JP4450107B1 - Adhesive composition - Google Patents

Abstract

The present invention provides an adhesive composition excellent in fast curability and storage stability.
100 parts by mass of 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, and an epoxy resin 3 to 100 parts by mass, a ketimine obtained by reacting a carbonyl compound represented by a specific formula and a polyamine, and a polyether having a number average molecular weight of 100 to 5,000 and a terminal hydroxy group blocked. The adhesive composition which contains 5-50 mass parts and a curing catalyst, and 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.
[Selection figure] None

Description

  The present invention relates to an adhesive composition.

Conventionally, room temperature moisture-curable compositions containing a modified polyoxyalkylene polymer having a hydrolyzable silyl group have been used as the main polymer for adhesives and sealants, which balances the flexibility and viscosity of the cured product. Polymers having superior dimethoxysilyl groups at the end have been widely used.
On the other hand, in recent years, there is an increasing need for shortening the curing time for the purpose of shortening the tact time for the adhesive. When a composition containing a modified polyoxyalkylene polymer having a methyldimethoxysilyl group as a hydrolyzable silyl group is used, the curing time can be shortened even if a curing catalyst is studied because the terminal reactivity is low. There was a limit.
For example, when a composition containing a modified polyoxyalkylene polymer having a methyldimethoxysilyl group as a hydrolyzable silyl group is used and the tack-free time (TFT) is within 30 minutes, the composition It is necessary to mix an amine catalyst and a large amount of tin catalyst in the catalyst. As a result, there is a concern about heat-resistant adhesion, and the adjustment range of physical properties is reduced (specifically, the composition is increased by increasing the amount of the catalyst). And the adhesiveness is deteriorated). F. T. T. Was about 10 minutes.
The above attempts to use polyoxyalkylene whose terminal reactive group of polyoxyalkylene is trimethoxysilyl group or triethoxysilyl group for the purpose of shortening the curing time (Patent Document 1, Patent Document 2), or isocyanate-modified polyoxyalkylene Techniques using a silylated urethane having a terminal end of a trimethoxysilyl group or a triethoxysilyl group obtained by reacting a polyol with a secondary aminosilane compound have been proposed (Patent Document 3, Patent Document 4, Patent Document 5, Patent Document 6 and Patent Document 7). Among these, silylated urethane usually has two or more urethane bonds in the molecule, so that it has a problem of higher viscosity than hydrolyzable silyl group-modified polyoxyalkylene obtained by hydrosilylation.
In addition, compositions such as adhesives and sealants containing hydrolyzable silyl group-modified polyoxyalkylene polymers include phthalates such as dioctyl phthalate (DOP) and diisononyl phthalate (DINP) to control viscosity and thixotropy. An ester plasticizer is widely used, such as acid ester plasticizers, adipates such as dioctyl adipate (DOA), and phosphate esters (Patent Document 1). When these ester plasticizers are added to a polyoxyalkylene having a trimethoxysilyl group or a triethoxysilyl group in order to lower the viscosity of the composition, T. F. T. T. A composition capable of realizing rapid curing of less than 5 minutes has been developed as the T.V. F. T. T. The present inventor has found a phenomenon that the curing is delayed as the time exceeds 10 minutes.
Furthermore, since these ester plasticizers bleed out to the surface of the cured product after the adhesive composition is cured, there are problems in residual tack and paintability after curing, and in particular phthalates are so-called environmental hormones. Since it is considered as an environmental problem such as being listed, an alternative plasticizer is also desired from the environmental viewpoint.

Japanese Patent No. 3341453 Japanese Patent No. 328649 Patent No. 3030020 Japanese Patent No. 3317353 Japanese Patent No. 3350011 Japanese Patent No. 3471667 Patent No. 393020

  An object of this invention is to provide the adhesive composition which is excellent in quick-curing property and storage stability (it is hard to thicken and workability | operativity and a cure rate do not change with time).

