JP2017088740A - Liquid epoxy resin for semiconductor and thermosetting resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid epoxy resin providing a cured article high in heat resistance.SOLUTION: There is provided a thermosetting resin composition containing a liquid epoxy resin obtained by reacting an epoxy group-containing alkoxysilicon compound represented by the following formula (1a), where Rrepresents a substituent having a glycidyl group and Rrepresents an alkyl group having 4 or less carbon atoms and a substituted alkoxysilicon compound represented by the following formula (1b), where Rrepresents an alkyl group, an aryl group or an unsaturated aliphatic residue having 10 or less carbon atoms and Rrepresents an alkyl group having 4 or less carbon atoms.SELECTED DRAWING: None

Description

  The present invention relates to a thermosetting resin for a semiconductor containing a liquid epoxy resin which gives a cured product excellent in heat resistance used for semiconductor materials such as insulating materials for various electric and electronic parts and laminated boards (printed wiring boards). Relates to the composition.

  Epoxy resins are widely used in various electric / electronic parts, structural materials, adhesives, paints and the like because of their excellent heat resistance, electrical properties, mechanical properties, and the like. In addition, with the recent development of the electric and electronic fields, the demand for epoxy resins has become high, and package defects especially when exposed to high temperature conditions during solder reflow have become a priority issue during semiconductor manufacturing. .

  As a technique for solving these problems, developments have been made to improve the glass transition temperature of epoxy resins and maintain the elastic modulus at high temperatures. Specifically, the structural improvement of the epoxy resin itself, such as a method of increasing the crosslink density of the cured product by increasing the functional group density in the epoxy resin, a method of introducing a rigid skeleton into the resin skeleton, glass fiber, There is a method of filling a filler such as silica particles or mica. However, such a structural improvement of the epoxy resin itself and addition of a filler, etc. often use a high molecular weight and polyfunctional solid epoxy resin, and since the viscosity is high, the filler cannot be highly filled, resulting in sufficient The improvement effect was not obtained.

A method of using an alkoxy group-containing silane-modified epoxy resin obtained by dealcoholizing a bisphenol A type epoxy resin and a hydrolyzable alkoxysilane as a method for improving the modulus of elasticity other than the structural improvement of the epoxy resin itself or the addition of fillers ( Patent Document 1) has been proposed, but it has been pointed out that defects such as voids are likely to occur in the cured product due to alcohol and water produced as by-products.
Further, as the epoxy resin for semiconductors, the shrinkage and shortening of the device has led to a demand for a highly shrinkable and highly elastic epoxy resin as the package becomes thinner. However, when a filler or the like is added to give an elastic modulus, the shrinkage rate becomes small, and it has been difficult to achieve both of these characteristics.

JP 2001-59013 A

  An object of the present invention is to provide an epoxy resin that has a high elastic modulus as a mother skeleton and can be filled with a high amount of filler with a low viscosity without depending on a conventional elastic modulus improving method. . Another object of the present invention is to provide an epoxy resin particularly useful as a resin for semiconductors because the mother skeleton itself has a high shrinkage property.

（式中Ｒ_１ａは、グリシジル基を有する置換基を示す。Ｒ_２は炭素数４以下のアルキル基を示す。）
で表されるエポキシ基含有アルコキシケイ素化合物と下記式（１ｂ）

（式中Ｒ_１ｂは、炭素数１０以下のアルキル基、アリール基又は不飽和脂肪族残基を示す。Ｒ_３は炭素数４以下のアルキル基を示す。）
で表される置換アルコキシケイ素化合物の反応物であることを特徴とする液状エポキシ樹脂を含有する半導体用熱硬化性樹脂組成物。
（２）前記液状エポキシ樹脂において、式（１ａ）の化合物のＲ_１ａが、炭素数３以下のグリシドキシアルキル基で置換されたアルキル基を有する化合物であり、式（１ｂ）の化合物がＲ_１ｂとして、炭素数６以下のアルキル基又はアリール基を有する化合物である（１）記載の半導体用熱硬化性樹脂組成物。
（３）前記液状エポキシ樹脂のエポキシ当量が１８５〜２５０ｇ／ｅｑであることを特徴とする（１）に記載の半導体用硬化性樹脂組成物。
（４）前記液状エポキシ樹脂において、ゲルパーミエーションクロマトグラフィーの測定で前記式（１ａ）及び前記式（１ｂ）の含有割合が１〜２０面積％であることを特徴とする（１）記載の半導体用熱硬化性樹脂組成物。
（５）前記式（１ａ）と前記式（１ｂ）を重量比で１：１〜５００：１で反応させて液状エポキシ樹脂を得ることを特徴とする液状エポキシ樹脂の製造方法。
（６）前記液状エポキシ樹脂以外のエポキシ樹脂を含有する（１）〜（４）のいずれか一項に記載の半導体用熱硬化性樹脂組成物。
（７）前記液状エポキシ樹脂以外にフェノール樹脂を含有する（１）〜（４）のいずれか一項に記載の半導体用熱硬化性樹脂組成物。
（８）（１）〜（４）、（６）、（７）のいずれか一項に記載の熱硬化性樹脂組成物を硬化してなる硬化物を備える半導体装置。 As a result of intensive studies to solve the above problems, the present inventors have reached the present invention. That is, the present invention relates to the following (1) to (7).
(1) The following formula (1a)

