JPH11140161A - Rapidly curable epoxy resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a rapidly curable epoxy resin compsn. which has a high reactivity, a good storage stability, a low odor, an excellent workability, and improved mechanical and electrical properties and chemical resistance by compounding an epoxy compd. with an episulfide compd. contg. a compd. having episulfide and epoxy groups in the molecule. SOLUTION: Epoxy compd. having at least one oxirane ring in the molecule in an amount of 50-99 wt.% pref, 70-99 wt.%, 1-50 wt.% pref. 1-30 wt.%, episulfide compd. contg. at least 0.1 mol% compd. having episulfide and epoxy groups in the molecule, 1-90 wt.%, pref. 5-80 wt.% diluent, a curing agent, 0.01-10 wt.%, pref. 0.05-5 wt.%, cure accelerator, and additives such as a plasticizer, a reactive diluent, a filler, a reinforcement, a colorant, a flow modifier, a flame retardant, and a lubricant for molding are compounded.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fast-curing epoxy resin composition which gives a cured product having excellent curability and good performance. More specifically, the present invention relates to a fast-curing epoxy having excellent curability and good performance, which is useful as an industrial material in paints, electric / electronic materials, adhesives, composites, jigs and civil engineering. It relates to a resin composition.

[0002]

2. Description of the Related Art Epoxy resins are widely used as industrial materials because of their excellent heat resistance, chemical resistance and adhesiveness. However, with the growing needs in recent years,
There is a need for an epoxy resin having a higher function.
In particular, from the viewpoint of work efficiency, rapid curing has become a major issue, and the emergence of an epoxy resin material that can respond to this has been strongly demanded.

As a technique for quick curing, a method utilizing high reactivity between a double bond of an epoxy acrylate and an amine compound or a method utilizing high reactivity between a thiol group and an epoxy group is used. However, the former has the disadvantage that the reactivity at low temperatures is not sufficient, and the latter has the disadvantage that the odor is strong and the pot life is short.

On the other hand, it is known that the reaction between an episulfide group and an amino group is extremely fast, and that the curability at low temperatures is excellent. U.S. Pat. No. 3,378,522 discloses various episulfide compounds. Also, German Patent No. 2,505,36
No. 8 discloses that an episulfide compound is excellent in low-temperature curability. JP-A-7-138
No. 254 describes that a thermosetting composition containing an episulfide compound can provide a low dielectric constant copper-clad laminate. However, Die Angewandte
The greatest disadvantage of episulfide compounds, as described in Macromolekulare Chemie 240 (1996) 67-81, is the extremely poor storage stability.

[0005]

SUMMARY OF THE INVENTION The present invention has solved the above-mentioned problems, that is, it has high reactivity, good storage stability, low odor, excellent workability, and mechanical properties.
It is an object of the present invention to provide a fast-curing epoxy resin composition that gives a cured product having good electrical properties and chemical resistance.

[0006]

Means for Solving the Problems As a result of intensive studies on various curable epoxy resin compositions, the present inventors have found that a cured product having both high reactivity and storage stability, low odor and excellent workability is obtained. In order to solve all of the above, such as good mechanical and electrical properties and chemical resistance, it has been found that a specific epoxy resin composition has particularly excellent properties, and the present invention has been completed. That is, the present invention provides:
Hereinafter, a fast-curing epoxy resin composition comprising (B) an episulfide compound containing 0.1 mol% or more of a compound having an episulfide group and an epoxy group in one molecule in an amount of 1% to 50% by weight. provide. In addition, (A) more than 70% by weight and 99% by weight or less of an epoxy compound, and (B) 1% by weight or more of an episulfide compound containing 0.1 mol% or more of a compound having an episulfide group and an epoxy group in one molecule. Less than 30% by weight. Also,

[0007] The epoxy compound (A) is characterized in that it mainly contains a compound containing an aromatic ring. Further, there is provided a fast-curing epoxy resin composition comprising the resin composition described in any one of the above and a diluent (C) as essential components. Further, the present invention provides a fast-curing epoxy resin composition comprising, as essential components, the resin composition according to any one of the above and a curing agent (D). It is also characterized in that the curing agent (D) is a low-temperature curing agent. Another characteristic is that the curing agent (D) is a room temperature curing agent. Another characteristic is that the curing agent (D) is a heating curing agent. Further, there is provided a photocurable epoxy resin composition comprising the resin composition according to any one of the above and a photocuring agent as essential components. In addition, (10) the curable composition for a coating material, an electric / electronic material, an adhesive, a composite material, a jig / tool, or an industrial material in the civil engineering field, which contains the resin composition according to any one of the above as a main component. Resin composition.

Hereinafter, the present invention will be described in detail. [1] Curable epoxy resin composition: The curable epoxy resin composition of the present invention basically comprises an epoxy compound (A)
And a composition comprising an episulfide compound (B) containing an episulfide group and an epoxy group in one molecule. (1) Epoxy compound (A): Here, the epoxy compound is a compound having at least one or more oxirane rings represented by the formula (1) in one molecule.