As a result of intensive studies to solve the above problems, the present inventors have found that a polyether having a number average molecular weight of 500 to 3,000 and having a terminal hydroxy group blocked is not suitable for a curing catalyst or a hydrolyzable silyl group. Found to be active.
The catalytic activity of a metal catalyst [for example, Sn ⁴⁺ (Ligand)] as a curing catalyst varies greatly depending on the ligand. This is because the catalyst itself is hydrolyzed to release the ligand during the catalyst cycle during the curing reaction. Therefore, if a metal (for example, Sn) as a ligand forms a stable bond, it is difficult to hydrolyze and the catalytic activity tends to decrease. For example, thiol, long-chain carboxylic acid and the like form a stable bond with a metal (for example, Sn) as a ligand, and therefore, when mixed in the system, the curing rate is significantly reduced.
In addition, a curing catalyst for a hydrolyzable silyl group (methoxysilyl group, ethoxysilyl group, etc.) acts in nature as a transesterification catalyst or a reverse esterification reaction. Accordingly, ester plasticizers such as DOP and DINP are not stable to the metal as a ligand (for example, Sn), and when heated, long-chain alcohol, phthalic acid, etc. are obtained by reverse esterification reaction or transesterification reaction. Produce. The generated phthalic acid binds to a metal as a ligand (for example, Sn) and loses its activity.
On the other hand, polyethers do not inactivate the catalyst because they are chemically stable to a metal as a ligand (eg, Sn). However, if the polyether has a hydroxyl group at the end, it undergoes an alcohol exchange reaction with a trialkoxysilyl group-modified polyoxyalkylene polymer (for example, a methoxysilyl group-terminated polymer) in the presence of a catalyst, resulting in thickening and slight curing delay Cause.
The inventor of the present application infers the above as a mechanism of delay in curing.
That is, the present inventors consider that if the terminal hydroxy group of the polyether is blocked, the polyether is stable against the curing catalyst and the trialkoxysilyl group-modified polyoxyalkylene polymer.
It should be noted that even if the mechanism related to the curing delay is different from the above, it is within the scope of the present invention.

  Furthermore, the present inventors have added 100 parts by mass of 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. And 3-100 parts by mass of an epoxy resin, a ketimine obtained by reacting a carbonyl compound represented by the following formula (I) and a polyamine, a number average molecular weight of 100 to 5,000, and a terminal hydroxy group It contains 5 to 50 parts by weight of blocked polyether and a curing catalyst, and 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 present inventors have found that a certain composition can be an adhesive composition excellent in fast curability and storage stability, and completed the present invention.

That is, this invention provides the following 1-8.
1.
A trialkoxysilyl group-modified poly having a trimethoxysilyl group and / or a triethoxysilyl group as a reactive group and an oxyalkylene group 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 100 parts by mass of an oxyalkylene polymer;
3 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;
5 to 50 parts by mass of a polyether having a number average molecular weight of 500 to 3,000 and a terminal hydroxy group blocked;
Containing a curing catalyst,
The amount of imino groups of the ketimine has found the epoxy groups of the epoxy resin has, Ri 0.5-1.5 equivalents der,
In the polyether, the terminal hydroxy group is blocked with an alkyl group, an alkoxy group or an alkylsilyl group,
Furthermore, the adhesive composition which contains 0.2-30 mass parts of N-silylamide compounds shown by following formula (2) with respect to 100 mass parts of said trialkoxysilyl 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.)
(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.)
2.
2. The adhesive composition according to 1 above, wherein the polyether main chain is a polyoxypropylene polymer.
3.
3. The adhesive composition according to 1 or 2 above, wherein the trialkoxysilyl group-modified polyoxyalkylene polymer does not contain a urethane bond or a urea bond.
4).
Furthermore, fumed silica is contained, The quantity of the said fumed silica is 1-10 mass parts with respect to 100 mass parts of the said trialkoxysilyl group modified polyoxyalkylene polymers, Any one of said 1-3. Adhesive composition.
5.
Furthermore, the surface-treated calcium carbonate is contained, and the amount of the surface-treated calcium carbonate is 10 to 100 parts by mass with respect to 100 parts by mass of the trialkoxysilyl group-modified polyoxyalkylene polymer. The adhesive composition as described.
6).
Further, the adhesive according to any one of the above 1 to 5, 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.
7).
Furthermore, the adhesion according to any one of 1 to 6 above, comprising 0.2 to 20 parts by mass of an amino group-substituted alkoxysilane compound and / or a derivative thereof with respect to 100 parts by mass of the trialkoxysilyl group-modified polyoxyalkylene polymer. Agent composition.
8).
8. The adhesive composition according to any one of 1 to 7 above, wherein the tack free time under conditions of 20 ° C. and 55% RH is 30 minutes or less.

  The adhesive composition of the invention is excellent in fast curability and storage stability.

