JPH0236128B2 - TEISHUSHUKUSEIKOKAGATAJUSHISOSEIBUTSU - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a low-shrinkage curable resin composition, and more particularly to a low-shrinkage curable resin composition that is cured by actinic light such as ultraviolet rays and then completely cured by heating. In order to solve the defects of conventional ultraviolet curable resins and thermosetting resins, the present inventors developed a photopolymerizable compound containing an epoxy compound and a photopolymerizable compound having a carboxyl group in the molecule, and a photoinitiator. We have already proposed a curable resin composition consisting of the following (Japanese Patent Application No. 152936/1983). However, this curable resin composition is extremely superior in rapid curing and workability compared to conventional thermosetting resins.
In addition, compared to conventional ultraviolet curable resins, it was extremely superior in terms of hardening of thick film parts and adhesion to various base materials, which could be called revolutionary, but the shrinkage of the cured resin was It turned out that some problems remained. In general, UV-curable resins have the disadvantage of large curing shrinkage, and therefore, for example, IC, LSI, etc.
When encapsulated and hardened into electronic components such as diodes, capacitors, relays, and switches, there are problems such as increased internal residual stress and destruction of the encapsulated elements. Although the shrinkage of the above-mentioned curable resin composition is lower than that of conventional ultraviolet curable resins, the present inventors have found that it has even lower shrinkage, and also has good adhesion, chemical resistance, As a result of intensive research to obtain a low-shrinkage curable resin composition with excellent properties such as water resistance and electrical insulation, we were able to create the desired low-shrinkage curable resin composition by incorporating saturated polyester resin. The present invention was achieved based on the discovery that the following can be obtained. 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 a combination of the compound (B) and another photopolymerizable compound ( C) mixture with
This is a low-shrinkage curable resin composition comprising a curable resin comprising a photoinitiator and a saturated polyester resin soluble in the curable resin. When the low-shrinkage curable resin composition of the present invention is irradiated with actinic rays such as ultraviolet rays, the fluidity of the resin disappears within a very short time, so it requires much more work than conventional thermosetting resins. In addition, it is possible to cure thick materials with a thickness of 10 mm or more, which was impossible with conventional UV-curable resins alone, and it also significantly reduces curing shrinkage, which was considered a drawback. By using the low-shrinkage curable resin of the present invention, it is possible to solve various defects that have hitherto existed in thermosetting resins and ultraviolet curable resins. It became. Curing of the low shrinkage curable resin composition of the present invention is carried out by
First, a photopolymerizable compound (B) having a carboxyl group in the molecule or this compound (B) and another photopolymerizable compound
A reaction in which the mixture with (C) is polymerized by irradiation with actinic rays to form a carboxyl group-containing polymer, and then,
2. A reaction in which the epoxy compound (A) reacts with the carboxyl group-containing polymer and is completely cured by heating.
At the same time, a saturated polyester resin is uniformly dissolved in a curable resin composition.
(D) imparts low shrinkage properties, and this type of curing reaction is essentially different from the conventional curing reaction using ultraviolet light alone or the curing reaction using UV curing in combination with a thermosetting reaction using an organic peroxide. These are different curing methods. The completely cured product obtained from the low shrinkage curable resin composition of the present invention has low shrinkage properties, adhesive properties, chemical resistance,
It has excellent performance such as water resistance and electrical insulation.
Furthermore, as a curable resin composition, it has the great advantage of being excellent in storage stability. The epoxy compound (A) 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 It is 100-1000. Representative compounds include bisphenol A,
Bisphenol F, halogenated bisphenol A
Representative examples include bisphenol type epoxy resins, which are diglycidyl ethers such as 2, and novolac type epoxy resins, which are polyglycidyl ethers such as phenol novolak and cresol novolak.
polyglycidyl ethers of polyhydric phenols with a valence of more than 2, polyhydric alcohols with a valence of 2 or more such as ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, etc. Polyglycidyl ethers of phthalic acid, isophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, polyglycidyl esters of divalent or higher polycarboxylic acids such as adipic acid, aniline, isocyanuric acid, etc. polyglycidyl ethers in which the active hydrogen is substituted with a glycidyl group, vinylcyclohexene diepoxide obtained by epoxidizing the olefin bond in the molecule, 3,4-epoxycyclohexylmethyl-
3,4-epoxycyclohexanecarboxylate, 2-(3,4-epoxy)cyclohexyl-
Alicyclic polyepoxy compounds such as 5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane, N,N,N',N'-tetraglycidylmethaxylene diamine, N,N,N', Examples include aminopolyepoxy compounds such as N'-tetraglycidyl-1,3-bis(aminomethyl)cyclohexane. These epoxy compounds can be used alone or in combination of two or more. In addition, one epoxy group is added in the molecule of allyl glycidyl ether, phenyl glycidyl ether, etc.
