JPH1017780A - Resin composition, curable adhesive and curable tacky adhesive - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition composed of a compound containing an acid anhydride group and a specific compound, having highly balanced adhesivity to a substrate and a storage stability as a one-pack type composition, curable with moisture without necessitating heating, irradiation, mixing of two liquids, etc., and useful as a curable (tacky) adhesive, etc. SOLUTION: This resin composition contains (A) a compound containing an acid anhydride group (e.g. a copolymer of an ethylenic acid anhydride such as itaconic anhydride and other copolymerizable monomer or an addition reaction product of maleic anhydride and a resin having unsaturated double bond in the main chain such as polybutadiene) and (B) a compound forming a primary amino group, secondary amino group or ammonia by reacting with water e.g. an imine compound such as a compound of the formula [R<1> to R<4> are each H, a 1-6C alkyl or an (alkyl-substituted)phenyl; X<1> to X<3> are each a 2-6C alkylene; (n) is 0 or 1], an enamine compound, a silamine compound, a silazane compound or an oxazolidine compound}.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a resin composition which can be cured by moisture.

[0002]

2. Description of the Related Art Curable resin compositions are widely used in various fields as adhesives, pressure-sensitive adhesives, adhesives such as sealing materials, and the like. As such a curable resin composition, for example, one that is cured by heating using a phenol resin or the like, one that is cured by mixing two liquids that use an epoxy resin, or the like, or a light that uses an acrylic resin or the like Curing by irradiation of radiation, etc., curing by moisture using silicone resin or the like, and curing by oxygen in air using polysulfide resin or the like.

[0003] Of these, there is no need for a heating device, a light / radiation irradiating device, and the like, and there is no need to measure and mix the two components. Attention has been paid.

Examples of so-called moisture-curable resin compositions which cure with moisture include moisture-curable polyurethane resins ("Polyurethane Resin Handbook", published by Nikkan Kogyo Shimbun, 1987), one-pack RTV silicone rubber, and modified silicone resins. ("Silicone Handbook" 19
1990 Nikkan Kogyo Shimbun (published by Nikkan Kogyo Shimbun), room temperature curing one-part epoxy resin using ketimine ("New development of epoxy resin curing agent", published by CMC Corporation in 1994), cyanoacrylate adhesive ("adhesion") Handbook (2nd
Edition) ”published by Nikkan Kogyo Shimbun in 1980) and polysulfite resin (“ High Performance Liquid Polymer Material ”published by Maruzen in 1990).

As a resin composition which is cured by oxygen in the air (hereinafter referred to as “oxygen-curable resin composition”), for example, a modified polysulfide resin (“High-performance liquid polymer material”, published by Maruzen Co., Ltd. in 1990) , Drying oil (from "Crosslinking Agent Handbook" Taiseisha, 1981)
And the like.

These moisture-curable resin compositions and oxygen-curable resin compositions include liquid reactive adhesives, solvent reactive adhesives, reactive hot melt adhesives, and adhesive (post-curable adhesives). ) It is suitable as a pressure-sensitive adhesive, a sealing material, a reactive hot-melt type sealing material, etc., and is already widely used in various fields.

On the other hand, an acid anhydride resin composition using an acid anhydride resin as a base resin is known as a resin composition capable of exhibiting a very wide range of properties, but is particularly excellent in adhesion to various substrates. Is widely used.

[0008] An acrylic resin composition using an acrylic resin as a base resin is known as a resin composition capable of exhibiting a very wide range of properties. Anaerobic polymerization reaction, two-component mixing, etc. are used, which have excellent adhesion to various substrates, and can be cured into various forms such as rubber-like soft cured products and glass-like hard cured products. It is also highly useful in terms of its capability ("Adhesion Handbook (2nd edition)" 19
1980 Published by Nikkan Kogyo Shimbun).

However, any of the conventional moisture-curable resin compositions and oxygen-curable resin compositions satisfy both good adhesion to the substrate and sufficient storage stability as a one-pack type at the same time. Was not something to do.

Further, the conventional anhydrous acid resin compositions cannot be easily cured like resin compositions which are cured by moisture or oxygen in the air. In order to cure the conventional acrylic resin composition, a curing device such as a heating device or a light / radiation irradiating device is required, two-component measurement and mixing are required, and oxygen shielding is required. And it could not be easily cured.

[0011]

SUMMARY OF THE INVENTION In view of the above-mentioned circumstances, the present invention satisfies a good balance between good adhesion to a substrate and sufficient storage stability as a one-pack type at the same time. Object of providing a resin composition that can be cured without the need for a radiation irradiation device, two-component measurement mixing, blocking of oxygen, and the like, and a curable adhesive and a curable adhesive comprising the same. And

[0012]

The resin composition of the present invention comprises:
It comprises an acid anhydride group-containing compound (A1) and a compound (B) which produces at least one of a primary amino group, a secondary amino group and ammonia by reaction with water. Hereinafter, the present invention will be described in detail.

[0013] The resin composition of the present invention contains an acid anhydride group-containing compound (A1). The compound containing an acid anhydride group (A
1) is composed of an organic compound having anhydrous acidity, and may be any of a monomer, an oligomer, and a polymer. The acid anhydride-containing compound (A1) includes carbon, hydrogen,
It contains organic compound constituent atoms such as oxygen, nitrogen, sulfur, and phosphorus.

The acid anhydride group contained in the acid anhydride group-containing compound (A1) may be present at the terminal of the molecular bone or as a side chain, and its structure and molecular weight are not limited. However, an organic compound having an average of two or more acid anhydride groups per molecule is preferable. Here, the average number of anhydride groups per molecule can be determined by dividing the total number of anhydride groups in the anhydride group-containing compound (A1) by the total number of molecules in the anhydride group-containing compound (A1). it can.

When the compound containing the acid anhydride group (A1) is solid at room temperature, which can be melted by heating, and the compound is solid at room temperature, the resin composition of the present invention can be used as a hot melt. It can be a melt-type composition.

The acid anhydride-containing compound (A1) may have another functional group in the molecule, if necessary. Examples of the functional group include a hydroxyl group, an epoxy group, a carboxyl group, a saturated aliphatic alkyl group, an unsaturated aliphatic alkyl group, an alicyclic alkyl group, an aromatic alkyl group, a vinyl group, an allyl group, an isocyanate group, and an alkoxyl group. Group, silyl group, halogen group, phosphate group, thioether group, thiol group, thiocarboxyl group, amide group, urethane group,
Imide group, carbonate group, sulfonic acid group, carbonyl group, tertiary amino group, acryloyl group, methacryloyl group, group which forms at least one of primary amino group, secondary amino group and ammonia by reaction with water, etc. Is mentioned.

Examples of the acid anhydride group-containing compound (A1) include the following. Phthalic anhydride, trimellitic anhydride, trimellitic anhydride triglyceride, trimellitic anhydride ethylene glycol ester, pyromellitic anhydride, pyromellitic anhydride triglyceride, pyromellitic anhydride ethylene glycol ester, benzophenone anhydride-3,4,3 ', 4'-tetracarboxylic acid, chlorendic anhydride, pyromellitic dianhydride, tetrabromophthalic anhydride.

Maleic anhydride, succinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hymic anhydride, methylhymic anhydride;
Methylbutenyltetrahydrophthalic anhydride, 4- (4-
Methyl-3-pentenyl) tetrahydrophthalic anhydride,
Trialkyltetrahydrophthalic anhydride, methylcyclohexenedicarboxylic anhydride, methylcyclohexenetetracarboxylic anhydride, hydrogenated trimellitic anhydride, hydrogenated trimellitic anhydride triglyceride, hydrogenated trimellitic anhydride ethylene glycol ester, hydrogenated anhydride Pyromellitic acid, hydrogenated pyromellitic anhydride triglyceride, hydrogenated pyromellitic anhydride ethylene glycol ester, alkenyl succinic anhydrides such as dodecenyl succinic anhydride, polyadipic anhydride, polyazeleic anhydride, polysebacic anhydride, poly (Ethyl octadecane diacid) anhydride, poly (phenylhexadecane diacid) anhydride.

Unsaturated fatty acids such as linoleic acid, linolenic acid, and eleostearic acid, or methyl ester thereof, addition products of triglycerides with maleic anhydride; ethylenic anhydrides such as itaconic anhydride, maleic anhydride and others (Eg, styrene, α-methylstyrene, acrylates, methacrylates, acrylamide, methacrylamide, α-olefins, polyunsaturated fatty acid derivatives, vinyl ethers, vinyl acetate, ethylene, etc.) With polybutadiene, polyisoprene, EPDM rubber, natural rubber, SB
A maleic anhydride addition product of a resin having an unsaturated double bond in the main chain, such as S, SEBS, or SIS.

Examples of the above-mentioned acid anhydride group-containing compound (A1) include, in addition to the above-mentioned acid anhydride group-containing compounds, a hydroxyl group, an epoxy group, a carboxyl group, a saturated aliphatic alkyl group, an unsaturated aliphatic alkyl group, an aliphatic Aliphatic alkyl group, aromatic alkyl group, vinyl group, allyl group, isocyanate group, alkoxyl group, silyl group, halogen group, phosphoric acid group, thioether group, thiol group, thiocarboxyl group, amide group, urethane group, imide group, Functional groups such as carbonate groups, sulfonic acid groups, carbonyl groups, tertiary amino groups, acryloyl groups, methacryloyl groups, and groups that form at least one of primary amino groups, secondary amino groups, and ammonia by reaction with water Are bonded. These may be used alone or in combination of two or more.

The method for producing the acid anhydride-containing compound (A1) is not particularly limited, and examples thereof include the following methods. 1) Ethylene anhydride such as itaconic anhydride and maleic anhydride and other copolymerizable monomers (for example, styrene, α-methylstyrene, acrylates, methacrylates, acrylamide, methacrylamide, etc.) Are copolymerized by radical polymerization or the like.

2) Polybutadiene, polyisoprene, E
A resin having an unsaturated double bond in the main chain, such as PDM rubber, natural rubber, SBS, SEBS, or SIS, is subjected to an addition reaction with maleic anhydride or the like.

3) A compound having two or more acid anhydride groups in a hydroxyl group of a hydroxyl group-containing compound such as polyether such as polyethylene glycol or polypropylene glycol, or one or more acid anhydride groups and one or more carboxyl groups. The compound having is condensed.

Any of the above methods can be carried out at normal temperature or, if necessary, under heating, under atmospheric pressure or, if necessary, at a pressure higher than or lower than atmospheric pressure. Any of the above methods can be performed under anhydrous conditions.

In any of the above methods, a compound which is solid at room temperature and can be melted by heating is used as a starting material, or an appropriate compound which is liquid even at room temperature is selected and used as a starting material. An acid anhydride group-containing compound (A1) which can be melted and is solid at ordinary temperature can be obtained.

The above-mentioned acid anhydride group-containing compound (A1) comprises a hydroxyl group, an epoxy group, a carboxyl group, an unsaturated aliphatic alkyl group, a vinyl group, an allyl group, an isocyanate group, an alkoxyl group, a silyl group, a halogen group, a phosphate group, Thiol group, thiocarboxyl group, amide group, urethane group, imide group, carbonate group, sulfonic acid group, carbonyl group,
When it has a functional group such as an acryloyl group or a methacryloyl group, the above-mentioned acid anhydride group-containing compound (A1) is heated by reacting with a solid resin at a normal temperature at which the functional group capable of reacting with the functional group can be melted by heating. Can be solidified at normal temperature at which it can be melted.

When any of the starting materials or the product is a material having a high viscosity at room temperature or is a solid, under an appropriate heating condition, or ethyl acetate, cyclohexane, aromatic hydrocarbon, ether , Dioxane, halogenated hydrocarbon, ketone and the like. The above-mentioned production methods can be carried out alone or in combination of two or more.

The resin composition of the present invention comprises a compound (B) containing an acid anhydride group-containing compound (A1) and producing at least one of a primary amino group, a secondary amino group and ammonia by reaction with water. ).

The above compound (B) reacts with water such as moisture contained in the air or moisture contained in a substrate to which the compound is applied, and thereby reacts with at least one of a primary amino group, a secondary amino group and ammonia. Generate

The compound (B) may be any of a monomer, an oligomer and a polymer. The compound (B) contains an organic compound constituent atom such as carbon, hydrogen, oxygen, nitrogen, sulfur, and phosphorus.

The compound (B) used together with the acid anhydride group-containing compound (A1) is not limited in its structure or molecular weight, but is preferably a primary amino group and / or a secondary amino group, Further, it is preferable that the polymer does not have another functional group capable of reacting with the acid anhydride group in the molecule. The compound (B) further comprises at least one of a primary amino group, a secondary amino group, and ammonia by a reaction with water such as moisture contained in air or moisture contained in a substrate to which the compound is applied.
Although it generates seeds, it is more preferable that the total number of primary amino groups and secondary amino groups generated by the reaction with water is at least 2 on average per molecule.

Here, the total number of primary amino groups and secondary amino groups on average per molecule is defined as the number of primary amino groups and secondary amino groups that can be produced by the reaction of compound (B) with water. Can be determined by dividing by the total number of molecules of the compound having at least one of a primary amino group and a secondary amino group that the compound (B) can produce by reaction with water.

The above-mentioned compound (B) may optionally have other functional groups such as a hydroxyl group, an epoxy group, a carboxyl group, an acid anhydride group, a saturated aliphatic alkyl group, an unsaturated aliphatic alkyl group and an alicyclic alkyl group. Group, aromatic alkyl group, vinyl group, allyl group, isocyanate group, alkoxyl group, silyl group, halogen group, phosphoric acid group, thioether group, thiol group, thiocarboxyl group, amide group, urethane group, imide group, carbonate group , A sulfonic acid group, a carbonyl group, a tertiary amino group, an acryloyl group, a methacryloyl group, or the like in the molecule.

If the compound (B) is solid at room temperature, which can be melted by heating, and the compound is solid at room temperature, the resin composition of the present invention can be used in a hot melt type. It can be a composition.

Examples of the compound (B) include a primary amino group-containing compound, a secondary amino group-containing compound, a polyamidoamine compound, a dehydration condensate of an aldehyde and / or a ketone, an imine compound, and an enamine. Compounds, silamine compounds, silazane compounds, oxazolidine compounds and the like. More specifically, examples of the compound (B) include an imine compound (1) represented by the following general formula (1).

[0036]

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In the formula, R ¹ , R ² , R ³ and R ⁴ are the same or different and represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or a phenyl group having or not having an alkyl group. X ¹ , X ² and X ³ are the same or different and represent an alkylene group having 2 to 6 carbon atoms. n represents an integer of 0 to 1.

More specifically, the imine compound (1) is, for example, 2,5,8-triaza-1,8-nonadiene, 2,10-dimethyl-3,6,9-triaza-2, 9-undecadiene, 2,10-diphenyl-
3,6,9-triaza-2,9-undecadiene, 3,
11-dimethyl-4,7,10-triaza-3,10-
Tridecadiene, 3,11-diethyl-4,7,10-
Triaza-3,10-tridecadiene, 2,4,12,
14-tetramethyl-5,8,11-triaza-4,1
1-pentadecadiene, 2,4,20,22-tetramethyl-5,12,19-triaza-4,19-trieicosadiene, 2,4,15,17-tetramethyl-5
8,11,14-tetraaza-4,14-octadecadiene and the like.

Other examples of the compound (B) include an imine compound (2) obtained by reacting at least one of components capable of reacting with the imine compound. More specifically, the components capable of reacting with the imine compound include, for example, styrene oxide, butyl glycidyl ether, allyl glycidyl ether, pt
tert-butylphenyl glycidyl ether, p-se
c-butylphenyl glycidyl ether, m, p-cresyl glycidyl ether, p-cresyl glycidyl ether, vinylcyclohexanedioxide, versidic acid glycidyl ester, cardanol-modified glycidyl ether, dimer acid glycidyl ester, 1,6-hexanediol di Examples include glycidyl ether, resorcinol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, and neopentyl glycol diglycidyl ether.

The compound (B) further includes an imine compound (3) represented by the following general formula (3).

[0041]

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In the formula, R ¹ , R ² , R ³ and R ⁴ are the same or different and represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or a phenyl group having or not having an alkyl group. R ⁵ represents the skeleton of the base diamine,
As the diamine, polyoxyethylene diamine,
Polyetherdiamines such as polyoxypropylenediamine; aliphatic aromatic diamines such as xylenediamine; aromatic diamines such as phenylenediamine and diaminodiphenylmethane; alicyclic diamines such as mensendiamine and isophoronediamine; 3,9-bis (3 -Aminopropyl)-
Heterocyclic diamines such as 2,4,8,10-tetraoxaspiro [5,5] undecane; aliphatic diamines such as hexamethylene diamine;

Examples of the compound (B) include, for example, an imine compound (4) represented by the following general formula (4):
And the like.

[0044]

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Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R
⁶ is the same or different and represents hydrogen, an alkyl group having 1 to 6 carbon atoms, or a phenyl group having or not having an alkyl group. R ⁷ is a skeleton of a base triamine, which is a polyether triamine such as an aliphatic triamine derived from a triol; an alicyclic triamine such as a polycycloaliphatic triamine; a polycycloaliphatic having an allylamine Represents an alicyclic / aromatic triamine such as fatic triamine.

The compound (B) further includes an imine compound (5) represented by the following general formula (5-1) or (5-2).

[0047]

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In the formula, R represents hydrogen, a hydrocarbon group or a substituted hydrocarbon group. R ¹ represents a divalent hydrocarbon group or a divalent substituted hydrocarbon group. n represents an integer of 1 to 6.

More specifically, examples of the imine compound (5) include the following. 4,
7,10-triaza-3,10-tridecadiene, 3,
11-dimethyl-4,7,10-triaza-3,10-
Tridecadiene, 5,8,12-triaza-4,12-
Heptadecadiene, 4,13-diisopropyl-5,
8,12-triaza-4,12-heptadecadiene,
3,11-dicyclohexenyl-4,7,10-triaza-3,10-tridecadiene, 7,10,13-triaza-6,13-nonadecadiene, 3,11-diallyl-4,7,10-triaza- 3,10-tridecadiene, 4,13-dicyclopentyl-5,8,12-triaza-4,12-heptadecadiene, N, N'-di (allylidiene) -1,4-benzenediamine, N- (2-
Propylidene) -1,5-pentanediamine, N- (1
-Propylidene) -1,6-hexanediamine, N,
N'-di (2-propylidene) 3-aza-1,5-pentanediamine, N- (2-butylidene) -1,4-cyclohexanediamine, N, N'-di (2-butylidene)
-3,6-aza-1,8-octanediamine.

Other examples of the compound (B) include an imine compound (6) represented by the following general formula (6-1) or (6-2).

[0051]

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In the formula, R represents hydrogen, a hydrocarbon group or a substituted hydrocarbon group. R ¹ represents a divalent hydrocarbon group or a divalent substituted hydrocarbon group. n represents an integer of 1 to 6. X
Represents the remaining portion of the monoepoxy compound molecule, where one X is hydrogen and the other represents the remainder of the compound when the epoxy group in the compound is terminal.

More specifically, examples of the imine compound (6) include the following. 5,
8,11-Triaza-2,4,12,14-tetramethyl-8- (2-hydroxy-2-phenyl) ethyl-
4,11-pentadecadiene, 4,7,10-triaza-3,11-dimethyl-7- (2-hydroxy-2-phenyl) ethyl-3,10-tridecadiene, 5,8,
11-triaza-2,4,12,14-tetramethyl-
8- (2-hydroxy-3-allyloxy) propyl-
4,11-pentadecadiene, 5,8,11-triaza-3,13-dimethyl-8- (2-hydroxy-3-allyloxy) -propyl-4,11-pentadecadiene,
4,7,10-Triaza-3,11-dimethyl-7-
(2-hydroxycyclohexyl) 3,10-tridecadiene, 5,8,11-triaza-3,13-dioctyl-8- (2-hydroxy-3-pentoxy) -propyl-4,11-pentadecadiene, 5, 8,11-Triaza-3,13-didodecyl-8- (2-hydroxy-
3-vinyloxy) -propyl-4,11-pentadecadiene.

