JP6900949B2 - Epoxy resin, curable resin composition and its cured product - Google Patents

Description

The present invention relates to an epoxy resin having a low melt viscosity, high heat resistance in a cured product, and little change in heat resistance after heat history, a curable resin composition containing the epoxy resin, a cured product thereof, a semiconductor encapsulant material, and a print. Regarding the wiring board.

Epoxy resins are used as materials for adhesives, molding materials, paints, etc., and because the obtained cured products have excellent heat resistance and moisture resistance, they are used as semiconductor encapsulants, insulating materials for printed wiring boards, etc. Widely used in the electrical and electronic fields.

Of these, power semiconductors represented by in-vehicle power modules are important technologies that hold the key to energy saving in electrical and electronic equipment, and have been conventionally developed with the further increase in current, miniaturization, and efficiency of power semiconductors. The transition from silicon (Si) semiconductors to silicon carbide (SiC) semiconductors is underway. The advantage of SiC semiconductors is that they can operate under higher temperature conditions. Therefore, semiconductor encapsulants are required to have higher heat resistance than ever before and to have less change in physical properties in a high temperature environment. In addition to this, it is an important performance requirement for resins for semiconductor encapsulants that it exhibits high flame retardancy without using halogen-based flame retardants, has low viscosity and excellent fluidity, and is capable of high filling of fillers. , There is a demand for a resin material that has all of these performances.

As a resin material for meeting these various required characteristics, for example, the following structural formula

（式中、Ｇはグリシジル基を表す。）
で表されるエポキシ化合物を含有するエポキシ樹脂が知られている（特許文献１参照）。このようなエポキシ樹脂は耐熱性に優れる特徴を有するものの、溶融粘度が高い。したがって、高耐熱かつ低粘度の新規エポキシ樹脂材料が求められていた。

(In the formula, G represents a glycidyl group.)
An epoxy resin containing an epoxy compound represented by (see Patent Document 1) is known. Although such an epoxy resin has a feature of excellent heat resistance, it has a high melt viscosity. Therefore, a new epoxy resin material having high heat resistance and low viscosity has been required.

Japanese Unexamined Patent Publication No. 2004-339371

Therefore, the problem to be solved by the present invention is an epoxy resin having a low melt viscosity, high heat resistance in a cured product, and little change in heat resistance after a heat history, a curable resin composition containing the epoxy resin, and its curing. The purpose is to provide products, semiconductor encapsulant materials, and printed wiring substrates.

As a result of diligent studies to solve the above problems, the present inventors have determined that the epoxy resin has a triphenylmethane skeleton, the epoxy equivalent value of the epoxy resin is (α), and the epoxy group and the molar of the epoxy resin. When the value of the hydroxyl equivalent of the reaction product obtained by reacting the phenol of the above is (β), the epoxy resin having a value of 1000 × [(β-α) / α] of 480 or less has a melt viscosity. We have found that the temperature is low, the heat resistance of the cured product is high, and the change in heat resistance after the heat history is small, and the present invention has been completed.

That is, the present invention is an epoxy resin having a structural portion (I) represented by the following structural formula (1) as a repeating structural unit, and the value of the epoxy equivalent of the epoxy resin is (α), and the epoxy contained in the epoxy resin. When the value of the hydroxyl equivalent of the reaction product obtained by reacting the group with this molar phenol is (β), the value of 1000 × [(β-α) / α] is 480 or less. Regarding epoxy resin.

［式中Ｒ^１、Ｒ^２はそれぞれ独立に水素原子、炭素原子数１〜４の炭化水素基、炭素原子数１〜４のアルコキシ基、ハロゲン原子、又は構造式（１）で表される構造部位（Ｉ）と＊印が付されたメチレン基を介して連結する結合点の何れかであり、ｍは１〜３の整数、ｎは１〜４の整数である。］

[In the formula, R ¹ and R ² are independently represented by a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, or a structure represented by the structural formula (1). It is any of the bonding points connected to the site (I) via the methylene group marked with *, and m is an integer of 1 to 3 and n is an integer of 1 to 4. ]

The present invention further relates to a curable resin composition containing the epoxy resin and a curing agent.

The present invention further relates to a cured product obtained by subjecting the curable resin composition to a curing reaction.

The present invention further relates to a printed wiring board made of the curable resin composition.

The present invention further relates to a semiconductor encapsulating material containing the epoxy resin, a curing agent, and an inorganic filler.

