JP2015189920A - resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition for encapsulation having many silica fillers, low linear expansion coefficient, a certain degree of flowability and good handling during potting.SOLUTION: There is provided a liquid resin composition containing 75 wt.% or more a silica filler and a matrix resin.

Description

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

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

JP 2004-27005 A JP 2009-67890 A

Device sealing differs depending on the type of resin. When sealing with an epoxy-based resin, sealing is performed by transfer molding or the like, and with silicone-based resin, sealing is performed by potting. In any method, the sealing resin has fluidity. Necessary.
On the other hand, in order to reduce the linear expansion coefficient of the sealing resin, it is necessary to contain a large amount of filler such as silica filler. However, if the amount of the silica filler is increased to decrease the linear expansion coefficient, the sealing resin There was a problem that the fluidity of the composition was too low and handling during molding became very difficult. In particular, when sealing by potting, a certain degree of fluidity is required. Generally, when a silica filler is contained in an amount of 70% by weight or more, the viscosity becomes too high and the fluidity is lost. The offer was not possible.
Even if it is a resin composition containing many silica fillers, this invention makes it a subject to provide the resin composition for sealing which has a certain amount of fluidity | liquidity.

The inventors of the present invention have made researches to solve the above-mentioned problems and examined the fluidity of a resin composition containing 75% by weight or more of silica filler. It was found that a liquid resin composition containing 75% by weight or more of silica filler that could not exist conventionally can be provided by adding a small amount of a compound having the solubility parameter of. That is, the present invention is as follows.
[1] A liquid resin composition comprising 75% by weight or more of a silica filler and a matrix resin.
[2] The liquid resin composition according to [1], wherein the viscosity at 30 ° C. is 50 Pa · s or less.
[3] Further, the solubility parameter is 7.5 (cal / cm ³ ) ^0.5 or more and 18 (cal / cm ³ ) ^0.5 or less of the compound is contained in an amount of 5% by weight or less, [1] or [2] Liquid resin composition as described in 2.
[4] The liquid resin composition according to any one of [1] to [3], wherein the matrix resin is an epoxy silicone resin.
[5] The liquid resin composition according to any one of [1] to [4], including 80% by weight or more of silica filler.
[6] A power semiconductor device encapsulated with the liquid resin composition according to any one of [1] to [5].

  According to the present invention, it is possible to provide a liquid resin composition containing 75% by weight or more of silica filler that could not exist conventionally. That is, although the linear expansion coefficient when cured is very low, it is possible to provide a resin composition having fluidity as a composition and capable of being sealed by potting.

  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 30 ° 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. Liquid resin composition The liquid resin composition which is the 1st embodiment of this invention is characterized by including 75 weight% or more of silica fillers in addition to matrix resin.
In this embodiment, liquid means having fluidity at normal temperature and normal pressure (1 atm, 25 ° C.). More specifically, when the composition is tilted by 45 °, the shape cannot be maintained for 10 minutes or more, and the shape changes.
More specifically, at 30 ° C. and 1 atm, the viscosity is usually 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.
Hereinafter, the components contained in the liquid resin composition will be described.

1-1. Matrix resin The matrix resin included in the present embodiment is not particularly limited as long as it can be used as a matrix resin. In the case of device sealing applications, silicone resin, epoxy resin, etc. are usually used, but are not limited thereto. Hereinafter, an epoxy resin, a silicone resin, and an epoxy silicone resin that are usually used in the case of device sealing will be described.

1-1-1. Epoxy resin The epoxy resin is not particularly limited as long as it is a thermosetting resin. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, 3,3 ′, 5,5′-tetramethyl-4,4 ′. -Biphenol type epoxy resin such as biphenol type epoxy resin or 4,4'-biphenol type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, naphthalenediol type epoxy resin, trispheny Well-known epoxy resins which are liquid at room temperature, such as roll methane type epoxy resin, tetrakisphenylol ethane type epoxy resin, epoxy resin obtained by hydrogenating aromatic ring of phenol dicyclopentadiene novolac type epoxy resin, alicyclic epoxy resin, etc. It is below. If necessary, a certain amount of epoxy resin other than the above can be used in combination.