It can also be used in combination with its own epoxy compounds. Among these epoxy compounds having at least two epoxy groups in the molecule, preferred epoxy compounds include diglycidyl ether of bisphenol A, phenol novolak type polyepoxy compounds, and cresol novolak type polyepoxy compounds. can give. Examples of the photopolymerizable compound (B) having one or more carboxyl groups in the molecule used in the present invention include (i) acrylic acid, methacrylic acid, itaconic acid,
There are unsaturated carboxylic acid compounds such as crotonic acid and fumaric acid, and (ii) compounds represented by the following general formula (). (In the formula, R ₁ represents hydrogen or a methyl group, R ₂ and R ₃ each represent an aliphatic, aromatic, or alicyclic residue, A represents an ester bond, and m and n each represent 1 to 1. Indicates a positive integer of 3.) In the general formula (), R ₂ is a carbon atom number of 2 to
10, or a hydroxyl group-containing hydrocarbon group, and R ₃
is a di- to tetravalent aliphatic polybasic acid residue having 2 to 10 carbon atoms, a di- to tetravalent aromatic polybasic acid residue having 6 to 15 carbon atoms, or a residue having 6 to 10 carbon atoms. Preferably, it is a certain di- to tetravalent alicyclic polybasic acid residue. Examples of the compound represented by the general formula () include the following compounds. Examples of the compound where m=1 and n=1 include succinic acid mono(meth)acryloyloxyethyl ester (acryloyloxyethyl ester and methacryloyloxyethyl ester).
The rest will be abbreviated in the same way. ), phthalic acid mono(meth)acryloyloxyethyl ester, maleic acid mono(meth)acryloyloxyethyl ester,
Tetrahydrophthalic acid mono(meth)acryloyloxyethyl ester, hexahydrophthalic acid mono(meth)acryloyloxyethyl ester, endo-bicyclo(2.2.1)-5-heptene-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, succinic acid mono-
Examples include 2-hydroxy-3-(meth)acryloyloxypropyl ester. 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 pyromellitic acid mono-2-(meth)acryloyloxyethyl ester. Examples of compounds where m=2 and n=1 include phthalic acid mono-[2,3-bis(meth)acryloyloxyisopropyl] ester, methyltetrahydrophthalic acid mono-[2,3-bis(meth)
Examples include acryloyloxyisopropyl] ester, tetrahydrophthalic acid mono-[2,3-bis(meth)acryloyloxyisopropyl] ester, and succinic acid mono-[2,3-bis(meth)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)acryloyloxyisobutyl] ] Esters, 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-tris(meth)acryloyloxyneopentyl] ester. As the photopolymerizable compound (B), among the above-mentioned compounds, compound (ii) is particularly preferable. 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 100% by weight. If the amount is less than 10% by weight,
The resulting resin composition has significantly poor curability. The photopolymerizable compound (C) used in the present invention is a photopolymerizable compound having one or more photopolymerizable double bonds in the molecule. Examples of photopolymerizable compounds having one photopolymerizable double bond in the molecule include (i) styrene, α
- Styrenic compounds such as methylstyrene and chlorostyrene, (ii) methyl (meth)acrylate,
Ethyl (meth)acrylate, n- and i-propyl (meth)acrylate, n-, sec- and t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate Alkoxyalkyl (meth)acrylates such as methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, etc.
