (CH 2) 13 -, - (CH 2) 14 -, - (CH 2) 15 -, - (CH 2) 16 -, - (CH 2) 17 -, - ( _{CH 2) 18 -, - (} CH 2) 19 -, - (CH 2) 20 - and the like.

Examples of the cyclohexylene group include a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, and a norbornylene group. The cyclohexylene group may have a substituent such as an alkyl group.
Examples of the arylene group include a phenylene group and a naphthylene group. The arylene group may have a substituent such as an alkyl group.

Among these, X is preferably an alkylene group, and more preferably — (CH ₂ ) ₈ —, from the viewpoint of excellent quick curability, adhesiveness, and deep curability.

In the present invention, the hydrolyzable silyl group-modified polyester has at least a polyester containing a repeating unit represented by the formula (1) as a main chain and a hydrolyzable silyl group as a terminal.
The repeating unit represented by Formula (1) is the total number of moles of repeating units constituting the polyester as the main chain of the hydrolyzable silyl group-modified polyester, from the viewpoint of excellent fast curability, adhesiveness, and deep curability. It is preferably contained in an amount of 20 mol% or more, more preferably 30 to 100 mol%.
The repeating unit other than the repeating unit represented by the formula (1) that can be contained in the hydrolyzable silyl group-modified polyester is not particularly limited.

式（５）中、Ｒ⁴、Ｒ⁵はそれぞれアルキル基を示し、ｍは１〜３の整数である。
アルキル基としては、例えば、メチル基、エチル基、プロピル基が挙げられる。
Ｒ⁴は速硬化性に優れるという観点から、メチル基あるいはエチル基であるのが好ましい。
ｍは、速硬化性に優れるという観点から、３であるのが好ましい。
加水分解性シリル基は、硬化物の伸び（Ｅｍａｘ）に優れるという観点から、加水分解性シリル基変性ポリエステルの両末端に結合するのが好ましい。 The hydrolyzable silyl group possessed by the hydrolyzable silyl group-modified polyester is not particularly limited. For example, what is represented by Formula (5) is mentioned.

In formula (5), R ⁴ and R ⁵ each represents an alkyl group, and m is an integer of 1 to 3.
Examples of the alkyl group include a methyl group, an ethyl group, and a propyl group.
R ⁴ is preferably a methyl group or an ethyl group from the viewpoint of excellent rapid curability.
m is preferably 3 from the viewpoint of excellent fast curability.
The hydrolyzable silyl group is preferably bonded to both ends of the hydrolyzable silyl group-modified polyester from the viewpoint of excellent elongation (Emax) of the cured product.

  The hydrolyzable silyl group-modified polyester preferably has at least one urethane bond and more preferably has 1 to 6 urethane bonds from the viewpoint of excellent strength (Tmax) of the cured product, that is, cohesive force. .

In the hydrolyzable silyl group-modified polyester, the hydrolyzable silyl group and the main chain can be directly bonded. In addition, the hydrolyzable silyl group and the main chain can be bonded via a hydrocarbon group that can have a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom.
The hydrocarbon group via the hydrolyzable silyl group and the main chain can have, for example, a urethane bond.

Examples of the hydrolyzable silyl group-modified polyester include those represented by the formula (4).

In the formula (4), R and R ³ each represent an alkylene group that may be branched, R ¹ represents a hydrocarbon group, R ² represents a hydrogen atom or a hydrocarbon group, and R ⁴ and R ⁵ each represent Represents an alkyl group, m is an integer of 1 to 3, and X represents at least one selected from the group consisting of an alkylene group having 6 to 20 carbon atoms, a cycloalkylene group, and an arylene group. The number average molecular weight of the hydrolyzable silyl group-modified polyester is 300 to 6000.

The alkylene group may be linear or branched. The alkylene group preferably has 3 to 10 carbon atoms. Examples of the alkylene group include trimethylene group and 3-methyl-1,5-pentylene group.
R is preferably a 3-methyl-1,5-pentylene group from the viewpoint of excellent adhesiveness.
R ³ is preferably — (CH ₂ ) _n — (n = 1 to 3) from the viewpoint of rapid curing.