Embedded image

Specific examples include (i) a compound containing one or more carboxylic acid groups per molecule and epichlorohydrin, glycerol dichlorohydrin or β.
Glycidylated product and (β-methyl-glycidyl) ester obtained by reacting -methyl epichlorohydrin with an alkali. Glycidyl esters are derived from aliphatic carboxylic acids such as, for example, acetic acid, benzoic acid, versamic acid, oxalic acid, succinic acid, adipic acid, sebacic acid or dimerized or trimerized linoleic acid; hexahydrophthalic acid, tetrahydrophthalic acid, It is derived from cycloaliphatic carboxylic acids such as 4-methylhexahydrophthalic acid and 4-methyltetrahydrophthalic acid; or from aromatic carboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid.

(Ii) Other epoxy compounds which can be used include compounds having one or more alcoholic hydroxy groups per molecule or one or more phenolic hydroxy groups per molecule and epichlorohydrin Glycidyl and (β-methylglycidyl) obtained by reacting with glycerol dichlorohydrin or β-methylepichlorohydrin under alkaline conditions or by reacting in the presence of an acidic catalyst and then treating with alkali. ) Ether. Such glycidyl ethers are derived from aliphatic alcohols such as butanol, higher aliphatic (C12-13) alcohols;

Diethylene glycol and triethylene glycol, propylene glycol and poly (oxypropylene) glycol, propane-1,3-diol, butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol , Hexane-2,4,
From 6-triol, glycerol, 1,1,1-trimethylolpropane, pentaerythritol, ethylene glycol and poly (oxyethylene) glycol: cyclohexanol, quinitol, 1,1-bis (hydroxymethyl) cyclohex-3-ene From an alicyclic alcohol such as bis (4-hydroxy-cyclohexyl) methane and 2,2-bis (4-hydroxy-cyclohexyl) propane: or N, N-bis (2-hydroxyethyl) aniline and 4,4 It can be derived from an alcohol containing an aromatic nucleus such as' -bis (2-hydroxyethylamino) diphenylmethane.

Preferably, the polyglycidyl ether is a compound containing one or more phenolic hydroxy groups per molecule, such as phenol, resorcinol, catechol, hadroquinone, bis (4-hydroxyphenyl) methane, 1,1,1,2. , 2-tetrakis (4-
Hydroxyphenyl) ethane, 4,4′-dihydroxyphenyl, bis (4-hydroxyphenyl) sulfone, 2,2-bis- (4-hydroxyphenyl) propane, 1,1-bis- (4-hydroxyphenyl) ethane, 4,4'-hydroxy-1,3,1 ', 3'-tetramethylbiphenyl, 1,6-dihydroxynaphthalene, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane and phenol- It is derived from a formaldehyde-based or cresol-formaldehyde-based novolak resin.

(Iii) Furthermore, for example, epichlorohydrin and amines containing at least one hydrogen atom directly bonded to a nitrogen atom, such as piperidine, aniline, N-butylamine, bis (4-aminophenyl) methane, bis ( Poly (N-glycidyl) obtained by subjecting a reaction product of 4-aminophenyl) sulfone and bis (4-methylaminophenyl) methane to a dehydrochlorination reaction
Compounds can be used. Other poly (N-glycidyl) compounds that can be used include triglycidyl isocyanurate, N, N'-diglycidyl derivatives of cyclic alkylene ureas such as ethylene urea and 1,3-propylene urea and 5,5-dimethyl N, N'-diglycidyl derivatives of hydantoins are mentioned.

(Iv) Epoxy resins obtained by epoxidation of cyclic and acrylic polyolefins, such as vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene oxide, 3,4-epoxydicyclopentadioxide Enyl glycidyl ether, bis (3,4-epoxydihydroxydicyclopentadienyl) glycidyl ether of ethylene glycol, 3,4-epoxycyclohexylmethyl-
3 ′, 4′-epoxycyclohexanecarboxylate and 6,6′-dimethyl derivative, bis (3,4-epoxycyclohexanecarboxylate) of ethylene glycol, 3,4-epoxycyclohexanecarboxaldehyde and 1,1-bis (hydroxy Methyl) -3,4
Acetal formed with epoxycyclohexane, bis (2,5-epoxy-cyclopentyl) ether and epoxidized butadiene or a copolymer of butadiene with an ethylenic compound such as styrene and vinyl acetate, glycidylated epoxidized soybean oil Can also be used.

The preferred epoxy compound for the novel fast-curing epoxy resin composition of the present invention is mainly composed of a compound having an aromatic ring in one molecule. Specific examples include mixtures containing more than 50% of glycidyl ethers of aromatic carboxylic acids, glycidyl ethers of aromatic amines, and glycidyl ethers of various phenols and derivatives thereof. Epoxy compounds particularly suitable for the novel fast-curing epoxy resin composition of the present invention include 2,2-bis (4-hydroxy-phenyl) propane and phenol (a chlorine atom or an alkyl group having 1 to 4 carbon atoms in the ring). And a polyglycidyl ether of a novolak resin from the same. They are,
Each of them may be used alone, or two or more kinds may be used in combination.

