JP2002201256A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition showing no corrosiveness to metallic materials, good in workability without a solvent, and excellent in rapid curing, mechanical properties, adhesion, and chemical resistance, by curing a curable resin such as epoxy resin, etc., using a material which generates a base by light. SOLUTION: This composition comprises a compound of a specific structure containing a hetero ring, a compound containing at least two electrophilic groups which react with a thiol group or -S- group in a molecule, and a compound having a carbonyloxyimino group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a resin composition and a cured product thereof. More specifically, the present invention relates to a curable composition comprising a novel compound which is curable by light or electron beam and moisture, and a cured product thereof.

[0002]

2. Description of the Related Art Epoxy resins have excellent mechanical properties, electrical properties, adhesive properties, chemical resistance and the like, and are used in various industrial applications such as adhesives, paints and linings. It is a typical resin, and in the field of electronics, a method using an electron beam or UV (ultraviolet) is employed as a method for curing this epoxy resin.

[0003]

However, in the method using the electron beam or UV (ultraviolet ray) curing, since an acid is used as an initiator, there is a concern that a metal material may be corroded by a residual acid. The present invention solves the above problem in a method using electron beam or UV (ultraviolet) curing,
By using a material that generates a base by light, it cures epoxy resin etc., shows no corrosiveness to metal materials, has good workability without solvent, and has high-speed curability, mechanical properties, and adhesiveness Another object of the present invention is to provide a curable composition having excellent chemical resistance.

[0004]

Means for Solving the Problems As a result of intensive studies, the present inventors have reached the present invention. That is, the present invention relates to [1] a heterocyclic-containing compound (A) represented by the following general formula (1), a compound (B) having two or more electrophilic groups which react with a thiol group or -S- group in a molecule. A curable composition comprising a compound (C) having a carbonyloxyimino group;

[0005]

Embedded image

[In the general formula (1), n is an integer of 1 to 10,
X ¹ , Y ¹ and Z ¹ are each independently an oxygen or sulfur atom; R ¹ is a residue or a hydrogen atom of the cyclic ether group-containing compound (D); R ² is a hydrocarbon group having 2 to 10 carbon atoms . [2] After irradiating the above (A) and (C) with light or an electron beam,
(B) a curing agent (T1) which is reacted with water; [3] It comprises a cured product obtained by curing the curable composition.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the hetero ring-containing compound (A) is represented by the above general formula (1). In the formula, n is an integer of 1 to 10, preferably 2 to 8, X ¹ , Y ¹ and Z ¹
Is an oxygen or sulfur atom, respectively. Preferably X ¹
Is a sulfur atom (S), and ^one of Y ¹ and Z ¹ is a sulfur atom (S)
And the other is an oxygen atom (O). R ² has 2 to 10 carbon atoms
And a trivalent hydrocarbon group> CH (C
H ₂ ) _m — (m is an integer of 1 to 9), for example,> CHCH ₂ —,> CHCH ₂ CH ₂ —,> CHCH _{2
CH 2 CH 2 -,> CHCH} 2 CH 2 CH 2 CH 2 CH 2 -
Etc .; tetravalent hydrocarbon group> CH (CH ₂ ) _m CH <(m is 0
-8), for example,> CHCH
<,> CHCH ₂ CH <,> CHCH ₂ CH ₂ CH <,>
CHCH ₂ CH ₂ CH ₂ CH ₂ CH <and the like, preferably a trivalent hydrocarbon group, particularly preferably> CH
CH ₂ — and> CHCH ₂ CH ₂ —. R ¹ is a hydrogen atom or a residue of a cyclic ether group-containing compound (D);
R ² is a residue constituting a ring other than an oxygen atom in the cyclic ether group. (D) is represented by the general formula (15). General formula

[0008]

Embedded image

[0009] The cyclic ether group is not particularly limited as long as it has one oxygen atom in the ring.
For example, compounds having 1 to 10 cyclic ether groups in the molecule can be mentioned. Examples of the cyclic ether group-containing compound (D) include an epoxy group-containing compound (D1) and an oxetane compound (D2) described below, and preferably the epoxy group-containing compound (D2). As the epoxy group-containing compound (D1), monoepoxide (d1
1) and polyepoxide (D11) having two or more epoxy groups in the molecule. Monoepoxide (d1
1) is not particularly limited as long as it has one epoxy group in the molecule, and can be appropriately selected depending on the use and purpose. Examples include the following.
For example, hydrocarbon oxides having 2 to 24 carbon atoms (ethylene oxide, propylene oxide, 1-butene oxide, 2-butene oxide, α-olefin oxides having 5 to 24 carbon atoms, styrene oxide, etc.), 3 to 10 carbon atoms
Glycidyl ethers of hydrocarbons (n-butyl glycidyl ether, allyl glycidyl ether, 2-ethyl-
Hexyl glycidyl ether, 2-methyloctyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, p-sec-butylphenyl glycidyl ether, P-tert-butylphenyl glycidyl ether, etc.), and monocarboxylic acids having 3 to 30 carbon atoms. Examples include glycidyl esters (glycidyl acrylate, glycidyl methacrylate, etc.), epihalohydrins such as epichlorohydrin and epibromohydrin, and hydroxyl-containing oxides such as glycidol. Preferred are hydrocarbon oxides having 2 to 24 carbon atoms, 3 to 10 carbon atoms.
Is a glycidyl ether of a hydrocarbon.

The polyepoxide (D11) is not particularly limited as long as it has two or more epoxy groups in the molecule, and can be appropriately selected depending on the use and purpose. Preferred are those having 2 to 6 epoxy groups in the molecule. The epoxy equivalent (molecular weight per epoxy group) of the polyepoxide is preferably 65 to 1,000.
And more preferably 90 to 500. When the epoxy equivalent is 1,000 or less, the crosslinked structure is not loose and the cured product has good physical properties such as water resistance, chemical resistance, and mechanical strength. On the other hand, when the epoxy equivalent is 65 or more, the cured product is cured. A crosslinked structure having good water resistance, chemical resistance, mechanical strength and the like of the product is obtained. Examples of the polyepoxide (D11) include the following (D11-1) to (D11-5).

(D11-1) Glycidyl ether type
(I) Diglycidyl ether of dihydric phenols Diglycidyl ether of dihydric phenols having 6 to 30 carbon atoms, for example, bisphenol F diglycidyl ether;
Bisphenol A diglycidyl ether, bisphenol B diglycidyl ether, bisphenol AD diglycidyl ether, bisphenol S diglycidyl ether, halogenated bisphenol A diglycidyl ether, tetrachlorobisphenol A diglycidyl ether, catechin diglycidyl ether, resorcinol diglycidyl ether, Hydroquinone diglycidyl ether, 1,5-dihydroxynaphthalenediglycidyl ether, dihydroxybiphenyldiglycidyl ether, octachloro-4,4'-dihydroxybiphenyldiglycidyl ether, tetramethylbiphenyldiglycidyl ether, 9,9'-bis (4- (Hydroxyphenyl) flow orange glycidyl ether, 2 mol of bisphenol A and epichloro Diglycidyl ether obtained from Drinks 3 moles of reaction or the like;

(Ii) Polyglycidyl ethers of polyhydric phenols having 3 to 6 or more valences, having 6 to 50 or more carbon atoms, and having a molecular weight of 250 to 3.0.
Polyglycidyl ethers of polyhydric phenols having a trivalent or hexavalent value of 00 or more, such as pyrogallol triglycidyl ether, dihydroxynaphthyl cresol triglycidyl ether, tris (hydroxyphenyl) methane triglycidyl ether, dinaphthyltriol triglycidyl ether, tetrakis (4-hydroxyphenyl) ethane tetraglycidyl ether, p-glycidylphenyldimethyltolyl bisphenol A glycidyl ether, trismethyl-tert-butyl-butylhydroxymethane triglycidyl ether, 4,4′-oxybis (1,4-phenylethyl) tetra Cresol glycidyl ether, 4,4'-oxybis (1,4-
Phenylethyl) phenylglycidyl ether, bis (dihydroxynaphthalene) tetraglycidyl ether, glycidyl ether of phenol or cresol novolak resin (molecular weight 400 to 5,000), limonenephenol novolak resin (molecular weight 400 to 5,000)
0) glycidyl ether, polyphenols obtained by the condensation reaction of phenol with glyoxal, glutaraldehyde or formaldehyde (molecular weight 400
5,000) and a molecular weight of 4 obtained by the condensation reaction of resorcinol and acetone.
And polyglycidyl ethers of polyphenols having a molecular weight of 00 to 5,000.

