JP6657566B2 - Low viscosity resin composition - Google Patents

Description

  The present invention relates to a resin composition suitably used as a sealing material for a semiconductor device or 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 to prevent the sealing resin from expanding or cracking due to heat generated from the semiconductor device when a resin having a high coefficient of linear expansion is used as the sealing material. In order to lower the coefficient of linear expansion, it is common to add a filler to the sealing material (for example, Patent Documents 1 and 2).

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

JP 2004-27005 A JP 2009-67890 A

  As described above, in order to lower the coefficient of linear expansion 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) decreases, and handling during molding becomes difficult. In particular, when sealing by potting, a certain degree of fluidity is required. In general, when the filler is contained in an amount of 50% by weight or more, the viscosity becomes too high, the fluidity is lost, and a liquid resin composition is provided. Could not.

  In addition, in order to reduce the viscosity of the resin composition highly filled with filler, it is common to pre-treat the surface of the filler, or to disperse in a non-polar solvent, but the surface treatment of the filler is costly, A system containing a solvent has a problem in that the removal of the solvent requires a high process cost.

  An object of the present invention is to provide a sealing resin composition having fluidity, even if the resin composition contains many fillers, without performing the surface treatment of the fillers, and without using a general-purpose solvent. I do.

  The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, added a small amount of a low molecular weight compound having a specific Hansen solubility parameter to a resin composition containing 50% by weight or more of a filler, thereby obtaining the resin composition. It has been found that the fluidity of a product can be effectively improved. That is, the present invention is as follows.

[1] A resin composition containing 50% by weight or more of a filler, which contains a cyclic ether compound having a hydrogen bond term in a Hansen parameter of 0.5 or more and 8.1 or less and a weight average molecular weight of less than 500. Characterized by a resin composition.
[2] The resin composition according to the above [1], wherein the filler has a hydroxyl group.
[3] The resin composition according to the above [1] or [2], wherein the filler is silica.
[4] The resin composition according to any one of the above [1] to [3], wherein the resin composition contains a cyclic ether compound having a weight average molecular weight of 500 or more.
[5] The resin composition according to any one of [1] to [4], wherein the resin composition contains silicone.
[6] The resin composition according to the above [5], wherein the silicone is an epoxy silicone.
[7] The resin composition according to any one of [1] to [6], wherein the resin composition contains a metal catalyst.
[8] The resin composition according to the above [7], wherein the metal catalyst is a gallium compound.
[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 the above [9].

  According to the present invention, a liquid resin composition containing 50% by weight or more of a filler can be provided without performing surface treatment of the filler and without using a general-purpose solvent. In other words, it is possible to provide a resin composition having fluidity as a composition and capable of coping with sealing by potting, although the coefficient of linear expansion when a cured product can be reduced.

  The mechanism of achieving the effect of the present invention is to add a small amount of a low molecular weight compound having a specific Hansen solubility parameter, so that the low molecular weight compound has a good affinity with the polar group on the filler surface, between the filler and the matrix resin or filler. This is presumably because the composition is easily located at the interface, thereby effectively blocking the interaction such as hydrogen bonding between the filler and the matrix resin or the filler, thereby reducing the structural viscosity of the composition.

Hereinafter, the present invention will be described in detail with reference to embodiments. However, the invention is not limited to the embodiments explicitly or implicitly described herein.
In the following description, when referring to the viscosity of the resin composition, it means the viscosity measured at 25 ° C. using a vibrating viscometer according to JISZ 8803-2011.

  In the following description, when referring to the average coefficient of linear expansion of the cured product of the resin composition, the average linear expansion measured in a compression mode using a thermomechanical analyzer (TMA) in accordance with JIS K7197 standard. Rate (CTE).

1. Resin Composition A first embodiment of the present invention relates to a resin composition containing at least 50% by weight of a filler, wherein a hydrogen bond term in a Hansen parameter is 0.5 or more and 8.1 or less, and A resin composition comprising a cyclic ether compound having an average molecular weight of less than 500 ". The resin composition is in a liquid state.
In the present embodiment, “liquid” means having fluidity under predetermined conditions. The detailed measuring 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 20 Pa · s or less. Is more preferably, 15 Pa · s or less, particularly preferably 10 Pa · s or less. By satisfying the physical properties in this range, handling is easy particularly in sealing by potting.