As the molecular weight of the epoxy resin, the average molecular weight (Mw) measured by GPC is preferably 100,000 or less, and more preferably 50,000 or less, from the viewpoints of handleability and viscosity reduction.
The content of the epoxy resin is preferably 3% by weight or more and more preferably 5% by weight or more when the total amount of the liquid resin composition is 100% by weight from the viewpoint of viscosity reduction. Moreover, 25 weight% or less is preferable and 20 weight% or less is more preferable.

1-1-2. Silicone resin The silicone resin is not particularly limited as long as it is a thermosetting silicone resin. Examples thereof include dimethylpolysiloxane and diphenylpolysiloxane.
As the molecular weight of the silicone resin, the average molecular weight (Mw) measured by GPC is preferably 500 or more, and more preferably 700 or more, from the viewpoints of handleability and viscosity reduction. Moreover, it is preferable that it is 100,000 or less, and it is more preferable that it is 50,000 or less.
The content of the silicone resin is preferably 3% by weight or more and more preferably 5% by weight or more when the total amount of the liquid resin composition is 100% by weight from the viewpoint of viscosity reduction. Moreover, 25 weight% or less is preferable and 20 weight% or less is more preferable.

1-1-3. Epoxy silicone resin The epoxy silicone resin has an epoxy group in the molecule, and the epoxy group may be a glycidyl group or an alicyclic epoxy group, and preferably contains an alicyclic epoxy group having a cyclohexyl epoxy group.
As the molecular weight of the epoxy silicone resin, the average molecular weight (Mw) measured by GPC is preferably 300 or more, and more preferably 500 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.
The content of the epoxy silicone resin is preferably 3% by weight or more and more preferably 5% by weight or more when the total amount of the liquid resin composition is 100% by weight from the viewpoint of viscosity reduction. Moreover, 25 weight% or less is preferable and 20 weight% or less is more preferable.

As the epoxy silicone resin, one in which a self-polymerization reaction of an epoxy compound catalyzed by a gallium compound and a silanol supplied from a silanol source compound is involved in at least a part of its curing mechanism. The epoxy silicone resin can be cured only by the self-polymerization reaction, but is not limited thereto.
Hereinafter, each component of this epoxy silicone resin will be described.

1-1-3-1. Epoxy compound The epoxy compound is a compound having an epoxy group in the molecule, and preferably an alicyclic epoxy compound having a cyclohexyl epoxy group. Structural formulas of typical alicyclic epoxy compounds are shown in formulas (1) to (3).

エポキシ化合物はグリシジル基を有する化合物であってもよいが、脂環式エポキシ化合物に比べて自己重合反応の活性が低い場合がある。

The epoxy compound may be a compound having a glycidyl group, but the activity of the self-polymerization reaction may be lower than that of the alicyclic epoxy compound.

  As a suitable example of an epoxy compound having a glycidyl group, a glycidyl ether containing an alicyclic structure as shown in formulas (4) to (8), or an ester compound, and an alicyclic structure as shown in formula (9) are not included. There are glycidyl ether compounds, glycidyl ether compounds having a disiloxane skeleton as shown in formula (10), and glycidyl amide compounds having an isocyanuric acid skeleton as shown in formula (11). In the formula (9), R represents an alkylene group having 1 to 20 carbon atoms.

  The epoxy compound may be an aromatic epoxy compound. Examples of such epoxy compounds include bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethyl bisphenol A, tetramethyl bisphenol F, tetramethyl bisphenol AD, tetramethyl bisphenol S, tetrafluoro as shown in formula (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. In formula (13), R independently represents hydrogen, an alkyl group having 1 to 3 carbon atoms, or a phenyl group.

エポキシ化合物は、芳香族エポキシ化合物を水素化して得られる脂環構造を有するエポキシ化合物であってもよい。

The epoxy compound may be an epoxy compound having an alicyclic structure obtained by hydrogenating an aromatic epoxy compound.