(In the formula, R _1a represents a substituent having a glycidyl group. R ₂ represents an alkyl group having 4 or less carbon atoms.)
An epoxy group-containing alkoxysilicon compound represented by the following formula (1b)

(In the formula, R _1b represents an alkyl group having 10 or less carbon atoms, an aryl group, or an unsaturated aliphatic residue. R ₃ represents an alkyl group having 4 or less carbon atoms.)
A thermosetting resin composition for semiconductors containing a liquid epoxy resin, which is a reaction product of a substituted alkoxysilicon compound represented by the formula:
(2) In the liquid epoxy resin, R _1a of the compound of the formula (1a) is a compound having an alkyl group substituted with a glycidoxyalkyl group having 3 or less carbon atoms, and the compound of the formula (1b) is R _The thermosetting resin composition for a semiconductor according to (1), which is a compound having an alkyl group or aryl group having 6 or less carbon atoms as _1b .
(3) The epoxy equivalent of the liquid epoxy resin is 185 to 250 g / eq, and the curable resin composition for semiconductor as described in (1).
(4) The semiconductor according to (1), wherein in the liquid epoxy resin, the content ratio of the formula (1a) and the formula (1b) is 1 to 20 area% as measured by gel permeation chromatography. Thermosetting resin composition.
(5) A method for producing a liquid epoxy resin, wherein the formula (1a) and the formula (1b) are reacted at a weight ratio of 1: 1 to 500: 1 to obtain a liquid epoxy resin.
(6) The thermosetting resin composition for a semiconductor according to any one of (1) to (4), which contains an epoxy resin other than the liquid epoxy resin.
(7) The thermosetting resin composition for a semiconductor according to any one of (1) to (4), which contains a phenol resin in addition to the liquid epoxy resin.
(8) A semiconductor device comprising a cured product obtained by curing the thermosetting resin composition according to any one of (1) to (4), (6), and (7).

  Since the cured film of the thermosetting resin composition of the present invention is excellent in high elastic modulus, low in viscosity, and excellent in handling properties, the filler can be highly filled. Furthermore, since it has a high shrinkage characteristic peculiar to a silicon-oxygen bond, it exhibits particularly excellent performance when applied to semiconductor applications.

The epoxy group-containing group R _{1a in} the epoxy group-containing alkoxysilicon compound of the formula (1a) used in the present invention is not particularly limited as long as it is a substituent having a glycidyl group, but a β-glycidoxyethyl group, Examples thereof include glycidoxyalkyl groups and glycidyl groups having 4 or less carbon atoms, preferably 3 or less, such as γ-glycidoxypropyl group and γ-glycidoxybutyl group. Of these, β-glycidoxyethyl group and γ-glycidoxypropyl group are preferable. Preferable specific examples of compounds that can be used as the compound of the formula (1a) having these substituents R _1a include β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, γ-glycol. Sidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane and the like can be mentioned.

In the substituted alkoxysilicon compound represented by the formula (1b), the substituent R _1b is an alkyl group having 10 or less carbon atoms, an aryl group, or an unsaturated aliphatic residue, preferably the compatibility of the composition, From the viewpoint of the physical properties of the cured product, a compound having a combination of an alkyl group or aryl group having 6 or less carbon atoms and R ₂ being an alkyl group having 4 or less carbon atoms is preferable. Specifically, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, n-propyltrimethoxysilane , N-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane and other alkyltrialkoxysilanes, phenyltrimethoxysilane, phenyltriethoxysilane and other aryltrialkoxysilanes And the like.
In addition, as an alkoxy group in the said epoxy group containing alkoxy silicon compound and a substituted alkoxy silicon compound, a methoxy group or an ethoxy group is preferable at the point of reaction conditions, and a methoxy group is especially preferable.