The hydrocarbon group as R ¹ is not particularly limited as long as it is a divalent hydrocarbon group. Examples thereof include a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, a divalent aromatic hydrocarbon group, and a divalent aromatic hydrocarbon group having an alkyl group. R ¹ can be a residue other than the isocyanate group in the diisocyanate compound.
Examples of R ¹ include 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), 4,4′-diphenylmethane diisocyanate (4,4′- MDI), 2,4′-diphenylmethane diisocyanate (2,4′-MDI), p-phenylene diisocyanate, polymethylene polyphenylene polyisocyanate, xylylene diisocyanate (XDI), 1,5-naphthalene diisocyanate (NDI), etc. Residues of diisocyanates; Residues of aliphatic diisocyanates such as hexamethylene diisocyanate (HDI) and norbornane diisocyanate methyl (NBDI); Isophorone diisocyanate (IPDI), H ₆ XDI (hydrogenated XDI), H ₁₂ MDI (hydrogenated) MDI) and other fats Residue of formula diisocyanate; residues of tetramethylxylylene diisocyanate (TMXDI) and the like.

The hydrocarbon group as R ² is not particularly limited as long as it is a monovalent hydrocarbon group. Examples thereof include a monovalent aliphatic hydrocarbon group, a monovalent alicyclic hydrocarbon group, a monovalent aromatic hydrocarbon group, and a monovalent aromatic hydrocarbon group having an alkyl group.
R ⁴ , R ⁵ and m are as defined in the above formula (5). X is synonymous with the above formula (1).
N in Formula (4) can be a numerical value corresponding to a molecular weight of 300 to 6000.

The hydrolyzable silyl group-modified polyester is preferably a compound represented by the formula (4) from the viewpoint of excellent adhesion and deep part curability and no odor, and X is — (CH ₂ ) ₈ —, R Is a 3-methyl-1,5-pentylene group, R ³ is a trimethylene group, R ¹ is a phenylene group having an alkyl group, R ² is a phenyl group, and R ⁴ is a methyl group, More preferably, m is 3.

In the present invention, the hydrolyzable silyl group-modified polyester has a number average molecular weight of 300 to 6,000.
The number average molecular weight of the hydrolyzable silyl group-modified polyester is preferably 1000 to 5000 from the two points of the balance between the viscosity of the composition and the elongation (Emax) of the cured product and the difficulty of volatilization.
The hydrolyzable silyl group-modified polyesters can be used alone or in combination of two or more.

In the present invention, the mass ratio of trialkoxysilyl group-modified polyoxyalkylene polymer to hydrolyzable silyl group-modified polyester (trialkoxysilyl group-modified polyoxyalkylene polymer: hydrolyzable silyl group-modified polyester) is 10: 90-90: 10. When the mass ratio between the trialkoxysilyl group-modified polyoxyalkylene polymer and the hydrolyzable silyl group-modified polyester is within such a range, it is excellent in fast curability, adhesiveness and deep curability, and has no odor.
The mass ratio between the trialkoxysilyl group-modified polyoxyalkylene polymer and the hydrolyzable silyl group-modified polyester is preferably 20:80 to 80:20 from the viewpoint of excellent adhesion and deep part curability.

The hydrolyzable silyl group-modified polyester is not particularly limited for its production. For example, a polyester polyol [for example, a polyol containing at least 3-methyl-1,5-pentanediol as a polyol component and HOOC-X-COOH as a carboxylic acid component (X is synonymous with X in the above formula (4)). What you can get from ] And R- (NCO) _a (R is synonymous with R in the above formula (4) and a is 2 or more) to obtain a urethane prepolymer under the conditions of 90 to 140 ° C., Next, hydrolyzable silyl group modification | denaturation is carried out by mixing the obtained urethane prepolymer and aminosilane (for example, what is represented by following formula (7)), and making it react on the conditions of 50-90 degreeC. Polyester can be produced.