The present invention will be described in detail below.
The adhesive composition of the present invention comprises:
100 parts by mass of 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, and 3 to 100 parts by mass of an epoxy resin A ketimine obtained by reacting a carbonyl compound represented by the following formula (I) with a polyamine, a polyether having a number average molecular weight of 100 to 5,000 and a terminal hydroxy group blocked: An adhesive composition containing 50 parts by mass and a curing catalyst,
The amount of imino group possessed by the ketimine is 0.5 to 1.5 equivalents relative to the epoxy group possessed by the epoxy resin.
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 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.
By containing the trialkoxysilyl group-modified polyoxyalkylene polymer, the curing time at room temperature can be shortened without foaming (fast curing property, tack-free time: 30 minutes or less is possible).

The main chain of the trialkoxysilyl group-modified polyoxyalkylene polymer is substantially polyoxyalkylene. The polyoxyalkylene is not particularly limited. Examples include polyoxyethylene and polyoxypropylene, which are selected in consideration of adhesiveness and hydrophilicity. 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, a tougher cured product can be obtained.

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 preferably 1 to 4 per molecule of trialkoxysilyl group-modified polyoxyalkylene polymer from the viewpoint of being excellent in rapid curability and excellent in the balance between viscosity and flexibility.
The reactive group can be attached to the end of the main chain and / or as a side chain. From the viewpoint of excellent breaking strength and breaking elongation of the cured product, the reactive group is preferably bonded to at least both ends of the main chain.
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 is superior in fast curability and storage stability, and from the viewpoint of excellent balance between viscosity and flexibility, a polyoxypropylene polymer having a trimethoxysilyl group at the terminal, A polyoxypropylene polymer having a triethoxysilyl group at a terminal is preferred, a polyoxypropylene polymer having one trimethoxysilyl group at each of two or more terminals, and a triethoxysilyl group at each of two or more terminals. More preferred are polyoxypropylene polymers having a trimethoxysilyl group at both ends, linear polyoxypropylene polymers having a triethoxysilyl group at both ends, It has a trimethoxysilyl group at the end and a trimethoxysilyl group at the end of the side chain. That trifunctional branched polyoxypropylene polymer, a trifunctional branched polyoxypropylene polymer is more preferably a terminus triethoxysilyl group having side chains triethoxysilyl groups at both ends.

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 of not extremely reducing.

  The molecular weight of the trialkoxysilyl group-modified polyoxyalkylene polymer is preferably 3,000 to 50,000 from the viewpoint of being excellent in fast curability and storage stability and excellent in the balance between viscosity and flexibility, More preferably, it is 10,000 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.

The epoxy resin will be described below.
The adhesive composition of this invention is excellent in heat resistance, storage stability, and shear strength 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 polyphenol such as bixylenol with epichlorohydrin; aliphatic polyglycol such as glycerin, neopentyl glycol, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, polyethylene glycol, polypropylene glycol 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 curability and storage stability, excellent heat resistance, high shear strength, and excellent balance between viscosity and flexibility.
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 3 to 100 parts by mass with respect to 100 parts by mass of the trialkoxysilyl group-modified polyoxyalkylene polymer. From the viewpoint of excellent quick curing and storage stability, excellent heat resistance, high shear strength, and excellent balance between viscosity and flexibility, the amount of epoxy resin is the 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.

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 from the viewpoint of excellent storage stability and excellent heat resistance.

The polyether will be described below.
The polyether contained in the adhesive composition of the present invention is a compound having a number average molecular weight of 100 to 5,000 and a terminal hydroxy group blocked.
The polyether contained in the adhesive composition of the present invention is inactive with respect to the trialkoxysilyl group-modified polyoxyalkylene polymer and the curing catalyst contained in the adhesive composition of the present invention. Will not be 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 polymers and curing catalysts, fast curing, and excellent storage stability to trialkoxysilyl group-modified polyoxyalkylene polymers.

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 terminal hydroxy group is blocked with an alkyl group, an alkoxy group, or an alkylsilyl group for the reason that the curing rate and the physical properties after curing do not change depending on the amount added and are easy to handle .
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 polyether has a number average molecular weight of 500 to 3,000 . 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. Further, Ru can lower viscosity no volatile components from the composition.
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 producing the polyether is particularly a polyether having one or more hydroxy groups (including polyoxyalkylene monool and polyoxyalkylene polyol). Not limited.