In the condensation reaction for obtaining the liquid epoxy resin of the present invention, an epoxy group-containing alkoxysilicon compound of the formula (1a) and a substituted alkoxysilicon compound of the formula (1b) are (co) condensed in the presence of a basic catalyst. I can get it. Moreover, in order to accelerate | stimulate (co) condensation, water can be added as needed. The amount of water added is usually 0.05 to 1.5 mol, preferably 0.07 to 1.0 mol, more preferably 0.1 to 0.5 mol, relative to 1 mol of alkoxy groups in the entire reaction mixture. . In the present invention, it is preferable to condense the formulas (1a). Here, the molecular weight can be influenced by adjusting the amount of water added. That is, 0.1 to 0.5 mol is preferable because the molecular weight is reduced and a low-viscosity epoxy resin can be synthesized.
The reaction ratio of the epoxy group-containing alkoxysilicon compound of the formula (1a) and the formula (1b) is preferably 1:10 to 500: 1 in terms of molar ratio, and preferably 1: 1 to 500: 1. Is more preferable, 1: 1 to 300: 1 is particularly preferable, and 1: 1 to 200: 1 is very preferable. In this way, by reacting a large amount of the epoxy group-containing alkoxysilicon compound of the formula (1a), it is possible to realize a low viscosity and to exhibit the effects of suitable high shrinkage and high elastic modulus. Become.
The reaction temperature in the condensation reaction is preferably adjusted to 45 ° C. to 55 ° C. (for example, the reaction time is 1 hour or more, preferably 5 hours or more). By controlling the reaction temperature, it is possible to prevent a specific molecular weight peak from becoming too sharp in the molecular weight distribution, and a liquid epoxy resin having a suitable molecular weight distribution can be obtained. Here, when it is desired to obtain a sharp peak, the reaction temperature is 55 ° C. or higher, preferably 60 ° C. or higher (for example, the reaction time is 1 hour or longer, preferably 5 hours or longer). .

The catalyst used in the above condensation reaction is not particularly limited as long as it is basic, but inorganic such as sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, etc. Organic bases such as base, ammonia, triethylamine, diethylenetriamine, n-butylamine, dimethylaminoethanol, triethanolamine, tetramethylammonium hydroxide can be used. Among these, an inorganic base or ammonia is preferable because the catalyst can be easily removed from the product. The addition amount of the catalyst is usually 5 × 10 ^{−4 to} 7.5% by weight, preferably 1 × 10 ^{−3 to} 5% by weight, based on the total of the epoxy group-containing alkoxysilicon compound and the substituted alkoxysilicon compound.

  The condensation reaction can be carried out without a solvent or in a solvent. The solvent is not particularly limited as long as it is a solvent that dissolves the epoxy group-containing alkoxysilicon compound and the substituted alkoxysilicon compound. Examples of such solvents include aprotic polar solvents such as dimethylformamide, dimethylacetamide, tetrahydrofuran, methyl ethyl ketone, and methyl isobutyl ketone, and aromatic hydrocarbons such as toluene and xylene.

After completion of the reaction, the excess catalyst can be quenched. The quench treatment is preferably performed using an acidic compound. It is also preferable to use a reducing agent and an acidic compound in combination. As a preferable treatment method, there is a method of quenching the remaining catalyst using a reducing agent after neutralization adjustment to pH 6 to 10 with an acidic compound. If the pH is less than 6, the heat generated when reducing the excess catalyst is large, which may cause decomposition products, and the molecular weight may not be stable.
The quenching agent is not particularly limited as long as it is a known quenching agent, and examples thereof include phosphoric acid, boric acid, citric acid, acetic acid, and sodium dihydrogen phosphate. Here, it is preferable from being able to obtain a colorless and transparent liquid epoxy resin by suppressing coloring of the liquid epoxy resin from which sodium dihydrogen phosphate is obtained. Furthermore, since it has a buffer region in the neutral region, it contributes to stabilization of the molecular weight.
Although it does not specifically limit as the usage-amount of a quenching agent, From a viewpoint of stabilizing molecular weight, it is preferable to set it as 3 mol or more (especially 5 mol or more) with respect to 1 mol of remaining catalysts. When the amount of the quenching agent used is less than 3 mol, silanol groups present in the epoxy resin act as a Lewis acid, and the quenching agent may be consumed, and neutralization may not be performed sufficiently.
As a form of the quenching agent, for example, an aqueous solution or a solid quenching agent having a constant concentration of 10% or the like can be used, but it is preferable to use a solid type from the viewpoint of stabilization of molecular weight.

