JP2016166279A - Thermosetting resin composition and molded article thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition containing much inorganic filler, and nonetheless securing flowability and providing a cured product which has high flexibility and resistance to bending, and hardly causes cracks by suppressing a stress.SOLUTION: The resin composition securing flowability and providing a cured product which has high flexibility and resistance to bending, and hardly causes cracks by suppressing a stress can be provided by adding an epoxy compound having a high elongation rate and breaking strength at a tension test to a resin composition that is blended with an inorganic filler at high concentration, specifically, contains 70 wt.% or more of the inorganic filler.SELECTED DRAWING: None

Description

  The present invention relates to a thermosetting resin composition suitably used as a sealing material for semiconductor devices and the like.

  In addition to insulation and thermal reliability, a sealing material for power devices is required to have a low coefficient of linear expansion. This is because when the resin having a high linear expansion coefficient is used as the sealing material, the sealing resin is prevented from expanding due to heat from the power device and cracking the sealing resin. And in order to reduce a linear expansion coefficient, adding a filler (filler) to a semiconductor sealing material is generally performed (for example, patent document 1 or 2).

JP 2004-27005 A JP 2009-67890 A

In order to lower the linear expansion coefficient of the sealing resin, it is necessary to contain a large amount of an inorganic filler such as a silica filler. However, when the amount of the inorganic filler is increased, the fluidity of the encapsulating resin composition is lowered, and the brittleness at the time of curing is caused. Increasing the elastic modulus of the cured product can be cited as a means for solving the problem. However, since the thermal stress generated with temperature change increases, cracks are likely to occur during thermal curing and cooling.
Furthermore, if the stress at the time of curing remains in the sealing resin, cracks due to long-term use or temperature changes during use tend to occur. That is, the present situation is that it is difficult to provide a resin composition that contains a high amount of an inorganic filler and is less likely to cause cracks during curing and use.

  The present invention is a resin that has a certain degree of fluidity even if it is a resin composition containing a large amount of inorganic filler, and the cured product is highly flexible and resistant to bending, and is less susceptible to cracking by suppressing stress. It is an object to provide a composition.

As a result of intensive studies to solve the above problems, the present inventors have added an epoxy compound having a high elongation and a high breaking strength to a resin composition containing a high concentration of inorganic filler. The present inventors have found that a resin composition capable of ensuring fluidity and having a cured product having high flexibility and resistance to bending and suppressing stress can be provided with less cracking, thereby completing the present invention. That is, the present invention is as follows.
[1] A thermosetting resin composition comprising a thermosetting resin, an inorganic filler, and a curing catalyst,
The composition contains an epoxy compound having an elongation of 15% or more and a breaking strength of 0.5 MPa or more in a tensile test,
The cured product of the thermosetting resin composition has a bending strain at 25 ° C. of 2% or more, and is a thermosetting resin composition.
[2] The thermosetting resin composition according to [1], wherein the composition contains an inorganic filler of 70% by weight or more.
[3] The thermosetting resin composition according to the above [1] or [2], wherein the inorganic filler is a spherical filler.
[4] The thermosetting resin composition according to any one of [1] to [3], wherein the inorganic filler is silica.
[5] The thermosetting resin composition according to any one of the above [1] to [4], comprising an epoxy silicone.
[6] The thermosetting resin composition according to any one of [1] to [5] above, comprising an organometallic compound and a silanol source.
[7] The thermosetting resin composition according to the above [6], wherein the organometallic compound is a gallium compound.
[8] A molded product obtained by curing the thermosetting resin composition according to any one of [1] to [7].
[9] A semiconductor device that is sealed with the thermosetting resin composition according to any one of [1] to [7].

  ADVANTAGE OF THE INVENTION According to this invention, even if it is a resin composition which mix | blended the inorganic filler with high density | concentration, fluidity | liquidity can be ensured and the resin composition which is hard to produce a crack by suppressing stress can be provided. That is, although the linear expansion coefficient when cured is very low, the composition has fluidity, and the cured product is highly flexible and resistant to bending. It is possible to provide a resin composition that does not easily occur.

Hereinafter, the present invention will be described in detail according to embodiments. However, the present invention is not limited to the embodiments described explicitly or implicitly in the present specification.
In the following description, when referring to the bending strain of the cured product of the thermosetting composition, according to JIS K7171, RS Instruments III manufactured by TA Instruments and measuring jig: 3-PT
Meaning measured using BENDING TOOL under the following conditions: Geometry: Three Point Bending Geometry
Test Setup: MultiExtension
Test Parameters: Temperature 25 [° C.]
Extension Rate -0.01 [mm / s]
Delay Before Test 5 [s]
Moreover, in the following description, when referring to the elongation and break strength in the tensile test of the epoxy group-containing compound, in accordance with JIS K7162, using the STA-1225 type manufactured by ORIENTEC as the tensile test apparatus, the following conditions Means measured at

Full scale load: 500N
Initial material length: 20mm
Test speed: 20 mm / min
Environmental humidity: 60% RH; Temperature: 25 ° C

1. Resin Composition The resin composition according to the first embodiment of the present invention is liquid.
Here, “liquid” means fluidity at normal temperature and normal pressure (1 atm, 30 ° C.). More specifically, when the composition is tilted by 45 °, the shape cannot be maintained for 10 minutes or more, and the shape changes. More specifically, at 30 ° C. and 1 atm, the viscosity is usually 80,000 cp or less, preferably 50,000 cp or less, more preferably 40,000 cp or less, and 30,000 cp or less. Is more preferable. By satisfying the physical properties in this range, handling becomes easy especially in sealing by potting.
Hereinafter, the components contained in the resin composition will be described.

1-1. Inorganic filler The resin composition according to the present embodiment contains an inorganic filler at a high concentration, specifically, 70% by weight or more. From the viewpoint of reducing the linear expansion coefficient of the cured product of the resin composition, it is preferably 75% by weight or more, more preferably 80% by weight or more, and still more preferably 85% by weight or more.

  In a normal resin composition, when the amount of filler added increases, the viscosity of the composition increases significantly. In the present invention, depending on the shape of the inorganic filler, the type of the particle surface functional group, etc., the interaction between the particles and between the substances constituting the composition consisting of the particles and the epoxy resin is controlled, and the inorganic filler is 70% by weight. The fluidity can be maintained even in a composition containing a high concentration as described above.

