JP2003128787A - Curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition having low-temperature curability at <=0 deg.C, short in tack-free time and scarcely leaving tackiness. SOLUTION: This curable resin composition comprises a resin component with the content ratio: oxirane ring/thiirane ring of (95:5) to (0:100) and a modified xylene resin bearing at least one kind of group selected from hydroxy, amino and carboxy groups; wherein it is more preferable that the modified xylene resin is such that at least one resin selected from the group consisting of nonvolak-type phenolic resin, alkylphenolic resin and phonelics is incorporated in a xylene resin.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a curable resin composition, and more particularly to a curable resin composition which is excellent in low-temperature curability at 0 ° C. or lower, has a short tack free time, and is hard to leave tack.

[0002]

2. Description of the Related Art Epoxy resin compositions have an insufficient crosslinking reaction at a low temperature of 0 ° C. or lower, and their curability is deteriorated. Therefore, it has been found that the use of a thiirane-containing resin having a thiirane ring sufficiently crosslinks and improves the curability even under conditions of 0 ° C or lower. However, at low temperatures, the viscosity of the composition increases and the workability such as workability deteriorates, so in practice, a diluent such as a bisphenol epoxy resin or an aliphatic epoxy resin is added to the thiirane-containing resin composition. Therefore, it was necessary to reduce the viscosity at low temperature. As described above, these diluents have insufficient curability at low temperatures, so that the curability of the composition as a whole is lowered, so that tack on the surface of the composition after application remains for a long time. When the tack remains on the surface, it is impossible to move to the next process such as painting, and there is a problem that the tack must be left until it disappears.

[0003]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a curable resin composition which is excellent in low-temperature curability at 0 ° C. or lower, has a short tack free time, and is hard to leave tack.

[0004]

According to the present invention, a resin component having an oxirane ring / thiirane ring content ratio of oxirane ring / thiirane ring = 95/5 to 0/100, a hydroxyl group, an amino group, and There is provided a curable resin composition containing a modified xylene resin having at least one selected from the group consisting of carboxyl groups.

According to the present invention, the modified xylene resin is a xylene resin containing a novolac type phenol resin,
The curable resin composition is provided with at least one selected from the group consisting of an alkylphenol resin and phenols.

According to the present invention, the amount of the modified xylene resin compounded is 100 parts by weight of the resin component.
The curable resin composition is provided in an amount of 3 to 20 parts by weight.

According to the present invention, the resin component is
20 of oxirane ring of bisphenol F type epoxy resin
There is provided the curable resin composition, in which ˜60% is substituted with a thiirane ring.

As described above, a curable resin composition containing a specific modified xylene resin containing a resin component having an oxirane ring / thiirane ring = 95/5 to 0/100 (hereinafter also referred to as "resin component of the present invention"). By improving the low temperature curability of the curable resin composition at 0 ° C. or less and shortening the tack free time, a curable resin composition in which tack is less likely to remain can be obtained.

This is because the active hydrogen of the functional groups such as hydroxyl group, amino group and carboxyl group of the modified xylene resin of the present invention is
It is considered that the reaction is promoted by activating the thiirane ring of the thiirane-containing resin and the functional group such as the amino group of the curing agent. Furthermore, the xylene portion of the modified xylene resin has affinity with the skeleton of the thiirane-containing resin, and particularly when the skeleton of the thiirane-containing resin is aromatic, the affinity becomes remarkable, and the thiirane-containing resin and the modified xylene are It is considered that the resin and the oriented xylene have a crystalline structure and are oriented, and the active hydrogen of the functional group of the modified xylene resin can efficiently act to accelerate the curing of the thiirane-containing resin. Therefore, even if the curable resin composition contains an epoxy resin having poor curability at a low temperature as a diluent, or even a curable resin composition containing a thiirane-containing resin having only a thiirane ring, The curability can be improved and the tack free time can be improved.

Further, according to the present invention, there is provided the curable resin composition containing 100 parts by weight of the resin component of the present invention and a phosphite compound.