In the novel fast-curing epoxy resin composition of the present invention, the content of the epoxy compound (A) is in the range of 50% by weight or more and 99% by weight or less. If the content is less than 50% by weight, the storage stability is not sufficient, and if it exceeds 99% by weight, the curability deteriorates. A more preferred content range is more than 70% by weight and 99% by weight.
The range is as follows.

(2) Compound having episulfide group (B) 1) In the novel epoxy resin composition of the present invention, the compound having an episulfide group refers to one or more compounds represented by the formula (2) in one molecule. Aliphatic, cycloaliphatic, heterocyclic, saturated and unsaturated compounds having a group.

Embedded image Specific examples thereof include epithio hydrocarbons, epithioethers, epithioesters, epithiourethanes and epithioepoxys. Further, preferred compounds of the present invention include the compounds of formula (3), especially including the polyhydric alcohols and polyhydric phenols epithioalkyl and epithiocycloalkyl.

Embedded image (Here, R is derived from a polyhydric phenol or polyhydric alcohol, and n is preferably 2 to 6.)

2) Specific examples of these compounds include 4
-(Epithioethyl) -1-epithiocyclohexene,
Di (epithiopropyl) phthalate, epithioester of unsaturated fatty acid polymer, epithioester of acrylic acid, tri (2,3-epithiopropyl) of glycerol
Ether, di (3,4-epithiobutyl) ether of diethylene glycol, di (2,3-epithiocyclohexyl) ether of 1,4-butanediol, 1,5
2,3-epithiocyclohexyl) ether of pentanediol and di (3,4) of 1,6-hexanediol
-Epithiooctyl) ether, tri (3,4-epithiohexyl) ether of 1,2,6-hexanetriol,

Di (2,3-) of sulfonyldipropanol
Epithiocyclohexyl) ether, di (2,3-epithiopropyl) ether of 1,4-dimethylolbenzene, tri (2,3-epithiopropyl) ether of trimethylolpropane, tetrakis (3,4) of pentaerythritol -Epithiooctyl) ether, poly (2,3-epithiopropyl) ether of polyallyl alcohol, di (3,4-epithiocyclohexyl) ether of 1,5-cyclopentanediol, di (3,3) of ethylene glycol 4-epithiotridecyl) ether, di (2,3-epithiododecyl) ether of polyoxyethylene glycol having a molecular weight of about 400, (3,4-epithiododecyl) ether of resorcinol, di (3,3) of resorcinol 4-epithiohexyl) ether,
Tri (2,3-) of 1,3,5-trihydroxybenzene
Epithiodecyl) ether, resorcinol di (2,2
3-epithiocyclohexyl) ether,

2,2-bis (4-hydroxyphenyl)
Di (2,3-epithiopropyl) ether of butane,
1,1,2,2, -tetra (4-hydroxyphenyl)
Ethane tetrakis (2,3-epithiopropyl) ether, 1,1,5,5-tetra (4-hydroxyphenyl) pentane tetrakis (3,4-epithiododecyl) ether, 2,2-bis (4 -(Hydroxyphenyl) sulfone di (2,3-epithiopropyl) ether, 2,2-bis (4-hydroxyphenyl) propane di (2,3-epithiopropyl) ether, 1,1
Di (2,3) -bis (4-hydroxyphenyl) methane
-Epithiopropyl) ether, di (2,3-epithiopropyl) ether of 2,2-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2-
Bis- (4-hydroxyphenyl) propane di (2,2
3-epithiopropyl) ether,

Di (2,3-epithiopropyl) ether of 1,1-bis- (4-hydroxyphenyl) ethane and 4,4′-hydroxy-1,3,1 ′, 3′-tetramethylbiphenyl Di (2,3-epithiopropyl)
Ether, 1,6-dihydroxynaphthalene di (2,
3-epithiopropyl) ether, 2,2-bis (3,
Di (2,3-epithiopropyl) ether of 5-dibromo-4-hydroxyphenyl) propane and poly (2,3-epithiopropyl) ether of phenol-formaldehyde or cresol-formaldehyde novolak resin, 2, 2-bis (4-hydroxy-5
-Methoxyphenyl) 1,1-dichloropropane di (2,3-epithiopropyl) ether;

3) The novel epithioether of the present invention can be produced by various methods. Examples include thermal hydrolysis of hydroxymercaptan, treatment of 1,2-chlorothiol with a weak alkaline solution, treatment of ethylenically unsaturated ethers with compounds such as sulfur or polysulfidedialkyl. In addition, a method for obtaining an episulfide compound by exchanging all or part of oxygen atoms in an epoxy ring with a sulfur atom from an epoxy compound as a raw material is already known. For example, the reaction of an epoxy compound with a thiocyanate such as potassium thiocyanate or ammonium thiocyanate (British Patent No. 968,424) and the reaction of an epoxy compound with thiourea (J. Polym. Sci., Symposium, No.
47,155 (1974)), but not limited thereto.