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.
The amount of the polyether is 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 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 with 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 more preferably 0.1 to 3.0 parts by mass with respect to 100 parts by mass of the trialkoxysilyl group-modified polyoxyalkylene polymer from the viewpoint of excellent quick curing and storage stability. preferable.

The adhesive compositions of the invention further N- silylamide compound including to enhance storage stability.
Examples of the N-silylamide compound that can be used in the present invention include compounds 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 that can be used in the present invention includes a compound represented by the above formula (2) and a partial hydrolysis-condensation product 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. 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.

  If the N-silylamide compound used for this invention is mix | blended in the moisture curable resin composition containing the inorganic filler mentioned later, storage stability can be improved like the case where a silyl ester is mix | blended.

The N-silylamide compound is preferably a compound represented by the formula (2) from the viewpoint of being superior in storage stability, and more preferably N-trimethylsilyloleic acid amide and 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 trialkoxysilyl group-modified polyoxyalkylene polymer from the viewpoint of being superior in storage stability. More preferred is part by mass.

The adhesive composition of the present invention can further contain fumed silica.
When the adhesive composition of the present invention further contains fumed silica, the resin is reinforced and higher 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 of better storage stability than hydrophilic fumed silica.
It is preferable that the average particle size of fumed silica is 0.005 to 0.5 μm because the effect of reinforcement 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 storage stability, balance between shear strength and viscosity of the composition. preferable.

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 dispersibility in the resin, 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 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 that the initial strength is exhibited and unnecessary residual moisture is negligible. preferable. Furthermore, in order to facilitate mixing with the adhesive composition, water is preferably mixed with an appropriate filler or resin to form a paste.

The adhesive composition of the present invention is superior in rapid curability, and can further contain an amino group-substituted alkoxysilane compound and / or a derivative thereof in order to enhance adhesiveness.
The amino group-substituted alkoxysilane compound or derivative thereof used in the present invention is
For example, H ₂ NCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
H ₂ NCH ₂ CH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃ ,
H ₂ NCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
H ₂ NCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃ ,
An amino group-substituted alkoxysilane, and the amino group-substituted alkoxysilane
A reaction product with an epoxy silane compound such as
Although the reaction material with the methacryloxysilane compound like this is mentioned, it is not limited to this.

  Furthermore, a derivative obtained by reacting a methacryloxysilane compound with an amino group-substituted alkoxysilane compound can obtain more preferable adhesion and stability during storage. A methacrylsilane compound and an amino group-substituted alkoxysilane that are actively reacted at a temperature up to about 160 ° C. or a simple addition of a methacrylsilane compound may be used. However, when a considerable amount of unreacted amino group remains, it reacts with the epoxy resin and gels. Therefore, when an amino group-substituted alkoxysilane compound or / and its derivative is added, the two-component type is used. It is preferable.

  The amino group-substituted alkoxysilane compound and / or its derivative may be a single amino group-substituted alkoxysilane compound, a single derivative of an amino group-substituted alkoxysilane compound, or an amino group-substituted alkoxysilane compound and its derivatives. It may be in the form of a mixture of two or more. Such an amino group-substituted alkoxysilane compound can be produced by a known method, but commercially available products such as those manufactured by Nippon Unicar Co., Ltd. and Shin-Etsu Chemical Co., Ltd. can also be used.

Examples of amino group-substituted alkoxysilane compounds that can be preferably used in the present invention include diaminosilane KBM603 manufactured by Shin-Etsu Chemical Co., Ltd., a reaction product of KBM603 and methacrylsilane KBM503 manufactured by Shin-Etsu Chemical Co., Ltd., KBM603 and Shin-Etsu Chemical Co., Ltd. A reaction product with Epoxysilane KBM403 manufactured by the company is mentioned.
The amount of the amino group-substituted alkoxysilane compound and / or its derivative (the total amount of these when the amino group-substituted alkoxysilane compound and its derivative are used in combination) is trialkoxysilyl from the viewpoint of excellent fast curing and adhesiveness. The amount is preferably 0.2 to 20 parts by mass, particularly preferably 0.4 to 10 parts by mass with respect to 100 parts by mass of the group-modified polyoxyalkylene polymer. If it is less than 0.2 parts by mass, adhesiveness cannot be expected, and if it exceeds 20 parts by mass, there is a problem in stability during storage such as gelation.

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 viewpoints of generating no harmful substances such as dioxins and phosphine, being excellent in rapid curability and 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 filler may be surface-treated. Examples of the surface treatment agent include fatty acids, silane compounds, and resin acids. Among these, fatty acids and silane compounds are preferable from the viewpoint of being excellent by dispersion in a resin.