2. Filler The resin composition of the present invention contains 50% by weight or more of a filler. As the filler, any of general organic fillers and inorganic fillers can be used. As organic fillers, styrene-based polymer particles, methacrylate-based polymer particles, ethylene-based polymer particles, propylene-based polymer particles, polyamide-based polymer particles, synthetic polymer particles such as polynylon-based polymer particles, starch, natural products such as 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, silicic anhydride, fused silica, crystalline silica, ultrafine amorphous silica Such as silica-based inorganic filler, 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, clay, talc, aluminum hydroxide, calcium carbonate, manganese carbonate, magnesium carbonate, barium sulfate, potassium titanate, calcium silicate, inorganic balloons, silver powder and the like. These may be used alone or in combination of two or more. Moreover, you may give 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 content of the filler 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, the content 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, coefficient of thermal expansion, thermal conductivity, heat dissipation, electrical properties, light reflectance, flame retardancy, fire resistance, thixotropic property, and gas barrier of the obtained molded article are obtained. Various physical properties such as properties can be improved.
It is preferable to use a silica filler among the above fillers. 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 an ordinary resin composition, as the amount of the filler added increases, the viscosity of the composition increases remarkably.

  From the viewpoint of viscosity control, the shape is preferably spherical rather than fibrous or amorphous. Here, the term “spherical” means a true spherical shape, an elliptical shape, or a substantially spherical shape including an oval shape. Specifically, the aspect ratio (the ratio between the major axis and the minor axis) is usually 1 0.3 or less, preferably 1.2 or less, more preferably 1.1 or less.

Further, from the viewpoint of blending, the filler preferably has a hydroxyl group on the surface. By having a hydroxyl group, the polarity of the filler surface can be improved, so that it becomes easier to mix an organic polymer having a higher polarity than an inorganic substance.
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.

The average particle size is measured using (Particle Size Analyzer CILAS 1064), and is preferably 0.1 μm or more, more preferably 1 μm or more. Further, it is preferably 100 μm or less, more preferably 50 μm or less.
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.

The silica may be appropriately surface-treated. Examples of the surface treatment include an alkylation treatment, a trimethylsilylation treatment, a silicone treatment, and a treatment with a silane coupling agent, but are not particularly limited. The type of the functional group on the surface of the particle can be controlled by the surface treatment. From the viewpoint of reducing the viscosity, it is preferable to use a (glycidylated) treated filler.
One type of silica may be used, or two or more types may be used in combination.

3. The details of the Hansen parameter of the cyclic ether compound in which the hydrogen bond term in the Hansen parameter is 0.5 or more and 8.1 or less and the weight average molecular weight is less than 500 , and the measurement method at 25 ° C. are described in C.I. M. An article by Hansen: "The three dimensions solubility parameters". Paint Technology. 39, 105 (1967), and Hansen Solubility Parameters, A User's Handbook by Charles M.M. Hansen, CRC Press Boca Raton Fl (2007), both of which are expressly incorporated herein by reference.

Here, δD indicates the characteristics of cohesive dispersive force (non-polar interaction and the like), δH indicates the characteristics of specific interaction force (interaction such as hydrogen bond, acid / base, donation / acceptance), δP characterizes the Debye interaction force between the permanent dipoles and the Keesom interaction force between the induced dipole and the dipole.
The Hansen parameters δD, δH and δP are represented by the unit Mpa1 / 2. The term “hydrogen bond” in the Hansen parameter of the present invention means δH.

  The cyclic ether compound is not particularly limited as long as it has a hydrogen bond parameter (δH) in the Hansen parameter of 0.5 or more and 8.1 or less and a weight average molecular weight of less than 500. When the content is in the above range, the interaction between particles due to hydrogen bonding between fillers can be cut off, and the viscosity of the resin composition can be reduced.

  For example, the above-mentioned 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. Biphenol type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, naphthalene diol type epoxy resin, trisphenylolmethane type epoxy resin, tetrakisphenylolethane type epoxy resin, and phenol diphenol Known epoxy resins which are liquid at room temperature, such as an epoxy resin in which the aromatic ring of a cyclopentadiene novolak type epoxy resin is hydrogenated, an alicyclic epoxy resin, and the like. Further, the same oxetane resin may be used. If necessary, a certain amount of a cyclic ether compound other than those described above can be used in combination.

