JPS60243114A - Curable resin composition - Google Patents

Abstract

PURPOSE:The titled composition, consisting of a specific epoxy compound, photopolymerizable compound and thermal polymerization initiator, primarily curable by active rays, e.g. ultraviolet rays, and completely curable by heating, and having improved adhesive property and chemical and water resistance, etc. CONSTITUTION:A curable resin composition obtained by incorporating (A) an epoxy compound having at least two epoxy groups in the molecule with (B) a photopolymerizable compound having one or more carboxyl groups in the molecule, e.g. acrylic acid, methacrylic acid and a compound expressed by the formula (R1 is H or methyl; R2 and R3 are general residue; A is ester bond; m and n are integers 1-3) alone or together with (C) a photopolymerizable compound other than the component (C), and further adding (D) a thermal polymerization initiator, e.g. a peroxy ester or peroxyketal, thereto. The compounding ratio of the components is preferably as follows; 20:80-80:20 weight ratio between the components (A) and the total of the components (B) and (C), and the amount of the component (D) is 0.5-10wt% based on the total of the components (A), (B) and (C).

Description

[Detailed description of the invention] <Industrial application field> The present invention relates to a curable resin composition.

More specifically, the present invention relates to a curable resin composition that is primarily cured by actinic light such as ultraviolet rays and then completely cured by heating.

<Relationship with Prior Art> In recent years, development of ultraviolet curable resins, which are so-called solvent-free resins, has been actively pursued in response to social demands such as resource saving, non-pollution, and safety. However, UV curable resins generally have a fatal flaw in that they cannot be completely cured in areas that are difficult to be irradiated with UV rays or in thick film areas where UV rays do not reach sufficiently.

As an improvement method, there is a known method that uses a combination of ultraviolet curing and thermal curing using an organic peroxide. In this method, the fluidity of the resin is first lost by ultraviolet curing, and then the resin is completely cured by thermal curing with an organic peroxide, and is applied to ultraviolet curing paints and the like. However, since organic peroxides are usually used in this method, 1) storage stability is poor, 2) adhesion is poor, 3) resin tends to foam during heat curing, and 4) due to oxygen in the air. It has many disadvantages such as inhibited curing.

As a result of extensive research in order to resolve the defects of conventional ultraviolet curable resins, the present inventors have developed a photopolymerizable compound containing an epoxy compound and a photopolymerizable compound having a carboxyl group in the molecule. It was discovered that the above-mentioned defects of conventional ultraviolet curable resins could be solved by a curable resin composition, and the authors proposed it earlier (Japanese Patent Application Laid-Open No. 59-4301).
No. 5). However, although this curable resin composition has excellent curability in thick parts and adhesion to various substrates compared to conventional ultraviolet curable resins, it has It was found that there remained some problems in curability when completely shielded from light.

<Purpose of the Invention> Therefore, the present inventors have found that a completely cured product can be obtained even in a state where active rays such as ultraviolet rays are completely blocked, and that the product also has adhesive properties, chemical resistance, water resistance, and electrical insulation properties. As a result of further intensive research in order to obtain a curable resin composition with excellent performance such as and/or by adding a thermal polymerization initiator selected from peroxyketals, it is possible to obtain a curable resin composition that can be completely cured even when active rays such as ultraviolet rays are completely blocked. We have finally arrived at the present invention.

<Detailed Description of the Invention> That is, the present invention provides an epoxy compound (A) having at least two epoxy groups in the molecule, a photopolymerizable compound (B) having a carboxyl group in the molecule, or the compound (B)
and another photopolymerizable compound (C), and a thermal polymerization initiator selected from peroxyesters and peroxyketals.

The epoxy compound (5) having at least two epoxy groups in the molecule used in the present invention is an epoxy compound having two or more epoxy groups in one molecule, and its epoxy equivalent is 100 to 4000, preferably 100-10
It is 00.