4) A compound obtained by replacing an oxygen atom in the epoxy ring of the epoxy compounds (i) to (iv) with a sulfur atom by using this method as an example of a suitable episulfide compound in the present invention. Can be mentioned. These may be used alone or in combination of two or more. The episulfide compound having both an episulfide group and an epoxy group in one molecule of the present invention can be used when an episulfide compound is synthesized by replacing an oxygen atom in an epoxy ring with a sulfur atom by using an epoxy compound as a raw material to synthesize an episulfide compound. Alternatively, it can be obtained by adjusting the reaction conditions. In addition, a partially episulfide compound obtained by chromatographic separation can be obtained by mixing all episulfide compounds. Preferred episulfide compounds are compounds containing 0.1 mol% or more of a compound having both an episulfide group and an epixy group. If it is less than 0.1 mol%, sufficient storage stability cannot be obtained. More preferably 1 mol%
These are episulfide compounds that exist.

5) In the novel fast-curing resin composition of the present invention, the content of the episulfide compound (resin) is in the range of 1% by weight to 50% by weight. If the content exceeds 50% by weight, storage stability will be poor. If the content is less than 1% by weight, the curability of the coating film or the like will not be sufficient. A particularly preferred content range is from 1% by weight to less than 30% by weight.

(3) Diluent (C): The novel fast-curing epoxy resin of the present invention, which is non-reactive as the diluent (C) and is preferably used for decreasing the viscosity of the epoxy resin. Organic solvents are used. The amount of the diluent (C) to be added is not particularly limited as long as the reaction of each reaction component is not hindered.
It is generally from 1 to 90% by weight, preferably from 5 to 80% by weight. Specific examples include acetone, methyl ethyl ketone,
Examples include methyl isobutyl ketone, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, toluene, xylene, N, N-dimethylformamide, dioxane, tetrahydrofuran, n-butyl alcohol, Solvesso 100 and the like.

(4) Curing agent (D): The novel fast-curing epoxy resin composition of the present invention can be cured with a curing agent for epoxy. Examples of curing agents include aliphatic, alicyclic, aromatic and heterocyclic amine curing agents or isocyanates, phenols, thiols, polycarboxylic acids and anhydrides, secondary amines, tertiary amines And curing agents for epoxy resins containing imidazoles or cationic curing agents.

For example, 1) aliphatic, alicyclic, aromatic and heterocyclic amine curing agents include: m- and p-phenylenediamine, bis (4-aminophenyl) methane, aniline formaldehyde resin, bis ( 4-aminophenyl) sulfone, ethylenediamine, propane-
1,2-diamine, propane-1,3-diamine, N,
N-diethylethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine,
Tetraethylenepentamine,

N- (2-hydroxyethyl)-, N-
(2-hydroxypropyl)-and N- (2-cyanoethyl) -diethylenetriamine, 2,2,4-trimethylhexane-1,6-diamine, 2,3,3-trimethylhexane-1,6-diamine, m- Xylylenediamine, N, N-dimethyl and N, N-diethylpropane-1,3-diamine, ethanolamine, bis (4-
(Aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, 2,2-bis (4-amino-3-methylcyclohexyl) propane, 3-aminomethyl-3,5,5-trimethylcyclohexylamine ( Isophoronediamine) and N- (2-aminoethyl) -piperazine, dicyandiamide, polyaminoamide, Mannich modifications of these amines, polyaminoamides prepared from aliphatic polyamines and dimerized or trimerized unsaturated fatty acids, amines and diglycidyls Adduct with less than the stoichiometric amount of polyepoxides such as ethers,

2) As the isocyanates, 2,6-
Toluene diisocyanate, hexamethylene diisocyanate, diaminodiphenylmethane diisocyanate and its adducts, isothiocyanate, 3) as phenols; polyhydric phenols such as resorcinol, hydroquinone, 2,2-bis (4-hydroxyphenyl) propane, phenol-aldehyde Resins, oil-modified phenol-aldehyde resins, 4) as thiols: polythiols such as thiocol

5) The polycarboxylic acids and anhydrides thereof include: tetrahydrophthalic anhydride, methylendomethylene tetrahydrophthalic anhydride, nonylsuccinic anhydride, dodecenylsuccinic anhydride, hexahydrophthalic anhydride, hexachloroendomethylenetetrahydrophthalic anhydride,
And endomethylenetetrahydrophthalic anhydride, and mixtures thereof, maleic anhydride, succinic anhydride,
Pyromellitic dianhydride, benzophenone-3,3 ',
4.4'-tetracarboxylic dianhydride, polysebacic anhydride, polyazellaic anhydride, the acids corresponding to the acid anhydrides and isophthalic acid, terephthalic acid, citric acid and melitic acid;

6) The secondary amine and tertiary amine include;
2,4,6-tris (dimethylaminoethyl) phenol and other Mannich bases, n-benzylmethylamine and triethanolamine, 7) imidazoles include: 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-methylimidazolium isocyanurate,

8) As a cationic curing agent: boron trifluoride and its complex, and boron trifluoride such as 1,3-
Chelates formed by reaction with diketones, which can also be used as curing agents for photocuring. When used as a photocuring agent, an auxiliary agent such as a bezophenone-based, anthraquinone-based, acetophenone-based, or benzoin-based photopolymerization accelerator can be added. 9) Alternatively; a polymerization catalyst such as an alkali metal alkoxide of an alcohol (for example, sodium alcoholate of 2,4-dihydroxymethylpentane) or a stannous alkanoic acid can be used as a curing agent.