As the molecular weight of the cyclic ether compound, the weight average molecular weight (Mw) in terms of polystyrene measured by GPC is preferably less than 500, and more preferably 400 or less, from the viewpoints of handleability and viscosity reduction.
From the viewpoint of viscosity reduction, the content of the cyclic ether compound is preferably 0.1% by weight or more, more preferably 0.5% by weight or more, when the total amount of the resin composition is 100% by weight. Further, it is preferably at most 25% by weight, more preferably at most 20% by weight.
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. ]

Further, the cyclic ether compound may be an aromatic epoxy compound or an aromatic oxetane compound. Examples of such epoxy compounds include bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol AD, tetramethylbisphenol S, and tetrafluorocarbon as shown in formula (12). Bisphenol type epoxy resin obtained by glycidylation of bisphenols such as bisphenol A, biphenyl type epoxy resin represented by formula (13), and dihydric phenols such as dihydroxynaphthalene and 9,9-bis (4-hydroxyphenyl) fluorene Glycidylation of epoxy resins, epoxy resin of glycidylation of 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 a hydrocarbon group having 1 to 12 carbon atoms which may be substituted or halogen]
The aromatic epoxy compound and the aromatic oxetane compound may be hydrogenated to form an epoxy compound and an oxetane compound having an alicyclic structure.

Further, as long as the above-mentioned cyclic ether compound is contained as a component of the composition, another cyclic ether, specifically, a cyclic ether compound having a weight average molecular weight of 500 or more may be contained. Specifically, the cyclic ether compounds exemplified above and having a weight average molecular weight (Mw) of 500 or more in terms of polystyrene measured by GPC are exemplified. In such a cyclic ether compound, the hydrogen term in the Hansen parameter is not particularly limited. From the viewpoint of viscosity reduction, the content of the cyclic ether compound is preferably 0.1% by weight or more, more preferably 0.5% by weight or more, when the total amount of the liquid thermosetting resin composition is 100% by weight. preferable. Further, it is preferably at most 25% by weight, more preferably at most 20% by weight.

As described above, the composition according to the first embodiment of the present invention has been described. Hereinafter, a specific example in a case where the composition is applied as a semiconductor sealing material will be described. 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.

From the viewpoint of viscosity reduction and curability, the content of the thermosetting resin is preferably 3% by weight or more, more preferably 5% by weight or more, when the total amount of the resin composition is 100% by weight. Further, it is preferably at most 25% by weight, more preferably at most 23% by weight.
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 a molecule. However, in the present invention, it is distinguished from the above-described cyclic ether compound and the later-described epoxy silicone resin. That is, as the resin composition of the present invention, a known epoxy resin may be mixed with the composition in addition to the above-described cyclic ether compound and the later-described epoxy silicone resin.

2) Silicone resin The silicone resin is not particularly limited as long as it is a thermosetting silicone resin. For example, dimethylpolysiloxane, diphenylpolysiloxane and the like can be mentioned. 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 viewpoint of handling properties 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, a resin containing an epoxy silicone resin is 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 viewpoint of handleability and viscosity reduction. Is more preferred. Further, it is preferably 100,000 or less, more preferably 50,000 or less. From the viewpoint of viscosity reduction, 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. % Or more. Further, it is preferably at most 25% by weight, more preferably at most 20% by weight.
Hereinafter, each component of the epoxy silicone resin will be described.
Epoxy silicone resin is a silicon-containing compound having an epoxy group. The silicon-containing compound is a silane compound or a siloxane compound.

Silicon-containing compounds 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) dimethylsilane Ethoxysilane, (γ-glycidoxypropyl) (ethyl) diethoxysilane, [2- (3,4-epoxycyclohexylethyl) (methyl) dimethoxysilane, [2- (3,4-epoxycyclohexyl) ethyl] ( Ethyl) dimethoxysilane, [2- (3,4-epoxycyclohexyl) Tyl] (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-epoxycyclohexyl) ethyl] (dimethyl) disiloxane, 1,3-bis (3-glycidoxypropyl) 1,1,3,
Examples include 3-tetramethyldisiloxane, (3-glycidoxypropyl) pentamethyldisiloxane, and 3-epoxypropyl (phenyl) dimethoxysilane.

The silicon compound containing an epoxy group also includes an organopolysiloxane represented by the formula (14).
^{_{(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 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 and M ^units, _R 12 _{2 SiO 2/2} is D ^units, R 13 _{SiO 3/2} is T _unit, the _{SiO 4/2} is Q units, expressed respectively I have. a1, b1, c1, and d1 are each an integer of 0 or more, and a1 + b1 + c1 + d1 ≧ 3.