Allyloxyalkyl (meth) such as acrylates
acrylates, hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, halogen-substituted alkyl (meth)acrylates, or polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, etc. Substituted alkyl mono(meth)acrylates such as oxyalkylene glycol mono(meth)acrylates or alkoxypolyoxylalkylene mono(meth)acrylates, heterocycle-containing (meth)acrylates such as tetrahydrofurfuryl (meth)acrylate, (iii) )Bisphenol A
mono(meth)acrylates of alkylene oxide adducts of bisphenol A, such as ethylene oxide and propylene oxide adducts; alkylene oxide adducts of hydrogenated bisphenol A, such as ethylene oxide and propylene oxide adducts of hydrogenated bisphenol A; Things (meta)
Acrylates, (iv) diisocyanate compound and 1
One (meth)acryloyloxy group in the molecule obtained by further reacting a terminal isocyanate group-containing compound obtained by preliminarily reacting two or more alcoholic hydroxyl group-containing compounds with an alcoholic hydroxyl group-containing (meth)acrylate. (v) epoxy mono(meth)acrylates obtained by reacting a compound having one or more epoxy groups in the molecule with acrylic acid or methacrylic acid, and (vi) Acrylic acid or methacrylic acid and polyhydric carboxylic acid as carboxylic acid component and 2 as alcohol component
There are oligoester mono(meth)acrylates obtained by reacting polyhydric alcohols with higher valences. Examples of photopolymerizable compounds having two photopolymerizable double bonds in the molecule include (i) ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di (meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-
Alkylene glycol di(meth)acrylates such as hexanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate , polypropylene glycol di(meth)
Polyoxyalkylene glycol di(meth)acrylates such as acrylates, substituted alkylene glycol di(meth)acrylates such as halogen-substituted alkylene glycol di(meth)acrylates, (ii) ethylene oxide and propylene oxide adducts of bisphenol A, etc. di(meth)acrylates of alkylene oxide adducts of bisphenol A, di(meth)acrylates of alkylene oxide adducts of hydrogenated bisphenol A, such as ethylene oxide and propylene oxide adducts of hydrogenated bisphenol A; iii) A terminal isocyanate group-containing compound obtained by reacting a diisocyanate compound and two or more alcoholic hydroxyl group-containing compounds in advance is further reacted with an alcoholic hydroxyl group-containing (meth)acrylate; Epoxy di(meth)acrylates obtained by reacting urethane-modified di(meth)acrylates having (meth)acryloyloxy groups, (iv) compounds having two or more epoxy groups in the molecule with acrylic acid and/or methacrylic acid. Acrylates, (v) oligoester di(meth) obtained by reacting acrylic acid or methacrylic acid and polyhydric carboxylic acid as the carboxylic acid component with a polyhydric alcohol of dihydric or higher valence as the alcohol component
There are acrylates, etc. Examples of photopolymerizable compounds having three or more photopolymerizable double bonds in the molecule include (i) trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate,
Poly(meth)acrylates of trivalent or higher aliphatic polyhydric alcohols such as pentaerythritol tetra(meth)acrylate, poly(meth)acrylates of trivalent or higher halogen-substituted aliphatic polyhydric alcohols, (ii) diisocyanate compounds A terminal isocyanate group-containing compound obtained by reacting a compound containing three or more alcoholic hydroxyl groups in advance with a (meth)acrylate containing an alcoholic hydroxyl group has three or more (meth)acryloyl groups in the molecule. Urethane-modified poly(meth)acrylates having an oxy group, (iii) epoxy poly(meth)acrylates obtained by reacting a compound having three or more epoxy groups in the molecule with acrylic acid or/and methacrylic acid, etc. There is. Epoxy compound (A) used in the present invention and the above photopolymerizable compound having a carboxyl group in the molecule
The blending ratio of (B) or a mixture of (B) and another photopolymerizable compound (C) is epoxy compound (A):photopolymerizable compound [(B) or (B) + (C)] = 10 :90 to 90:10 (weight ratio), preferably epoxy compound (A):photopolymerizable compound [(B) or (B) + (C)] = 20:80 to 80:20
(weight ratio). If the amount of the epoxy compound (A) 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 cured products with excellent chemical resistance. Also,
If the amount of the epoxy compound (A) exceeds 90% 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, fast curing. do not have. The photoinitiator used in the present invention is a compound that promotes the photopolymerization reaction of a photopolymerizable compound, and includes, for example, ketals such as benzyl dimethyl ketal, benzoin methyl ether, benzoin ethyl ether, and benzoin-i-propyl ether. , benzoin, benzoins such as α-methylbenzoin, 9,10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone,
Anthraquinones such as 2-ethylanthraquinone, benzophenones such as benzophenone, p-chlorobenzophenone, p-dimethylaminobenzophenone, 2-hydroxy-2-methylpropiophenone, 1-(4-isopropylphenyl) Propiophenones such as -2-hydroxy-2-methylpropiophenone, suberones such as dibenzosuberone, diphenyl disulfide,
Sulfur-containing compounds such as tetramethylthiuram disulfide and thioxanthone, methylene blue,
Examples include pigments such as eosin and fluorescein, which may be used alone or in combination of two or more. In the present invention, the amount of this photoinitiator is based on the total amount of the epoxy compound (A) and the photopolymerizable compound.
