JPH11209689A - Resin composition for coating and coating agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin compsn. which emits a low odor, adheres well to a substrate, and is ecxellent in curability regardless of its long pot life by incorporating a compd. formed by completely or partly substituting oxirane rings of an epoxy compd. with thiirane rifigs and a curing agent into the same. SOLUTION: This. resin compsn. is prepd. by compounding a compsn. comprising (A) a compd. which is prepd. by reacting an epoxy compd. with an episulfidizing agent in a polar solvent to completely or partly substitute the oxirane rings of the epoxy compd. with thiirane rings of the formula and has thiirane rings only or thiiran rings and oxirane rings in the molecule or comprising compd. A and (B) a compd. having oxirane rings but no thiirane ring, the ratio of the content of oxirane ring to that of thiirane ring in the compsn. being (90/10)-(0/100), with at least one curing agent selected from among hydroxyl, mercapto. amino, and carboxyl compds.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating composition and a resin composition for a coating agent, and more particularly, to a coating composition having excellent potting life, excellent curability, excellent substrate adhesion, and low odor. And a resin composition for a coating agent.

[0002]

2. Description of the Related Art Conventionally, epoxy resin compositions have been applied to various fields such as paints, coating agents, adhesives, etc. because of their excellent properties, especially adhesive strength. However, most of the commonly used epoxy resin compositions are of the two-component type comprising a main agent and a curing agent, and the curing reaction proceeds immediately after mixing, so that the usable time is short and there is a problem in workability. Was. For this reason, as a method of extending the pot life, for example, there is a method of using a latent curing agent such as a blocked isocyanate-modified epoxy resin, and the curing agent is originally a heat-curable type, and is practically used for drying at room temperature. Not satisfactory. In addition, there is a method of using, for example, an aliphatic epoxy resin having low reactivity as a main agent. However, in this method, although the pot life is long, the drying property is reduced, and the curing of the film is extremely slow, and the work efficiency is reduced. However, there was a problem that was reduced. If a thiol-based compound is used as a curing agent, quick curing properties can be obtained, but the thiol-based compound has a strong odor and deteriorates the working environment.

[0003]

By the way, it is considered that the adhesive strength of the epoxy resin composition is mainly exhibited by a hydroxyl group generated by a curing reaction. However, this hydroxyl group has low reactivity (acidity), and it is considered that the adhesive force is developed by physical affinity. Therefore, if a highly reactive functional group capable of generating a substituent having a higher chemical reactivity than a hydroxyl group upon curing is introduced into a molecule, a higher adhesive force or a substrate than a conventional epoxy resin composition can be obtained. It is expected that a paint or a coating agent having an adhesive force and a fast curing property can be obtained.

Accordingly, an object of the present invention is to provide a paint and a coating agent which are excellent in curability despite having a long pot life, have higher substrate adhesion than conventional epoxy resin adhesives, and have low odor. To provide a resin composition for use.

[0005]

According to the present invention, in order to solve the above problems, all or a part of the oxirane ring of the epoxy compound is represented by the following formula (1):

Embedded image Or a compound (A) obtained by substituting the thiirane ring represented by the formula (I) or a compound (B) having an oxirane ring in the molecule and not containing a thiirane ring, wherein the oxirane ring / thiirane ring Is 90/10 to 0/100, and further contains at least one curing agent selected from the group consisting of compounds containing a hydroxyl group, a mercapto group, an amino group, or a carboxyl group. A composition is provided.