(Iii) Diglycidyl ether of an aliphatic dihydric alcohol Diglycidyl ether of a diol having 2 to 100 carbon atoms and a molecular weight of 150 to 5,000, for example, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol Diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol (molecular weight 150 to 4.0
00) diglycidyl ether, polypropylene glycol (molecular weight: 180 to 5,000) diglycidyl ether, polytetramethylene glycol (molecular weight: 200 to 5,000)
(5,000) diglycidyl ether, neopentyl glycol diglycidyl ether, diglycidyl ether of alkylene oxide of bisphenol A [ethylene oxide or propylene oxide (1 to 20 mol)] adduct, and the like; (vi) trivalent to hexavalent or more Polyglycidyl ether of aliphatic alcohol having 3 to 50 or more carbon atoms and having a molecular weight of 92 to 10,0
Glycidyl ethers of polyhydric alcohols having 3 to 6 or more valencies of 00, such as trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether,
Sorbitol hexaglycidyl ether, poly (n = 2
To 5) glycerol polyglycidyl ether and the like.

(D11-2) Glycidyl ester type: a glycidyl ester of an aromatic polycarboxylic acid having 6 to 20 or more carbon atoms and having 2 to 6 or more carbon atoms; Glycidyl esters of aliphatic or alicyclic polycarboxylic acids having 6 to 6 or more valences are exemplified. (I) As an aromatic polycarboxylic acid, for example, glycidyl esters of phthalic acids, diglycidyl phthalate, diglycidyl isophthalate, diglycidyl terephthalate, triglycidyl trimellitate and the like; (II) aliphatic or As the glycidyl ester of alicyclic polycarboxylic acid, the aromatic nucleus water additive of the phenolic glycidyl ester, diglycidyl dimer acid, diglycidyl oxalate, diglycidyl malate, diglycidyl succinate, diglycidyl gluta Rate, diglycidyl adipate, diglycidyl pimerate, a (co) polymer of glycidyl (meth) acrylate (polymerization degree is, for example, 2 to 10), triglycidyl tricarballylate, and the like.

(D11-3) Glycidylamine-type glycidylamine, an aromatic amine having 6 to 20 or more carbon atoms and having 2 to 10 or more active hydrogen atoms, and an aliphatic, alicyclic or heterocyclic ring Glycidylamine of the formula amines may be mentioned. As glycidylamines of aromatic amines, N, N-diglycidylaniline,
N, N-diglycidyl toluidine, N, N, N ', N'
-Tetraglycidyldiaminodiphenylmethane, N,
N, N ', N'-tetraglycidyldiaminodiphenylsulfone, N, N, N', N'-tetraglycidyldiethyldiphenylmethane, N, N, O-triglycidylaminophenol and the like. Examples of the aliphatic amine glycidylamine include N, N, N ', N'-tetraglycidylxylylenediamine, N, N, N', N'-tetraglycidylhexamethylenediamine and the like. Examples of the alicyclic amine include hydrogenated compounds of N, N, N ', N'-tetraglycidylxylylenediamine.
Examples of the glycidylamine of the heterocyclic amine include trisglycidylmelamine.

(D11-4) Chain aliphatic epoxide A chain aliphatic epoxide having 6 to 50 or more carbon atoms and having 2 to 6 valences or more, for example, an epoxy equivalent of 130 to
1,000 epoxidized polybutadiene (molecular weight 90-
2,500), epoxidized soybean oil (molecular weight 130-2,
500) and the like. (D11-5) Alicyclic epoxide having 6 to 50 or more carbon atoms and having a molecular weight of 90 to 2,50
0, an alicyclic epoxide having 1 to 4 or more epoxy groups, for example, vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl) ether, ethylene glycol bisepoxydioxide Cyclopentyl ether, 3,4 epoxy-6-methylcyclohexylmethyl 3 ', 4'-epoxy-6'-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, and bis (3
4-epoxy-6-methylcyclohexylmethyl) butylamine and the like. It also includes a nuclear hydrogenated product of the phenolic epoxy compound. (D11-1)
Other than (D11-5), any epoxy resin having a glycidyl group capable of reacting with active hydrogen can be used. In addition, two or more of these polyepoxy compounds can be used in combination. Of these, glycidyl ether type (D11-1) and glycidyl ester type (D11-1) are preferable.
11-2), and particularly preferred is a glycidyl ether type (D11-1). Of (D11-1), preferred are dihydric phenols and diglycidyl ethers of dihydric aliphatic alcohols.

As the oxetane compound (D2), an aliphatic oxetane compound having 6 to 20 carbon atoms (3-ethyl-
3-hydroxymethyloxetane, etc.), having 7 to 30 carbon atoms
Aromatic oxetane compounds (benzyloxetane, xylylenebisoxetane, etc.), aliphatic carboxylic acid oxetane compounds having 6 to 30 carbon atoms (adipate bisoxetane, etc.), and aromatic carboxylic acid oxetane compounds having 8 to 30 carbon atoms (Such as terephthalate bisoxetane), an alicyclic carboxylic acid oxetane compound having 8 to 30 carbon atoms (such as bisoxetane cyclohexanedicarboxylate), and an aromatic isocyanate oxetane compound [(D11-
2) Oxetane, MDI bis oxetane, etc.].

The method for producing the heterocyclic compound (A) in the composition of the present invention is not particularly limited. For example, it is 0.5 to 10 times the cyclic ether group of the cyclic ether group-containing compound (D). It is obtained by reacting one or more compounds selected from the group consisting of equivalent amounts of carbon disulfide, carbonyl sulfide and carbon dioxide in a solvent in the presence of a catalyst. Preferably it is carbon disulfide. The solvent is not particularly limited as long as it does not hinder the reaction and dissolves the raw materials and products, and usually an aprotic solvent is used. For example, ethers (tetrahydrofuran, dioxane, diethyl cellosolve, dioxolan, trioxane, dibutyl cellosolve, diethyl carbitol,
Dibutyl carbitol, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, etc.), esters (methyl acetate, ethyl acetate, n-butyl acetate, etc.), and other polar solvents (acetonitrile, dimethylformamide, N-methyl) Pyrrolidone, dimethylsulfoxide, etc.), and preferably, tetrahydrofuran, acetone, ethyl acetate and the like. The catalyst is
It is a halide of an alkali metal or an alkaline earth metal, for example, lithium chloride, lithium bromide, lithium iodide, potassium chloride, calcium bromide, etc., preferably lithium bromide. The amount of the catalyst is 0.001 to 1.0 times equivalent to the cyclic ether group of (D). Preferably it is 0.01 to 0.1 times equivalent. The reaction temperature is generally 0-100 ° C, preferably 20-70 ° C.
It is. The heterocyclic compound (A1) using the epoxy group-containing compound (D1) as the cyclic ether group-containing compound (D) is represented by the following general formulas (2) and (3). General formula

[0019]

Embedded image

Wherein n is an integer of 1 to 10; X ² , Y ² and Z ² are each independently an oxygen or sulfur atom, more preferably X ² is S, Y ² is O, Z ² is S.
R ³ is a residue of the polyepoxy compound (B1) or the monoepoxy compound (b1). R ⁴ is the residue of (D11-5). The weight average molecular weight of the hetero ring-containing compound (A) is from 120 to
12,000, preferably from 200 to 8,000. The weight average molecular weight is measured by gel permeation chromatography (GPC). The heterocyclic equivalent is preferably from 120 to 1,200, and more preferably from 200 to 800. The heterocycle equivalent is a value obtained by dividing the above weight average molecular weight by the number of heterocycles in the molecule. 25
The viscosity at ° C is usually 20 Pa · s or less, preferably 10 Pa · s or less, more preferably 5 Pa · s or less, and particularly preferably 1 Pa · s or less. The viscosity is B
By viscometer. Specific examples of the hetero ring-containing compound (A) obtained as described above include those described in Table 1.

[0021]

[Table 1]

The heterocyclic group in the heterocyclic-containing compound (A) has no active hydrogen and therefore has a low viscosity, and has an irritating odor such as a phenol compound or a polyamine compound added for the purpose of promoting curing. There is no peculiar smell like polymercaptan compound, and skin irritation is lower than low-molecular epoxy group-containing compound added for the purpose of reducing viscosity.
Excellent workability. Furthermore, since the heterocyclic-containing compound (A) is incorporated into the network structure of the cured product through a curing reaction, the cured product has water resistance, chemical resistance,
There is no decrease in physical properties such as weather resistance and mechanical strength.

Examples of the electrophilic group of the compound (B) having two or more electrophilic groups which react with a thiol group or an -S- group in the molecule include an epoxy group, an isocyanate group, a thiol group, an acid anhydride group, Acid halide groups, oxazoline groups,
Examples thereof include an unsaturated carboxylic acid group, an allyl group, and the like, and are at least one group selected from these groups. Examples of (B) include polyepoxide (B1), polyisocyanate (B2), polythiol (B3), polyanhydride (B4), polyacid halide (B5), polyoxazoline (B6), and unsaturated carboxylic acid polyester. (B7), a polyallyl compound (B8) and the like, and at least one selected from these groups is preferable, and polyepoxide (B1) is preferable. Polyepoxide (B1)
Is the same as the above-described polyepoxide (D11).