In Formula (14), R ¹¹ , R ¹² , and R ¹³ are preferably a hydrocarbon group having 1 to 10 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. Alkyl groups such as vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group; aryl groups such as phenyl group, tolyl group, xylyl group; benzyl group, phenethyl group, etc. Aralkyl group; and substituted alkyl groups such as chloromethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group and nonafluorobutylethyl group.

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

In the formula (14), e1 is an integer of 0 or more, and represents the number of hydroxyl groups (silanols) directly bonded to silicon atoms.
The epoxy compound has a hydrolyzable group bonded to a silicon atom, and when the hydrolyzable group is hydrolyzed, an organopolysiloxane represented by the formula (14) (where e1 ≧ 1) May be a compound that produces In other words, in the organopolysiloxane represented by the formula (14) (e1 ≧ 1), a compound in which all or a part of a hydroxyl group directly bonded to a silicon atom is replaced with a hydrolyzable group may be used. .

  Here, the hydrolyzable group is a group that generates a hydroxyl group (silanol) bonded to a silicon atom by hydrolysis, and specific examples thereof include a hydroxy group, an alkoxy group, hydrogen, an acetoxy group, an enoxy group, an oxime group, Halogen group. Preferred hydrolyzable groups are alkoxy groups, especially alkoxy groups having 1 to 3 carbon atoms, that is, methoxy, ethoxy and propoxy groups.

The organopolysiloxane type epoxy compound represented by the above formula (14) can be produced, for example, by the following method.
(Method 1) A method in which a silane compound having an epoxy group and a silane compound having no epoxy group and / or an oligomer thereof are co-hydrolyzed and polycondensed.
(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 of oxidizing the double bond portion of a polysiloxane having an organic group containing a carbon-carbon double bond to convert it to an epoxy group.
The raw materials that can be used when producing the polysiloxane type epoxy compound by the above method 1 are as follows.

As a raw material for introducing the M unit, trimethylmethoxysilane, trimethylethoxysilane, triphenylmethoxysilane, triphenylsilanol and the like are exemplified.
As a raw material for introducing the D unit, dimethyldimethoxysilane, methylphenyldimethoxysilane, methylvinyldimethoxysilane, diphenyldimethoxysilane, dimethyldiethoxysilane, methylphenyldiethoxysilane, and a hydrolytic condensate (oligomer) thereof are used. Is exemplified.

As dialkylsiloxane oligomers having hydroxyl groups at both ends, compounds having both ends silanol-modified such as polydimethylsiloxane, polymethylphenylsiloxane, dimethylsiloxane-diphenylsiloxane copolymer, and polydiphenylsiloxane are commercially available.
Raw materials for introducing the T unit include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, 3,3,3-trifluoropropyl Examples are trimethoxysilane and their hydrolyzed condensates.
Examples of the raw material for introducing the Q unit include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and a hydrolyzed condensate thereof.

Raw materials for introducing 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) 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-epoxy) Rohekishiru) ethyl] (dimethyl) disiloxane, 1,3-bis (3-glycidoxypropyl) 1,1,
Examples thereof include 3,3-tetramethyldisiloxane, (3-glycidoxypropyl) pentamethyldisiloxane, and 3-epoxypropyl (phenyl) dimethoxysilane.
As the thermosetting resin in the matrix resin, one of the above resins may be used alone, or two or more may be used in combination. From the viewpoint of viscosity reduction, it is preferable to include an epoxy silicone resin.

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

Among these, polyvinyl acetal such as polyvinyl butyral, and vinyl-based resin such as (meth) acrylic resin are particularly preferable, and polyvinyl acetal such as polyvinyl butyral is particularly preferable. Polyvinyl acetal has hydroxyl groups and is excellent in dispersibility, and when the curing agent has reactivity with hydroxyl groups (such as acid anhydride), it is partially taken in and hardly separates from the thermosetting resin. . It is also possible to positively introduce a reactive group by previously modifying with an acid anhydride.
Further, it is preferable that the thermoplastic resin has elongation. Due to the extensibility, stress can be relieved and cracks are suppressed.