式中、Ｒ²は水素原子、炭化水素基を示し、Ｒ³は分岐してもよいアルキレン基を示し、Ｒ⁴、Ｒ⁵はそれぞれアルキル基を示し、ｍは１〜３の整数である。Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、ｍは上記式（４）と同義である。

In the formula, R ² represents a hydrogen atom or a hydrocarbon group, R ³ represents an alkylene group which may be branched, R ⁴ and R ⁵ each represents an alkyl group, and m is an integer of 1 to 3. R ² , R ³ , R ⁴ , R ⁵ , and m are as defined in the above formula (4).

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.
Among these, a tin compound is preferable and a tetravalent tin compound is more preferable from the viewpoints of being excellent in fast curability, adhesiveness, and deep part curability, having no odor, and excellent in shear strength and storage stability.
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.

式中、Ｒ⁵は炭素原子数１〜１０の炭化水素基であり、Ｒ⁶は炭素原子数１〜１０の炭化水素基でありＲ⁵，Ｒ⁶は同一でも異なっていてもよい。ｍは０〜３の整数である。
炭素原子数１〜１０の炭化水素基（Ｒ⁵）としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基が挙げられる。
炭素原子数１〜１０の炭化水素基（Ｒ⁶）としては、例えば、ブチル基が挙げられる。
（ジアルキルスタノキサン）ジシリケート化合物としては、例えば、ジブチル錫塩（例えば、ジブチル錫アセテートが挙げられる。）と正珪酸エチルとの反応生成物が挙げられる。 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 superior to quick curing, adhesiveness, and deep part curability, has no odor, and has excellent shear strength and storage stability, based on 100 parts by mass of the trialkoxysilyl group-modified polyoxyalkylene polymer. It is more preferably 0.1 to 3.0 parts by mass.

The adhesive composition of the present invention can further contain a polyether having a molecular weight of 100 to 5,000 and having a terminal hydroxy group blocked.
The polyether will be described below.
The polyether that can be further contained in the adhesive composition of the present invention is a compound having a molecular weight of 100 to 5,000 and a terminal hydroxy group blocked.
The polyether that can be further contained in the adhesive composition of the present invention is inert to the trialkoxysilyl 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 show that the polyether having a number average molecular weight of 100 to 5,000 and having a terminal hydroxy group blocked has stability to a trialkoxysilyl group-modified polyoxyalkylene polymer and a curing catalyst. I found it.
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 trialkoxysilyl group-modified polyoxyalkylene polymer and curing catalyst, fast curing, excellent storage stability to trialkoxysilyl group-modified polyoxyalkylene polymer, hard to increase viscosity, workability and The curing rate 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 preferable because it is easy to handle from the viewpoint that the curing rate and the physical properties after curing do not change depending on the addition amount.
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 molecular weight of the polyether is 100 to 5,000. When the 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 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 for producing the polyether is not particularly limited as long as it is a polyether having one or more hydroxy groups (for example, polyoxypropylene monool, polyoxypropylene polyol). .

In the present invention, the amount of the polyether is 5 to 50 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. preferable.
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 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 0.5 to 5 equivalents relative to the alkoxy group of the trialkoxysilyl group-modified polyoxyalkylene polymer in terms of a region where initial strength is manifested and unnecessary residual moisture can be ignored. Is preferred.

The adhesive composition of the present invention can further contain an epoxy resin.
When the adhesive composition of the present invention further contains an epoxy resin, it has excellent shear strength.
The epoxy resin that can be 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.

Of these, bisphenol A type epoxy resins and bisphenol F type epoxy resins are preferred from the viewpoints of excellent fast curing properties, adhesive properties, and deep portion curability, no odor, and excellent balance between shear strength, viscosity, and flexibility.
The epoxy resins can be used alone or in combination of two or more.

