JP2020164713A - Curable resin composition - Google Patents

Abstract

To provide a thiol-ene curable composition having an excellent pot life even when containing an inorganic filler.SOLUTION: A curable composition contains (A) a compound having two or more unsaturated carbon bonds in the molecular structure, (B) a compound having two or more thiol groups in the molecular structure, (C) a Lewis basic compound, (D) an inorganic filler, and (E) a radical generator.SELECTED DRAWING: None

Description

The present invention relates to thiol-ene curable compositions.

The thiol-ene reaction, which is a radical addition of a thiol group and an unsaturated carbon bond, has an advantage that it is not easily inhibited by oxygen and has excellent quick curing property. Therefore, a composition containing a compound having a thiol group and a compound having an unsaturated carbon bond (thiol-ene curable composition) has been proposed as a curable composition useful for applications such as optical parts and adhesives. (See Patent Document 1).

Special table 2009-503143

On the other hand, in the curable composition, from the viewpoint of high functionality, a method of imparting the characteristics of the inorganic filler to the curable composition or the cured product by filling the composition with the inorganic filler has been widely studied. There is. In such a case, it is important to prepare the curable composition so that the curable composition is filled with the inorganic filler so as not to reduce the fluidity and impair the coatability and moldability.

However, in the thiol-ene curable composition, since the composition is excellent in curability, the composition may thicken, gel, or harden, and the handling property in coating and molding and the long-term storage of the composition are not good. The problem was that it was difficult and the pot life (pot life) was short. In particular, when an inorganic filler such as silica is blended, the pot life of the composition is significantly deteriorated.

Therefore, it is an object of the present invention to provide a thiol-ene curable composition having a good pot life. In particular, it is an object of the present invention to provide a thiol-ene curable composition having a good pot life even when an inorganic filler is blended.

As a result of diligent studies toward the realization of the above object, the present inventors presumed that the factor that excessively promotes the thiol-ene reaction was the acidity of the composition, and added a compound that is Lewis-basic. However, although the detailed mechanism is not clear, it has been found that the thiol-ene reaction is stabilized and a good pot life can be obtained even if an inorganic filler such as silica is filled, and the present invention has been completed. ..

That is, the present invention includes (A) a compound having two or more unsaturated carbon bonds in the molecular structure, (B) a compound having two or more thiol groups in the molecular structure, and (C) a Lewis basic compound. , (D) Inorganic filler and (E) Radical generator are provided.

The content of (C) Lewis basic compound is 100, which is the total content of (A) a compound having two or more unsaturated carbon bonds in the molecular structure and (B) a compound having two or more thiol groups in the molecular structure. It may be 0.5 to 3 parts by mass with respect to the mass part.

(C) The Lewis basic compound may be a phosphine compound. The phosphine compound may be a phosphine compound having an aryl group and / or an alkylaryl group, and may be particularly triphenylphosphine.

Further, according to the present invention, a cured product obtained by curing the curable composition is provided.
Further, according to the present invention, a laminated board containing the cured product is provided.
Further, according to the present invention, an electronic component having the cured product is provided.

According to the present invention, it is possible to provide a thiol-ene curable composition having a good pot life. In particular, even when an inorganic filler is blended, it becomes possible to provide a curable composition having a good pot life.

Hereinafter, the thiol-ene curable composition of the present invention will be described in detail. When isomers are present in the described compounds, all possible isomers can be used in the present invention unless otherwise specified.

<Component (A): Compound having unsaturated carbon bond>
The curable composition of the present invention contains, as the component (A), a compound having two or more unsaturated carbon bonds in the molecular structure. In the present invention, the "unsaturated carbon bond" means an ethylenic double bond unless otherwise specified.

The compound having two or more unsaturated carbon bonds in the molecular structure is typically a compound having a total of two or more functional groups of one or more selected from a vinyl group, an allyl group, an acryloyl group, and a methacryloyl group. Can be mentioned.