The amount is 0.05 to 20% by weight, preferably 0.5 to 10% by weight. In the present invention, when it is necessary to promote the reaction between an epoxy group and a carboxyl group, it is effective to add a reaction promoter. As a reaction accelerator,
For example, 2-methylimidazole, 2-ethylimidazole, 2,4-dimethylimidazole, 2
-Ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecyl imidazole, 1-vinyl-2-methylimidazole, 1-
Benzyl-2-methylimidazole, 2-phenylimidazole, 1-vinyl-2-ethylimidazole, imidazole, 2-phenyl-4-methylimidazole, 1-vinyl-2,4-dimethylimidazole, 1-vinyl-2- Imidazoles such as ethyl-4-methylimidazole, benzyldimethylamine, 2,4,6-tridimethylaminophenol, triethanolamine, triethylamine, N,N'-dimethylpiperidine, α
-Methylbenzyldimethylamine, N-methylmorpholine, N,N-dimethylaminoethanol,
These include tertiary amines such as N,N-diethylaminoethanol, N,N-dipropylaminoethanol, and dimethylaminomethylphenol, and tertiary amine salts such as triacetate and tribenzoate of tridimethylaminomethylphenol. or in combination of two or more. In the present invention, 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.
Weight%. The saturated polyester resin (D) used in the present invention is a polyester resin synthesized from a saturated polycarboxylic acid or a derivative thereof and a polyhydric alcohol. Examples of saturated polycarboxylic acid components include terephthalic acid, isophthalic acid, orthophthalic acid,
Aromatic dicarboxylic acids such as 2,6-naphthalene dicarboxylic acid and 5-sodium sulfoisophthalic acid, aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, and dodecanedioic acid, 1,4-cyclohexanedicarboxylic acid , alicyclic dicarboxylic acids such as tetrahydrophthalic acid, hexahydrophthalic acid, and chlorendic acid. These components may be used alone or in combination. Examples of polyhydric alcohol components include ethylene glycol, propylene glycol, 1,4-
Butanediol, 1,5-pentanediol,
Alkylene glycols such as 1,6-hexanediol and neopentyl glycol, diethylene glycol, triethylene glycol, polyalkylene glycols such as tetra or higher polyethylene glycol, dipropylene glycol, tri or higher polypropylene glycol, and halogenated dibromoneopentyl glycol. Examples include alkylene glycol, 1,4-cyclohexanediol, ethylene oxide and propylene oxide adducts of bisphenol A, ethylene oxide and propylene oxide adducts of hydrogenated bisphenol A, and 1,4-cyclohexanedimethanol. These glycol components may be used alone or in combination. As the saturated polycarboxylic acid component, in addition to the above-mentioned dicarboxylic acids, saturated carboxylic acids having a valence of 3 or more, such as trimellitic acid and pyromellitic acid, may be used.
As the polyhydric alcohol component, in addition to the above-mentioned glycols, it is also possible to use polyhydric alcohols of trihydric or higher hydricity, such as trimethylolpropane, trimethylolethane, and pentaerythritol. If necessary, a small amount of monohydric carboxylic acid or monohydric alcohol may be used in combination. These saturated polyester resins may be used alone or in combination of two or more. There are no particular restrictions on the method for producing the saturated polyester resin (D) used in the present invention, and known methods such as transesterification and direct esterification may be employed. Known catalysts such as stannous acids are used. The saturated polyester resin (D) used in the present invention is
The above-described compound, 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 (B) and another photopolymerizable compound (C) and a photoinitiator. If it is insoluble, it will not exhibit practical low shrinkage. Highly crystalline saturated polyesters such as polyethylene terephthalate and polybutylene terephthalate have poor solubility and cannot be used.