（Ｒ１ａ〜Ｒ１ｂは炭素数１０以下のアルキル基、アリール基、不飽和脂肪族残基、もしくはグリシジル基を有する置換基であり、Ｒ１ａ〜Ｒ１ｂの少なくとも１つはグリシジルを有する置換基である。また、Ｒ_１〜Ｒ_４は水素、ヒドロキシル基又は炭素数５以下のアルコキシ基を表す。） The liquid epoxy resin of the present invention thus obtained has a weight average molecular weight of preferably 400 to 50000, more preferably 750 to 30000, in terms of weight average molecular weight. When the weight average molecular weight is less than 400, the effect of improving the elastic modulus is poor, and when it is greater than 50000, the physical properties of the composition such as a decrease in compatibility and an increase in viscosity are reduced, which is not preferable.
Moreover, as an epoxy equivalent, it is preferable that it is 185-250 g / eq, and it is preferable that it is 190-230 g / eq. By setting it as such an epoxy equivalent, it becomes possible to express the effect of a high elastic modulus and a high shrinkage suitably.
Furthermore, in the obtained liquid epoxy resin, it is preferable that said formula (1a) and said formula (1b) are 1-20 area% in the measurement of a gel permeation chromatography (GPC), and 2-15 area % Is more preferable. By being in such a suitable range, a liquid epoxy resin having an excellent balance between elastic modulus and viscosity can be obtained. The viscosity is preferably 100 mPa · s or less.
The total chlorine content of the liquid epoxy resin obtained is 100 ppm or less, preferably 10 ppm or less. It is generally known that the organic chlorine contained in the epoxy resin causes a wiring failure of the semiconductor. However, the electrical reliability of the semiconductor can be greatly improved by using the epoxy resin of the present invention. Further, the residual free sodium is preferably 1.2 ppm or less, and the residual free chlorine is preferably 0.5 ppm or less.
Moreover, as a specific example of the structure of the obtained liquid epoxy resin, it becomes a compound having a silsesquioxane skeleton represented by the following formula as a repeating unit. And the said liquid epoxy resin takes well-known shapes, such as chain | strand shape, ladder shape, and basket shape, as frame | skeleton of a silicone resin.

(R1a to R1b are substituents having an alkyl group, aryl group, unsaturated aliphatic residue, or glycidyl group having 10 or less carbon atoms, and at least one of R1a to R1b is a substituent having glycidyl. R _{1 to} R ₄ represent hydrogen, a hydroxyl group, or an alkoxy group having 5 or less carbon atoms.)

  The liquid epoxy resin of the present invention is used for various applications, but is usually used as a thermosetting resin composition in combination with a curing agent. Moreover, when applying to various uses, various epoxy resins can also be used together according to the use. In particular, from the viewpoints of high elastic modulus, low viscosity, high shrinkage, and high purity, it can be suitably used in the field of electrical insulating materials such as IC sealing materials, laminated materials, rewiring layers, and die attach paste resist materials.