Further, by selecting the curing agent, a low-temperature curable, room-temperature curable, thermosetting or photocurable composition can be obtained. 1) For example, when the curing agent is an amine, usually about 0.75 to 1.25 amino active hydrogen equivalents per epoxy equivalent are used. 2) When a polycarboxylic acid or its anhydride is used, usually about 0.4 to 1.1 equivalents of carboxylic acid per epoxy equivalent is used. 3) On the other hand, in the case of polyhydric phenol, a curing agent having about 0.75 to 1.25 phenolic hydroxy equivalent per epoxy equivalent is used.

The curing is carried out at a low temperature (for example, −15 ° C. to 5 ° C.) to a room temperature (for example, 15 ° C. to 3 ° C.) depending on the properties of the curing agent.
5 ° C.) and can be carried out at higher temperatures (eg, 50 ° C. to 250 ° C.) Preferably in the range of -5 ℃ ~ 200 ℃,
More preferably, it can be carried out in the range of -5 ° C to 180 ° C. Typical curing agents for low temperature are amine curing agents and thiols, curing agents for normal temperature are typically amine curing agents and the like, and curing agents for heating are polycarboxylic acids and anhydrides thereof. , Phenols, imidazoles and the like.

(6) Curing accelerator (E): An appropriate curing accelerator (E) can be used together with the curing agent. When poly (aminoamide), dicyandiamide, polythiol or polycarboxylic anhydride is used as a curing agent, a tertiary amine or a salt thereof, a quaternary ammonium compound or an alkali metal alkoxide can be provided as an accelerator. Specific promoters include, for example, N-benzyldimethylamine, 2,4,6-tris (dimethyl-aminomethyl) -phenol, imidazole and trimethylammonium phenoxide.

Other accelerators which can be used include metal nitrates, especially magnesium and manganese nitrates, fluorinated and chlorinated carboxylic acids and salts thereof,
For example, magnesium trifluoroacetate, sodium trifluoroacetate, magnesium trichloroacetate and sodium trichloroacetate, trifluoromethanesulfonic acid and its salts (eg, manganese, zinc, magnesium, nickel and cobalt salts)
And magnesium perchlorate and calcium perchlorate. The amount of the curing accelerator (E) used is usually 0.01 to 10
%, Preferably 0.05 to 5% by weight, the optimum amount being determined by the desired range of the curing agent.

(7) Additives The composition of the present invention comprises a plasticizer such as dibutyl phthalate, dioctyl phthalate or tricresyl phosphate: an insoluble diluent and a so-called reactive diluent such as diglycidyl formal and monoepoxide (for example, Butyl glycidyl ether, isooctyl glycidyl ether, phenyl glycidyl ether, styrene oxide, glycidyl acrylate, glycidyl methacrylate and highly branched glycidyl esters of mainly tertiary aliphatic monocarboxylic acids, or carbonates such as propylene carbonate. Further, it may be contained.

Further, the composition of the present invention may contain additives such as fillers, reinforcing agents, coloring agents, flow control agents, flame retardants and molding lubricants. Suitable extenders include asphalt, bitumen and the like. Fillers and reinforcing agents include asbestos, glass fiber, spun fiber, carbon fiber, mica, alumina, gypsum, titania, chalk, quartz powder, cellulose,
Kaolin, ground dolomite, woolusnite, colloidal silica (aerosil), clay (benton) modified by treatment with long-chain amine, powdered polyvinyl chloride,
Powdered polyolefins, powdered aminoplasts and metal powders such as aluminum or iron powders.
A flame retardant aid such as antimony trioxide can also be incorporated.

[II] Uses of the curable composition: The curable composition of the present invention may contain various curing agents (as needed, a curing accelerator).
By combining with, it is possible to provide materials suitable for various uses for epoxy resins: paints, electric / electronic materials, adhesives, composite materials, jigs and tools, industrial materials for civil engineering, and the like. (A) As a suitable metal surface protective material for paints, it is possible to provide a paint that gives a fast-curing, excellent workability and good coating film for cans, automobiles, ships or construction materials. (B) For electrical and electronic materials, a laminated board, especially a printed wiring board, a sealing material, particularly a sealing material for semiconductors, and other insulating materials, and the like, to provide a material having fast curing and excellent electrical properties. Can be.

(C) For adhesives, it becomes a material that can be bonded in a very short time, and provides a cured composition suitable as a contact adhesive or a structural adhesive such as dental cement. (D) When used as composite materials, they are used as structural materials for mobile bodies such as aircraft and automobiles, and as sports and leisure products. Can be. (E) In the use of jigs and tools such as resin molds, the working time can be remarkably reduced due to the quick curing property. (F) Particularly suitable application fields are civil engineering applications such as flooring materials, injection materials and adhesives for concrete, and coating materials for construction, which cannot be cured by heating and sometimes require low-temperature curing.