The present invention further reacts the phenolic hydroxyl group-containing compound (A) represented by the following structural formula (2) with the formyl group-containing phenolic hydroxyl group-containing compound (B) represented by the following structural formula (3). The present invention relates to a method for producing an epoxy resin, which comprises reacting the resulting triphenylmethane type resin with epihalohydrin in the presence of water and alcohols.

［式中Ｒ^３、Ｒ^４はそれぞれ独立に水素原子、炭素原子数１〜４の炭化水素基、炭素原子数１〜４のアルコキシ基、ハロゲン原子の何れかであり、ｍは１〜３の整数、ｎは１〜４の整数である。］

[In the formula, R ³ and R ⁴ are independently any of a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a halogen atom, and m is 1 to 3. An integer, n is an integer of 1 to 4. ]

According to the present invention, an epoxy resin having a low melt viscosity, high heat resistance in a cured product, and little change in heat resistance after heat history, a curable resin composition containing the epoxy resin, a cured product thereof, and a semiconductor encapsulating material. , A printed wiring board can be provided.

FIG. 1 is a GPC chart of the epoxy resin (1) obtained in Example 1.

Hereinafter, the present invention will be described in detail.
The epoxy resin of the present invention has the following structural formula (1).

［式中Ｒ^１、Ｒ^２はそれぞれ独立に水素原子、炭素原子数１〜４の炭化水素基、炭素原子数１〜４のアルコキシ基、ハロゲン原子、又は構造式（１）で表される構造部位（Ｉ）と＊印が付されたメチレン基を介して連結する結合点の何れかであり、ｍは１〜３の整数、ｎは１〜４の整数である。］
で表される構造部位（Ｉ）を繰り返し構造単位として有する。

[In the formula, R ¹ and R ² are independently represented by a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, or a structure represented by the structural formula (1). It is any of the bonding points connected to the site (I) via the methylene group marked with *, and m is an integer of 1 to 3 and n is an integer of 1 to 4. ]
It has a structural part (I) represented by, as a repeating structural unit.

^{R 1} and R ² in the structural formula (1) are independently hydrogen atoms, hydrocarbon groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, halogen atoms, or structural formula (1). It is one of the bonding points connected via the structural site (I) represented by (I) and the methylene group marked with *. Examples of the hydrocarbon group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group and a butyl group. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propyloxy group, a butoxy group and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom. Among them, since the epoxy resin has an excellent balance between the melt viscosity and the heat resistance of the cured product, R ¹ and R ² are marked with a hydrogen atom or a structural part (I) represented by the structural formula (1) and *. It is preferably one of the bonding points connected via the attached methylene group.

Specifically, the fact that R ¹ and R ² are the bonding points connecting the structural site (I) represented by the structural formula (1) via the methylene group marked with * is one structure. The aromatic ring in the site (I) is linked to another structural site (I) via a methylene group marked with *. For example, when ^{one of R 2} is a bond point connected to the structural site (I) represented by the structural formula (1) via a methylene group marked with *, the following structural formula (1- It has a structure as represented by 1).

［式中Ｒ^１、Ｒ^２はそれぞれ独立に水素原子、炭素原子数１〜４の炭化水素基、炭素原子数１〜４のアルコキシ基、ハロゲン原子、又は構造式（１）で表される構造部位（Ｉ）と＊印が付されたメチレン基を介して連結する結合点の何れかであり、ｍは１〜３の整数、ｎは１〜４の整数である。］

[In the formula, R ¹ and R ² are independently represented by a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, or a structure represented by the structural formula (1). It is any of the bonding points connected to the site (I) via the methylene group marked with *, and m is an integer of 1 to 3 and n is an integer of 1 to 4. ]

Since the epoxy resin of the present invention is an epoxy resin having an excellent balance between melt viscosity and heat resistance in a cured product, the epoxy equivalent is preferably in the range of 150 to 200 g / equivalent. Further, the melt viscosity of the epoxy resin of the present invention is preferably in the range of 0.01 to 3 dPa · s measured at 150 ° C.

In the epoxy resin of the present invention, in addition to the structural part (I) represented by the structural formula (1), the structural part (I') in which one or both of the two epoxy groups in the structural part (I) are ring-opened. May have. The abundance ratio of the structural part (I) and the structural part (I') is preferably a ratio in which the epoxy equivalent is within the above range.