Further, according to the present invention, an amine curing agent,
Preferably, an aliphatic amine curing agent, an alicyclic amine curing agent, an aromatic amine curing agent, a heterocyclic amine curing agent, a polyamine curing agent, a modified polyamine curing agent, and a polyamide amine curing agent. There is provided the curable resin composition containing at least one selected from the group consisting of agents. Further, the curable resin composition containing a tertiary amine is provided.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The curable resin composition of the present invention is a composition containing a resin component containing an oxirane ring and a thiirane ring in a specific ratio (hereinafter also referred to as "composition of the present invention"). In the resin component of the present invention, the content ratio of the oxirane ring and the thiirane ring is such that oxirane ring / thiirane ring = 95/5 to 0.
/ 100, preferably in the range of 95/5 to 10/90, in the molecule with the compound (A) obtained by substituting all or part of the oxirane ring of the epoxy compound with a thiirane ring. The epoxy compound (B) having only an oxirane ring may be contained, or when the compound (A) has both a thiirane ring and an oxirane ring, only the compound (A) may be contained. Compound (A)
The epoxy compound is a compound (A-1) in which all of the oxirane ring in the molecule is substituted with a thiirane ring, or only a part of the oxirane ring in the molecule is substituted with a thiirane ring. And the compound (A-2) having both an oxirane ring. That is, the resin component of the present invention may be, for example, a combination of any of the components shown below. (I) Composition containing only compound (A-2) (ii) Composition containing compound (A-1) and compound (B) (iii) Compound (A-2), Compound (B) A composition (iv) containing the compound (A-1) and a composition (v) containing the compound (A-2), the compound (A-1), the compound (A-2), and the compound (B). In particular, the composition comprising the combination of the above (iii) is preferable because the viscosity and stability with good workability can be obtained, and the low temperature curability is exhibited.

The compound (A) can be synthesized from an epoxy compound. The epoxy compound used to obtain the compound (A) is, for example, one of the following formulas (a), (b),
In (d), (e) or (f), a compound in which all the substituents Y are oxirane rings represented by the following formula (1) or a compound in which all Z are oxygen atoms in the following formula (c) is Can be mentioned. The following formulas (a) and (b)
In the formula, n is 0 or an integer of 1 or more, and in the following formula (f), R is not particularly limited as long as it is a divalent organic group.

[0014]

[Chemical 1]

[0015]

[Chemical 2]

[0016]

[Chemical 3]

Further, these epoxy compounds may have a hydrogen atom or other group in the molecule substituted with a halogen atom. For example, the following formula (g):

[0018]

[Chemical 4] (In the formula, Hal represents a halogen atom). As the halogen atom, bromine, chlorine,
Examples thereof include fluorine.

In the present invention, the compound (A) is, for example, the above formula (a), (b), (d), (e), (f),
Alternatively, in (g), at least one of two or more Y is a thiirane ring represented by the following formula (2), and Y other than the thiirane ring is an oxirane ring represented by the above formula (1), In the above formula (c), a compound in which at least one Z is S and the other Z is O can be mentioned.

[0020]

[Chemical 5]

As will be described later, when the composition of the present invention contains a phosphite compound, it has improved storage stability while maintaining low-temperature curability and adhesiveness equivalent to those when it is not contained. When the composition of the present invention contains these compounds as a resin component, even when the phosphite compound is not contained, the curing time can be shortened while maintaining the storage stability equivalent to the case of containing the compound. There is an advantage that you can. When the composition of the present invention contains these compounds as the resin component, it may further contain a phosphite compound.

Among them, modified products of aliphatic epoxy compounds such as bisphenol A having an epoxy equivalent of 150 to 300, bisphenol F, and hydrogenated bisphenol A are preferable from the viewpoint of stability and curability.

The compound (A) can be produced by a method of reacting the epoxy compound with an episulfide agent in a polar solvent with vigorous stirring. Examples of the episulfide agent used include potassium thiocyanate (KSCN) and thiourea.

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

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

The compound (B) having an oxirane ring and not having a thiirane ring in the molecule which can be contained in the composition of the present invention is an epoxy compound used for obtaining the above-mentioned compound (A). All of the exemplified epoxy compounds are available. Specifically, the compound (A)
In all the above formulas given as specific examples of, a compound in which all the substituents Y are oxirane rings represented by the above formula (1), all Zs are O, and n is 0
Alternatively, a compound having an integer of 1 or more is exemplified. Among these, the bifunctional epoxy compound having two oxirane rings in the molecule has good adhesiveness of the composition of the present invention to be obtained, and further, the aromatic bifunctional epoxy compound having two oxirane rings in the molecule. The compound is excellent in the adhesiveness of the obtained composition of the present invention. In particular, a bisphenol F type epoxy compound is preferable because it has a low viscosity and good workability.

In the composition of the present invention, the oxirane ring /
The content ratio of the thiirane ring is in the range of 95/5 to 0/100, preferably 95/5 from the viewpoint of storage stability and curability.
It is in the range of 10 to 90, and more preferably in the range of 90/10 to 60/40 because of its excellent storage stability.

