JP2003292568A - Method for curing thermosetting epoxy resin composition, cured product and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive, a coating material, a sealing material for electric materials, a sealing material for optical semiconductors, or a heat which can be used for a printed circuit board or its insulating layer, having excellent heat resistance and flexibility. Provided is a method for curing a curable epoxy resin composition. An epoxy resin (A) comprising a cycloaliphatic epoxy compound (a) and another epoxy compound (b) optionally added, An epoxy resin, comprising: curing an epoxy resin composition comprising a compound (B) which reacts with a cationic species to be added accordingly and a compound (C) which generates a cationic species by heating under predetermined conditions in two or more steps. A method for curing the resin composition.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an epoxy resin composition containing at least a cycloaliphatic epoxy compound, which is subjected to primary curing under specific conditions by cationic polymerization.
The present invention relates to a curing method for performing secondary curing and thereafter. The obtained cured product is excellent in heat resistance, flexibility and the like, and thus can be used as an adhesive, a coating material, a sealing material for electrical materials, a sealing material for optical semiconductors, or a printed circuit board or an insulating layer thereof.

[0002]

2. Description of the Related Art Epoxy resins are used in large amounts in adhesives, coating agents, encapsulating materials and the like. In particular, when an epoxy resin is used as a sealing material for electronic materials, an acid anhydride is often used as a curing agent to perform heat curing. As a problem of curing with an acid anhydride, it takes a long curing time, a short pot life in the case of forming a resin composition, a hydroxyl group is generated by a reaction between an epoxy group and an acid, and an increase in water absorption due to this. It's a problem. Therefore, in recent years, attention has been paid to thermal cationic curing of an epoxy resin using a compound that produces a cationic species by heating. However, when a glycidyl ether type epoxy compound is used when an epoxy resin is cured by thermal cation curing, the glass transition point (Tg) of the cured product is low, and coloring is large, and coating or transparency that requires sealing is required. There was a problem in applying it to wood. The use of a glycidyl ester type epoxy compound has problems of high cost and little room for material selection. On the other hand, when an alicyclic epoxy compound having an epoxy group in the alicyclic skeleton is used, it can be cured at a relatively low temperature because of its good reactivity with cationic species, but the cured product has a Tg of about 100 ° C. It was difficult to use for things that require sex.

[0003]

An object of the present invention is to provide an adhesive, a coating material, a sealing material for electrical materials, a sealing material for optical semiconductors, or a printed circuit board or the like, which has excellent heat resistance and flexibility. A method for curing a thermosetting epoxy resin composition that can be used for an insulating layer is provided.

[0004]

Means for Solving the Problems The present inventors have performed a primary curing at 80 ° C. or lower to form a gel, and then from 100 ° C. to 2 ° C.
It was found that a cured product excellent in heat resistance, flexibility, etc. can be obtained by performing secondary curing after 00 ° C. and completed the present invention.