4,7,10-Triaza-3,11-dimethyl-7- (2,3-dihydroxy) propyl-3,1
0-tridecadiene, 5,8,11-triaza-3,1
3-dimethyl-8- (2-hydroxy) dodecyl-4,
11-pentadecadiene, 5,8,11-triaza
3,13-dioctadecyl-8- (2-hydroxy) octadecyl-4,11-pentadecadiene, 5,8,1
1-triaza-3,13-diisopropyl-8- (2-
(Hydroxy) tetradecyl-4,11-octadecadiene, 5,8,11-triaza-3,13-dimethyl-8
-(2-hydroxy-2-cyclohexyl) -ethyl-
3,10-tridecadiene.

5,8,11-triaza-3,13-dimethyl-8- (2-hydroxy-3-pentachlorophenyloxy) propyl-4,11-pentadecadiene,
4,7,10-Triaza-3,11-dimethyl-7-
(2-hydroxy-3-chloro) -propyl-3,10
-Tridecadiene, 5,8,11-Triaza-3,13
-Dioctyl-8- (2-hydroxy-3-pentanolyloxy) propyl-4,11-pentadecadiene,
5,8,11-triaza-2,4,12,14-tetramethyl-8- (2-hydroxy-3-octadecanonyloxy) propyl-4,11-pentadecadiene;
8,11-Triaza-2,4,12,14-tetraoctyl-8- (2-hydroxy-3-benzoyloxy)
Propyl-4,11-pentadecadiene, 4,7,10
-Triaza-3,11-dimethyl-7- (2-hydroxy-3-cyclohexanonyloxy) propyl-3,1
0-tridecadiene, 5,8,11,14-tetraaza-2,4,15,17-tetramethyl-8,11-di [(2-hydroxy-2-phenyl) ethyl] -4,1
4-octadecadien.

5,8,11,14-tetraaza-2,
4,15,17-tetramethyl-8,11-di [(2-
Hydroxy-3-allyloxy) propyl] -4,14-
Octadecadienes, 5,8,11,14-tetraaza-
2,4,15,17-tetramethyl-8,11-di [(2-hydroxy-3-phenyloxy) propyl]
-4,14-octadecadien, 5-8-diaza-4-
Methyl-8-di [(2-hydroxy-2-phenyl) ethyl] -4-octene, 5,8,11-triaza-2,
4,12,14-tetramethyl-8- (2-hydroxy-3-glycidyloxy) propyl-4,11-pentadecadiene, 4,7,10-triaza-3,11-dimethyl-7- (2- (Hydroxy-2-epoxycyclohexylethyl) -3,10-tridecadiene.

5,8,11-Triaza-2,4,12,
14-tetramethyl-8- (2-hydroxyethyl)-
4,11-pentadecadiene, 5,8,11-triaza-2,4,12,14-tetramethyl-8- (2-hydroxy-3-hydroxyethoxy) propyl-4,11
-Pentadecadiene, 5,8,11-triaza-2,
4,12,14-tetramethyl-8- (2-hydroxy-3-hydroxypropoxy) propyl-4,11-pentadecadiene, 5,10,15-triaza-10 (2
-Hydroxy-3-hydroxypropoxy) propyl 4,14-octadecadiene, 3,12,18-triaza-12 (2-hydroxy-3-propoxy) propyl-2,17-eicosadiene.

Other examples of the compound (B) include an imine compound (7) represented by the following general formula (7).

[0059]

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In the formula, R 'represents the backbone of the base diamine. R ² represents an organic group introduced based on the aldehyde or ketone used to make this compound.
R ³ represents an organic group or hydrogen introduced based on the aldehyde or ketone used to make this compound. n
Represents a number of 1 to 20. R ⁴ is hydrogen or the following general formula (71);

[0061]

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Wherein R ⁵ represents hydrogen or a methyl group; X represents an organic group introduced based on the monoepoxide used to make this compound.

The compound (B) further includes an imine compound (8) represented by the following general formula (8-1), (8-2) or (8-3).

[0064]

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In the formula, X represents the residual chain of the polyoxyalkylenediamine used to make this compound. Y
Represents the residual chain of the polyoxyalkylene triamine used to make this compound. Z represents the remaining chain of the polyoxyalkylene polyamine having a polyester polyol in the molecular chain used to make this compound.
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R
^{9, R 10, R 11,} R 12 represents hydrogen, an alkyl group or a phenyl group having 1 to 6 carbon atoms. n represents an integer of 4 to 6.

The compound (B) includes, for example, the following imine compounds. 1,2-ethylenebis (isopentylideneimine), 1,2-hexylenebis (isopentylideneimine), 1,2-propylenebis (isopentylideneimine), p, p'-biphenylenebis (isopentylideneimine) ), 1,2-
Ethylenebis (isopropylideneimine), 1,3-propylenebis (isopropylideneimine), p-phenylenebis (isopentylideneimine).

The compound (B) further includes an enamine compound (9) represented by the following general formula (9-1) or (9-2).

[0068]

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In the formula, Y ^{1 to} Y ⁿ are the same or different,
Hydrogen, a hydrocarbon group, a substituted hydrocarbon group, or the following general formula (91);

[0070]

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Represents the following. R¹, R^Two, R^Three, R⁶, R⁷,
R⁸, R⁹, R^Ten, R¹¹Is the same or different and is hydrogen,
Show hydrocarbon group, substituted hydrocarbon group or substituted amino group
You. R ^Four, R^FiveAre the same or different and represent a hydrocarbon group,
Represents a substituted hydrocarbon group or a substituted amino group. X¹~ XⁿIs
Same or different, divalent hydrocarbon group or divalent substituted carbon
Represents a hydride group. n is 0 or a natural number. Also,
R¹, R^Two, R^Three, R^Four, R ^Five, R⁶, R⁷, R⁸, R
⁹, R^Ten, R¹¹Are connected to each other in a cyclic structure
It may be.

The compound (B) further includes a silamine compound (1) represented by the following general formula (11).

[0073]

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In the formula, R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are
The same or different represents a hydrocarbon group or a substituted hydrocarbon group. n represents 0 or a natural number. R ¹ represents the residue of the diamine after removing two primary amino groups. In particular, R
² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different and are an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 10 carbon atoms, and n is an integer of 0 to 10 And R ¹ is a group after removing two primary amino groups such as a xylylene group, a bis (phenylene) methane group, a bis (phenylene) sulfone group, a 2,2-bis (phenylene) propane group and a phenylene group. Aromatic or araliphatic primary diamine 6 to
It is preferably a divalent residue having 20 carbon atoms.

The compound (B) further includes a silane derivative represented by the following general formula (12).

[0076]

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In the formula, X, Y ^{1 to} Y ⁿ represent the remaining chain of the amine, diamine, polyamine, amide or urea used to make this compound. ^{R 1-1 ~R 1-n, R} 2-1 ~R
^2-n and R ^{3-1 to} R ^3-n are the same or different and represent a hydrocarbon group, a substituted hydrocarbon group or a substituted amino group. n represents a natural number. Further, R ^{1-1 to} R ^1-n , R ^{2-1 to} R ^2-n , R
^{3-1 to} R ^3-n , X, and Y ^{1 to} Y ⁿ may be bonded to each other to form a cyclic structure.

As the silane derivative represented by the above general formula (12), more specifically, for example, the following compounds may be mentioned. N, N'-bis (trimethylsilyl) urea, N-trimethylsilylacetamide, dimethyltrimethylsilylamine, diethyltrimethylsilylamine, N-trimethylsilylimidazole, t-butyldimethylsilylimidazole, N-trimethylsilylphenylurea, N-methyl-N-trimethylsilyltriure Fluoroacetamide, N-6,9-bis (trimethylsilyl) adenine, bis-N, N '-(trimethylsilyl) piperazine, t-butylaminotriethylsilane, t-butylaminotrimethylsilane. Other examples of the compound (B) include a silazane compound represented by the following general formula (13-1) or (13-2).

[0079]

Embedded image

Where R¹, R^Two, R^Three, R^4-1~
R^4-n, R^5-1~ R^5-n, R⁶, R⁷, R ⁸, R^9-1~
R^9-3, R^10-1~ R^10-3, R^11-1~ R^11-3Are the same or
Differently, hydrogen, hydrocarbon group, substituted hydrocarbon group or substituted
Represents an amino group and binds to each other to form a cyclic structure
It may be no longer. n represents 0 or a natural number
You.

The above general formula (13-1) or (13-2)
More specifically, the silazane compound represented by
For example, the following are mentioned. Hexamethyldisilazane, 1,1,3,3-tetramethyldisilazane,
2,2,5,5-tetramethyl-2,5-disila-1-
Azacyclopentane, 1,1,3,3,5,5-hexamethylcyclotrisilazane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasilazane, 1,3 , 5-Trimethyl-1,3,5-trivinylcyclotrisilazane, 1,3-bis (chloromethyl)
-1,1,3,3-tetramethyldisilazane, octamethylcyclotetrasilazane, 1,3-di-n-octyltetramethyldisilazane, 1,3-diphenyltetramethyldisilazane, 1,3-di ( (pt-butylphenethyl) tetramethyldisilazane, 1,3-divinyl-1,
3-diphenyl-1,3-dimethyldisilazane, 1,3
-Divinyltetramethyldisilazane, 1,1,3,3-
Tetraphenyl-1,3-dimethyldisilazane, nonamethyltrisilazane.

Examples of the compound (B) include oxazolidine compounds represented by the following general formula (14).

[0083]

Embedded image

In the formula, R ¹ is a divalent to tetravalent, straight-chain, branched or cyclic hydrocarbon group having 1 to 22 carbon atoms. R ² represents a methyl group, an ethyl group, an isopropyl group, an isoamyl group, a phenyl group or hydrogen. n is 2-4
Represents an integer.

The compound (B) according to the present invention may be used alone or in combination of two or more. Also, in particular,
When long-term storage is unnecessary, a compound containing a primary amino group and / or a secondary amino group such as an aliphatic polyamine, an aromatic polyamine, an araliphatic polyamine, an alicyclic polyamine, or a polyamide may be used in combination. .

The method for producing the compound (B) is not particularly limited, and examples thereof include the following methods.

When the above compound (B) is an imine compound. 1) A compound having a primary amino group, a carbonyl group and / or
Alternatively, a compound having an aldehyde group is subjected to a dehydration condensation reaction. 2) In particular, when the imine compound (2) is obtained from the imine compound (1), any method capable of reacting the imine compound (1) with a component capable of reacting with the imine compound (1) is used.

3) In particular, when the imine compound (6) is obtained from the imine compound (5), any method capable of reacting the imine compound (5) with the monoepoxy compound is used. 4) Particularly when the imine compound (6) is obtained from the imine compound (5), it is preferably at room temperature or 200 if necessary.
The imine compound (5) and the monoepoxy compound are mixed at a temperature up to ° C. and under atmospheric pressure or, if necessary, at or above atmospheric pressure or below atmospheric pressure. 5) Particularly when the imine compound (7) is obtained, a hydroxyl-containing polyamine obtained by reacting an epihalohydrin or a glycerin dihalohydrin which may have a substituent with a polyamine in the presence of an alkali metal hydroxide is converted to a ketone or a ketone or a polyamine. It is reacted with an aldehyde or further followed by an addition reaction with a monoepoxide.

When the above compound (B) is an enamine compound. 6) The compound having a secondary amino group and a carbonyl compound capable of being enolized are subjected to a dehydration condensation reaction by heating.

When the above compound (B) is a silamine compound. 7) React primary amine with halosilane. 8) In particular, when the silamine compound (1) is obtained, a primary diamine, a monohalosilane and, if necessary, a dihalosilane are mixed at 50 to 150 ° C. with ethyl acetate, cyclohexane, aromatic hydrocarbon, ether, dioxane, halogenated carbon. The reaction is performed in an inert solvent such as hydrogen or ketone in the presence of a tertiary amine such as pyridine or triethylamine.

When the above compound (B) is a silazane compound. 9) React ammonia with halosilane. When the compound (B) is an oxazolidine compound. 10) The β-amino alcohol is condensed with an aldehyde or ketone. 11) React ethyleneimine, aziridine compound and the like with aldehyde. 12) The Schiff base is reacted with the epoxy resin in the presence of a Lewis acid. 13) Using a metal halide such as lithium chloride as a catalyst,
Reacting the epoxy resin with aldoimine or ketoimine.

Each of the above methods must be carried out under anhydrous conditions, and particularly preferably carried out in a nitrogen stream. In addition, any of the above methods can be carried out at normal temperature or under heating if necessary, under atmospheric pressure, or at or above atmospheric pressure or under atmospheric pressure if necessary.

In any of the above methods, a compound which can be melted by heating and is solid at room temperature is used as a starting material, or an appropriate compound which is liquid even at room temperature is selected and used as a starting material to obtain a compound ( B) can be solid at normal temperature, which can be melted by heating.

The compound (B) may be a hydroxyl group, an epoxy group, a carboxyl group, an acid anhydride group, an unsaturated aliphatic alkyl group, a vinyl group, an allyl group, an isocyanate group, an alkoxyl group, a silyl group, a halogen group, or a phosphoric acid. When it has a functional group such as a group, a thiol group, a thiocarboxyl group, an amide group, a urethane group, an imide group, a carbonate group, a sulfonic acid group, a carbonyl group, an acryloyl group and a methacryloyl group, it can react with the functional group. Having a functional group,
In addition, the compound (B) can be made into a solid at room temperature which can be melted by heating by reacting with a solid resin at room temperature which can be melted by heating.

When any one of the starting materials or the product is a material having a high viscosity at room temperature or is a solid, under a suitable heating condition, ethyl acetate, cyclohexane, aromatic hydrocarbon, ether, etc. , Dioxane, halogenated hydrocarbon, ketone and the like. The above-mentioned production methods can be performed alone or in combination of two or more.

In the resin composition of the present invention, at least one of a primary amino group, a secondary amino group and ammonia is reacted with water with respect to the acid anhydride group-containing compound (A1).
The content of the seed-forming compound (B) is appropriately determined according to the degree of curing at the time when the curing reaction is completed, but is preferably contained in a weight ratio of 1/100 to 100/1. .

Further, when the compound (B) contains an acid anhydride group, and when the acid anhydride-containing compound (A1) reacts with water to form at least one of a primary amino group, a secondary amino group and ammonia. In this case, the resin composition of the present invention can be constituted by a single compound.

In the resin composition of the present invention, in addition to the compound (B) which forms at least one of a primary amino group, a secondary amino group and ammonia by reacting with an acid anhydride group-containing compound (A1) and water If a solvent capable of dissolving these compounds is added so that the mixture is a homogeneous solution, a solvent-type resin composition can be obtained.

The solvent is not particularly limited as long as it dissolves the material to be used, but includes a primary amino group and / or a secondary amino group, and another functional group capable of reacting with an acid anhydride group in the molecule. Are preferred. Examples of the solvent include inert solvents such as ethyl acetate, cyclohexane, aliphatic hydrocarbons, aromatic hydrocarbons, ethers, dioxane, halogenated hydrocarbons, and ketones. The above solvents may be used alone or in combination of two or more.

In producing the resin composition of the present invention, a compound (B) which forms at least one of a primary amino group, a secondary amino group and ammonia by reacting with an acid anhydride-containing compound (A1) and water. ), Other resins can be added as required.

The resin composition of the present invention can be made into a hot melt type composition by adding a thermoplastic resin, a solid tackifying resin and the like so that the composition is solid at room temperature. it can. When the resin composition of the present invention is applied to a substrate, the adhesion to the substrate can be improved by adding a tackifier resin or the like.

The thermoplastic resin and the tackifying resin are not particularly limited, and include low-molecular-weight resins to polymers, but those which can be mixed and dispersed in other materials to be used are more preferable. It does not have a secondary amino group and / or a secondary amino group and other functional groups capable of reacting with an acid anhydride group in the molecule. Examples of the thermoplastic resin and the tackifying resin include the following.

The thermoplastic resin includes ethylene-vinyl acetate copolymer resin, ethylene-ethyl acrylate copolymer resin, ethylene-methyl acrylate copolymer resin, propylene copolymer resin, vinyl chloride copolymer resin, vinyl acetate Resins, acrylic copolymer resins, polyamide resins, polyester resins, polyolefin resins, polyurethane resins, polycarbonate resins, and various modifications thereof.

Isoprene-styrene block copolymer resin, butadiene-styrene block copolymer resin, styrene-ethylene-butylene-styrene block copolymer resin, styrene-ethylene-propylene-styrene block copolymer resin, ethylene-propylene copolymer resin, Rubber resins such as butyl rubber, isoprene rubber, isobutylene rubber, acrylic rubber, nitrile rubber, urethane rubber, and various modified products thereof.

As the tackifying resin, rosin resin,
Rosin ester resin, rosin ester derivative, polymerized rosin resin, hydrogenated polymerized rosin resin, polymerized rosin ester resin, polymerized rosin ester derivative, hydrogenated rosin resin, hydrogenated rosin ester resin, hydrogenated rosin ester derivative, rosin phenol resin, terpene Resin, hydrogenated terpene resin,
Terpene phenol resin, hydrogenated terpene phenol resin, petroleum resin (aliphatic, aromatic, alicyclic, copolymer, coumarone indene resin), hydrogenated petroleum resin, alkylphenol resin, xylene resin, ketone resin , Styrene resin, modified styrene resin, epoxy resin and various modified products thereof.

The above resins may be used alone or in combination of two or more. The resin is preferably mixed and added in an amount of 5 to 2,000 parts by weight based on 100 parts by weight of the normal-temperature liquid component in the composition.

When the resin composition of the present invention is cured, a catalyst may be added if the curing time is to be further shortened or extended. As the above catalyst,
The following are mentioned.

Trimethylamine, triethylamine, dimethylcyclohexylamine, dimethylbenzylamine, 1,3-dimethylimidazolidinone, 1,2-dimethylimidazole, tetramethylethylenediamine, tetramethylpropane-1,3-diamine, tetramethylhexane-1 , 6-diamine.

Pentamethyldiethylenetriamine, pentamethyldipropylenetriamine, tetramethylguanidine, triethylenediamine, dimethylpiperazine, N
-Methyl-N '-(2-dimethylamino) -ethylpiperazine, N-methylmorpholine, N- (N', N'-dimethylaminoethyl) morpholine, dimethylaminoethanol, dimethylaminoethoxyethanol, N, N,
N'-trimethylaminoethyl-ethanolamine, N
-Methyl-N '-(2-hydroxyethyl) piperazine, N- (2-hydroxyethyl) morpholine, bis (2-dimethylaminoethyl) ether, ethylene glycol bis (3-dimethyl) aminopropyl ether;
Niax A-1 (Toyo Soda Co., Ltd.), TOYOCAT-
TF (manufactured by UCC), TOYOCAT-ETF
(Manufactured by U.C.C.), TOYOCAT-THN (U.C.
C. C. Tertiary amines; sodium methylate,
Basic catalysts such as sodium hydroxide, sodium hydroxide, and lithium carbonate.

Acidic catalysts such as boron trifluoride; dibutyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, dibutyltin diphthalate, dibutyltin marker peptide, dibutyltin thiocarboxylate, dibutyltin dimaleate, dibutyltin maleate laurate, Dibutyltin diacetylacetonate, dioctyltin laurate, dioctyltin malate, dioctyl field marker peptide, dioctyltin thiocarboxylate, tin naphthenate, tin octylate, tin stearate, tin acetylacetone, dimethyltin compound, tributyltin compound,
A reaction product of dibutyltin oxide and phthalic acid ester,
Organotin compounds such as sulfur-containing organotin compounds.

Phenylmercuric propionate, lead octenoate, organometallic aluminum compounds, organometallic iron compounds,
Organometallic compounds such as organometallic zinc compounds. Co-curing agents, hydrochloric acid, benzoyl chloride; sulfonic acid compounds such as p-toluenesulfonic acid; phosphate compounds, phosphite compounds. The above catalysts may be used alone or in combination of two or more.

The catalyst is preferably one that can be mixed and dispersed in other materials used. The above-mentioned catalyst may be appropriately added as needed, but the acid-containing compound (A1)
It is preferable to add about 0.01 to 10 parts by weight to 100 parts by weight.

In the case where the resin composition of the present invention is applied to a substrate, in order to further improve the adhesion to the substrate,
And / or an adhesion promoter may be added for other purposes. Examples of the adhesiveness improver include the following.

Γ-chloropropyltrimethoxysilane,
Vinyltrichlorosilane, vinyltriethoxysilane,
Vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3
4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ
-Mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, N-β- (aminoethyl) -β A silane coupling agent such as aminopropylmethyldimethoxysilane;

Isopropyl triisostearoyl titanate, isopropyl tridecyl benzene sulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2, Titanium coupling agents such as 2-diallyloxymethyl-1-butyl) bis (di-tridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, and tris (dioctylpyrophosphate) ethylene titanate.