The following are specific examples of the compounds (B2) to (B8). Polyisocyanate (B2); aromatic polyisocyanate having 6 to 20 carbon atoms (excluding the number of carbon atoms in the NCO group) and 2 to 6 or more functional groups, and a crude product thereof [2,4-
And 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4'- and 4,4'-diphenylmethane diisocyanate (MDI), crude MDI, polyaryl polyisocyanate (PAPI), etc.];
8, aliphatic polyisocyanate having 2 or more functional groups [hexamethylene diisocyanate (HDI), lysine isocyanate, etc.]; 4 to 15 carbon atoms, 2 functional groups
Or more alicyclic polyisocyanates [isophorone diisocyanate (IPDI), dicyclohexyl diisocyanate, etc.]; araliphatic polyisocyanates having 8 to 15 carbon atoms, two or more functional groups [xylylene diisocyanate, etc.]; Modified polyisocyanate of [urethane group, carboimide group, allophanate group, urea group, buret group, uretdione group,
Isocyanurate group, oxadridone group-containing modified product, etc.]
And a combination of two or more of these. Among these, preferred are TDI, 4,4'-MDI, IPD
I and HDI.

Polythiol (B3); having 1 to 20 carbon atoms;
Alkyl thiol compounds having 2 to 6 or more functional groups, such as 1,4-butanedithiol, 1,8-octadiendithiol and the like. Thiol obtained by reacting polyepoxide (B1) with hydrogen sulfide;
0, a mercaptocarboxylic acid having 2 to 3 or more functional groups (mercaptoacetic acid, mercaptopropionic acid, mercaptobutyric acid, mercaptohexanoic acid, mercaptooctanoic acid, mercaptostearic acid, etc.) and a functional group having 2 to 6 or more carbon atoms An esterified product with a polyol having a number of 2 to 30 is exemplified. Of these, thiols obtained by reacting polyepoxide (B1) with hydrogen sulfide are preferred. Polyacid anhydride (B4); Examples of the acid include sulfonic acid, carboxylic acid and the like, and carboxylic acid is preferable, and alicyclic acid anhydride having 8 to 18 carbon atoms and 2 to 4 carboxyl groups;
For example, methylcyclohexene dicarboxylic anhydride and the like,
Examples thereof include aromatic acid anhydrides having 6 to 30 carbon atoms and 2 to 6 functional groups, for example, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis trimellitate, glycerin trimellitate and the like. Of these, preferred are alicyclic acid anhydrides having 8 to 18 carbon atoms and 2 to 4 carboxyl groups.

Polyacid halide (B5) having 8 to 10 carbon atoms
Halides of polycarboxylic acids having 0, 2 to 6 valences or more, such as phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methyltetrahydrophthalic acid, methylhexahydrophthalic acid, methylnadic acid, dodecylsuccinic acid, Merritic acid, polyazeleic acid (degree of polymerization 2
To 10) and the like (chloride, bromide,
Iodide, etc.). Of these, phthalic acid and halides of tetrahydrophthalic acid (particularly chloride) are preferred. Polyoxazoline (B6); a reaction product of N-hydroxyalkyl (C1-30) -oxazolidine and polyisocyanate (B2), an ester of N-hydroxyalkyl (C1-30) -oxazolidine and polycarboxylic acid, etc. Is mentioned. The N-hydroxyalkyl-oxazolidine used is formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde,
Aldehyde or ketone such as acetone, methyl ethyl ketone, methyl isobutyl ketone and diethanolamine,
It is obtained by reaction with a dialkanolamine such as diisopropanolamine and di-sec-butanolamine. As polycarboxylic acids, succinic acid, adipic acid,
Azelaic acid, sebacic acid, phthalic acid, isophthalic acid,
Maleic acid, fumaric acid or the like having 2 to 100 carbon atoms;
Or higher organic acids.

The unsaturated carboxylic polyester compound (B)
7) Compounds obtained by an esterification reaction between polyol and (meth) acrylic acid. Polyallyl compound (B8); polyesters of di- or hexavalent or higher polycarboxylic acid and allyl alcohol, triallyl isocyanurate and the like.

The compound (C) having a carbonyloxyimino group of the present invention is not particularly limited as long as it has one or more carbonyloxyimino groups in the molecule, and specific examples thereof include ether compounds, vinyl compounds, It has at least one main chain structure or skeleton selected from the group consisting of ester compounds, amide compounds, carbonate compounds, novolaks and hydrocarbons which may have a hydroxyl group in the side chain, and has carbonyloxyimino in the side chain or terminal. Examples of such compounds include compounds having a skeleton structure represented by the following general formulas (6) to (14). It does not prevent these main chain structures from being mixed with each other in a random or block manner. General formula

[0029]

Embedded image

[0030]

Embedded image

[0031]

Embedded image

[0032]

Embedded image

[0033]

Embedded image

Hereinafter, these will be described in detail. In the general formulas (6) to (14), a to i represent an integer of 1 to 2,000. From the viewpoint of the viscosity of the resin composition and the hardness of the cured product after curing, a to i are preferably 1 to 1,000, more preferably 1 to 100, and particularly preferably 1 to 1
0. In the general formula (6), A ¹ represents an alkylene group, an arylene group, an arylene alkyl group, a haloalkylene group or a glycidyl group, which is substituted or unsubstituted by a —XZ group. In the present specification, the group -XZ is -X-
A group represented by Z wherein X represents a direct bond or a divalent organic group; Z represents a carbonyloxyimino group represented by the following general formula (5). ] Represents a group. General formula

[0035]

Embedded image

[In the general formula, R ⁶ and R ⁷ are each independently a linear or branched alkyl or alkenyl group having 1 to 35 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group or a glycidyl group. And R ⁶ and R ⁷ may combine to form a cycloalkylidene ring having 4 to 35 carbon atoms, but preferably, R ⁶ and R ⁷ are a methyl group, an ethyl group, a propyl group or a phenyl group. , R ⁶ and R ⁷ may be the same or different. The divalent organic group represented by X has at least one group selected from the group consisting of an ether group, a thioether group, a carbonate group, an ester group, an imino group, an amide group, a urethane group, and a urea group. Also good hydrocarbon groups and the like,
_{Specifically, -CH 2 -, - CH 2} CH 2 -, - CH 2 OC
_{H 2 CH 2 -, - CH} 2 SCH 2 CH 2 -, - CHOC (=
_{O) OCH 2 -, - CH} 2 NHCH 2 CH 2 -, - CH 2 N
HC (= O) NH (CH 2) 6 NHC (= O) O- and -
_{CH 2 S (CH 2) 2} C (= O) O (CH 2) 2 - a hydrocarbon group having 1 to 35 carbon atoms having a structure and the like.

In formula (6), at least one of a 1 A ¹ groups represents an alkylene group substituted with a -XZ group. From the viewpoint of the hardness of the cured product, it is preferable that an alkylene group in which at least 5% is substituted with -X-Z groups of a number of A ^1. Specific examples of the A ¹ in the general formula (6), a methylene group, an ethylene group, trimethylene group, propylene group, tetramethylene group, pentamethylene group, hexamethylene group, an alkylene group such as octamethylene group; a phenylene group An arylene group such as a naphthylene group; a haloalkylene group such as a chloromethylene group or a trichloropropylene group; butyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, cresyl glycidyl ether;
Heterocyclic oxy formed by ring-opening polymerization of glycidyl ethers such as diglycidyl ether, (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, butanediol diglycidyl ether, and trimethylolpropane triglycidyl ether. Examples thereof include a 3-hydrocarbyloxy-1,2-propylene group and a 3-acyloxy-1,2-propylene group excluding O in the alkylene group.

The compound (C) having the structure represented by the general formula (7) has a polyvinyl main chain. In the general formula (7), Q ¹ represents a hydrogen atom, an alkoxycarbonyl group,
It represents an acetoxy group or an alkyl group, an aryl group, a haloalkyl group, a haloaryl group, a haloaralkyl group and a -XZ group containing these substituents. At least one of b Q ^{1 in} the general formula (7) represents a —XZ group. In terms of hardness of the cured product, at least 5% of b Q ¹
Is preferably a -XZ group. Specific examples of the above Q ^{1 in} the general formula (7) include a hydrogen atom; an alkyl group such as a methyl group and an ethyl group; an aryl group such as a phenyl group and a tolyl group; a haloalkyl group such as a chloromethyl group and a chloroethyl group; Chloromethylphenyl group, chloroethylphenyl group, 2,4,6-trichlorophenyl group, 2,4,6-
A haloaryl group and a haloaralkyl group such as a tribromophenyl group; an alkoxycarbonyl group such as a methoxycarbonyl group, an ethoxycarbonyl group and a butoxycarbonyl group; an acetoxy group and a -XZ group.