In the above resin composition for paints and coating agents, when the molar fraction of thiirane rings in the total of oxirane rings and thiirane rings is X, and the equivalent ratio of the curing agent to the total of oxirane rings and thiirane rings is Y. It is preferable that X and Y have the following relationship. When 10% ≦ X <50% Y = (100−X) /100±0.2 When 50% ≦ X ≦ 100% Y = 0.1 to 0.7

It is preferable that the compound (A) or the total amount of the compound (A) and the compound (B) is 100 parts by weight, and further contains 3 to 50 parts by weight of a modifying filler.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a resin composition for a paint and a coating agent of the present invention (hereinafter, referred to as a composition of the present invention)
Will be described in detail. The compound (A), which is the main component of the composition of the present invention, is a compound obtained by substituting all or a part of the oxirane ring of the epoxy compound with a thiirane ring. Compound (A-1), which is substituted and has only a thiirane ring, or Compound (A-2), in which only a part of the oxirane ring in the molecule is substituted with a thiirane ring, and which has both a thiirane ring and an oxirane ring There may be.

The epoxy compound used for obtaining the compound (A) includes, for example, the following formulas (a), (b),
In (c), (d), (e) or (f), all the substituents Y are represented by the following formula (2):

Embedded image Or an compound in which Z is an oxygen atom. N is 0 or a number equal to or greater than 0.

[0010]

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[0011]

Embedded image These epoxy compounds may be those in which a hydrogen atom or other group in the molecule is substituted with a halogen atom. For example, the following formula (g):

Embedded image (Wherein, Hal represents a halogen atom). As halogen atoms, bromine, chlorine,
Fluorine and the like.

In the present invention, the compound (A) is a compound represented by the formula (a), (b), (c), (d), (e), (f) or (g). One is a thiirane ring represented by the above formula (1), Y other than the thiirane ring is a compound which is an oxirane ring represented by the above formula (2), or at least one of Z is S, and A compound wherein Z is O.

Specific examples of the compound (A) include those represented by the following formula. In each of the following formulas, a compound in which at least one of two or more Y is a thiirane ring represented by the formula (1), and Y other than the thiirane ring is an oxirane ring represented by the formula (2); Or Z
Is a compound wherein at least one is S and the other Z is O. N is 0 or a number equal to or greater than 0.

[0014]

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[0015]

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[0016]

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[0017]

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[0018]

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The production of the compound (A) can be carried out according to a method of reacting the epoxy compound and an episulfide agent in a polar solvent with vigorous stirring.

The episulfide agent used includes:
For example, potassium thiocyanate (KSCN), thiourea and the like can be mentioned.

As the polar solvent, for example, methanol,
Ethanol, acetone, water, or a mixed solvent thereof can be used. In particular, when KSCN is used as the episulfide agent, the thiirination rate is 50%, that is, the content ratio of oxirane ring / thiirane ring is 1/1.
In order to obtain the compound (A), it is necessary to use 2 /
It is preferable to use one mixed solvent. In order to obtain a compound (A) having a thiirane conversion rate of 100%, that is, a content ratio of oxirane ring / thiirane ring of 0/100, it is preferable to use acetone as a solvent.

The reaction is usually carried out in a temperature range of 10 to 35 ° C.
For example, the reaction can be performed at room temperature for a reaction time of about 10 to 40 hours, for example, about 20 hours. The reaction atmosphere may be air or an inert atmosphere such as nitrogen.

As a specific example of the production of the compound (A),
Taking a method for producing a compound (A) having a thiirane ring using a bisphenol A type epoxy resin as a starting material, the method can be carried out according to a method represented by the following reaction formula. Here, X is S or O.

Embedded image

The compound (B) having an oxirane ring in the molecule and not containing a thiirane ring contained in the composition of the present invention is exemplified as the epoxy compound used for obtaining the above-mentioned compound (A). All of the available epoxy compounds are available. Specifically, a compound in which the substituent Y in any of the above formulas as a specific example of the compound (A) is an oxirane ring represented by the formula (2), or
Compounds wherein all Z are O are illustrated. n is 0 or a number greater than or equal to 0. Among these, from the viewpoint of substrate adhesion, a bifunctional epoxy compound having two oxirane rings in the molecule is preferable, and an aromatic bifunctional epoxy compound having two oxirane rings in the molecule is more preferable.