Typical compounds include bis7 ether type epoxy resins, which are diglycidyl ethers such as bisphenol A, bisphenol F, and halogenated bisphenol A; and novolac type epoxy resins, which are polyglycidyl ethers such as phenol novolak and cresol novolak. Polyglycidyl ethers of dihydric or higher polyhydric phenols represented by resins, dihydric phenols such as ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, l,6-hexanediol, trimethylolpropane, etc. Examples include polyglycidyl ethers of the above-mentioned polyhydric alcohols. These epoxy compounds can be used alone or in combination of two or more.

Further, epoxy compounds having one epoxy group in the molecule such as allyl glycidyl ether and phenyl glycidyl ether can also be used in combination.

Among these epoxy compounds having at least two epoxy groups in the molecule, preferred epoxy compounds include bisphenol A type epoxy compounds, phenol novolak type polyepoxy compounds, and talesol novolak type polyepoxy compounds.

Examples of the photopolymerizable compound (B) having one or more carboxyl groups in the molecule used in the present invention include (1)
Acrylic acid, methacrylic acid, itaconic acid, crotonic acid,
Unsaturated carboxylic acid compounds such as fumaric acid and (11)
There is a compound represented by the following general formula (I).

1 (CH2=CCOO+ThI(R2+A÷R3HCOO
H). ...σ) (In the formula, R1 represents hydrogen or a methyl group, R2 and R3 each represent an aliphatic, aromatic, or alicyclic residue, A represents an ester bond, and m and n each represent Indicates a positive integer of 1 to 3.) In the general formula (I), R2 is preferably a divalent to tetravalent hydrocarbon group having 2 to 1 carbon atoms or a hydroxyl group-containing hydrocarbon group, and R3 has 2 to 1 carbon atoms
0 di- to tetravalent aliphatic polybasic acid residue, carbon number 6
It is preferable that it is a di- to tetravalent aromatic polybasic acid residue having a valence of ~15 or a di- to tetravalent alicyclic polybasic acid residue having a carbon number of 6 to 1 o.

Examples of the compound represented by the general formula (I) include the following compounds.

Examples of the compound where m=1 and n=1 include succinic acid mono(meth)acryloyloxyethyl ester, -
(Indicates acryloyloxyethyl ester and methacryloyloxyethyl ester.

The same abbreviations are given below. ) Phthalic acid mono(meth)acryloyloxyethyl ester, maleic acid mono(meth)acryloyloxyethyl ester, tetrahydrophthalic acid mono(meth)acryloyloxyethyl ester,
Hexano\hydrophthalic acid mono(meth)acryloyloxyethyl ester, endo-bicyclo(2.2.1)
-s-hebutene-2,3-dicarboxylic acid mono(meth)acryloyloxyethyl ester, tetrahydrophthalic acid mono-2-(meth)acryloyloxy-1-(phenoxymethyl)ethyl ester, phthalic acid mono-2-
Hydroxy-3-(meth)acryloyloxypropyl ester, cono-mono-2-hydroxy-3-(meth)acryloyloxypropyl ester, and the like.

Examples of the compound where m=1 and n=2 include trimellitic acid mono-2-(meth)acryloyloxyethyl ester. Examples of the compound where m-1 and n=3 include pyromelli, nodic acid mono-2'-(meth)acryloyloxyethyl ester, and the like.

Examples of the compound where m, = 2, n = 1 include phthalic acid mono-[2,3-bis(meth)acryloyloxyisopropyl] ester, methyltetranohydrophthalic acid mono-(2,3-bis(meth)acryloyl) oxyisopropyl] ester, tetrahydrophthalic acid mono-[
2,3-bis(meth)acryloyloxyisopropyl] ester, conollic acid mono-[2,3-bis(meth)
Examples include acryloyloxyisopropyl ester.

Examples of the compound where m == 2 and n = 2 include trimellitic acid mono-[4,5-bis(meth)acryloyloxyneopentyl] ester, trimellitic acid mono-
(3,4-bis(meth)acryloyloxypropyl ester, etc.)

Examples of the compound where m = 3 and n = 2 include trimellitic acid mono-[3,4,5-tris(meth)acryloyloxyneopentyl] ester.