[0041]

The present invention will be described below by way of examples, which do not limit the present invention. Partial episulfides and total episulfides can be separated by high performance liquid chromatography, and each component can be quantified from the peak area. For the measurement of high performance liquid chromatography, Novapack C-18 manufactured by Waters Co. was used as a column, and acetonitrile was used for a moving bed. Reaction components used: 1) Episulfide compound A : 300 g of A. A. 26
0 (bisphenol A type epoxy resin EEW = 190;
1.587 eq) was dissolved in 600 g of toluene.
The mixture was placed in a four-necked flask equipped with a gas inlet tube, a thermometer, and a reflux tube, and N2 gas was introduced. Start stirring, 96.
82 g of thiourea (1.272 eq) was added. An additional 300 g of methanol was added, the temperature was raised to 40 ° C.
The reaction was performed for 3 hours under two atmospheres. After the reaction solution was washed 3 to 5 times with 300 g of water, toluene was recovered at 60 ° C. under reduced pressure. As a result, episulfide compound A (the content of the episulfide compound at one terminal was 47 mol% according to the analysis of high performance liquid chromatography, and the content of the episulfide compound was 92% by weight) was obtained. Episulfide compound B:

2) Episulfide compound B : 300 g of A. A. 260 (bisphenol A type epoxy resin EE
W = 190; 1.587 eq) was dissolved in 600 g of toluene, placed in a four-necked flask equipped with a N2 gas inlet tube, a thermometer, and a reflux tube, and N2 gas was introduced. Stirring was started and 120.80 g of thiourea (1.587 eq) was added. A further 300 g of methanol were added and the temperature was
The temperature was raised to 0 ° C., and the reaction was performed under an N 2 atmosphere for 3 hours. After the reaction solution was washed 3 to 5 times with 300 g of water, toluene was recovered at 60 ° C. under reduced pressure. Thereby, the episulfide compound B (according to the analysis of high performance liquid chromatography, the content of the episulfide compound at one terminal was 10.3 mol%, and the content of the episulfide compound was 94% by weight).
I got

3) Episulfide compound C : 300 g of A. A. 260 (bisphenol A type epoxy resin EE
W = 190; 1.587 eq) was dissolved in 600 g of toluene, placed in a four-necked flask equipped with a N2 gas inlet tube, a thermometer, and a reflux tube, and N2 gas was introduced. Stirring was started and 126.84 g of thiourea (1.666 eq) was added. A further 300 g of methanol were added and the temperature was
The temperature was raised to 0 ° C., and the mixture was reacted under an N 2 atmosphere for 5 hours. After the reaction solution was washed 3 to 5 times with 300 g of water, toluene was recovered at 60 ° C. under reduced pressure. The obtained solid was recrystallized from a mixed solvent of methyl ethyl ketone / methanol to obtain a substantially pure episulfide compound C (the episulfide compound at one end was 0 mol% according to the analysis of high performance liquid chromatography. The content of the episulfide compound was 100% by weight
Met. ) Got.

4) Episulfide compound D : Episulfide compound A was fractionated by chromatography to obtain almost pure one-terminal episulfide compound D (according to high performance liquid chromatography, the amount of one-terminal episulfide compound was 100 mol%. The content of the episulfide compound was 100% by weight.)

5) Episulfide compound E : 300 g of A. A. 260 (bisphenol A type epoxy resin EE
W = 190; 1.587 eq) was dissolved in 600 g of toluene, placed in a four-necked flask equipped with a N2 gas inlet tube, a thermometer, and a reflux tube, and N2 gas was introduced. Stirring was started and 1.26 g of thiourea (0.017 eq) was added. Further, 300 g of methanol was added, and the temperature was increased to 40 ° C.
And reacted for 3 hours under N2 atmosphere. 30
After washing with 0 g of water 3 to 5 times, toluene was recovered at 60 ° C. under reduced pressure. Thus, the episulfide compound E
(As a result of analysis by high performance liquid chromatography, the content of the episulfide compound at one terminal was 100 mol%, and the content of the episulfide compound was 1% by weight.)

6) Episulfide compound F : 300 g of A. A. 260 (bisphenol A type epoxy resin EE
W = 190; 1.587 eq) was dissolved in 600 g of toluene, placed in a four-necked flask equipped with a N2 gas inlet tube, a thermometer, and a reflux tube, and N2 gas was introduced. Stirring was started and 30.4 g of thiourea (0.399 eq) was added. Further, 300 g of methanol was added, and the temperature was increased to 40 ° C.
And reacted for 3 hours under N2 atmosphere. 30
After washing with 0 g of water 3 to 5 times, toluene was recovered at 60 ° C. under reduced pressure. Thereby, the episulfide compound F
(According to the analysis by high performance liquid chromatography, the episulfide compound at one terminal was 86 mol%, and the content of the episulfide compound was 25% by weight.)