The composition of the present invention may contain both the compound (A-1) having only a thiirane ring and the compound (A-2) having both a thiirane ring and an oxirane ring. It may include only one of them. For example, it may be a combination of any of the following components. (I) Composition containing compound (A-1) and compound (B) (ii) Composition containing only compound (A-2) (iii) Compound (A-2) and compound (B) (Iv) Composition containing compound (A-1), compound (A-2), and compound (B) Particularly, in the present invention, when a composition exhibiting high adhesion is required. Is preferably a composition comprising the combination of the above (iii).

In the composition of the present invention, an oxirane ring /
The content ratio of the thiirane ring can be determined in the range of 90/10 to 0/100 according to the balance between the curing time and the pot life. It is preferably in the range of 50/50 to 90/10 in that both a hydroxyl group and a mercapto group can be generated at the time of curing, and a composition exhibiting high adhesion is obtained. When a compound having only a thiirane ring is used and a compound having only an oxirane ring is not used, extremely fast curability is exhibited.

The composition of the present invention further contains at least one curing agent selected from the group consisting of compounds containing a hydroxyl group, a mercapto group, an amino group or a carboxyl group. Examples of the curing agent include amine curing agents, carboxylic acid curing agents, basic active hydrogen compounds, imidazoles,
Examples include polymercaptan-based curing agents, phenolic resins, urea resins, melamine resins, latent curing agents, and the like.

The composition of the present invention comprises the compound (A), or the compounds (A) and (B), and a curing agent.
The two-part composition can be prepared separately, and when used as an adhesive, they are mixed at a predetermined ratio to prepare an adhesive. Further, the composition of the present invention,
Compound (A), or compound (A) and compound (B)
Can be mixed with a latent curing agent that exerts a curing effect by heating or pressurizing to form a one-part composition.

Specific examples of the amine curing agent include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, iminobispropylamine, bis (hexamethylene) triamine, and 1,3,6-trisaminomethyl. Polyamines such as hexane; polymethylene diamines such as trimethylhexamethylenediamine, polyetherdiamine, diethylaminopropylamine; mensendiamine, isophoronediamine, bis (4-amino-3-methylcyclohexyl) methane, N-aminoethylpiperazine,
Diaminodicyclohexylmethane, bisaminomethylcyclohexane, 3,9-bis (3-aminopropyl)-
Alicyclic polyamines such as 2,4,8,10-tetraoxaspiro (5.5) undecane; aliphatic polyamines containing an aromatic ring such as metaxylylenediamine, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diamino Aromatic polyamines such as diethyldiphenylmethane, and 3,9-bis (3-aminopropyl) -2,4,8,10-tetraspiro [5.5]
And undecane. Also, amine adducts (polyamine epoxy resin adducts), polyamine-ethylene oxide adducts, polyamine-propylene oxide adducts, cyanoethylated polyamines, ketimines which are reactants of aliphatic polyamines and ketones; linear diamines, tetramethylguanidine, triethanol Amine,
Piperidine, pyridine, benzyldimethylamine, picoline, 2- (dimethylaminomethyl) phenol, dimethylcyclohexylamine, dimethylbenzylamine,
Dimethylhexylamine, dimethylaminophenol,
Dimethylamino p-cresol, N, N'-dimethylpiperazine, piperidine, 1,4-diazadicyclo (2,
2,2) octane, 2,4,6-tris (dimethylaminomethyl) phenol, 1.8-diazabicyclo (5.
4.0) Secondary amines or tertiary amines such as undecene-1 or liquid polyamide obtained by reacting dimer acid with a polyamine such as diethylenetriamine or triethylenetetramine.

Specific examples of the carboxylic curing agent include polycarboxylic acids such as adipic acid, azelaic acid and decanedicarboxylic acid.

Specific examples of the basic active hydrogen compound include:
Dicyandiamide, organic acid dihydrazide and the like can be mentioned.