The compound (C) having a structure represented by the general formula (8) has a polyester main chain. In the general formula (8), A ² and A ³ are the same or different and are represented by -X-
Represents an alkylene group substituted or unsubstituted with a Z group, an arylene group substituted or unsubstituted with an -XZ group, an aralkylene group or a haloalkylene group. C pieces of A2 and c-number of A ³ in the general formula (8)
At least one represents at least one selected from the group consisting of an arylene group substituted with an -XZ group. From the viewpoint of the hardness of the cured product, at least 5% is -XZ
At least one selected from the group consisting of an alkylene group substituted with a group and an arylene group substituted with a -XZ group.
Preferably, it represents a species. Specific examples of the A ² and the A ³ in the general formula (8), a methylene group, an ethylene group, a propylene group, a tetramethylene group, ethylethylene group, hexamethylene group, heptamethylene group, such as octamethylene Alkylene group; aryl group such as phenylene group, tolylene group; aralkylene group such as benzylidene group, ethylenephenylene group; haloalkylene group such as chloroethylene group, bromoethylene group, chloromethylethylene group, 1,2-dichloroethylene group or And a group in which the hydrogen atom is substituted with an -XZ group.

The compound (C) having a structure represented by the general formula (9) has a polyester main chain. In the general formula (9), A ⁴ represents an alkylene group substituted or unsubstituted by an —X—Z group, an arylene group substituted or unsubstituted by an —X—Z group, an aralkylene group, or a haloalkylene. Represents a group. At least one of d A ^{4 in} the general formula (9) is at least one selected from the group consisting of an alkylene group substituted with an -XZ group and an arylene group substituted with an -XZ group. Represents one type. From the viewpoint of the hardness of the cured product, at least 5% is -X-
It preferably represents at least one selected from the group consisting of an alkylene group substituted with a Z group and an arylene group substituted with a -XZ group. The above A ⁴ in the general formula (9)
Specific examples of the such as those shown as specific examples of the A ² and the A ³ and the like.

The compound (C) having the structure represented by the general formula (10) has a polyamide main chain structure. A ⁵ and A ⁶ in the general formula (10) are the same or different and are each an alkylene group substituted or unsubstituted with an -XZ group, an arylene group substituted or unsubstituted with an -XZ group. , An aralkylene group or a haloalkylene group. E of A ⁵ and e in the general formula (10)
At least one of A ⁶ represents at least one selected from the group consisting of an alkylene group substituted with a —XZ group and an arylene group substituted with a —XZ group.
From the viewpoint of the hardness of the cured product, at least 5% preferably represents at least one selected from the group consisting of an alkylene group substituted with an -XZ group and an arylene group substituted with an -XZ group. . Specific examples of A ⁵ and A ^{6 in} the general formula (10) include those described above as specific examples of A ² and A ³ .

The compound (C) having a structure represented by the general formula (11) has a polyamide main chain. In the general formula (11), A ⁷ represents an alkyl group substituted or unsubstituted with an -XZ group, an arylene group substituted or unsubstituted with an -XZ group, an aralkylene group, or a haloalkylene. Represents a group. At least one of f A ^{7 in} the general formula (11) is at least one selected from the group consisting of an alkylene group substituted with an -XZ group and an arylene group substituted with an -XZ group. Represents one type. At least one of f A ^{7 in} the general formula (11)
Are an alkylene group substituted with a -XZ group and -X-
Represents at least one selected from the group consisting of an arylene group substituted with a Z group. From the viewpoint of the hardness of the cured product, at least 5% represents at least one selected from the group consisting of an alkylene group substituted with an -XZ group and an arylene group substituted with an -XZ group. preferable. Specific examples of A ^{7 in} the general formula (11) include those shown as the specific examples of A ⁴ above.

A compound having a structure represented by the general formula (12)
Compound (C) has a polycarbonate main chain structure
It is. In the general formula (12), A⁸Is substituted with a -XZ group.
Substituted or unsubstituted alkylene group, -XZ
Arylene substituted or unsubstituted with a group
Group, aralkylene group or haloalkylene group. one
G of A in general formula (12) ⁸At least one of the
An alkylene group substituted with a -XZ group and a -XZ group
Selected from the group consisting of substituted arylene groups
Represents at least one species. In terms of the hardness of the cured product, at least
An alkylene group having 5% substituted with an -XZ group and -X-
Selected from the group consisting of arylene groups substituted with a Z group
It is also preferable that at least one kind be represented. The general formula (1
A in 2)⁸As a specific example of A4,
Those shown are mentioned.

The compound (C) having a structure represented by the general formula (13) has a novolak main chain. In the general formula (13), Ar represents a benzene ring, a tolyl group, or a xylyl group. Q ² is a hydrogen atom, an epoxy group, a glycidyl group or an alkylene group substituted with a -XZ group;
Represents an arylene group substituted with a -Z group. The general formula (1
At least one of the h Q ^{2 in} 3) is -XZ
Represents a group. In terms of hardness of the cured product, at least 5%
It is preferable to represent at least one selected from the group consisting of an alkylene group substituted with an XZ group and an arylene group substituted with an -XZ group. Specific examples of the above Ar in the general formula (13) include a substituted phenylene group which is a residue of a phenol novolak resin, and a substituted tolylene group which is a residue of a cresol novolak resin.

The compound (C) having a structure represented by the general formula (14) has a hydrocarbon main chain structure which may have a hydroxyl group in a side chain. In the general formula (14), A ⁹ is a linear or branched alkylene group which may contain a hydroxyl group, or an arylene group, and the number of hydroxyl groups represents 0 to 5. Preferably, it is a linear or branched alkylene group having 2 to 10 carbon atoms of A ⁹ or an arylene group having 6 to 30 carbon atoms, which may be substituted or unsubstituted with an -XZ group. However, in general formula (14), at least one -X
It has a -Z group. In terms of hardness of the cured product, at least 5
% Of an alkylene group substituted with an -XZ group and -XZ
It preferably represents at least one selected from the group consisting of an arylene group substituted with a group. General formula (14)
Specific examples of A ^{9 in} the above include those shown as specific examples of A ² and A ³ above.

Among these main chain structures or skeletons, the main chain structures or skeletons represented by the general formulas (6), (7), (9), (13) and (14) are preferable, and more preferably the general formula (7) ) The main chain structure or skeleton represented by (14). In the compound (C) having the structure represented by any of the general formulas (6) to (14), the ratio of the group having the -XZ group to the other group, the type of the other group, the type of X, and the a to By changing the value of i, the viscosity of the resin composition of the present invention and the physical properties such as hardness, flexibility, weather resistance and chemical resistance of the cured product after curing can be controlled.

The compound (C) having a carbonyloxyimino group of the present invention is obtained by, for example, a reaction between an oxime and an acid halide or a reaction between an oxime and an acid anhydride, and is not particularly limited. The oxime group of the compound (E) having an oxime group is preferably 0.1 to 3 equivalents to the acid halide group of the acid halide having
More preferably 0.5 to 2 equivalents,
It is obtained by reacting in the presence of a catalyst in a solvent.
Acid halide groups (haloformyl groups) of acid halides having a main chain structure include acid chloride groups (chloroformyl groups),
Examples thereof include an acid bromide group (bromoformyl group), and preferably an acid chloride group. The main chain structure is a compound having a skeletal structure represented by any one of the above general formulas (6) to (14), and the acid halogen group is a precursor of the carbonyloxyimino group represented by Z in the formula. is there. Therefore, the number of the acid halogen groups is the same as that of the -XZ group in the formula. (E) is represented by the following general formula (16).