Examples of such a compound include an ester compound of a polyol and acrylic acid, an ester compound of a polyol and methacrylic acid, and an ester compound of allyl alcohol and polycarboxylic acid.

Examples of the ester compound of the polyol and acrylic acid include glycerin diacrylate, glycerin triacrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and tris. Examples thereof include (2-hydroxyethyl) isocyanurate diacrylate and tris (2-hydroxyethyl) isocyanurate triacrylate.

Examples of the ester compound of the polyol and methacrylic acid include glycerin dimethacrylate, glycerin trimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane tetramethritol, pentaerythritol trimethacrylate, pentaerythritol tetramethritol, dipentaerythritol hexamethacrylate, and tris. Examples thereof include (2-hydroxyethyl) isocyanurate dimethacrylate and tris (2-hydroxyethyl) isocyanurate trimethacrylate.

Examples of the ester compound of the allyl alcohol and the polycarboxylic acid include diallyl orthophthalate, diallyl isophthalate, diallyl terephthalate, diallyl 1,2-cyclohexanedicarboxylic acid, diallyl 1,3-cyclohexanedicarboxylic acid, and diallyl 1,4-cyclohexanedicarboxylic acid. , Diaryl oxalate, diallyl succinate, diallyl maleate, diallyl fumarate.

Examples of the compound having an unsaturated carbon bond include diallylbenzene, triallyl cyanurate, butadiene, vinyl ether and the like in addition to the above-mentioned compounds.

Among these, a compound having an allyl group, specifically, an ester compound of allyl alcohol and a polycarboxylic acid is preferable, diallyl phthalate is more preferable, and diallyl orthophthalate is particularly preferable, because excellent potlive can be obtained. Further, from the viewpoint of improving the heat resistance and strength of the cured product, it is preferable to use diallyl phthalate and triallyl cyanurate together.

<Component (B): Compound having a thiol group>
The curable composition of the present invention contains, as the component (B), a compound having two or more thiol groups in the molecular structure.

Examples of such a compound include an ester compound of a polyol and a mercapto organic acid (thiol group-containing ester compound).

Examples of the thiol group-containing ester compound include trimethylolpropanthris (thioglycolate), pentaerythritol tetrakis (thioglycolate), ethylene glycol dithioglycolate, trimethylpropanthris (β-thiopropionate), and pentaerythritol. Tetrakis (β-thiopropionate), dipentaerythritol poly (β-thiopropionate), 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobuti) Lyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione and the like can be mentioned.

Examples of the compound having a thiol group include 1,4-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol, 1,9-nonandithiol, and 1,10-decane. Alkyl polythiol compounds such as dithiols; polyethers with terminal thiol groups; polythioethers with terminal thiol groups; thiol compounds obtained by the reaction of epoxy compounds with hydrogen sulfide; terminal thiols obtained by the reaction of polythiol compounds with epoxy compounds. Thiol compounds having a group; and the like.

Among these, a thiol group-containing ester compound is preferable, and from the viewpoint of excellent toughness of the cured product, 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4 , 6 (1H, 3H, 5H) -trions are particularly preferred.

The content ratio of the compound having an unsaturated carbon bond (A) and the compound having an unsaturated carbon bond (B) is 0 in an equivalent ratio of the compound having an unsaturated carbon bond to the compound having a thiol group from the viewpoint of pot life. The ratio is preferably 5 or more and 19.0 or less, and more preferably 3.0 or more and 10.0 or less from the viewpoint of improving the heat resistance and strength of the cured product.

The "equivalent ratio" as used herein is the ratio of (A) the equivalent of a compound having an unsaturated carbon bond to the equivalent of a thiol group-containing compound. The mass of a compound having one equivalent of a thiol group is the number obtained by dividing the molecular weight of the compound having a thiol group by the number of thiol groups in one molecule. The mass of a compound having one equivalent of unsaturated carbon bonds is the number obtained by dividing the molecular weight of the compound having unsaturated carbon bonds by the number of unsaturated carbon bonds in one molecule. That is, a compound having an unsaturated carbon bond is 0.5 to 2.0 in an equivalent ratio to a compound having a thiol group, that is, the number of thiol groups is 1 and the number of unsaturated carbon bonds is 0. It means .5-2.0.