The maximum elongation of the thermoplastic resin is preferably 5% or more, 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.
Further, 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, and 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, the stress is easily dispersed, and cracks are less likely to occur because no interface is formed.
The content of the thermoplastic resin in the matrix resin is preferably 0.001% to 10.0%, more preferably 0.003% to 5.0%, and more preferably 0.005% to 5.0% in the liquid resin composition. % To 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 as needed. The curing agent and / or the curing catalyst may be appropriately contained depending on the type of the resin used. When a thermosetting resin is used, the curing catalyst is not particularly limited as long as the compound can cure the thermosetting resin. Hereinafter, examples of a curing catalyst and a curing agent for an epoxy resin, an epoxy silicone resin, and a silicone resin will be described.

1) Catalyst for Curing Epoxy Resin or Epoxy Silicone Resin When an epoxy resin and / or epoxy silicone resin is used as a matrix resin, a catalyst used for ordinary epoxy resin curing can be used. For example, tertiary amines such as benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, cyclohexyldimethylamine, and 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 adduct of ethyl-s-triazine; organic phosphorus compounds such as diphenylphosphine, triphenylphosphine, and triphenyl phosphite; benzyltriphenylphosphonium chloride, tetra-n-butylphospho Phonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, ethyltriphenylphosphonium iodide, Tyltriphenylphosphonium acetate, methyltributylphosphonium dimethylphosphate, 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 actylate, aluminum acetylacetone complex, gallium compounds and indium compounds; tetraethylammonium bromide, tetra-n- Quaternary ammonium salts such as tillammonium bromide; boron compounds such as boron trifluoride and triphenyl borate; metal halides such as zinc chloride and stannic chloride; adducts of dicyandiamide and amines with epoxy resins; High melting point dispersion type latent curing accelerators such as amine addition type accelerators; Microcapsule type latent curing agents in which the surface of a curing accelerator such as the above imidazoles, organic phosphorus compounds and quaternary phosphonium salts is coated with a polymer Curing accelerators; amine salt-type latent curing accelerators; latent curing accelerators such as high-temperature dissociation-type thermal cationic polymerization-type latent curing accelerators such as Lewis acid salts and Bronsted acid salts other than gallium compounds. Can be mentioned.

Among these, an inorganic compound is preferable because strong catalytic activity is required, a gallium compound or an indium compound is more preferable, and a gallium compound is particularly preferable.
Particularly preferred are gallium acetylacetonate and gallium acetate.

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 below. 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 a chelating ligand, gallium acetate, gallium oxyacetate, triethoxygallium, tris (8-quinolinolato) gallium, gallium oxalate, gallium ethylxanthogenate, 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 chelating ligands include β-diketone type compounds and o-ketophenol type compounds. Some β-diketone type compounds have a structure 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, and hexafluoroacetylacetone, and specific examples of the compound of the formula (16) include ethyl acetoacetate and the compound of the formula (17). Specific examples thereof 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 the formula (18) include salicylaldehyde and ethyl-O-hydroxyphenyl ketone.
A gallium complex having a chelating ligand is a preferred example of a gallium compound, and among them, gallium acetylacetonate can be particularly preferably used. Two or more gallium compounds can be used in any combination.
When a Ga catalyst is used, weight loss due to heating of a cured product is smaller 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 smaller than that of the Al catalyst.

Specifically, at 150 to 200 ° C. for 500 hours, the weight loss is preferably 20% by weight or less before heating, more preferably 10% by weight or less.
The gallium compound is usually at least 0.001 part by weight, preferably at least 0.01 part by weight, and at most 5.0 parts by weight, preferably at most 1.0 part by weight, based on 100 parts by weight of the epoxy compound.
The silanol source compound is a compound that is a 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 thought to be a cation source necessary for initiating 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 has a function of increasing the acidity of the silanol hydroxyl group, that is, a function of enhancing the action of the silanol as a cation source. it seems to do.
The silanol source compound may be a potential source of silanol. For example, a compound having a silicon atom to which a hydrolyzable group is bonded and generating 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. Preferred hydrolyzable groups are alkoxy groups, especially alkoxy groups having 1 to 3 carbon atoms, that is, methoxy, ethoxy and propoxy groups.

Examples of silanol source compounds include silicon atoms to which hydroxyl groups such as phenyldimethylsilanol, diphenylmethylsilanol, triphenylsilanol, dihydroxydiphenylsilane (diphenyldisilanol), trimethylsilanol, triethylsilanol, dihydroxydimethylsilane, and trihydroxymethylsilane are bonded. 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) a2}} (R 22 2 SiO 2/2) b2 (R 23 SiO 3/2) c2 (SiO 4/2) d2 (O 1/2 H) e2 ··· (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. I have. a2, b2, c2, and d2 are each 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 (silanols) directly bonded to silicon atoms.