[0048]

Embedded image

Wherein R ⁶ and R ⁷ are each independently a linear or branched alkyl or alkenyl group having 1 to 35 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group or a glycidyl group; R ⁶ and R ⁷ combine to form 4 carbon atoms
Or a cycloalkylidene ring of from 35 to 35]. Specific examples of (E) include acetoxime, methyl ethyl ketone oxime, dibutyl ketone oxime, acetophenone oxime, benzophenone oxime, acenaphthone oxime, cyclohexanone oxime and the like, and are preferable. Is a group in which R ⁶ and R ⁷ are an alkyl group having 1 to 8 carbon atoms and an aryl group having 6 to 10 carbon atoms, more preferably acetoxime and acetophenone oxime. The solvent is not particularly limited as long as it does not hinder the reaction and dissolves the raw materials and products, and may be the same as the solvent used in the production of (A). The catalyst is a heterocyclic compound exhibiting basicity, for example, pyridine, pyrazine, triazine, piperazine, piperidine and the like, and preferably pyridine. The amount of the catalyst is based on the oxime group of (E).
It is 0.1 to 1.0 equivalent. Preferably 0.3 to 0.
7 equivalents. The reaction temperature is preferably from 0 to 100.
° C, more preferably 20 to 70 ° C. The end point of the reaction can be confirmed by NMR, IR and the like, and can be used even if purified by a method such as topping, washing, recrystallization and the like. The carbonyloxyimino group is, for example, 1760 cm in IR.
It can be quantified by the standard curve method by the characteristic absorption of the imino group of -1 (C = N). This is because the absorption of the raw material oxime (C = N-OH) can be observed at 1650 to 1700 cm-1 and can be distinguished from the absorption of the imino group.

In particular, when (C) is a polymer, the polymer is obtained by polymerizing or condensing a low molecule having a carbonyloxyimino group or by polymerizing or condensing a low molecule having a carboxyl group. Thereafter, it is obtained by changing to an acid halogen group and further modifying to a carbonyloxyimino group.
After polymerizing or condensing a low molecule having an acid halogen group into a high molecule, it may be modified to a carbonyloxyimino group. The method for forming a polymer depends on the structure of the functional group (for example, an unsaturated group, an epoxy group, a carboxyl group, a hydroxyl group, etc.) of the low-molecular compound, and each can be produced by a known method. The compound (C) having a carbonyloxyimino group preferably has a weight average molecular weight of 100
~ 200,000, more preferably 200 ~ 1
00,000, particularly preferably 300 to 50,000.
00. The carbonyloxy imino equivalent is preferably 100 to 100,000, more preferably 1 to 100,000.
00 to 50,000, particularly preferably 100 to 3
It is 0000. The melting point or glass transition temperature (Tg) is preferably from 5 to 300 ° C, more preferably from 5 to 300 ° C.
180 ° C.

Preferably, in the general formula (14), i =
1 is the case where the number of -XZ groups is two, and the carbonyloxyimino compound (C) is represented by the following general formula (17). In the formula ^{Z-X-R 8 -X-} Z (17) Formula (17), R ⁸ represents a non-substituted with -X-Z group of A ^9. Specific examples of R ⁸ include those shown as specific examples of A ⁴ above, and are preferably a methylene group, an ethylene group or a propylene group. X represents a direct bond or a divalent organic group as described above, and is preferably selected from the group consisting of an ether group, a thioether group, a carbonate group, an ester group, an imino group, an amide group, a urethane group, and a urea group. Examples include a hydrocarbon group which may have one or more groups, and particularly preferably a direct bond. Specific examples of the compound (C) having a carbonyloxyimino group obtained as described above include those shown in Table 2 in the general formula (17).

[0052]

[Table 2]

In the curable composition of the present invention, the ratio of the compound (B) having two or more electrophilic groups to the compound (C) having a carbonyloxyimino group is such that one electrophilic group in (B) is used. On the other hand, the carbonyloxyimino group in (C) is preferably from 0.7 to 1.3, and more preferably from 0.9 to 1.1. When the ratio is 0.7 or more, or 1.3 or less, the curability of the curable composition, the water resistance of the cured product, and the decrease in mechanical strength are preferred, and this is preferred. (B)
The ratio of the heterocyclic group-containing compound (A) to the one electrophilic group in (B) is preferably such that the heterocyclic group in (A) is 0.01 to 1.0, more preferably 0.05 ~
0.8. This ratio is 0.01 or more;
When it is 0 or less, the curability of the curable composition, the water resistance of the cured product, and the decrease in mechanical strength are preferred, which is preferable. The amount of (A) to be added is usually preferably from 0.1 to 200 parts, more preferably from 0.5 to 1 part, per 100 parts of the curable composition.
00 parts, particularly preferably 1 to 50 parts. When the addition amount is 0.1 part or more, the curing acceleration effect and the viscosity reduction effect are sufficient, and when it is 200 parts or less, the water resistance of the cured product,
Physical properties such as chemical resistance and mechanical strength do not decrease.

The curable composition of the present invention may further contain a basic compound (F) if necessary for the purpose of further accelerating the curing speed. Thiol group or -S-
The compound (B) having two or more electrophilic groups in the molecule that reacts with the group may further use the basic compound (F) if necessary. By using this in combination, high-speed curability at room temperature is improved. Examples of the basic compound (F) include a tertiary amine compound (F1), sodium methylate,
Alkaline compounds such as caustic soda, caustic potash, and lithium carbonate (F2); and Lewis base compounds such as triethylphosphine and triphenylphosphine (F3). Of these, preferred are tertiary amine compounds (F
1). The type and amount of the basic compound (F) may be appropriately selected depending on the curing speed and the pot life to be obtained, but the basic compound (F) may be added in an amount of 0.1 to 100 parts by weight of the heterocyclic-containing compound (A). It is preferable to add about 50 parts by weight.

The tertiary amine compound (F1) preferred as (F) above is not particularly limited as long as it has a tertiary amino group in the molecule. For example, carbon number 3-20,
Examples of the aliphatic amine having 1 to 4 amino groups include trimethylamine, triethylamine, tetraethylmethylenediamine, tetramethylpropane-1,3-diamine, tetramethylhexane-1,6-diamine, pentamethyldiethylenetriamine, pentamethyldipropylenetriamine, Bis (2-dimethylaminoethyl) ether, ethylene glycol (3-dimethyl) aminopropyl ether, dimethylaminoethanol, dimethylaminoethoxyethanol, N, N, N'-trimethylaminoethyl-ethanolamine, dimethylcyclohexylamine, etc. Examples of aromatic amines and araliphatic amines having 9 to 20 amino groups and 1 to 4 amino groups include dimethylbenzylamine, N, N-dimethylaminomethylphenol, and tris (N, N-dimethylamine). Examples of heterocyclic compounds having 4 to 20 carbon atoms and 1 to 6 amino groups, such as minomethyl) phenol, include 1,2-dimethylimidazole, dimethylpiperazine, N-methyl-N ′-(2-dimethylamino) -ethylpiperazine, N-methylmorpholine, N- (N ',
N'-dimethylaminoethyl) morpholine, N-methyl-N '-(2-hydroxyethyl) morpholine, 1,8
-Diazabicyclo (5,4,0) -undecene-7,
1,5-diazabicyclo (4,3,0) -nonene-5,
6-dibutylamino-1,8-diazabicyclo (5,
4,0) -undecene-7, triethylenediamine, hexamethylenetetramine and the like.

In order to increase the curing speed of the curable composition,
If necessary, a catalyst for a photolysis reaction of the compound (C) having a carbonyloxyimino group may be added. The catalyst is not particularly limited as long as it is a quinone compound (G). For example, benzoquinone, naphthoquinone, anthraquinone and the like can be mentioned, and preferably naphthoquinone. The type and amount of the catalyst may be appropriately selected depending on the curing speed and the pot life to be obtained, but the catalyst is added in an amount of about 0.01 to 10 parts by weight based on 100 parts by weight of (C). Is preferred. As the catalyst for the reaction between the primary amine generated by the reaction with water and the electrophilic group (preferably the epoxy group) of (B) after irradiation with light or electron beam, the above-mentioned tertiary amines and phosphines, triphenylphosphine And hydrocarbon phosphines having 3 to 30 carbon atoms, such as tributylphosphine and the like. Of these, tertiary amines are preferred, and N, N-dimethylpropylamine, N, N,
Aliphatic tertiary amines such as N ', N'-tetramethylhexamethylenediamine; N-methylpyrrolidine, N, N'
Heterocyclic tertiary amines such as -dimethylpiperazine; aromatic tertiary amines such as benzyldimethylamine and dimethylaminomethylphenol are particularly preferable.