The above-mentioned adhesion improver can be used alone.
More than one species may be used in combination. The adhesion improver is preferably one that can be mixed and dispersed in another material used. The adhesiveness improver may be added in an appropriate amount as needed, but is preferably added in an amount of about 0.01 to 10 parts by weight per 100 parts by weight of the acid anhydride group-containing compound (A1).

In producing the resin composition of the present invention, if necessary, a dehydrating agent, a storage stability improver, an antioxidant, a stabilizer, a plasticizer, a wax, a non-reactive diluent, a reactive diluent, Agents, fillers, pigments, dyes, flame retardants, foaming agents, ultraviolet absorbers, antistatic agents, fungicides, fragrances, viscosity modifiers and the like can be added.

Examples of the dehydrating agent include the following. Vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane; acetylacetone, ethyl orthoformate, orthoformate, calcium chloride, cement and zeolite; monoisocyanates such as p-toluenesulfonic acid isocyanate.

As the storage stability improver, for example,
The following are mentioned. A blocked isocyanate obtained by reacting a polyol / diisocyanate / alkylphenol, and a terminally acrylated urethane prepolymer obtained by reacting a polyol / diisocyanate / hydroxyethyl acrylate.

Examples of the antioxidants include the following. Aldol-α-naphthylamine, phenyl-α-naphthylamine, phenyl-β-naphthylamine, octylated diphenylamine, octylated diphenolamine, 1,2-dihydro-2,2,4
-Trimethylquinoline, acetone-diphenylamine reaction product, 6-ethoxy-1,2-dihydro-2,2,
4-trimethylquinoline, N, N'-diphenyl-p-
Phenylenediamine, N, N'-di-β-naphthyl-p
-Phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, N-isopropyl-
N'-phenyl-p-phenylenediamine, N, N'-
Di (1-ethyl-3-methylpentyl) -p-phenylenediamine, N, N'-di (1-methylheptyl) -p
-Diphenyldiamine, diallyl-p-phenylenediamine, N-phenyl-N '-(1,3-dimethylbutyl) -p-phenylenediamine, N, N'-bis (1,
4-dimethyl) pentyl-p-phenylenediamine,
N, N'-di (1,4-dimethylpentyl) -p-phenylenediamine, N-phenyl-N '-(1-methylpropyl) -p-phenylenediamine, N-phenyl-
N '-(1-methylheptyl) -p-phenylenediamine, N, N'-diheptyl-p-phenylenediamine.

P-isopropoxydiphenylamine,
N, N'-diphenylethylenediamine, 6-dodecyl-1,2-dihydro-2,2,4-trimethylquinolyl, DP + D, 2,6-di-t-butyl-p-cresol, 4,4'-dihydro Oxydiphenylcyclohexane, 2,5-di-t-amylhydroquinone, 2,5-
Di-t-butylhydroquinone, 2,2'-methylene-
Bis (4-methyl-6-t-butylphenol), 4,
4'-thiobis- (6-t-butyl-m-cresol), 2,2'-methylene-bis (4-ethyl-6-t
-Butylphenol), 4,4'-butylidene-bis-
(6-t-butyl-m-cresol).

Styrenated phenol, 6-t-butyl-
Reaction product of m-cresol and SCl ₂ , 4,4′-dioxydiphenyl, dioxydiphenyl methane derivative, hydroquinone monobenzyl ether, 1-oxy-3-methyl-4-isopropible benzene, 2,4 ,
5-trihydroxybutyrophenone, 2,4-dimethyl-6-t-butylphenol, 2,6-di-t-butylphenol, 4,4'-methylene-bis- (2,6-
Di-t-butylphenol), 2,6-di-t-butyl-α-dimethylamino-p-cresol, 4,4′-bis- (2,6-di-t-butylphenol), 4,4 ′
-Derivatives of methylene-bis- (6-t-butyl-o-cresol), 6-t-butyl-3-methylphenol.

1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, butylated hydroxyanisole, bis-
(3-methyl-4-hydroxy-5-tbutylbenzyl) sulfite, 4,4'-thiobis- (6-t-butyl-o-cresol), 2,2'-thiobis- (4-
Methyl-6-t-butylphenol), thiobis- (di-sec-amylphenol), 2,2'-dihydroxy-3,3'-di (α-methylcyclohexyl) -5,
5'-dimethyl-diphenylmethane, 2,6-di-t-
Mixtures of butylphenol, 2,4,6-tri-t-butylphenol and ot-butylphenol.

Special waxes, 2-mercapto-benzimidazole, Zn-mercapto-benzimidazole, nickel salt of dibutyldithiocarbamic acid, alkylated aryl phosphite, alkylthiourea, nickel isopropyl xanthate, aromatic humanrazine derivative and hydroquinone derivative , A reaction product of morpholinium-N-oxy-diethylene-dithiocarbamate and dibenzothiazyl disulfide, 1,1-bis-
A reaction product of (4-hydroxyphenyl) -cyclohexane and an organic amine, dilauryl thiodipropionate,
Distearyl thiodipropionate, dimyristyl
Thiodipropionate, triphenyl phosphite, diphenyl decyl phosphite, diphenyl isodecyl phosphite, didecyl phenyl phosphite, tridecyl phosphite, trioctyl phosphite, tridodecyl phosphite, trioctadecyl phosphite, trinonyl phenyl Phosphite, tridodecyltrithiophosphite, tri-β-naphthyl phosphite, trioctylphenyl phosphite, tri-2-ethylhexyl phosphite, trioleyl phosphite, triallyl phosphite, tricyclohexyl phosphite,
Tritetrahydrofurfuryl phosphite, tribenzyl phosphite, diphenylisooctyl phosphite, nonylphenyl di-n-propyl phosphite.

2,4-dioxybenzophenone, 2-oxy-4-methoxybenzophenone, diphenylolpropane, 2,2-bis- (3-methyl-4-oxyphenyl) propane, 1,1-bis- ( 3-molecular condensate of 4-oxyphenyl) -cyclohexane, 2,2 ', 4,4'-tetraoxyadipophenone, 2,2', 4,4'-tetraoxysebacatiphenone, dodecahydrotriphenylene, and cyclohexanone , Cyclohexanone six-molecule condensate, resorcinol dibenzoate, disalicyl resorcinol, phenyl salicylate, β-naphthoxypropene oxide.

2,2-bis- (4-hydroxyphenyl) propane, 2,2-bis- (4-hydroxyphenyl) butane, 2,2-bis- (4-hydroxy-3-methylphenyl) propane, , 2-bis- (4-hydroxy-3-isopropylphenyl) propane, 2,6-
Bis- (2-hydroxy-5-methylbenzyl) -4-
Methylphenol, bis- (2-hydroxy-5-chlorophenyl) sulfide, bis- (2-hydroxy-
5-methylphenyl) sulfide, bis- (hydroxy-5-methylphenyl) sulfide.

Octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, tetrakis [methylene 3- (3 ', 5'-di-t-butyl-
4'-hydroxyphenyl) propionate] methane,
1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, stearyl-propionate-β- (3,5-di-tert-butyl-4-hydroxyphenyl), 4, 4'-butylidene-bis (3-methyl-
6-t-butylphenyl-ditridecyl) phosphite, cyclic neopentanetetraylbis (octadecyl)
Phosphite. Other hindered phenols, phosphites, and sulfur-containing compounds.

Examples of the stabilizer include the following. Inorganic salts such as tribasic lead sulfate, dibasic lead phosphite, basic lead sulfite, lead silicate, and basic lead carbonate; dibasic lead stearate, lead stearate, dibasic lead phthalate, and salicylic acid Lead, tribasic lead maleate,
Cadmium stearate, cadmium laurate, cadmium octylate, cadmium ricinoleate, cadmium benzoate, cadmium naphthenate, barium stearate, barium laurate, barium ricinoleate, calcium stearate, calcium laurate,
Zinc stearate, zinc octylate, zinc laurate,
Metal soaps such as aluminum stearate, basic aluminum stearate, magnesium stearate, and strontium stearate.

Dibutyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, dibutyltin diphthalate, dibutyltin marker peptide, dibutyltin thiocarboxylate, dibutyltin dimaleate, a mixture of dibutyltin malate laurate, dibutyltin diacetylacetonate, dioctyltin dilaurate , Dioctyltin maleate, dioctyltin marker lactide, dioctyltin thiocarboxylate, tin naphthenate, tin octylate, tin stearate, acetylacetone tin, dimethyltin compound, tributyltin compound, reaction product of dibutyltin oxide and phthalate, Organotin compounds such as sulfur-containing organotin compounds.

Organic phosphites such as trinonylphenyl phosphite and triphenyl phosphite; epoxy compounds, sterically hindered amines, sterically hindered phenols, hydroxybenzotriazole, hydroxybenzophenone, β-
Diketone.

Examples of the plasticizer include the following. Dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dibutyl phthalate,
Diheptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, dicyclohexyl phthalate, diisooctyl phthalate, diisodecyl phthalate, di-n-decyl phthalate, di-n-dodecyl phthalate, ditridecyl phthalate, diisotridecyl Phthalate, dibenzyl phthalate, dinonyl phthalate, butyl benzyl phthalate, butyl lauryl phthalate, methyl oleyl phthalate, n-octyl-n-decyl phthalate, heptyl nonyl phthalate,
Phthalate esters such as di-2-ethylhexyl isophthalate, dicapryl phthalate and di (79 alkyl) phthalate.

Phosphates such as tributyl phosphate, trioctyl phosphate, octyl diphenyl phosphate, tricresyl phosphate, triphenyl phosphate, trichloroethyl phosphate, cresyl diphenyl phosphate; diethylene glycol dibenzoate, dipentaerythritol hexaester, pentaerythritol Glycol esters such as esters; diisodecyl succinate, dioctyl adipate, diisodecyl adipate, di-n-decyl adipate, dioctyl azelate, di-2-ethylhexyl azelate, dibutyl sebacate, dioctyl sebacate, tetrahydrophthalic acid Aliphatic dibasic acid esters such as dioctyl; butyl oleate, methoxyethyl oleate, stearin Butyl, methyl acetyl ricinoleic acid, acetyl ricinoleic acid methoxyethyl, glycerin tri heptanoic acid esters, chlorinated fatty acid methyl, fatty acid esters such as methoxy chlorinated fatty acid methyl.

Epoxy plasticizers such as epoxidized soybean oil, epoxidized tall oil fatty acid-2-ethylhexyl, epoxidized linseed oil, butyl epoxy stearate, octyl epoxy stearate, benzyl epoxy stearate, and dioctyl epoxy hexahydrophthalate. Citrates such as triethyl citrate and acetyl triethyl citrate; trioctyl trimellitate, tris-2-ethylhexyl trimellitate, ethyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate;
Tributyl acetylcitrate, polypropylene adipate, polypropylene sebacate, triacetylene, tributyrin, toluene-sulfonamide, castor oil, liquid paraffin, chlorinated paraffin, liquid polybutene, liquid polyisobutylene, liquid polybutadiene, liquid polyisoprene, hydrogenated liquid polybutadiene, Hydrogenated liquid polyisoprene, alkylbenzene, biphenyl, partially hydrogenated terphenyl, camphor, alkyl polycyclic aromatic hydrocarbons, naphthenic oil.

Examples of the wax include the following. Paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polymerized wax, low molecular weight polyethylene, low molecular weight polypropylene, modified wax, atactic polypropylene; natural waxes such as beeswax, whale wax, carnauba wax, wood wax, montan wax, ozokerite .

As the non-reactive diluent, for example, tar, bitumen and the like can be mentioned. Examples of the reactive diluent include the following. Glycidyl esters of n-butyl glycidyl ether, isooctyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, mixed tertiary aliphatic monocarboxylic acid mixtures.

Examples of the filler include the following. Calcium carbonate powder, magnesium carbonate powder, kaolin, talc, mica, bentonite, clay, clay, sericite, asbestos, glass fiber, carbon fiber, cotton fiber, nylon fiber, acrylic fiber, rayon, glass sphere, glass powder, glass balloon , Shirasu balloon, coal powder, urea melamine resin powder, acrylic resin powder, phenolic resin powder, mica, quartz powder, diatomaceous earth, metal powder, alumina powder, wollastonite, silica powder, colloidal silica powder, white carbon, powdered PVC , Powdered polyolefin hydrocarbons; silicate minerals such as calcium silicate, zeolite, pumice powder, and slate powder; bentone, silicic anhydride, urea derivatives, barium sulfate, calcium sulfate,
Fillers such as zinc oxide powder, magnesium oxide powder, aluminum hydroxide powder, molybdenum disulfide, wood flour, fruit flour, etc., which have not been subjected to surface treatment, and those which have been subjected to surface treatment.

Examples of the pigment or dye include the following. Carbon black, titanium oxide, zinc white, lithopone, lead white, graphite, titanium yellow, zinc chromate, loess, benzidine yellow, hansa yellow, chrome vermillion, red pigment, amber, yellow iron oxide, red iron oxide, lithol red, alizarin Rake, cadmium yellow, cadmium orange, cadmium red, cadmium maroon, pigment scarlet 3
B, Brilliant Carmine 6B, Permanent Red F
-5R, permanent red 4R, permanent yellow HR, lake red C, lead red, rhodamine lake B, rhodamine lake Y, para red, peacock blue lake, navy blue.

Phthalocyanine blue, phthalocyanine green, ultramarine, chromium oxide green, mineral violet, cobalt violet, cobalt blue, iron black,
Aniline black, PV violet BL, quinacridone, quinacridone red, perinone, perylene, anthraquinone flavanthrone yellow, anthraquinone violet, anthraquinone blue, dioxazine violet, indathrene blue, chromophtal yellow 6
G, Chromophtal Yellow 3G, Chromophtal Yellow GR, Oil Yellow 2G, Oil Red, Pyrazolone Orange, Pyrazolone Red, Bengala, Carmine 6B,
Mercury Red, Bordeaux 10B, Bon Maroon,
Inorganic pigments, organic pigments or organic dyes such as thioindigo maroon, phthalocyanine blue, pearl essence and ultramarine blue.

Examples of the flame retardant include the following. Chlorinated paraffin 70, chlorinated polyethylene, chlorinated polyphenyl, brominated polyphenylene oxide, brominated polycarbonate, brominated polybenzyl acrylate, brominated polystyrene, brominated styrene, brominated epoxy, brominated phenol, brominated phenyl acrylate, Brominated phenyl methacrylate, brominated diallyl phthalate, brominated polyol, chlorine-containing polymer, antimony oxide, chlorendic acid, chlorentic acid, chlorenic anhydride, perchloropentacyclodecane, bisphenol A tetrachloride, bisphenol tetrachloride A, phthalic anhydride tetrabromide, phthalic anhydride tetrachloride, organic bromine compound, organic chlorine compound, brominated long chain glyceride, hexabromocyclododecane, ethane tetrabromide, butane tetrabromide, acetylene tetrabromide, Bromide Of ethane, dibromide acid, pentabromide ethylbenzene, nucleus-substituted pentabromide benzene, six bromide benzene, pentabromide - cyclohexane chloride, hexachloroethane, Two iodide methane bromide Ammon.

Decabromobiphenyl ether, dibromodichloropropane, trischloroethyl phosphate,
Tris (dichloropropyl) phosphate, tris (dibromopropyl) phosphate, trischloropropyl phosphate, trisdichloropropyl chloropropyl phosphate, bischloropropyl dichloropropyl phosphate, bischloropropyl chloroethyl phosphate, bischloroethyl dichloropropyl phosphate , Tris (dibromopropyl) phosphate,
Tris (dibromophenyl) phosphate, tris (bromochloropropyl) phosphate, diethylbis (hydroxyethyl) aminomethylphosphonate, tricresyl phosphate, diphenylcresyl phosphate,
Diphenyl octyl phosphate, tributyl phosphate, triphenyl phosphate, chlorophosphonate, bromophosphonate, phosphorus-containing polyol, antimony trioxide, sodium antimonate, tin oxide, barium metaborate, zirconium oxide, red phosphorus, aluminum hydroxide, magnesium hydroxide.

Examples of the foaming agent include the following. Azobisformamide, azobisisobutyronitrile, barium azodicarboxylate, azodicarboxylic amide, diethylazodicarboxylate, diazoaminobenzene, N, N'-dimethyl-N, N'-
Dinitrosoterephthalamide, N, N'-dinitrosopentamethylenetetramine, benzenesulfonylhydrazide, p-toluenesulfonylhydrazide, benzene-
1,3-disulfonyl hydrazide, diphenylsulfone-3,3'-disulfonyl hydrazide, 4,4'-
Oxybis (benzenesulfonylhydrazide), sulfonehydrazide, allylbis (sulfonehydrazide), p-toluylenesulfonyl semicarbazide,
4,4'-oxybis (benzenesulfonyl) semicarbazide, 5-morphoryl-1,2,3,4-thiatriazole, sodium hydrogen carbonate, ammonium carbonate, ammonium hydrogen carbonate, ammonium nitrite; azide compounds such as CaN ₆ ; hydrogenation Sodium boron; light metals such as magnesium and aluminum.

Examples of the ultraviolet absorber include the following. 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2, 2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-
5-sulfobenzophenone, 2,2'-dihydroxy-
4,4'-dimethoxy-5-sulfobenzophenone, 2
-Hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4- (2-hydroxy-3
-Methyl-acryloxy) propoxybenzophenone,
Benzophenones such as 2-hydroxy-4-chlorobenzophenone.

2 (2'-hydroxy-5-methylphenyl) benzotriazole, 2 (2'-hydroxy-
3 ', 5'-di-t-butylphenyl) benzotriazole, 2 (2'-hydroxy-3'-t-butyl-5'
-Methylphenyl) benzotriazole, 2 (2'-hydroxy-3'-t-butyl-5'-methylphenyl)
-5-chlorobenzotriazole, 2 (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2 (2'-hydroxy-3',
5'-di-t-amylphenyl) benzotriazole,
Benzotriazoles such as 2 (2'-hydroxy-4'-octylphenyl) benzotriazole.

Methyl salicylate, dodecyl salicylate, phenyl salicylate, carboxyphenyl salicylate, p-octylphenyl salicylate, pt-
Salicylates such as butylphenyl salicylate and strontium salicylate; nickel bisoctylphenyl sulfide, [2,2'-thiobis (4-t-
Octylphenolate)]-n-butylamine nickel,
Nickel dibutyl dithiocarbamate, nickel isopropyl xanthate, nickel complex-3,5-di-t-
Metal complex salts such as butyl-4-hydroxybenzyl / phosphate monoethylate; ethyl-2-cyano-3-phenylcinnamate, 2'-ethylhexyl-2-cyano-3
-Phenylcinnamate, 2-ethylhexyl-2-cyano-3,3-diphenylacrylate, ethyl-2-
Cyano-3,3-diphenyl acrylate, resorcinol monobenzoate, acrylonitriles, hindered amines, ethyl p-aminobenzoate.

Examples of the antistatic agent include the following. Polyoxyethylene alkylamine, polyoxyethylene alkylamide, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, glycerin fatty acid ester, sorbitan fatty acid ester, fatty acid ester of polyhydric alcohol, ester of higher alcohol, polyethylene glycol Fatty acid ester, alkyl sulfonate, alkyl benzene sulfonate, alkyl sulfate, alkyl phosphate, polyamide resin, polyvinyl benzene sulfonic acid type anion, polyvinyl benzyl type cation, polyacrylic acid type cation, polyamidoamine Type cation, alkanolamide, quaternary ammonium chloride, quaternary ammonium sulfate, quaternary ammonium nitrate, alkyl betaine, alkyl Midazorin, alkyl alanine, amino acids, ethylene oxide adducts.

Examples of the above fungicides include the following. Organic mercury compounds such as phenylmercury phthalate; sulfur compounds such as tetramethylthiuram disulfide; phenol compounds such as o-phenylphenol.

Examples of the above-mentioned fragrances include the following. Animal flavors such as musk, civet, castorium, ambergris; turpentine oil, pine oil, citronella oil, camphor oil, orange oil, lemon oil, lemongrass oil, peppermint oil, eucalyptus oil, lavender oil,
Vegetable flavors such as Boadulose Yuzu, Bergamot Oil, Lime Oil, Spearmint Oil, Clove Oil, Petit Glen Oil, Geranium Oil, Sandalwood Oil, Anise Oil, Cassia Yuzu;
Methyl salicylate, cinamic aldehyde, coumarin, yonone, hydroxyntronellal, heliotropin, β-naphthol methyl ether, aldehyde C1
4. Synthetic flavors such as aldehyde C16, aldehyde C18, maltol, ethyl maltol, cycloten, vanillin, ethyl vanillin and the like.