R ²¹ , R ²² and R ²³ in the formula (19) are usually a hydrocarbon group having 1 to 10 carbon atoms, and 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 chloromethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group, and nonafluorobutylethyl group.

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

When the silanol source compound is an organopolysiloxane, and this is used together with an epoxy compound containing no siloxane structure, from the viewpoint of ensuring compatibility between the organopolysiloxane and the epoxy compound, the organopolysiloxane is made of silicon. It is preferable that the compound 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, more preferably 700 or more, so as not to 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 increases and the handleability deteriorates. Therefore, 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 to which a hydroxyl group or a hydrolyzable group is bonded in one molecule. Such a silanol source compound, when heated, undergoes polycondensation due to the action of a gallium compound to have a high molecular weight, so that it does not bleed out after curing.
Organopolysiloxanes that can be suitably used as the silanol source compound include those having the 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 a hydroxyl group at both terminals): It can be obtained by polycondensation. As the polycondensation catalyst, besides acids and bases, metal catalysts can be used, and gallium compounds such as gallium acetylacetonate can also be used.
The organopolysiloxane represented by the formula (23) can be obtained by polycondensing a compound represented by the formula (21) and a compound represented by the formula (24). As the polycondensation catalyst, besides acids and bases, metal catalysts can be used, and gallium compounds such as gallium acetylacetonate can also be used.

  In the formulas (20) to (24), m, n, M, N, m1, and m2 are each an integer of 1 or more. If these numbers are too large, that is, if the degree of polymerization of the polysiloxane is too high, the viscosity becomes too high and handling becomes difficult, and the catalytic performance tends to decrease due to a decrease in the silanol content. It should be noted that From the viewpoint of handling properties, the viscosity of the organopolysiloxane or the viscosity of the liquid resin composition obtained by using the organopolysiloxane is 50,000 cp or less, preferably 40,000 cp or less at 30 ° C. and 1 atm. It is preferable to set the degree of polymerization so as to be 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.

  Organopolysiloxanes obtained by polycondensing one or more selected from the organopolysiloxanes represented by the formulas (20) to (23) with a trifunctional silane compound such as methyltrimethoxysilane and phenyltrimethoxysilane are also provided. And silanol source compounds. As the polycondensation catalyst, besides acids and bases, metal catalysts can be used, and gallium compounds such as gallium acetylacetonate can also be used. Such an organopolysiloxane has 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 a silanol source, a monosilane compound and an organopolysiloxane may be used in combination.

The amount of the silanol source compound is usually 0.05 part by weight or more, preferably 0.5 part 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 to the silanol source compound is preferably from 1: 0.05 to 0.001: 100, more preferably from 1:10 to 0.01: 100 by weight.
The content of the curing catalyst in the thermosetting resin composition is preferably adjusted to be 0.003% by weight to 0.3% by weight based on 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 participate in the curing, A good thermosetting resin composition is obtained. Since the gallium compound also serves as a catalyst for the dealcoholization condensation reaction between the silanol and the alkoxy group, the same effect can be obtained when the silanol and the alkoxy group are introduced into the organopolysiloxane structure. When the thermosetting resin has a silanol group, the gallium compound also serves as a catalyst for siloxane condensation, and the crosslinking system proceeds simultaneously, which is preferable. Further, it has good compatibility with siloxane and silica, and contributes to dispersion of silica. Furthermore, when epoxysilicone is reacted with a gallium catalyst, the coefficient of linear expansion of the obtained 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 the addition, a thermosetting resin composition having good curability, in which both the self-polymerization reaction and the hydrosilylation reaction of the epoxy compound participate in curing, can be obtained.

  Alternatively, an epoxy compound may be introduced by introducing a hydrosilyl group into an organopolysiloxane structure portion of one or both of an epoxy compound and a silanol source compound, and adding an organopolysiloxane having a vinylsilyl group and a hydrosilylation reaction catalyst. Thus, a thermosetting resin composition is obtained in which both the self-polymerization reaction and the hydrosilylation reaction participate in curing. By modifying this example, a vinylsilyl group may be introduced into the organopolysiloxane structure portion of one or both of the epoxy compound and the silanol source compound, and the organopolysiloxane to be added may have a hydrosilyl group introduced.