In the present application, the components (A) and (B) may be collectively referred to as a resin component.

<Component (C): Lewis basic compound>
The curable composition of the present invention contains a Lewis basic compound as the component (C). A Lewis basic compound is a compound having an unshared electron pair. By using such a compound, it has become possible to stabilize the thiol-ene reaction of the composition in the composition containing the inorganic filler. When an inorganic filler such as silica is added to the thiol-ene reaction system, the curing reaction is promoted (that is, the pot life is shortened). Therefore, it has not been possible to add an inorganic filler such as silica to the thiol-ene curable composition.

(C) Lewis basic compounds include compounds having an ether bond in the molecule such as tripropylene glycol diacrylate and diethylene glycol diacrylate, tetrahydrofuran, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, and tetrahydrofurfuryl alcohol acrylic acid multimer ester. Oxolan ring-containing compounds such as: trimethylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, isopropyldiphenylphosphine, triphenylphosphine, 1,2-bisdiphenylphosphinebenzene, bisdiphenylphosphinomethane, tri (p-tolyl) phosphine, Hosphine compounds such as tri (o-tolyl) phosphine, 1,2-bis (diphenylphosphine) ethane, tris (4-methoxyphenyl) phosphine, tris (3-methoxyphenyl) phosphine, triphenylphosphine, tri- Phosphite compounds such as p-triphenylphosphine; phosphorus compounds; The phosphine compound forms a stable phosphine oxide compound even when it reacts with oxygen, and the risk of causing a side reaction is small. Next, the phosphine compound will be described in detail.

Typical examples of the phosphine compound include a monophosphine compound represented by the general formula (A) and a diphosphane compound represented by the general formula (B).

Here, P in the general formula (1) and the general formula (2) represents a phosphorus atom. R in the general formula (1) and the general formula (2) individually represent a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms. It is preferable that at least one of R is a hydrocarbon group, and it is preferable that all R are hydrocarbon groups. X in the general formula (2) represents a single bond or a divalent hydrocarbon group having 1 to 12 carbon atoms.

The hydrocarbon group may be saturated or unsaturated, and may have a linear, branched, or cyclic structure. Examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, and an alkynyl group. It may have each of an alkylcycloalkyl group, an alkylaryl group, an arylalkyl group and the like as a substituent. Among the hydrocarbon groups, an alkyl group, an aryl group, an arylalkyl group and an alkylaryl group are preferable, an aryl group or an alkylaryl group is more preferable, and a phenyl group is particularly preferable.

Examples of the monophosphine compound represented by the general formula (1) include trimethylphosphine, triethylphosphine, tri-n-propylphosphine, tri-iso-propylphosphine, t-butylphosphine, t-butyldimethylphosphine, and di-. t-butyldimethylphosphine, tri-n-butylphosphine, tri-n-octylphosphine, dicyclohexylphosphine, dicyclohexylhexylphosphine, diethylphenylphosphine, dicyclohexylphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, diphenylbenzyl Phosphine can be mentioned.

Examples of the diphosphin compound represented by the general formula (2) include bis (dicyclohexylphosphino) methane, bis (diphenylphosphino) methane, 1,2-bis (diphenylphosphino) ethane, and 1,3-bis ( Examples thereof include diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, and 1,2-bis (diphenylphosphino) benzene.

As the Lewis basic compound, since the phosphine oxide compound formed by oxidation has higher stability, the phosphine compound having an aryl group and / or an alkylaryl group (specifically, R in the formula). A monophosphine compound in which is an aryl group and / or an alkylaryl group) is more preferable, and triphenylphosphine (TPP) is most preferable.

