JP6609935B2 - Resin composition - Google Patents

Description

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

  A sealing material such as a semiconductor device is required to have a low coefficient of linear expansion in addition to insulation and thermal reliability. This is because when a resin having a high linear expansion coefficient is used as the sealing material, the sealing resin is prevented from expanding or cracking due to heat generated from the semiconductor device. In order to lower the linear expansion coefficient, a filler (filler) is generally added to the sealing material (for example, Patent Document 1 or 2).

  The device sealing method varies depending on the type of resin. Generally, when sealing with an epoxy resin, sealing is performed by transfer molding or the like, and with silicone resin, sealing is performed by potting. In any method, the sealing resin needs fluidity.

JP 2004-27005 A JP 2009-67890 A

  As described above, in order to reduce the linear expansion coefficient of the sealing material, it is necessary to contain a large amount of a filler such as a filler. However, when the amount of the filler is increased, there is a problem that the fluidity of the sealing material (resin composition) is lowered and handling during molding becomes difficult. In particular, a certain level of fluidity is required for sealing by potting. Generally, when a filler is contained in an amount of 50% by weight or more, the viscosity becomes too high and the fluidity is lost, thereby providing a liquid resin composition. I couldn't.

In order to lower the viscosity of the resin composition highly filled with filler, it is common to pre-treat the filler surface or disperse it in a nonpolar solvent, but the filler surface treatment is costly, A system containing a solvent has a problem in that it requires a process cost to remove the solvent.
An object of the present invention is to provide a sealing resin composition having fluidity without performing a surface treatment of the filler, and without using a general-purpose solvent, even if the resin composition contains many fillers. To do.

As a result of intensive studies to solve the above problems, the inventors of the present invention have a specific Hansen solubility parameter (hereinafter simply referred to as “Hansen parameter”) in a resin composition containing 50% by weight or more of filler. It has been found that the flowability of the resin composition can be effectively improved by adding a matrix resin having a bond term value. That is, the present invention is as follows.
[1] A resin composition comprising 50% by weight or more of a filler and a matrix resin, wherein the matrix resin has a hydrogen bond term in the Hansen parameter of 0.5 or more and 5.0 or less. A resin composition.
[2] The resin composition according to the above [1], wherein the matrix resin contains a cyclic ether compound.
[3] The resin composition according to the above [1] or [2], wherein the resin composition contains silicone.
[4] The resin composition according to [3], wherein the silicone includes epoxy silicone.
[5] The resin composition according to any one of [1] to [4], wherein the filler has a hydroxyl group.
[6] The resin composition according to any one of [1] to [5], wherein the filler is silica.
[7] The resin composition according to any one of [1] to [6], wherein the resin composition includes a metal catalyst.
[8] The resin composition according to the above [7], wherein the metal catalyst is a gallium catalyst.
[9] A cured resin obtained by curing the resin composition according to any one of [1] to [8].
[10] A semiconductor device sealed with the cured product according to [9].

According to the present invention, a liquid resin composition containing 50% by weight or more of a filler can be provided without performing a surface treatment of the filler and without using a general-purpose solvent. That is, although the linear expansion coefficient when cured can be lowered, it is possible to provide a resin composition having fluidity as a composition and capable of being sealed by potting.
The mechanism that exerts the effect of the present invention is that the matrix resin having a specific Hansen parameter has a good affinity with the polar group on the filler surface, so that it effectively blocks the interaction such as hydrogen bonding between the fillers. This is probably because the structural viscosity can be lowered.

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 viscosity of the resin composition, it means the viscosity measured at 25 ° C. using a vibration viscometer in accordance with JISZ 8803-2011.
Further, in the following description, when referring to the average linear expansion coefficient of the cured product of the resin composition, the average linear expansion measured according to the JIS K7197 standard in a compression mode using a thermomechanical analysis (TMA) apparatus. It means rate (CTE).