That is, the first aspect of the present invention is an epoxy resin (A) comprising a cycloaliphatic epoxy compound (a) and another epoxy compound (b) optionally added, and a cationic species optionally added. A compound (B) that reacts with
And an epoxy resin composition comprising a compound (C) that generates a cationic species by heating, is cured in two or more steps, and primary curing (curing in the first step) is performed as (a) another epoxy compound (b), glycidyl. Ether type epoxy resin,
An epoxy resin composition characterized in that when it is blended in the epoxy resin (A) in an amount of 0 to 60% by weight, it is carried out at 80 to 110 ° C, and in the cases other than (b) and (a), it is carried out at 40 ° C or lower. A method of curing the same is provided. The second of the present invention is that the Mn of the primary cured product is 200 to 20000, and the raw material Mn / the primary cured product Mn is 1.0 / 1.1 to 1.0 / 100.0. A method for curing an epoxy resin composition is provided. The third aspect of the present invention is a cycloaliphatic epoxy compound (a).
And a weight ratio of the other epoxy compound (b) to be added as necessary, the epoxy compound (a) / epoxy compound (b) = 100/0 to 40/60. A method of curing a composition is provided. A fourth aspect of the present invention is that the compound (B) is alcohol, oxetane,
There is provided a method for curing an epoxy resin composition according to any one of 1 to 3 of the present invention, which is one or more selected from the group consisting of vinyl ether, propenyl ether, and a compound containing a phenolic hydroxyl group. 5th of this invention WHEREIN: The ratio of an epoxy resin (A) and a compound (B) is epoxy resin (A) /
There is provided a method for curing an epoxy resin composition according to any one of the first to fourth aspects of the present invention, wherein compound (B) is 100/0 to 60/40 (% by weight ratio). The sixth aspect of the present invention is that after the secondary curing (second stage curing), in the case of (a) of the first aspect of the present invention, at 120 to 200 ° C., the first curing of the present invention is performed.
In the case of (b), the method for curing the epoxy resin composition according to any one of the first to fifth aspects of the present invention is performed at 100 to 200 ° C. The seventh aspect of the present invention is an epoxy resin (A) comprising a cycloaliphatic epoxy compound (a) and another epoxy compound (b) optionally added, and a compound which reacts with a cationic species optionally added. A cured product obtained by heating and curing an epoxy resin composition comprising (B) and a compound (C) which produces a cationic species upon heating. An eighth aspect of the present invention provides a cured product obtained by the curing method according to any one of the first to seventh aspects of the present invention. The ninth aspect of the present invention provides the eighth cured product of the present invention, which has a glass transition point of 120 ° C. or higher. Tenth of the present invention is an adhesive,
The eighth or ninth cured product of the present invention is used for one or more applications selected from the group consisting of a coating material, a sealing material for electrical materials, an optical semiconductor sealing material, and a printed circuit board or an insulating layer thereof. . The eleventh aspect of the present invention is an epoxy resin (A) comprising a cycloaliphatic epoxy compound (a) and another epoxy compound (b) added as necessary.
A primary cured product having the following physical properties of an epoxy resin composition comprising a compound (B) that reacts with a cationic species that is added as necessary, and a compound (C) that produces a cationic species by heating. Molecular weight Mn 200 to 20000 Ratio of raw material Mn to primary cured product Mn 1.0 / 1.1 to
1.0 / 100.0 The twelfth aspect of the present invention is: (a) When a glycidyl ether type epoxy resin is added as the other epoxy compound (b) in the epoxy resin (A) in an amount of 0 to 60% by weight, ~
200 ° C, 100 to 200 in the case other than (b) and (a)
When it is secondarily cured under the condition of ℃, the glass transition point is 120.
The primary cured product of the eleventh epoxy resin composition of the present invention, which provides a cured product at a temperature of not less than 0 ° C.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Epoxy Resin (A) In the present invention, the epoxy resin (A) comprises a cycloaliphatic epoxy compound (a) and another epoxy compound (b) which is added as necessary. The epoxy resin (A) undergoes ring-opening polymerization in the presence of a cationic species generated by heating the compound (C) described below. Cycloaliphatic epoxy compound (a) The cycloaliphatic epoxy compound (a) is a cycloaliphatic compound having an epoxy group in the cyclic skeleton. The epoxy compound (a) may have an epoxy group outside the cyclic skeleton. The number of cyclic skeletons in the epoxy compound (a) is
It is 1 or more and may be plural, and is not particularly limited, but is usually 1 to 4. The number of carbon atoms constituting one cyclic skeleton is 5 to 20, preferably 6 to 12. Each cyclic skeleton in one molecule may not necessarily have an epoxy group, or may have two or more epoxy groups in the same cyclic skeleton. The number of epoxy groups that the epoxy compound (a) has is not particularly limited, and the number of epoxy groups in the cyclic skeleton is generally 1 to 4, usually 1 to 2, and alicyclic exoskeleton epoxy groups are generally. 0-4, usually 0-2 are used.
The epoxy compound (a) is a compound having a molecular weight of 100 or more, preferably 120 or more and 2000 or less, preferably 1000 or less. If the molecular weight of the epoxy compound (a) is too small, the volatility is high, and the working properties and the processing characteristics during coating are significantly deteriorated. If the molecular weight is too large, the viscosity of the composition becomes high, and therefore the epoxy compound (a) is cast into a predetermined shape. It becomes difficult to mold or apply it uniformly.