It is used by copolymerizing propylene glycol and 1,6-hexanediol to solubilize it. Saturated polyester resin (D) that satisfies the above solubility
Examples of preferred components include a binary system of terephthalic acid and isophthalic acid, a three-component system of terephthalic acid, isophthalic acid, and adipic acid, a two-component system of terephthalic acid and adipic acid, terephthalic acid, and isophthalic acid. There are three-component systems of acid and sebacic acid, and polyhydric alcohol components include two-component systems of ethylene glycol and propylene glycol, two-component systems of ethylene glycol and 1,6-hexanediol, and ethylene glycol and neopentyl. Examples include two-component glycol systems, but are not limited to these, of course. In addition, the solubility of the saturated polyester resin (D) is greatly affected by the acid value and molecular weight of the saturated polyester resin (D), so the molecular weight must be in the range of 1000 to 15000. The value is preferably 50 or less. Saturated polyester resin used in the present invention
The blending amount of (D) is 3 to 80 parts by weight, preferably 5 to 60 parts by weight, based on 100 parts by weight of the curable resin of the present invention. If the amount of the saturated polyester resin (D) is less than 3 parts by weight, the low shrinkage property will be insufficient;
If it exceeds 60 parts by weight, the viscosity will become too high. The low-shrinkage curable resin composition of the present invention can be easily produced by stirring and mixing at room temperature or, if necessary, under heating. Hydroquinone, hydroquinone monomethyl ether, 1-butyl-catechol, p-benzoquinone, 2,5-t-butyl-
It is desirable to add a known thermal polymerization inhibitor such as hydroquinone or phenothiazine. The amount added is 0.001 to 0.1% by weight, preferably 0.001 to 0.05% by weight, based on the photopolymerizable compound of the present invention. In addition to the above-mentioned additives, various additives such as known fillers, colorants, surface smoothing agents, and antifoaming agents can be added to the low-shrinkage curable resin composition of the present invention, as necessary. . The method for curing the low-shrinkage curable resin composition of the present invention is to first prepare a photopolymerizable compound (B) having a carboxyl group or a mixture of (B) and another photopolymerizable compound (C) by irradiation with actinic rays. The process consists of two steps: polymerizing to form a carboxyl group-containing polymer, and then heating to cause the epoxy compound (A) to react with the carboxyl groups contained in the polymer to completely cure it. Photopolymerization reaction conditions include light intensity of 20 mW/cm ² ~
The time is preferably 0.1 seconds to 15 minutes at 200 mW/cm ² . In addition, the temperature of the thermosetting reaction is 40°C to 250°C.
Preferably, the time is 10 seconds to 120 minutes at ℃. The low-shrinkage 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, metal halide lamps, etc. are used. A photoinitiator is not necessarily required when irradiating with an electron beam. The low-shrinkage curable resin composition of the present invention is heated to a completely cured product following the above-described polymerization reaction. Examples of heat sources used for heating include:
Known heating methods such as infrared heaters, hot air heating, and high frequency heating hot plates are used. As mentioned above, the low shrinkage curable resin composition of the present invention has a curing reaction that is essentially different from that of conventional ultraviolet curable resin compositions or thermosetting resin compositions. By using the mold resin composition, it is possible to obtain a final cured product that has excellent properties such as low shrinkage, adhesiveness, chemical resistance, water resistance, and electrical insulation. The effects of the present invention include the following points. 1. Curing shrinkage can be significantly reduced. 2. Since the resin composition of the present invention has a small curing shrinkage, when used for example to seal electronic parts, it is possible to seal without destroying the element function, and at the same time, it can be used for plastics, ceramics, glass, etc. It also has excellent adhesion to metals. 3. The resin composition of the present invention is economical because the area required for the equipment required for its curing process is relatively small. 4 Epoxy compound (A) and photopolymerizable compound (B) or
The mixture of (B) and (C) has good compatibility, and the viscosity of the resin composition can be adjusted freely. 5. Since the resin composition of the present invention is one-component, it has excellent workability and good storage stability. 6. Since the resin composition of the present invention loses its fluidity within a very short time when exposed to ultraviolet rays,