In the epoxy resin of the present invention, the value of the epoxy equivalent of the epoxy resin was defined as (α), and the value of the hydroxyl equivalent of the reaction product obtained by reacting the epoxy group of the epoxy resin with the phenol of this molar was defined as (β). In this case, the value of 1000 × [(β-α) / α] is 480 or less. In the present invention, the epoxy equivalent value (α) of the epoxy resin is a value measured in accordance with JIS K 7236. The hydroxyl group equivalent value (β) is a value measured in accordance with JIS K 0070 according to the following procedure.
1. 1. The epoxy resin and an excess amount of phenol with respect to the epoxy group in the epoxy resin are heated and stirred at 150 ° C. for 6 hours under base catalyst conditions.
2. Unreacted phenol is removed from the reaction mixture under reduced pressure at 180 ° C. to give the reaction product.
3. 3. The hydroxyl equivalent of the reaction product is measured based on JIS K 0070.

The value of 1000 × [(β-α) / α] is more preferably in the range of 430 to 475, and more preferably 450 to 475, because the epoxy resin has an excellent balance between the melt viscosity and the heat resistance of the cured product. It is particularly preferably in the range of 470.

The epoxy resin of the present invention is, for example, a phenolic hydroxyl group-containing compound (A) represented by the following structural formula (2) and a formyl group-containing phenolic hydroxyl group-containing compound (B) represented by the following structural formula (3). The triphenylmethane-type resin obtained by reacting with can be produced by a method of reacting with epihalohydrin and an alkali metal hydroxide in the presence of water and alcohols.

［式中Ｒ^３、Ｒ^４はそれぞれ独立に水素原子、炭素原子数１〜４の炭化水素基、炭素原子数１〜４のアルコキシ基、ハロゲン原子の何れかであり、ｍは１〜３の整数、ｎは１〜４の整数である。］

[In the formula, R ³ and R ⁴ are independently any of a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a halogen atom, and m is 1 to 3. An integer, n is an integer of 1 to 4. ]

^{R 3} and R ^{4 in the} structural formulas (2) and (3) are independently any of a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a halogen atom. Is. Examples of the hydrocarbon group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group and a butyl group. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propyloxy group, a butoxy group and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom. Above all, it is preferable that all of ^{R 3} and R ⁴ are hydrogen atoms because the epoxy resin has an excellent balance between the melt viscosity and the heat resistance of the cured product.

The hydroxyl group in the structural formula (3) may be bonded to any of the ortho-position, meta-position, and para-position of the formyl group. Above all, it is preferable that the hydroxyl group is bonded to the ortho position of the formyl group because it is excellent in reactivity with the phenolic hydroxyl group-containing compound (A).

The reaction ratio of the phenolic hydroxyl group-containing compound (A) to the formyl group-containing phenolic hydroxyl group-containing compound (B) is an epoxy resin having an excellent balance between melt viscosity and heat resistance in the cured product. The amount of the formyl group-containing phenolic hydroxyl group-containing compound (B) is preferably in the range of 0.01 to 0.9 mol with respect to 1 mol of the sex hydroxyl group-containing compound (A).

The reaction between the phenolic hydroxyl group-containing compound (A) and the formyl group-containing phenolic hydroxyl group-containing compound (B) is preferably carried out in the presence of an acid catalyst because the reaction proceeds efficiently. The acid catalyst includes, for example, inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, organic acids such as methanesulfonic acid, paratoluenesulfonic acid and oxalic acid, and Lewis acids such as boron trifluoride, aluminum chloride anhydride and zinc chloride. Can be mentioned. At this time, the amount of the polymerization catalyst used is preferably in the range of 0.1 to 5% by mass with respect to the total mass of the reaction raw materials.

The reaction between the phenolic hydroxyl group-containing compound (A) and the formyl group-containing phenolic hydroxyl group-containing compound (B) is usually carried out under a temperature condition of 100 to 200 ° C. for 1 to 20 hours. The reaction may be carried out in an organic solvent if necessary. The organic solvent used here is not particularly limited as long as it can be used under the above temperature conditions, and specific examples thereof include methyl cellosolve, ethyl cellosolve, toluene, xylene, and methyl isobutyl ketone. .. When these organic solvents are used, they are preferably used in the range of 10 to 500% by mass with respect to the total mass of the reaction raw materials.