The content of the Lewis basic compound (C) is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 4 parts by mass, and 0.5 to 4 parts by mass with respect to 100 parts by mass of the total content of the resin components. 3 parts by mass is more preferable, and 0.5 to 1.0 parts by mass is particularly preferable.

<Component (D): Inorganic filler>
The curable composition of the present invention contains an inorganic filler as the component (D).

Inorganic fillers are not limited as long as the effects of the present invention are not impaired. Examples of the inorganic filler include silica (non-crystalline silica, crystalline silica), Neuburg silica soil, aluminum oxide (alumina), titanium oxide, zirconia, boron nitride, aluminum nitride, glass powder, talc, clay, magnesium carbonate, and the like. Inorganic such as calcium carbonate, natural mica, synthetic mica, aluminum hydroxide, barium sulfate, barium titanate, iron oxide, non-fibrous glass, hydrotalcite, mineral wool, aluminum silicate, calcium silicate, calcium zirconate, zinc flower, etc. Fillers can be used.
The curable composition of the present invention is also excellent even if it contains metals such as silica, zirconia, titanium oxide and activated alumina which are acidic in the composition, and silicate minerals such as talc and clay (kaolin). You can get a pot live.

Inorganic fillers are selected according to the properties to be imparted, silica from the viewpoint of thermal dimensional stability (low thermal expansion), low dielectric loss, and high strength, aluminum oxide and boron nitride from the viewpoint of thermal conductivity, whitening and light. Titanium oxide is preferable from the viewpoint of reflective use. Further, the shape of the inorganic filler is more preferably spherical from the viewpoint of filling property and mechanical strength of the cured product.

The average particle size of the inorganic filler is preferably 0.02 to 10 μm, more preferably 0.02 to 3 μm. Here, the average particle size can be obtained as the median diameter (d50, volume standard) based on the cumulative distribution from the measured value of the particle size distribution by the laser diffraction / scattering method using a commercially available laser diffraction / scattering type particle size distribution measuring device. it can.

It is also possible to use inorganic fillers having different average particle sizes in combination. From the viewpoint of increasing the filling of the inorganic filler, for example, a nano-order fine inorganic filler having an average particle size of less than 1 μm may be used in combination with the inorganic filler having an average particle size of 1 μm or more.

The inorganic filler is preferably surface-treated with a coupling agent. By treating the surface with a silane coupling agent, the affinity / compatibility with other components of the composition can be improved, and the pot life of the composition can be improved.

As the silane coupling agent, for example, an epoxysilane coupling agent, a mercaptosilane coupling agent, a vinylsilane coupling agent, a phenylsilane coupling agent, an aminosilane coupling agent and the like can be used. As the epoxysilane coupling agent, for example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane and the like can be used. As the mercaptosilane coupling agent, for example, γ-mercaptopropyltriethoxysilane or the like can be used. As the vinylsilane coupling agent, for example, vinyltriethoxysilane or the like can be used. Of these, vinylsilane coupling agents, phenylsilane coupling agents, and aminosilane coupling agents are preferable because they improve pot life.

The amount of the silane coupling agent used may be, for example, 0.1 to 5 parts by mass or 0.5 to 3 parts by mass with respect to 100 parts by mass of the inorganic filler.

The mass content ratio of the resin component and the (D) inorganic filler is preferably in the range of 50:50 to 70:30 for the resin component: inorganic filler. With such a mass content ratio with the inorganic filler, a curable resin composition having excellent pot life can be obtained.

<Component (E): Radical generator>
The curable composition of the present invention contains a radical generator as the component (E). Examples of the radical generator include a thermal radical generator and a photoradical generator.

Examples of the thermal radical generator include azo-based, peroxide-based, and redox-based agents.

Examples of the azo-based thermal radical generator include 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile, and 2,2'-azobis (2-methylpropionic acid). Dimethyl, 4,4'-azobis-4-cyanovaleric acid, azobisisobutaleronitrile, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis [2- (5-methyl-) 2-Imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis (2-methylpropionamidine) disulfate, 2,2'-azobis (N, N'-dimethyleneisobutyramidine) dihydrochloride, etc. Can be mentioned.