Examples of the compound where m=3 and n=3 include pyromellitic acid mono-[3,4,5-)lis(meth)acryloyloxyneopentyl]ester.

Among the above-mentioned compounds, as the photopolymerizable compound (B),
Particularly preferred is (11). These photopolymerizable compounds (B) having a carboxyl group in the molecule can be used alone or in combination of two or more, or in combination with one or more of the other photopolymerizable compounds (C) described below. used.

The amount of the photopolymerizable compound (B) containing one or more carboxyl groups in the molecule in the photopolymerizable compound (B+C) used in the present invention is 10 to 10% by weight. If the amount is less than 10% by weight, the curability of the resulting resin composition will be significantly poor.

The photopolymerizable compound (C) used in the present invention has 1
It is a photopolymerizable compound having one or more photopolymerizable double bonds.

Examples of photopolymerizable compounds having one photopolymerizable double bond in the molecule include (1) methyl (meth)acrylate, ethyl (meth)acrylate, n- and l-
Propyl (meth)acrylate, n-5ec- and t
-Butyl (meth)acrylate, 2-ethylhexyl (
meth)acrylate, lauryl(meth)acrylate,
Alkyl (meth)acrylates such as, hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, or polyoxyalkylene glycol mono(meth)acrylate such as polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, etc. (meth)acrylates, heterocycle-containing (meth)acrylates such as tetrahydrofurfuryl (meth)acrylate, aminoalkyl (meth)acrylates such as dimethylaminoethyl (meth)acrylate, diethylamide/ethyl (meth)acrylate, etc. , (11) mono(meth)acrylates of alkylene oxide adducts of bisphenol A such as ethylene oxide and propylene oxide adducts of bisphenol A, (iiD diisocyanate compound and one or more alcoholic hydroxyl group-containing compound reacted in advance) urethane-modified mono(meth)acrylates having one (meth)acryloyloxy group in the molecule obtained by reacting the terminal incyanate group-containing compound obtained by further reacting with an alcoholic hydroxyl group-containing (meth)acrylate; 6■) Epoxy mono(meth)acrylates obtained by reacting acrylic acid or methacrylic acid with a compound having one or more epoxy groups in the molecule, and (■) acrylic acid or methacrylic acid as a carboxylic acid component and Orico is obtained by reacting a polyhydric carboxylic acid with a dihydric or higher polyhydric alcohol as an alcohol component.

These include ester mono(meth)acrylates.

Examples of photopolymerizable compounds having two photopolymerizable double bonds in the molecule include (1) ethylene glycol di(meth)acrylate, brobylene glycol di(meth)acrylate, 1,4- Alkylene glycol di(meth)acrylates such as butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanethiol di(meth)acrylate, diethylene glycol di(meth)acrylate,
Polyoxyalkylene glycol di(meth)acrylates such as triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, (i
i) di(meth)acrylates of alkylene oxide adducts of bisphenol A, such as ethylene oxide and propylene oxide adducts of bisphenol A; (ii)
i) A terminal inocyanate group-containing compound obtained by reacting a diisocyanate compound and two or more alcoholic hydroxyl group-containing compounds in advance, and further reacting an alcoholic hydroxyl group-containing (meth)acrylate, resulting in two groups in the molecule. urethane-modified di(meth)acrylates having (meth)acryloyloxy groups; ) acrylates, (■) oligoester di(meth)acrylates obtained by reacting acrylic acid or methacrylic acid or polycarboxylic acid as a carboxylic acid component with a polyhydric alcohol of dihydric or higher valence as an alcohol component, etc. .