The epoxy compound may be a silicon-containing compound having an epoxy group. The silicon-containing compound is a silane compound or a siloxane compound.
Examples of the silicon-containing compound having an epoxy group include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltriethoxysilane, (γ-glycidoxypropyl) (methyl) dimethoxysilane, (γ-glycidoxypropyl) (ethyl) dimethoxysilane, (γ-glycidoxypropyl) (methyl) di Ethoxysilane, (γ-glycidoxypropyl) (ethyl) diethoxysilane, [2- (3,4-epoxycyclohexylethyl) (methyl) dimethoxysilane, [2- (3,4-epoxycyclohexyl) ethyl] ( Ethyl) dimethoxysilane, [2- (3,4-epoxycyclohexyl) Til] (methyl) diethoxysilane, [2- (3,4-epoxycyclohexyl) ethyl] (ethyl) diethoxysilane, (γ-glycidoxypropyl) (methoxy) dimethylsilane, (γ-glycidoxypropyl) ) (Methoxy) diethylsilane, (γ-glycidoxypropyl) (ethoxy) dimethylsilane, (γ-glycidoxypropyl) (ethoxy) diethylsilane, [2- (3,4-epoxycyclohexyl) ethyl] (methoxy ) Dimethylsilane, [2- (3,4-epoxycyclohexyl) ethyl] (methoxy) diethylsilane, [2- (3,4-epoxycyclohexyl) ethyl] (ethoxy) dimethylsilane, [2- (3,4- Epoxycyclohexyl) ethyl] (ethoxy) diethylsilane, [2- (3,4-epoxycyclo Hexyl) ethyl] (dimethyl) disiloxane, 3-epoxypropyl (phenyl) dimethoxysilane, and the like.
Moreover, the organopolysiloxane represented by Formula (14) is also contained in the silicon compound containing an epoxy group.
(R ¹¹ ₃ SiO _1/2 ) _a1 (R ¹² ₂ SiO _2/2 ) _b1 (R ¹³ SiO _3/2 ) _c1 (SiO _4/2 ) _d1 (O _1/2 H) _e1 (14)

In the formula (14), R ¹¹ , R ¹² and R ¹³ each independently represent a monovalent organic group, and at least one is an organic group containing an epoxy group in one molecule.

In the formula (14), R ¹¹ ₃ SiO _1/2 represents an M unit, R ¹² ₂ SiO _2/2 represents a D unit, R ¹³ SiO _3/2 represents a T unit, and SiO _4/2 represents a Q unit. Yes. Each of a1, b1, c1, and d1 is an integer of 0 or more, and a1 + b1 + c1 + d1 ≧ 3.

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

In formula (14), examples of the organic group containing an epoxy group include epoxy alkyl groups such as 2,3-epoxypropyl group, 3,4-epoxybutyl group, and 4,5-epoxypentyl group; 2-glycidoxyethyl Group, glycidoxyalkyl group such as 3-glycidoxypropyl group, 4-glycidoxybutyl group; β- (or 2-) (3,4-epoxycyclohexyl) ethyl group, γ- (or 3-) Examples thereof include an epoxycyclohexylalkyl group such as (3,4-epoxycyclohexyl) propyl group.
In the formula (14), e1 is an integer of 0 or more, and represents the number of hydroxyl groups (silanol) directly bonded to the silicon atom.

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

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

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

  Examples of the raw material for introducing the M unit include trimethylmethoxysilane, trimethylethoxysilane, triphenylmethoxysilane, and triphenylsilanol.

  As raw materials for introducing D unit, dimethyldimethoxysilane, methylphenyldimethoxysilane, methylvinyldimethoxysilane, diphenyldimethoxysilane, dimethyldiethoxysilane, methylphenyldiethoxysilane, and their hydrolysis condensates (oligomers) Illustrated.

  As dialkylsiloxane oligomers having hydroxyl groups at both ends, compounds having silanol-modified compounds such as polydimethylsiloxane, polymethylphenylsiloxane, dimethylsiloxane-diphenylsiloxane copolymer, and polydiphenylsiloxane 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-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-epoxysilane) Examples include (rohexyl) ethyl] (dimethyl) disiloxane, 3-epoxypropyl (phenyl) dimethoxysilane, and the like.