In the reaction between the phenolic hydroxyl group-containing compound (A) and the formyl group-containing phenolic hydroxyl group-containing compound (B), various antioxidants and reducing agents may be used for the purpose of suppressing the coloring of the reaction product. good. Examples of the antioxidant include hindered phenol compounds such as 2,6-dialkylphenol derivatives, divalent sulfur compounds, and phosphite ester compounds containing a trivalent phosphorus atom. Examples of the reducing agent include hypophosphorous acid, phosphorous acid, thiosulfuric acid, sulfurous acid, hydrosulfite, salts thereof, zinc and the like.

After the reaction between the phenolic hydroxyl group-containing compound (A) and the formyl group-containing phenolic hydroxyl group-containing compound (B) is completed, an unreacted reaction raw material, by-products, etc. are distilled off to form an intermediate. A triphenylmethane type resin can be obtained.

Next, the triphenylmethane type resin obtained above is reacted with epihalohydrin to obtain a target epoxy resin. In the reaction, for example, both were used at a ratio of epihalohydrin in the range of 2 to 10 mol with respect to 1 mol of the phenolic hydroxyl group in the triphenylmethane type resin, and 0.9 to 2 with respect to 1 mol of the phenolic hydroxyl group. Examples thereof include a method of reacting at a temperature of 20 to 120 ° C. for 0.5 to 10 hours while adding 0.0 mol of the basic catalyst in a batch or in portions.

In the first batch of epoxy resin production, all of the epihalohydrins used for preparation are new during industrial production, but after the next batch, the epihalohydrins recovered from the crude reaction product are consumed in the reaction. It is preferable to use in combination with a new epihalohydrin corresponding to the amount that disappears in minutes. At this time, the epichlorohydrin used is not particularly limited, and examples thereof include epichlorohydrin, epibromohydrin, and β-methylepichlorohydrin. Of these, epichlorohydrin is preferable because it is easily available industrially.

Specific examples of the basic catalyst include alkaline earth metal hydroxides, alkali metal carbonates and alkali metal hydroxides. Of these, alkali metal hydroxides are preferable from the viewpoint of excellent catalytic activity, and specifically, sodium hydroxide, potassium hydroxide and the like are preferable.

By carrying out the reaction between the triphenylmethane type resin and epihalohydrin in the presence of water and alcohols, it becomes easy to adjust the value of 1000 × [(β-α) / α] to 480 or less. Examples of the alcohol solvent include methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, 1-butanol, secondary butanol, tertiary butanol and the like. These may be used alone or in combination of two or more. The mass ratio of water to alcohols (water) / (alcohols) is preferably in the range of 1/1 to 1/20, and more preferably in the range of 1/3 to 1/10.

After completion of the reaction, the reaction mixture is washed with water, and then unreacted epihalohydrin and an organic solvent are distilled off by distillation under heating and reduced pressure. Further, in order to obtain an epoxy resin having a lower hydrolyzable halogen, the obtained epoxy resin is dissolved again in an organic solvent, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added for further reaction. Can also be done. At this time, a phase transfer catalyst such as a quaternary ammonium salt or a crown ether may be present for the purpose of improving the reaction rate. When the phase transfer catalyst is used, the amount used is preferably 0.1 to 3.0 parts by mass with respect to 100 parts by mass of the epoxy resin. After completion of the reaction, the produced salt is removed by filtration, washing with water, or the like, and the organic solvent is distilled off under heating and reduced pressure to obtain the desired epoxy resin of the present invention.

The curable resin composition of the present invention contains the epoxy resin described in detail above and a curing agent as essential components.

Examples of the curing agent used here include amine compounds, amide compounds, acid anhydrides, phenol resins and the like, and these may be used alone or in combination of two or more. The amine compound may, for example, diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenyl sulfone, isophoronediamine, imidazo - Le, BF 3 _- amine complex, guanidine derivatives and the like. Examples of the amide compound include dicyandiamide, an aliphatic dibasic acid and dimer acid, a polyamide resin synthesized by a carboxylic acid compound of a fatty acid and an amine such as ethylenediamine. The acid anhydrides include, for example, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methylhexahydro. Examples include phthalic anhydride. The phenol resin is a multivalent value represented by, for example, phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadienephenol addition type resin, phenol aralkyl resin (Zyroc resin), resorcin novolac resin. Polyvalent phenol novolac resin synthesized from hydroxy compound and formaldehyde, naphthol aralkyl resin, trimethylolmethane resin, tetraphenylol ethane resin, naphthol novolac resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolac resin, biphenyl Modified phenol resin (polyvalent phenol compound with phenol nuclei linked by bismethylene group), biphenyl-modified naphthol resin (polyvalent naphthol compound with phenol nuclei linked by bismethylene group), aminotriazine modified phenol resin (melamine, benzoguanamine, etc.) Examples thereof include polyvalent phenol compounds in which phenol nuclei are linked) and polyvalent phenol compounds such as an alkoxy group-containing aromatic ring-modified novolak resin (polyphenol compounds in which a phenol nuclei and an alkoxy group-containing aromatic ring are linked with formaldehyde). .. Each of these may be used alone, or two or more types may be used in combination.