Examples of the peroxide-based thermal radical generator include dibenzoyl peroxide, t-butyl permalate, lauroyl peroxide, and 1,1-bis (3,3-dimethylbutylperoxy) cyclohexane.

Examples of the photoradical generator include benzoin ether type, acetophenone type, α-ketol type, aromatic sulfonyl chloride type, photoactive oxime type, benzoin type, benzyl type, benzophenone type, ketal type, thioxanthone type and acylphosphine. Oxime type and the like can be mentioned.

Examples of the benzoin ether-based photoradical generator include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethane-1-one [commodity]. Name: Irgacure 651, manufactured by BASF], anisoin and the like.

Examples of the acetophenone-based photoradical generator include 1-hydroxycyclohexylphenylketone [trade name: Irgacure 184, manufactured by BASF], 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 1- [4-( 2-Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one [trade name: Irgacure 2959, manufactured by BASF], 2-hydroxy-2-methyl-1-phenyl-propane- 1-on [trade name: DaroCure 1173, manufactured by BASF], methoxyacetophenone and the like can be mentioned.

Examples of the α-ketol photoradical generator include 2-methyl-2-hydroxypropiophenone and 1- [4- (2-hydroxyethyl) -phenyl] -2-hydroxy-2-methylpropane-1-. On, etc. can be mentioned.

Examples of the aromatic sulfonyl chloride-based photoradical generator include 2-naphthalene sulfonyl chloride and the like. Examples of the photoactive oxime-based photopolymerization initiator include 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) -oxime and the like.

Examples of the benzoin-based photoradical generator include benzoin and the like.

Examples of the benzyl-based photoradical generator include benzyl and the like.

Examples of the benzophenone photoradical generator include benzophenone, benzoylbenzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, α-hydroxycyclohexylphenylketone and the like.

Examples of the ketal-based photoradical generator include benzyldimethyl ketal and the like.

Examples of the thioxanthone-based photoradical generator include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-dichlorothioxanthone, and isopropylthioxanthone. Examples thereof include 2,4-diisopropylthioxanthone and dodecylthioxanthone.

Examples of the acylphosphine oxide-based photoradical generator include bis (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) (2,4,4-trimethylpentyl) phosphine oxide, and bis. (2,6-dimethoxybenzoyl) -n-butylphosphine oxide, bis (2,6-dimethoxybenzoyl)-(2-methylpropan-1-yl) phosphine oxide, bis (2,6-dimethoxybenzoyl)-(1 -Methylpropan-1-yl) phosphine oxide, bis (2,6-dimethoxybenzoyl) -t-butylphosphine oxide, bis (2,6-dimethoxybenzoyl) cyclohexylphosphine oxide, bis (2,6-dimethoxybenzoyl) octyl Phosphine oxide, bis (2-methoxybenzoyl) (2-methylpropan-1-yl) phosphine oxide, bis (2-methoxybenzoyl) (1-methylpropan-1-yl) phosphin oxide, bis (2,6-di) Ethoxybenzoyl) (2-methylpropan-1-yl) phosphine oxide, bis (2,6-diethoxybenzoyl) (1-methylpropan-1-yl) phosphine oxide, bis (2,6-dibutoxybenzoyl) ( 2-Methylpropan-1-yl) phosphine oxide, bis (2,4-dimethoxybenzoyl) (2-methylpropan-1-yl) phosphine oxide, bis (2,4,6-trimethylbenzoyl) (2,4- Dipentoxyphenyl) phosphine oxide, bis (2,6-dimethoxybenzoyl) benzyl phosphine oxide, bis (2,6-dimethoxybenzoyl) -2-phenylpropylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2- Phenylethylphosphine oxide, bis (2,6-dimethoxybenzoyl) benzylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2-phenylpropylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2-phenylethylphosphine Oxide, 2,6-dimethoxybenzoylbenzylbutylphosphine oxide, 2,6-dimethoxybenzoylbenzyloctylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,5-diisopropylphenylphosphine oxide, bis (2,4) , 6-trimethylbenzoyl) -2-methylphenylphosphino Xido, bis (2,4,6-trimethylbenzoyl) -4-methylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,5-diethylphenylphosphine oxide, bis (2,4,6- Trimethylbenzoyl) -2,3,5,6-tetramethylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,4-di-n-butoxyphenylphosphine oxide, 2,4,6-trimethyl Benzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) isobutylphosphine oxide, 2,6-dimethyloxybenzoyl-2 , 4,6-trimethylbenzoyl-n-butylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,4-dibutoxyphenylphosphine oxide , 1,10-Bis [bis (2,4,6-trimethylbenzoyl) phosphine oxide] decane, tri (2-methylbenzoyl) phosphine oxide and the like.