2) Curing Agent for Epoxy Resin or Epoxy Silicone Resin Curing agent that forms a crosslinked product by reacting with an epoxy group includes amine, polyamide resin, acid anhydride, phenol and the like. From the viewpoint of reducing the coefficient of linear expansion, controlling the polymerization rate, and reducing the viscosity, it is preferable to use an acid anhydride. Examples of the acid anhydride include an aliphatic acid anhydride, an alicyclic acid anhydride, an aromatic acid anhydride, and a halogen acid anhydride. When the resin composition is used for an optical semiconductor device, it is preferable to use an alicyclic carboxylic anhydride from the viewpoint of light resistance.
The content of the acid anhydride is not particularly limited, but if it is too large, the Tg of the acid anhydride may affect the linear expansion coefficient of the obtained cured product.

  Examples of the alicyclic carboxylic anhydride include compounds represented by Formulas (25) to (30), 4-methyltetrahydrophthalic anhydride, methylnadic anhydride, dodecenylsuccinic anhydride, Examples include Diels-Alder reaction products of an alicyclic compound having a conjugated double bond such as α-terpinene and allocymene with maleic anhydride, and hydrogenated products thereof.

As the Diels-Alder reaction product or a hydrogenated product thereof, any structural isomer and any geometric isomer can be used.
In addition, the alicyclic carboxylic 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, improvement of handling and leveling, and prevention of coloring may be obtained. The content of the acid anhydride is not particularly limited, but is preferably 1.5 equivalent or less based on the epoxy amount. It is more preferably at most 1 equivalent, more preferably at most 0.8 equivalent, even more preferably at most 0.6 equivalent.
3) Catalyst for curing silicone resin

  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, an alkoxide, or the like of zirconium, hafnium, yttrium, tin, zinc, titanium, or gallium can be used. From the viewpoint of the coefficient of linear expansion of the cured product, it is preferable to use the gallium compound described above.

7. Others In addition to the above-mentioned components, the liquid resin composition according to the embodiment of the present invention further includes a dispersant, an antioxidant, an antifoaming agent, a coloring agent, a modifier, and a leveling agent from the viewpoints of improving physical properties and imparting functions. It may further contain additives such as an agent, a light diffusing agent, a heat conductive agent, a flame retardant, a reactive or non-reactive diluent, and an adhesion / adhesion improver.

1) Antioxidant An antioxidant can be contained in the liquid resin composition according to the embodiment of the present invention in order to suppress yellowing under a use environment. Phenolic antioxidants, phosphorus antioxidants, hindered amines and the like are preferably used, and among them, hindered phenol antioxidants having an alkyl group at an ortho position on one or both sides of a phenol hydroxyl group are particularly preferred. Used.

2) Silane Coupling Agent The liquid resin composition of the present invention can contain a silane coupling agent 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- Aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane and the like can be mentioned.

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

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

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

Further, the average linear expansion coefficient at 210 to 240 ° C. is usually 100 ppm / K or less, preferably 75 ppm / K or less, more preferably 50 ppm / K or less.
Further, the average coefficient of linear expansion at 70 to 210 ° C. is preferably 100 ppm / K or less, more preferably 50 ppm / K or less, and even more preferably 40 ppm / K or less.

Moreover, it is 25 ° C. storage elastic modulus not more than 1.0 × ¹⁰ 5 Pa or more 1.0 × ¹⁰ 10 Pa and preferably, 1.0 × ¹⁰ 6 Pa or more 1.0 × ¹⁰ 10 Pa or less More preferred. If the storage elastic modulus at 25 ° C. is 1.0 × 10 ¹⁰ Pa or more, the stress is not sufficiently relaxed, which causes cracks. If the pressure is less than 1.0 × 10 ⁵ Pa, the mechanical strength of the composition is not sufficient, and there is a concern that the wire may fall due to vibration.
Since the coefficient of linear expansion is small and the storage modulus of elasticity is small, stress due to a difference in linear expansion from the substrate during curing or a change in temperature can be reduced, and cracks can be suppressed.

10. Sealing Method The liquid resin composition of the present invention is preferably used as a sealing material for a semiconductor device, but the sealing method may be a conventional 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 particularly preferably used for potting. Specifically, a liquid containing the resin composition and a liquid containing the curing catalyst are respectively prepared, and then mixed to prepare a mixed liquid, which can be subjected to potting. Place the part in the housing and pour the mixture into it. Then, it is cured. Depending on the matrix resin used, it may be cured at room temperature or cured by heating. For the heat curing, for example, 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 as long as the resin composition can be brought into a desired cured state, and may be determined according to the matrix resin, the concentration of the catalyst, the thickness of the member to be formed from the composition, and the like.