Examples of the viscosity modifier include the following. Sodium alginate, propylene glycol alginate, sodium caseinate, sodium carboxymethylcellulose, calcium carboxymethylcellulose, sodium cellulose glycolate, sodium starch glycolate, sodium starch phosphate, sodium polyacrylate, methylcellulose, gum arabic, alginic acid, casein, Guar gum, gluten, starch, locust bean gum, hydrogenated castor oil derivatives, adducts of diisocyanates or triisocyanates with monoamines or diamines, soy lecithin. These components may be used alone or in combination of two or more. It is preferable that these components can be mixed and dispersed in other materials used.

In the resin composition of the present invention, if necessary, one or more curing reactions other than the curing reaction of the above compound (B) by moisture can be used. Examples of the other curing reaction include the following reactions.

Curing of an isocyanate group-containing compound by moisture; curing of a hydrolyzable silyl group-containing compound by moisture; curing of a cyanoacrylate compound by moisture; curing of a polysulfide resin by moisture; a functional group capable of reacting with an amino group. A curing reaction initiated by moisture, such as a reaction between a compound having other than an acid anhydride group and a compound which produces at least one of a primary amino group, a secondary amino group and ammonia by reaction with water.

Curing reaction initiated by irradiating an unsaturated double bond-containing compound, an azide compound, a diazo compound, a cinnamic acid compound, an epoxy resin, etc. with light such as ultraviolet light, infrared light, visible light, or electron beam irradiation. Starting by heating such as curing of a one-part heat-curable epoxy resin composition, reaction using a blocked isocyanate compound, curing of a thermosetting resin such as a phenolic resin or a urea resin, and heat curing of an unsaturated double bond-containing compound. Curing reaction initiated by oxygen; curing reaction initiated by oxygen such as curing of polysulfide resin by oxygen, curing of unsaturated aliphatic compound by oxygen such as drying oils, etc .; anaerobic initiated by blocking oxygen such as anaerobic adhesive Polymerization reaction.

[0152] Curing of two-component mixed epoxy resin, curing of two-component mixed urethane resin, curing of two-component mixed polyester resin, curing of two-component mixed acrylic resin, curing of second-generation acrylic adhesive, various cross-linking Curing reaction initiated by mixing two or more compounds, such as a crosslinking reaction with an agent; curing of an oligomer-type pressure-sensitive adhesive using a reactive oligomer such as a rubber-based oligomer, an acrylic-based oligomer, or a urethane-based oligomer.

In the resin composition of the present invention, the method for using the above other curing reaction in combination is not particularly limited, and examples thereof include the following methods. 1) The other functional group which causes the curing reaction is introduced into the molecule of the compound constituting the resin composition of the present invention. 2) The other composition that causes a curing reaction is mixed with the resin composition of the present invention. 3) The above-mentioned other composition that causes a curing reaction and the resin composition of the present invention are used as a laminate. 4) A method of applying the above-mentioned other composition which causes a curing reaction and the resin composition of the present invention to different parts of the same article.

In the resin composition of the present invention, the above-mentioned compound (B) is reacted after the other curing reaction has previously occurred.
The curing reaction may be caused by the moisture of the compound (B), the curing reaction of the compound (B) may be caused by the moisture in advance, and then the other curing reaction may be caused. The curing reaction of the compound (B) with moisture may occur simultaneously. In the resin composition of the present invention, the cured state can be adjusted stepwise with time by the other curing reaction described above. Examples of the case where this adjustment is applied include the following cases.

1) Only the surface portion of the composition which is thickly applied to the substrate and which comes into contact with the air is cured by moisture and the inside is cured by blocking oxygen, thereby forming a thick cured layer in a short time. 2) Only the portion of the composition sandwiched between non-moisture-permeable materials, such as metal and glass, that is in contact with air is cured by moisture and the inside is cured by blocking oxygen, so that the large-area moisture-impermeable material can be cured in a short time. Glue the materials together. 3) When applied to a base material, it can be easily used as a pressure-sensitive adhesive, and then cures due to moisture in the air to improve the bonding strength and bonding durability, or to easily peel off Easier to do. 4) The composition applied to the base material is first cured by light and radiation, and the portion where irradiation of light and radiation is impossible is later cured by moisture in the air.

In the production of the resin composition of the present invention, it is preferable that the material used is previously free of water contained in the material. Examples of the method include the following methods. 1) Dewater sufficiently by mixing in a molecular sieve or the like. 2) Place in a heated oven. 3) Heat with a heater or the like. 4) Degas under reduced pressure.

The process for producing the resin composition of the present invention includes
The method is not particularly limited as long as the method can mix and disperse the materials used, and examples thereof include the following methods. 1) In a suitable container such as a glass bottle, a can or a plastic cup, knead by hand with a stirring rod, a spatula or the like. 2) Kneading with double helical ribbon, gate, etc. 3) Knead with a planetary mixer. 4) Kneading with three rolls. 5) Knead with a kneader-ruder type kneader. 6) Knead with an extruder-type kneading extruder.

However, any of the above production methods must be carried out under anhydrous conditions, and particularly in the case of a composition which does not cause anaerobic polymerization, it is preferable to carry out the composition in a nitrogen stream. In addition, any of the above production methods can be carried out at normal temperature or under heating if necessary, under atmospheric pressure, or at atmospheric pressure or higher or lower than atmospheric pressure if necessary.

When any of the materials used for the resin composition of the present invention or the obtained resin composition is a high viscosity or solid at ordinary temperature, it may be used under appropriate heating conditions, or ethyl acetate, cyclohexane , Aromatic hydrocarbons, ethers,
It is preferable to produce in an inert solvent such as dioxane, halogenated hydrocarbon, ketone and the like. When the composition starts to be cured by irradiation with light such as ultraviolet light, visible light, infrared light, or the like, it is preferable to manufacture the composition under conditions in which such light is blocked. In the case of a composition that initiates an anaerobic polymerization reaction, it is preferable to manufacture the composition under conditions that can always supply sufficient oxygen. The above production methods may be performed alone or in combination of two or more.

The method for storing the resin composition of the present invention includes:
The method is not particularly limited as long as the method is maintained under anhydrous conditions, and examples thereof include the following methods. 1) Store in an atmosphere that does not contain moisture or moisture. 2) Place in a non-permeable container or sealed container such as a pail, tin, drum or aluminum cartridge. 3) Nitrogen gas is sealed in a non-permeable container or a sealed container such as a pail, tin can, drum, or aluminum cartridge. 4) A sufficient amount of a hygroscopic material such as silica gel or molecular sieve is mixed. 5) Packing with a sufficient amount of a hygroscopic material such as silica gel or molecular sieve. When the resin composition of the present invention is photopolymerized, it is preferable to store the resin composition under light-shielded conditions. In the case where anaerobic polymerization is carried out, it is preferable to store under conditions capable of always supplying sufficient oxygen.

The above storage methods may be used alone or in combination of two or more. The resin composition of the present invention may be used immediately after production without employing the above storage method.

In the case where the resin composition of the present invention is used by coating it on a substrate surface, the coating method is not particularly limited, and examples thereof include the following methods. 1) Brush, spatula, absorbent cotton, brush, comb iron, gun,
The resin composition of the present invention is applied on the surface of a substrate by a coater or the like. 2) The base material surface is immersed in the resin composition of the present invention. 3) The resin composition of the present invention is sprayed on a substrate surface. 4) A method of transferring the resin composition of the present invention to a substrate surface using a roll, and the like.

When the resin composition of the present invention has a high viscosity or a solid at room temperature, it is preferable to apply the resin composition of the present invention under appropriate heating conditions. The application method in this case is not particularly limited, and examples thereof include the following methods. 1) The resin composition of the present invention, which has been heated and melted by an ordinary hot-melt applicator, hot-melt coater, or the like, is applied on a substrate surface. 2) The base material surface is immersed in the resin composition of the present invention that has been heated and melted. 3) The resin composition of the present invention, which has been heated and melted by a hot melt gun or the like, is sprayed on the substrate surface.

4) The resin composition of the present invention, which has been heated and melted using a hot melt roll, is transferred to the substrate surface. 5) The resin composition of the present invention, which has been heated and melted using a knife blade coater, a coating die or the like, is applied to the substrate surface. 6) The resin composition of the present invention, which has been heated and melted by an extruder or the like, is extruded onto a substrate surface. 7) The resin composition of the present invention is printed on the surface of the base material by means of graphic printing.

In the above coating method, the resin composition of the present invention may be sent to a hot melt applicator using a pail unloader, a cartridge dispenser, or the like, or may be a stick, a pellet, a slug, a block, a pillow, a pillaret. And the like, and may be sent to each of the above coating devices. When the resin composition of the present invention is photopolymerized, it is preferable to send the resin composition to each coating device under the condition that light is blocked. In the case of anaerobic polymerization, it is preferable to send the solution to each coating device under conditions that can always supply sufficient oxygen.

Before performing the above coating, the resin composition of the present invention may be degreased and washed with a solvent, an emulsion, an acid, an alkali or the like as required; polishing by electrolytic polishing, chemical polishing, etc .; water jet treatment; Treatment; primer application; rust preventive agent application; silane coupling agent treatment; chemical conversion treatment with phosphoric acid, chromate, oxalic acid, etc .; anodization treatment; ultraviolet irradiation; electron beam irradiation; corona discharge treatment; plasma treatment; Plating; thermal spraying;
Coating; treatment such as enamel may be performed on the surface of the substrate to be coated.

The above coating is preferably carried out under anhydrous conditions so that the resin composition of the present invention is not exposed to moisture. In particular, when the composition does not cause anaerobic polymerization, it is placed in a nitrogen stream. Preferably, it is performed. As for the heating in the above application, the entire resin composition of the present invention may be heated and melted, or only the vicinity of the heating body may be heated and melted.

In the above coating, air, nitrogen, carbon dioxide, or a water-containing gas containing a small amount of water added thereto is mixed and foamed at the time of coating in order to impart flexibility and sound insulation to the coated portion. May be used. In particular, when the resin composition of the present invention is a high-viscosity or solid at room temperature, the resin composition of the present invention can be melted and foamed with a hot melt applicator such as a foam melt applicator (manufactured by Nordson). it can.

The resin composition of the present invention can be used as a pressure-sensitive adhesive by applying it to a sheet material such as a polyethylene terephthalate film, paper, or nonwoven fabric. Examples of the coating method include the following methods.

1) When the resin composition of the present invention is of a solvent type, it is applied and dried in the same manner as a usual solvent type pressure sensitive adhesive. 2) When the resin composition of the present invention is of a hot-melt type, it is applied using a usual hot-melt coater. 3) When a light / radiation curing reaction is used in combination with the resin composition of the present invention, it is applied and cured in the same manner as the light / radiation acid-curable pressure-sensitive adhesive. 4) When a reactive oligomer such as a rubber-based oligomer, an acrylic-based oligomer, or a urethane-based oligomer is used in combination with the resin composition of the present invention, it is applied and cured in the same manner as the oligomer-type pressure-sensitive adhesive.

When the resin composition of the present invention is used as a solvent-type adhesive, it can be used, for example, by the following method. 1) After applying the resin composition of the present invention to the adhesive surface of one of the adherends, the adherend surface of the other adherend is bonded after drying the solvent or without drying the solvent. Pressurize at appropriate pressure and temperature for the required time. 2) After applying the resin composition of the present invention to the adherend surfaces of both adherends, the adherend surfaces are adhered to each other with or without drying the solvent, and necessary pressure and temperature are required. Pressurize for a suitable time

When the resin composition of the present invention is used as a hot-melt adhesive, it can be used, for example, by the following method. 1) After applying the resin composition of the present invention to the adhesive surface of one of the adherends, the adherend surfaces of the other adherends are bonded together and pressurized at a required pressure and temperature for a required time. 2) After applying the resin composition of the present invention to the adherend surfaces of both adherends, pressurize at the required pressure and temperature for the required time. These coating methods may be used alone or in combination of two or more.

In the case where the resin composition of the present invention is required to have a further long-term storage stability, a reaction between the acid anhydride-containing compound (A1) and water with a primary amino group, a secondary amino group and ammonia. The compound (B), which forms at least one of them, may be divided into individual containers, stored and mixed when used. In this case, the resin composition of the present invention can be separately manufactured for each of the two components in the same manner as described above. In addition, the two components can be stored separately in the same manner as described above.

In this case, the resin composition of the present invention comprises:
It is necessary to mix the components of the two components before use, and the mixing method is not particularly limited as long as the components of the two components can be mixed and dispersed, and examples thereof include the following methods. 1) In a suitable container such as a glass bottle, a can or a plastic cup, mix by hand with a stirring rod, a spatula or the like. 2) Mix well with double helical ribbon and gate. 3) Mix with a planetary mixer. 4) Mix with a Miki roll. 5) Mix using a kneader-ruder type kneader. 6) Mix with an extruder-type kneading extruder.

As a more preferable method, a two-liquid automatic metering mixing / discharging apparatus (for example, manufactured by Tomita Engineering Co., Ltd.)
Lambda I / II). The above mixing method is preferably performed under anhydrous conditions, particularly when the composition does not cause anaerobic polymerization,
It is preferably performed in a nitrogen stream. The above-mentioned mixing method can be carried out at normal temperature or under heating if necessary, under atmospheric pressure or at atmospheric pressure or higher or lower than atmospheric pressure if necessary.

When any one of the components of the above two liquids has a high viscosity or a solid at room temperature, under appropriate heating conditions, or ethyl acetate, cyclohexane, aromatic hydrocarbon, ether, dioxane, halogenated hydrocarbon. It is preferable to carry out the mixing in an inert solvent such as ketone or ketone. When any one of the components of the above two components undergoes photopolymerization, it is preferable to carry out the mixing under the condition that light is blocked. In the case of anaerobic polymerization, it is preferable to carry out mixing under conditions that can always supply sufficient oxygen. The above mixing methods may be used alone or in combination of two or more.

In the case where the resin composition of the present invention is used by being coated on a substrate surface, the substrate is not particularly limited, and examples thereof include the following. Metals such as iron, aluminum, copper, lead, tin, zinc, nickel, magnesium, titanium, gold, silver, platinum or alloys thereof; phenolic resins, urea resins, melamine resins, unsaturated polyester resins, diallyl phthalate resins, epoxy resins , Silicon resin, alkyd resin, furan resin, urethane resin, vinyl chloride resin, vinylidene chloride resin, vinyl acetate resin, A
BS resin, methacrylic resin, polyphenylene oxide,
Ionomer resins, fluororesins, cellulosic plastics, polyethylene, polypropylene, polyamide, polyimide, polystyrene, polycarbonate, polyacetal, polyphenylene sulfide, polyethylene terephthalate, and other plastics or mixtures thereof; glass, concrete, asphalt, plaster, stone, wood, mortar, Ceramics, ceramics, papers, cellulosic materials, leather. The form of the substrate is not particularly limited, and examples thereof include a plate, a lump, a rod, a sheet, a string, a fiber, a honeycomb, a tube, and a particle. Also,
The resin composition of the present invention may be used for bonding these different substrates.

The resin composition of the present invention cures sufficiently under ordinary conditions, but if it is desired to further shorten the curing time, it may be used before and / or when applied to a base and / or applied to a substrate. After, before lamination of another substrate and / or at the time of curing, appropriate heating and / or humidification can be performed.
As the heating method and the humidifying method in this case, an optimal method can be appropriately adopted depending on the shape, properties, and the like of the resin composition and the base material of the present invention, and heating and humidifying conditions. Is mentioned.

1) Hot air and / or humid air are blown onto the resin composition of the present invention. 2) The resin composition network of the present invention is placed in a heated and / or humidified oven. 3) Heat the resin composition of the present invention with a heater. 4) Water or hot water is sprayed on the resin composition of the present invention. 5) The resin composition of the present invention is brought into contact with water or hot water directly or through a semipermeable membrane.

6) The resin composition of the present invention is brought into contact with a porous material such as wood, brick, concrete and the like. 7) Water or hot water is mixed into the resin composition of the present invention before use. 8) The resin composition of the present invention is heated before use. These curing methods, these may be used alone,
Two or more types may be used in combination.

The resin composition of the present invention can be used as an elastic adhesive having excellent flexibility; a structural adhesive; a solvent-type reactive adhesive; a reactive hot melt adhesive; Adhesive-type (post-curing) pressure-sensitive adhesives that exhibit the same adhesive strength, heat-resistant adhesiveness and adhesive durability as adhesives; sealing materials; hot-melt sealing materials; putty; Matrix resin for laminates, etc .; resin used for impregnation, casting, molding, etc.

The specific application of the resin composition of the present invention is not particularly limited. For example, polyolefin foams for cushioning, sound insulating and heat insulating materials used in automobiles, building materials, electric appliances and the like and various base materials Adhesion to materials; door panels, partitions, shutters, furniture, blackboards, whiteboards, adhesion of sandwich panel cores and surface materials such as office equipment housing panels; furniture, partitions, door panels and ceiling materials for automotive interior materials, etc. Adhesion of core material and surface material; Adhesion of lamp lens; Sponge abrasive, abrasive cloth, scourer, foam mattress, joinery, packaging material, seat sheet, electric carpet, table, desk, system kitchen, TV, speaker Manufacture; Lamination of plywood and decorative boards; Lamination of optical audio / video discs and magneto-optical discs;
Adhesion of automotive side moldings; pressure-sensitive adhesives used for adhesive tapes, double-sided adhesive tapes, adhesive films, adhesive seals, adhesive labels, masking tabs, surface protection films, etc .; metal panels, concrete panels, ALC panels,
Sealing for building materials such as siding boards, slate boards, sashes, and coated glass; sealing for manufacturing various vehicles; potting, sealing, and insulating for manufacturing electrical and electronic equipment materials such as semiconductors; coating of various materials; Coating; anticorrosion treatment of various metal materials; fiber-reinforced laminates and prepregs thereof; and various molded products.

The resin composition of the present invention is excellent in storage stability because acid anhydride groups do not react in a state where moisture is blocked, and an amine having active hydrogen is generated in a state where moisture is present. The reaction with the acid anhydride groups proceeds to cure.

The resin composition of the present invention 2 comprises an unsaturated aliphatic compound (A2) and a compound (B) which forms at least one of a primary amino group, a secondary amino group and ammonia by reaction with water. ).

The resin composition of the present invention 2 contains an unsaturated aliphatic compound (A2). The unsaturated aliphatic compound (A
2) comprises an organic compound having an unsaturated aliphatic group,
It preferably comprises an organic compound having an unsaturated fatty alkyl ester group, an unsaturated fatty acid ester group and / or a tricyclodecenyl ester group, and more preferably has an average of 12 to 20 carbon atoms, and 50-20
An unsaturated fatty alkyl ester group having an iodine value of 0,
It consists of an organic compound having an unsaturated fatty acid ester group and / or a tricyclodecenyl ester group, and may be any of a monomer, an oligomer and a polymer. Further, the unsaturated aliphatic compound (A2) includes carbon, hydrogen, oxygen,
It contains organic compound constituent atoms such as nitrogen, sulfur and phosphorus.

The unsaturated aliphatic group contained in the unsaturated aliphatic compound (A2) may be present at the terminal of the molecular chain or as a side chain, and its structure and molecular weight are limited. Although not limited, organic compounds having an average of two or more unsaturated aliphatic groups per molecule are preferred. Here, the average number of unsaturated aliphatic groups per molecule means the total number of unsaturated aliphatic groups in the unsaturated aliphatic compound (A2) by the number of molecules in the unsaturated aliphatic compound (A2). It can be determined by dividing by the total number.

As the unsaturated aliphatic compound (A2), a solid at room temperature which can be melted by heating is used, and if the compound is solid at room temperature, the resin composition of the present invention 2 can be used. And a hot-melt composition.

The unsaturated aliphatic compound (A2) of the present invention comprises
If necessary, other functional groups can be included in the molecule. Examples of the functional group include a hydroxyl group, an epoxy group, a carboxyl group, an anhydride group, a saturated aliphatic alkyl group, an unsaturated aliphatic alkyl group, an alicyclic alkyl group, an aromatic alkyl group, a vinyl group, an allyl group, and an isocyanate. Group, alkoxyl group, silyl group, halogen group, phosphate group, thioether group, thiol group, thiocarboxyl group, amide group, urethane group, imide group, carbonate group, sulfonic acid group, carbonyl group, tertiary amino group, acryloyl Groups, methacryloyl groups, and groups that generate at least one of a primary amino group, a secondary amino group, and ammonia by reaction with water.