Specific examples of imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole , 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4
-Methylimidazole, 2-methylimidazolium isocyanate, 2,4-diamino-6- [2-methylimidazoline- (1)]-ethyl-S-triazine,
2,4-diamino-6- [2-ethyl-4-methylimidazoline- (1)]-ethyl-S-triazine and the like.

Specific examples of polymercaptan curing agents include partial epoxy adducts of 2,2'-bismercaptoethyl ether, pentaerythritol tetrathioglycolate, dipentaerythritol hexathioglycolate, and trimethylolpropanetrithioglycol. And esters containing a mercapto group such as polysulfide rubber having a mercapto group at the terminal.

The latent curing agent used for preparing the one-part curing agent includes amines such as n-hexylamine, monoethylamine, benzylamine, diethylamine, piperidine, triethylamine and aniline, and boron trifluoride. A boron trifluoride-amine complex which is a compound of dicyandiamide or o-tolylbiguanide;
derivatives of dicyandiamide such as α-2,5-dimethylbiguanide, α, ω-diphenylbiguanide, 5-hydroxynaphthyl-1-biguanide; succinic hydrazide,
Adipic hydrazide, isophthalic hydrazide, p-
Acid hydrazides such as oxybenzoic acid hydrazide, salicylic acid hydrazide, phenylaminopropionic acid hydrazide; diaminomaleonitrile or derivatives thereof; melamine derivatives such as diallyl melamine; amine imides synthesized from carboxylic acid esters, dimethyl hydrazine and epoxy compounds; , Salts of diamines such as hexamethylenediamine and piperidine with aliphatic dicarboxylic acids such as sebacic acid, 2,4,4-trimethyl-
Salts of polyamines such as 2,4,7-trihydroxyflavan and polyhydroxyphenols such as N, N'-dimethyl-1,3-propanediamine, phenylphosphonates of polyamines, phenylphosphates of polyamines; Is mentioned.

When the thiirane introduction ratio in the composition of the present invention is X and the equivalent ratio of the curing agent to the total of the oxirane ring and the thiirane ring is Y, it is preferable that X and Y have the following relationship. Here, the thiirane introduction rate X means the molar fraction (%) of the thiirane ring in the total of the oxirane ring and the thiirane ring in the compound (A) or the compound (A) and the compound (B). 10% ≦ X <50% Y = (100−X) /100±0.2 50% ≦ X ≦ 100% Y = 0.1 to 0.7 If it is large, the curing agent is conventionally expensive, so that the raw material cost increases, which is not preferable. If the equivalent ratio of the curing agent is smaller than this range, the curing reaction does not proceed sufficiently and the composition is not cured, resulting in poor adhesion. In the composition of the present invention, a compound containing only an oxirane ring is used because the contained thiirane ring has high chemical reactivity and —SH generated by ring opening of the thiirane ring contributes to the curing reaction. Compared with the case, the curability can be kept good even if the amount of the curing agent used is smaller than that of the thiirane ring. However, when X is in the range of 50% or more, the reactivity of the curing agent is saturated, and the equivalent ratio of the curing agent to be used is in the range of Y = 0.1 to 0.7 regardless of the value of X. The curing reaction proceeds well. When X is less than 50%, the curability is excellent if X and Y are in the above ranges, and more preferably Y is
Is given by Y = (100−X) /100−0.1.

The composition of the present invention may further contain a modifying filler. As the modifying filler,
Examples include titanium oxide, zinc oxide, iron oxide, aluminum oxide, aluminum powder, barium sulfate, calcium sulfate, aluminum carbonate, magnesium carbonate, talc, clay, kaolin, mica, graphite, silica, diatomaceous earth, and asbestos. These may be used alone or in combination of two or more. Of these, talc and calcium carbonate are preferred. The content of the modifying filler in the composition of the present invention is based on 100 parts by weight of the compound (A) or the compound (A) and the compound (B).
The amount is preferably 3 to 50 parts by weight, more preferably 10 to 30 parts by weight. This is because when the content is within this range, the composition of the present invention can have good thixotropy.