  The matrix resin of the present invention contains a thermosetting resin. By raising the curing temperature to around 100 ° C. at first and then to around 150 ° C., foaming due to the residual solvent or dissolved water vapor in the composition can be prevented. In addition, since the difference in curing speed between the deep part and the surface can be reduced, a cured product having a smooth surface and no wrinkles and having 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 occurrence of cracks can be prevented.

11. Use of the liquid thermosetting resin composition The use of the resin composition according to the embodiment of the present invention is not particularly limited, and may be used as a sealing material in various semiconductor devices including light-emitting devices such as LED devices. Can be. Further, the molded article obtained by curing the resin composition of the present invention has a low coefficient of thermal expansion even at a high temperature because it contains a silica filler in an amount of 50% by weight or more. Therefore, it is particularly suitably 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 the composition, can be suitably used for sealing by potting, and has a very low coefficient of linear expansion when it is a cured product, so that it has a wide range of sizes. It can be suitably used for power devices. The present invention can be used for power devices such as home electric appliances and computers, and can be used for large power devices for controlling automobiles, railway vehicles and substations.

Hereinafter, the present invention will be described in detail with reference to examples.
<Synthesis of epoxy silicone resin>
A mixture of 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, stirred at room temperature for 3 hours, and further added potassium hydroxide 1 After adding .51 g and 148 g of isopropyl alcohol, the mixture was heated and stirred under reflux conditions of isopropyl alcohol for 4 hours. Thereafter, the reaction solution is neutralized with an aqueous solution of sodium dihydrogen phosphate (10% by weight), washed with water until the washed water becomes neutral, and volatile components are removed under reduced pressure. Polysiloxane EPSi-1 was obtained.

[Example 1]
0.5 g of the above-mentioned EPSi-1, E-PO (manufactured by Nippon Rika) 0.5 g, JER871 (manufactured by Mitsubishi Chemical) 0.25 g, YED216D (manufactured by Mitsubishi Chemical) 0.36 g, spherical filler HL- 16.9 g of 3100 (manufactured by Tatsumori Co., Ltd.) was added to THIKY Planetary
Stir and mix using Vacuum Mixer ARV-300. Thereafter, gallium acetylacetoacetate was added to 0.20 g of an acid anhydride hardener, Ricacid MH-700 (manufactured by Shin Nippon Rika Co., Ltd.) and polymethylphenyl siloxane FLD516 (manufactured by BLUESTARS SILICONES) having a polystyrene-equivalent weight average molecular weight of about 900 at both ends. 0.069 g of a solution (Ga (acac) ₃ solution) in which 2% by weight of a salt (manufactured by Strem Chemicals, Inc.) was dissolved was further added, followed by stirring and mixing to obtain a composition.

[Examples 2 to 7]
According to the method of Example 1, the compounds shown in Table 1 were added to obtain a resin composition.
[Comparative Examples 1 to 3]
According to the method of Example 1, the compounds shown in Table 1 were added to obtain a resin composition.

<Evaluation of composition fluidity>
In this embodiment, the fluidity is defined as follows. Aluminum cup with handle No. 2 (manufactured by AS ONE Corporation) weighs 2 g of the resin composition, and when the resin composition is tilted at 90 ° on a hot plate at 40 ° C., it means that the resin cannot maintain its shape for 30 minutes or more.

  As is clear from the results in Table 1, the resin compositions of Examples 1 to 7 had fluidity. On the other hand, the resin compositions of Comparative Examples 1 to 3 did not have fluidity.

Claims (5)

A resin composition containing 50% by weight or more of a filler and silicone,
The filler is silica,
The silicone is an epoxy silicone,
Including a cyclic ether compound having a hydrogen bond term in the Hansen parameter of 0.5 or more and 8.1 or less and a weight average molecular weight of less than 500,
A semiconductor device sealed with a cured resin obtained by curing a resin composition in which the cyclic ether compound is an epoxy resin . The semiconductor device according to claim 1, wherein the filler has a hydroxyl group . 3. The semiconductor device according to claim 1, wherein the resin composition contains a cyclic ether compound having a weight average molecular weight of 500 or more. The semiconductor device according to claim 1, wherein the resin composition contains a metal catalyst. The semiconductor device according to claim 4, wherein the metal catalyst is a gallium compound.