1-1-3-2. Gallium Compound A gallium compound is a component that acts as a catalyst for a self-polymerization reaction of an 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 exhibits the above action, and can be selected from the following candidate compounds: gallium complex having a chelate ligand, tris (2,2,6,6-tetramethyl-3,5- Heptanedionate) gallium (III), gallium trifluoromethanesulfonate (III), gallium acetate, gallium sulfate, gallium nitrate, gallium oxyacetate, triethoxygallium, triisopropoxygallium, tris (8-quinolinolato) gallium, gallium oxalate, Examples include gallium ethyl xanthate, diethyl ethoxy gallium, and gallium maleate. Gallium salts of long-chain carboxylic acids such as n-octylic acid, 2-ethylhexanoic acid and naphthenic acid.

  Examples of chelate ligands 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).

式（１５）〜式（１７）において、Ｒは独立してアルキル基、又はハロゲン置換アルキル基を表している。

In the formulas (15) to (17), R independently 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).

式（１８）において、Ｒ’は独立して水素原子、アルキル基、ハロゲン置換アルキル基又はアルコキシ基を表している。
式（１８）の化合物の具体例としては、サリチルアルデヒド、エチル−Ｏ−ヒドロキシフェニルケトンなどが挙げられる。
キレート配位子を有するガリウム錯体はガリウム化合物の好適例であり、その中でもガリウムアセチルアセトネートは特に好適に使用することができる。
Ｇａ触媒を用いるとＡｌ触媒に比べて硬化物の加熱による重量減少が少ない。特に硬化物がシロキサン構造を含む場合にはＡｌ触媒に比べて硬化物の加熱による重量減少が少ない。
具体的には、１５０〜２００℃×５００時間で、重量減少が加熱前の２０重量％以下が好ましく、１０重量％以下が更に好ましい。

In the formula (18), R ′ independently 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.
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.

The gallium compound is usually 0.001 part by weight or more with respect to 100 parts by weight of the epoxy compound,
Preferably they are 0.01 weight part or more, 5.0 weight part or less, Preferably it is 1.0 weight part or less.

1-1-3-3. Silanol source compound A 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 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 not containing 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 formulas (20) to (23).

  The organopolysiloxane represented by the formula (22) can be obtained by polycondensation of the compound represented by the formula (24) and the compound represented by the formula (25). 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 the formulas (20) to (25), 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 Pa · s or less, preferably 40 Pa · s or less, at 30 ° C. and 1 atm. The degree of polymerization is preferably set so that it is preferably 30 Pa · s or less, more preferably 20 Pa · s or less, particularly preferably 15 Pa · s or less, and most preferably 10 Pa · s 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.

  In the epoxy silicone resin obtained from the above-mentioned epoxy compound, gallium compound, and silanol source compound, 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.

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

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

  As 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 use an epoxy silicone resin.

1-2. Silica filler The resin composition according to this embodiment contains 75% by weight or more of silica filler. From the viewpoint of reducing the linear expansion coefficient of the cured product of the resin composition, it is preferably 80% by weight or more, more preferably 85% by weight or more, and further preferably 90% by weight or more.

  In a normal resin composition, when the amount of filler added increases, the viscosity of the composition increases significantly. In the present invention, the interaction between the particles and the matrix composition composed of particles-epoxy resin, etc. is controlled by the shape of the silica filler, the type of the particle surface functional group, etc. Even in the contained composition, high fluidity can be maintained. Therefore, handling at the time of potting as a liquid resin composition is easy.

  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.

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.
Control of particle size distribution can be used as means for increasing the amount of addition. That is, a higher filling rate can be obtained by mixing fillers having different particle sizes.
The average particle size is measured using a Particle Size Analyzer CILAS 1064 (CILAS, type 1064), preferably 0.1 μm or more, and more preferably 1 μm or more. 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.

Further, the silica filler 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 a glycidylated filler.
A silica filler may use 1 type and may use 2 or more types together.