1. Resin Composition A first embodiment of the present invention is a “resin composition characterized by having a filler of 50% by weight or more and having a hydrogen bond term in the Hansen parameter of the matrix resin of 5.0 or less”. is there. The resin composition is liquid.
In this embodiment, liquid means having fluidity under predetermined conditions. The detailed measurement method conforms to the method described in the examples.

  More specifically, at 30 ° C. and 1 atm, the viscosity is usually 50 Pa · s or less, preferably 40 Pa · s or less, more preferably 30 Pa · s or less, and more preferably 20 Pa · s or less. Is more preferably 15 Pa · s or less, and most preferably 10 Pa · s or less. By satisfying the physical properties in this range, handling is easy especially in sealing by potting.

2. Filler The resin composition of the present invention contains 50% by weight or more of filler. As the filler, both general organic fillers and inorganic fillers can be used. Organic fillers include styrene polymer particles, methacrylate polymer particles, ethylene polymer particles, propylene polymer particles, polyamide polymer particles, synthetic polymer particles such as polynylon polymer particles, natural products such as starch and wood flour, Examples thereof include cellulose which may be modified and various organic pigments. 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, quartz, fumed silica, precipitated silica, anhydrous silicic acid, fused silica, crystalline silica, ultrafine powder amorphous silica. Silica-based inorganic fillers such as 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, potassium titanate, calcium silicate, inorganic balloon, silver powder and the like. These may be used alone or in combination of two or more. Moreover, you may perform a surface treatment suitably. 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.

The filler content in the composition is usually 50% 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 further preferably 90% by weight or more.
By using a filler, the strength, hardness, elastic modulus, thermal expansion coefficient, thermal conductivity, heat dissipation, electrical properties, light reflectance, flame retardancy, fire resistance, thixotropy, and gas barrier of the molded product obtained Various physical properties such as properties can be improved.
Among the fillers, silica filler is preferably used. Hereinafter, the silica filler will be described in detail.

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.
In a normal resin composition, when the amount of filler added increases, the viscosity of the composition increases significantly.

From the viewpoint of viscosity control, the spherical shape is preferable to the fibrous or amorphous shape. 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.
Furthermore, it is preferable to have a hydroxyl group on the filler surface from the viewpoint of blending. Since the polarity of the filler surface can be improved by having a hydroxyl group, an organic polymer having a higher polarity than an inorganic substance can be easily mixed.

It is also possible to increase the amount of addition by controlling the particle size distribution. That is, a higher filling rate can be obtained by mixing fillers having different particle sizes.
An average particle diameter is measured using (Particle Size Analyzer CILAS 1064), 0.1 micrometer or more is preferable and 1 micrometer or more is more preferable. Moreover, 100 micrometers or less are preferable and 50 micrometers or less are more preferable.

The surface area, preferably at least 0.2 m ² / g, more preferably at least 0.5 m ² / g, preferably ^{15 m} 2 / g or less, ^{10 m} 2 / g or less is more preferable.
Silica may be appropriately surface-treated. 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. By the surface treatment, the type of particle surface functional group can be controlled. From the viewpoint of reducing the viscosity, it is preferable to use (glycidylated) treated filler.
One type of silica may be used, or two or more types may be used in combination.

3. Details of the matrix resin Hansen parameter, in which the hydrogen bond term in the Hansen parameter is 5.0 or less , and the measurement method at 25 ° C. are described in C.I. M.M. An article by Hansen: "The three dimensional solubility parameters" Paint Technol. 39, 105 (1967), and Hansen Solubility Parameters, A User's Handbook by Charles M .; Hansen, CRC Press Boca Raton Fl (2007), both of which are expressly incorporated herein by reference.