The resin component of the present invention is preferably a liquid having a viscosity at 25 ° C. of 100,000 mPa · s or less. The resin composition of the present invention containing such a resin component is excellent in fast curing even at room temperature. Also, 25
The resin component having a viscosity at 100 ° C. of 100,000 mPa · s or less has an equivalent weight of 450 g / eq or less as an epoxy compound before thiirane modification, or has an average equivalent weight of 450.
A mixture having a combination of g / eq or less is preferable. Among these, epoxy equivalent 150 to 3
Most preferred are bisphenol A of 00 and bisphenol F. Further, from the viewpoint of storage stability, aliphatic epoxy compounds such as hydrogenated bisphenol A are preferable.

As the resin component of the present invention, 20 to 60% of the oxirane ring of the bisphenol F type epoxy resin is used.
Is preferably substituted with a thiirane ring. The bisphenol F type epoxy resin is hard to crystallize like the bisphenol A type epoxy resin, has a low viscosity, is excellent in low-temperature curability, has good workability, and has a thiirane ring ratio of 20% or more. This is because the effects of the invention are more easily exhibited, and conversely, when it is 60% or less, the storage stability of the composition of the present invention can be improved.

The modified xylene resin of the present invention is a modified xylene resin having at least one selected from the group consisting of a hydroxyl group, an amino group and a carboxyl group in one molecule, or at least two, preferably xylene. At least one selected from the group consisting of novolac type phenolic resins, alkylphenolic resins, and phenols is introduced into the resin. Specifically, for example, those represented by the following formula can be enumerated. The molecular weight is not particularly limited, but it is 380-2.
A value of 000 is preferred because the resin viscosity after addition is low and stable, and the low temperature curability is excellent.

[0031]

[Chemical 6] (In the above formula, R is an arbitrary organic group, and n is an integer.)

The content of the modified xylene resin of the present invention is preferably 3 to 20 parts by weight, more preferably 5 to 10 parts by weight, based on 100 parts by weight of the resin component of the present invention. By setting this amount to 3 parts by weight or more, the effect of the present invention can be further improved, and by setting it to 20 parts by weight or less, the strength and adhesiveness of the composition of the present invention can be further improved. is there.

The curing agent used in the present invention is not particularly limited, and those commonly used as a curing agent for epoxy resin compositions can be used. In the present invention, in particular,
At least one selected from a compound having a hydroxyl group, a mercapto group, an amino group, a carboxyl group or an isocyanate group, and a compound having an acid anhydride structure is preferable.

Examples of the curing agent include amine curing agents, acid or acid anhydride curing agents, basic active hydrogen compounds, imidazoles, polymercaptan curing agents, phenol resins, urea resins, melamine resins, and isocyanate curing agents. Agents, latent curing agents, ultraviolet curing agents and the like. Among them, amine curing agents are particularly preferable, aliphatic amine curing agents, alicyclic amine curing agents, aromatic amine curing agents,
At least one selected from the group consisting of a heterocyclic amine curing agent, a polyamine curing agent, a modified polyamine curing agent, and a polyamidoamine curing agent may be used.

Specific examples of amine-based curing agents include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, iminobispropylamine, bis (hexamethylene) triamine, 1,3,6-trisaminomethyl. Hexane and other polyamines; trimethylhexamethylenediamine, polyetherdiamine, diethylaminopropylamine and other polymethylenediamines; Mensendiamine (M
DA), isophorone diamine (IPDA), bis (4
-Amino-3-methylcyclohexyl) methane, N-aminoethylpiperazine (N-AEP), diaminodicyclohexylmethane, bisaminomethylcyclohexane,
3,9-bis (3-aminopropyl) -2,4,8,1
Cycloaliphatic polyamines such as 0-tetraoxaspiro (5.5) undecane; Aliphatic polyamines containing aromatic rings such as metaxylylenediamine, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiethyldiphenylmethane and other aromatics Polyamine and also 3,9-bis (3-aminopropyl)-
2,4,8,10-tetraspiro [5.5] undecane and the like can be mentioned. Further, amine adduct (polyamine epoxy resin adduct), polyamine-ethylene oxide adduct, polyamine-propylene oxide adduct,
Cyanoethylated polyamine, ketimine which is a reaction product of aliphatic polyamine and ketone; linear diamine, tetramethylguanidine, triethanolamine, 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)
Liquid polyamide obtained by reacting secondary amines or tertiary amines such as phenol, 1.8-diazabicyclo (5.4.0) undecene-1 or the like, or dimer acid with polyamines such as diethylenetriamine and triethylenetetramine. And so on.