1-3. Compound The resin composition of the present invention may contain a compound such as a solvent or a polymer. In the present invention, the addition of a specific compound to the resin composition is preferable because the viscosity of the resin composition can be reduced and the fluidity can be improved. Thus, it is very simple, low cost, and beneficial to improve the fluidity of the resin composition by adding a specific compound.

The compound preferably has a solubility parameter of 7.5 to 18 (cal / cm ³ ) ^0.5 , more preferably 8.0 to 16 (cal / cm ³ ) ^0.5 from the viewpoint of viscosity reduction. It is.
In the present invention, the solubility parameter (SP value) is calculated based on the following Fedors estimation method.
Fedors formula:
SP value (δ) = (Ev / v) ^1/2 = (ΣΔei / ΣΔvi) ^1/2
Ev: Evaporation energy v: Molar volume Δei: Evaporation energy of each component atom or atomic group Δvi: Molar volume of each atom or atomic group Evaporation energy, molar volume of each atom or atomic group used in the calculation of the above formula is R. F. Fedors, Polym. Eng. Sci. , 14, 147 (1974).

  Usually, silicone resins and epoxy resins are often liquid at room temperature and do not need to contain a solvent. In the present invention, the fluidity of the resin composition is usually a liquid used as a solvent, and even when a specific amount of a specific compound is added to the resin composition, the silica filler is contained at a high concentration. The present inventors have found that this can be maintained. Specific examples of the solvent that can be used as the compound include lower alkyl alcohols such as methanol, ethanol, propanol, and butanol; aromatics such as benzene, xylene, and toluene; acetone, acetonitrile, THF, and the like.

  In addition, as compounds, low molecular weight epoxy such as hexanediol diglycidyl, cyclohexanedicarboxylate diglycidyl, bisphenol A diglycidyl, hydrogenated bisphenol A diglycidyl, plasticizers such as adipic acid ester, phthalic acid ester, hydrogenated phthalic acid ester, A surfactant having a hydrophilic part such as an alkyl ether can be used.

Among these, it is preferable to select a compound having energy suitable for breaking the hydrogen bond between the silica filler and the hydroxyl group of the water molecule formed on the surface of the silica filler.
On the other hand, a compound having an SP value that is too large, such as water, has poor compatibility with the binder, and a compound having an SP value that is too small, such as dimethylsiloxane, has a poor affinity with the filler surface.
When the total amount of the resin composition is 100% by weight, the content of the compound is preferably 0.1% by weight or more, more preferably 0.3% by weight or more from the viewpoint of viscosity reduction. Moreover, 5 weight% or less is preferable from a viewpoint of the bubble suppression at the time of hardening, and 2 weight% or less is more preferable.

1-4. Curing Agent The liquid resin composition of the present invention usually contains a curing agent.
The curing agent may be called a curing catalyst or a curing accelerator, and may be appropriately contained depending on the type of matrix resin.

1-4-1. Curing Agent for Epoxy Resin or Epoxy Silicone Resin When an epoxy resin and / or an epoxy silicone resin is used as the 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, 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 of 2-methylimidazole Imidazoles such as an adduct, an isocyanuric acid adduct of 2-phenylimidazole, an isocyanuric acid adduct of 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)] ethyl-s-triazine; Organophosphorus compounds such as fin, triphenylphosphine, triphenyl phosphite; benzyltriphenylphosphonium chloride, Tra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, ethyltriphenylphosphonium iodide Id, ethyl triphenyl phosphonium acetate, methyl tributyl phosphonium dimethyl phosphate, tetrabutyl phosphonium diethyl phosphodithionate, tetra-n-butyl phosphonium benzotriazolate, tetra-n-butyl phosphonium Quaternary such as tetrafluoroborate, tetra-n-butylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate Phosphonium salts; Diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] undecene-7 and organic acid salts thereof; Organometallic compounds such as zinc octylate, tin actylate, and aluminum acetylacetone complex; Quaternary ammonium salts such as tetraethylammonium bromide and tetra-n-butylammonium bromide; Boron compounds such as boron trifluoride and triphenyl borate; Metal halides such as zinc chloride and stannic chloride, dicyandiamide and amines High melting point dispersion type latent curing accelerators such as amine addition type accelerators such as adducts of styrene and epoxy resins; polymerizing the surface of curing accelerators such as imidazoles, organophosphorus compounds and quaternary phosphonium salts -Coated microcapsule type latent curing accelerator; amine Type latent curing agent accelerators; Lewis acid salts other than gallium compounds, and the like latent curing accelerators such as high-temperature dissociation type thermally cationic polymerization latent curing accelerators such as Bronsted acid salts.