In the curable resin composition of the present invention, other epoxy resins other than the epoxy resin of the present invention may be used as the epoxy resin component. The blending ratio of the epoxy resin of the present invention and other epoxy resins is not particularly limited, but since the effects of the present invention are sufficiently exhibited, the epoxy resin of the present invention has a mass of 30 mass with respect to the total mass of the epoxy resin components. It is preferable to use other epoxy resins in combination in the range of% or more, preferably 40% by mass or more.

Various epoxy resins can be used as the other epoxy resins. For example, 2,7-diglycidyloxynaphthalene, α-naphthol novolac type epoxy resin, β-naphthol novolac type epoxy resin, α-naphthol / β- Naphthol cocondensation type novolac polyglycidyl ether, naphthol aralkyl type epoxy resin, naphthalene skeleton-containing epoxy resin such as 1,1-bis (2,7-diglycidyloxy-1-naphthyl) alkane; bisphenol A type epoxy resin, bisphenol Biphenyl type epoxy resin such as F type epoxy resin; biphenyl type epoxy resin such as biphenyl type epoxy resin and tetramethyl biphenyl type epoxy resin; phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin, biphenyl novolac Examples thereof include novolak type epoxy resins such as type epoxy resins; tetraphenylethane type epoxy resins; dicyclopentadiene-phenol addition reaction type epoxy resins; phenol aralkyl type epoxy resins; phosphorus atom-containing epoxy resins and the like. The phosphorus atom-containing epoxy resin is obtained by reacting an epoxy compound of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter abbreviated as "HCA"), HCA, with quinones. The resulting phenolic resin epoxie, phenol novolac type epoxy resin modified with HCA, cresol novolac type epoxy resin modified with HCA, bisphenol A type epoxy resin, and HCA and quinones are reacted. Examples thereof include an epoxy resin obtained by modifying the phenol resin obtained in the above process. Each of these may be used alone, or two or more types may be used in combination.

In the curable resin composition of the present invention, the mixing ratio of the epoxy resin component and the curing agent is such that a cured product having excellent curability and excellent heat resistance and toughness can be obtained. The amount of the active group in the curing agent is preferably 0.7 to 1.5 equivalents with respect to 1 equivalent.

The curable resin composition of the present invention may contain various additives such as a curing accelerator, a flame retardant, an inorganic filler, a silane coupling agent, a mold release agent, a pigment, and an emulsifier, if necessary.

Examples of the curing accelerator include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, amine complex salts and the like. Among them, 2-ethyl-4-methylimidazole for imidazole compounds, triphenylphosphine for phosphorus compounds, and 1,8-diazabicyclo for tertiary amines are excellent in curability, heat resistance, electrical properties, moisture resistance reliability, etc. -[5.4.0] -Undecene (DBU) is preferred.

The flame retardant may be, for example, red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium phosphate such as ammonium polyphosphate, inorganic phosphorus compound such as phosphoric acid amide; phosphoric acid ester compound, phosphonic acid. Compounds, phosphinic acid compounds, phosphine oxide compounds, phosphoran compounds, organic nitrogen-containing phosphorus compounds, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5-dihydrooxyphenyl) ) -10H-9-Oxa-10-phosphaphenanthrene-10-oxide, 10- (2,7-dihydrooxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide and other cyclic organic phosphorus Organophosphorus compounds such as compounds and derivatives obtained by reacting them with compounds such as epoxy resins and phenol resins; nitrogen-based flame retardants such as triazine compounds, cyanuric acid compounds, isocyanuric acid compounds and phenothiazine; silicone oils, silicone rubbers and silicones. Silicone-based flame retardants such as resins; examples thereof include metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and inorganic flame retardants such as low melting point glass. When these flame retardants are used, it is preferably in the range of 0.1 to 20% by mass in the curable resin composition.