Further, the composition of the present invention comprises a compound (A),
Alternatively, the compound (A) and the compound (B) include a curing agent, a modifying filler, a colorant, a thickener,
It may contain at least one of a preservative and an emulsifier. These amounts are 1 to 100 parts by weight of compound (A) or compound (A) and compound (B).
-30 parts by weight are preferred.

The coloring agents include inorganic pigments and organic pigments. Examples of the inorganic pigments include titanium dioxide, zinc oxide, ultramarine, red iron, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochloride, sulfate and the like. Examples of organic pigments include azo pigments and copper phthalocyanine pigments. Methylcellulose (CM
C) and those capable of imparting high viscosity, such as calcium carbonate, are preferred. Preservatives include organotin, copper, arsenic,
Chlorine compounds and the like can be used. Specifically, pentachlorophenol, pentachlorophenol laurate, copper-8-
Examples include hydroxyquinoline, bis (tri-n-butyltin) oxide, and quaternary ammonium salts. By including these preservatives, it is possible to effectively prevent deterioration and cracks caused by bacteria and fungi under favorable conditions of appropriate temperature and humidity. As emulsifiers, bentonite,
And filled soil.

The composition of the present invention may contain a curing accelerator in addition to the curing agent. Examples of the curing accelerator include phosphites, phenols, tertiary amines, and the like. Among these, the composition of the present invention containing a phosphite is preferred because it does not cause thickening or other problems during storage.

The phosphites used include:
Triphenyl phosphite, tris (nonylphenyl)
Phosphite, triethyl phosphite, tributyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, tris (tridecyl) phosphite, diphenyl mono (2-ethylhexyl) phosphite, diphenyl monodecyl phosphite, diphenyl mono (Tridecyl) phosphite, tetraphenyldipropylene glycol diphosphite, tetraphenyltetra (tridecyl) pentaerythritol tetraphosphite, trilauryltrithiophosphite, bis (tridecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol Diphosphite, tristearyl phosphite, distearyl pentaerythritol diphosphite, tris (2,
Triesters such as 4-di-t-butylphenyl) phosphite and hydrogenated bisphenol A / pentaerythritol phosphite polymer are exemplified. Further, di- or monoesters obtained by partially hydrolyzing these triesters can also be used. These may be used alone or in combination of two or more. Among these, tetraphenyltetra (tridecyl) pentaerythritol tetraphosphite, bis (tridecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, distearylpentaerythritol diphosphite, hydrogenated bisphenol A. A pentaerythritol phosphite polymer or the like has a particularly high effect of accelerating curing and is preferably used.

As the tertiary amine, benzylmethylamine, triethylamine, dimethylaminomethylphenol, trisdimethylaminomethylphenol, 1,8-
Diazabicyclo [5.4.0] undecene-1,1,4
-Diazabicyclo [2.2.2] octane and the like.

The composition of the present invention includes the compound (A),
Or at least one of compound (B) or a curing agent, a modifying filler, a coloring agent, a thickener, a preservative, and an emulsifier
In addition to the species, various additives can be blended as needed. For example, a plasticizer, a thixotropic agent,
An antioxidant, an antioxidant, an antistatic agent, a flame retardant, an adhesion-imparting agent, a dispersant, a solvent, and the like can be added.

As a plasticizer, dioctyl phthalate (D
OP), dibutyl phthalate (DBP); dioctyl adipate, isodecyl succinate; diethylene glycol dibenzoate, pentaerythritol ester; butyl oleate, methyl acetyl ricinoleate; tricresyl phosphate, trioctyl phosphate; propylene glycol adipate polyester, adipic acid Butylene glycol polyester and the like. These plasticizers may be used alone or in combination of two or more.