Here, δD indicates the characteristics of cohesive dispersion force (nonpolar interaction, etc.), δH indicates the characteristics of specific interaction force (interaction such as hydrogen bond, acid / base, donation / acceptance, etc.) δP indicates the characteristics of Debye interaction force between permanent dipoles and Keesom interaction force between induced dipoles and dipoles.
The Hansen parameters δD, δH, and δP are expressed in the unit Mpa1 / 2. The hydrogen bond term in the Hansen parameter of the present invention means δH.

The calculation method of the Hansen parameter of the matrix resin is the sum of products of the hydrogen bond term and the volume fraction in the Hansen parameter of each component that is a constituent component of the matrix resin. A specific calculation method is as described in the examples.
The matrix resin is not particularly limited as long as the hydrogen bond term (δH) in the Hansen parameter is 0.5 or more and 5.0 or less. Further, it is preferably 2.0 or more and 5.0 or less, more preferably 3.0 or more and 5.0 or less. If it is the said range, it will become possible to cut off the interaction between particle | grains by the hydrogen bond of fillers, and it will become possible to make a resin composition low viscosity.

The matrix resin is formed of all organic monomers and polymers except the silicone resin and the epoxy silicone resin contained in the resin composition.
For example, the bisphenol A type epoxy resin, bisphenol F type epoxy resin, 3,3 ′, 5,5′-tetramethyl-4,4′-biphenol type epoxy resin or 4,4′-biphenol type epoxy resin described above. Biphenol type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, naphthalenediol type epoxy resin, trisphenylol methane type epoxy resin, tetrakisphenylol ethane type epoxy resin, and phenol di Known epoxy resins that are liquid at room temperature, such as epoxy resins obtained by hydrogenating the aromatic ring of cyclopentadiene novolac-type epoxy resins and alicyclic epoxy resins. Moreover, the same oxetane resin is also mentioned. If necessary, a certain amount of a cyclic ether compound other than the above can be used in combination.

The content of the cyclic ether compound is preferably 0.1% by weight or more and more preferably 0.5% by weight or more when the total amount of the 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.
Specific structural examples of the cyclic ether compound are shown in formulas (1) to (12).

[R represents an optionally substituted aliphatic, alicyclic, or aromatic divalent hydrocarbon group. ]
The cyclic ether compound may be an aromatic epoxy compound and an aromatic oxetane 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 (12). Bivalent phenols such as bisphenol type epoxy resins obtained by glycidylation of bisphenols such as bisphenol A, biphenyl type epoxy resins represented by the formula (13), 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 Tetrakis phenols glycidylated epoxy resins, such as hydroxyphenyl) ethane, phenol novolac, cresol novolac, bisphenol A, novolak, such as novolaks the glycidylated novolak type epoxy resins such as brominated bisphenol A novolak and the like.

[R represents an optionally substituted hydrocarbon group or halogen having 1 to 12 carbon atoms]
The aromatic epoxy compound and the aromatic oxetane compound may be hydrogenated epoxy compounds and oxetane compounds having an alicyclic structure.
Although the composition according to the first embodiment of the present invention has been described above, specific examples in the case where the composition is applied as a semiconductor sealing material will be described below. However, the present invention is not limited to the embodiments described in detail below.
The resin component contained in the resin composition of the present invention includes a thermosetting resin and / or a thermoplastic resin.

4). Thermosetting resin Thermosetting resin is not particularly limited, but phenol resin, epoxy resin, melamine resin, urea resin, polyurethane, thermosetting polyimide, unsaturated polyester resin, thermosetting silicone resin, epoxy silicone resin, etc. Used. Among these, an epoxy resin, a silicone resin, and an epoxy silicone resin are preferable, and a matrix resin containing 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 resin composition is 100% by weight from the viewpoint of viscosity reduction and curability. Moreover, 25 weight% or less is preferable and 23 weight% or less is more preferable.
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, it distinguishes from the cyclic ether compound mentioned above and the epoxy silicone resin mentioned later. That is, as the resin composition of the present invention, a known epoxy resin may be mixed with the composition separately from the cyclic ether compound described above and the epoxy silicone resin described later.