The compounding amount of the curing agent used for curing the composition of the present invention is such that the equivalent ratio is 0.5 to 1.5 with respect to the total of the thiirane ring and the oxirane ring. If the curing agent has an equivalent ratio of less than 0.5 to the total of thiirane ring and oxirane ring, the composition will not cure, and if the equivalent ratio exceeds 1.5, the obtained cured product becomes brittle. . Further, when the adhesive composition has both low temperature curability under an environment of 0 ° C. or less and pot life, it is preferable to add an aliphatic polyamine compound.

In this case, as the curing agent, only the aliphatic polyamine compound may be used, or another curing agent and the aliphatic polyamine compound may be used in combination. When used in combination, the proportion of the aliphatic polyamine compound in the curing agent is 30.
~ 90 mol% is preferred.

The composition of the present invention may contain a phosphite compound. The composition of the present invention containing a phosphite ester compound together with a thiirane-containing resin has a low temperature curability and an adhesive property while being equal to those of a composition containing a thiirane-containing resin and not containing a phosphite ester compound. , Storage stability is improved. In particular, a phosphite compound having a structure with low steric hindrance around the phosphorus atom is effective for improving storage stability. In the thiirane-containing resin, the thiol group generated when the thiirane ring is opened by water is a chemically highly reactive substituent, so that self-polymerization between the thiol group and the thiirane ring is likely to occur. When a phosphite compound is blended, the thiol group is stabilized by the interaction between the phosphorus atom contained in the phosphite compound and the sulfur atom contained in the thiol group generated by ring opening of the thiirane ring, It is considered that the self-polymerization between the thiol group and the thiirane ring is suppressed, and the storage stability of the thiirane-containing resin is improved. The phosphite compound is a liquid compound and has a low viscosity. On the other hand, the thiirane-containing resin has a higher viscosity and is more easily crystallized than an epoxy resin having an oxirane ring instead of the thiirane ring. Therefore, when the phosphite compound is added to the thiirane-containing resin, it is possible to reduce the crystallization of the thiirane-containing resin easily, the viscosity of the composition containing the thiirane-containing resin can be lowered, and the workability becomes good, preferable.

As the phosphite compound used in the present invention, various compounds which are esters of phosphonic acid can be used, but the phosphite compound represented by the following formulas (3) and (4) is preferable. At least one phosphite compound selected from the group consisting of is used.

[0040]

[Chemical 7] In the formula, R ^{1 to} R ⁵ each represent a hydrocarbon group having 30 or less carbon atoms.

Specifically, as the compound represented by the formula (3), triphenylphosphite, tris (nonylphenyl) phosphite, triethylphosphite, tridecylphosphite, tris (tridecyl) phosphite, diphenyl Mono (2-ethylhexyl) phosphite, diphenyl monodecyl phosphite, diphenyl mono (tridecyl) phosphite, tristearyl phosphite, etc .; as the compound represented by the formula (4), bis (tridecyl) pentaerythritol diphosphite ,
Bis (nonylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite and the like; and their triesters or 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. These phosphite compounds have small steric hindrance around the phosphorus atom.

From the viewpoint of storage stability, among the phosphite compounds represented by the above formulas (3) and (4),
It is particularly preferable that at least one of the ester moieties (-P-O-R) has a structure containing an aromatic ring such as a benzene ring. When the aromatic ring has a substituent, the substituent is preferably an alkyl group having 1 to 6 carbon atoms, and the substitution position is preferably the meta position or the para position. Further, in the compound represented by the formula (4), the ester moiety (-P-O
A structure having an alkyl group in -R) is also preferable.
Among the compounds represented by the formula (3), a diaryl monoalkyl phosphite, and among the compounds represented by the formula (4), a chemistry of diaryl pentaerythritol diphosphite or dialkyl pentaerythritol diphosphite. Those having a structure are preferable because they each have a large effect on storage stability. Specifically, examples of the diarylmonoalkyl phosphite include diphenylmono (2-ethylhexyl) phosphite, diphenylmonodecylphosphite, diphenylmono (tridecyl) phosphite, and examples of the diarylpentaerythritol diphosphite include bis ( Nonylphenyl) pentaerythritol diphosphite and the like, and examples of the dialkylpentaerythritol diphosphite include distearyl pentaerythritol diphosphite and the like.