The unsaturated aliphatic compound (A2) is not particularly restricted but includes, for example, the following.
Tung oil, linseed oil, soybean oil, cottonseed oil, rapeseed oil; ethylene, propylene, isobutylene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1
Α- having up to 20 carbon atoms, such as octadecene
Olefin, vinyl acetate, acrylic acid, methacrylic acid,
Copolymers such as acrylic acid esters, methacrylic acid esters, and maleic anhydrides having an alkyl substitution at the α-position and having an acid group and / or an ester group can be used as unsaturated fatty alcohols and / or tricyclodecenes. A polymer obtained by at least partially esterifying and / or transesterifying a copolymer having a hydroxyl group and / or an ester group with an unsaturated fatty acid.

Examples of the unsaturated aliphatic compound (A2) include, in addition to the unsaturated aliphatic compounds exemplified above, a hydroxyl group, an epoxy group, a carboxyl group, an acid anhydride group,
Saturated aliphatic alkyl group, unsaturated aliphatic alkyl group, alicyclic alkyl group, aromatic alkyl group, vinyl group, allyl group, isocyanate group, alkoxyl group, silyl group, halogen group, phosphoric acid group, thioether group, thiol Group, thiocarboxyl group, amide group, urethane group, imide group,
Functional groups such as carbonate groups, sulfonic acid groups, carbonyl groups, tertiary amino groups, acryloyl groups, methacryloyl groups, and groups that form at least one of primary amino groups, secondary amino groups, and ammonia by reaction with water Are bonded. These may be used alone or in combination of two or more.

The method for producing the unsaturated aliphatic compound (A2) is not particularly limited, and examples thereof include the following methods. 1) The acid group-containing compound is esterified with an unsaturated fatty alcohol and / or tricyclodecenol. 2) The hydroxyl group-containing compound is esterified with an unsaturated fatty acid.

3) The compound having an ester group is transesterified with an unsaturated fatty alcohol, an unsaturated fatty acid and / or tricyclodecenol. 4) An isocyanate group of the isocyanate group-containing compound is subjected to an addition reaction with an unsaturated fatty alcohol, an unsaturated fatty acid and / or tricyclodecenol. 5) A diisocyanate compound is reacted with a hydroxyl group of a hydroxyl group-containing compound such as polyether such as polyethylene glycol or polypropylene glycol to form an isocyanate group, and an unsaturated fatty alcohol, unsaturated fatty acid and / or tricyclodecenol is added thereto. Addition reaction is performed.

6) A diisocyanate compound is reacted with an acid group-containing compound to form an isocyanate group, and an unsaturated fatty alcohol, unsaturated fatty acid and / or tricyclodecenol is added to the isocyanate group. 7) Reacting the epoxy group of the epoxy group-containing compound with the unsaturated fatty acid.

The above transesterification reaction or esterification reaction can be carried out in the presence of a usual acid catalyst such as Swedcut 5. Any of the above methods can be carried out at room temperature or under heating if necessary, under atmospheric pressure, or at above atmospheric pressure or below atmospheric pressure if necessary. Any of the above methods can be performed under anhydrous conditions if necessary.

In any of the above methods, if a solid compound at room temperature that can be melted by heating is used as a starting material, or if an appropriate compound is selected as a starting material even if it is liquid at room temperature, it can be heated. The unsaturated aliphatic compound (A2) which can be melted and is solid at ordinary temperature can be obtained.

The unsaturated aliphatic compound (A2) is selected from hydroxyl, epoxy, carboxyl, acid anhydride, vinyl, allyl, isocyanate, alkoxyl, silyl, halogen, phosphate, thiol, When it has a functional group such as a thiocarboxyl group, an amide group, a urethane group, an imide group, a carbonate group, a sulfonic acid group, a carbonyl group, an acryloyl group, and a methacryloyl group, it is melted by heating having a functional group capable of reacting with the functional group. The unsaturated aliphatic compound (A2) can be made into a solid at room temperature at which the unsaturated aliphatic compound (A2) can be melted by heating by reacting with a solid resin at normal room temperature.

When any of the starting materials or the product is a material having a high viscosity at room temperature or is a solid, it may be used under an appropriate heating condition, or ethyl acetate, cyclohexane, an aromatic hydrocarbon, an ether. , Dioxane, halogenated hydrocarbon, ketone and the like. The above-mentioned production methods can be carried out alone or in combination of two or more.

The compound (B) used in the present invention 2 together with the unsaturated aliphatic compound (A2) is the same as the compound (B) in the resin composition of the present invention 1; In the above, instead of having no other functional group capable of reacting with the acid anhydride group in the molecule, it is preferable that the other functional group capable of reacting with the unsaturated aliphatic group is not present in the molecule. .

In the resin composition of the present invention 2, the compound (B) which forms at least one of a primary amino group, a secondary amino group and ammonia by reacting the unsaturated aliphatic compound (A2) with water. Is appropriately determined according to the degree of curing at the time when the curing reaction is completed,
Preferably, it is contained in a weight ratio range of 1/100 to 100/1.

When the compound (B) contains an unsaturated aliphatic group, and when the unsaturated aliphatic compound (A2) reacts with water, at least one of a primary amino group, a secondary amino group, and ammonia When one kind is formed, the resin composition of the present invention 2 can be constituted by a single compound.

The resin composition of the present invention 2 can be made into a solvent-type resin composition by adding a solvent. As the solvent, those similar to the ones exemplified in the present invention 1 can be used, but instead of having no other functional group capable of reacting with an acid anhydride group in the molecule, an unsaturated aliphatic group is used. It is preferable that the compound does not have another functional group capable of reacting with the compound in the molecule.

In producing the resin composition of the present invention 2, by adding other resins such as a thermoplastic resin and a tackifying resin, a hot-melt type composition can be obtained or adhesion to a substrate can be improved. Or can be. As the thermoplastic resin and the tackifying resin, those similar to those exemplified in the present invention 1 can be used, but those having no other functional group capable of reacting with an acid anhydride group in the molecule. Instead, it is preferable that the compound does not have another functional group capable of reacting with the unsaturated aliphatic group in the molecule.

In the case of curing the resin composition of the present invention 2, the curing time can be adjusted by adding a catalyst. As the above-mentioned catalyst, those similar to those exemplified in the first embodiment of the present invention can be used. The addition amount of the catalyst in the present invention 2 is preferably 0.01 to 10 parts by weight based on 100 parts by weight of the unsaturated aliphatic compound (A2).

When the resin composition of the present invention 2 is applied to a substrate, the adhesion to the substrate can be improved by adding an adhesion improver. As the adhesion improver, the same one as exemplified in the first embodiment of the present invention can be used. In the second aspect of the present invention, the amount of the adhesion improver to be added is preferably an unsaturated aliphatic compound (A2).
0.01 to 10 parts by weight per 100 parts by weight is preferred.

In preparing the resin composition of the present invention 2, a dehydrating agent, a storage stability improver, an antioxidant, a stabilizer, a plasticizer, a wax, a non-reactive diluent,
Reactive diluents, fillers, pigments, dyes, flame retardants, blowing agents,
UV absorbers, antistatic agents, fungicides, fragrances, viscosity modifiers and the like can be added. As such a thing, the same thing as illustrated in the present invention 1 can be used.

In the resin composition of the present invention 2, one or more of the other curing reactions exemplified in the present invention 1 can be used in combination. In this case, the resin composition is a functional group capable of reacting with an amino group. A functional group capable of reacting with an amino group instead of a compound having at least one of a primary amino group, a secondary amino group and ammonia by reacting a compound having other than an anhydride group with water. Preferably, a reaction between a compound having a group other than an unsaturated aliphatic group and a compound that generates at least one of a primary amino group, a secondary amino group, and ammonia by reaction with water is preferably used. be able to.

The resin composition of the present invention 2 is, similarly to the resin composition of the present invention 1, prepared by reacting an unsaturated aliphatic compound (A2) with water to form a primary amino group, a secondary amino group and ammonia. A compound (B) that forms at least one of them;
It may be a two-pack type that is stored separately in individual containers and mixed at the time of use.

The resin composition of the present invention 2 is particularly used for the purpose of adjusting the curing state in multiple stages during the curing process.
A curing catalyst for curing the unsaturated aliphatic compound with oxygen may be added.

The curing catalyst is not particularly restricted but includes, for example, heavy metal salts of carboxylic acids such as cobalt octylate, cobalt naphthenate and lead naphthenate; manganese salts such as manganese linoleate; calcium salts, cerium salts and zinc. Salts, zircon salts and the like. The above curing catalysts may be used alone or in combination of two or more.

The curing catalyst is preferably one that can be mixed and dispersed in other materials used. The curing catalyst may be added in an appropriate amount as needed, but is preferably added in an amount of about 0.001 to 10 parts by weight based on 100 parts by weight of the unsaturated aliphatic compound.

[0211] The resin composition of the present invention 2 has excellent storage stability because the unsaturated aliphatic group does not react when moisture is blocked, and has an amine having active hydrogen in the presence of moisture. Are generated and the reaction with the unsaturated aliphatic group proceeds to cure.

The resin composition of the present invention 3 comprises a (meth) acryloyl group-containing compound (A3) and a compound which forms at least one of a primary amino group, a secondary amino group and ammonia by reaction with water. (B).

The resin composition of the present invention 3 contains a (meth) acryloyl group-containing compound (A3). Above (meta)
The acryloyl group-containing compound (A3) comprises an organic compound having an acryloyl group or a methacryloyl group, and may be any of a monomer, an oligomer, and a polymer. In addition, the (meth) acryloyl group-containing compound (A
3) includes an organic compound constituting atom such as carbon, hydrogen, oxygen, nitrogen, sulfur, and phosphorus.

The (meth) acryloyl group contained in the (meth) acryloyl group-containing compound (A3) may be present at the terminal of the molecular skeleton or as a side chain, and its structure and molecular weight are limited. However, an organic compound having an average of two or more (meth) acryloyl groups per molecule is preferable. Here, the average number of (meth) acryloyl groups per molecule refers to the total number of (meth) acryloyl groups in the (meth) acryloyl group-containing compound (A3) and the number of (meth) acryloyl group-containing compounds (A3) in the (meth) acryloyl group-containing compound (A3). Can be determined by dividing by the total number of molecules.

As the above (meth) acryloyl group-containing compound (A3), a solid that can be melted by heating at room temperature is used, and the compound is solid at room temperature. Can be a hot melt type.

The (meth) acryloyl group-containing compound (A3) can be contained in another functional group molecule as required. Examples of the functional group include a hydroxyl group, an epoxy group, a carboxyl group, an acid anhydride group, a saturated aliphatic alkyl group, an unsaturated aliphatic alkyl group, an alicyclic alkyl group,
Aromatic alkyl group, vinyl group, allyl group, isocyanate group, alkoxyl group, silyl group, halogen group, phosphate group, thioether group, thiol group, thiocarboxyl group, amide group, urethane group, imide group, carbonate group, sulfone Examples include an acid group, a carbonyl group, a tertiary amino group, and a group that forms at least one of a primary amino group, a secondary amino group, and ammonia by reaction with water.

The (meth) acryloyl group-containing compound (A3) is not particularly limited, and examples thereof include the following. Long chain aliphatic acrylates such as dodecyl acrylate and tridecyl acrylate; allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, butoxyethyl acrylate, butoxyethyl methacrylate, butanediol monoacrylate, butoxytriethylene glycol acrylate, butyl acrylate modified butyl acrylate , T-butylaminoethyl methacrylate, caprolactone acrylate, 3-chloro-2-hydroxypropyl methacrylate, 2-cyanoethyl acrylate,
Cyclohexyl acrylate, cyclohexyl methacrylate, dicyclopentanyl acrylate, dicyclopentanyl methacrylate.

Alicyclic modified neopentyl glycol acrylate, 2,3-dibromopropyl acrylate,
3-dibromopropyl methacrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentenyloxyethyl methacrylate, N, N-diethylaminoethyl acrylate, N,
N-diethylaminoethyl methacrylate, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, 2-ethoxyethyl acrylate, 2-ethoxyethyl methacrylate, 2- (2
-Ethoxyethoxy) ethyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate.

Glycerol methacrylate, glycidyl acrylate, glycidyl methacrylate, heptadecafluorodecyl acrylate, heptadecafluorodecyl methacrylate, 2-hydroxyethyl acrylate,
-Hydroxyethyl methacrylate, caprolactone-modified 2-hydroxyethyl acrylate, caprolactone-modified 2-hydroxyethyl methacrylate, 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, isobonyl acrylate, Isobonyl methacrylate, isodecyl acrylate, isodecyl methacrylate, isooctyl acrylate, lauryl acrylate, lauryl methacrylate.

Γ-methacryloxypropyltrimethoxysilane, 2-methoxyethyl acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, methoxytetraethylene glycol methacrylate, methoxypolyethylene glycol 400 methacrylate, methoxypolyethylene glycol 1000 Methacrylate, methoxydipropylene glycol acrylate, methoxylated cyclodecatriene acrylate, morpholine acrylate, nonylphenoxy polyethylene glycol acrylate, nonylphenoxy polypropylene glycol acrylate, octafluoropentyl acrylate, octafluoropentyl methacrylate, Chill acrylate.

Phenoxyhydroxypropyl acrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, phenoxydiethylene glycol acrylate, phenoxytetraethylene glycol acrylate, phenoxyhexaethylene glycol acrylate, ethoxy-modified phenoxylated phosphate acrylate,
Ethoxy-modified phenoxy-modified phosphate methacrylate, phenoxy methacrylate, ethoxy-modified phosphate acrylate, ethoxy-modified phosphate methacrylate, ethoxy-modified butoxy-phosphate acrylate, ethoxy-modified butoxy-phosphate methacrylate, ethoxy-modified octoxy-phosphate acrylate, ethoxy-modified octoxy Phosphoric acid methacrylate, ethoxy-modified phthalic acrylate, ethoxy-modified phthalic methacrylate, ethoxy-propoxy-modified phthalic methacrylate.

Polyethylene glycol 90 methacrylate, polyethylene glycol 200 methacrylate, polyethylene glycol 400 methacrylate, polypropylene glycol 300 methacrylate, polypropylene glycol methacrylate, polypropylene glycol 500 methacrylate, polypropylene glycol 8
00 methacrylate, polyethylene glycol / polypropylene glycol methacrylate, polyethylene glycol / polybutylene glycol methacrylate, stearyl acrylate, stearyl methacrylate.

Ethoxy-modified succinic acrylate, ethoxy-modified succinic methacrylate, sodium sulfonic acrylate, sodium sulfonic methacrylate, tetrafluoropropyl acrylate, tetrafluoropropyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, caprolactone-modified tetrahydro Furfuryl acrylate, trifluoroethyl acrylate, trifluoroethyl methacrylate.

Bisphenol A dimethacrylate, bisphenol A diglycidyl ether diacrylate, ethoxy-modified bisphenol A diacrylate, ethoxy-modified bisphenol A dimethacrylate, ethoxy-modified bisphenol F diacrylate, ethoxy-modified bisphenol S diacrylate, ethoxy-modified hydrogenated bisphenol A Diacrylate, tetrabromobisphenol A diacrylate, 1,3-butylene glycol diacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,4-
Butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, glycidyl ether-modified 1,6-hexanediol diacrylate.

Polyethylene glycol 200 diacrylate, polyethylene glycol 200 dimethacrylate, polyethylene glycol 400 diacrylate, polyethylene glycol 400 dimethacrylate, polyethylene glycol 600 diacrylate, polyethylene glycol 600 dimethacrylate, polyethylene glycol 1000 dimethacrylate, polypropylene glycol 400 diacrylate Propylene glycol 400 dimethacrylate, ethylene glycol dimethacrylate, glycidyl ether-modified ethylene glycol diacrylate, glycidyl ether-modified ethylene glycol dimethacrylate.

Diethylene glycol diacrylate, diethylene glycol dimethacrylate, glycidyl ether-modified diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, glycidyl ether-modified propylene glycol diacrylate, Tripropylene glycol diacrylate, glycerol acrylate / methacrylate, glycerol dimethacrylate, glycidyl ether-modified glycerol triacrylate, triglycerol diacrylate.

Propoxy-modified glyceryl triacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol-modified trimethylolpropane diacrylate, neopentyl glycol diacrylate hydroxypivalate, neopentyl glycol diacrylate hydroxypivalate, neopentyl glycol hydroxypivalate diacrylate , Bis (acryloxyneopentyl glycol) adipate, dicyclopentanyl diacrylate, allylated cyclohexyl diacrylate, methoxylated cyclohexyl diacrylate; 1,
14-tetradecanediol diacrylate, 1,15
Long chain aliphatic diacrylates such as pentadecanediol diacrylate.

Long-chain aliphatic dimethacrylates such as 1,14-tetradecanediol dimethacrylate and 1,15-pentadecanediol dimethacrylate; trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethoxy-modified trimethylolpropane triacrylate, propoxy Modified trimethylolpropane triacrylate, glycidyl ether-modified trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, stearic acid-modified pentaerythritol diacrylate.

Pentaerythritol triacrylate,
Pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol triacrylate, alkyl-modified dipentaerythritol tetraacrylate, alkyl-modified dipentaerythritol pentaacrylate, caprolactone-modified Dipentaerythritol hexaacrylate.

Bis (acryloxyethyl) isocyanurate, tris (acryloxyethyl) isocyanurate, tris (methacryloxyethyl) isocyanurate, caprolactone-modified tris (acryloxyethyl)
Isocyanurate, ethoxy-modified phosphate diacrylate, ethoxy-modified phosphate dimethacrylate, ethoxy-modified phosphate triacrylate, caprolactone / ethoxy-modified phosphate dimethacrylate, glycidyl ester-modified phthalate diacrylate, zinc diacrylate, zinc dimethacrylate.

N-hexyl acrylate, propoxy-modified bisphenol A bis (hydroxyfluoropropyl acrylate), N-methacryloxy-N-carboxymethylpiperidine, N-methacryloxy-N, N-dicarboxymethyl-p-phenylenediamine, hydroxynaphthoxy Propyl methacrylate, methacryloxyethyl phosphorisphenyl, 4-methacryloxyethyl trimellitic acid, 4-methacryloxyethyl trimellitic anhydride, isocyanateethyl methacrylate.

Epoxy acrylate, epoxidized oil acrylate, urethane acrylate, polyester acrylate, polyether acrylate, silicon acrylate, polybutadiene acrylate, polystyrylethyl methacrylate, polycarbonate diacrylate.

Those in which part or all of the acryloyl groups of these acryloyl group-containing compounds are replaced by methacryloyl groups, and those in which these methacryloyl group-containing compounds have part or all of the methacryloyl groups replaced by acryloyl groups.

Examples of the (meth) acryloyl group-containing compound (A3) include, in addition to the (meth) acryloyl group-containing compounds exemplified above, a hydroxyl group, an epoxy group,
Carboxyl group, acid anhydride group, saturated aliphatic alkyl group, unsaturated aliphatic alkyl group, alicyclic alkyl group, aromatic alkyl group, vinyl group, allyl group, isocyanate group, alkoxyl group, silyl group, halogen group, phosphoric acid Group, thioether group, thiol group, thiocarboxyl group, amide group, urethane group, imide group, carbonate group, sulfonic acid group, carbonyl group, tertiary amino group, primary amino group by reaction with water, secondary amino group And those having a functional group such as a group that forms at least one of ammonia and the like.

Examples of the (meth) acryloyl group-containing compound (A3) include, in addition to the above-mentioned (meth) acryloyl group-containing compounds, ethoxy-modified, propoxy-modified, glycidyl ether-modified, glycidyl ester-modified, caprolactone-modified compounds and the like. Is mentioned. These may be used alone or in combination of two or more.

The method for producing the (meth) acryloyl group-containing compound (A3) is not particularly limited.
The following methods are mentioned. 1) Addition reaction of hydroxy (meth) acrylate to an isocyanate group of an isocyanate group-containing compound. 2) A diisocyanate compound is reacted with a hydroxyl group of a hydroxyl group-containing compound such as a polyether such as polyethylene glycol or polypropylene glycol to form an isocyanate group, and a hydroxy (meth) acrylate is added thereto.