Specific examples of the cycloaliphatic epoxy compound (a) include, for example, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate (Celoxide produced by Daicel Chemical Industries (hereinafter CEL
2021P, etc. and Asahi Ciba Araldite CY
179 and Chisso Knox 206) manufactured by Chisso Co., Ltd .; 3,4
-CEL-2080 series having a structure in which at least one ε-caprolactone is ring-opening polymerized on average between an epoxycyclohexylmethyl group and a 3 ', 4'-epoxycyclohexanecarboxyl group (CEL-2081 manufactured by Daicel Chemical Industries, Ltd., CEL-such as 2083 and 2085
Examples thereof include those having two cycloaliphatic epoxy groups in the molecule such as 2021P modified caprolactone). As a compound having one cycloaliphatic epoxy group in the molecule and one epoxy group outside the cyclic skeleton, 1,2,8,9-diepoxylimonene (CEL-300 manufactured by Daicel Chemical Industries, Ltd.
0) and the like. 1-Vinyl-3,4-epoxycyclohexane (CEL-200 manufactured by Daicel Chemical Industries, Ltd.) having one cycloaliphatic epoxy group in the molecule.
0), epoxidized tetrahydrobenzyl alcohol and the like.

[0008]

[Chemical 1]

The one having three or more cycloaliphatic epoxy groups in the molecule is a polycarboxylic acid ester of epoxycyclohexanol, or at least one or more between the epoxycyclohexanol group and the polycarboxylic acid residue. Having a structure obtained by ring-opening polymerization of caprolactone of (GT-301, GT-302, GT-, manufactured by Daicel Chemical Industries, Ltd.
401, GT-403, etc.) and the like. Other than the above, those having the following cycloaliphatic epoxy groups can be used.

[0010]

[Chemical 2]

Among the cycloaliphatic epoxy compounds (a), 3,4-epoxycyclohexylmethyl-3 ',
4′-epoxycyclohexanecarboxylate is preferable from the viewpoint of the effect of lowering the viscosity and improving the heat resistance of the composition of the present invention.

Other Epoxy Compound (b) The other epoxy compound (b) can be added to the epoxy resin (A), if necessary. The other epoxy compound (b) is preferably liquid. As an example of the epoxy compound (b), a compound having an internal epoxy group can be mentioned. Specifically, as a commercially available epoxidized polybutadiene, PB3600 (manufactured by Daicel Chemical Industries);
E-1800-6.5, E-1000-8.0 and the like (manufactured by Nippon Petrochemical); BF-1000 (manufactured by Asahi Denka Kogyo) and the like. Examples of the compound having an internal epoxy group include epoxides of styrene-butadiene-styrene copolymer other than the above. Specifically, commercially available Epofriend A
1020 (manufactured by Daicel Chemical Industries) and epoxidized soybean oil,
An alicyclic epoxy resin having a structure in which a unit having an epoxy group as a side chain is connected to a cyclohexane ring by an ether bond [EHPE-3 manufactured by Daicel Chemical Industries Ltd.]
150 (epoxy equivalent 185, softening point 80 ° C.)], epoxidized linseed oil and the like. Epoxy compound (b)
As another example, an aromatic epoxy resin generally widely used as a glycidyl ether type epoxy resin can be used. For example, bisphenol-type epoxy resins such as diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F and diglycidyl ether of bisphenol S, and hydrogenated aromatic rings thereof; phenol novolac epoxy resin, cresol novolac epoxy resin and hydroxy Examples thereof include novolac type epoxy resins such as benzaldehyde phenol novolac epoxy resin; and polyfunctional epoxy resins such as glycidyl ether of tetrahydroxyphenylmethane, glycidyl ether of tetrahydroxybenzophenone, and epoxidized polyvinylphenol. Others, cyclohexane dimethanol diglycidyl ether, ethylene glycol diglycidyl ether,
Examples thereof include epoxidized polyols such as propylene glycol diglycidyl ether and neopentyl glycol diglycidyl ether, and epoxidized polyether polyols. Other additives that can be added include acrylic acid-modified products of epoxy resins, such as glycidyl (meth) acrylate, 2-methyl-glycidyl (meth) acrylate, and epoxidized isoprenyl (meth) acrylate. Of these, the epoxy equivalent is 150-
300 g / eq. The bisphenol A type epoxy resin and bisphenol F type epoxy resin, hydrogenated bisphenol A diglycidyl ether, cyclohexanedimethanol diglycidyl ether and the like within the range are preferable because they are liquid. Other examples of the epoxy compound (b) include:
The following glycidyl ethers can also be used.

[0013]

[Chemical 3]

In addition, glycidyl ester type, for example,
A compound having an epoxy group such as an aliphatic or aromatic polycarboxylic acid polyglycidyl ester such as adipic acid diglycidyl ester or phthalic acid diglycidyl ester can be used.