  As the curing agent, an amine compound, an acid anhydride compound, an amide compound, a phenol compound, etc., which are usually used as a curing agent for epoxy resins, can be used without any particular limitation. From the viewpoint of thermal stability, a phenol resin can be suitably used as the curing agent. Specifically, phenylenediamine, diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, tetraethylenepentamine, dimethylbenzylamine, oxydianiline, para-phenylenediamine, meta-phenylenediamine, 4 , 4'-diaminobenzanilide, 2,2'-dimethylbenzidine, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-oxydianiline, 3,4'-oxydianiline 1,8-octamethylenediamine, 1,6-hexamethylenediamine, 4,7,10-trioxatridecane-1,13-diamine, 4,9-dioxadodecane-1,12-diamine, 1, 3-bis- ( -Aminophenoxy) benzene, 1,3-bis- (3-aminophenoxy) benzene, 4,4 '-[1,4-phenylenebis (1-methylidene)] bisaniline, 2,4'-diaminodiphenylmethane; 4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 1,5-diaminonaphthalene, 2,4-bis (β-amino -T-butyl) toluene, bis (p-β-amino-t-butylphenyl) ether, ketimine compound, polyamide resin synthesized from dimer of linolenic acid and ethylenediamine, phthalic anhydride, trimellitic anhydride, anhydrous Pyromellitic acid, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydride Phthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, bisphenols, phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes Polycondensates, polymers of phenols with various diene compounds, polycondensates of phenols with aromatic dimethylol, or condensates of bismethoxymethylbiphenyl with naphthols or phenols, biphenols and these Modified products, imidazoles, boron trifluoride-amine complexes, guanidine derivatives and the like can be mentioned. 0.2-1.5 equivalent is preferable with respect to 1 equivalent of epoxy groups in a composition, and, as for the usage-amount of a hardening | curing agent, 0.3-1.2 equivalent is especially preferable. In addition, the amount of the curing agent used when a tertiary amine such as benzyldimethylamine is used as the curing agent is preferably 0.3 to 20% by weight based on the epoxy group-containing compound in the composition. 0.5 to 10% by weight is particularly preferred.

  If necessary, the thermosetting resin composition of the present invention may contain a photopolymerization initiator and / or a curing accelerator. As photopolymerization initiators, benzyl, benzoin ether, benzoin butyl ether, benzoin propyl ether, benzophenone, 3,3′-dimethyl-4-methoxybenzophenone, benzoylbenzoic acid, esterified product of benzoylbenzoic acid, 4-benzoyl-4 ′ -Methyldiphenyl sulfide, benzyldimethyl ketal, 2-butoxyethyl-4-methylaminobenzoate, chlorothioxanthone, methylthioxanthone, ethylthioxanthone, isopropylthioxanthone, dimethylthioxanthone, diethylthioxanthone, diisopropylthioxanthone, dimethylaminomethylbenzoate, 1- (4 -Dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl Ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, methylbenzoylformate, 2-methyl- 1- (4-Methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2,4-bis (trichloromethyl)- 6- (4-methoxyphenyl) -1,3,5-s-triazine, 2,4,6-tris (trichloromethyl) -1,3,5-s-triazine, 2,4-bis (tribromomethyl) ) -6- (4′-methoxyphenyl) -1,3,5-s-triazine, 2,4,6-tris (tribromomethyl) -1,3,5-s-triazine, 2,4 Bis (trichloromethyl) -6- (1,3-benzodioxolan-5-yl) -1,3,5-s-triazine, benzophenone, benzoylbenzoic acid, 1- (4-phenylsulfanylphenyl) butane-1, 2-dione-2-oxime-o-benzoate, 1- (4-methylsulfanylphenyl) butane-1,2-dione-2-oxime-o-acetate, 1- (4-methylsulfanylphenyl) butane-1 -Onoxime-o-acetate, 4,4'-bis (diethylamino) benzophenone, p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid ethyl ester, 2,2'-bis (o-chlorophenyl) -4, 4 ', 5,5'-Tetraphenyl-1,2'-biimidazole, diazonaphthoquinone based In addition, commercially available Kayacure DMBI, Kayacure BDK, Kayacure BP-100, Kayacure BMBI, Kayacure DETX-S, Kayacure EPA (all manufactured by Nippon Kayaku), Darocure 1173, Darocure 1116 (all manufactured by Merck Japan), Irgacure 907 (Made by BASF Japan), Irgacure 369 (made by BASF Japan), Irgacure 379EG (made by BASF Japan), Irgacure OXE-01 (made by BASF Japan), Irgacure OXE-02 (made by BASF Japan), Irgacure PAG103 ( BASF Japan), TME-triazine (manufactured by Sanwa Chemical), biimidazole (manufactured by Kurokin Kasei), STR-110, STR-1 (all manufactured by Respe Chemical), etc. Examples of the curing accelerator include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, 1,8-diaza-bicyclo (5,4). , 0) Tertiary amines such as undecene-7, phosphines such as triphenylphosphine, metal compounds such as tin octylate, quaternary phosphonium salts 2-methylimidazole, 2-phenylimidazole, 2-undecyl Imidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2- Phenylimidazole, 1-cyanoethyl-2 Undecylimidazole, 2,4-diamino-6 (2′-methylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-undecylimidazole (1 ′)) ethyl-s -Triazine, 2,4-diamino-6 (2'-ethyl, 4-methylimidazole (1 ')) ethyl-s-triazine, 2,4-diamino-6 (2'-methylimidazole (1')) ethyl -S-triazine-isocyanuric acid adduct, 2-methylimidazole isocyanuric acid 2: 3 adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethylimidazole, 2-phenyl-4- Various kinds of hydroxymethyl-5-methylimidazole and 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole Dazoles, and salts of these imidazoles with oligoesters of terminal carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid, and oxalic acid, and amides such as dicyandiamide , Diaza compounds such as 1,8-diaza-bicyclo (5.4.0) undecene-7 and salts thereof such as tetraphenylborate and phenol novolak, oligoesters of the terminal carboxylic acids, or phosphinic acids Quaternary ammonium salts such as salts, tetrabutylammonium bromide, cetyltrimethylammonium bromide, trioctylmethylammonium bromide, hexadecyltrimethylammonium hydroxide (preferably C1-C20 alkylammonium salt, Phosphines and phosphonium compounds such as nylphosphine, tri (toluyl) phosphine, tetraphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate, phenols such as 2,4,6-trisaminomethylphenol, amine adducts, tin octylate, Examples include, but are not limited to, metal compounds such as zinc octoate, zinc stearate, copper naphthenate, cobalt naphthenate and the like, and microcapsule type curing accelerators in which these curing accelerators are microcapsules. Absent. 0.01-15 weight part is used for a photoinitiator and / or a hardening accelerator as needed with respect to 100 weight part of epoxy group-containing compounds in the composition.