The content of the radical generator (E) is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 4 parts by mass, and 0.5 to 3 parts by mass with respect to 100 parts by mass of the total content of the resin components. Parts by mass are particularly preferred.

The composition of the present invention further contains additives such as a silane coupling agent, an ion trapping agent, a leveling agent, a defoaming agent, a stiffening agent, a viscosity modifier, a flame retardant, and a surfactant, if necessary. You may.

<Cured product>
The cured product is obtained by curing the curable composition described above.

The method for obtaining the cured product from the curable composition is not particularly limited, and can be appropriately changed depending on the composition of the curable composition. As an example, after performing a step of applying a curable composition on a base material such as a printed wiring board (for example, coating with an applicator or the like), a drying step of drying the curable composition as necessary is performed. If it contains a thermal radical generator as a component, it is heated (for example, heated by an inert gas oven, a hot plate, a vacuum oven, a vacuum press, etc.), and if it contains a photoradical generator, it is exposed (as a light source). , Exposure by a light irradiation device equipped with a high-pressure mercury lamp, a metal halide lamp, or the like) to generate radical species and carry out a curing step that causes a thiol-oven reaction. The conditions for implementation in each step (for example, coating thickness, drying temperature and time, heating temperature and time, etc.) may be appropriately changed according to the composition, application, and the like of the curable composition.

<Encapsulant / underfill material>
Since the curable composition of the present invention has fast curing properties and has a small curing shrinkage, it can be used as a sealing material or an underfill material for electronic parts.

More specifically, support substrates such as lead frames, pre-wired tape carriers, rigid and flexible wiring boards, glass, and silicone wafers, active elements such as semiconductor chips, transistors, diodes, and thyristors, capacitors, resistors, and resistance arrays , A device such as a passive element such as a coil or a switch is mounted, and the curable composition of the present invention is injected and coated by a diode method, a casting method, a printing method, etc. so as to cover the element or between the supporting base material and the element. And cure. In particular, it is suitable for a mounting method in which a semiconductor element is flip-chip bonded by bump connection to a rigid or flexible wiring board or wiring formed on glass.

<Electronic components>
The cured product made of the curable composition of the present invention has a small curing shrinkage, and can be used for a wide variety of electronic components because it can impart strength, thermal conductivity, and light reflectivity by the inorganic filler contained therein. ..

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

The raw materials used in Examples and Comparative Examples are listed below.

A-1: Dialyl orthophthalate (manufactured by Tokyo Chemical Industry Co., Ltd.)
A-2: Dialyl Isophthalate (manufactured by Tokyo Chemical Industry Co., Ltd.)
A-3: Triallyl cyanurate (manufactured by Tokyo Chemical Industry Co., Ltd.)
B-1: 1,3,5-Tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -Trione (manufactured by Showa Denko KK)
C-1: Triphenylphosphine (manufactured by Fuji Film Frame Junyaku Co., Ltd.)
D-1: Silica without surface modification ("SQC6 (particle size 500 nm)" manufactured by Admatex)
D-2: Vinyl-modified silica (“SV-C10 (particle size 500 nm)” manufactured by Admatex)
D-3: Phenyl-modified silica ("5SP-E1 (particle size 600 nm)" manufactured by Admatex)
E-1: 1,1-bis (3,3-dimethylbutylperoxy) cyclohexane

The curable compositions of Examples and Comparative Examples were prepared with the compositions shown in Table 1. These compositions were evaluated by the following tests. The evaluation results are also shown in Table 1.