The inorganic filler is blended, for example, when the curable resin composition of the present invention is used for semiconductor encapsulation material applications. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide and the like. Among them, the molten silica is preferable because it is possible to blend a larger amount of the inorganic filler. The molten silica can be used in either a crushed form or a spherical shape, but in order to increase the blending amount of the molten silica and suppress an increase in the melt viscosity of the curable resin composition, a spherical one is mainly used. It is preferable to use it. Further, in order to increase the blending amount of spherical silica, it is preferable to appropriately adjust the particle size distribution of spherical silica. The filling rate is preferably in the range of 0.5 to 95 parts by mass in 100 parts by mass of the curable resin composition.

In addition, when the curable resin composition of the present invention is used for applications such as conductive paste, a conductive filler such as silver powder or copper powder can be used.

The curable resin composition of the present invention can be obtained by uniformly mixing the above-mentioned components. The curable resin composition of the present invention containing an epoxy tree component, a curing agent, and, if necessary, a curing accelerator can be easily made into a cured product by a method similar to a conventionally known method. Examples of the cured product include molded products such as laminates, cast products, adhesive layers, coating films, and films.

When the curable resin composition of the present invention is used for a printed wiring board application or a build-up adhesive film application, it is preferable to add an organic solvent. Examples of the organic solvent include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxy propanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether acetate and the like. The type and amount of the organic solvent can be appropriately adjusted according to the usage environment of the curable resin composition. For example, in the case of printed wiring board applications, polar solvents having a boiling point of 160 ° C. or lower such as methyl ethyl ketone, acetone, and dimethylformamide are used. It is preferable to use it at a ratio of 40 to 80% by mass of the non-volatile content. For build-up adhesive film applications, ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone, acetate solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, and carbitol such as cellosolve and butyl carbitol. It is preferable to use a solvent, an aromatic hydrocarbon solvent such as toluene or xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone or the like, and it is preferable to use the non-volatile content at a ratio of 30 to 60% by mass.

Further, in the method for producing a printed wiring substrate using the curable resin composition of the present invention, for example, a varnish-like curable resin composition containing an epoxy resin component, a curing agent, an organic solvent, other additives and the like is used. Examples thereof include a method in which a reinforcing base material is impregnated and cured to obtain a prepreg, which is then overlapped with a copper foil and heat-bonded. Examples of the reinforcing base material include paper, glass cloth, glass non-woven fabric, aramid paper, aramid cloth, glass mat, and glass roving cloth. The impregnation amount of the curable resin composition is not particularly limited, but it is usually preferable to prepare the curable resin composition so that the resin content in the prepreg is 20 to 60% by mass.

When the curable resin composition of the present invention is used as a semiconductor encapsulant material, for example, a compound such as an epoxy resin component, a curing agent, and a filler is uniformly applied using an extruder, a kneader, a roll, or the like. A semiconductor encapsulating material can be obtained by a method of sufficiently mixing until it becomes. Examples of the filler used here include the above-mentioned inorganic filler, and as described above, it is preferable to use the filler in the range of 0.5 to 95 parts by mass in 100 parts by mass of the curable resin composition. Among them, flame retardancy, moisture resistance, solder crack resistance are improved, and the coefficient of linear expansion can be reduced. Therefore, it is preferably used in the range of 70 to 95 parts by mass, and particularly preferably used in the range of 80 to 95 parts by mass. preferable.

As a method of molding a semiconductor package using the obtained semiconductor encapsulating material, for example, the semiconductor encapsulating material is molded by casting or using a transfer molding machine, an injection molding machine, or the like, and further, the temperature is 50 to 200 ° C. A method of heating under the conditions for 2 to 10 hours can be mentioned, and a semiconductor device which is a molded product can be obtained by such a method.

Next, the present invention will be specifically described with reference to Examples and Comparative Examples. In the following, "parts" and "%" are based on mass unless otherwise specified. The epoxy equivalent, melt viscosity at 150 ° C., GPC, NMR and MS spectra were measured under the following conditions.

◆ Measurement of epoxy equivalent Measured based on JIS K 7236.

◆ Measurement method for melt viscosity at 150 ° C. Measured with an ICI viscometer in accordance with ASTM D4287.