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 weight 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 weight 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. More preferably. 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 0.01% by weight or more, preferably 0.1% by weight or more, more preferably 1% by weight when the total amount of the liquid resin composition is 100% by weight from the viewpoint of viscosity reduction. % Or more. 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. A 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
Examples include 3-tetramethyldisiloxane, (3-glycidoxypropyl) pentamethyldisiloxane, and 3-epoxypropyl (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 when the polysiloxane type epoxy compound is produced 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) Rohekishiru) ethyl] (dimethyl) disiloxane, 1,3-bis (3-glycidoxypropyl) 1,1,
Examples include 3,3-tetramethyldisiloxane, (3-glycidoxypropyl) pentamethyldisiloxane, and 3-epoxypropyl (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.

5. Thermoplastic resin The thermoplastic resin is not particularly limited, but it is not limited to polyethylene, polypropylene, polystyrene, polyvinyl chloride, (meth) acrylic resin, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer and other vinyl polymers, poly Polyester such as lactic acid resin, polyethylene terephthalate, polybutylene terephthalate, polyamide such as nylon, polyamide amine, polyvinyl acetal resin such as polyvinyl acetoacetal, polyvinyl benzal, polyvinyl butyral resin, ionomer resin, polyphenylene ether, polyphenylene sulfide, polycarbonate, poly Ether ether ketone, polyacetal, ABS resin, LCP (liquid crystal polymer), fluorine resin, urethane resin, elastomer, Others include modified products of these resins.

  Of these, polyvinyl acetals such as polyvinyl butyral and vinyl resins such as (meth) acrylic resins are preferable, and polyvinyl acetal such as polyvinyl butyral is particularly preferable. Polyvinyl acetal has a hydroxyl group and is excellent in dispersibility. In addition, when the curing agent is reactive with a hydroxyl group (such as an acid anhydride), a part of the acetal is taken in, so that separation from the thermosetting resin hardly occurs. . It is also possible to positively introduce a reactive group by modification with an acid anhydride in advance.

The thermoplastic resin is preferably stretchable. The elongation can relieve stress and suppress cracks.
The maximum elongation of the thermoplastic resin is preferably 5% or more, and more preferably 10% or more. The maximum elongation of the thermoplastic resin is a value measured by a measuring method based on JIS K7113 or ASTM D638.

The thermoplastic resin is preferably soluble in at least one component of the thermosetting resin in the matrix resin. 1% or more, preferably 3% or more, more preferably 5% or more, still more preferably 10% or more is soluble in at least one component of the thermosetting resin.
When the thermoplastic resin is soluble in at least one component of the thermosetting resin, the uniformity of the composition is maintained, stress is easily dispersed, and cracks are less likely to occur due to the absence of an interface.

  The content of the thermoplastic resin in the matrix resin is preferably 0.001% to 10.0%, more preferably 0.003% to 5.0% in the liquid resin composition, It is still more preferable that it is% -2.0%.

6). Curing catalyst and curing agent The resin composition of the present invention may contain a curing agent and / or a curing catalyst, if necessary. The curing agent and / or curing catalyst may be appropriately contained depending on the type of resin used. When using a thermosetting resin, 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 an epoxy resin and / or an epoxy silicone resin as a matrix resin, a catalyst used for curing an ordinary epoxy resin 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 compounds, indium compounds; 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 addition products of dicyandiamide and amines with epoxy resins High melting point dispersion type latent curing accelerators such as amine addition type accelerators of the above; 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 liquid resin composition obtained using the organopolysiloxane is 50,000 cp or less, preferably 40,000 cp or less at 30 ° C. and 1 atm. The degree of polymerization is preferably set so that it is preferably 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.

It is preferable to prepare the content of the curing catalyst in the thermosetting resin composition so as to be 0.003% by weight 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 such that a vinylsilyl group is introduced into the organopolysiloxane structure part 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.