  The inorganic filler is not particularly limited as long as it is an inorganic substance or a compound containing an inorganic substance. Specifically, for example, alumina, zircon, iron oxide, zinc oxide, titanium oxide, silicon nitride, boron nitride, aluminum nitride, silicon carbide, Glass fiber, glass flake, alumina fiber, carbon fiber, mica, graphite, carbon black, ferrite, graphite, diatomaceous earth, clay, talc, aluminum hydroxide, calcium carbonate, manganese carbonate, magnesium carbonate, barium sulfate, titanic acid Examples thereof include potassium, calcium silicate, inorganic balloon, and silver powder.

1 type may be used and 2 or more types may be used together.
Further, the filler may be appropriately subjected to a surface treatment. Examples of the surface treatment include alkylation treatment, trimethylsilylation treatment, silicone treatment, treatment with a silane coupling agent, and the like, but are not particularly limited.
As the inorganic filler, silica filler is desirable. In the present invention, the silica filler refers to a filler such as silica-based inorganic filler such as quartz, fumed silica, precipitated silica, silicic anhydride, fused silica, crystalline silica, and ultrafine powder amorphous silica.
A silica filler may use 1 type and may use 2 or more types together.

From the viewpoint of viscosity control, the inorganic filler is preferably spherical in shape rather than fibrous or amorphous. Here, the spherical shape may be a true spherical shape, an elliptical shape, or a substantially spherical shape including an oval shape. Specifically, the aspect ratio (ratio of major axis to minor axis) is usually 1. .3 or less, preferably 1.2 or less, more preferably 1.1 or less.
Control of particle size distribution can be used as means for increasing the amount of addition. That is, a higher filling rate can be obtained by mixing fillers having different particle sizes.

The average particle size is measured using a Particle Size Analyzer CILAS 1064, and the average particle size is preferably 0.1 μm or more, more preferably 1 μm or more. Moreover, 100 micrometers or less are preferable and 50 micrometers or less are more preferable.
The surface area, more preferably at least preferably at least ^{0.2m 2 / g 0.5m 2 / g} , preferably ^{15 m} 2 / g or less, ^{10 m} 2 / g or less is more preferable.

1-2. Thermosetting resin The thermosetting resin included in this embodiment is not particularly limited, but is phenol resin, epoxy resin, melamine resin, urea resin, polyurethane, thermosetting polyimide, unsaturated polyester resin, thermosetting silicone resin. Epoxy silicone resin or the like is used. Among these, an epoxy resin, a silicone resin, and an epoxy silicone resin are preferable, and a thermosetting resin including an epoxy silicone resin is particularly preferably used.

The content of the thermosetting resin is preferably 3% by weight or more and more preferably 5% by weight or more when the total amount of the liquid resin composition is 100% by weight from the viewpoint of viscosity reduction and curability.
Further, it is preferably 2530% or less, more preferably 25% by weight or less, and further preferably 20% by weight or less and 15% by weight or less.
Hereinafter, the epoxy resin, the silicone resin, and the epoxy silicone resin will be described.

1) Epoxy resin Epoxy resin is a general term for compounds having two or more oxirane rings (epoxy groups) in the molecule. However, in this invention, the epoxy silicone resin mentioned later is distinguished from an epoxy resin. Preferably, an alicyclic epoxy compound having an alicyclic epoxy group such as a cyclohexyl epoxy group or a compound having a glycidyl group is used.
Structural examples of typical alicyclic epoxy compounds are shown in formulas (1) to (3).

[In the formulas (1) to (3), R ₁ represents an optionally substituted aliphatic, alicyclic or aromatic monovalent hydrocarbon group, and R ₂ represents a divalent hydrocarbon group. Indicates. ]
The epoxy compound may be a compound having a glycidyl group, but the activity of the self-polymerization reaction may be lower than that of the alicyclic epoxy compound.
As a suitable example of the epoxy compound which has a glycidyl group, the glycidyl ether containing an alicyclic structure as shown to Formula (4)-Formula (7), or an ester compound, and an alicyclic structure as shown in Formula (8) are not included. There are glycidyl ether compounds and glycidyl amide compounds having an isocyanuric acid skeleton as shown in Formula (9).

[In the formulas (4) to (9), R ₁ represents an optionally substituted aliphatic, alicyclic or aromatic trivalent hydrocarbon group, and R ₂ represents a divalent hydrocarbon group. Indicates. ]
The epoxy compound may be an aromatic epoxy compound. Examples of such epoxy compounds include bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethyl bisphenol A, tetramethyl bisphenol F, tetramethyl bisphenol AD, tetramethyl bisphenol S, tetrafluoro as shown in formula (10). Bivalent phenols such as bisphenol type epoxy resins obtained by glycidylating bisphenols such as bisphenol A, biphenyl type epoxy resins represented by the formula (11), dihydroxynaphthalene, 9,9-bis (4-hydroxyphenyl) fluorene Resin glycidylated, epoxy resin glycidylated trisphenols such as 1,1,1-tris (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4 Epoxy resin glycidylated tetrakisphenols such as hydroxyphenyl) ethane, phenol novolak, cresol novolak, bisphenol A novolak, brominated bisphenol A novolak, phenol dicyclopentadiene novolak, novolak glycidylated novolak Type epoxy resin.

[In the formula (10), R represents an optionally substituted aliphatic, alicyclic, or aromatic divalent hydrocarbon group. ]

[In Formula (11), R ₁ represents a monovalent hydrocarbon group or halogen group which may be modified with 1 to 12 carbon atoms, and R ₂ is an optionally substituted aliphatic, alicyclic, Or an aromatic divalent hydrocarbon group; ]
The epoxy compound may be an epoxy compound having an alicyclic structure obtained by hydrogenating an aromatic epoxy compound. These epoxy compounds may be used alone or in combination of two or more.

In the present invention, among the above epoxy compounds, by containing an epoxy compound having a high elongation rate and high breaking strength in a tensile test in the resin composition, fluidity can be secured, and the cured product is highly flexible and can be bent. It is possible to provide a resin composition which is strong and hardly causes cracks by suppressing stress.
The elongation is preferably 15% or more, more preferably 30% or more, and further preferably 40% or more. As such an epoxy compound, for example, Sansosizer E-PO (Epoxyhexahydrophthalic acid diepoxy stearyl manufactured by Shin Nippon Chemical Co., Ltd .: elongation 32.0%), YL-7410 (Mitsubishi Chemical Corporation: elongation 18.6) , JER-871 (Mitsubishi Chemical: Elongation: 44.0%), YX-7105 (Mitsubishi Chemical: Elongation 210%), EXA-4850-150 (DIC: Elongation 115%) It is done.

  Among epoxy compounds having a high elongation rate, an epoxy compound having a breaking strength of 0.5 MPa or more is particularly preferable. Further, it is more preferably 1 MPa or more, further preferably 5 MPa, and further preferably 10 MPa. Examples of such epoxy compounds include epoxy resin jER-871 (breaking strength 1.30 MPa), epoxy resin YX-7105 (breaking strength 27.00 Pa), EXA-4850-150 (breaking strength 19.00 Pa), and the like. .