The weight ratio of the cycloaliphatic epoxy compound (a) (including the internal epoxy resin) to the other epoxy compound (b) added as necessary in the epoxy resin (A) is the epoxy compound (a). / Epoxy compound (b)
100 / 0-40 / 60, preferably 100 / 0-55 /
45.

Compound (B) Reacting with Cationic Species The compound (B) reacts with the compounds (B) or with the epoxy resin (A) in the presence of the cation species generated by heating the compound (C) described later. It is a thing. Examples of the compound (B) include an oxetane compound (o), a vinyl ether (v), a polyester (ps) and a polyether (p) which will be described later.
e), low molecular weight polyol (po), carboxylic acid and its anhydride (ca), phenol resin (pr) and the like. The following oxetane compound (o) can be added to the epoxy resin composition.

[0017]

[Chemical 4] 3-ethyl-3-hydroxymethyl oxetane

[0018]

[Chemical 5] 3-methyl-3-hydroxymethyl oxetane

[0019]

[Chemical 6] 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene

Other than the above, the following oxetanes can be used.

[0021]

[Chemical 7]

Vinyl ether (v) may be added to the epoxy resin composition. Vinyl ether (v)
Examples thereof include cyclohexanedimethanol divinyl ether and diethylene glycol divinyl ether. The epoxy resin composition may be blended with a polyester (ps) or polyether (pe) having a hydroxyl group at the terminal as long as it is soluble in the epoxy resin composition. As polyester (ps), for example, 2 in the molecule
PCL-205, a polyester with one hydroxyl group
H, PCL-210 (manufactured by Daicel Chemical Industries), PCL-30 which is a polyester having three hydroxyl groups in the molecule
5, PCL-308 (manufactured by Daicel Chemical Industries), PCL-4 which is a polyester having four hydroxyl groups in the molecule.
10D etc. (made by Daicel Chemical Industries) are mentioned. Also, Curapol P-1010, P-2010, P-3010 (made by Kuraray) and the like can be used. Examples of the polyether (pe) include polyethers such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol. Examples of commercially available products include polyether P-400, P-1000, and P-3000 manufactured by ADEKA. Examples of the low molecular weight polyol (po) include glycols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-butanediol and 1,6-hexanediol.

Carboxylic acid and its anhydride (ca) A curing agent selected from known acid anhydrides can be used. For example, as the acid anhydrides, aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl anhydride Examples thereof include cycloaliphatic acid anhydrides such as hexahydrophthalic acid, methylendoethylenetetrahydrophthalic anhydride, and trialkyltetrahydrophthalic anhydride. Among these, it is preferable to use hexahydrophthalic anhydride and methylhexahydrophthalic anhydride from the viewpoint of improving the weather resistance of the composition of the present invention. Examples of the carboxylic acid include carboxylic acids corresponding to the above acid anhydrides, butanetetracarboxylic acid, and the like. Further, in the present invention, a curing accelerator can be added to the epoxy resin composition for the purpose of promoting curing by the acid anhydride. Examples of the curing accelerator include tertiary amines, imidazoles, organic phosphine compounds and salts thereof. A phenolic resin (pr) can be blended as it reacts with an epoxy resin. Examples of the phenol resin (pr) include phenol, cresol, xylenol, butylphenol, nonylphenol and the like, and novolac resins and resole resins using a mixture thereof as a raw material. Compound (B) that reacts with these epoxy resins (A)
Is epoxy resin (A) / compound (B) = 100/0
It is 60/40 (weight% ratio). The proportion of the carboxylic acid and its anhydride (ca) used is in the range of 0 to 200 parts by weight with respect to the total amount of the epoxy resin of the component (a) and the epoxy resin of the component (b).