Examples of the thixotropic agent include aerosil (manufactured by Nippon Aerosil Co., Ltd.), disparone (manufactured by Kusumoto Kasei Co., Ltd.), calcium carbonate, Teflon, and the like. Examples include quaternary ammonium salts and hydrophilic compounds such as polyglycols and ethylene oxide derivatives.

Examples of the antioxidant include hindered phenol compounds. Examples of the antioxidant include butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA).

Examples of the flame retardant include chloroalkyl phosphate, dimethyl methylphosphonate, bromine.
Examples include phosphorus compounds, ammonium polyphosphate, neopentyl bromide-polyether, and brominated polyether.

Examples of the adhesion-imparting agent include terpene resins, phenol resins, terpene-phenol resins, rosin resins, xylene resins and the like.

In the composition of the present invention, the compound (A) as a main component contains at least one thiirane ring in the molecule,
During curing, the thiirane ring opens to generate a thiol group having a higher acidity than the hydroxyl group, so it shows higher adhesion than conventional epoxy resin-based paints and coating agents, and while maintaining sufficient pot life In addition, the thiirane ring is more reactive than the oxirane ring, so that it can exhibit rapid curability. Therefore, the composition of the present invention is suitable for use as a paint or a coating agent for various materials such as metals and plastics.
Further, the composition of the present invention has a low odor. Therefore, when a coating work or the like is performed using the composition of the present invention, the work period can be shortened due to the quick curing property, and the work environment can be favorably maintained because of low odor. In addition, peeling does not occur on the painted surface after painting due to high adhesiveness. In addition, the composition of the present invention containing a modifying filler exhibits higher thixotropy than conventional epoxy resin-based paints and coating agents, and does not cause dripping during painting.

[0049]

The present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples.

Synthesis Example 1 of Compound Having Thiirane Ring 121 g of potassium thiocyanate was added to 75 ml of ethanol.
And 100 ml of water, and dissolved in a mixed solvent of 85 g of bisphenol A diglycidyl ether. Thereafter, 85 g of bisphenol A diglycidyl ether was further added, and the mixture was vigorously stirred at room temperature for 40 hours. Next, the reaction mixture was extracted with chloroform, washed with water, and dried over magnesium sulfate using magnesium sulfate. The chloroform was distilled off under reduced pressure, followed by drying under reduced pressure to obtain a reaction product. The content ratio of oxirane ring / thiirane ring in the obtained reaction product was measured by NMR and found to be 55/45.

According to this synthesis example, bisphenol A type epoxy resin (1) (manufactured by Sumitomo Chemical Co., Ltd., trade name:
Using ELA-128), all or part of the oxirane ring in the bisphenol A type epoxy resin (1) is substituted with a thiirane ring, and the oxirane ring / thiirane ring content ratio is 80/20, 50/50, 30/70, 20/8
0 and 100/0 compounds (hereinafter, (1)
80% modified thiirane, 50% modified thiirane of (1), 30% modified thiirane of (1), 20% modified thiirane of (1) or 100% modified thiirane of (1)) did. Similarly, an aliphatic epoxy resin (2) (trade name: EP4080, manufactured by Asahi Denka Co., Ltd.)
Content ratio of oxirane ring / thiirane ring is 80/20
(Hereinafter referred to as a thiirane 80% modified product of (2)).

(Examples 1 to 6, Comparative Examples 1 to 3) In each example, compositions were prepared according to the formulation shown in Table 1, and the pot life, peel strength (substrate adhesion) and curing time (curability) ). Table 1 shows the results. In addition, the coating composition obtained by blending 50 parts by weight of talc as a modifying filler with respect to 100 parts by weight of the compositions obtained in Examples 1 to 6 also has the same curability and excellent properties of excellent substrate adhesion. Met.