3) The hydroxyl group of the hydroxyl group-containing compound is esterified with (meth) acrylic acid,
(Meth) acryloyl group. 4) The hydroxyl group of the hydroxyl group-containing compound is
(Meth) acryloyl groups are obtained by transesterification with (meth) acrylic esters. 5) The epoxy group of the epoxy group-containing compound is reacted with (meth) acrylic acid to form a (meth) acryloyl group.

The above transesterification reaction and esterification reaction can be carried out in the presence of a usual acid catalyst such as Swedcut 5. Any of the above methods can be carried out at room temperature or under heating if necessary, under atmospheric pressure, or at above atmospheric pressure or below atmospheric pressure if necessary. Any of the above methods can be performed under anhydrous conditions if necessary.

In any of the above methods, if a starting material is a compound which is solid at room temperature and can be melted by heating, or if an appropriate compound is selected as a starting material even if it is liquid at room temperature, the starting material can be used. Thus, a (meth) acryloyl group-containing compound (A3) which can be melted and is solid at ordinary temperature can be obtained.

The above (meth) acryloyl group-containing compound (A3) may be a hydroxyl group, an epoxy group, a carboxyl group, an acid anhydride group, an unsaturated aliphatic alkyl group, a vinyl group, an allyl group, an isocyanate group, an alkoxyl group, a silyl group, a halogen group. When it has a functional group such as a group, a phosphate group, a thiol group, a thiocarboxyl group, an amide group, a urethane group, an imide group, a carbonate group, a sulfonic acid group, and a carbonyl group, it has a functional group capable of reacting with the functional group. By reacting with a solid resin at room temperature that can be melted by heating,
The (meth) acryloyl group-containing compound (A3) can be solid at normal temperature and can be melted by heating.

When any of the starting materials or the product is a material having a high viscosity at room temperature or is a solid, it may be used under appropriate heating conditions, or ethyl acetate, cyclohexane, aromatic hydrocarbon, ether, or the like. , Dioxane, halogenated hydrocarbon, ketone and the like. The above-mentioned production methods can be performed alone or in combination of two or more.

In the present invention 3, the compound (B) used together with the (meth) acryloyl group-containing compound (A3) is the compound (B) in the resin composition of the present invention 1.
But having no other functional group capable of reacting with a (meth) acryloyl group in the molecule instead of having another functional group capable of reacting with an acid anhydride group in the molecule It is preferred that

In the resin composition of the present invention 3, the compound (A3) containing at least one of a primary amino group, a secondary amino group and ammonia by reacting the (meth) acryloyl group-containing compound (A3) with water. The content of B) is appropriately determined according to the degree of curing at the time when the curing reaction is completed, but is preferably contained in a weight ratio of 1/100 to 100/1.

When the compound (B) contains a (meth) acryloyl group, and when the (meth) acryloyl group-containing compound (A3) reacts with water to form a primary amino group,
In the case where at least one of a primary amino group and ammonia is produced, the compound of the present invention
Can be constituted.

The resin composition of the present invention 3 can be made into a solvent type resin composition by adding a solvent. As the solvent, those similar to those exemplified in the present invention 1 can be used, but instead of having no other functional group capable of reacting with an acid anhydride group in the molecule,
It is preferable that the compound does not have another functional group capable of reacting with the (meth) acryloyl group in the molecule.

In producing the resin composition of the present invention 3, by adding other resins such as a thermoplastic resin and a tackifying resin, a hot-melt type composition can be obtained or the adhesion to a substrate can be improved. Or can be. As the thermoplastic resin and the tackifying resin, those similar to those exemplified in the present invention 1 can be used, but those having no other functional group capable of reacting with an acid anhydride group in the molecule. Instead, it is preferable that the compound does not have another functional group capable of reacting with the (meth) acryloyl group in the molecule.

In the case of curing the resin composition of the present invention 3, the curing time can be adjusted by adding a catalyst. As the above-mentioned catalyst, those similar to those exemplified in the first embodiment of the present invention can be used. In the present invention 3, the addition amount of the catalyst is 0.01 to 100 parts by weight of the (meth) acryloyl group-containing compound (A3).
-10 parts by weight is preferred.

When the resin composition of the present invention 3 is applied to a substrate, the adhesion to the substrate can be improved by adding an adhesion improver. As the adhesion improver, the same one as exemplified in the first embodiment of the present invention can be used. In the present invention 3, the addition amount of the adhesion improver is preferably 0.01 to 10 parts by weight based on 100 parts by weight of the (meth) acryloyl group-containing compound (A3).

In producing the resin composition of the present invention 3, a dehydrating agent, a storage stability improver, an antioxidant, a stabilizer, a plasticizer, a wax, a non-reactive diluent,
Reactive diluents, fillers, pigments, dyes, flame retardants, blowing agents,
UV absorbers, antistatic agents, fungicides, fragrances, viscosity modifiers and the like can be added. As such a thing, the same thing as illustrated in the present invention 1 can be used.

In the resin composition of the present invention 3, one or more of the other curing reactions exemplified in the present invention 1 can be used in combination. In this case, the resin composition is a functional group capable of reacting with an amino group. A functional group capable of reacting with an amino group instead of a compound having at least one of a primary amino group, a secondary amino group and ammonia by reacting a compound having other than an anhydride group with water. Preferably, a reaction between a compound having a group other than a (meth) acryloyl group and a compound that forms at least one of a primary amino group, a secondary amino group, and ammonia by reaction with water is preferably used. be able to.

The resin composition of the present invention 3 comprises, similarly to the resin composition of the present invention 1, a primary amino group, a secondary amino group and a (meth) acryloyl group-containing compound (A3) by reaction with water. The compound (B) that produces at least one of ammonia may be stored in a separate container and stored in a separate container to be mixed at the time of use.

In the case where the resin composition of the present invention 3 is a hot-melt type composition, in order to prevent the above (meth) acryloyl group-containing compound (A3) from being thermally polymerized during heating, And / or a thermal polymerization inhibitor may be added for other purposes. The thermal polymerization inhibitor is not particularly limited, for example, hydroquinone,
Methoquinone (hydroquinone monomethyl ether), benzoquinone, p-benzoquinone, 2,6-t-butyl-
p-cresol, 2,3-dimethyl-6-t-butylphenol, anthraquinone and the like. The thermal polymerization inhibitors may be used alone or in combination of two or more.

The thermal polymerization inhibitor is preferably one that can be mixed and dispersed in another material to be used. The thermal polymerization inhibitor may be added in an appropriate amount as needed, but is preferably added in an amount of about 0.01 to 50 parts by weight based on 100 parts by weight of the (meth) acryloyl group-containing compound (A3). .

The resin composition of the present invention 3 is particularly used for forming a thick cured layer in a short time, or for bonding a large-area non-moisture-permeable material such as metal or glass in a short time. ,
A polymerization initiator or a polymerization accelerator for an anaerobic polymerization reaction initiated by blocking oxygen used for an anaerobic adhesive or the like may be added.

The polymerization initiator and the polymerization accelerator are not particularly limited, and include, for example, cumene hydroperoxide, benzoquinone and the like. The above-mentioned polymerization initiators and polymerization accelerators may be used alone or in combination of two or more.

The (meth) acryloyl group-containing compound (A3) used in the case of utilizing the above anaerobic polymerization reaction is not particularly limited, but ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate. Methacrylate, polyethylene glycol dimethacrylate, ethoxy-modified bisphenol A dimethacrylate, hydrogenated ethoxy-modified bisphenol A dimethacrylate, ethoxy-modified phthalic dimethacrylate, trimethylolpropane trimethacrylate, cyclohexyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate ,
N, N-diethylaminoethyl methacrylate, tetrahydrofurfuryl methacrylate, butylaminoethyl methacrylate and the like are preferred.

The (meth) acryloyl group-containing compound (A3) is preferably a compound which can be mixed and dispersed in another material to be used. The (meth) acryloyl group-containing compound (A3) may be used alone,
More than one kind may be used in combination.

The resin composition of the present invention 3 is used for an ultraviolet curable adhesive or the like, particularly for the purpose of curing a portion which can be irradiated with light or radiation before curing with moisture. Such a photopolymerization initiator or a photopolymerization initiation assistant may be added. The photopolymerization initiator is not particularly limited,
For example, the following are mentioned.

4-phenoxydichloroacetophenone,
4-t-butyldichloroacetophenone, 4-t-butyltrichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2
-Hydroxy-2-methylpropan-1-one, 1-
(4-Dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, an allyl ketone-containing photoinitiator.

1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether Benzoin isobutyl ether, benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone.

4-benzoyl-4'-methyldiphenyl sulfide, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, Isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, α-acyloxime ester, 1-phenyl-1,2-propanedione-2 (O-ethoxycarbonyl) oxime, acylphosphine oxide.

2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethylbenzoyldiphenylphosphine oxide, benzoyldiethoxyphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone,
Camphorquinone, dibenzosuberone, 2-ethylanthraquinone, 4 ', 4 "-diethylisophthalophenone, 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; methylphenylglyoxy Glyoxyesters such as acrylates; 3-ketocoumarin, tetramethylthiuram monosulfide, azobisisobutylnitrile, acetophenone, α-naphthyl,
Acenaphthene, p, p'-dimethoxybenzyl, p,
p'-Dichlorobenzyl.

The photopolymerization initiation aid is not particularly limited, and examples thereof include the following. Triethanolamine, methyldiethanolamine, triisopropanolamine, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, Michler's ketone, ethyl 2-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylamino Polymerizable tertiary amines such as (n-butoxy) ethyl benzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylaminoethyl methacrylate; other aliphatic amines; Aromatic amines.

The above-mentioned photopolymerization initiator and the above-mentioned photopolymerization initiation auxiliary agent are preferably those which can be mixed and dispersed in other materials used. The optimal amount of the photopolymerization initiator and the photopolymerization initiation aid is determined by the curing speed of the composition by light, the intensity of the irradiated light, the thickness of the composition, and the like. It is preferable to add 0.1 to 4 parts by weight per part. The photopolymerization initiator and the photopolymerization initiation aid may be used alone or in combination of two or more.

When a polymerization reaction initiated by light or radiation is used, the resin composition of the present invention 3 may contain a radically polymerizable vinyl compound other than the (meth) acryloyl group-containing compound (A3). Good. Examples of the radically polymerizable vinyl compound include the following.

Vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether and cyclohexyl vinyl ether; alkenyl benzenes such as styrene, vinyl toluene, α-methyl styrene, chloromethyl styrene, and still benzene; N-vinylpyrrolidone, N-vinylcaprolactam, α-olefin, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride.

The above-mentioned radical polymerizable vinyl compound is preferably a compound which can be mixed and dispersed in another material to be used, and further comprises a primary amino group and / or a secondary amino group, and
Those having no other functional group capable of reacting with the (meth) acryloyl group in the molecule are preferred. The above radical polymerizable vinyl compounds may be used alone or in combination of two or more. The curing reaction of the hydrolyzable silyl group-containing resin, the anaerobic polymerization reaction, and the light / radiation polymerization reaction may be used in combination of two or more.

In the case where the resin composition of the present invention 3 starts curing by irradiation with light such as ultraviolet light, visible light, infrared light, etc., the light having an effective wavelength can be applied directly or through a transparent or translucent substrate. Can be cured by irradiating an effective amount of

The light irradiation source in this case is not particularly limited as long as it is generally used as an irradiation source of light having an effective wavelength, and examples thereof include a carbon arc, a mercury vapor arc, a fluorescent lamp, and an argon glow lamp. , Incandescent lamp,
Halogen lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, flash UV lamps, deep UV lamps, high-pressure mercury lamps, low-pressure mercury lamps, xenon short lamps, high-power water-cooled xenon lamps, xenon flash lamps; gallium halide lamps, thallium halide lamps, etc. Metal halide lamps; tungsten filament lamps,
Sunlight and the like.

Further, the resin composition of the present invention 3 can be cured by an electron beam. In this case, curing is performed by irradiating an effective amount of an electron beam directly or through a transparent or translucent substrate to the electron beam. The irradiation source of the electron beam at this time is not particularly limited as long as it is generally used. These curing methods may be performed alone or in combination of two or more.

The resin composition of the present invention 3 has excellent storage stability because the (meth) acryloyl group does not react when moisture is blocked, and has an amine having active hydrogen when moisture is present. Is generated and the reaction with the (meth) acryloyl group proceeds to cure.

The present invention 4 is a curable adhesive mainly comprising the resin composition of the present invention 1, the resin composition of the present invention 2 or the resin composition of the present invention 3. As described above, the resin composition of the present invention 1, the resin composition of the present invention 2 and the resin composition of the present invention 3 have good adhesion to a substrate and sufficient storage stability, and Since a heating device, a light / radiation irradiating device, and the like are not required, and operations such as two-component measurement mixing and blocking of oxygen are not required, it can be suitably used as a curable adhesive.

The present invention 5 relates to the curable adhesive of the present invention 4,
Further, it is a curable adhesive containing at least one of a thermoplastic resin and a tackifier resin. Invention 5
The thermoplastic resin used in is not particularly limited, and includes, for example, those similar to the thermoplastic resins exemplified above in the description of the present invention 1. The tackifier resin used in the present invention 5 is not particularly limited, and includes, for example, those similar to the tackifier resins exemplified above in the description of the present invention 1.

The present invention 6 relates to the curable adhesive of the present invention 4,
Further, it is a curable adhesive comprising a resin having a hydrolyzable silyl group and a curing catalyst for curing the resin. The curable adhesive of the present invention 6 has excellent storage stability and flexibility after curing because a resin having a hydrolyzable silyl group and a curing catalyst for curing the resin are added. Since it is large and exhibits tackiness, a temporary fixing jig is not required in the curing process.

The resin having a hydrolyzable silyl group is not particularly limited, and examples thereof include an alkoxylyl group, an acyloxysilyl group, a ketoximesilyl group, an aminoxysilyl group, an amidosilyl group, an aminosilyl group, an alkenyloxy group. A polymer having a hydrolyzable silyl group such as a mercaptosilyl group in a molecule is exemplified. Preferably, the following general formula (15);

[0276]

Embedded image

(In the formula, R ¹ represents a monovalent hydrocarbon group having 1 to 12 carbon atoms, and R ² represents a monovalent hydrocarbon group having 1 to 6 carbon atoms. A polymer having hydrolyzable silyl groups at both ends of the molecular chain, for example, di (methyldimethoxysilyl) polypropylene glycol and the like. The resin having a hydrolyzable silyl group may be used alone or in combination of two or more.

The resin having a hydrolyzable silyl group is preferably a resin which can be mixed and dispersed in another material to be used, and more preferably has a primary amino group and / or a secondary amino group in the molecule. Not something.

When the resin having a hydrolyzable silyl group is used together with the acid anhydride-containing compound (A1), the resin having no other functional group capable of reacting with the acid anhydride group in the molecule is used. When used together with the unsaturated aliphatic compound (A2), the compound does not have a functional group capable of reacting with the unsaturated aliphatic group in the molecule, and the compound containing the (meth) acryloyl group ( When used together with A3), it is preferable that the compound does not have a functional group capable of reacting with a (meth) acryloyl group in the molecule.

The resin having a hydrolyzable silyl group is as follows:
An appropriate amount may be added as needed, but 10 to 1000 parts by weight based on 100 parts by weight of the acid anhydride group-containing compound (A1), the unsaturated aliphatic compound (A2) or the (meth) acryloyl group-containing compound (A3). It is preferable to add to the extent.

The curing catalyst for curing the resin having a hydrolyzable silyl group is not particularly limited, and examples thereof include the following. Lead carboxylate such as lead octylate; dibutyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, dibutyltin diphthalate, dibutyltin marker peptide, dibutyltin thiocarboxylate, dibutyltin dimaleate, dibutyltin malate laurate mixture, dibutyltin Diacetylacetonate, dioctyltin laurate, dioctyltin malate, dioctyltin marker peptide, dioctyltin thiocarboxylate, tin naphthenate, tin octylate, tin stearate, tin acetylacetone, dimethyltin compound, tributyltin compound, dibutyltin oxide, phthalate Organic tin compounds such as reaction products with acid esters and sulfur-containing organic tin compounds.

Titanates such as tetrabutyl titanate and titrapropyl titanate; organic aluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate; butylamine, octylamine, laurylamine , Dibutylamine, monoethanolamine, diethanolamine,
Triethanolamine, diethylenetriamine, triethylenetetraamine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, Amine compounds such as N-methylmorpholine, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo [5,4,0] undecene-7 (DBU);

Salts of amine compounds such as dibutylamine-2-ethylhexoate with carboxylic acids; low molecular weight polyamide resins obtained from excess polyamines and polybasic acids; reaction of excess polyamines with epoxy compounds Product, γ-aminopropyltrimethoxysilane, N- (β
Silane coupling agents having an amino group such as -aminoethyl) aminopropylmethyldimethoxysilane; The above curing catalysts may be used alone or in combination of two or more.

The curing catalyst is preferably one that can be mixed and dispersed in another material to be used. The curing catalyst may be added in an appropriate amount as needed, but may be added in an amount of 0.1 to 100 parts by weight based on the added resin having a hydrolyzable silyl group.
It is preferable to add about 10 parts by weight.

[0285]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Examples 1 to 5, Comparative Examples 1 and 2 The materials used in Examples 1 to 5 and Comparative Examples 1 and 2 were as follows. The acid anhydride resin 1 was made of maleic anhydride polybutadiene (BN-1015, acid value 140 KOHmg).
/ G, liquid at normal temperature, manufactured by Nippon Soda Co., Ltd.). Silane compound 1 is vinyltrimethoxysilane (KBM1003,
Shin-Etsu Chemical Co., Ltd.). Ketimine 1 was ketimine (H-2, liquid at room temperature, manufactured by Yuka Shell Epoxy).

Oxazolidine 1 is bisoxazolidine (Incozol4, molecular weight 500, liquid at normal temperature,
ustria1 Copolymers Limited). Silamine 1 was 1,3-bis (trimethylsilylaminomethyl) benzene and was prepared as follows.

M-Xylenediamine 12.6 g (0.1
Mol) and 20.2 g (0.2 mol) of triethylamine were stirred in 100 ml of dry toluene and treated with 21.7 g (0.2 mol) of trimethylchlorosilane for 1 hour. After stirring the mixture for another 10 hours, the mixture was heated under reflux for 1 hour, cooled and filtered. The filtrate was evaporated to give 25.2 g of silamine 1.
Obtained. The theoretical equivalent of active hydrogen of the amino group generated by the reaction of this 1,3-bis (trimethylsilylaminomethyl) benzene with water was 70.

Silazane 1 was hexamethyldisilazane (TSL8802, molecular weight 161, liquid at normal temperature, manufactured by Toshiba Silicone Co., Ltd.). Enamine 1 is N, N'-bis (1-cyclohexen-1-yl) piperazine,
It was prepared as follows.

8.6 g (0.1 mol) of piperazine, 19.6 g (0.2 mol) of cyclohexanone and 0.5 g of p-toluenesulfonic acid were added to 100 ml of xylene to give 2
After heating under reflux for 4 hours, xylene and the reaction product were distilled off to obtain 20.3 g of enamine 1. This N, N'-bis (1
-Cyclohexen-11-yl) piperazine has a theoretical equivalent of 12 active hydrogens of the active hydrogen of the amino group formed by the reaction with water.
It was 3.

In the compounding amounts shown in Table 1, an acid anhydride resin, calcium carbonate, and titanium oxide were charged into a planetary mixer, the pressure was reduced to 20 Torr or less, and the mixture was cooled at room temperature to 30 rpm.
After mixing for 30 minutes, the remaining components were charged, and further mixed at room temperature under a nitrogen stream at 30 rpm for 30 minutes. Storage stability of the resulting formulation, curing time,
The adhesiveness was evaluated by the following method. The results are shown in Table 1.

Evaluation Method (1) Storage Stability The composition was sealed in a can, stored at 23 ° C., and opened 7 days later. X. (2) Curing time The compound was placed on a polyethylene terephthalate film for 25 minutes.
mm × 50mm × 3mm, 23 ℃,
The mixture was left in an atmosphere of 60%, and the time until the composition was cured was measured.

(3) Adhesion The composition was applied to a mortar piece so as to have a size of 25 mm × 50 mm × 3 mm, left in an atmosphere of 23 ° C. and 60% for 7 days, and then peeled off by hand.も の indicates that the composition was cohesively fractured, △ indicates that the composition was broken at the interface between the composition and the mortar piece, and x indicates that the composition was not cured and remained liquid.