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, rosin acid, and the like.
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 balance between flame retardancy and the 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 carbon black, fused silica, silica sand, calcium silicate, mica, talc, alumina, montmorillonite, and other thermally conductive fillers such as aluminum nitride and boron nitride, 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.
From the viewpoint that the adhesive composition of the present invention further contains water when it contains water, a trialkoxysilyl group-modified polyoxyalkylene polymer, an epoxy resin, a ketimine, a polyether, and a main agent containing a curing catalyst; One of the preferred embodiments is a two-component type having at least a curing agent containing water. Fumed silica, surface-treated calcium carbonate, flame retardants, and additives can be added to the main agent and / or curing agent, respectively.

  The adhesive composition of the present invention can be cured at room temperature (5-35 ° C.), but can be cured at a higher temperature in order to further increase the curing rate. In addition, the adhesive composition of the present invention can be cured by moisture in the atmosphere, moisture contained in a component such as a filler that can be contained in the composition, moisture adhered to the adherend, and the like. Can do.

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, it has excellent adhesion to metal, plastic, rubber, glass, and ceramic. 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.

Examples of the use of the adhesive composition of the present invention include an adhesive, a sealing material, a coating material, a primer, a paint, and a potting material.
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 1
Polymerization of propylene oxide was performed using dehydrated polyoxypropylene diol (linear, number average molecular weight of about 3,000, number of hydroxy groups per molecule: 2) as an initiator, and hydroxyl terminal having a number average molecular weight of about 20,000. Polypropylene oxide 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 mass of the obtained bifunctional allyl polypropylene oxide, 150 ppm of an isopropanol solution having a platinum content of 3 wt% of 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 polyoxyalkylene polymer 1.

(2) Trialkoxysilyl group-modified polyoxyalkylene polymer 2
Hydroxyl-terminated polypropylene having a number average molecular weight of about 20,000 by polymerization of propylene oxide using dehydrated polyoxypropylene triol (branched, number average molecular weight of about 3,000, number of hydroxy groups per molecule: 3) as an initiator. The oxide 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.
The following chemical formula: HSi (Si (OCH ₃ ) ₃ is used for 100 parts by mass of the obtained bifunctional allylpolypropylene oxide, using 150 ppm of an isopropanol solution containing 3 wt% platinum as a platinum vinylsiloxane complex as a catalyst.
And 90 ° C. for 2 hours to obtain a polymer having a trimethoxysilyl group (terminal silyl branched 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 3 trimethoxysilyl groups per molecule at the molecular end.

<Production of end-capped polyether>
(1) End-capped polyether 1
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.

(2) End-capped polyether 2
The hydroxyl group terminal of dried polyoxypropylene diol having a number average molecular weight of 4000 (trade name: Exenol 510, manufactured by Asahi Glass Co., Ltd.) is alcoholated with sodium hydroxide, and then reacted with methyl chloride to convert the terminal hydroxy group to methyl ether (methoxy). Group). The complete disappearance of the hydroxyl group was confirmed by IR spectrum.

<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 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, thickening rate, tack free time, shear strength, heat resistance, and flame retardancy by the following methods. The results are shown in Tables 1, 2, and 3.
(1) Thickening rate (storage stability)
Thickening rate Initial viscosity: Initial viscosity (unit: Pa · s) of the adhesive composition obtained as follows using a TV20 viscometer (rotor # 7, 1 rpm) at 20 ° C. Was measured.
-Viscosity after storage promotion: The adhesive composition obtained as described below was placed at 70 ° C for 24 hours, and the viscosity (unit: Pa · s) after storage promotion of the adhesive composition was the initial viscosity. Measured in the same manner as above.
The thickening rate was obtained by applying the initial viscosity obtained as described above and the viscosity after storage acceleration to the following formula.
Thickening rate (%) = viscosity after accelerated storage / initial viscosity × 100

(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. Further, after the obtained specimen was placed under 70 ° C. for 1 hour, the shear strength of the specimen placed under 70 ° C. for 1 hour under the same conditions as the initial shear strength was measured (first table).
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 2).
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 described above (Table 3). .

(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 table, and they were mixed using a planetary mixer to obtain an adhesive composition.