The resin composition of the present invention may further contain, if necessary, (1) an adhesion improver such as a silane coupling agent and a titanium coupling agent, (2) hindered amines, hydroquinones, and hindered phenols. , Antioxidants such as sulfur-containing compounds, (3) UV absorbers such as benzophenones, benzotriazoles, salicylates, metal complex salts, (4) metal soaps, heavy metals (eg, zinc, tin, lead, cadmium) Etc.) inorganic and organic salts,
Light stabilizers such as organotin compounds, (5) phthalic esters,
Plasticizers such as phosphate esters, fatty acid esters, castor oil, liquid paraffin alkyl polycyclic aromatic hydrocarbons, (6)
Paraffin wax, microcrystalline wax,
Waxes such as polymerized wax, beeswax, spermaceti low molecular weight polyolefin, (7) benzyl alcohol, tar,
Non-reactive diluents such as picumen, (8) reactive diluents such as low-molecular aliphatic glycidyl ethers, aromatic monoglycidyl ethers and (meth) acrylate esters;
(9) calcium carbonate, kaolin, talc, mica, bentonite, clay, sericite, asbestos, glass fiber, carbon fiber, aramid fiber, nylon fiber, acrylic fiber, glass powder, glass balloon, shirasu balloon,
Fillers such as coal powder, acrylic resin powder, phenol resin powder, metal powder, ceramic powder, zeolite, slate powder, etc. (10) Pigments or dyes such as carbon black, titanium oxide, red iron oxide, lead red, para red, navy blue, etc. , (1
1) Solvents such as ethyl acetate, toluene, alcohols, ethers and ketones, (12) blowing agents, and (13) dehydrating agents such as monoisocyanate compounds and carbodiimide compounds. (14) an antistatic agent, (15)
Antibacterial agent, (16) fungicide, (17) fragrance, (18) flame retardant, (19) phenols, (20) leveling agent,
(21) Dispersant (22) Radical polymerization initiator and the like can be added. Two or more of these can be used in combination. These addition amounts are preferably in a weight ratio of (B): additive = 1.0: 0.01 to 2, more preferably 1: 0.02 to 1.

The curing mechanism of the curable composition of the present invention can be obtained by irradiating light or an electron beam.
The carbonyloxyimino group in (C) is decomposed to generate ketimine and carbon dioxide. Next, a primary amine is produced by the reaction between the produced ketimine and water. The primary amine thus formed reacts with the cyclic (thio) carbonate group of (A) to open the ring, thereby generating a hydroxyl (mercapto) group. The generated hydroxyl (mercapto) group reacts with the electrophilic group (preferably epoxy group) of (B), and (B) is cured. In this case, (C) may also react with (B), but the reaction rate with (B) is much higher for hydroxyl (mercapto) groups than for (C). Preferably it is a mercapto group. General formula

[0059]

Embedded image

Accordingly, the following (a) to (c) are exemplified as the use and storage form of each component of the curable composition of the present invention. (A) (A), (B) and (C) are stored in an independent three-liquid form, and the three components are mixed and cured at the time of use. [(Basic compound (F) and quinone compound (G) as optional components)
Can be stored alone as the fourth component, and used as a mixture with other components at the time of use, or can be stored in the form added in (A) and / or (C). )] (B) Store in the form of a mixture of (A) and (B) and two independent liquids of (C), and mix and cure the two components at the time of use. [(The basic compound (F) and the quinone compound (G), which are optional components, may be stored alone as the third component and used in combination with other components at the time of use. (C) The mixture of (A), (B), and (C) is stored in the form of one liquid, and used as it is when used. [(The basic compound (E) and the quinone compound (G), which are optional components, may be stored alone as the second component, and may be used by mixing with other components at the time of use, or may be added to the mixture. They can be stored.)] These use and storage forms can be appropriately selected according to conditions such as the use, purpose, temperature and humidity at the time of use.

The preferred use and storage form of each component in the curable composition of the present invention is that the compound (C) having an acyloxyimino group is stable unless it comes into contact with light or an electron beam. The curable composition (c) can be stored as a one-part curable composition in a state where the curable composition is completely shielded from light or electron beams. The product can be used in its native form at the point of use. The method for producing the curable composition of the present invention is not particularly limited as long as it is a method capable of mixing and dispersing (A) to (C), and examples thereof include the following methods. In a suitable container such as a glass beaker, can or plastic cup, knead by hand with a stirring rod, spatula, etc., or a device equipped with double helical ribbon blade, gate blade, universal mixer, planetary mixer, bead mill, Kneading can be performed by a conventionally known mixing device such as a three-roll extruder-type kneading extruder, but a mixing device such as a universal mixer is preferable. The viscosity of the composition at 25 ° C. is preferably from 2.5 to 4 Pa · s from the viewpoint of pouring workability, curability, and adhesiveness.
Is preferably 5 to 7 Pa · s.

The method of using the curable composition of the present invention is not particularly limited. For example, (a) room temperature from 5 ° C. to 40 ° C. and (b) high temperature conditions from 40 ° C. to around 200 ° C. However, by changing the reactivity of the compound (C), it can be used under practical conditions. The condition (a) is a normal environment, and (C) is an acyloxyimino equivalent such as O, O'-diacetphenone oxime succinate (SDAPO) or O, O'-diacetphenone oxime glutarate (GDAPO). Is less than 300 and can be cured by using a polyfunctional acyloxyimino compound having two or more functional groups. The condition (b) is an environment that requires heating, and (C) is not particularly limited. However, when the same acyloxyimino compound as that used under the condition (a) is used, the pot life is shortened. Since it is difficult to use, the workability is improved by using an acyloxyimino compound having an acyloxyimino equivalent of 300 or more.

The method of using the one-pack type curable composition of the present invention is not limited to a general method of curing by irradiation of light or an electron beam with moisture in the air or moisture from a substrate such as concrete or the like before use. After irradiating the surface with light or an electron beam, water can be added and mixed, or spray can be used to entrain moisture in the air, or two-fluid spray can be used to entrain water at the same time as spraying. It is a method of irradiating light or an electron beam immediately before use, and then adding and mixing water.

When the curable composition of the present invention is applied, there is no particular limitation on line coating or on-site coating, and conventionally known coating means such as a roll coater (size press, gate roll coater, etc.), A coating machine such as a bar coater, a gravure coater, an air knife coater, a blade coater or the like, or a means such as a brush or a roll can be used. The coating amount is preferably 1 as a weight after drying.
To 50 g / m2, more preferably 3 to 30 g / m2. Drying is performed by heating with hot air or the like. The drying temperature varies depending on the type of the dryer, but the temperature inside the dryer is usually 50 to 200C, preferably 100 to 1C.
50 ° C. The drying time depends on the drying temperature,
Usually 15 minutes to 5 hours, preferably 30 minutes to 3 hours. Although the film thickness varies depending on the application, for example, in the case of in-situ coating, it is preferably 50 μm to several cm, more preferably 100 μm to 1 cm, and in the case of line coating,
Preferably it is 1 to 150 μm, more preferably 5 μm.
１００100 μm. At this time, if necessary, a solvent that dissolves the curable composition can be used. The solvent is not particularly limited as long as it dissolves the curable composition,
It may be the same as the solvent used in the production of (A). These solvents are used alone or as a mixture.

The active energy rays applied to the coated curable composition of the present invention include ultraviolet rays and electron beams. When irradiating with ultraviolet rays, a known ultraviolet irradiator equipped with a high-pressure mercury lamp, a metal halide lamp, or the like can be used. The irradiation amount of ultraviolet rays is preferably 30 to
It is 2,000 mJ / cm ² . Irradiation amount is 30mJ / c
If it is less than m ² , the curing of the curable composition will be insufficient,
If it exceeds 000 mJ / cm ² , the film may be yellowed and deteriorated. When irradiating an electron beam, a known electron beam irradiation device can be used. The irradiation amount of the electron beam is preferably 1 to 10 Mrad. When the irradiation amount is less than 1 Mrad, the curing of the curable composition becomes insufficient and the curing amount becomes 10 Mrad.
If it exceeds, the film or substrate (paper, film, resist,
Laminates, printed circuit boards, etc.) may be damaged and deteriorated.

The reaction temperature with water after irradiation with light or an electron beam in this manner is preferably 25 ° C. or higher, more preferably 25 to 180 ° C., and particularly preferably 80 to 120 ° C. It cures at room temperature, and shows higher curability as the reaction temperature increases. The humidity condition is preferably 20 to
100% R. H. And particularly preferably 30 to 80%.
R. H. It is. The curing time is a few minutes to 100 hours.
This cured product corresponds to the cured product [3] of the present invention, and has excellent properties such as water resistance, chemical resistance, mechanical properties, and adhesiveness.

The substrate to which the curable composition of the present invention is applied is not particularly limited, but may be a plastic film, paper, a composite sheet of paper and plastic film, a metal plate, concrete, a pavement material, a laminate. Boards, printed circuit boards and the like. Specifically, for example, plastic films such as a PVC sheet, a polyethylene film, and a polyester film; tissue paper, reinforced paper, titanium paper,
Papers such as latex-impregnated paper and gypsum board base paper; composite sheets of these; metal plates such as iron plates, aluminum plates, steel plates, copper plates, and SUS plates; concrete; paving materials such as asphalt;
Resist; laminated board for electric / electronic parts; printed circuit board for electric / electronic parts; Plastic films coated with the curable composition of the present invention, paper, resist, laminates, the surface of the printed circuit board, etc., hardly scratch,
Further, the appearance is good. Because it has such an effect,
As the use of the curable composition of the present invention, materials for electric / electronic parts (resist, laminate, printed circuit board, etc.) are particularly suitable.