It can be immediately transferred to the next process, and productivity can be greatly improved compared to conventional thermosetting resins. 7 The resin composition of the present invention can be cured to a thickness of 10 mm or more, which was difficult with conventional ultraviolet curable resins, and can also be cured with resin compositions containing large amounts of fillers and colorants. be. Taking advantage of these advantages, the low-shrinkage resin composition of the present invention can be used in ICs, LSIs, diodes, transistors, thyristors, hybrid ICs, resistors, capacitors, laser devices, solar cells, light-emitting diodes, liquid crystal display devices, and optical devices. Used for sealing and coating electronic components such as sensors, pressure sensors, and humidity sensors. In addition, paint applications, ink applications,
It can also be used in fields such as adhesive applications. EXAMPLES Hereinafter, examples will be given to specifically explain the present invention, but the present invention is not limited to these examples in any way. In the examples, parts and percentages indicate parts by weight and percentages by weight, respectively. The resin properties of the low-shrinkage curable resin composition and the performance of the cured product thereof were measured by the following method. 1. Viscosity: Measured at 25°C using a Bruckfield viscometer according to JIS W6901. 2 Shrinkage rate: Using the quartz mold shown in Figure 1, measure the dimensions of the cured resin after curing and the dimensions of the quartz mold at 25°C, and calculate the shrinkage rate using the following formula. I asked for it. Shrinkage rate = 1/2 {(L ₁ −L′ ₁ /L ₁ )+(L ₂ −L′ ₂ /
L ₂ )}×100% L ₁ , L ₂ ... Length of quartz formwork at 25℃ (mm) L' ₁ , L' ₂ ... Length of cured resin material at 25℃ (mm) 3 Adhesiveness: Thickness of untreated curable resin composition
It was coated on a 100 μm polyester film to a thickness of about 20 μm using a bar coater, and the adhesion after curing was measured using a goban-cellophane tape peel test method. 4 Chemical resistance: cured product in 5% caustic soda at 25℃,
The specimens were immersed in 5% sulfuric acid, trichlene, toluene, and isopyropanol for 24 hours, and the presence or absence of abnormalities in appearance was determined. 5 Water resistance: immerse the cured product in boiling water for 60 minutes,
The presence or absence of any abnormality in appearance was determined. 6 Transparency: The light transmittance of a 3 mm thick cured product was measured using a Hitachi Model 124 spectrophotometer.
Measured at 700 mμ. 7 Electrical insulation: A casting plate with a thickness of 3 mm was prepared according to JIS K6911, and the volume resistivity value was measured. Example 1 38 parts of Epicote 828 (manufactured by Yuka Ciel Epoxy Co., Ltd.), a bisphenol A type epoxy compound, 22 parts of succinic acid monoacryloyloxyethyl ester
Part, neopentyl glycol diacrylate 20
1 part, 0.4 part of 2-hydroxy-2-methylpropiophenone and 0.4 part of N,N-diethylaminoethanol were placed in a stirring container, mixed and stirred at room temperature,
A transparent resin composition (1) was obtained. The viscosity of the resulting resin composition was 2.6 poise. This resin composition (1)
20 parts of a saturated polyester resin (A) having the following composition synthesized by a conventional method was added to 100 parts, and the mixture was mixed and stirred at 70°C to obtain a low-shrinkage curable resin composition (a) of the present invention. Composition of saturated polyester resin (A) Saturated polycarboxylic acid component Polyhydric alcohol component Terephthalic acid 50 mol% Ethylene glycol 40 mol% Isophthalic acid 50 mol%
1,6-hexanediol 60 mol% Next, the obtained resin composition (a) was poured into the quartz mold shown in Figure 1, and ultraviolet rays of 85 mW/cm ² were applied for 10 minutes.
When irradiated for seconds, this resin composition (a) lost its fluidity and became semi-solid. Next, the resin composition (a) was heated at 120° C. for 20 minutes to obtain a cured product for shrinkage measurement. The obtained cured product was removed from the quartz mold and left to cool in the air at 25°C _.
and L′ ₂ were measured to determine the curing shrinkage rate. Next, the obtained curable resin composition (a) was applied to an untreated 100 μm thick polyethylene terephthalate film to a thickness of approximately 20 μm using a bar coater, and irradiated with ultraviolet light at 85 mW/cm ² for 5 seconds. As a result, this resin composition (a) lost its fluidity and became semi-solid. After curing by heating at 120° C. for 10 minutes, adhesion to polyethylene terephthalate film was measured by a cellophane tape peel test method. The results of curing shrinkage and adhesion obtained were as follows. Shrinkage rate: 0.78% Adhesiveness: 100/100 Separately, a release agent was applied to a 15 cm square glass plate with a thickness of 2 mm, and the resulting resin composition ( a) was injected.