Each component shown in Table 1 is as follows.
Trialkoxysilyl group-modified polyoxyalkylene polymers 1 and 2: manufactured as described above MS polymer S-303: dialkoxysilyl group-modified polyoxyalkylene polymer, trade name MS polymer S-303, Inc. Made by Kaneka Corporation ・ BPA type epoxy resin: bisphenol A type epoxy resin, trade name YD-128, Toto Kasei Co., Ltd., epoxy equivalent 190 g / equivalent ・ Surface treatment calcium carbonate: reaction of biscolite MBP (tolylene diisocyanate and stearyl alcohol Calcium carbonate surface-treated with the product), manufactured by Shiraishi Calcium Co., Ltd. • Fumed silica: hydrophobic fumed silica, R-972, manufactured by Nippon Aerosil Co., Ltd., particle size 0.016 μm
End-capped polyether 1: manufactured as described above. End-capped polyether 2: manufactured as described above. Polyether polyol: polyoxypropylene glycol, trade name Exenol 510, Asahi Glass Co., Ltd. DINP: diisononyl Phthalates, J Plus Co., Ltd. ・ Vinylsilane: KBM 1003, Shin-Etsu Chemical Co., Ltd. ・ Epoxysilane: KBM 403, Shin-Etsu Chemical Co., Ltd. ・ Sililamide: manufactured as described above ・ 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 )

As is apparent from the results shown in Table 1, Comparative Examples I-1 and II having a small amount of epoxy resin were inferior in shear strength and heat resistance. Comparative Example I-3 in which the epoxy resin was excessive was poor in storage stability, and Comparative Examples I-4 and 5 in which the ketimine equivalent was not appropriate were inferior in shear strength. Comparative Example I-6 containing an ester plasticizer instead of the end-capped polyether was inferior in rapid curability after storage. Comparative Example I-7 containing no trialkoxysilyl group-modified polyoxyalkylene polymer was inferior in rapid curability. Comparative I-8 containing a polyether polyol that does not block the ends was inferior in storage stability and fast curability after storage.
In contrast, Examples I-1 to 5 and Reference Examples I-6 and 7 have a low viscosity increase, excellent storage stability, fast curability, excellent fast curability after storage, and high shear strength. Thus, it was excellent in heat resistance. Example I-2 to 5 containing fumed silica was higher shear strength than Example I-1. Further, when Example I-1 and Reference Example I-7 which differ only in the presence or absence of silylamide were compared, Example I-1 containing silylamide was superior in storage stability.

<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 planetary mixer to obtain an adhesive composition.

Details of the components shown in Table 2 are as follows.
Trialkoxysilyl group-modified polyoxyalkylene polymer: Same as trialkoxysilyl group-modified polyoxyalkylene polymer 1 in Table 1. BPA type epoxy resin: bisphenol A type epoxy resin, trade name YD-128, Toto Kasei Co., Ltd. Company, epoxy equivalent 190 g / equivalent ・ Aluminum hydroxide (untreated, 8 μ): Aluminum hydroxide, surface untreated, particle size 8 μm, B103, Nippon Light Metal Co., Ltd. ・ Aluminum hydroxide (untreated, 2 μ): Aluminum hydroxide Surface untreated, particle size 2 μm, B703, Nippon Light Metal Co., Ltd. ・ Colloidal aluminum hydroxide (untreated, 1 μm): Colloidal aluminum hydroxide, surface untreated, particle size 1 μm, BF013, Nippon Light Metal Co., Ltd. ・ Aluminum hydroxide (Fatty acid treatment, 2μ): Aluminum hydroxide, surface fatty acid treatment, particle size 2 μm, B70 S, Nippon Light Metal Co., Ltd. Aluminum hydroxide (silane treatment, 2 μ): Aluminum hydroxide, surface silane treatment, particle size 2 μm, B703ST, Nippon Light Metal Co., Ltd. Aluminum hydroxide (fatty acid treatment, 1 μ): aluminum hydroxide, Surface fatty acid treatment, 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. Fumed silica: Hydrophobic fumed silica, R-972, manufactured by Nippon Aerosil Co., Ltd., particle size 0.016 μm
End-capped polyether: Same as end-capped polyether 1 in Table 1.
Vinyl silane: KBM 1003, Shin-Etsu Chemical Co., Ltd. Epoxy silane: KBM 403, Shin-Etsu Chemical Co., Ltd. Silyl amide: Same as silyl amide in Table 1 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 )
For each flame retardant, the surface treatment state and average particle diameter are shown in parentheses.