7). In addition to the above-mentioned components, the liquid 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 from the viewpoint of improving physical properties and imparting functions. It may further contain additives such as an agent, a light diffusing agent, a thermal conductivity, a flame retardant, a reactive or non-reactive diluent, an adhesive, and an adhesion improver.

1) Antioxidant The liquid 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 liquid resin composition of the present invention may 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.

8). Method for Producing Resin Composition The resin composition of the present invention can be produced by mixing the filler, the specific cyclic ether, and other components such as the resin, diluent, and antioxidant described above as necessary. it can. The order of mixing the fillers is not particularly limited. For example, in order to prevent the curing reaction from proceeding due to heat generation during mixing, it is desirable to mix with an epoxy compound in the absence of a catalyst used for curing a gallium compound, a silanol source compound, or other epoxy resin.

The means for mixing the filler is not particularly limited, but specifically, for example, a two-roll or three-roll, a planetary stirring and defoaming device, a homogenizer, a dissolver, a planetary mixer, etc., a plast mill And a melt kneader. 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.

9. Resin cured product Since the resin composition according to the present embodiment contains 50% by weight or more of silica filler, the linear expansion coefficient of the cured product is very low, and the average linear expansion coefficient at 70 to 100 ° C. is usually It is preferably 100 ppm / K or less, more preferably 75 ppm / K or less, further preferably 50 ppm / K or less, further preferably 40 ppm / K or less, and 30 ppm / K or less. Is particularly preferred.

Moreover, the average linear expansion coefficient in 210-240 degreeC is 100 ppm / K or less normally, it is preferable that it is 75 ppm / K or less, and it is more preferable that it is 50 ppm / K or less.
Moreover, it is preferable that the average linear expansion coefficient of 70-210 degreeC is 100 ppm / K or less, It is more preferable that it is 50 ppm / K or less, It is still more preferable that it is 40 ppm / K or less.

The 25 ° C. storage elastic modulus is preferably 1.0 × 10 ⁵ Pa or more and 1.0 × 10 ¹⁰ Pa or less, and preferably 1.0 × 10 ⁶ Pa or more and 1.0 × 10 ¹⁰ Pa or less. Further preferred. If the storage elastic modulus at 25 ° C. is 1.0 × 10 ¹⁰ Pa or more, the stress relaxation is not sufficient, which causes cracks. When it is less than 1.0 × 10 ⁵ Pa, the mechanical strength of the composition is not sufficient, and there is a concern such as wire collapse due to vibration.
Since the linear expansion coefficient is small and the storage elastic modulus is small, it is possible to reduce stress due to a difference in linear expansion from the substrate during curing or temperature change, and it is possible to suppress the generation of cracks.

10. 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.

11. Use of liquid thermosetting resin composition The use of the resin composition according to the embodiment of the present invention is not particularly limited, and is used as a sealing material for various semiconductor devices including light emitting devices such as LED devices. Can do. In addition, the molded body obtained by curing the resin composition of the present invention contains 50% by weight or more of silica filler, so that it has a low coefficient of thermal expansion even at high temperatures and is less likely to cause cracks by relaxing stress, and has excellent reliability. Therefore, it is particularly preferably used for power devices. Examples of the power device include those used as rectification, frequency conversion, a regulator, an inverter, and the like. The liquid resin composition of the present invention has fluidity as a composition, can be suitably used for sealing by potting, and has a very low coefficient of linear expansion when cured, so it has a wide range of sizes. It can be suitably used for power devices. 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, although an example of an experiment (an example and a comparative example) explains the present invention still in detail, the present invention is not limited by the following examples, unless the gist is exceeded. In addition, the values of various production conditions and evaluation results in the following examples have meanings as preferable values of the upper limit or the lower limit in the embodiment of the present invention, and the preferable range is the value of the upper limit or the lower limit. It may be a range defined by a combination of values of the following examples or values of the examples.