Examples of photopolymerizable compounds having three or more photopolymerizable double bonds in the molecule include (+))'J methylolpropane tri(meth)acrylate, trimethylolethane(meth)acrylate, penta Poly(meth)acrylenides of trihydric or higher aliphatic polyhydric alcohols such as erythritol tetra(meth)acrylate, (it)
A terminal inocyanate group-containing compound obtained by reacting a diisocyanate compound and a compound containing three or more alcoholic hydroxyl groups in advance is further added with an alcoholic hydroxyl group-containing compound (
Urethane-modified poly(meth)acrylates having three or more (meth)acryloyloxy groups in the molecule obtained by reacting meth)acrylates, (acrylic acid in compounds having three or more epoxy groups in the HD molecule) or/
and epoxy poly(meth)acrylates obtained by reacting methacrylic acid.

The blending ratio of the epoxy compound (A) used in the present invention and the photopolymerizable compound having a carboxyl group in the molecule (color) or (B) and another photopolymerizable compound (C) is epoxy, Compound (4): Photopolymerizable compound [(B)
Or) + (C)] = 1o: 90~9゛0:10
(weight ratio), preferably the epoxy compound (
A): Photopolymerizable compound [(B) or (B)+(C)
) -=20:80 to 80:20 (weight ratio). If the amount of the epoxy compound (4) is less than 10% by weight, the reaction between the photopolymerizable compound (B) having a carboxyl group in the molecule and the epoxy compound (A) will be substantially too small, resulting in poor adhesiveness. , it is difficult to obtain a cured product with excellent heat resistance. In addition, the blending amount of the epoxy compound (4) was 9
If it exceeds 0% by weight, the curable resin composition will have a high viscosity and will be difficult to handle, and will not be able to take advantage of the advantage of curing reaction with actinic rays, that is, rapid curing.

The thermal polymerization initiator (1) used in the present invention is a compound selected from peroxyester acids and peroxyketals. Only these two types of organic peroxides are effective, and even if other organic peroxides are used, the curability of the light-shielding part is not sufficient.

Peroxy esters include t-butyl leno-oxyacetate, t-butyl peroxyisobutyrate,
t-Butylperoxyoctoate, t-butylperoxy 3,5.5-)dimethyl hexa/ate, t-butylperoxylaurate, -butylperoxybenzoate, di-t-butylciba-oxyisophthalate , 2,5-dimethyl=2,5-di(benzoylperoxy)hexane, t-butylperoxyimprobyl carbonate, etc., and peroxyketals include 1,1-bis(t-butylperoxy). 3,3.5
) dimethylcyclohexane, 1,1-bis(1-butylperoxy)cyclohexane, 2,2-bis(t-
butylperoxy)octane, n-butyl-4,4-bis(t-butylperoxy)nochlorate, 2゜2-bis(1-butylperoxy)butane, etc., used singly or in combination of two or more. Used in combination.

The amount of this thermal polymerization initiator (D) is the same as that of the epoxy compound (A).
) and the photopolymerizable compound in an amount of 0.05 to 5% by weight, preferably 0.1 to 3% by weight.

If the amount of the thermal polymerization initiator) is less than 0.05% by weight, the curability of the light-shielding portion will decrease, making it difficult to obtain a completely cured product.

Furthermore, when the blending amount of the thermal polymerization initiator () exceeds 5% by weight, the curability decreases, making it difficult to obtain a completely cured product, and at the same time, foaming and coloring of the resin become significant during heating.

be.

Examples of photoinitiators include ketals such as benzyl dimethyl ketal, benzoins such as benzoin methyl ether, benzoin ethyl ether, benzoin-i-propyl ether, benzoin, and α-methylbenzoin, 9110-anthraquinone, and 1-chloroanthraquinone. , anthraquinones such as 2-chloroanthraquinone and 2-ethylanthraquinone, benzophenone, p
-benzophenones such as chlorbenzophenone, p-dimethylamine benzophenone, 2-hydroxy-2-
Propiophenones such as methylpropiophenone, 1-(4-isobropylphenyl)-2-hydroxy-2-methylpropiophenone, suberones such as dibenzosuberone, diphenyl disulfide, tetramethylthiuram disulfide, thioxanthone, etc. Examples include sulfur-containing compounds, and pigments such as methylene blue, eosin, and fluorescein, which may be used alone or in combination of two or more.