Compound (C) which produces a cationic species upon heating Compound (C) is a cationic polymerization initiator of the epoxy resin (A) and / or compound (B). Examples of the cationic polymerization initiator include the following types (i) to (iii). (I) As a thermal cationic polymerization initiator that generates a cationic species or a Lewis acid by heating, US Pat.
Metal fluoroboron complex salts and boron trifluoride complex compounds as described in US Pat. No. 3, bis (perfluoroalkylsulfonyl) methane metal salts as described in US Pat. No. 3,586,616; US Pat. No. 3,708,296. Diazonium compounds as described; US Pat. No. 405.
Aromatic onium salts of Group VIa elements as described in 8400; Aromatic onium salts of Group Va elements as described in US Pat. No. 4069055; US Pat. No. 4068
Dicarbonyl chelates of IIIa-Va elements as described in U.S. Pat. No. 091; thiopyrylium salts as described in U.S. Pat. No. 4,139,655; U.S. Pat.
Group VIb elements in the form of MF ^6- anions as described in US Pat. No. 78, where M is selected from phosphorus, antimony and arsenic; arylsulfonium complex salts as described in US Pat. No. 4,231,951; US Pat. No. 4,256,828
Aromatic iodonium complex salts and aromatic sulfonium complex salts as described in the publication; WRWatt et al., “Journal of Polymer S
cience), Polymer Chemistry (Po1ymer Chemistr
y) ", Vol. 22, p. 1789 (1984), and bis [4- (diphenylsulfonio) phenyl] sulfide-bis-hexafluorometal salts (e.g. phosphates, arsenates, antimonates). Etc.) are included. Preferred cationic polymerization initiators include aryl sulfonium complex salts, aromatic sulfonium or iodonium salts of halogen-containing complex ions and aromatic onium salts of Group II, V and VI elements. Some of these salts are FX-512 (3M Company); UVACURE15.
91 (Daicel UCB); UVI-6990 and U
VI-6974 [Union Carbide Company]; UVE-
1014 and UVE-1016 [General Electric Company]; KI-85 [Degussa Company]; SP-15
0 and SP-170 (Asahi Denka); Sun-Aid SI-
60L, SI-80L and S1-100L (Sanshin Chemical Industry Co., Ltd.); (Ii) As another thermal cationic polymerization initiator, a cationic or protic acid catalyst such as a triflic acid salt, a boron trifluoride ether complex compound, or boron trifluoride can be used. Preferably, triflate,
Examples include diethylammonium triflate, triethylammonium triflate, diisopropylammonium triflate, ethylsiisopropylammonium triflate, etc., many of which are available as FC-520 from 3M Company, many of which are Modern Coatings issued by RRA1m in October 1980. It is described in]. Among the above cationic polymerization initiators, aromatic onium salts are preferable because they are excellent in handleability and the balance between the latent property and the curability. The amount of the cationic polymerization initiators of types (i) and (ii) used is 0.01 to 15 parts by weight, and more preferably 0, to 100 parts by weight of the total of the epoxy resin (A) and the compound (B). It is preferably added in an amount of 1 to 10 parts by weight.

(Iii) As another thermal cationic polymerization initiator, a combination of a metal chelate and a compound which produces bisphenol S or silanol can be used.

Aluminum, titanium, zinc and the like can be used as the metal of the metal chelate. As the chelating agent, diketones such as acetoacetic acid ester and acetylacetone can be used. As the acetoacetic ester, the following R1 part is an alkyl chain having 1 to 12 carbon atoms, and may be linear or branched.

[0027]

[Chemical 8]

The diketones have the following structures, and R2 and R3 are both hydrogen or an alkyl chain having 1 to 10 carbon atoms and may be linear or branched.

[0029]

[Chemical 9]

Examples of compounds that produce silanol include triphenyl silanol and the like. In addition, bisphenol S or the like can be used as bisphenol S. The cationic polymerization initiator of the type (iii) has a total amount of the metal chelate and bisphenol S or silanol-forming compound of 10 to 0 relative to 100 parts by weight of the epoxy resin (A) and the compound (B). 0.1 parts by weight, preferably 8 to 0.2 parts by weight.

Further, the epoxy resin composition of the present invention may contain the following components if necessary. (1) Reinforcing agent and filler: Examples of powdery materials include metal oxides such as aluminum oxide and magnesium oxide, metal carbonates such as calcium carbonate and magnesium carbonate, diatomaceous earth powder, basic magnesium silicate, and calcination. Clay, fine powder silica, fused silica, silicon compounds such as crystalline silica, metal hydroxide such as aluminum hydroxide,
Others, kaolin, mica, quartz powder, graphite,
Molybdenum disulfide and the like; fibrous ones include, for example, glass fiber, ceramic fiber, carbon fiber, alumina fiber, silicon carbide fiber, boron fiber, polyester fiber and polyamide fiber. These are blended in an amount of 10 to 900 parts by weight based on 100 parts by weight of the epoxy resin composition used in the present invention. (2) Colorants, pigments, flame retardants: Examples of colorants, pigments, flame retardants include titanium dioxide, iron black, molybdenum red, navy blue, ultramarine blue, cadmium yellow, cadmium red, antimony trioxide, red phosphorus, and bromine compounds. And triphenyl phosphate. These are added in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the epoxy resin composition used in the present invention. (3) Further, various curable monomers, oligomers and synthetic resins can be blended for the purpose of improving the properties of the resin in the final coating film, adhesive layer, molded product and the like.
Other additives that can be added include acrylates such as epoxy acrylate. For example, a diluent for epoxy resin such as monoepoxy, phenol resin, alkyd resin, melamine resin, fluorine resin, vinyl chloride resin, acrylic resin, silicone resin, polyester resin, etc.
There may be mentioned one kind or a combination of two or more kinds. The mixing ratio of these resins is 50 parts by weight or less with respect to 100 parts by weight of the epoxy resin composition used in the present invention, that is, an amount in a range that does not impair the original properties of the epoxy resin composition used in the present invention. preferable. Examples of means for blending the epoxy resin composition and optional components used in the present invention include hot melt mixing, melt kneading with a roll and a kneader, wet mixing using an appropriate organic solvent, and dry mixing.