Next, when 85 mW/cm ² of ultraviolet rays were irradiated for 10 seconds, this resin composition (a) lost its fluidity and became semi-solid. Next, the mixture was heated at 120° C. for 20 minutes to obtain a cured product with a thickness of 3 mm. The properties of the obtained cured product were as follows. Chemical resistance: No swelling or cracking was observed, showing good chemical resistance. Water resistance There was no change in appearance. Electrical insulation 2×10 ¹⁵ Ω・cm Comparative example 1 The results were measured in the same manner as in Example 1 except that the saturated polyester resin (A) was not added. There was no significant difference, but the shrinkage rate was 2.74%. Example 2 38 parts of Epicote 828 (manufactured by Yuka Ciel Epoxy Co., Ltd.), a bisphenol A type epoxy compound, 22 parts of succinic acid monoacryloyloxyethyl ester
1,6-hexanediol, 0.5 part of benzyl dimethyl ketal, and 0.5 part of N,N-diethylaminoethanol were placed in a stirring vessel and mixed and stirred at room temperature to obtain a transparent resin composition (2). The viscosity of the obtained resin composition was 1.7 poise. 20 parts of the saturated polyester resin (A) obtained in Example 1 was blended with 100 parts of this resin composition (2) at 70°C.
The mixture was mixed and stirred to obtain a low shrinkage resin composition (b) of the present invention. Next, shrinkage properties and adhesion properties were measured in exactly the same manner as in Example 1, and the following results were obtained. Shrinkage rate: 0.72% Adhesion: 100/100 Separately, in the same manner as in Example 1, a cured product with a thickness of 3 mm was obtained. The properties of the obtained cured product were as follows. Chemical resistance: Good chemical resistance was observed with no swelling or cracking observed. Water resistance There was no change in appearance. Electrical insulation 1×10 ¹⁵ Ω・cm Examples 3 to 9 Low-shrinkage curable resin compositions listed in Table 1 were prepared in the same manner as in Example 2 except that the amount of saturated polyester resin (A) was changed. were prepared, and the shrinkage rate and adhesion were measured. Separately, a cured product with a thickness of 3 mm was obtained in the same manner as in Example 1. The measurement results of shrinkage rate, adhesion, chemical resistance, water resistance and electrical insulation are summarized in Table 1. Comparative Example 2 Measurements were made in the same manner as in Example 2 except that saturated polyester resin (A) was not blended. The results showed that there was no significant difference in adhesion, chemical resistance, water resistance, and electrical insulation, but the shrinkage rate was It was 2.58%. The measurement results are also listed in Table 1.

[Table] Comparative Example 3 To 100 parts of the resin composition (2) obtained in Example 2, 10 parts of commercially available polymethyl methacrylate resin was mixed and stirred at 100°C for more than 5 hours, but the resin composition ( 2) was not dissolved. Similarly, 10 parts of commercially available polystyrene resin was blended with 100 parts of resin composition (2) and mixed and stirred at 100° C. for more than 5 hours, but it similarly did not dissolve in resin composition (2). Furthermore, a commercially available methyl methacrylate-n-butyl methacrylate copolymer (methyl methacrylate: n-methacrylate copolymer) was added to 100 parts of the resin composition (2).
10 parts of butyl (60:40 weight ratio) was mixed and stirred at 100°C for more than 5 hours, but it similarly did not dissolve in the resin composition (2). Comparative Example 4 40 parts of diacrylate of 4 moles of ethylene oxide adduct of bisphenol A, 15 parts of tetrahydrofurfuryl acrylate, and 15 parts of trimethylolpropane triacrylate were charged in a stirring container.
The mixture was mixed and stirred at room temperature to obtain a transparent resin composition (3).