- The amount of the photoinitiator is 0.05 to 20% by weight, preferably 0.5 to 10% by weight, based on the total amount of the epoxy compound (A) and the photopolymerizable compound.

In the present invention, if it is necessary to promote the reaction between the epoxy group and the carboxyl group, it is effective to add a reaction promoter. Examples of the reaction accelerator include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, and ■-benzy-2-methylimidazole, benzyldimethylamine, triethanolamine, N, Tertiary compounds such as N-dimethylaminoethanol, I'tLN-diethylaminoethanol, N,N-dipropylaminoethanol, etc.
amines, and tertiary amine salts such as triacetate and tribenzoate of tridimethylaminomethylphenol, which may be used alone or in combination of two or more.

The amount of these reaction accelerators added is 0.05 to 5% by weight, preferably 0.1 to 3.5% by weight, based on the total amount of the epoxy compound (A) and the photopolymerizable compound.

The curable resin composition of the present invention is easily produced by stirring and mixing at room temperature or under heating if necessary. In order to prevent thermal polymerization during production and dark reactions during storage, known agents such as hydroquinone, hydroquinone monomethyl ether, l-butyl-catechol, p-henzoquinone, 2.5-t-butyl-hydroquimene, and phenothiazine are used. It is desirable to add a thermal polymerization inhibitor. The amount added is 0.001 to 0.1% by weight, preferably 0.001 to 0.05% by weight, based on the photopolymerizable compound used in the present invention.

In addition to the above-mentioned additives, various additives such as known colorants, surface smoothing agents, antifoaming agents, etc. can be added to the curable resin composition of the present invention, if necessary.

The method for curing the curable resin composition of the present invention is to first cure the photopolymerizable compound C having a carboxyl group by irradiation with actinic rays.
B) or a mixture of (B) and another photopolymerizable compound (C) is polymerized to obtain a carboxyl group-containing polymer, and then the epoxy compound (4) and the carboxyl group contained in the above polymer are reacted by heating. It consists of two steps: allowing it to harden completely.

The photopolymerization reaction conditions include a light amount of 20 mW/ca~2
The time is preferably 0.1 seconds to 5 minutes at 00 mW/crl.

The thermosetting reaction conditions are preferably 40°C to 250°C and 10 seconds to 120 minutes.

The curable resin composition of the present invention is irradiated with actinic light such as ultraviolet rays and electron beams to induce a polymerization reaction.

Light sources used for ultraviolet irradiation include sunlight, chemical lamps, low-pressure mercury lamps, high-pressure mercury lamps, carbon arc lamps,
Xenon lamps, metallized lamps, etc. are used. A photoinitiator is not necessarily required when irradiating with an electron beam.

As the heat source used for heating, for example, known heating methods such as an infrared heater, hot air heating, and high frequency heating are used.

<Effects of the Invention> The curable resin composition of the present invention is essentially different from ultraviolet curable resin compositions or conventional ultraviolet thermosetting resin compositions that use both ultraviolet curing and thermal curing using an organic peroxide. The final cured product is cured by a curing reaction and has excellent properties such as adhesiveness, chemical resistance, water resistance, transparency, and electrical insulation.

Particularly excellent effects of the present invention include the following points.

1) By using the thermal polymerization initiator of the present invention), it is possible to obtain a completely cured resin even in thick parts that are difficult to irradiate with actinic rays such as ultraviolet rays or in parts that are completely shielded from light. In addition, it has fast curing properties, which is a feature of ultraviolet curable resins.

2) Epoxy compound and photopolymerizable compound (B) or (
The mixture of B) and 2) has good compatibility, and the viscosity of the resin composition can be adjusted freely.

3) When a large amount of filler is mixed or even in thick parts, the fluidity of the resin will be lost in a very short time due to ultraviolet irradiation, so it can be moved to the next process immediately, and the conventional It is possible to greatly improve productivity compared to thermosetting resins or ultraviolet thermosetting resins.

4) The resin composition of the present invention also has excellent adhesion to various plastics, ceramics, glass, metals, etc.