Curing Conditions In the present invention, a tough cured product can be prepared by using curing conditions of two or more stages under predetermined conditions. Primary curing is performed as follows. (A) A glycidyl ether type epoxy resin as the other epoxy compound (b), 0 to 6 in the epoxy resin (A).
When blending 0% by weight, 80 to 110 ° C, (b)
In cases other than (a), 15 at 50 ℃ to 80 ℃
Do it in 2 hours from a minute. After that, the secondary curing and subsequent curing are performed in order to obtain predetermined physical properties. Although the curing conditions after the secondary curing vary depending on the target physical properties, they are performed as follows. In the case of the above (a), it is 120 to 200 ° C., and in the case of the above (b), it is 100 to 200 ° C.
Within hours is desirable. It is also possible to cure in three or four steps. When the curing temperature of the primary curing is higher than the above-mentioned temperature range, the reaction proceeds too fast, and various physical properties such as heat resistance and weather resistance cannot be adjusted after the secondary curing. On the other hand, if the temperature is lower than the above range, it hardly reacts and does not serve the role of primary curing, which is not desirable.

The primary cured product has Mn of 200 to 20000.
And raw material Mn / primary cured product Mn = 1.0 / 1.1 to 1.0
It is preferably /100.0.

The epoxy resin composition according to the present invention can be used for printed boards, various insulating layers, transparent encapsulants, encapsulants such as coils and capacitors and semiconductors, thermosetting paints and coating materials. In particular, the cured product obtained by the curing method of the present invention is excellent in heat resistance, flexibility and the like when used for the above applications.

[0035]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited thereto. In the following, unless otherwise indicated, parts indicate parts by weight and% indicates% by weight. The Mn was measured by GPC with reference to standard polystyrene.

Example 1 All materials such as the cycloaliphatic epoxy resin (a), compound (B) and compound (C) shown in Table 1 were put into a glass sample tube and mixed at room temperature. A resin composition was prepared. This was cast in an aluminum cup and cured at a predetermined temperature to prepare a Tg measurement sample (transparent sealant). In addition, the shear strength was measured by applying a resin composition to an aluminum plate with a bar coater # 8 and laminating the resin composition and curing it as shown in Table 1.

[Examples 2 to 5 and Comparative Examples 1 to 3] As an example of the transparent encapsulant, curing was performed in the same manner as in Example 1 except that various compounds and curing conditions as shown in Table 1 were used. I got a thing.

[0038]

[Table 1]

HBE-100: hydrogenated bisphenol A diglycidyl (manufactured by Shin Nippon Rika) MH-700: methyl hexahydrophthalic anhydride (manufactured by Shin Nippon Rika) SI-100L: sulfonium salt-based cation curing catalyst (manufactured by Sanshin Chemical Co., Ltd.) ) ALCH-TR: Aluminum trisethylacetoacetate (Kawaken Fine Chemicals) PCL-305: Polycaprolactone polyol (Daicel Chemical Industries)

The results of measuring the physical properties of the obtained cured product are shown in Table 1. Glass transition point (Tg) is measured according to JIS
The measurement was performed by TMA (TMA / SS 6000 manufactured by Seiko Denshi) according to K7196. Shear strength is aluminum plate (A1050P)
They were adhered to each other and measured according to JIS 6850.