From the viewpoint of compatibility, at least one of the ester moieties (—P—O—R) in the phosphite compound represented by the above formulas (3) and (4).
One having a structure containing an aromatic ring such as a benzene ring is
preferable. When the aromatic ring has a substituent, the substituent is preferably an alkyl group having 1 to 6 carbon atoms, and the substitution position is preferably the meta position or the para position. As such a phosphite compound, for example, as the compound represented by the formula (3), diaryl monoalkyl phosphite, monoaryl dialkyl phosphite,
Examples of the compound represented by the formula (4) include aryl monoalkyl pentaerythritol diphosphite. Specifically, examples of the diaryl monoalkyl phosphite include diphenyl mono (2-ethylhexyl) phosphite, diphenyl monodecyl phosphite, diphenyl mono (tridecyl) phosphite, and the like.
Examples of the monoaryldialkyl phosphite include phenyl didecyl phosphite, and examples of the aryl monoalkyl pentaerythritol diphosphite include bisphenyl tridecyl pentaerythritol diphosphite.

As the phosphite compound, a commercially available product can be used. For example, JPM manufactured by Johoku Chemical Co., Ltd.
-308, JPM-311, JPM-313, JPP-
13, JPP-31 and the like.

The addition amount of the phosphite ester compound is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the resin component of the present invention. It is more preferably 3 to 10 parts by mass.
If it is less than 0.1 part by mass, the effect of storage stability is not obtained and
When it exceeds the mass part, curability and adhesiveness are deteriorated.

The composition of the present invention may be used in combination with a curing accelerator. As the curing accelerator, for example, phenols,
Examples include tertiary amines and the like. Examples of the tertiary amine include benzylmethylamine, triethylamine, dimethylaminomethylphenol, trisdimethylaminomethylphenol and 1,8-diazabicyclo [5.4.0].
Undecene-1,1,4-diazabicyclo [2.2.
2] Examples include octane. The amount of the tertiary amine compounded is not particularly limited and may be appropriately set. For example, it may be 0.05 to 10 parts by weight with respect to 100 parts by weight of the resin component of the present invention.

The composition of the present invention may further contain various other additives, if desired. For example,
Fillers, plasticizers, thixotropy imparting agents, pigments, dyes, antioxidants, antioxidants, antistatic agents, flame retardants, adhesion imparting agents, dispersants, solvents and the like can be added.

As the filler, various shapes can be used, and examples thereof include fumed silica, calcined silica, precipitated silica, ground silica, fused silica; diatomaceous earth; iron oxide, zinc oxide, titanium oxide, Barium oxide, magnesium oxide; calcium carbonate, magnesium carbonate,
Examples include organic or inorganic fillers such as zinc carbonate; wax stone clay, kaolin clay, calcined clay; carbon black, and fatty acid, resin acid, and fatty acid ester-treated products thereof. These may be used alone or in combination of two or more.

As the plasticizer, dioctyl phthalate (DOP), dibutyl phthalate (DBP); dioctyl adipate, isodecyl succinate; diethylene glycol dibenzoate, pentaerythritol ester;
Examples include butyl oleate, methyl acetylricinoleate; tricresyl phosphate, trioctyl phosphate; propylene glycol adipate polyester, butylene glycol adipate polyester. These plasticizers may be used alone or in combination of two or more.

Examples of the antioxidant include butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA). Examples of the antiaging agent include compounds such as hindered phenols.

As the pigment, titanium dioxide, zinc oxide,
Examples include inorganic pigments such as ultramarine, red iron oxide, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochlorides and sulfates, and organic pigments such as azo pigments and copper phthalocyanine pigments.

As the thixotropy-imparting agent, for example, Aerosil (manufactured by Nippon Aerosil Co., Ltd.), Disparlon (manufactured by Kusumoto Kasei Co., Ltd.), calcium carbonate, Teflon (registered trademark), etc., and as an antistatic agent, generally, Examples thereof include quaternary ammonium salts or hydrophilic compounds such as polyglycol and ethylene oxide derivatives.

Examples of the adhesiveness-imparting agent include terpene resin, phenol resin, terpene-phenol resin, rosin resin and xylene resin.

Examples of the flame retardant include chloroalkyl phosphate, dimethyl methylphosphonate, bromine.
Phosphorus compounds, ammonium polyphosphates, neopentyl bromide-polyethers, brominated polyethers and the like can be mentioned.