Taking advantage of these advantages, the curable resin composition of the present invention can be used for IC1LS, diodes, thyristors, biralid ICs, resistors, capacitors, light emitting diodes, liquid crystal display elements, optical sensors, pressure sensors, humidity sensors, etc. Used for sealing and coating electronic components. It can also be used in fields such as paints, inks, and adhesives.

<Examples> Examples will be given below to specifically explain the present invention, but the present invention is not limited to these Examples in any way.

In the examples, parts and % indicate parts by weight and % by weight, respectively. The resin properties of the curable resin composition and the performance of the cured product were measured by the following method.

1) Viscosity: Measured at 25°C using a Brookfield viscometer according to JIS K 6901.

2) Hardness: Barcol hardness was measured according to JIS K 6919.

3) Chemical resistance: immerse the cured product in various reagents at 25°C,
After 4 hours, the presence or absence of any abnormality in appearance was determined.

4) Adhesion: Measured by peeling off cellophane tape [test].

5) Water resistance: The cured product was immersed in boiling water for 60 minutes, and the presence or absence of any abnormality in appearance was determined.

6) Light transmittance: The light transmittance of the three cured products was measured at a wavelength of 700 nm using a new model 124 spectrophotometer manufactured by Hitachi.

7) Electrical insulation: A casting board with a thickness of 3 mm was prepared according to JIS K6911, and the volume resistivity was measured.

Example 1 Epicote 1, a bisphenol A type epoxy compound
001 (manufactured by Yuka Shell Epoxy Co., Ltd.) lo.

Part, succinic acid monoacryloyloxyethyl ester 4
8 parts and te) lahydrofurfuryl acrylate 70
A portion of the mixture was placed in a stirring vessel and mixed and stirred at 80°C to obtain a transparent resin composition (1). The resulting resin composition (1) had a viscosity of 15 voids. This resin composition (1) 100
0.5 parts of t-butylperoxybenzoate as a thermal polymerization initiator, and 0.5 parts of 2-hydroxybenzoate as a photoinitiator.
A curable resin composition (a) of the present invention was obtained by blending 0.5 part of 2-methylpropiophenone and 0.5 part of N,N-diethylaminoethanol as a curing accelerator. Next, the obtained resin composition (
After injecting a), half of the glass plate was covered with aluminum foil to completely block light, and then 80 mw/ (yi
It was irradiated with ultraviolet rays for 42 seconds, and then heated at 120° C. for 30 minutes to produce a casting plate with a length of 10 c1 ns, a width of 10 crns, and a thickness of 3 cm.

Table 1 shows the performance of the exposed and light-shielding parts of the obtained casting plate.

Table 1 Example 2, Comparative Example 1.2 Bisphenol A type epoxy compound Ebico) 8
95 parts of No. 28 (manufactured by Yuka Shell Epoxy Co., Ltd.) and 108 parts of monoacryloyloxyethyl succinate were placed in a stirring vessel, and mixed and stirred at room temperature to obtain a transparent resin composition (2). The resulting resin composition (2) had a viscosity of 12 voids. To 100 parts of this resin composition (2), 0.5 part of benzyl dimethyl ket/l' as a photoinitiator and 0.5 part of benzyl dimethylamine as a curing accelerator were blended,
Furthermore, in Example 2, 1.1-bis(1
-butylperoxy)3.3.5-)limethylcyclohexane in 1. Om, in Comparative Example 1, 1.0 part of cyclohexane peroxide was blended as a thermal polymerization initiator, and in Comparative Example 2, 1.0 part of methyl ethyl ketone peroxide was blended as a thermal polymerization initiator to form a curable resin composition (b) (c
) (d) was obtained.

Next, in the same manner as in Example 1, a resin composition (b) was obtained between two glass plates sandwiching a spacer with a thickness of 3 mm.
(c) After each of (a) was injected and half of the glass plate was shielded from light, it was irradiated with ultraviolet rays of 80 mw/ca for 42 seconds, then heated at 120°C for 30 minutes, and was heated to 10 Iyn vertically and horizontally. A casting plate with a thickness of 10cn1 and a thickness of 3 stages was produced. Table 2 shows the performance of the exposed and light-shielding parts of the casting plate obtained.