7) Episulfide compound G : 300 g of A. A. 260 (bisphenol A type epoxy resin EE
W = 190; 1.587 eq) was dissolved in 600 g of toluene, placed in a four-necked flask equipped with a N2 gas inlet tube, a thermometer, and a reflux tube, and N2 gas was introduced. Stirring was started and 60.80 g of thiourea (0.799 eq) was added. An additional 300 g of methanol was added and the temperature was increased to 40
C. and reacted under N2 atmosphere for 3 hours. Reaction solution 3
After washing 3 to 5 times with 00 g of water, toluene was recovered at 60 ° C. under reduced pressure. Thus, the episulfide compound G
(A high-performance liquid chromatography analysis revealed that the amount of one-sided episulfide was 36 mol%, and the content of the episulfide compound was 54% by weight.)

8) Episulfide compound H : 300 g of Epolite 1230 (Kyoeisha Chemical Co., Ltd. higher alcohol (C12-13) glycidyl ether EEW = 30)
4; 0.987 eq) in 600 g of toluene,
The mixture was placed in a four-necked flask equipped with an N2 gas introduction tube, a thermometer and a reflux tube, and N2 gas was introduced. Start stirring and 7
8.87 g of thiourea (1.036 eq) was added. Further, 300 g of methanol was added, the temperature was raised to 40 ° C., and the mixture was reacted under an N 2 atmosphere for 5 hours. 300 g of reaction solution
After washing with water three to five times, toluene was recovered at 60 ° C. under reduced pressure. Thus, episulfide compound H (episulfide compound was 100% by weight according to the analysis of high performance liquid chromatography) was obtained.

9) Episulfide compound I : 300 g of Epolite 1600 (Kyoeisha Chemical Co., Ltd. 1.6 glycidyl ether of hexanediol EEW = 152; 1.9)
74 eq) was dissolved in 600 g of toluene, placed in a four-necked flask equipped with an N2 gas inlet tube, a thermometer, and a reflux tube, and N2 gas was introduced. Start stirring and 120.2g
Of thiourea (1.577 eq) was added. Further 300
g of methanol was added, the temperature was raised to 40 ° C., and the mixture was reacted under an N 2 atmosphere for 5 hours. The reaction solution is prepared for 3 to 5 with 300 g of water.
After washing twice, toluene was recovered at 60 ° C. under reduced pressure.
As a result, an episulfide compound I was obtained (the episulfide compound at one terminal was 45 mol% according to the analysis by high performance liquid chromatography, and the content of the episulfide compound was 90% by weight).

10) Episulfide compound J : 300 g
Of Celloxide 2021 (Cyclohexene epoxy EEW = 131; 2.29 eq) from Daicel Chemical Co., Ltd.
The resultant was dissolved in 00 g of toluene, placed in a four-necked flask equipped with a N2 gas introduction tube, a thermometer, and a reflux tube, and N2 gas was introduced. Stirring was started and 139.5 g of thiourea (1.83 eq) was added. Further, 300 g of methanol was added, the temperature was raised to 40 ° C., and the mixture was reacted under an N 2 atmosphere for 5 hours. After the reaction solution was washed 3 to 5 times with 300 g of water, toluene was recovered at 60 ° C. under reduced pressure. As a result, the episulfide compound J (according to the analysis of high performance liquid chromatography, the episulfide compound at one terminal was 48 mol%
Met. The content of the episulfide compound was 92% by weight. ) Got.

[0051]

Examples 1 to 8 and Comparative Examples 1 to 6 The storage stability and reactivity of the blends shown in Tables 1 and 2 were measured. The results are shown in Tables 1 and 2. The measurement was performed by the following method. Storage stability 1: In the case of a liquid state, the viscosity was measured after being left at 40 ° C. for one week. ；: Thickening within 2 times the initial viscosity. Δ: Thickening within 2 times the initial viscosity, but crystal precipitation. X: Thickening more than twice the initial viscosity. Storage stability 2: In the case of a solid, a solubility test was conducted after standing at 40 ° C. for one week. ；: 30% by weight dissolved in THF. ×: 30% by weight insoluble in THF. Gel time: measured on a metal plate at 35 ° C. The unit is minute. Odor; by sensory test.

[0052]

Examples 9 to 11 and Comparative Examples 7 to 9 Physical properties were measured after curing the compounds shown in Table 3. The results are shown in Table 3. Also, the composition before adding the curing agent should be kept at 40 ° C for 1 hour.
Even after standing for a week, the thickening was within twice the initial viscosity. The curing and measurement were performed by the following methods. Curing conditions: Examples 9 and 10, Comparative Examples 7 and 8, 1 week at room temperature. Example 11, Comparative Example 9: 100 ° C. for 2 hours + 160 ° C. for 10 hours

Drying property: The time until the touch-free state was measured using a dry ingress recorder. Gel time: Measured on a metal plate at 120 ° C. Flexural strength: Measured according to JIS6911. Water absorption ratio 1: Measured by weight change after immersion in pure water at room temperature for one week. Water absorption 2: Measured from the change in weight after immersion in boiling water for 1 hour. Dielectric constant: Measured according to JIS6911. The EPS content in the table represents the weight% of the part of the episulfide compound excluding the curing agent, and the partial EPS represents the mole% of the partial episulfide compound in the episulfide compound.

[0054]

[Table 1]

[0055]

[Table 2]

[0056]

[Table 3] Note 1: Hardening agent triethylenetetramine Note 2: Hardening agent 1% ethylene glycol and 1% benzyldimethylamine are added to methyl hexahydrophthalic anhydride manufactured by Hitachi Chemical Co., Ltd.