  The amount of the epoxy resin is excellent in quick curing, adhesion, and deep-curing properties, has no odor, and has excellent balance of shear strength, viscosity and flexibility, trialkoxysilyl group-modified polyoxyalkylene polymer 100. It is preferable that it is 3-100 mass parts with respect to a mass part, and it is more preferable that it is 10-50 mass parts.

式中、Ｒ¹は炭素原子数１〜６のアルキル基であり、Ｒ²はメチル基またはエチル基であり、Ｒ³は水素原子、メチル基またはエチル基であり、Ｒ⁴は水素原子またはアルキル基であり、ｎは１または２である。
Ｒ¹とＲ²とは互いに結合して環構造を形成することができる。Ｒ¹とＲ⁴とは互いに結合して環構造を形成することができる。
ケチミンが有する１つのイミノ基（−Ｎ＝）は湿気と反応して加水分解することで１級のアミンになり、１個または２個のエポキシ基と反応することができる。 The adhesive composition of the present invention can further contain ketimine.
When the adhesive composition of the present invention further contains ketimine, the shear strength is excellent.
Examples of ketimines that can be contained in the adhesive composition of the present invention include compounds 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.
Examples of the carbonyl compound used in the production of the ketimine that can be contained in the adhesive composition of the present invention include those 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, the same thing as said C1-C6 alkyl group is mentioned.

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 excellent quick curability, excellent storage stability and shear strength, a ketone in which n in the formula (I) is 1 and R ⁴ is an alkyl group is preferable, 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 is preferably 1 to 10 carbon atoms from the viewpoint that it is more excellent in rapid curability and is excellent in storage stability and shear strength.
n is preferably 2 to 4 which has excellent shear strength and is 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, a polyamine having an alicyclic hydrocarbon group such as a diamine having a norbornane skeleton represented by NBDA (norbornanediamine) manufactured by Mitsui Toatsu Chemicals; Polyamine; m-xylylenediamine, polyamines having an aliphatic hydrocarbon group attached to an aromatic hydrocarbon group as tetramethyl xylylene diamine; polyamidoamine having an amino group at the molecular terminal of the polyamide.

  Of these, hexamethylene diamine (HMDA) and NBDA are preferred from the viewpoints of excellent fast curability, adhesiveness and deep part curability, no odor, excellent shear strength, and storage stability with an epoxy resin.

As a combination of a carbonyl compound and a polyamine, methyl isopropyl ketone (from the viewpoint that it is excellent in quick curing, adhesiveness and deep curability, has no odor, and has a good balance between shear strength, fast curing and storage stability. A combination of MIPK) and hexamethylenediamine (HMDA) and a combination of methyl isopropyl ketone (MIPK) and NBDA are preferred.
Ketimines can be used alone or in combination of two or more.

  The amount of the imino group possessed by the ketimine is 0.5 to 1. It is preferably 5 equivalents, more preferably 0.7 to 1.0 equivalents.

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 trialkoxysilyl group-modified polyoxyalkylene polymer from the viewpoint of excellent shear strength and excellent balance between the shear strength and the viscosity of the composition. Preferably there is.

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 trialkoxysilyl group-modified polyoxyalkylene polymer from the balance of shear strength and composition viscosity.

The adhesive composition of the present invention can further contain a flame retardant.
When the adhesive composition of the present invention further contains a flame retardant, the flame retardant is excellent.
Examples of the flame retardant include halogen compounds, antimony oxide, red phosphorus, phosphate esters, and inorganic filler flame retardants. Of these, inorganic filler-based flame retardants are preferred from the standpoint that they do not generate harmful substances such as dioxin and phosphine, are excellent in rapid curability, and are excellent in flame retardancy.
In the present invention, the inorganic filler-based flame retardant means a filler having a property of thermally decomposing at a high temperature to generate water.
Among the inorganic filler-based flame retardants, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, calcium sulfate hydrate, and magnesium sulfate hydrate are preferable from the viewpoint of large endotherm and low thermal decomposition temperature.
The flame retardant may be surface treated. Examples of the surface treatment agent include fatty acids, silane coupling agents, and resin acids. Of these, fatty acids and silane compounds are preferred from the viewpoint of superior flame retardancy.
A flame retardant can be used individually or in combination of 2 or more types, respectively.