2) Silicone resin The silicone resin is not particularly limited as long as it is a thermosetting silicone resin. Examples thereof include dimethylpolysiloxane and diphenylpolysiloxane. The curing mechanism is not particularly limited, such as a condensation type, an addition type, and a UV type.
As the molecular weight of the silicone resin, the average molecular weight (Mw) measured by GPC is preferably 500 or more, and more preferably 700 or more, from the viewpoints of handleability and viscosity reduction. Moreover, it is preferable that it is 100,000 or less, and it is more preferable that it is 50,000 or less.

3) Epoxy silicone resin The epoxy silicone resin has an epoxy group in the molecule. The epoxy group may be a glycidyl group or an alicyclic epoxy group, and preferably includes an alicyclic epoxy group having a cyclohexyl epoxy group. As the thermosetting resin contained in the matrix resin, those containing an epoxy silicone resin are particularly preferable.

  As the molecular weight of the epoxy silicone resin, the average molecular weight (Mw) measured by GPC is preferably 300 or more, more preferably 500 or more, and 700 or more from the viewpoints of handleability and viscosity reduction. Is more preferable. Moreover, it is preferable that it is 100,000 or less, and it is more preferable that it is 50,000 or less. The content of the epoxy silicone resin is preferably 0.1% by weight or more and more preferably 1% by weight or more when the total amount of the liquid resin composition is 100% by weight from the viewpoint of viscosity reduction. Moreover, 25 weight% or less is preferable and 20 weight% or less is more preferable.

Hereinafter, each component of this epoxy silicone resin will be described.
The epoxy silicone resin is a silicon-containing compound having an epoxy group. The silicon-containing compound is a silane compound or a siloxane compound.
Examples of the silicon-containing compound having an epoxy group include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltriethoxysilane, (γ-glycidoxypropyl) (methyl) dimethoxysilane, (γ-glycidoxypropyl) (ethyl) dimethoxysilane, (γ-glycidoxypropyl) (methyl) di Ethoxysilane, (γ-glycidoxypropyl) (ethyl) diethoxysilane, [2- (3,4-epoxycyclohexylethyl) (methyl) dimethoxysilane, [2- (3,4-epoxycyclohexyl) ethyl] ( Ethyl) dimethoxysilane, [2- (3,4-epoxycyclohexyl) Til] (methyl) diethoxysilane, [2- (3,4-epoxycyclohexyl) ethyl] (ethyl) diethoxysilane, (γ-glycidoxypropyl) (methoxy) dimethylsilane, (γ-glycidoxypropyl) ) (Methoxy) diethylsilane, (γ-glycidoxypropyl) (ethoxy) dimethylsilane, (γ-glycidoxypropyl) (ethoxy) diethylsilane, [2- (3,4-epoxycyclohexyl) ethyl] (methoxy ) Dimethylsilane, [2- (3,4-epoxycyclohexyl) ethyl] (methoxy) diethylsilane, [2- (3,4-epoxycyclohexyl) ethyl] (ethoxy) dimethylsilane, [2- (3,4- Epoxycyclohexyl) ethyl] (ethoxy) diethylsilane, [2- (3,4-epoxycyclo (Hexyl) ethyl] (dimethyl) disiloxane, 1,3-bis (3-glycidoxypropyl) 1,1,3,3-tetramethyldisiloxane, (3-glycidoxypropyl) pentamethyldisiloxane, 3-epoxy And propyl (phenyl) dimethoxysilane.

Moreover, the organopolysiloxane represented by Formula (14) is also contained in the silicon compound containing an epoxy group.
(R ¹¹ ₃ SiO _1/2 ) _a1 (R ¹² ₂ SiO _2/2 ) _b1 (R ¹³ SiO _3/2 ) _c1 (SiO _4/2 ) _d1 (O _1/2 H) _e1 (14)
In the formula (14), R ¹¹ , R ¹² and R ¹³ each independently represent a monovalent organic group, and at least one is an organic group containing an epoxy group in one molecule.

In the formula (14), R ¹¹ ₃ SiO _1/2 represents an M unit, R ¹² ₂ SiO _2/2 represents a D unit, R ¹³ SiO _3/2 represents a T unit, and SiO _4/2 represents a Q unit. Yes. Each of a1, b1, c1, and d1 is an integer of 0 or more, and a1 + b1 + c1 + d1 ≧ 3.
In the formula (14), R ¹¹ , R ¹² and R ¹³ are preferably a hydrocarbon group having 1 to 10 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and pentyl. Alkyl groups such as hexyl and heptyl groups; alkenyl groups such as vinyl, allyl, butenyl, pentenyl and hexenyl; aryl groups such as phenyl, tolyl and xylyl; benzyl and phenethyl And substituted alkyl groups such as a chloromethyl group, a 3-chloropropyl group, a 3,3,3-trifluoropropyl group, and a nonafluorobutylethyl group.

  In formula (14), examples of the organic group containing an epoxy group include epoxy alkyl groups such as 2,3-epoxypropyl group, 3,4-epoxybutyl group, and 4,5-epoxypentyl group; 2-glycidoxyethyl Group, glycidoxyalkyl group such as 3-glycidoxypropyl group, 4-glycidoxybutyl group; β- (or 2-) (3,4-epoxycyclohexyl) ethyl group, γ- (or 3-) Examples thereof include an epoxycyclohexylalkyl group such as (3,4-epoxycyclohexyl) propyl group.

In the formula (14), e1 is an integer of 0 or more, and represents the number of hydroxyl groups (silanol) directly bonded to the silicon atom.
The epoxy compound has a hydrolyzable group bonded to a silicon atom. When the hydrolyzable group is hydrolyzed, the organopolysiloxane represented by the formula (14) (however, e1 ≧ 1) The compound which produces | generates may be sufficient. In other words, in the organopolysiloxane represented by the formula (14) (however, e1 ≧ 1), it may be a compound in which all or part of hydroxyl groups directly bonded to silicon atoms are replaced with hydrolyzable groups. .

  Here, the hydrolyzable group is a group that generates a hydroxyl group (silanol) bonded to a silicon atom by hydrolysis. Specific examples include a hydroxy group, an alkoxy group, hydrogen, an acetoxy group, an enoxy group, an oxime group, A halogen group is mentioned. A preferred hydrolyzable group is an alkoxy group, and particularly an alkoxy group having 1 to 3 carbon atoms, that is, a methoxy group, an ethoxy group, or a propoxy group.