  In the thermosetting resin composition of the present invention, when the liquid epoxy resin of the present invention is used in combination with another epoxy resin, the proportion of the liquid epoxy resin of the present invention in the total epoxy group-containing compound is 10% by weight or more. preferable. Other epoxy resins that can be used are not particularly limited as long as they are epoxy resins that are usually used for electric and electronic parts, and can be obtained by glycidylating a compound having two or more phenolic hydroxyl groups. . Specific examples of epoxy resins that can be used include bisphenols such as tetrabromobisphenol A, tetrabromobisphenol F, bisphenol A, tetramethyl bisphenol F, bisphenol F, bisphenol S or bisphenol K, or biphenols such as biphenol or tetramethyl biphenol. Or hydroquinone, methyl hydroquinone, dimethyl hydroquinone, trimethyl hydroquinone or di-ter. Hydroquinones such as butyl hydroquinone, resorcinols such as resorcinol or methyl resorcinol, catechols such as catechol or methyl catechol, or glycidylated products or phenols of dihydroxynaphthalene such as dihydroxynaphthalene, dihydroxymethylnaphthalene or dihydroxydimethylnaphthalene, or Condensates of naphthols and aldehydes, or condensates of phenols or naphthols and xylylene glycol, condensates of phenols and isopropenylacetophenone, or reactants of phenols and dicyclopentadiene, or bismethoxymethyl Examples thereof include glycidylated products of condensates of biphenyl and naphthols or phenols. These can be obtained commercially or by known methods. These may be used alone or in combination of two or more.

  Furthermore, the thermosetting resin composition of the present invention includes fillers such as silica, alumina, glass fiber, and talc, mold release agents, pigments, surface treatment agents, viscosity modifiers, plasticizers, and stabilizers as necessary. Various compounding agents such as a coupling agent can be added.

Further, the thermosetting resin composition of the present invention can be dissolved in a solvent and used as a varnish. The solvent is not particularly limited as long as it dissolves each component of the composition, and examples thereof include toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide and the like. A prepreg obtained by impregnating a base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. with these solvent-dissolved varnishes and hot-pressing the prepreg is cured product of the present invention. Can also be obtained.
At that time, the solvent is used in such an amount that the ratio of the solvent to the total weight of the thermosetting resin composition of the present invention and the solvent is usually 10 to 70% by weight, preferably 15 to 65% by weight.

  The thermosetting resin composition of this invention is obtained by mixing each component uniformly. The thermosetting resin composition of this invention can be easily made into the hardened | cured material by the method similar to the method known conventionally. For example, an epoxy resin composition obtained by thoroughly mixing an epoxy group-containing compound, a curing agent, and if necessary, a curing accelerator and a compounding agent, if necessary, using an extruder, a kneader, a roll or the like until uniform. After the epoxy resin composition is melted, it is molded using a casting or transfer molding machine, and further heated at 80 to 200 ° C. for 2 to 10 hours to obtain a cured product.