The storage stability from the preparation of the pot life composition to the start of coating was observed and evaluated based on Comparative Example 1 (Conventional Example 1). Comparative Example 1
The composition obtained in the above was excellent in storage stability for about 10 minutes until the start of coating. In the table, ○ indicates that the storage stability was as good as that of Comparative Example 1.

A steel plate having a peel strength of 100 mm × 25 mm × 2 mm (JIS
G3141), and 12.5 × 25 mm from the end of each steel sheet according to JIS K6850.
The compositions obtained in Examples and Comparative Examples were applied to the area of
A test piece is prepared by overlapping and joining the portions of the steel sheet pieces to which the composition has been applied. For this test piece, 50 mm
A tensile shear test was performed at a rate of / min to measure the peel strength. The same tensile shear test was performed on polycarbonate.

Curing Time After the composition was prepared, it was left at 20 ° C., and the time until tack disappeared (tack free time) was measured as the curing time.

[0056]

[Table 1]

Note Bisphenol A type epoxy resin (1): manufactured by Sumitomo Chemical Co., Ltd., trade name: ELA-128 aliphatic epoxy resin (2): manufactured by Asahi Denka Co., Ltd., trade name:
EP4080 Heterocyclic amine curing agent: Yuka Shell Epoxy Co., Ltd.
Product name: Epomate QX-2: 100% modified thiirane of (1): 80% modified thiirane of compound (1) in which all oxirane rings of bisphenol A type epoxy resin (1) are substituted by thiirane rings: Bisphenol A type epoxy resin (1) is a compound obtained by substituting a part of the oxirane ring with a thiirane ring, wherein the content ratio of thiirane ring / oxirane ring is 80/20. 50% modified thiirane of (1): Bisphenol A type epoxy resin (1) is a compound obtained by substituting a part of the oxirane ring with a thiirane ring, wherein the content ratio of thiirane ring / oxirane ring is 50/50. 30% modified thiirane of (1): A compound in which a part of the oxirane ring of the bisphenol A type epoxy resin (1) is substituted with a thiirane ring, 30% / 70 in thiirane modified product of (2): a compound in which a part of the oxirane ring of the aliphatic epoxy resin (2) is substituted with a thiirane ring, and the content ratio of thiirane ring / epoxy group Is 8
What is 0/20

[0058]

According to the composition of the present invention, the compound (A) as the main component contains at least one thiirane ring in the molecule,
During curing, the thiirane ring is opened to generate a thiol group having a higher acidity than the hydroxyl group, so it shows a higher substrate adhesion than conventional epoxy resin paints and coating agents,
In addition, although the pot life is sufficient, the thiirane ring is more reactive than the oxirane ring, and thus exhibits a rapid curing property. Further, the composition of the present invention has low odor. Therefore, the composition of the present invention is suitably used for paints and coating agents.

Claims (3)

[Claims] (1) All or a part of the oxirane ring of an epoxy compound is represented by the following formula (1): Or a compound (A) obtained by substituting the thiirane ring represented by the formula (I) or a compound (B) having an oxirane ring in the molecule and not containing a thiirane ring, wherein the oxirane ring / thiirane ring Is 90/10 to 0/100, and further contains at least one curing agent selected from the group consisting of compounds containing a hydroxyl group, a mercapto group, an amino group, or a carboxyl group. Composition. 2. When the molar ratio of the thiirane ring in the total of the oxirane ring and the thiirane ring is X, and the equivalent ratio of the curing agent to the total of the oxirane ring and the thiirane ring is Y, X and Y are as follows. The resin composition for a paint and a coating agent according to claim 1, which has a relationship. When 10% ≦ X <50% Y = (100−X) /100±0.2 When 50% ≦ X ≦ 100% Y = 0.1 to 0.7 3. The compound (A) or a total of 100 parts by weight of the compound (A) and the compound (B), further containing 3 to 50 parts by weight of a modifying filler. 3. The resin composition for a paint and a coating agent according to 1 or 2.