The organopolysiloxane type epoxy compound represented by the above formula (14) can be produced, for example, by the following method.
(Method 1) A method of cohydrolyzing and polycondensing a silane compound having an epoxy group and a silane compound having no epoxy group and / or an oligomer thereof.
(Method 2) A method of adding an organic compound having an epoxy group and a carbon-carbon double bond group to a polysiloxane having a hydrosilyl group.
(Method 3) A method in which the double bond portion of the polysiloxane having an organic group containing a carbon-carbon double bond is oxidized and converted to an epoxy group.

The raw materials that can be used in the production of the polysiloxane type epoxy compound by the method 1 are as follows.
Examples of the raw material for introducing the M unit include trimethylmethoxysilane, trimethylethoxysilane, triphenylmethoxysilane, and triphenylsilanol.

As raw materials for introducing D unit, dimethyldimethoxysilane, methylphenyldimethoxysilane, methylvinyldimethoxysilane, diphenyldimethoxysilane, dimethyldiethoxysilane, methylphenyldiethoxysilane, and their hydrolysis condensates (oligomers) Illustrated.
As dialkylsiloxane oligomers having hydroxyl groups at both ends, compounds having silanol modifications at both ends such as polydimethylsiloxane, polymethylphenylsiloxane, dimethylsiloxane-diphenylsiloxane copolymer, polydiphenylsiloxane, and the like are commercially available.

Raw materials for introducing T unit include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, 3,3,3-trifluoropropyl Examples include trimethoxysilane and hydrolytic condensates thereof.
Examples of the raw material for introducing the Q unit include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and hydrolytic condensates thereof.

As raw materials for introducing an epoxy group, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3 , 4-epoxycyclohexyl) ethyltriethoxysilane, (γ-glycidoxypropyl) (methyl) dimethoxysilane, (γ-glycidoxypropyl) (ethyl) dimethoxysilane, (γ-glycidoxypropyl) (methyl) Diethoxysilane, (γ-glycidoxypropyl) (ethyl) diethoxysilane, [2- (3,4-epoxycyclohexyl) ethyl] (methyl) dimethoxysilane, [2- (3,4-epoxycyclohexyl) ethyl ] (Ethyl) dimethoxysilane, [2- (3,4-epoxycyclohexyl) ) Ethyl] (methyl) diethoxysilane, [2- (3,4-epoxycyclohexyl) ethyl] (ethyl) diethoxysilane, (γ-glycidoxypropyl) (methoxy) dimethylsilane, (γ-glycidoxy Propyl) (methoxy) diethylsilane, (γ-glycidoxypropyl) (ethoxy) dimethylsilane, (γ-glycidoxypropyl) (ethoxy) diethylsilane, [2- (3,4-epoxycyclohexyl) ethyl] ( Methoxy) dimethylsilane, [2- (3,4-epoxycyclohexyl) ethyl] (methoxy) diethylsilane, [2- (3,4-epoxycyclohexyl) ethyl] (ethoxy) dimethylsilane, [2- (3,4) -Epoxycyclohexyl) ethyl] (ethoxy) diethylsilane, [2- (3,4-epoxysilane) (Rohexyl) ethyl] (dimethyl) disiloxane, 1,3-bis (3-glycidoxypropyl) 1,1,3,3-tetramethyldisiloxane, (3-glycidoxypropyl) pentamethyldisiloxane, 3-epoxy Examples include propyl (phenyl) dimethoxysilane.
As a thermosetting resin in matrix resin, 1 type may be used independently from the resin mentioned above, and 2 or more types may be used together. From the viewpoint of viscosity reduction, it is preferable to include an epoxy silicone resin.

1-3. Curing catalyst The resin composition of the present invention contains a curing catalyst. The curing catalyst is not particularly limited as long as it is a compound that can cure the thermosetting resin. Hereinafter, examples of the curing catalyst and the curing agent for the epoxy resin, the epoxy silicone resin, and the silicone resin are shown.

1) Curing catalyst for epoxy resin or epoxy silicone resin When using epoxy resin and / or epoxy silicone resin as matrix resin,
The catalyst used for normal epoxy resin hardening can be used. For example, tertiary amines such as benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, cyclohexyldimethylamine, triethanolamine; 2-methylimidazole, 2-n-heptylimidazole, 2-n- Undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methyl Imidazole, 1- (2-cyanoethyl) -2-methylimidazole, 1- (2-cyanoethyl) -2-n-undecylimidazole, 1- (2-cyanoethyl) -2-phenylimidazole, 1- (2-cyanoethyl) ) -2-Ethyl-4-methylimidazo 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-di (hydroxymethyl) imidazole, 1- (2-cyanoethyl) -2-phenyl-4,5-di [( 2′-cyanoethoxy) methyl] imidazole, 1- (2-cyanoethyl) -2-n-undecylimidazolium trimellitate, 1- (2-cyanoethyl) -2-phenylimidazolium trimellitate, 1- ( 2-cyanoethyl) -2-ethyl-4-methylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-s-triazine, 2,4-diamino- 6- (2′-n-undecylimidazolyl) ethyl-s-triazine, 2,4-diamino-6- [2′-ethyl-4′-methylimidazolyl- ( 1 ′)] ethyl-s-triazine, isocyanuric acid adduct of 2-methylimidazole, isocyanuric acid adduct of 2-phenylimidazole, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)] Imidazoles such as isocyanuric acid adducts of ethyl-s-triazine; organophosphorus compounds such as diphenylphosphine, triphenylphosphine and triphenyl phosphite; benzyltriphenylphosphonium chloride, tetra-n-butylphosphine Phonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, ethyltriphenylphosphonium iodide, Tiltriphenylphosphonium acetate, methyltributylphosphonium dimethyl phosphate, tetrabutylphosphonium diethylphosphodithionate, tetra-n-butylphosphonium benzotriazolate, tetra-n-butylphosphonium tetrafluoroborate, tetra-n -Quaternary phosphonium salts such as butylphosphonium tetraphenylborate and tetraphenylphosphonium tetraphenylborate; diaza such as 1,8-diazabicyclo [5.4.0] undecene-7 and organic acid salts thereof Bicycloalkenes; Organometallic compounds such as zinc octylate, tin actinate, aluminum acetylacetone complex, gallium compound, indium compound; tetraethylammonium bromide, tetra-n- Quaternary ammonium salts such as tylammonium bromide; Boron compounds such as boron trifluoride and triphenyl borate; Metal halide compounds such as zinc chloride and stannic chloride, and dicyandiamide and adducts of amines and epoxy resins High melting point dispersion type latent curing accelerators such as amine addition type accelerators; Microcapsule type latents in which the surface of curing accelerators such as imidazoles, organophosphorus compounds and quaternary phosphonium salts are coated with a polymer Curing accelerator; amine salt type latent curing agent accelerator; latent curing accelerator such as high temperature dissociation type thermal cationic polymerization type latent curing accelerator such as Lewis acid salt other than gallium compound, Bronsted acid salt, etc. Can be mentioned.