[0294]

[Table 1]

Examples 6 to 15 and Comparative Examples 3 to 6 Materials used in Examples 6 to 15 and Comparative Examples 3 to 6 were as follows. The acid anhydride resin 1 was the same as described above. The acid anhydride resin 2 was maleic anhydride SEBS (Tuftec M1962, acid value 7 mg · CH ₃ Na / g, room temperature pellets, manufactured by Asahi Chemical Industry Co., Ltd.). Acid anhydride resin 3
Is a copolymer of itaconic anhydride and an acrylate, and was prepared as follows.

In a 1-liter separable flask, 120 parts by weight of butyl acetate was added, and the temperature was raised to 100 ° C., and 21 parts by weight of n-butyl acrylate and 95 parts by weight of n-butyl methacrylate were added.
Parts by weight, 34 parts by weight of 2-ethylhexyl methacrylate,
45 parts by weight of itaconic anhydride, 60 parts by weight of dioxane, t
A solution comprising 20 parts by weight of -butylperoxyhexanoate was added dropwise over 3 hours, and stirring was further continued for 2 hours to obtain a solution of the acrylate ester copolymer. I left. The molecular weight of this copolymer is 250
It was 0.

The thermoplastic resin 1 is a mixture of an ethylene-vinyl acetate copolymer resin and a tackifier resin, and was prepared as follows. Paraffin wax (SP-0145,
20 parts by weight of Nippon Seiro Co., Ltd.) and 40 parts by weight of rosin ester (ester gum HS, Arakawa Chemical Industries) are put into a beaker and melted in an oil bath set at 160 ° C., and ethylene-acetic acid is added thereto Vinyl copolymer resin (Evaflex # 220, vinyl acetate content 28% by weight, melt index 150, manufactured by Mitsui DuPont Polychemical Co., Ltd.) 4
0 parts by weight were charged and mixed for 1 hour.

The thermoplastic resin 2 is a mixture of an acrylate copolymer and a tackifier resin, and was prepared as follows. 100 parts by weight of cyclohexane is placed in a 1-liter separable flask, and n-butyl acrylate 85 is added.
Parts by weight, 15 parts by weight of methyl methacrylate, 2-polystyrylethyl methacrylate (macromer C-4500,
Weight average weight 13000, glass transition temperature 100 ° C,
10 parts by weight (manufactured by Sartomer Co., Ltd.) and 0.5 part by weight of lauryl mercaptan were added, mixed, and then heated. Under reflux of cyclohexane, azobisisobutyronitrile was added in an amount of 0.01 part by weight every hour. Radical copolymerization was performed for 6 hours to obtain a solution of an acrylate copolymer.
50 parts by weight of a tackifier resin (FTR-7125, manufactured by Mitsui Petrochemical Industries, Ltd.) was added thereto, and the solvent was distilled off under reduced pressure at 130 ° C.

The thermoplastic resin 3 was a rosin ester (Superester A-100, manufactured by Arakawa Chemical Industries, Ltd.). Silane compound 1 was the same as described above. The silane compound 2 was γ-glycidoxypropyltrimethoxysilane (KBM403, manufactured by Shin-Etsu Chemical Co., Ltd.). Ketimine 1 was the same as above. Oxazolidine 1 is
Same as above.

An acid anhydride resin, calcium carbonate, and a thermoplastic resin were charged into a jacketed planetary mixer capable of circulating heated oil at the compounding amounts shown in Tables 2 and 3, and the pressure was reduced to 20 Torr or less. , 160
After mixing at 30 rpm for 30 minutes at 30 ° C., the remaining components were charged and further mixed under nitrogen at 120 ° C. at 30 rpm for 3 minutes.
It was blended by mixing for 0 minutes. The storage stability, initial strength, and heat resistance of the obtained composition were evaluated by the following methods. The results are shown in Tables 2 and 3.

Evaluation method (1) Storage stability The composition was sealed in a can, stored at 23 ° C, opened 7 days later, heated to 120 ° C, melted, and Those that did not melt were rated as x.

(2) Preparation of Adhesion Test Specimen 5 g of the compound was sandwiched between polyethylene terephthalate films having been subjected to a release treatment, and heated and pressed at 120 ° C. for 1 minute.
A film having a thickness of 100 μm was obtained. This is 25mm x 1
Cut out to 2.5mm, 25mm x 125mm x 1.6
A single lap joint was produced by sandwiching between two SPCC dull steel plates having a thickness of 1 mm, heating and pressing at 120 ° C. for 1 minute, and then cooling and pressing at 23 ° C. for 1 minute.

(3) Initial Strength Immediately after producing the above-mentioned adhesive test piece, a tensile shear test was conducted at 23 ° C. at a tensile speed of 5 mm / min.も の indicates that the composition was cohesively broken, Δ indicates that the interface was broken between the composition and the SPCC dull steel sheet, and X indicates that no strength was exhibited.

(4) Heat Resistance The above-mentioned adhesive test piece was exposed to an atmosphere of 23 ° C. and 60% for 7 days, and subjected to a tensile shear test at 120 ° C. at a tensile speed of 5 mm / min.凝集 indicates that the compound was cohesively broken, SP and SP
A sample in which the interface was broken between the CC dull steel plates was rated as Δ, and a sample in which no strength was exhibited was rated as x.

[0305]

[Table 2]

[0306]

[Table 3]

Examples 16 to 19 and Comparative Examples 7 to 10 The materials used in Examples 16 to 19 and Comparative Examples 7 to 10 were as follows. The acid anhydride resin 1 was the same as described above. The thermoplastic resin 4 is a mixture of an acrylate copolymer and a tackifier resin, and was prepared as follows.

In a 1-liter separable flask, 100 parts by weight of cyclohexane was added, and n-butyl acrylate 3 was added.
0 parts by weight, 70 parts by weight of 2-ethylhexyl acrylate,
2-Polystyrylethyl methacrylate (macromer C
-4500, weight average molecular weight 13000, glass transition temperature 100 ° C., 10 parts by weight of Sartomer Co., Ltd., and 0.12 part by weight of 3-mercaptopropyltrimethoxysilane (TSL8215, manufactured by Chisso Corporation) were added, mixed, and then heated. Under reflux of cyclohexane, azobisisobutyronitrile was added in an amount of 0.01 part by weight every hour, and radical copolymerization was carried out for 6 hours to obtain a solution of an acrylate copolymer. Add a tackifier resin (FTR-611)
0, manufactured by Mitsui Petrochemical Industry Co., Ltd.)
The solvent was distilled off under reduced pressure at 0 ° C.

The resin solution 1 was a mixture of an acrylate copolymer and cyclohexane, and was prepared as follows. 66 parts by weight of cyclohexane is placed in a 1-liter separable flask, 20 parts by weight of n-butyl acrylate, 80 parts by weight of 2-ethylhexyl acrylate, 2-polystyrylethyl methacrylate (macromer C-45).
00, weight average molecular weight 13000, glass transition temperature 10
At 0 ° C., 10 parts by weight of Sartomer) and 0.1 part by weight of 3-mercaptopropyltrimethoxysilane (TSL8215, manufactured by Chisso) were added, mixed, heated, and refluxed with azobisisobutyrocyclohexane. Nitrile was added in an amount of 0.01 part by weight every hour and radical copolymerization was carried out for 6 hours to obtain a solution of an acrylate copolymer.

The silane compound 1 was the same as described above.
Ketimine 1 was the same as above. Oxazolidine 1
Was the same as above.

In Examples 16 and 17, and Comparative Examples 7 and 8, an acid anhydride resin and a thermoplastic resin were added to a planetary mixer equipped with a jacket capable of circulating heated oil in the amounts shown in Table 4. 20Torr
After reducing the pressure to 150 ° C. and mixing at 30 rpm for 30 minutes, the remaining components were added and further mixed under nitrogen stream for 150 minutes.
It was blended by mixing at 30 ° C. and 30 rpm for 30 minutes.

In Examples 18 and 19 and Comparative Examples 9 and 10, the respective components were charged into the resin solution 1 at the compounding amounts shown in Table 4 and mixed under a nitrogen stream. In Examples 16 and 17, and Comparative Examples 7 and 8, the composition was applied on a 50 μm-thick polyethylene terephthalate film using a hot melt coater at 150 ° C. so as to have a thickness of 30 μm to prepare an adhesive sheet. did.

In Examples 18 and 19 and Comparative Examples 9 and 10, the composition was applied on a 50 μm-thick polyethylene terephthalate film using a baker-type applicator, and the sheet was dried at 120 ° C. for 3 minutes. Then, a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer thickness of 30 μm was prepared.

The storage stability, initial strength, and heat resistance of the obtained compound and pressure-sensitive adhesive sheet were evaluated by the following methods. The results are shown in Table 4. Evaluation method (1) Storage stability The formulation was sealed in a can, stored at 23 ° C, opened 7 days later, and then heated to 150 ° C in Examples 16 and 17 and Comparative Examples 7 and 8. The sample that was melted by the heat treatment was evaluated as ○, and the sample that did not melt due to progress of the curing was evaluated as ×. Example 18, 1
In Examples 9 and Comparative Examples 9 and 10, those that were liquid were evaluated as ○, and those that had progressed in curing were evaluated as X.

(2) Initial Adhesive Force Immediately after producing the adhesive sheet, a 180 ° peeling force at 23 ° C. was measured at a tensile speed of 300 mm / min using a stainless steel plate as an adherend according to JIS Z 0237.

(3) Initial holding force Immediately after the pressure-sensitive adhesive sheet was prepared, it was adhered to a stainless steel plate in an area of 25 mm × 25 mm according to JIS Z 0237, and a 1 kg weight was hung in a 40 ° C. oven.
The time until the weight fell was measured.

(4) Heat-resistant holding force Immediately after the pressure-sensitive adhesive sheet was prepared, the pressure-sensitive adhesive sheet was adhered to a stainless steel plate in an area of 25 mm × 25 mm according to JIS Z 0237, and then left in an atmosphere of 23 ° C. and 60% for 7 days. , A 1 kg weight was hung in an 80 ° C. oven, and the time until the weight fell was measured.

[0318]

[Table 4]

Examples 20 to 22, Comparative Examples 11 to 13 The materials used in Examples 20 to 22 and Comparative Examples 11 to 13 were as follows. The acid anhydride resin 1 was the same as described above. Modified Silicone 1 was poly (methyldimethoxysilyl ether) (Kanekasilyl 5B25, average molecular weight 8000, manufactured by Kaneka Chemical Co., Ltd.). The curing catalyst 1 was dibutyltin dilaurate (SB65, manufactured by Sankyo Kiki Co., Ltd.).

The thermoplastic resin 2 was the same as described above.
The thermoplastic resin 3 was the same as described above. Silane compound 1 was the same as described above. Ketimine 1 was the same as above.

In Example 20 and Comparative Example 11, Table 5
The acid anhydride resin, modified silicone, calcium carbonate, and titanium oxide are charged into the planetary mixer at the mixing amount shown in the above, the pressure is reduced to 20 Torr or less, and the mixture is mixed at room temperature at 30 rpm for 30 minutes, and then the remaining components are charged. The mixture was further mixed at room temperature under a stream of air at 30 rpm for 30 minutes.

In Examples 21 and 22, and Comparative Examples 12 and 13, the acid anhydride resin, the thermoplastic resin, and the jacketed planetary mixer capable of circulating the heated oil were added in the amounts shown in Table 5. The modified silicone and calcium carbonate were charged and the pressure was reduced to 20 Torr or less.
After mixing at 20 ° C. at 30 rpm for 30 minutes, the remaining components are charged, and further at 120 ° C. at 30 rpm under a nitrogen stream.
For 30 minutes.

In Example 22 and Comparative Example 13, 50
The composition was applied to a thickness of 30 μm on a polyethylene terephthalate film having a thickness of μm using a baker-type applicator, and allowed to stand at 23 ° C. and a 60% atmosphere for 1 hour.
An adhesive sheet was produced. The following evaluations were performed on the storage stability, curing time, adhesiveness, initial strength, heat resistance, initial adhesive strength, initial holding power, and heat holding power of the obtained composition and pressure-sensitive adhesive sheet. Table 5 shows the results.

Evaluation method (1) Storage stability The composition was sealed in a can, stored at 50 ° C. and opened 14 days later.
The sample which was heated and melted at 20 ° C. was evaluated as ○, and the sample which did not melt due to progress of the curing was evaluated as ×. In Examples 20 and 22, and Comparative Examples 11 and 13, those which were in a liquid state were evaluated as ○, and those in which curing was advanced were evaluated as ×.

(2) Adhesiveness The same procedure as in Example 1 was performed. (3) Preparation of Adhesion Test Specimen The same procedure as in Example 6 was performed. (4) Initial strength This was performed in the same manner as in Example 6.

(5) Heat Resistance The same procedure as in Example 6 was carried out. (6) Initial adhesive strength The same procedure as in Example 16 was carried out. (7) Heat-resistant holding force The same as in Example 16.

[0327]

[Table 5]

Examples 23 to 27 and Comparative Examples 14 and 15 The materials used in Examples 23 to 27 and Comparative Examples 14 and 15 were as follows. Unsaturated resin 1 was Chinese chestnut oil (liquid at normal temperature). Silane compound 1 was the same as described above. Ketimine 1 was the same as above. Oxazolidine 1 was the same as described above.

Sylamine 1 was the same as described above. Silazane 1 was the same as above. Enamine 1 was the same as above.

The unsaturated resin, calcium carbonate, and titanium oxide were charged into the planetary mixer at the compounding amounts shown in Table 6, and the pressure was reduced to 20 Torr or less, and the mixture was cooled at room temperature to 30 rpm.
After mixing for 30 minutes, the remaining components were charged, and further mixed at room temperature under a nitrogen stream at 30 rpm for 30 minutes.

The storage stability, curing time,
The adhesiveness was evaluated by the following method. The results are shown in Table 6. Evaluation method (1) Storage stability The evaluation was performed in the same manner as in Example 1.

(2) Curing time 25 minutes of the compound was placed on a polyethylene terephthalate film.
mm × 50 mm × 2 mm, applied at 23 ℃
The mixture was left in an atmosphere of 60%, and the time until the composition was cured was measured.

(3) Adhesiveness The composition was applied to a mortar piece so as to have a size of 25 mm × 50 mm × 2 mm, left in an atmosphere of 23 ° C. and 60% for 7 days, and peeled off by hand. ○ indicates that the compound has undergone cohesive failure.
The one that was broken at the interface between the composition and the mortar piece was rated as Δ, and the one that was not cured and remained liquid was rated as x.

[0334]

[Table 6]

Examples 28 to 37 and Comparative Examples 16 to 19 The materials used in Examples 28 to 37 and Comparative Examples 16 to 19 were as follows. Unsaturated resin 1 was the same as described above. Unsaturated resin 2 is a double-ended unsaturated fatty alkylated polyester and was prepared as follows.

To a crystalline polyester polyol (Dynacol 7360, molecular weight: 3500, melting point: 60 ° C., hydroxyl value: 30, manufactured by Huls) was added diphenylmethane diisocyanate (Sumidur 44V20, molecular weight: 250, manufactured by Sumitomo Bayer Urethane Co.) to the number of isocyanate groups / The mixture was mixed at 100 ° C. so that the ratio of the number of hydroxyl groups became 2.2, and reacted under a nitrogen stream for 3 hours. The mixture was stirred at a reduced pressure of 20 Torr or less to remove excess diphenylmethane diisocyanate, and the unsaturated C ₁₆ -C ₁₈ fatty alcohol (iodine value 150-170) was converted into the number of hydroxyl groups of the unsaturated C ₁₆ -C ₁₈ fatty alcohol / polyester. The ester polyol is added so that the ratio of the original number of hydroxyl groups becomes 1.1.
In a nitrogen stream for 3 hours. The molecular weight of this terminally unsaturated fatty alkylated polyester was 4,500.

The unsaturated resin 3 is an unsaturated fatty alkyl esterified ethylene-methacrylic acid copolymer and was prepared as follows. Ethylene-methacrylic acid copolymer (Elvacs II5610, methacrylic acid content 9.2
%, Acid value 65) 327 parts by weight, unsaturated C ₁₆ -C ₁₈ fatty alcohol (iodine value 150-170) 47 parts by weight, tin-based esterification catalyst (Swedecut 5) 0.4 part by weight At 230 ° C. under a nitrogen stream in a reactor
Stirred for hours. Thereafter, the pressure was reduced until no bubbles were generated, and the reaction water was removed.

The thermoplastic resin 1 was the same as described above.
The thermoplastic resin 2 was the same as described above. The thermoplastic resin 3 was the same as described above. Silane compound 1 was the same as described above. Silane compound 2 was the same as described above. Ketimine 1 was the same as above. Oxazolidine 1 was the same as described above.

In Examples 28 to 31, Comparative Examples 16 and 17, Examples 33 to 36, and Comparative Examples 18 and 19, the heated oil can be circulated in the amounts shown in Tables 7 and 8. For a planetary mixer with a jacket,
The unsaturated resin, calcium carbonate, and thermoplastic resin are charged and the pressure is reduced to 20 Torr or less, and the mixture is mixed at 120 ° C. at 30 rpm for 30 minutes. For 30 minutes.

In Examples 32 and 37, Table 7
And into the planetary mixer equipped with a jacket capable of circulating the heated oil at the compounding amount shown in Table 8, the unsaturated resin, calcium carbonate, and thermoplastic resin were charged, and the pressure was reduced to 20 Torr or less, and the pressure was reduced to 230 ° C. 30 rp
After mixing for 30 minutes at m, the remaining components were charged and further mixed at 120 ° C. at 30 rpm for 30 minutes under a nitrogen stream.

The storage stability, initial strength,
The heat resistance was evaluated by the following method. The results are shown in Tables 7 and 8. Evaluation method (1) Storage stability The evaluation was performed in the same manner as in Example 6.

(2) Preparation of Adhesion Test Specimen The same procedure as in Example 6 was carried out. (3) Initial strength This was performed in the same manner as in Example 6. (4) Heat Resistance The same as in Example 6.

[0343]

[Table 7]

[0344]

[Table 8]

Examples 38 to 41 and Comparative Examples 20 to 23 Materials used in Examples 38 to 41 and Comparative Examples 20 to 23 were as follows. Unsaturated resin 1 was the same as described above. The thermoplastic resin 4 was the same as described above.
Resin solution 1 was the same as described above. Silane compound 1
Was the same as above. Ketimine 1 was the same as above. Oxazolidine 1 was the same as described above.

In Examples 38 and 39 and Comparative Examples 20 and 21, the unsaturated resin and the thermoplastic resin were mixed in the jacketed planetary mixer capable of circulating the heated oil in the amounts shown in Table 9. 20Torr
After reducing the pressure to 150 ° C. and 30 rpm at 30 ° C. for 30 minutes, the remaining components are added, and the mixture is further placed under nitrogen flow for 15 minutes.
It was blended by mixing at 0 rpm at 30 rpm for 30 minutes.

In Examples 40 and 41 and Comparative Examples 22 and 23, the respective components were added to the resin melt 1 at the compounding amounts shown in Table 9 and mixed by mixing under a nitrogen stream. In Examples 38 and 39 and Comparative Examples 20 and 21, 50 μm was used.
Using a hot melt coater, the mixture was applied at a temperature of 150 ° C. on a m-thick polyethylene terephthalate film using a hot melt coater to prepare an adhesive sheet.

In Examples 40 and 41 and Comparative Examples 22 and 23, the composition was applied on a 50 μm thick polyethylene terephthalate film using a baker-type applicator, and the sheet was dried at 120 ° C. for 3 minutes. A pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer thickness of 30 μm was prepared.

The storage stability, initial strength, and heat resistance of the obtained compound and pressure-sensitive adhesive sheet were evaluated by the following methods. The results are shown in Table 9. Evaluation method (1) Storage stability The formulation was sealed in a can, stored at 23 ° C, opened 7 days later, and then heated to 150 ° C in Examples 38 and 39 and Comparative Examples 20 and 21. The sample that was melted by the heat treatment was evaluated as ○, and the sample that did not melt due to progress of the curing was evaluated as ×. Example 40,
In 41 and Comparative Examples 22 and 23, those which were in liquid state were evaluated as ○, and those in which curing proceeded were evaluated as ×.

(2) Initial adhesive strength The same procedure as in Example 16 was carried out. (3) Initial holding force The same as in Example 16. (4) Heat-resistant protective force The test was performed in the same manner as in Example 16.