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 can be used individually or in combination of 2 or more types, respectively.

  The amount of the flame retardant is preferably 30 to 70% by mass in the total weight of the adhesive composition from the viewpoint of excellent shear strength, flame retardancy, and excellent balance of viscosity and physical properties of the composition.

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 fumed silica and fillers other than surface-treated calcium carbonate (for example, colloidal calcium carbonate, calcium carbonate such as heavy calcium carbonate, wet silica), and the adhesive composition of the present invention. Plasticizers other than polyethers, dehydrating agents such as vinyl silane, epoxy silane coupling agents, amine silane coupling agents, thixotropic agents such as fatty acid polyamide waxes, pigments, dyes, anti-aging agents, and antioxidants Agents, antistatic agents, adhesion-imparting agents, dispersants, solvents, and curing agents.
Examples of amine-based silane coupling agents include N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyltrimethoxysilane, and 3-aminopropyltrimethoxy. Silane and 3-aminopropyltriethoxysilane are mentioned.
Further, the adhesive composition of the present invention may not contain a solvent.

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 trialkoxysilyl group-modified polyoxyalkylene polymer, hydrolyzable silyl group-modified polyester, epoxy resin, ketimine, polyether, flame retardant and curing catalyst. One preferred embodiment is a two-component type having a main agent 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 adhesive composition of the present invention preferably has a tack-free time of 30 minutes or less under the conditions of 20 ° C. and 55% RH, more preferably 15 minutes or less, and further preferably 10 minutes or less. preferable.
In the present invention, the tack-free time is determined by placing the adhesive composition under the conditions of 20 ° C. and 55% RH and pressing the polyethylene film against the surface of the adhesive composition until the adhesive composition does not adhere to the film. Time.

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.

  The adhesive composition of the present invention is excellent in adhesiveness. Especially, it is excellent in the adhesiveness (adhesiveness in normal state, heat resistant adhesiveness, hot water resistant adhesiveness) with respect to ABS resin. Moreover, the adhesive composition of this invention can achieve coexistence with adhesiveness and deep part sclerosis | hardenability.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.
1. Production of trialkoxysilyl group-modified polyoxyalkylene polymer Dehydrated polyoxypropylene diol (linear, number average molecular weight of about 3,000, number of hydroxy groups per molecule: 2) is used as an initiator to polymerize propylene oxide. 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.

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

3. Production of hydrolyzable silyl group-modified polyester (1) Hydrolyzable silyl group-modified polyester 1
Polyester polyol represented by the following formula (2) (carboxylic acid component: sebacic acid, polyol component: 3-methyl-1,5-pentanediol, trade name P-3050, manufactured by Kuraray Co., Ltd., hydroxyl value: 37, number average A urethane prepolymer (index: 2.0) by reacting 100 parts by weight of molecular weight 3000) and 11.4 parts by weight of 2,4-tolylene diisocyanate (manufactured by Mitsui Chemicals, the same applies hereinafter) at 90 ° C. for 24 hours. )
The obtained urethane prepolymer is represented by the following formula (3).

111.4 parts by mass of the urethane prepolymer obtained and 6.3 parts by mass of N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., the same shall apply hereinafter) were mixed, and the conditions were 70 ° C. For 9 hours to produce a hydrolyzable silyl group-modified polyester.
When NCO% of the obtained compound was measured, it was 0.07%, and the isocyanate component in the obtained compound reacted to have a trimethoxysilyl group at both ends and two urethane bonds. It was confirmed that it was a trimethoxysilyl group-modified polyester represented by the formula (6). The number average molecular weight of the obtained compound was 4,000, and it was used as hydrolyzable silyl group-modified polyester 1 in the examples.