  The liquid epoxy resin of the present invention is used in semiconductor applications. For example, in semiconductor substrate and resist material applications, it is useful to alleviate the deformation of a cured product that is observed during transfer from a reflow furnace, which becomes more serious as the core becomes thinner and thinner. In the semiconductor encapsulant application, it contributes to suppressing the reverse warping of the package accompanying the reduction in the encapsulant's height. The underfill material can be filled in a narrow pitch region because of its low viscosity. Since the rewiring layer is a high-purity product with a small amount of total chlorine, it can contribute to the suppression of electrical failures.

Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to these examples. Moreover, unless otherwise indicated in an Example, a part shows a weight part. In addition, each physical property value in an Example was measured with the following method.
(1) Weight average molecular weight: Measured by GPC (gel permeation chromatography) method.
GPC measurement condition Manufacturer: Shimadzu Corporation Column: Guard column SHODEX GPC KF-802.5 (2) KF-802 KF-803
Flow rate: 1.0 ml / min.
Column temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Detector: RI (differential refraction detector)
Various conditions of ¹³ C-NMR (2) Epoxy equivalent: Measured by a method according to JIS K-7236.
(3) E-type viscosity: measured by a method according to JIS K-7117-2.
(4) Total chlorine content: measured by a method according to JIS K-7243-3.

Example 1
A reaction vessel was charged with 118.2 parts of γ-glycidoxypropyltrimethoxysilane, 0.7 parts of methyltrimethoxysilane, 178.3 parts of methyl isobutyl ketone, and 21.4 parts of methanol. 7.3 parts of 0.5% KOH was continuously added dropwise over 30 minutes. The cloudiness phenomenon did not occur at the time of dropping. After dropping, the temperature was raised to 50 ° C. and reacted for 5 hours. After completion of the reaction, the mixture was cooled to 40 ° C. or lower, 0.4 parts of sodium dihydrogen phosphate dihydrate was added all at once, stirred at 40 ° C. or lower for 30 minutes, and then repeatedly washed with water until the washing solution became neutral. . Subsequently, the liquid epoxy resin (A) 112.9 parts of this invention was obtained by concentrating at 120 degreeC. The epoxy equivalent of the obtained compound was 198 g / eq, the weight average molecular weight was 1029, the viscosity was 52 mPa · s, the sum of formula (1a) and formula (1b) in GPC was 9.4 area%, and the total chlorine content was 8. It was 5 ppm. In addition, gelation was not observed even at room temperature for 1 month. Furthermore, gelation was not observed even at 60 ° C. for 1 month. In addition, no gelation was observed over time at 5 ° C. for 7 days.

Example 2
112.9 parts of liquid epoxy resins (B) were obtained in the same manner as in Example 1 except that 12.3 parts were used instead of 7.3 parts of 0.5% KOH. The epoxy equivalent of the obtained compound was 175 g / eq, the weight average molecular weight was 1755, the viscosity was 2322 mPa · s, and the total of formula (1a) and formula (1b) in GPC was 0.3 area%.

Example 3
111.3 parts of a liquid epoxy resin (B) was obtained in the same manner as in Example 1 except that 13.7 parts were used instead of 7.3 parts of 0.5% KOH. The epoxy equivalent of the obtained compound was 170 g / eq, the weight average molecular weight was 1927, the viscosity was 2893 Pa · s, and the total of formula (1a) and formula (1b) in GPC was 0.2 area%.

Example 4
A liquid epoxy resin (C) (112.3 parts) was obtained in the same manner as in Comparative Example 1 except that the reaction was performed at 72 ° C. The epoxy equivalent of the obtained compound was 185 g / eq, the weight average molecular weight was 1950, the viscosity was 2065 mPa · s, the sum of formula (1a) and formula (1b) in GPC was 0.3 area%, and the total chlorine content was 9. 1 ppm.

Example 5
Instead of 118.2 parts of γ-glycidoxypropyltrimethoxysilane, instead of 82.7 parts of γ-glycidoxypropyltrimethoxysilane, 29.7 parts of phenyltrimethoxysilane, 7.3 parts of 0.5% KOH 107.5 parts of liquid or more epoxy resin (D) was obtained in the same manner as in Example 1 except that 12.3 parts were used. The epoxy equivalent of the obtained compound was 236 g / eq, the weight average molecular weight 2289, the viscosity was 4913 mPa · s, and the total of the formulas (1a) and (1b) in GPC was 0.1 area%.