Examples of the curing agent that forms a crosslinked 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 (26) to formula (31), 4-methyltetrahydrophthalic acid anhydride, methyl nadic 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.

なお、前記ディールス・アルダー反応生成物やこれらの水素添加物としては、任意の構造異性体及び任意の幾何異性体を使用することができる。

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.

  When a thermosetting resin is used for the matrix resin, the curing agent is not particularly limited as long as it is a compound capable of curing the thermosetting resin, but is preferably an inorganic compound, and more preferably, since strong catalytic activity is required. Is a gallium compound or an indium compound, and particularly preferably a gallium compound. By using a gallium compound as a curing catalyst, the average linear expansion coefficient of the cured product can be made almost constant over a wide temperature range.

  As the gallium compound, 1-1-3-2. As described above, the 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. Specific examples include gallium acetylacetonate, gallium acetate, gallium oxyacetate, triethoxygallium, tris (8-quinolinolato) gallium, gallium oxalate, gallium ethylxanthate, diethylethoxygallium, and gallium maleate. . Of these, gallium acetylacetonate and gallium acetate are particularly preferable. Two or more kinds of gallium compounds can be used in any combination.

  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.

  The content of the curing catalyst in the thermosetting resin composition is preferably adjusted to 0.03% to 0.3% by weight with respect to 100% by weight of the thermosetting resin composition.

1-4-2. Silicone resin curing agent When a silicone resin is used as the matrix resin, examples of the curing agent include metal compounds. As the metal compound, a chelate complex, an organic acid salt, an inorganic salt, or an alkoxide of zirconium, hafnium, yttrium, tin, zinc, titanium, or gallium can be used. From the viewpoint of the linear expansion coefficient of the cured product, the above-described gallium compound is preferably used.

1-5. Others 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. An additive 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, or various fillers may be further contained.

1-5-1. 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. Phenolic antioxidants and hindered amines act as radical scavengers. The phosphorus antioxidant acts as a peroxide decomposer.

  Examples of the phenolic antioxidant include 2,6-di-t-butylphenol, 2,6-di-t-butyl-4-methylphenol, and n-octadecyl-3- (3 ′, 5′-di- t-butyl-4′-hydroxyphenyl) propionate, tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4-hydroxyphenyl) propionate)] methane, tris (3,5-di-t -Butyl-4-hydroxybenzyl) isocyanurate, triethylene glycol-bis- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], 2,2'-methylenebis- (4-methyl -6-tert-butylphenol), 4,4'-thiobis (6-tert-butyl-m-cresol), 4,4'-thiobis (3-methyl-6-tert-butyl) Phenol), 4,4'-thiobis (4-methyl -6-t-butylphenol), 4,4'-butylidene bis (3-methyl -6-t-butylphenol) and the like.

  The hindered amine system is considered to be stabilized by the oxidation of the nitroxy radical by capturing the radical. Examples of the nitroxy free radical compound include 2,2,6,6-tetramethyl-1-piperidinyloxy radical (TEMPO), 2,2,6,6-tetraethyl-1-piperidinyloxy radical, 2,2,6,6-tetramethyl-4-oxo-1-piperidinyloxy radical, 2,2,5,5-tetramethyl-1-pyrrolidinyloxy radical, 1,1,3,3- Examples thereof include tetramethyl-2-isoindolinyloxy radical and N, N-di-t-butylamineoxy radical. A hindered amine system exhibits a synergistic effect when used in combination with a phosphorus-based antioxidant and improves weather resistance.