(2) Hydrolyzable silyl group-modified polyester 2
111.4 parts by mass of the urethane prepolymer represented by the above formula (3) and 5.8 parts by mass of N- (n-butyl) -3-aminopropyltrimethoxysilane (manufactured by DEGUSSA, the same shall apply hereinafter) were mixed. The mixture was reacted at 70 ° C. for 9 hours to produce a hydrolyzable silyl group-modified polyester.
When NCO% of the obtained compound was measured, it was 0.05%, and the isocyanate component in the obtained compound reacted, had trimethoxysilyl groups at both ends, and had two urethane bonds. It was confirmed that the polyester was a trimethoxysilyl group-modified polyester represented by the formula (7). The number average molecular weight of the obtained compound was 4,000, and it was used as the hydrolyzable silyl group-modified polyester 2 in the examples.

(3) Hydrolyzable silyl group-modified polypropylene glycol Polypropylene glycol (trade name EXL3020, manufactured by Asahi Glass Co., Ltd., hydroxyl value: 35.6, number average molecular weight 3,000) 10.67 parts by mass and 2,4-tolylene diisocyanate ( 11.4 parts by mass of Mitsui Chemicals) was reacted for 24 hours at 90 ° C. to obtain a urethane prepolymer (index: 2.0).
100 parts by mass of the obtained urethane prepolymer and 16.2 parts by mass of N-phenyl-3-aminopropyltrimethoxysilane are reacted at 70 ° C. for 9 hours to produce hydrolyzable silyl group-modified polypropylene glycol. did.
When NCO% of the obtained compound was measured, it was 0.07%, and the isocyanate component in the obtained compound reacted, and the obtained compound had a trimethoxysilyl group having trimethoxysilyl groups at both ends. It was confirmed that it was a modified polypropylene glycol.
The obtained compound was used as trimethoxysilyl group-modified PPG in Examples.

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

5. Evaluation The adhesive composition obtained as described below was evaluated for tack-free time, shear strength, deep curability, odor, and adhesiveness by the following methods. The results are shown in Tables 1 and 2.

(1) Tack free time (TFT, fast curability)
-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.

(2) Shear strength One steel plate using two steel plates having a length of 150 mm, a width of 25 mm, and a thickness of 1 mm so that the adhesive area is 10 mm × 25 mm and the adhesive layer thickness is 0.3 mm. The two pieces were immediately overlapped and brought into close contact with each other, and cured for 1 hour under the 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 under the condition of a tensile speed of 10 mm / min using a test equipment tensile tester (AGS-10kNG, manufactured by Shimadzu Corporation).
Further, after the steel plates were superposed and brought into close contact with each other, they were cured for 14 days under the conditions of 20 ° C. and 55% RH, and then the shear strength after 14 days was measured for the obtained specimens in the same manner as described above.

(3) Deep Curability The test piece was obtained by applying the adhesive composition obtained as described below to a cylindrical container so as to have a film thickness of 30 mm. The obtained test piece was cured under the conditions of 20 ° C. and 55% RH for 24 hours, and the thickness from the coating surface of the portion where curing after curing was advanced was measured.

(4) Odor The odor of the adhesive composition obtained as described below was confirmed by human olfaction.

(5) Adhesiveness An adhesive composition obtained as described below was coated on an adherend [anodized aluminum, polyethylene terephthalate (PET), polycarbonate, acrylonitrile butadiene styrene copolymer (ABS)] with a film thickness of about 10 mm. After being applied in the form of a bead so as to be, it was allowed to cure under the conditions of 20 ° C. and 55% RH for 7 days to obtain a test specimen.
About the obtained test body, the bead part was peeled by hand and the area ratio of the cohesive failure was recorded.