[Examples 6 to 8 and Comparative Example 3] As an example of the transparent encapsulant, the same procedure as in Example 1 was carried out except that various compounds and curing conditions as shown in Table 2 were used. Obtained. The evaluation results are shown in Table 2.

[0042]

[Table 2]

[Examples 9 to 12 and Comparative Examples 7 to 9] Table 3 shows examples of adhesives, coating materials, encapsulants for electric materials, and encapsulants for printed boards or insulating layers thereof. A cured product was obtained according to various formulations and curing conditions.

[0044]

[Table 3]

EOXA: 3-ethyl-3-hydroxymethyl oxetane (manufactured by Ube Industries) ETHB: epoxidized terrahydrobenzyl alcohol

The results of measuring the physical properties of the obtained cured product are shown in Table 3. Pencil hardness was measured according to JIS K5400. The DuPont impact test was performed according to JIS K5400.
Adhesion was measured by the cross-cut tape method according to JIS K5400.

[0047]

According to the present invention, an adhesive, a coating material, a sealing material for electrical materials, which has excellent heat resistance and flexibility,
A cured product that can be used for the optical semiconductor encapsulant, or the printed circuit board or its insulating layer can be obtained.

Claims (12)

[Claims] 1. An epoxy resin (A) comprising a cycloaliphatic epoxy compound (a) and another epoxy compound (b) optionally added, and a compound (B) reacting with a cationic species optionally added. ), And an epoxy resin composition comprising a compound (C) that generates a cationic species by heating, is cured in two or more stages, and primary curing (curing in the first stage) is performed (a) another epoxy compound (b). When the glycidyl ether type epoxy resin is blended in the epoxy resin (A) in an amount of 0 to 60% by weight, it is carried out at 80 to 110 ° C. A method for curing an epoxy resin composition, comprising: 2. The Mn of the primary cured product is 200 to 20000.
And raw material Mn / primary cured product Mn = 1.0 / 1.1 to 1.0
The method for curing the epoxy resin composition according to claim 1, which is /100.0. 3. The weight ratio of the cycloaliphatic epoxy compound (a) to the other epoxy compound (b) optionally added is such that the epoxy compound (a) / epoxy compound (b) =
The method for curing an epoxy resin composition according to claim 1 or 2, which is 100/0 to 40/60. 4. The epoxy resin composition according to claim 1, wherein the compound (B) is one or more selected from the group consisting of alcohols, oxetanes, vinyl ethers, propenyl ethers, and compounds having a phenolic hydroxyl group. How to cure things. 5. The ratio of epoxy resin (A) to compound (B) is such that epoxy resin (A) / compound (B) = 100/0.
It is 60/40 (weight% ratio), The hardening method of the epoxy resin composition in any one of Claims 1-4. 6. Curing after the secondary curing (curing in the second step) is performed in the case of (a) in claim 1 to 120 to 20.
At 0 ° C., in the case of (b) in claim 1, 100 to
The method for curing an epoxy resin composition according to any one of claims 1 to 5, which is performed at 200 ° C. 7. An epoxy resin (A) comprising a cycloaliphatic epoxy compound (a) and another epoxy compound (b) optionally added, a compound (B) reacting with a cationic species optionally added. ), And a cured product obtained by heating and curing an epoxy resin composition comprising a compound (C) that produces a cationic species by heating. 8. A cured product obtained by the curing method according to claim 1. 9. The cured product according to claim 8, which has a glass transition point of 120 ° C. or higher. 10. An adhesive, a coating material, an encapsulant for electrical materials, an optical semiconductor encapsulant, and one or more applications selected from the group consisting of printed circuit boards or insulating layers thereof. The cured product according to. 11. An epoxy resin (A) comprising a cycloaliphatic epoxy compound (a) and another epoxy compound (b) optionally added, a compound (B) reacting with a cationic species optionally added. ), And a primary cured product having the following physical properties of an epoxy resin composition comprising a compound (C) that generates a cationic species by heating. Molecular weight Mn 200
Ratio of Mn of 20,000 raw materials to Mn of primary cured product 1.
0 / 1.1 to 1.0 / 100.0 12. When (b) a glycidyl ether type epoxy resin as another epoxy compound (b) is added to the epoxy resin (A) in an amount of 0 to 60% by weight, 120 to 2
00 ° C, 100 to 200 except for (b) and (a)
When it is secondarily cured under the condition of ℃, the glass transition point is 120.
The primary cured product of the epoxy resin composition according to claim 11, which gives a cured product at a temperature of not less than ° C.