<Synthesis of epoxy silicone resin>
64.8 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 40.1 g of trimethylethoxysilane, 45 g of isopropyl alcohol and 24.39 g of 1N hydrochloric acid were mixed and stirred at room temperature for 3 hours. .51 g and 148 g of isopropyl alcohol were added, and the mixture was heated and stirred for 4 hours under reflux conditions of isopropyl alcohol. Thereafter, the reaction solution was neutralized with an aqueous solution of sodium dihydrogen phosphate (10% by weight), washed with water until the washed water became neutral, volatile components were removed under reduced pressure, and Mw = 4002. Polysiloxane EPSi-1 was obtained.

[Example 1]
0.5 g of the above EPSi-1, 0.5 g of E-PO (manufactured by Shin Nippon Chemical Co., Ltd.), 0.25 g of JER871 (manufactured by Mitsubishi Chemical Corporation), 0.36 g of YED216D (manufactured by Mitsubishi Chemical Corporation), true spherical filler HL- 3100 (manufactured by Tatsumori) 16.9 g of Planetary made by THIKY
Stir and mix using Vacuum Mixer ARV-300. Then, 0.20 g of acid anhydride curing agent Rikacid MH-700 (manufactured by Shin Nippon Rika Co., Ltd.), polymethylphenylsiloxane FLD 516 (both terminal STARS SILICONES) having a weight average molecular weight of about 900 in terms of polystyrene was added to gallium acetylacetate. 0.069 g of a solution (Ga (acac) ₃ solution) in which 2% by weight of Nate (Strem Chemicals, Inc.) was dissolved was added and further stirred and mixed to obtain a composition.

  The hydrogen bond term in the Hansen parameter of the matrix resin of this composition was calculated as follows. E-PO, JER871, YED216D, and MH-700 correspond to the matrix resin in this composition. The weight percentage of each component is 38.2, 19.1, 27.4, 15.3. The specific gravity of each component is 0.985, 0.985, 1.03, and 1.15. Moreover, the hydrogen bond term in the Hansen parameter of each component is 3.9, 4, 6.9, 6. Based on these values, the product of the hydrogen bond term in each component's Hansen parameter and the volume fraction of each component is calculated to be 1.51, 0.78, 1.83, and 0.80, respectively. 4.92. This value is the hydrogen bond term in the Hansen parameter of the matrix resin.

[Examples 2 to 4]
Based on the method of Example 1, the compounds shown in Table 1 were added to obtain a resin composition.
[Comparative Examples 1-3]
Based on the method of Example 1, the compounds shown in Table 1 were added to obtain a resin composition.
<Evaluation of fluidity of composition>
In this embodiment, fluidity is defined as follows. Aluminum cup with handle No. When 2 g of the resin composition is weighed into 2 (manufactured by ASONE Co., Ltd.) and tilted at 90 degrees on a 40 ° C. hot plate, it means that the resin cannot maintain the form for 30 minutes or more.

  As is clear from the results in Table 1, the resin compositions of Examples 1 to 4 were fluid. On the other hand, the resin compositions of Comparative Examples 1 to 3 did not have fluidity.

Claims (6)

A resin composition comprising 50% by weight or more of a filler, a matrix resin, and silicone,
The silicone includes an epoxy silicone,
The filler is silica;
The said matrix resin is an epoxy resin, The hydrogen bond term in the Hansen parameter is 2.0 or more and 5.0 or less, The resin composition characterized by the above-mentioned. The resin composition according to claim 1, wherein the filler has a hydroxyl group. The resin composition according to claim 1 or 2, wherein the resin composition contains a metal catalyst. The resin composition according to claim 3 , wherein the metal catalyst is a gallium catalyst. Cured resin formed by curing a resin composition according to any one of claims 1-4. A semiconductor device sealed with the cured product according to claim 5 .