Among these, since strong catalytic activity is required, it is preferably an inorganic compound, more preferably a gallium compound or an indium compound, and particularly preferably a gallium compound.
Of these, gallium acetylacetonate and gallium acetate are particularly preferable.

The gallium compound is a component that acts as a catalyst for the self-polymerization reaction of the epoxy compound in combination with silanol supplied from a silanol source compound described in detail later. The gallium compound is not particularly limited as long as it is a compound containing gallium as a metal atom, and various forms such as an oxide, a salt, and a chelate complex can be used. Gallium complex having chelate ligand, gallium acetate, gallium oxyacetate, triethoxygallium, tris (8-quinolinolato) gallium, gallium oxalate, gallium ethylxanthate, diethylethoxygallium, gallium maleate, n-octylic acid, Examples include gallium salts of long chain carboxylic acids such as 2-ethylhexanoic acid and naphthenic acid.

  Examples of the chelate ligand include β-diketone type compounds and o-ketophenol type compounds. Some β-diketone type compounds have structures represented by the following formulas (15) to (17).

In the formulas (15) to (17), R represents an alkyl group or a halogen-substituted alkyl group.
Specific examples of the compound of the formula (15) include acetylacetone, trifluoroacetylacetone, pentafluoroacetylacetone, hexafluoroacetylacetone and the like, and specific examples of the compound of the formula (16) include ethylacetoacetate and the compound of the formula (17). Specific examples of such include diethyl malonate.
The o-ketophenol type compound is a compound represented by the following formula (18).

In the formula (18), R ′ represents a hydrogen atom, an alkyl group, a halogen-substituted alkyl group or an alkoxy group.
Specific examples of the compound of formula (18) include salicylaldehyde, ethyl-O-hydroxyphenyl ketone and the like.
A gallium complex having a chelate ligand is a preferred example of a gallium compound, and among them, gallium acetylacetonate can be particularly preferably used. Two or more kinds of gallium compounds can be used in any combination.

When a Ga catalyst is used, the weight loss due to heating of the cured product is less than that of an Al catalyst. In particular, when the cured product contains a siloxane structure, the weight loss due to heating of the cured product is less than that of the Al catalyst.
Specifically, the weight loss is preferably 20% by weight or less before heating at 150 to 200 ° C. × 500 hours, and more preferably 10% by weight or less.

A gallium compound is 0.001 weight part or more normally with respect to 100 weight part of epoxy compounds, Preferably it is 0.01 weight part or more, 5.0 weight part or less, Preferably it is 1.0 weight part or less.
A silanol source compound is a compound which is a supply source of silanol. Silanol, in combination with the aforementioned gallium compound, acts as a catalyst for the self-polymerization reaction of the epoxy compound.

The role of silanol is considered to be a cation source necessary for the initiation of the self-polymerization reaction of the epoxy compound. When an aromatic group such as a phenyl group is bonded to the silicon atom of the silanol source compound, the aromatic group functions to increase the acidity of the silanol hydroxyl group, that is, to enhance the action of silanol as a cation source. it seems to do.
The silanol source compound may be a potential silanol source. For example, it is a compound which has a silicon atom to which a hydrolyzable group is bonded and which produces silanol when the hydrolyzable group is hydrolyzed. Specific examples of the hydrolyzable group include a hydroxy group, an alkoxy group, hydrogen, an acetoxy group, an enoxy group, an oxime group, and a halogen group. A preferred hydrolyzable group is an alkoxy group, and particularly an alkoxy group having 1 to 3 carbon atoms, that is, a methoxy group, an ethoxy group, or a propoxy group.

  An example of a silanol source compound is a silicon atom to which hydroxyl groups such as phenyldimethylsilanol, diphenylmethylsilanol, triphenylsilanol, dihydroxydiphenylsilane (diphenyldisilanol), trimethylsilanol, triethylsilanol, dihydroxydimethylsilane, and trihydroxymethylsilane are bonded. It is a monosilane compound having

Another example of the silanol source compound is an organopolysiloxane represented by the formula (19) having a silicon atom to which a hydroxyl group is bonded.
(R ²¹ ₃ SiO _1/2 ) a ₂ (R ²² ₂ SiO _2/2 ) _{b 2} (R ²³ SiO _3/2 ) _{c 2} (SiO _4/2 ) _{d 2} (O _1/2 H) _{e 2} (19)
In the formula (19), R ²¹ , R ²² and R ²³ each independently represent a monovalent organic group.

In the formula (19), R ²¹ ₃ SiO _1/2 represents an M unit, R ²² ₂ SiO _2/2 represents a D unit, R ²³ SiO _3/2 represents a T unit, and SiO _4/2 represents a Q unit. Yes. Each of a2, b2, c2, and d2 is an integer of 0 or more, and a2 + b2 + c2 + d2 ≧ 3. e2 is a natural number of 1 or more, and represents the number of hydroxyl groups (silanol) directly bonded to the silicon atom.

R ²¹ , R ²² and R ²³ in the formula (19) are usually hydrocarbon groups having 1 to 10 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, Alkyl groups such as hexyl group and heptyl group; alkenyl groups such as vinyl group, allyl group, butenyl group, pentenyl group and hexenyl group; aryl groups such as phenyl group, tolyl group and xylyl group; aralkyl groups such as benzyl group and phenethyl group Groups; substituted alkyl groups such as a chloromethyl group, a 3-chloropropyl group, a 3,3,3-trifluoropropyl group, and a nonafluorobutylethyl group.

The silanol source compound has a hydrolyzable group bonded to a silicon atom, and produces a organopolysiloxane represented by the formula (19) when the hydrolyzable group is hydrolyzed. Also good. In other words, the organopolysiloxane represented by the formula (19) may be a compound in which all or a part of hydroxyl groups directly bonded to silicon atoms are replaced with hydrolyzable groups.

When the silanol source compound is an organopolysiloxane and is used together with an epoxy compound that does not contain a siloxane structure, the organopolysiloxane is silicon from the viewpoint of ensuring compatibility between the organopolysiloxane and the epoxy compound. It preferably has an aromatic group bonded to an atom.
When the silanol source compound is an organopolysiloxane, the weight average molecular weight is preferably 500 or more and more preferably 700 or more so that it does not volatilize during or after curing of the thermosetting resin composition. preferable. On the other hand, if the degree of polymerization is too high, the viscosity becomes high and the handleability deteriorates, so that the weight average molecular weight is preferably 20,000 or less, more preferably 15,000 or less.