Further, the composition of the present invention can be suitably used as an adhesive for civil engineering and construction, a paint, an anticorrosive paint, a sealing material, a sealing material, a potting material, a coating material and the like.

[0056]

The present invention will be further described below with reference to examples, but the scope of the present invention is not limited to these examples. Examples 1 to 4 and Comparative Examples 1 to 3 The compounds shown in Table 1 below were blended in the composition (mass ratio) shown in Table 1 to obtain resin compositions. With respect to the obtained resin composition, in order to evaluate the curability and tack under low temperature conditions, the tack free time at -5 ° C below was measured, and the results are shown in Table 1.

-5 ° C. tack free time (hr) Each of the obtained compositions was placed in a thermostatic chamber at -5 ° C. to give a thickness of 5
The sheet was molded into a sheet of mm and the tack free time was measured. The tack free time is indicated by the time (hours) taken until the molded product does not stick to the finger even if the sheet-shaped molded product is pressed with the finger.

[0058]

[Table 1]

The following components were used as the components used in Table 1 above. Bisphenol F type thiirane resin: resin represented by the following formula

[0060]

[Chemical 8]

Bisphenol F type epoxy resin: EPI
CLON830, Dainippon Ink and Chemicals, epoxy equivalent 1
70 Modified xylene resin 1: Resin represented by the following formula, Nikanol N
P-100, Mitsubishi Gas Chemical Company, number average molecular weight = 700

[0062]

[Chemical 9]

Modified xylene resin 2: resin represented by the following formula,
Nikanol HP-100, Mitsubishi Gas Chemical Company, number average molecular weight = 1200

[0064]

[Chemical 10]

Xylene resin: Resin represented by the following formula, Nikanol HH, Mitsubishi Gas Chemical Company, number average molecular weight = 500-6
00

[0066]

[Chemical 11]

Phenolic resin: Sumilite resin PR-
12603, Sumitomo Durez modified polyamine: EH-262W-2, Asahi Denka Kogyo phosphite compound: diphenyl monodecyl phosphite, JPM-311, Johoku Chemical Co. tertiary amine: trisdimethylaminomethylphenol, Epicure 3010, Japan Epoxy Company

As shown in Table 1 above, the compositions of Comparative Example 1 and Comparative Example 2 in which the modified xylene resin of the present invention was not added and Comparative Example 3 in which the thiirane-containing resin of the present invention was not added were cured. Poor performance and long tack free time at low temperature. On the other hand, Examples 1 to 1 containing the resin component of the present invention and the modified xylene resin of the present invention
The composition of No. 4 had good results that the low temperature curability was improved and the tack free time was reduced.

[0069]

According to the present invention, the curable resin composition is
Modified xylene having a resin component in which the content ratio of the oxirane ring and the thiirane ring is oxirane ring / thiirane ring = 95/5 to 0/100, and at least one selected from the group consisting of a hydroxyl group, an amino group, and a carboxyl group. By blending with a resin, it is possible to obtain a curable resin composition which is excellent in low-temperature curability at 0 ° C. or lower, has a short tack free time, and is hard to leave tack.

Claims (8)

[Claims] 1. The content ratio of oxirane ring and thiirane ring is such that oxirane ring / thiirane ring = 95/5 to 0/100.
And a modified xylene resin having at least one selected from the group consisting of a hydroxyl group, an amino group, and a carboxyl group. 2. The curable resin according to claim 1, wherein the modified xylene resin is a xylene resin into which at least one selected from the group consisting of novolac-type phenol resins, alkylphenol resins, and phenols is introduced. Composition. 3. The curable resin composition according to claim 1, wherein the modified xylene resin is blended in an amount of 3 to 20 parts by weight based on 100 parts by weight of the resin component. 4. The curable resin composition according to claim 1, wherein the resin component is a bisphenol F type epoxy resin in which 20 to 60% of the oxirane ring is substituted with a thiirane ring. . 5. The curable resin composition according to claim 1, further comprising a phosphite compound. 6. The method according to claim 1, further comprising an amine curing agent.
The curable resin composition according to any one of 1. 7. The amine curing agent is an aliphatic amine curing agent, an alicyclic amine curing agent, an aromatic amine curing agent, a heterocyclic amine curing agent, a polyamine curing agent, or a modified polyamine curing agent. The curable resin composition according to claim 6, which is at least one selected from the group consisting of a curing agent and a polyamidoamine-based curing agent. 8. The curable resin composition according to claim 1, further comprising a tertiary amine.