  Examples of phosphorus antioxidants include triphenyl phosphate, triisodecyl phosphate, isodecyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, trisnonyl phenyl phosphate, distearyl pentaerythritol diphosphate, tris ( 2,4-di-t-butylphenyl) phosphate and tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylene-diphosphate.

Among these, a hindered phenol antioxidant having an alkyl group at one or both ortho positions of the phenol hydroxyl group is particularly preferably used. Examples of the hindered phenol antioxidant include [3- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propanoyloxy] -2,2-bis [3- (3 5-di-t-butyl-4-hydroxyphenyl) propanoyloxymethyl] propyl] 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, octadecyl-3- (3,5-di -T-butyl-4-hydroxyphenyl) propionate.

1-5-2. Silane Coupling Agent The liquid resin composition of the present invention can contain a silane coupling agent in order to improve the adhesion to metal parts and inorganic fillers.

  Specific examples include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ- Examples include aminopropyltrimethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane.

1-5-3. Filler A fixed amount of filler other than the silica filler can be added to the resin composition of the present invention as necessary.

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, synthetic polymer particles such as polyamide, natural products such as starch and wood flour, cellulose that may be modified, Examples include 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, alumina, zircon, iron oxide, zinc oxide, titanium oxide, silicon nitride, boron nitride, aluminum nitride, silicon carbide, Glass fiber, glass flake, alumina fiber, carbon fiber, mica, graphite, carbon black, ferrite, graphite, diatomaceous earth, clay, talc, aluminum hydroxide, calcium carbonate, manganese carbonate, magnesium carbonate, barium sulfate, titanic acid Examples thereof include potassium, calcium silicate, inorganic balloon, and silver powder.
As additive fillers other than silica, 1 type may be used and 2 or more types may be used together.

  Further, the filler may be appropriately subjected to a surface treatment. Examples of the surface treatment include alkylation treatment, trimethylsilylation treatment, silicone treatment, treatment with a silane coupling agent, and the like, but are not particularly limited.

  By using a filler, in addition to reducing the viscosity, the strength, hardness, elastic modulus, thermal expansion coefficient, thermal conductivity, heat dissipation, electrical properties, light reflectance, flame retardancy, and fire resistance of the resulting molded product Various physical properties such as thixotropy and gas barrier properties can be improved.

1-6. Method for Producing Resin Composition The liquid resin composition of the present invention is a mixture of a matrix resin, a silica filler and a curing catalyst, and other components such as a filler other than the silica filler, a diluent, and an antioxidant, if necessary. Can be manufactured.

The order of mixing the silica filler is not particularly limited. In order to prevent the progress of the curing reaction due to heat generation during mixing, the epoxy is used in the absence of a gallium compound, a silanol source compound, and other catalysts used for curing the epoxy resin. It is desirable to mix with the compound.

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

  This resin composition may be a one-component curable type or a two-component curable type in consideration of storage stability.

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

3. Sealing Method Sealing using the resin composition according to the present embodiment 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.

3-1. Potting In the liquid resin composition of the present invention, for example, a liquid containing a resin composition and a liquid containing a curing catalyst are prepared, and then mixed to prepare a mixed liquid, which 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.

  When the matrix resin is a thermosetting resin, foaming due to residual solvent or dissolved water vapor in the composition can be prevented by setting the curing temperature to about 100 ° C. first and then to about 150 ° C. 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.

4). Application of Liquid Resin Composition The application of the resin composition according to the embodiment of the present invention is not particularly limited, and can be used as a sealing material for various semiconductor devices including light emitting devices such as LED devices. In addition, since the molded body obtained by curing the resin composition of the present invention contains 75% by weight or more of silica filler, it has a low coefficient of thermal expansion even at a high temperature and is excellent in reliability. Therefore, it is particularly suitable for a power device. .

4-1. Power device The power device is not particularly limited. For example, a power device used as rectification, frequency conversion, a regulator, an inverter, etc. is mentioned. The resin composition of the present invention has fluidity as a composition, can be suitably used for sealing by potting, and has a very low linear expansion coefficient when cured, so a wide range of power devices Can be suitably used. It can also be used for power devices such as home appliances and computers, and can also be used for large power devices for controlling automobiles, railway vehicles, and substations.