In a preferred embodiment, the silanol source compound may be an organopolysiloxane or a silane compound having two or more silicon atoms bonded to a hydroxyl group or a hydrolyzable group in one molecule. Such a silanol source compound is polycondensed by the action of the gallium compound to increase the molecular weight when heated, so that it does not bleed out after curing.
Examples of the organopolysiloxane that can be suitably used as the silanol source compound include those having structures represented by the above formulas (20) to (23).

  The organopolysiloxane represented by the formula (22) includes a compound represented by the formula (20) and a compound represented by the formula (24) (dihydroxydimethylsilane or polydimethylsiloxane having hydroxyl groups at both ends), It can be obtained by polycondensation. As the polycondensation catalyst, a metal catalyst can be used in addition to an acid and a base, and a gallium compound such as gallium acetylacetonate can also be used.

  The organopolysiloxane represented by the formula (23) can be obtained by polycondensing the compound represented by the formula (21) and the compound represented by the formula (24). As the polycondensation catalyst, a metal catalyst can be used in addition to an acid and a base, and a gallium compound such as gallium acetylacetonate can also be used.

  In Expression (20) to Expression (24), m, n, M, N, m1, and m2 are each an integer of 1 or more. When these numbers are increased too much, that is, when the degree of polymerization of the polysiloxane is increased too much, the viscosity becomes too high and handling becomes difficult, and the catalytic performance tends to decrease due to a decrease in the content of silanol. Note that occurs. From the viewpoint of handling properties, the viscosity of the organopolysiloxane or the viscosity of the resin composition obtained using the organopolysiloxane is 50,000 cp or less, preferably 40,000 cp or less, more preferably at 30 ° C. and 1 atm. Is preferably set to 30,000 cp or less, more preferably 20,000 cp or less, particularly preferably 15,000 cp or less, and most preferably 10,000 cp or less.

  An organopolysiloxane obtained by polycondensation of one or more selected from the organopolysiloxanes represented by formula (20) to formula (23) together with a trifunctional silane compound such as methyltrimethoxysilane or phenyltrimethoxysilane This is a preferred example of a silanol source compound. As the polycondensation catalyst, a metal catalyst can be used in addition to an acid and a base, and a gallium compound such as gallium acetylacetonate can also be used. Such organopolysiloxanes have the property of being cured by the action of a condensation catalyst such as an acid, a base or a metal compound such as a gallium compound. As the silanol source, a monosilane compound and an organopolysiloxane may be used in combination.

The silanol source compound is usually 0.05 parts by weight or more, preferably 0.5 parts by weight or more, and 500 parts by weight or less, preferably 200 parts by weight or less based on 100 parts by weight of the epoxy compound.
The content ratio of the gallium compound and the silanol source compound is preferably 1: 0.05 to 0.001: 100, more preferably 1:10 to 0.01: 100, by weight.

The content of the curing catalyst in the thermosetting resin composition is preferably adjusted to 0.03% to 0.3% by weight with respect to 100% by weight of the thermosetting resin composition.
In the epoxy silicone resin, either one or both of the epoxy compound and the silanol source compound may have an organopolysiloxane structure portion. In this case, when silanol is introduced into the organopolysiloxane structure, the gallium compound acts as a dehydration condensation catalyst between the silanols, so that both the self-polymerization reaction of the epoxy compound and the silanol condensation reaction are involved in curing. A good thermosetting resin composition is obtained. Since the gallium compound also serves as a catalyst for the dealcoholization condensation reaction between silanol and alkoxy group, the same effect can be obtained when silanol and alkoxy group are introduced into the organopolysiloxane structure. When the thermosetting resin has a silanol group, the gallium compound is preferable because it also serves as a catalyst for siloxane condensation and the crosslinking system proceeds simultaneously. Further, it has good compatibility with siloxane and silica and contributes to silica dispersion. Furthermore, when epoxy silicone is reacted with a gallium catalyst, the linear expansion coefficient of the resulting cured product becomes constant over a wide range.

In another example, a hydrosilyl group is introduced into one of the organopolysiloxane structure part of the epoxy compound and the organopolysiloxane structure part of the silanol source compound, and a vinylsilyl group is introduced into the other, and a hydrosilylation reaction catalyst such as a platinum compound is used. By adding, a thermosetting resin composition having good curability in which both the self-polymerization reaction and hydrosilylation reaction of the epoxy compound are involved in curing can be obtained.

  Alternatively, by introducing a hydrosilyl group into the organopolysiloxane structure part of either one or both of the epoxy compound and the silanol source compound and adding an organopolysiloxane having a vinylsilyl group and a hydrosilylation reaction catalyst, the epoxy compound Thus, a thermosetting resin composition in which both the self-polymerization reaction and hydrosilylation reaction are involved in curing is obtained. This example may be modified so that a vinylsilyl group is introduced into the organopolysiloxane structure portion of either one or both of the epoxy compound and the silanol source compound, and the organopolysiloxane to be added is introduced with a hydrosilyl group.

2) Curing agent for epoxy resin or epoxy silicone resin Examples of the curing agent that forms a cross-linked product by reaction with an epoxy group include amines, polyamide resins, acid anhydrides, and phenols. From the viewpoints of reducing the linear expansion coefficient, controlling the polymerization rate, and reducing the viscosity, it is preferable to use an acid anhydride. Examples of the acid anhydride include aliphatic acid anhydrides, alicyclic acid anhydrides, aromatic acid anhydrides, and halogen acid anhydrides. When using this resin composition for an optical semiconductor device, it is preferable to use an alicyclic carboxylic acid anhydride from the viewpoint of light resistance.

Although there is no restriction | limiting in particular as content of an acid anhydride, when too much, Tg of an acid anhydride may affect the linear expansion coefficient of the hardened | cured material obtained.
Examples of the alicyclic carboxylic acid anhydride include compounds represented by formula (25) to formula (30), 4-methyltetrahydrophthalic acid anhydride, methylnadic acid anhydride, dodecenyl succinic acid anhydride, Examples thereof include Diels-Alder reaction products of alicyclic compounds having a conjugated double bond such as α-terpinene and alloocimene and maleic anhydride, and hydrogenated products thereof.

In addition, arbitrary structural isomers and arbitrary geometrical isomers can be used as the Diels-Alder reaction product and hydrogenated products thereof.
In addition, the alicyclic carboxylic acid anhydride can be used after being appropriately chemically modified as long as the curing reaction is not substantially hindered.
By containing an acid anhydride, effects such as control of the epoxy reaction rate, handling, improvement in leveling, and prevention of coloring may be obtained. Although there is no restriction | limiting in particular as content of an acid anhydride, It is preferable that it is 1.5 equivalent or less with respect to the amount of epoxy. More preferably, it is 1 equivalent or less, More preferably, it is 0.8 equivalent or less, More preferably, it is 0.6 equivalent or less.