◆ GPC measurement conditions Measuring device: "HLC-8220 GPC" manufactured by Tosoh Corporation,
Column: Guard column "HXL-L" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G3000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G4000HXL" manufactured by Tosoh Corporation
Detector: RI (Differential Refractometer)
Data processing: "GPC-8020 Model II Version 4.10" manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent tetrahydrofuran
Flow velocity 1.0 ml / min Standard: The following monodisperse polystyrene with a known molecular weight was used in accordance with the measurement manual of "GPC-8020 Model II Version 4.10".
(Polystyrene used)
"A-500" manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
"F-1" manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
"F-4" manufactured by Tosoh Corporation
"F-10" manufactured by Tosoh Corporation
"F-20" manufactured by Tosoh Corporation
"F-40" manufactured by Tosoh Corporation
"F-80" manufactured by Tosoh Corporation
"F-128" manufactured by Tosoh Corporation
Sample: A solution obtained by filtering 1.0 mass% of a tetrahydrofuran solution in terms of resin solid content with a microfilter (50 μl).

Production Example 1 Production of triphenylmethane type resin (1) 122 g of salicylaldehyde, 370 g of phenol, and 2.4 g of p-toluenesulfonic acid were added to a flask equipped with a thermometer, a dropping funnel, a cooling tube, and a stirrer while purging with nitrogen gas. The mixture was charged, heated to 100 ° C., and stirred for 5 hours for reaction. After the reaction, the temperature was lowered to 80 ° C., and then 1.4 g of a 49 mass% sodium hydroxide aqueous solution was added to neutralize the catalyst and completely stop the reaction. Then, excess phenol was distilled off under reduced pressure conditions to obtain 220 g of a triphenylmethane type resin (1). The obtained triphenylmethane type resin (1) had a softening point of 127 ° C. and a hydroxyl group equivalent of 97 g / equivalent.

Example 1 Production of Epoxy Resin (1) 97 g (hydroxyl content 1 mol), epichlorohydrin 555 g (6.) of triphenylmethane-type resin (1) while performing nitrogen gas purging on a flask equipped with a thermometer, a cooling tube, and a stirrer. 0 mol), 111 g of n-butanol and 17 g of water were charged and dissolved. After the temperature was raised to 50 ° C., 220 g of a 20 mass% sodium hydroxide aqueous solution (1.10 mol of sodium hydroxide) was added over 3 hours, and the reaction was carried out at 50 ° C. for another 1 hour. After completion of the reaction, unreacted epichlorohydrin was distilled off under reduced pressure at 150 ° C. to obtain a crude product. To the obtained crude product, 300 g of methyl isobutyl ketone and 50 g of n-butanol were added and dissolved, 15 g of a 10 mass% sodium hydroxide aqueous solution was added, and the mixture was reacted at 80 ° C. for 2 hours. After completion of the reaction, washing with 100 g of water was carried out three times, and it was confirmed that the pH of the washing liquid became neutral. Next, the inside of the system was azeotropically boiled to dehydrate, and microfiltration was performed. Then, the solvent was distilled off under reduced pressure conditions to obtain 150 g of epoxy resin (1). The epoxy equivalent of the epoxy resin (1) was 167 g / equivalent. The GPC chart of the epoxy resin (1) is shown in FIG.

Comparative Production Example 1 Production of Epoxy Resin (1') 97 g of triphenylmethane type resin (1 mol), epichlorohydrin 555 g (1 mol of hydroxyl group content) while purging a flask equipped with a thermometer, a cooling tube, and a stirrer with nitrogen gas. 6.0 mol), 111 g of dioxane was charged and dissolved. After raising the temperature to 50 ° C., 220 g of a 20 mass% sodium hydroxide aqueous solution (1.10 mol of sodium hydroxide) was added over 3 hours while performing azeotropic dehydration under reduced pressure conditions, and further at 50 ° C. The reaction was carried out for 1 hour to obtain a crude product. During the reaction, the water distillate recovered by azeotropic dehydration was separated in the Dean-Stark trap, and the reaction was carried out by returning epichlorohydrin to the reactor. Further, the water content in the reaction solution was appropriately measured, and it was confirmed that the water concentration at the end of the reaction was 0.2% by mass. Next, 300 g of methyl isobutyl ketone and 50 g of n-butanol were added to the obtained crude product to dissolve it, and 15 g of a 10 mass% sodium hydroxide aqueous solution was added and reacted at 80 ° C. for 2 hours. After the reaction was completed, washing with 100 g of water was repeated 3 times. Next, the inside of the system was azeotropically boiled to dehydrate, and microfiltration was performed. Then, the solvent was distilled off under reduced pressure conditions to obtain 150 g of epoxy resin (1'). The epoxy equivalent of the epoxy resin (1') was 165 g / equivalent.