  Hereinafter, the present invention will be described in detail by way of examples.

<Synthesis of epoxy silicone resin>
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 = 1000. Polysiloxane EPSi-1 was obtained.

[Examples 1 to 6]
Stir 1.14 g of the above EPSi-1, 0.228 g of cyclohexanedicarboxylic acid diglycidyl ester, and 12.26 g of true spherical filler HL-3100 (manufactured by Tatsumori Co., Ltd.) using Planetary Vacuum Mixer ARV-300 manufactured by THIKY. , Mixed. Thereafter, phenol curing agent MEH-8000H (Maywa Kasei Co., Ltd.) 0.25 g, polystyrene-reduced weight average molecular weight of about 900 both-ends hydroxy group polymethylphenylsiloxane FLD516 (BLUESTARS SILICONES) gallium acetylacetonate (Strem A solution (Ga (acac) ₃ solution) 0.0375 g in which 2% by weight of Chemicals, Inc.) was dissolved was added and stirred and mixed to obtain a composition. Next, the compounds shown in Table 1 below were added to the composition, and the mixture was stirred and mixed using Planetary Vacuum Mixer ARV-300 manufactured by THIKY to obtain resin compositions 1 to 6.
[Comparative Example 1]
Resin composition 7 was obtained in the same manner as in Example except that no compound was added.
[Comparative Examples 2 to 5]
Resin compositions 8 to 11 were obtained in the same manner as in the examples except that the compounds of Comparative Examples 2 to 5 shown in Table 1 were added.

<Evaluation of viscosity of composition>
About 6 g of the obtained composition was put in a 6 cc ointment container, and the viscosity was measured at 40 ° C. to 20 ° C. using a vibration viscosity system (model: VM-10A-H) manufactured by Seconic Corporation. Table 1 shows the measured values obtained by dividing the viscometer display value at 25 ° C. by the specific gravity.

<Evaluation of linear expansion coefficient of cured product>
6 g of composition 1 is placed in an aluminum dish having an inner diameter of 5 mmφ and cured by heating in an oven at 80 ° C. for 30 minutes, 120 ° C. for 120 minutes, 150 ° C. for 60 minutes, and 200 ° C. for 60 minutes. In accordance with JIS K7197, SAI Nano Technology Co., Ltd. TMA / SS6100 was used as the thermomechanical analyzer, and the cured product obtained was compressed at 70 ° C to 270 ° C. The average linear expansion coefficient was measured and found to be 26 ppm.

＊：ＳＰ値については文献値を使用。その他は計算値を使用。
＊＊：アルキルグリシジルエーテルはＹＥＤ２１６Ｄ（三菱化学株式会社製）を使用。

*: Literature values are used for SP values. Others use calculated values.
**: YED216D (manufactured by Mitsubishi Chemical Corporation) is used as the alkyl glycidyl ether.

  As is clear from the results in Table 1, the resin composition of the present invention was fluid at room temperature. On the other hand, the resin compositions of Comparative Examples 1 to 5 were not fluid at room temperature and were not liquid resin compositions. Moreover, the average linear expansion coefficient in 70 to 270 degreeC of the hardened | cured material of the resin composition 1 was as low as 26 ppm.

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

Claims (6)

  A liquid resin composition comprising 75% by weight or more of a silica filler and a matrix resin.   The liquid resin composition according to claim 1, wherein the viscosity at 30 ° C. is 50 Pa · s or less. The liquid resin composition according to claim 1 or 2, further comprising 5% by weight or less of a compound having a solubility parameter of 7.5 (cal / cm ³ ) ^0.5 or more and 18 (cal / cm ³ ) ^0.5 or less. object.   The liquid resin composition according to any one of claims 1 to 3, wherein the matrix resin is an epoxy silicone resin.   The liquid resin composition of any one of Claim 1 to 4 containing 80 weight% or more of silica fillers.   A power semiconductor device that is sealed with the liquid resin composition according to claim 1.