The resulting resin composition (3) had a viscosity of 4 poise. 3 parts of benzoin ethyl ether as a photoinitiator was added to 100 parts of the obtained resin composition (3) to obtain an ultraviolet curable resin composition (c). Next, the obtained resin composition (c) was poured into a quartz mold for measuring the shrinkage rate, and it was irradiated with ultraviolet rays of 85 mW/cm ² for more than 2 minutes, but it remained almost liquid, and the shrinkage rate could not be measured. I was unable to do so. Example 10 100 parts of Epicote 1001 (manufactured by Yuka Ciel Epoxy Co., Ltd.), a bisphenol A type epoxy compound, 48 parts of succinic acid monoacryloyloxyethyl ester
parts, 70 parts of tetrahydrofurfuryl acrylate,
2-Hydroxy-2-methylpropiophenone 1
1 part and 1 part of N,N-diethylaminoethanol were placed in a stirring vessel and mixed and stirred at 60°C to obtain a transparent resin composition (4). The resulting resin composition (4) had a viscosity of 16 poise. Obtained resin composition (4)
20 parts of a saturated polyester resin (B) having the following composition synthesized by a conventional method was added to 100 parts and mixed and stirred at 60°C to obtain a low shrinkage curable resin composition (d) of the present invention. Composition of saturated polyester (B) Saturated polyhydric carboxylic acid component Terephthalic acid 49 mol% Isophthalic acid 49 mol% 5-Sodium sulfoisophthalic acid 2 mol% Polyhydric alcohol component Ethylene glycol 50 mol% Neopentyl glycol 50 mol% Next implementation When the resin composition (d) obtained was poured into a quartz mold in the same manner as in Example 1 and irradiated with ultraviolet light of 85 mW/cm ² for 10 seconds, the resin composition (d) lost fluidity. It became semi-solid. Then at 120℃ for 20
The resin composition (d) was heated for 1 minute to obtain a cured product for shrinkage measurement. The shrinkage rate of the obtained cured product is shown in Example 1.
It was found in the same way. Separately, the obtained resin composition (d) was added to the untreated thickness.
Apply it to a thickness of approximately 20 μm on a 100 μm polyethylene terephthalate film using a bar coater.
Irradiate with 85mW/ ^cm2 ultraviolet light for 5 seconds, then 120mW/cm2
After curing by heating at °C for 10 minutes, the adhesiveness to polyethylene terephthalate film was measured in the same manner as in Example 1. The shrinkage rate and adhesion results obtained were as follows. Shrinkage rate: 0.32% Adhesiveness: 100/100 Furthermore, in the same manner as in Example 1, a 15 cm film with a thickness of 2 mm was
A mold release agent was applied to square glass plates, two of these plates were stacked, a spacer with a thickness of 3 mm was sandwiched between them, and the resulting resin composition (d) was injected. Next, when 85 mW/cm ² of ultraviolet rays were irradiated for 8 seconds, this resin composition (d) lost its fluidity and became semi-solid. Then 15 at 120℃
The mixture was heated for a minute to obtain a cured product with a thickness of 3 mm. The properties of the obtained cured product were as follows. Chemical resistance: No swelling or cracking was observed, showing good chemical resistance. Water resistance No change in appearance was observed. Electrical insulation 2×10 ¹⁵ Ω・cm Examples 11 to 15 Low shrinkage curable resin compositions listed in Table 2 were prepared in the same manner as in Example 10 except that the amount of saturated polyester resin (B) was changed. were prepared, and the shrinkage rate and adhesion were measured. Separately, a cured product with a thickness of 3 mm was obtained in the same manner as in Example 10. The measurement results of shrinkage rate, adhesion, chemical resistance, water resistance and electrical insulation are summarized in Table 2. Comparative Example 5 Measurements were made in the same manner as in Example 10 except that the saturated polyester resin (B) was not blended. The results showed that there was no significant difference in adhesion, chemical resistance, water resistance, and electrical insulation, but the shrinkage rate was It was 0.78%. The measurement results are also listed in Table 2.

【table】 [Brief explanation of drawings]

FIG. 1 shows a sketch of the quartz mold used to measure the shrinkage rate. A is 1300mm, B is 25mm, C is
10mm, D is approximately 116mm, and E is approximately 10mm. FIG. 2 shows a side view of the resin injection part of the quartz mold. L ₁
is 111.05 mm, L ₂ is 116.42 mm, and d is 3 mm. FIG. 3 shows a side view of the cured product.

Claims (1)

[Claims] 1 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 a combination of this compound (B) and another photopolymerizable compound (C) 1. A low-shrinkage curable resin composition comprising a curable resin comprising a mixture and a photoinitiator, and a saturated polyester resin (D) soluble in the curable resin.