Measurement of (β) Value For the epoxy resin (1) and the epoxy resin (1'), the value (β) of the hydroxyl equivalent of the reaction product obtained by reacting the epoxy group of the epoxy resin with the phenol of this molar is determined. It was measured by the following procedure.
1. 1. The epoxy resin and an excess amount of phenol with respect to the epoxy group in the epoxy resin were heated and stirred at 150 ° C. for 6 hours under base catalyst conditions.
2. Unreacted phenol was removed from the reaction mixture under reduced pressure at 180 ° C. to obtain a reaction product.
3. 3. The hydroxyl equivalent of the reaction product was measured based on JIS K 0070.

Calculation of 1000 × [(β-α) / α] The value of 1000 × [(β-α) / α] was calculated for the epoxy resin (1) and the epoxy resin (1'), and the results are shown in Table 1.

Measurement of Melt Viscosity For the epoxy resin (1) and epoxy resin (1'), the melt viscosity at 150 ° C. was measured with an ICI viscometer in accordance with ASTM D4287. The results are shown in Table 1.

Example 2 and Comparative Example 1
For the epoxy resin (1) and the epoxy resin (1'), a curable resin composition and a cured product were prepared in the following manner, and the heat resistance was evaluated. The results are shown in Table 2.

Production of curable resin composition Epoxy resin (1) or epoxy resin (1'), phenol novolac type resin ("TD-2131" manufactured by DIC Co., Ltd., hydroxyl group equivalent 104 g / equivalent) as a curing agent, and curing accelerator Triphenylphosphine (hereinafter abbreviated as "TPP") was blended in the composition shown in Table 2 below to obtain a curable resin composition.

Production of cured product The curable resin composition obtained at the site was poured into a mold of 11 cm × 9 cm × 2.4 mm and molded by pressing at a temperature of 150 ° C. for 10 minutes. The molded product was taken out from the mold and cured at a temperature of 175 ° C. for 5 hours to obtain a cured product.

Evaluation of heat resistance About the cured product using a viscoelasticity measuring device (DMA: solid viscoelasticity measuring device RSAII manufactured by Leometric Co., Ltd., rectangular tension method; frequency 1 Hz, heating rate 3 ° C./min, maximum measurement temperature 300 ° C.) The temperature at which the change in viscoelasticity was maximum (the rate of change in tan δ was the largest) was measured and evaluated as the glass transition temperature (Tg). The results are shown in Table 2.

Evaluation of heat resistance change (ΔTg) after thermal history The glass transition temperature (Tg) measurement was repeated twice, and the difference (ΔTg) between the two was measured. The results are shown in Table 2.

Claims (6)

A triphenylmethane type which is a reaction product of a phenolic hydroxyl group-containing compound (A) represented by the following structural formula (2) and a formyl group-containing phenolic hydroxyl group-containing compound (B) represented by the following structural formula (3). An epoxy resin having a step (1) of dissolving the resin and epihalohydrin in the presence of water and alcohols, and a step (2) of raising the temperature after the step (1) and adding an aqueous solution of an alkali metal hydroxide. It is a manufacturing method of
The epoxy resin, those having a structural repeating unit structure site (I) represented by the following structural formula (1), the value of the epoxy equivalent of the epoxy resin (alpha), epoxy groups of the epoxy resin has When the value of the hydroxyl equivalent of the reaction product obtained by reacting this molar amount of phenol is (β), the value of 1000 × [(β-α) / α] is 480 or less. Epoxy resin manufacturing method .

[In the formula, R ³ and R ⁴ are independently any of a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a halogen atom, and m is 1 to 3. An integer, n is an integer of 1 to 4. ]

[In the formula, R ¹ and R ² are independently represented by a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, or a structure represented by the structural formula (1). It is any of the bonding points connected to the site (I) via the methylene group marked with *, and m is an integer of 1 to 3 and n is an integer of 1 to 4. ] The method for producing an epoxy resin according to claim 1, wherein the mass ratio [(water) / (alcohols)] of the water to the alcohols is in the range of 1/1 to 1/20. Method for producing a curable resin composition containing an epoxy resin obtained by the production method according to claim 1, and a curing agent. The method according to claim 3 cured product obtained by curing the curable resin composition obtained by the production method according. Printed circuit board manufacturing method comprising using a 3. The curable resin composition obtained by the production method according. An epoxy resin obtained by the process according to claim 1, wherein, a method of manufacturing a semiconductor sealing material containing a curing agent, and an inorganic filler.

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