  As is apparent from the results shown in Table 2, Examples II-1 to 8 further containing flame retardant, colloidal calcium carbonate, or heavy calcium carbonate are fast-curing property, heat resistance, storage stability, shear strength. Excellent. In particular, Examples II-1 to 6 containing flame retardant in an amount of 30 to 70% by mass in the total weight of the adhesive composition are excellent in flame retardancy.

<Production of Adhesive Composition ( Reference Example III)>
The components shown in Table 3 were used in the amounts (parts by mass) shown in the table, and they were mixed using a planetary mixer to obtain a two-pack type adhesive composition.

Details of the components shown in Table 3 are as follows.
Trialkoxysilyl group-modified polyoxyalkylene polymer: Same as trialkoxysilyl group-modified polyoxyalkylene polymer 1 in Table 1. BPA type epoxy resin: bisphenol A type epoxy resin, trade name YD-128, Toto Kasei Co., Ltd. Company, epoxy equivalent 190 g / equivalent ・ Aluminum hydroxide (no treatment, 2 μ): Aluminum hydroxide, surface no treatment, particle size 2 μm, B703, Nippon Light Metal Co., Ltd. ・ Colloidal calcium carbonate (0.07 μ): Calfine 200, Maruo Calcium Co., Ltd., 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: the same as end-capped polyether 1 in Table 1. Vinyl silane: KBM 1003, Shin-Etsu Chemical Co., Ltd. Aminosilane: γ- (2-aminoethyl) aminopropyltrimethoxysilane, trade name KBM 603, 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 3, the amount of water is 1.3 equivalents relative to the alkoxy group of the trialkoxysilyl group-modified polyoxyalkylene polymer.

As apparent from the results shown in Table 3, trialkoxysilyl group-modified polyoxyalkylene polymer 100 parts by mass, epoxy resin 3 to 100 parts by mass, ketimine, molecular weight 100 to 5,000, and terminal hydroxy The amount of the imino group which ketimine has is 0.5-1.5 equivalent with respect to the epoxy group which an epoxy resin has, containing 5-50 mass parts of polyether by which the group was blocked, and a curing catalyst. A two-component adhesive composition ( Reference Example III-1) having a certain main agent and a curing agent containing water has a one-component adhesive composition ( Reference Example III-2, a curing agent). Better at initial shear strength in metal-to-metal bonding than

Claims (8)

A trialkoxysilyl group-modified poly having a trimethoxysilyl group and / or a triethoxysilyl group as a reactive group and an oxyalkylene group 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 100 parts by mass of an oxyalkylene polymer;
3 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;
5 to 50 parts by mass of a polyether having a number average molecular weight of 500 to 3,000 and a terminal hydroxy group blocked;
Containing a curing catalyst,
The amount of imino groups of the ketimine has found the epoxy groups of the epoxy resin has, Ri 0.5-1.5 equivalents der,
In the polyether, the terminal hydroxy group is blocked with an alkyl group, an alkoxy group or an alkylsilyl group,
Furthermore, the adhesive composition which contains 0.2-30 mass parts of N-silylamide compounds shown by following formula (2) with respect to 100 mass parts of said trialkoxysilyl 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.)
(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 claim 1, wherein the polyether main chain is a polyoxypropylene polymer.   The adhesive composition according to claim 1 or 2, wherein the trialkoxysilyl group-modified polyoxyalkylene polymer does not contain a urethane bond or a urea bond.   Furthermore, fumed silica is contained, The quantity of the said fumed silica is 1-10 mass parts with respect to 100 mass parts of the said trialkoxysilyl group modified polyoxyalkylene polymers, The any one of Claims 1-3 Adhesive composition.   Furthermore, it contains surface-treated calcium carbonate, and the amount of the surface-treated calcium carbonate is 10 to 100 parts by mass with respect to 100 parts by mass of the trialkoxysilyl group-modified polyoxyalkylene polymer. The adhesive composition described in 1.   Furthermore, it contains water, The amount 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. 6. Adhesive composition.   Furthermore, amino group substituted alkoxysilane compound or / and its derivative 0.2-20 mass parts is included with respect to 100 mass parts of said trialkoxysilyl group-modified polyoxyalkylene polymers. Adhesive composition.   The adhesive composition according to any one of claims 1 to 7, wherein a tack-free time under conditions of 20 ° C and 55% RH is 30 minutes or less.