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

Each component shown in Table 1 is as follows.
-Trialkoxysilyl group-modified polyoxyalkylene polymer: produced as described above-Trialkoxysilyl group-modified acrylic resin: Trade name Silyl MA440, manufactured by Kaneka Corporation-Hydrolyzable silyl group-modified polyesters 1, 2: As described above Manufactured-Hydrolyzable silyl group-modified PPG: manufactured as described above-Surface treated calcium carbonate: Calfine 200, Maruo Calcium Co., Ltd., fatty acid surface treatment-Fumed silica: Hydrophobic fumed silica, R-972 Manufactured by Nippon Aerosil Co., Ltd., particle size 0.016μm
・ Plasticizer: End-capped polyether produced as described above ・ Thixotropic agent: Fatty acid amide (Disparon # 6500, Enomoto Kasei Co., Ltd.)
Aminosilane: aminoethyltrimethoxysilylpropylamine (KBM 603, Shin-Etsu Chemical Co., Ltd.)
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 )

As is apparent from the results shown in Table 1, Comparative Example 1 containing no trialkoxysilyl group-modified polyoxyalkylene polymer and hydrolyzable silyl group-modified polyester and containing a trialkoxysilyl group-modified acrylic resin is It was inferior in deep part curability and strong odor. Comparative Example 2 which did not contain hydrolyzable silyl group-modified polyester and contained hydrolyzable silyl group-modified polypropylene glycol instead had poor adhesion.
On the other hand, Examples I-1 to 4 were excellent in fast curability, deep part curability and adhesiveness, and had no odor. In addition, Examples I-1 to 4 are excellent in adhesion to ABS.

7). Production of Adhesive Composition (Example II)
The components shown in Table 2 were used in the amounts (parts by mass) shown in the 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: produced as described above Hydrolyzable silyl group-modified polyester: Hydrolyzable silyl group-modified polyester 1 produced as described above
Colloidal calcium carbonate (0.07μ): Calfine 200, Maruo Calcium Co., Ltd., average particle size 0.07μm
Fumed silica: hydrophobic fumed silica, R-972, manufactured by Nippon Aerosil Co., Ltd., particle size 0.016 μm
End-capped polyether: Same as plasticizer in Table 1.
・ Thixotropic agent: Fatty acid amide (Disparon # 6500, Enomoto Kasei Co., Ltd.)
Aminosilane: aminoethyltrimethoxysilylpropylamine (KBM 603, Shin-Etsu Chemical Co., Ltd.)
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 trialkoxysilyl group-modified polyoxyalkylene polymer.

  As is clear from the results shown in Table 2, the adhesive compositions of Examples II-1 and II-2 are excellent in fast curability and excellent in shear strength. There is no odor. The two-component adhesive composition is superior to the initial shear strength in bonding between metals than the one-component adhesive composition.

Claims (5)

A trialkoxysilyl group-modified polyoxyalkylene polymer having a trimethoxysilyl group and / or a triethoxysilyl group as a reactive group and the main chain being substantially polyoxyalkylene;
A hydrolyzable silyl group-modified polyester having a number average molecular weight of 300 to 6,000 having a repeating unit represented by the following formula (1) and having a hydrolyzable silyl group at the end;
Containing a curing catalyst,
An adhesive composition in which a mass ratio of the trialkoxysilyl group-modified polyoxyalkylene polymer and the hydrolyzable silyl group-modified polyester is 10:90 to 90:10.

(In the formula, X represents at least one selected from the group consisting of an alkylene group having 6 to 20 carbon atoms, a cycloalkylene group, and an arylene group.) The adhesive composition according to claim 1, wherein X is — (CH ₂ ) ₈ —.   The adhesive composition according to claim 1 or 2, further comprising a polyether having a molecular weight of 100 to 5,000 and having a terminal hydroxy group blocked.   The adhesive composition according to claim 1, wherein the hydrolyzable silyl group-modified polyester further has at least one urethane bond.   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 trialkoxy silyl group modified polyoxyalkylene polymer has. Adhesive composition.