(viscosity)
The viscosity [mPa · s] of the composition was measured with a cone plate type viscometer (TVH-33H manufactured by Toki Sangyo Co., Ltd.) under the conditions of 25 ° C. and 50 rpm. Measurements were taken immediately after preparation and at two timings 6 hours after preparation.

In the table, "viscosity (0h)" means the viscosity of the composition immediately after preparation, and "viscosity (6h)" means the viscosity of the composition 6 hours after the preparation.

(Pot life)
The pot life was evaluated by the thickening ratio (viscosity (6h) / viscosity (0h)) of the composition after 6 hours. Thickening ratio less than 1.2 is "◎", 1.2 or more and less than 1.5 is "○", 1.5 or more and less than 2.0 is "△", 2.0 or more The thing was evaluated as "x".

(Elastic modulus)
Polytetrafluoroethylene tape (PTFE tape: with glass cloth, rough surface) is attached to the glass plate, and PTFE tape of the same size with a smooth surface is overlaid on top of it. Prepare two glass plates with the tape. Then, two more tapes are laminated 1 cm from both ends of the tape on one of the glass plates to form a spacer. The sample was filled on a tape of a glass plate with a spacer, sandwiched between another glass plate, and both ends were fixed with clips. The glass plate filled with the sample was cured in a hot air circulation type drying oven heated at 110 ° C. for 1 hour to obtain a cured film. This cured film is cut to a width of 5 mm and a length of 70 mm, and a tensile test is performed under the following conditions. The average elastic modulus of N = 5 is obtained from the slope of the stress-strain curve when the test stress is from 0.5 MPa to 1.0 MPa. I asked.
[Measurement condition]
Testing machine: Tensile testing machine EZ-SX (manufactured by Shimadzu Corporation)
Distance between chucks: 50 mm
Test speed: 3 mm / min
Elongation calculation: (tensile movement amount / distance between chucks) x 100

(Glass-transition temperature)
The cured film prepared in the same manner as the evaluation of the elastic modulus was cut into a width of 5 mm and a length of 30 mm, and a dynamic viscoelasticity test (DMA) was performed under the following conditions to measure the glass transition temperature.
[Measurement condition]
Testing machine: G2 RSA (manufactured by TA Instruments)
Measurement mode: Tensile mode Chuck distance: 10 mm
Temperature conditions: Under a nitrogen atmosphere, the temperature is raised from -30 ° C to 150 ° C at 5 ° C / min, then lowered to 150 to -30 ° C at 5 ° C / min, and the glass transition temperature during the temperature lowering process is measured.

Claims (8)

(A) A compound having two or more unsaturated carbon bonds in the molecular structure, (B) a compound having two or more thiol groups in the molecular structure, (C) a Lewis basic compound, and (D) an inorganic filler. A curable composition containing (E) a radical generator. The total content of (C) Lewis basic compound is 100: (A) a compound having two or more unsaturated carbon bonds in the molecular structure and (B) a compound having two or more thiol groups in the molecular structure. The curable composition according to claim 1, wherein the amount is 0.5 to 3 parts by mass with respect to parts by mass. (C) The curable composition according to claim 1 or 2, wherein the Lewis basic compound is a phosphine compound. The curable composition according to claim 3, wherein the phosphine compound is a phosphine compound having an aryl group and / or an alkylaryl group. The curable composition according to claim 4, wherein the phosphine compound having an aryl group and / or an alkylaryl group is triphenylphosphine. A cured product obtained by curing the curable composition according to any one of claims 1 to 5. A laminated board comprising the cured product according to claim 6. An electronic component having the cured product according to claim 6.