Table 2 ★ Plane ratio Examples 3 to 7, Comparative Example 3.4 Epicor (bisphenol A type epoxy compound) 8
28 (manufactured by Yuka Shell Epoxy Co., Ltd.) 38 parts, succinic acid monoacryloyloxyethyl ester 22 parts, bisphenol A ethylene oxide 4 mol addition diacrylate 5
0 parts were placed in a stirring container and mixed and stirred at room temperature to obtain a transparent resin composition (3). The resulting resin composition (3) had a viscosity of 13 voids. This resin composition (3) 100
20.5 parts of 2-hydroxy-2-methylpropiophenone as a photoinitiator, 0.5 parts of N,N-diethylamine ethanol as a curing accelerator, and t-butylperoxybenzoate or 1,0% as a thermal polymerization initiator. Curable resin compositions (e) to (k) were obtained by blending 0.02 to 8 parts of 1-hys(t-butylperoxy)-3,3,5-)limethylcyclohexane. Next, in the same manner as in Example 1, the obtained resin compositions (e) to (k) were injected between two glass plates sandwiching a spacer with a thickness of 3 mm, and then half of the glass plates were shielded from light and heated to 80 mm. It was irradiated with ultraviolet rays of mw/crl for 42 seconds, and then heated at 120°C for 30 minutes to produce a casting plate with a length of 10α, a width of 10 crn, and a thickness of 3 cm. Table 3 shows the performance of the exposed and light-shielding parts of the obtained casting plate.

Example 8 Bisphenol A type epoxy compound Epi2) 1
001 (manufactured by Yuka Shell Epoxy Co., Ltd.), 50 parts of phthalic acid monoacryloyloxyethyl ester, and 70 parts of tetrahydrofurfuryl acrylate were placed in a stirring container, mixed and stirred at 80°C, and a transparent resin composition (4) was prepared. Obtained. The resulting resin composition (4) had a viscosity of 47 voids. 0 parts of 2-hydroxy-2-methylpropiophenone as a photoinitiator per 100 parts of this resin composition (4).
．． A curable resin composition (1) of the present invention was obtained by blending 5 parts of N,N-diethylaminoethanol as a curing accelerator and 1.0 part of t-butyl peroxybenzoate as a thermal polymerization initiator. . Next, a cast plate was obtained which was subjected to ultraviolet ray irradiation and heating in the same manner as in Example 1. Table 4 shows the performance of the exposed and light-shielding parts of the obtained casting plate.

Next, using the curable resin composition (1) of the present invention, screen printing was performed on various substrates to a size of 5 Crn x 5 cm (thickness: approximately 20 μm), half of the printed matter was shielded from light, and
irradiated with ultraviolet light of mw/crl for 42 seconds, then 1
After heating at 20°C for 30 minutes, adhesion to various substrates was evaluated. The results obtained are shown in Table 5.

4th Table 1 Table 5, Comparative Examples 5 to 8 0.5 part of 2-hydroxy-2-methylpropiophenone as a photoinitiator per 100 parts of the resin composition (4) prepared in Example 8, cured A curable resin composition 6Tl was prepared by blending 0.5 parts of N,N-diethylamide/ethanol as an accelerator.
) was obtained. Next, for Comparative Examples 5 to 8, 1.0 part of each of the thermal polymerization initiators shown in Table 5 was added, and cast plates were obtained by irradiating ultraviolet rays and heating in the same manner as in Example 1. Table 6 shows the performance of the exposed and light-shielding parts of the obtained casting plate.

Table 6

Claims (1)

[Claims] An epoxy compound (5) having at least two epoxy groups in the molecule, a photopolymerizable compound (8) having a carboxyl group in the molecule, or a mixture of this compound (B) and another photopolymerizable compound (C) and a thermal polymerization initiator selected from peroxyesters and peroxyketals.