3) Silicone resin curing catalyst When a silicone resin is used as the matrix resin, examples of the curing catalyst include metal compounds. As the metal compound, a chelate complex, an organic acid salt, an inorganic salt, or an alkoxide of zirconium, hafnium, yttrium, tin, zinc, titanium, or gallium can be used. From the viewpoint of the linear expansion coefficient of the cured product, the above-described gallium compound is preferably used.

1-4. Others In addition to the above-mentioned components, the resin composition according to the embodiment of the present invention includes a dispersant, an antioxidant, an antifoaming agent, a colorant, a modifier, and a leveling agent from the viewpoint of improving physical properties and imparting functions. Further, additives such as a light diffusing agent, thermal conductivity, a flame retardant, a reactive or non-reactive diluent, an adhesive, and an adhesion improver, or various fillers may be further contained.

1) Antioxidant The resin composition according to the embodiment of the present invention may contain an antioxidant in order to suppress yellowing under the use environment. Phenol-based antioxidants, phosphorus-based antioxidants, hindered amines, and the like are preferably used. Among n, hindered phenol-based antioxidants having an alkyl group at one or both ortho positions of the phenol hydroxyl group are particularly suitable. Used.

2) Silane Coupling Agent The resin composition of the present invention can contain a silane coupling agent in order to improve the adhesion to metal parts and inorganic fillers. Specific examples include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ- Examples include aminopropyltrimethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane.

3) Filler A fixed amount of a filler other than the inorganic filler can be added to the resin composition of the present invention as necessary. Examples of the filler include general organic fillers. Organic fillers include styrene polymer particles, methacrylate polymer particles, ethylene polymer particles, propylene polymer particles, synthetic polymer particles such as polyamide, natural products such as starch and wood flour, cellulose that may be modified, Examples include various organic pigments.
By using a filler, in addition to reducing the viscosity, the strength, hardness, elastic modulus, thermal expansion coefficient, thermal conductivity, heat dissipation, electrical properties, light reflectance, flame retardancy, and fire resistance of the resulting molded product Various physical properties such as thixotropy and gas barrier properties can be improved.

2. Method for Producing Resin Composition The resin composition of the present invention can be produced by mixing a thermosetting resin curing agent and an inorganic filler with other components such as a diluent and an antioxidant as necessary. . The order of mixing the inorganic filler is not particularly limited. In order to prevent the progress of the curing reaction due to heat generation during mixing, the epoxy is used in the absence of a gallium compound, a silanol source compound, and other catalysts used for curing the epoxy resin. It is desirable to mix with the compound.

The means for mixing the inorganic filler is not particularly limited, but specifically, for example, a two-roll or three-roll, a planetary stirring deaerator, a homogenizer, a dissolver, a planetary mixer, or the like, Examples thereof include a melt kneader such as a plast mill. Mixing may be performed at normal temperature, may be performed by heating, may be performed under normal pressure, or may be performed under reduced pressure. If the temperature during mixing is high, the composition may be cured before molding.
This resin composition may be a one-component curable type or a two-component curable type in consideration of storage stability.

3. Cured resin
Since the resin composition according to this embodiment refers to an epoxy compound having a high elongation rate and high breaking strength in a tensile test, the cured product is highly flexible and resistant to bending. The bending strain at 25 ° C. is preferably 2% or more. Further, it is more preferably 3% or more, further preferably 4% or more, and particularly preferably 5% or more.
By being highly flexible and resistant to bending at the time of curing, it is possible to provide a resin composition that can suppress stress and hardly generate cracks.

4). Sealing Method The liquid resin composition of the present invention is preferably used as a sealing material for semiconductor devices, but the sealing method may be performed by a commonly performed method.
Examples of the sealing method include transfer molding and potting. Since the resin composition of the present invention is a liquid resin composition having fluidity at room temperature, it is preferably used for potting. Specifically, a liquid containing a resin composition and a liquid containing a curing catalyst are respectively prepared and then mixed to prepare a mixed liquid that can be used for potting. A part is placed in the housing, and the above-mentioned mixed liquid is poured into it. Then it is cured. Depending on the matrix resin used, room temperature curing or heat curing may be used. For heat curing, conventionally known methods such as hot air circulation heating, infrared heating, and high-frequency heating can be employed. The heat treatment conditions may be determined according to the matrix resin, the catalyst concentration, the thickness of the member to be formed with the composition, and the like as long as the resin composition can be brought into a desired cured state.

  The matrix resin of the present invention contains a thermosetting resin. By setting the curing temperature to about 100 ° C. at first and then to about 150 ° C., foaming due to residual solvent or dissolved water vapor in the composition can be prevented. Moreover, since the difference in the curing rate between the deep part and the surface can be reduced, a cured product having a smooth surface and no wrinkles and a good appearance can be obtained. When the difference in curing speed between the deep part and the surface is small, the cured state becomes uniform, so that the generation of internal stress in the cured product is suppressed, and the generation of cracks can be prevented.

5. Application of Liquid Resin Composition The application of the resin composition according to the embodiment of the present invention is not particularly limited, and can be used as a sealing material for various semiconductor devices including light emitting devices such as LED devices. In addition, since the molded product obtained by curing the resin composition of the present invention contains an inorganic filler at a high concentration, it has a low coefficient of thermal expansion even at a high temperature, and is less susceptible to cracking by relaxing the stress, and is excellent in reliability. Especially, it is suitably used for a power device. Examples of the power device include those used as rectification, frequency conversion, a regulator, an inverter, and the like. The resin composition of the present invention has fluidity as a composition, can be suitably used for sealing by potting, and has a very low linear expansion coefficient when cured, so a wide range of power It can be suitably used for a device. It can also be used for power devices such as home appliances and computers, and can also be used for large power devices for controlling automobiles, railway vehicles, and substations.

Hereinafter, the present invention will be described in detail by way of examples.
<Synthesis of epoxy silicone resin>
2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane 13.00 g, trimethylethoxysilane 3.67 g, both-end silanol-type dimethylsiloxane (XC96-723 manufactured by Momentive) 53.4 g, isopropyl alcohol 34.59 g, and toluene 34.59 g and 1N potassium hydroxide (6.99 g) were mixed, stirred at room temperature for 2 hours, and further heated and stirred under reflux conditions at 73 ° C. ± 2 ° C. for 6 hours. Thereafter, the reaction solution was neutralized with an aqueous sodium dihydrogen phosphate solution (10 parts by weight), washed with water until the washed water became neutral, volatile components were removed under reduced pressure, Mw = 3300, Polysiloxane EPSi-1 having an epoxy value of 1160 was obtained.