ＥＰ−１：実施例３で得られたエポキシ樹脂
ＥＰ−２：o-クレゾールノボラック型エポキシ樹脂（日本化薬（株）製 EOCN-1020-62、エポキシ当量：199g/eq）
ＥＰ−３：トリスフェノールメタン型エポキシ樹脂（日本化薬（株）製 EPPN-502H、エポキシ当量：170g/eq）
ＥＰ−４：ビフェニル-フェノールアラルキル型エポキシ樹脂（日本化薬（株）製 NC-3000、エポキシ当量：277g/eq）
ＰＨ−１：ビスフェノールＦ（三井化学（株）製BPF-ST、水酸基当量：100g/eq）
ＰＨ−２：フェノールノボラック（明和化成（株）製 H-1、水酸基当量：103g/eq）
Ｃａｔ：トリフェニルホスフィン（純正化学（株）製） Example 6, Comparative Examples 1-3
An epoxy resin is blended in the proportions (parts) shown in Table 1, and a resin molded body is prepared, and heated at 160 ° C. for 2 hours and further at 180 ° C. for 8 hours. The epoxy resin composition of the present invention and the comparative resin composition A cured product was obtained. These linear expansion changes at 50 to 250 ° C. are shown in Table 1. TMA was measured under the following conditions.
-TMA measuring conditions TMA thermomechanical measuring device: TM-7000 manufactured by Vacuum Riko Co., Ltd.
Temperature increase rate: 2 ° C./min.

EP-1: Epoxy resin obtained in Example 3 EP-2: o-cresol novolak type epoxy resin (EOCN-1020-62 manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 199 g / eq)
EP-3: Trisphenolmethane type epoxy resin (Nippon Kayaku Co., Ltd. EPPN-502H, epoxy equivalent: 170 g / eq)
EP-4: Biphenyl-phenol aralkyl type epoxy resin (Nippon Kayaku Co., Ltd. NC-3000, epoxy equivalent: 277 g / eq)
PH-1: Bisphenol F (BPF-ST, Mitsui Chemicals, hydroxyl equivalent: 100 g / eq)
PH-2: phenol novolak (M-1 Kasei Co., Ltd. H-1, hydroxyl equivalent: 103 g / eq)
Cat: Triphenylphosphine (manufactured by Pure Chemical Co., Ltd.)

(A) Cured TMA chart of Example 6

Claims (9)

The following formula (1a)

(In the formula, R _1a represents a substituent having a glycidyl group. R ₂ represents an alkyl group having 4 or less carbon atoms.)
An epoxy group-containing alkoxysilicon compound represented by the following formula (1b)

(In the formula, R _1b represents an alkyl group having 10 or less carbon atoms, an aryl group, or an unsaturated aliphatic residue. R ₃ represents an alkyl group having 4 or less carbon atoms.)
A thermosetting resin composition for semiconductors containing a liquid epoxy resin, which is a reaction product of a substituted alkoxysilicon compound represented by the formula: In the liquid epoxy resin, R _1a of the compound of the formula (1a) is a compound having an alkyl group substituted with a glycidoxyalkyl group having 3 or less carbon atoms, and the compound of the formula (1b) is carbon as R _1b The thermosetting resin composition for a semiconductor according to claim 1, which is a compound having an alkyl group or an aryl group of several 6 or less. 2. The curable resin composition for a semiconductor according to claim 1, wherein the total chlorine content of the liquid epoxy resin is 100 ppm or less. 2. The curable resin composition for a semiconductor according to claim 1, wherein an epoxy equivalent of the liquid epoxy resin is 185 to 250 g / eq. The said liquid epoxy resin WHEREIN: The content rate of the said Formula (1a) and the said Formula (1b) is 1-20 area% by the measurement of a gel permeation chromatography, The thermosetting for semiconductors of Claim 1 characterized by the above-mentioned. Resin composition. A method for producing a liquid epoxy resin, wherein the formula (1a) and the formula (1b) are reacted at a weight ratio of 1:10 to 500: 1 to obtain a liquid epoxy resin. The thermosetting resin composition for semiconductors as described in any one of Claims 1-5 containing epoxy resins other than the said liquid epoxy resin. The thermosetting resin composition for semiconductors as described in any one of Claims 1-5 containing a phenol resin other than the said liquid epoxy resin. A semiconductor device provided with the hardened | cured material formed by hardening | curing the thermosetting resin composition as described in any one of Claims 1-5 and Claims 7, 8.