[0057]

EXAMPLES 12 AND 13 AND COMPARATIVE EXAMPLE 10 The formulations shown in Table 4 were measured for storage stability and dryness at 5.degree. The results are shown in Table 4. The measurement was performed by the following method. Storage stability 1: 4 per formulation before addition of TETA
After standing at 0 ° C. for one week, the viscosity was measured. ；: Thickening within 2 times the initial viscosity. X: Thickening more than twice the initial viscosity. Drying property: The time until the touch-free state was measured using a dry ingress recorder.

[0058]

[Table 4] From the results of Tables 1 to 4, it can be seen that the composition of the present invention has excellent storage stability, has no odor, has good curability and drying properties, and has good mechanical and electrical properties. .

[0059]

Industrial Applicability The novel fast-curing epoxy resin composition of the present invention has high reactivity, good storage stability, no odor, excellent workability, mechanical and electrical properties and chemical resistance. And a curable resin composition suitable for paints, electric / electronic materials, adhesives, composite materials, jigs and tools, and industrial materials for civil engineering.

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[Procedure amendment]

[Submission date] November 17, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0017

[Correction method] Change

[Correction contents]

(2) Compound having episulfide group (B) 1) In the novel epoxy resin composition of the present invention, the compound having an episulfide group refers to one or more compounds represented by the formula (2) in one molecule. Aliphatic, cycloaliphatic, heterocyclic, saturated and unsaturated compounds having a group.

Embedded image Specific examples thereof include epithio hydrocarbons, epithioethers, epithioesters, epithiourethanes and epithioepoxys. Further, preferred compounds of the present invention include the compounds of formula (3), especially including the polyhydric alcohols and polyhydric phenols epithioalkyl and epithiocycloalkyl.

Embedded image (Here, R is derived from a polyhydric phenol or polyhydric alcohol, and n is preferably from 2 to 6.) ─────────────────────────────

[Procedure amendment]

[Submission date] November 17, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0010

[Correction method] Change

[Correction contents]

Hereinafter, the present invention will be described in detail. [1] Structure of fast-curing resin composition: The fast-curing resin composition of the present invention basically comprises an episulfide compound (A) 1
A new compound comprising 0.01 parts by weight or more of a compound (B) having a structure represented by the formula (1) in the molecule and, if necessary, an epoxy resin (C) as an essential component. It is a curable resin composition.

Embedded image (Wherein X and Z are each independently O, S, NH, or NR, Y is O or S, and R in the NR is an alkyl group, a cycloalkyl group, an aryl group, or an allyl group. (1) Compound having episulfide group (A) (i) In the novel fast-curing low-viscosity resin composition of the present invention, the compound having an episulfide group is one or more in one molecule. An aliphatic, alicyclic, heterocyclic, saturated and unsaturated compound having a functional group represented by the following formula (3).

Embedded image Specific examples thereof include epithio hydrocarbons, epithioethers, epithioesters, epithiourethanes and epithioepoxys.

Claims (15)

[Claims] 1. An epoxy compound containing 50% by weight or more and 99% by weight or less of (A) an epoxy compound, and 1% by weight of an episulfide compound containing 0.1 mol% or more of a compound having an episulfide group and an epoxy group in one molecule. % Or more and 50% by weight or less. 2. An episulfide compound containing (A) an epoxy compound in an amount of more than 70% by weight and 99% by weight or less, and (B) an episulfide compound containing 0.1 mol% or more of a compound having an episulfide group and an epoxy group in one molecule. The fast-curing epoxy resin composition according to claim 1, comprising from 30% by weight to 30% by weight. 3. An epoxy compound (A) comprising a compound containing an aromatic ring as a main component.
Or the fast-curing epoxy resin composition according to 2. 4. A fast-curing epoxy resin composition comprising the resin composition according to claim 1 and a diluent (C) as essential components. 5. A quick-curing epoxy resin composition comprising the resin composition according to claim 1 and a curing agent (D) as essential components. 6. The low-temperature fast-curing epoxy resin composition according to claim 5, wherein the curing agent (D) is a low-temperature curing agent. 7. The room temperature fast-curing epoxy resin composition according to claim 5, wherein the curing agent (D) is a room temperature curing agent. 8. The heat-curable epoxy resin composition according to claim 5, wherein the curing agent (D) is a heating curing agent. 9. A photocurable epoxy resin composition comprising the resin composition according to claim 1 and a photocuring agent as essential components. 10. A curable resin composition for paint, comprising the resin composition according to claim 5 as a main component. 11. A curable resin composition for an electric / electronic material, comprising the resin composition according to claim 5 as a main component. 12. A curable resin composition for an adhesive, comprising the resin composition according to claim 5 as a main component. 13. A curable resin composition for a composite, comprising the resin composition according to claim 5 as a main component. 14. A curable resin composition for jigs and tools, comprising the resin composition according to claim 5 as a main component. 15. A curable resin composition for industrial materials in the field of civil engineering, comprising the resin composition according to claim 5 as a main component.