[0351]

[Table 9]

Examples 42 to 44 and Comparative Examples 24 to 26 The materials used in Examples 42 to 44 and Comparative Examples 24 to 26 were as follows. Unsaturated resin 1 was the same as described above. Modified silicone 1 was the same as described above. Curing catalyst 1 was the same as described above. The thermoplastic resin 2 was the same as described above. The thermoplastic resin 3 was the same as described above. Silane compound 1 was the same as described above. Ketimine 1 was the same as above.

In Example 42 and Comparative Example 24, Table 1
The unsaturated resin, the modified silicone, the calcium carbonate, and the titanium oxide were charged into the planetary mixer at the compounding amount shown in FIG.
After mixing for 30 minutes at m, the remaining components were charged and further mixed at 30 rpm for 30 minutes at room temperature under a nitrogen stream.

In Examples 43 and 44 and Comparative Examples 25 and 26, an unsaturated resin, a thermoplastic resin, and a jacketed planetary mixer capable of circulating heated oil were added in the amounts shown in Table 10. Modified silicone,
Charge calcium carbonate and reduce the pressure to 20 Torr or less,
After mixing at 120 ° C. for 30 minutes at 30 rpm, the remaining components are charged and further 30 rpm at 120 ° C. under a nitrogen stream.
m and mixed for 30 minutes.

In Example 44 and Comparative Example 26, 50
The composition was applied to a thickness of 30 μm on a polyethylene terephthalate film having a thickness of μm using a baker-type applicator, and allowed to stand at 23 ° C. and a 60% atmosphere for 1 hour.
An adhesive sheet was produced.

The storage stability, curing time, adhesiveness, initial strength, heat resistance, initial adhesive strength, initial holding power, and heat holding power of the obtained compound and pressure-sensitive adhesive sheet were evaluated by the following methods. The results are shown in Table 10. Evaluation method

(1) Storage stability The formulation was sealed in a can, stored at 50 ° C. and opened 14 days later.
The sample which was heated and melted at 20 ° C. was evaluated as ○, and the sample which did not melt due to progress of the curing was evaluated as ×. In Examples 42 and 44 and Comparative Examples 24 and 26, those that were in a liquid state were rated as ○, and those that had progressed in curing were rated as x.

(2) Adhesiveness The composition was applied to a mortar piece so as to have a size of 25 mm × 50 mm × 2 mm, left in an atmosphere of 23 ° C. and 60% for 7 days, and peeled by hand. ○ indicates that the compound has undergone cohesive failure.
The one that was broken at the interface between the composition and the mortar piece was rated as Δ, and the one that was not cured and remained liquid was rated as x.

(3) Preparation of Adhesion Test Specimen The same procedure as in Example 6 was carried out. (4) Initial strength This was performed in the same manner as in Example 6. (5) Heat resistance The same as in Example 6.

(6) Initial adhesive strength The same procedure as in Example 16 was carried out. (7) Heat-resistant holding force The same as in Example 16.

[0361]

[Table 10]

Examples 45 to 49 and Comparative Examples 27 and 28 The materials used in Examples 45 to 49 and Comparative Examples 27 and 28 were as follows. Acrylic resin 1 is ethoxy-modified bisphenol F-type diacrylate (Kayarad R-712, molecular weight 484, liquid at room temperature, manufactured by Nippon Kayaku Co., Ltd.)
Met.

The silane compound 1 was the same as described above.
Ketimine 1 was the same as above. Oxazolidine 1
Was the same as above. Silamine 1 was the same as above. Silazane 1 was the same as above. Enamine 1 was the same as above.

In the amounts shown in Table 11, acrylic resin,
Calcium carbonate and titanium oxide are charged into a planetary mixer, the pressure is reduced to 20 Torr or less, and the pressure is reduced to 30 r at room temperature.
After mixing at pm for 30 minutes, the remaining components were charged and further mixed at room temperature under a nitrogen stream at 30 rpm for 30 minutes.

The storage stability, curing time,
The adhesiveness was evaluated by the following method. The results are shown in Table 11. Evaluation method (1) Storage stability The evaluation was performed in the same manner as in Example 1.

(2) Curing time This was carried out in the same manner as in Example 1. (3) Adhesiveness The same as in Example 1.

[0367]

[Table 11]

Examples 50 to 59 and Comparative Examples 29 to 32 The materials used in Examples 50 to 59 and Comparative Examples 29 to 32 were as follows. The acrylic resin 1 was the same as described above. The acrylic resin 2 is a bisphenol A type epoxy acrylate (Lipoxy VR-90, molecular weight 1).
100, room temperature solid, melting point 50-60 ° C, manufactured by Showa Polymer Co., Ltd.).

Acrylic resin 3 is an acrylate polyester having both terminals and was prepared as follows. Crystalline polyester polyol (Dynacol 7360, molecular weight 3
500, melting point 60 ° C, hydroxyl value 30, manufactured by Huls)
And diphenylmethane diisocyanate (Sumidur 44V20, molecular weight 250, manufactured by Sumitomo Bayer Urethane Co., Ltd.) in a ratio of isocyanate groups / hydroxyl groups of 2.2.
, And reacted under a nitrogen stream for 3 hours. The mixture was stirred under reduced pressure of 20 Torr or less to remove excess diphenylmethane diisocyanate.
Hydroxypropyl acrylate (molecular weight 130, manufactured by Osaka Organic Chemical Industry Co., Ltd.) was added so that the ratio of the number of hydroxyl groups of 2-hydroxypropyl acrylate / the original number of hydroxyl groups of the polyester polyol was 1.1, and hydroquinone monomethyl ether was further added. The reaction mixture was added at 100 ppm and reacted at 100 ° C. for 3 hours under a nitrogen stream. The molecular weight of this double-ended acrylate polyester was 4,300.

The thermoplastic resin 1 was the same as described above.
The thermoplastic resin 2 was the same as described above. The thermoplastic resin 3 was the same as described above. Polymerization modifier 1 was cumene hydroperoxide.

The silane compound 1 was the same as described above.
Silane compound 2 was the same as described above. Ketimine 1
Was the same as above. Oxazolidine 1 was the same as described above.

An acrylic resin, a calcium carbonate, a thermoplastic resin, and a polymerization regulator were charged into a jacketed planetary mixer capable of circulating heated oil at the blending amounts shown in Tables 12 and 13, and 20 Torr.
After the pressure was reduced and mixed at 120 rpm at 30 rpm for 30 minutes, the remaining components were added, and the mixture was further mixed under nitrogen gas at 120 rpm.
It was blended by mixing at 30 ° C. and 30 rpm for 30 minutes.

The storage stability, initial strength,
The heat resistance was evaluated by the following method. The results are shown in Tables 12 and 13. Evaluation method (1) Storage stability The evaluation was performed in the same manner as in Example 6.

(2) Preparation of Adhesion Test Specimen The same procedure as in Example 6 was carried out. (3) Initial strength This was performed in the same manner as in Example 6. (4) Heat Resistance The same as in Example 6.

[0375]

[Table 12]

[0376]

[Table 13]

Examples 60 to 63 and Comparative Examples 33 to 36 The materials used in Examples 60 to 63 and Comparative Examples 33 to 36 were as follows. The acrylic resin 1 was the same as described above. The thermoplastic resin 4 was the same as described above. Resin solution 1 was the same as described above.

The polymerization modifier 1 was the same as described above. Silane compound 1 was the same as described above. Ketimine 1
Same as above. Oxazolidine 1 was the same as described above.

In Examples 60 and 61 and Comparative Examples 33 and 34, an acrylic resin, a thermoplastic resin, and a polymerized resin were mixed in a planetary mixer equipped with a jacket capable of circulating heated oil in the amounts shown in Table 14. The regulator was charged and the pressure was reduced to 20 Torr or less.
After mixing at pm for 30 minutes, the remaining components were charged and further blended at 30 ° C. for 30 minutes at 150 ° C. under a nitrogen stream.

In Examples 62 and 63 and Comparative Examples 35 and 36, each component was mixed with the resin solution 1 in the amounts shown in Table 14.
And mixed under a nitrogen stream.
In Examples 60 and 61 and Comparative Examples 33 and 34, 50
Using a hot melt coater, the composition was applied on a polyethylene terephthalate film having a thickness of μm at 150 ° C. so as to have a thickness of 30 μm to prepare an adhesive sheet.

In Examples 62 and 63 and Comparative Examples 35 and 36, after the composition was applied on a 50 μm-thick polyethylene terephthalate film using a baker type applicator, the sheet was dried at 120 ° C. for 3 minutes. Thus, a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer thickness of 30 μm was produced.

The storage stability, initial strength, and heat resistance of the obtained composition and pressure-sensitive adhesive sheet were evaluated by the following methods. The results are shown in Table 14. Evaluation method (1) Storage stability The composition was sealed in a can, stored at 23 ° C, opened 7 days later, and then heated to 150 ° C in Examples 60 and 61 and Comparative Examples 33 and 34. The sample that was melted by the heat treatment was evaluated as ○, and the sample that did not melt due to progress of the curing was evaluated as ×. Example 62,
In 63 and Comparative Examples 35 and 36, those that were liquid were rated as ○, and those that had undergone curing were rated as x.

(2) Initial Adhesion The same procedure as in Example 16 was carried out. (3) Initial holding force The same as in Example 16. (4) Heat-resistant holding force The same as in Example 16.

[0384]

[Table 14]

Examples 64 to 66 and Comparative Examples 37 to 39 The materials used in Examples 64 to 66 and Comparative Examples 37 to 39 were as follows. The acrylic resin 1 was the same as described above. Modified silicone 1 was the same as described above. Curing catalyst 1 was the same as described above.

The thermoplastic resin 2 was the same as described above.
The thermoplastic resin 3 was the same as described above. Polymerization regulator 1
Was the same as above. Silane compound 1 was the same as described above. Ketimine 1 was the same as above.

In Example 64 and Comparative Example 37, Table 1
Acrylic resin, modified silicone,
Calcium carbonate and titanium oxide are charged into a planetary mixer, the pressure is reduced to 20 Torr or less, and the pressure is reduced to 30 r at room temperature.
After mixing at pm for 30 minutes, the remaining components were charged and further mixed at room temperature under a nitrogen stream at 30 rpm for 30 minutes.

In Examples 65 and 66 and Comparative Examples 38 and 39, an acrylic resin, a thermoplastic resin, a modified resin were added to a planetary mixer equipped with a jacket capable of circulating heated oil in the amounts shown in Table 15. 20 Torr after adding silicone, calcium carbonate and polymerization regulator
After mixing at 120 ° C. and 30 rpm for 30 minutes, the remaining components were added, and the mixture was further mixed under nitrogen stream.
It was blended by mixing at 0 rpm at 30 rpm for 30 minutes.

In Example 66 and Comparative Example 39, 50
The composition was applied to a thickness of 30 μm on a polyethylene terephthalate film having a thickness of μm using a baker-type applicator, and allowed to stand at 23 ° C. and a 60% atmosphere for 1 hour.
An adhesive sheet was produced.

The storage stability, curing time, adhesiveness, initial strength, heat resistance, initial adhesive strength, initial holding power and heat holding power of the obtained compound and pressure-sensitive adhesive sheet were evaluated by the following methods. The results are shown in Table 15.

Evaluation Method (1) Storage Stability The composition was sealed in a can, stored at 50 ° C., and opened 14 days later.
The sample which was heated and melted at 20 ° C. was evaluated as ○, and the sample which was not melted due to progress of the curing was evaluated as ×. In Examples 64 and 66 and Comparative Examples 37 and 39, those which were in liquid state were evaluated as ○, and those in which curing progressed were evaluated as ×.

(2) Adhesion The same procedure as in Example 1 was carried out. (3) Preparation of Adhesion Test Specimen The same procedure as in Example 6 was performed. (4) Initial strength This was performed in the same manner as in Example 6.

(5) Heat Resistance The same procedure as in Example 6 was carried out. (6) Initial adhesive strength The same procedure as in Example 16 was carried out. (7) Heat-resistant holding force The same as in Example 16.

[0394]

[Table 15]

Examples 67 to 70 and Comparative Examples 40 to 43 The materials used in Examples 67 to 70 and Comparative Examples 40 to 43 were as follows. The acrylic resin 4 is made of tetraethylene glycol dimethacrylate (Blemmer PD).
E-200, molecular weight 330, liquid at normal temperature, manufactured by NOF Corporation)
Met. The acrylic resin 5 is ethoxy-modified bisphenol A dimethacrylate (SR-348, molecular weight 45
2, liquid at room temperature, manufactured by Sartomer).

The polymerization modifier 1 was the same as described above. Polymerization modifier 2 was benzoquinone. Polymerization regulator 3
Was benzoic acid sulfide. The polymerization modifier 4 is
N, N'-dimethylparatoluidine. Silane compound 1 was the same as described above. Ketimine 1 was the same as above. Oxazolidine 1 was the same as described above.

[0397] At the compounding amount shown in Table 16, the acrylic resin was charged into a planetary mixer, the pressure was reduced to 20 Torr or less, and the mixture was mixed at room temperature at 30 rpm for 30 minutes. In the released state, the mixture was further mixed by mixing at room temperature at 30 rpm for 30 minutes.

The storage stability, curability and adhesiveness of the obtained composition were evaluated by the following methods. Table 1 shows the results
6 is shown. Evaluation method (1) Storage stability The evaluation was performed in the same manner as in Example 1.

(2) Curability The composition was placed in a can having a diameter of 10 cm to a height of 5 cm from the bottom, and left in an atmosphere of 23 ° C. and 60% for 7 days without a cover. The case where the composition in the can was completely cured was evaluated as ○, the case where the composition had an uncured liquid portion was evaluated as Δ, and the case where the composition was not cured and remained liquid was evaluated as ×.

(3) Adhesion Acetone-degreased aluminum alloy # 5083-1
50% of the composition was placed on one side of a 25 mm x 125 mm x 2 mm plate.
0 μm, and the same aluminum alloy plate was overlapped so as to cover all of the composition.
After leaving it in an atmosphere of 60 ° C. and 60% for 7 days, it was peeled off by hand. When the whole composition was cured and completely adhered, it was evaluated as ○, and when there was an uncured liquid portion of the composition and adhesion was incomplete, it was evaluated as x.

[0401]

[Table 16]

Examples 71 to 74 and Comparative Examples 44 to 47 The materials used in Examples 71 to 74 and Comparative Examples 44 to 47 were as follows. The acrylic resin 1 was the same as described above. The polymerization modifier 1 was the same as described above.
The polymerization modifier 5 was benzyl dimethyl ketal (Irgacure 651, manufactured by Ciba Geigy).

The thermoplastic resin 2 was the same as described above.
Silane compound 1 was the same as described above. Ketimine 1
Was the same as above. Oxazolidine 1 was the same as described above.

Examples 71 and 72, Comparative Examples 44, 45 and 4
In No. 7, the acrylic resin was charged into a planetary mixer at a blending amount shown in Table 17, the pressure was reduced to 20 Torr or less, and the mixture was mixed at room temperature at 30 rpm for 30 minutes. State, put the remaining components, and further at room temperature under nitrogen flow at 30 rpm for 30 minutes.
It was blended by mixing for one minute.

In Examples 73 and 74 and Comparative Example 46, an acrylic resin, a thermoplastic resin, and a polymerization regulator were added to a planetary mixer equipped with a jacket capable of circulating heated oil in the amounts shown in Table 17. 1 and the pressure was reduced to 20 Torr or less, and 30 rpm at 120 ° C.
After mixing for 30 minutes at m, the surroundings were covered with aluminum foil to shield the light, the remaining components were charged, and the mixture was further mixed for 30 minutes at 120 ° C. and 30 rpm under a nitrogen stream.

The storage stability, initial strength,
The strength after curing was evaluated by the following method. The results are shown in Table 17. Evaluation method (1) Storage stability The formulation was sealed in a can, stored at 23 ° C, opened 7 days later, and then heated to 120 ° C in Examples 73, 74 and Comparative Example 46 to melt. The sample was evaluated as ○, and the sample that did not melt due to progress of the curing was evaluated as ×. Examples 71 and 7
2. In Comparative Examples 44, 45 and 47, those which were in a liquid state were evaluated as ○, and those in which curing was advanced were evaluated as ×.

(2) Production of Adhesion Test Specimens In Examples 71 and 72 and Comparative Examples 44, 45 and 47, 25 m × 125 mm × 5 mm
The composition is applied to an area of mx 25 mm with a thickness of 3 mm,
A single lap joint was manufactured by laminating the same Rawan plate on it. In Examples 73 and 74 and Comparative Example 46, 5 g of the compound was subjected to heat pressing at 120 ° C. for 1 minute between polyethylene terephthalate films which had been subjected to a release treatment to obtain a film having a thickness of 3 mm. This is 25mm
Cut out to 25mm x 25mm x 125mm x 5mm
Was pressed between 120 ° C for 1 minute and then cooled and pressed at 23 ° C for 1 minute to produce a single lap joint. Immediately after adhering any of the test pieces, a high-pressure UV lamp (Jetlight JL2 manufactured by ORK Mfg. Co., Ltd.)
300), ultraviolet rays were irradiated at an illuminance of 25 mW / cm ² for 2 minutes.

(3) Initial Strength Immediately after producing the above-mentioned adhesive test piece, a tensile shear test was conducted at 120 ° C. at a tensile speed of 5 mm / min.も の indicates that the adhesive strength was developed due to partial curing of the composition by ultraviolet light, and x indicates that no strength was observed at which the composition was hardened by ultraviolet light.

(4) Strength after curing The above adhesive test piece was left in an atmosphere of 23 ° C. and 60% for 7 days, and a tensile shear test was performed at 120 ° C. at a tensile speed of 5 mm / min to measure the strength.

[0410]

[Table 17]

[0411] From these results, it was found that the resin composition of the present invention exhibited good adhesion to various substrates. Further, it was found that the resin composition of the present invention has sufficient storage stability as a one-pack type. In addition, it was found that the resin composition of the present invention sufficiently cured without requiring heating, irradiation of light and radiation, two-component measurement mixing, blocking of oxygen, and the like. Further, the resin composition of the present invention,
Liquid reactive adhesive, solvent reactive adhesive, reactive hot melt adhesive, adhesive (post-curing) pressure-sensitive adhesive,
It was found that it can be suitably used as a sealing material, a reactive hot-melt type sealing material, a paint, a resin molded product, and the like.

Further, when the anaerobic polymerization reaction is used in combination with the resin composition of the present invention, a thick cured layer can be formed in a short time without requiring heating, irradiation of light or radiation, or two-component metering. In addition, a large-area non-moisture-permeable material such as metal and glass could be firmly bonded in a short time.
Furthermore, when the resin composition of the present invention is used in combination with a photo-radiation polymerization reaction, the materials opaque to light and radiation can be shortened without the necessity of heating, two-component measurement mixing, blocking of oxygen, and the like. It was able to adhere firmly in time.

[0413]

As described above, the resin composition of the present invention satisfies a good balance between good adhesion to the substrate and sufficient storage stability as a one-pack type at the same time. It can be cured without the need for light / radiation irradiators, two-component metering, or blocking of oxygen, etc .; liquid reactive adhesives, solvent reactive adhesives, reactive hot melt adhesives, adhesives Adhesive type (post-curing type) pressure sensitive adhesive, sealing material, reactive hot melt type sealing material, paint,
It can be suitably used as a resin molded product or the like.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical indication location C09J 157/04 JAQ C09J 157/04 JAQ 201/08 JAX 201/08 JAX

Claims (6)

[Claims] 1. An acid anhydride group-containing compound (A1), and
A resin composition comprising a compound (B) that produces at least one of a primary amino group, a secondary amino group, and ammonia by reacting with water. 2. An unsaturated aliphatic compound (A2), and
A resin composition comprising a compound (B) that produces at least one of a primary amino group, a secondary amino group, and ammonia by reacting with water. 3. A compound having a (meth) acryloyl group (A)
3) A resin composition comprising a compound (B) that produces at least one of a primary amino group, a secondary amino group, and ammonia by reaction with water. 4. A curable adhesive mainly comprising the resin composition according to claim 1, 2 or 3. 5. The curable adhesive according to claim 4, further comprising:
A curable adhesive comprising at least one of a thermoplastic resin and a tackifier resin. 6. The curable adhesive according to claim 4, further comprising:
A curable adhesive comprising a resin having a hydrolyzable silyl group and a curing catalyst for curing the resin.