[Example 1]
2.3 parts by weight of the above EPSi-1, 3.3 parts by weight of jER871 (Mitsubishi Chemical Corporation), 0.9 parts by weight of Denacol EX-216L (cyclohexanedimethanol diglycidyl ether manufactured by Nagase ChemteX), Sanso 2.3 parts by weight of sizer E-PO (Epoxyhexahydrophthalic acid diepoxy stearyl manufactured by Shin Nippon Rika Co., Ltd.) and 90.0 parts by weight of spherical filler HL-3100 (manufactured by Tatsumori) were added to a planetary mixer (THINKY). Stirring and mixing using Planetary Vacuum Mixer ARV-300).

Thereafter, 0.8 parts by weight of acid anhydride curing agent MH700 (manufactured by Shin Nippon Chemical Co., Ltd.), FLD516 (both terminal hydroxy group polymethylphenylsiloxane manufactured by BLUESTARS SILICONES: weight average molecular weight of about 900 in terms of polystyrene) and gallium acetylacetate 0.3 parts by weight of a solution (Ga (acac) ₃ solution) in which 2 wt% of Nate (Strem Chemicals, Inc.) was dissolved was added and stirred and mixed to obtain Composition 1.

[Comparative Example 1]
3.0 parts by weight of the above EPSi-1, 3.0 parts by weight of E-PO, 0.6 parts by weight of YED-216D (manufactured by Mitsubishi Chemical), 2.3 parts by weight of YL-7410 (manufactured by Mitsubishi Chemical) And 90 parts by weight of spherical filler HL-3100 (manufactured by Tatsumori Co., Ltd.) was stirred and mixed using a planetary mixer (Planetary Vacuum Mixer ARV-300 manufactured by THINKY).
Thereafter, 0.7 part by weight of acid anhydride curing agent MH700 and 0.3 part by weight of Ga (acac) ₃ solution were added and stirred and mixed to obtain composition 2.

<Tensile test of epoxy compound>
1 g of epoxy compound, acid anhydride curing agent MH700 (manufactured by Shin Nippon Chemical Co., Ltd.) is 1: 1 with respect to the epoxy equivalent of the epoxy compound, and 0.01 g of Hishicolin PX-4MP (manufactured by Nippon Chemical Industry Co., Ltd.) is weighed. Taken and stirred using a stirrer.
The obtained mixed solution was applied to an aluminum dish having an inner diameter of 7 mmφ with a thickness of about 1 mm and cured by heating in an oven at 100 ° C. for 1.5 hours and at 140 ° C. for 1.5 hours. The obtained cured product was cut out to 30 * 4 mm, and measured according to JIS K7162, using a STA-1225 type manufactured by ORIENTEC as a tensile test device under the following conditions.

Full scale load: 500N
Initial material length: 20mm
Test speed: 20 mm / min
Environmental humidity: 60% RH; Temperature: 25 ° C
The number of measurements was n = 3, and the average value of elongation at break and break strength was calculated.

<Evaluation of viscosity of composition>
The obtained composition (about 6 g) was placed in a 6 cc ointment container, and the viscosity was measured at 40 to 20 ° C. using a vibration viscosity system (model: VM-10A-H) manufactured by Seconic Corporation. 2
Table 1 shows the measured values obtained by dividing the viscometer display value at 5 ° C. by the specific gravity.

<Bending test of cured product>
Composition 1 or composition 2 is applied to a thickness of 2 mm using a self-made mold, and is oven-treated at 80 ° C. for 30 minutes, 120 ° C. for 60 minutes, 150 ° C. for 60 minutes, and 180 ° C. for 180 minutes. After sequentially heating and curing, the resulting cured product was cut out to 50 × 5 mm, and in accordance with JISK7171 (plastic-bending characteristics), TA Instruments RSA-III and measuring jig: 3-PT BENDING Measurement was performed under the following conditions using TOOL.

Geometry: Three Point Bending Geometry
Test Setup: MultiExtension
Test Parameters: Temperature 25 [° C.]
Extension Rate -0.01 [mm / s]
Delay Before Test 5 [s]
The number of measurements was n = 3, and the average value of bending strain at break was calculated.

<Hardened material production and crack generation observation>
A stainless steel plate is fixed around a copper-clad silicon nitride substrate (KO-PWR131845 manufactured by Kyocera Corporation) with Kapton tape, and about 34 to 38 g of compositions 1 and 2 are poured onto the substrate, respectively, at 80 ° C. for 30 minutes, 120 ° C. Were cured by sequentially heating under conditions of 60 minutes at 150 ° C. for 60 minutes at 150 ° C. and 180 minutes at 180 ° C. After the obtained cured product was cooled to room temperature over about 1 hour, the stainless steel plate was removed, and it was visually confirmed whether cracks and peeling occurred on the upper surface and side surfaces of the cured product.
The results are shown in Table 1.

The cured product 1 had no cracks, while the cured product 2 had cracks. From this result, the cured product 1 contains an epoxy compound having a high elongation rate in the tensile test and a high breaking strength, so that the bending strain in the bending test is large, the stress is suppressed, and the sealing resin is less prone to cracking. It is thought that it became a composition.

  The application of the resin composition provided by the present invention is not particularly limited, and may be used for any application, but can be suitably used for the sealing of semiconductor elements, and particularly power. It can be suitably used for a device.

Claims (9)

A thermosetting resin composition comprising a thermosetting resin, an inorganic filler and a curing catalyst,
The composition contains an epoxy compound having an elongation of 15% or more and a breaking strength of 0.5 MPa or more in a tensile test,
The cured product of the thermosetting resin composition has a bending strain at 25 ° C. of 2% or more, and is a thermosetting resin composition.   The thermosetting resin composition according to claim 1, wherein the composition contains 70% by weight or more of an inorganic filler.   The thermosetting resin composition according to claim 1, wherein the inorganic filler is a spherical filler.   The thermosetting resin composition according to claim 1, wherein the inorganic filler is silica.   The thermosetting resin composition according to claim 1, comprising an epoxy silicone.   The thermosetting resin composition according to claim 1, comprising an organometallic compound and a silanol source.   The thermosetting resin composition according to claim 6, wherein the organometallic compound is a gallium compound.   The molded object formed by hardening | curing the thermosetting resin composition in any one of Claims 1-7.   A semiconductor device which is sealed with the thermosetting resin composition according to claim 1.