The curing agent (T1) of the present invention [2] is obtained by irradiating (A) and (C) with light or an electron beam and then reacting with water. The number of heterocyclic groups in (A) is 0.01 to 1 relative to one acyloxyimino group in (C),
Preferably, the number is 0.05 to 0.8. When the ratio of the heterocyclic group in (A) is 1 or less, the cured product has good chemical resistance and mechanical properties, and when it is 0.01 or more, the curing speed increases. Preferred as (T1) is a compound having 2 to 6 active hydrogens derived from a hydroxyl (thiol) group and / or a primary amino group in the molecule. The active hydrogen equivalent of (T1) is preferably from 50 to 500, and more preferably from 50 to 350. Active hydrogen equivalent is 5
If it is not more than 00, the crosslinked structure does not become loose, and the cured product has good physical properties such as chemical resistance and mechanical strength.
When the active hydrogen equivalent is 50 or more, it can be easily synthesized.

Since (T1) has a hydroxyl (thiol) group and / or a primary amino group, it can cure (B), preferably (B1) at a high speed even at ordinary temperature or low temperature. When (T1) is used in combination with (B), preferably (B1), the equivalent ratio of the number of functional groups in (B) to the active hydrogen in (T1) is usually 0.5 to 5.0, Preferably, 0.
7 to 2.0. This curing acceleration effect is due to the high reactivity between the amino group of the compound in the composition and the heterocyclic group in (A), and the reaction between the thiol group generated by the reaction and the electrophilic group of the compound in the composition. It is considered that the property is high. Further, part of the amino group of (T1) is (A)
, It is less irritating to the skin than ordinary amine-based curing agents. Furthermore, a synergistic effect is exhibited by having both a thiol group and a basic amino group in the same molecule, and the chemical resistance, water resistance, and mechanical properties are higher than when a thiol-based curing agent and a basic substance are used in combination. Excellent physical properties such as strength.

[0070]

EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples. Parts represent parts by weight.

Production Example 1 90 parts of carbon disulfide, 5 parts of lithium bromide, and 120 parts of tetrahydrofuran (THF) were charged into a glass reaction vessel equipped with a dropping funnel, a thermometer and a stirring rod, and stirred and dissolved. Of propylene oxide (PO) was added dropwise while maintaining the temperature at 20 ° C. or lower, followed by stirring at 40 ° C. for 5 hours.
After distilling off THF and excess carbon disulfide under reduced pressure,
Filtration gave 60 parts of a pale yellow liquid heterocyclic compound (A-1) having a viscosity of 25 cP and a heterocyclic group equivalent of 135.

Production Example 2 90 parts of carbon disulfide, 5 parts of lithium chloride and 140 parts of THF were charged into a reaction vessel similar to that of Production Example 1 and stirred and dissolved, and then 140 parts of trimethylolpropane triglycidyl ether (epoxy equivalent: 140 parts) was added. ) Was added dropwise while maintaining the temperature at 20 ° C or lower, and the mixture was stirred at 40 ° C for 5 hours. Under reduced pressure,
After distilling off THF and excess carbon disulfide, the mixture was filtered,
70 parts of a pale yellow liquid heterocyclic compound (A-2) having a viscosity of 130 cP and a heterocyclic group equivalent of 218 was obtained.

Production Example 3 The procedure of Production Example 1 was repeated, except that the same amount of trimethylene oxide was used in place of PO.
80 parts of heterocyclic compound (A-3) as a slightly yellow liquid having cP and a heterocyclic group equivalent of 140 was obtained.

Production Example 4 117 parts of carbon disulfide, 5.3 parts of lithium chloride and 120 parts of THF were charged into a reaction vessel similar to that of Production Example 1 and stirred and dissolved, and 219 parts of glycidyl methacrylate was added to 25 parts of the same reaction vessel.
After the dropwise addition, the mixture was stirred at 40 ° C. for 5 hours. After distilling off THF and excess carbon disulfide under reduced pressure, the residue was filtered to obtain 120 parts of a heterocyclic compound (A-4) as a slightly yellow liquid having a viscosity of 31 cP and a heterocyclic group equivalent of 218.

Production Example 5 20 parts of pyridine, 40 parts of acetophenone oxime, and 280 parts of methylene chloride were charged and stirred and dissolved in the same reaction vessel as in Production Example 1, and 15 parts of succinic chloride was dissolved in 180 parts of methylene chloride at room temperature. The solution was added dropwise.
After reacting for 2 hours while maintaining the temperature in the reaction vessel at 40 ° C., the mixture was filtered, methylene chloride was distilled off under reduced pressure, and the mixture was recrystallized with a mixed solvent of toluene and cyclohexane.
25 parts of OO'-diacetophenone oxime succinate (SDAPO) (C-1) at 55-157 ° C was obtained.

Production Example 6 In a reaction vessel similar to that of Production Example 1, 20 parts of pyridine, 40 parts of acetophenone oxime, and 280 parts of methylene chloride were charged and dissolved by stirring.
0 parts were added dropwise. After reacting for 2 hours while maintaining the temperature in the reaction vessel at 40 ° C., the mixture was filtered, methylene chloride was distilled off under reduced pressure, and then recrystallized with cyclohexane to obtain 20 parts of acetophenone oxime acrylate (AAPO). Further, 10 parts of acetophenone oxime acrylate (AAPO) obtained in the reaction vessel, 20 parts of styrene,
2 parts of laurylmercaptandecanethiol as a chain transfer agent, 0.1 part of 2.2'-azobisisobutyronitrile (AIBN) as a polymerization initiator, and 50 parts of benzene were charged, and light was blocked. Solution polymerization
Performed for 4 hours. Thereafter, reprecipitation was performed three times with a THF / n-hexane system, and an acetophenone oxime acrylate-styrene copolymer having a weight average molecular weight of 5,300 (AAPO) was used.
-St copolymer) (C-2) (20 parts) was obtained.

Production Example 7 A solution polymerization was carried out in the same manner as in Production Example 6, except that glycidyl methacrylate (GMA) was used in the same amount as in Production Example 6, and no chain transfer agent was used. Thereafter, reprecipitation was performed with a methylene chloride-methanol system, and the weight average molecular weight was 300.000 and the AAPO content was 30 mol.
% Acetophenone oxime acrylate-glycidyl methacrylate copolymer (AAPO-GMA copolymer) (C-3) (20 parts) was obtained.

Examples 1 to 5 and Comparative Examples 1 and 2 Compounds having the compositions shown in Table 3 were uniformly mixed.
And the curable composition of Comparative Examples 1-2 was obtained. The test method of the evaluation items is as follows.

[Touch Drying Time] The curable composition was uniformly applied to a steel sheet specified by JIS K5400 using a film applicator to obtain a dry photosensitive layer having a thickness of 500 μm. Furthermore, it is left in an atmosphere of 25 ° C. and 65% RH,
The time until the surface of the coating film became non-sticky was measured.
Table 3 shows the evaluation results. [Aesthetics] The curable composition was uniformly applied to a steel plate specified by JIS K5400 using a film applicator to obtain a dry photosensitive layer having a thickness of 500 µm. Then, after irradiating 5 J / cm 2 ultraviolet rays with a high pressure mercury lamp,
Heating was performed for 0 minutes to obtain a cured film. The aesthetic appearance was determined by visually observing the obtained coating film surface. Those with gloss, without swelling, peeling, etc. were rated as ○, and those with swelling, peeling, etc. were rated as x. Table 3 shows the evaluation results.

[Adhesive strength]: 30 × 30 × at 25 ° C.
Wool roller B-2 on the surface of 5cm sidewalk PC board
A curable composition having the composition shown in Table 3 in Table 3 was applied at a thickness of 1 mm. After curing at a temperature of 25 ° C. for 7 days, it was measured by a Kenken-type adhesive strength test method (unit: kgf / cm 2). Table 3 shows the evaluation results. [Water resistance]: The curable composition was allowed to stand in an atmosphere of 25 ° C. and 65% RH for 7 days to be cured. This cured product is immersed in distilled water at room temperature for 30 days, and changes in weight before and after immersion (%)
Was measured. Table 3 shows the evaluation results.

[0081]

[Table 3]

Epoxy resin 1; Epicoat 828 (manufactured by Yuka Shell Epoxy Co., Ltd./molecular weight: 380) Epoxy resin 2: Epicoat 807 (manufactured by Yuka Shell Epoxy Co., Ltd./molecular weight: 356) Epoxy resin 3: Trimethylolpropane glycidyl ether (molecular weight: 356) GDAPO; O, O'-glutarate diacetphenone oxime (molecular weight 366) DMP-30; trisdimethylaminomethylphenol (molecular weight 265) Photocatalyst; naphthoquinone

[0083]

The curable composition of the present invention reacts with water after being irradiated with light or an electron beam to (1) exhibit no corrosiveness to a metal material, and (2) has a rapid curability. ) Excellent water resistance after curing. (4) Excellent effects such as excellent adhesion to adherend after curing.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 177/00 C09D 177/00 G03F 7/004 503 G03F 7/004 503Z F-term (Reference) 2H025 AA06 AA10 AB20 AC01 AC06 AD01 BD03 BD23 BE00 CB30 4J036 AA01 DA05 DC26 DD03 DD04 FB01 FB02 FB06 FB07 FB11 FB12 FB13 HA02 HA03 JA08 JA09 JA13 JA14 4J038 DB031 DB041 DB061 DB091 DB151 DB221 DB311 DB401 DG261 JA04 NA14 JA17 NA04 PB09 PC02 PC03 PC04 PC06 PC08

Claims (15)

[Claims] 1. A heterocyclic-containing compound (A) represented by the following general formula (1), a compound (B) having two or more electrophilic groups in a molecule that reacts with a thiol group or an —S— group, and A curable composition comprising a compound (C) having a carbonyloxyimino group. General formula [In the formula (1), n is an integer of 1 to 10, X ¹ , Y ¹ and Z ¹
Are each independently an oxygen or sulfur atom; R ¹ is a residue or a hydrogen atom of the cyclic ether group-containing compound (D); R ² is a hydrocarbon group having 2 to 10 carbon atoms. ] 2. The curable composition according to claim 1, wherein (A) is a hetero ring-containing compound (A1) represented by the following general formula (2) or (3). General formula [In the formula (2), n is an integer of 1 to 10, X ² , Y ² and Z ²
Are each independently an oxygen or sulfur atom; R ³ is a polyepoxy compound (B1) or a monoepoxy compound (b1)
Residue. In the formula (3), R ⁴ is a residue of an alicyclic epoxide. ] 3. The curable composition according to claim 2, wherein the compound (A1) is a heterocyclic-containing compound (A2) represented by the following general formula (4). General formula [In the formula (4), one of Y ² and Z ² is S and the other is O; R ⁵ is a residue excluding the glycidyl group of monoglycidyl ether (d11-2). ] 4. The method according to claim 1, wherein (B) is at least one selected from the group consisting of polyepoxides, polyisocyanates, polyanhydrides, polyacid halides, polyoxazolines, unsaturated carboxylic polyesters, and polyallyl compounds. The curable composition according to any one of claims 1 to 3. 5. The curable composition according to claim 1, wherein (B) is a polyepoxide. 6. The carbonyloxyimino group of (C) has a structure represented by the following general formula (5).
5. The curable composition according to any one of 5. General formula [Alkyl or alkenyl group wherein R ^6, R ⁷ carbon atoms straight or branched chain are independently 1 to 35, aryl group having 6 to 30 carbon atoms, an aralkyl group or a glycidyl group, and R ⁶ R ⁷ may combine to form a cycloalkylidene ring having 4 to 35 carbon atoms] 7. The method according to claim 1, wherein (C) is at least one member selected from the group consisting of ether compounds, vinyl compounds, ester compounds, amide compounds, carbonate compounds, novolaks and hydrocarbons which may have a hydroxyl group in the side chain. The curable composition according to any one of claims 1 to 6, which has a main chain and a carbonyloxyimino group at a side chain or at a terminal. 8. The compound represented by the following general formula (6) to (1):
Represented by at least one selected from the group consisting of 4)
A compound having a main chain structure or a skeleton.
7. The curable composition according to any one of 7. General formulaEmbedded imageEmbedded imageEmbedded imageEmbedded image[In general formulas (6) to (14), a to i are 1 to 2,000.
Represents an integer. In the general formula (6), A¹Is a -XZ group wherein
X represents a direct bond or a divalent organic group. Z is a general formula
Represents a carbonyloxyimino group represented by (5). ]
An alkylene group substituted or unsubstituted with
Arylene group, arylene alkyl group, haloalkylene
A glycidyl group or a glycidyl group. A A of the general formula (6)
¹At least one of which is substituted with an -XZ group.
Represents a alkylene group. In the general formula (7), Q¹Is a hydrogen atom,
Alkoxycarbonyl group, acetoxy group or their substitution
Alkyl group including a substituent, an aryl group, a haloalkyl group,
Haloaryl group, haloaralkyl group or -XZ group
Represents B Qs in the general formula (7) ¹At least
One represents a -XZ group. However, Q other than -XZ group¹
Except that all are hydrogen atoms. A in the general formula (8)
^Two, A^ThreeAre the same or different and are substituted with -XZ groups
Or unsubstituted alkylene group, -XZ group
An arylene group substituted or unsubstituted with
Represents an aralkylene group or a haloalkylene group. General formula
(8) c A in (8)^TwoAnd c A^ThreeAt least one of
Is a group consisting of an arylene group substituted with a -XZ group
Represents at least one selected from General formula (9)
Medium, A^FourIs substituted or substituted with a -XZ group
Not substituted with an alkylene group, -XZ group or
Unsubstituted arylene group, aralkylene group or
Represents a haloalkylene group. D of A in the general formula (9)^Four
At least one of which is substituted with a -XZ group.
From an arylene group substituted with a kylene group and a -XZ group
Represents at least one selected from the group consisting of: General formula
(10) Medium, A^Five, A⁶Are the same or different, and -X-
Alkylene substituted or unsubstituted by group Z
Or unsubstituted or substituted with an -XZ group
Arylene group, aralkylene group or haloalkylene group
Represents E of A in the general formula (10)^FiveAnd e A⁶of
At least one of which is substituted with an -XZ group;
And an arylene group substituted with an -XZ group.
At least one selected from the group consisting of: The general formula (1
1) Medium, A⁷Is substituted or substituted with -XZ group.
Substituted with an unsubstituted alkyl group or -XZ group
Is an unsubstituted arylene group, aralkylene group or
Represents a haloalkylene group. F of the general formula (11)
A⁷At least one of which is substituted with a -XZ group
Arylene group substituted by alkylene group and -XZ group
At least one selected from the group consisting of: General
In equation (12), A⁸Is substituted with a -XZ group or
Unsubstituted alkylene group, substituted with -XZ group
Or unsubstituted arylene group, alkyl
Represents a len group or a haloalkylene group. In general formula (12)
G of A ⁸At least one is replaced by a -XZ group
Ali substituted with a substituted alkylene group and a -XZ group
At least one selected from the group consisting of
You. In the general formula (13), Ar represents an aryl group. Q^Two
Represents a hydrogen atom, an epoxy group or a -XZ group. General formula
H Qs in (13)^TwoAt least one of them is -X
Represents a -Z group. In the general formula (14), A⁹Is a -XZ group
Contains a substituted or unsubstituted hydroxyl group
A linear or branched alkylene group or aryl
Represents a group. At least one -X in the general formula (14)
It has a -Z group. ] 9. The divalent organic group represented by X has at least one group selected from the group consisting of an ether group, a carbonate group, an ester group, an imino group, an amide group, a urethane group, a urea group and a sulfide group. The curable composition according to claim 8, which is a hydrocarbon group which may be used. 10. A thiol obtained by irradiating a heterocyclic-containing compound (A) represented by the following general formula (1) and a compound (C) having a carbonyloxyimino group with light or an electron beam and then reacting with water. A curing agent (T) for a compound (B) having two or more electrophilic groups in its molecule that react with a group or an —S— group
1). General formula [In the formula (1), n is an integer of 1 to 10, X ¹ , Y ¹ and Z ¹
Are each independently an oxygen or sulfur atom; R ¹ is a residue or a hydrogen atom of the cyclic ether group-containing compound (D); R ² is a hydrocarbon group having 2 to 10 carbon atoms. ] 11. The curable composition according to claim 10, comprising (T1) and (B). 12. A basic compound, a photolysis catalyst of the above (C), a thermoplastic resin, a deodorant, an adhesion improver, an antioxidant, an ultraviolet absorber, a stabilizer, a plasticizer, a wax, a reactive dilution. At least one selected from the group consisting of agents, fillers, pigments, dyes, solvents, foaming agents, dehydrating agents, antistatic agents, antibacterial agents, fungicides, phenols, fragrances, flame retardants, leveling agents, and dispersants. 10. A composition comprising a seed.
13. The curable composition according to any one of 11 and 12. 13. A cured product obtained by curing the curable composition according to any one of claims 1 to 9, 11, and 12. 14. A method for curing a curable composition according to claim 1, wherein the curable composition is irradiated with light or an electron beam and then reacted with water. 15. A plastic film, paper, resist, laminate, or printed circuit board coated with the cured product of claim 13.