TW201800438A - Epoxy resin, curable resin composition and cured product thereof - Google Patents

Abstract

The invention provides an epoxy resin with low melt viscosity, high heat resistance of hardened material, and small change in heat resistance after thermal history; a hardening resin composition containing the epoxy resin and its hardened material; semiconductor sealing material; printing Wiring board. The epoxy resin of the present invention has a structural portion (I) represented by the following structural formula (1) as a repeating structural unit, and is characterized in that the value of the epoxy equivalent of the epoxy resin is (α), When the value of the hydroxyl equivalent of the reaction product obtained by reacting the epoxy group possessed by the epoxy resin with the corresponding molar amount of phenol is set to (β), 1000 × [(β-α) / α] The value is 480 or less.

Description

Epoxy resin, curable resin composition, and cured product thereof

The invention relates to an epoxy resin with low melt viscosity, high heat resistance of hardened material, and small change in heat resistance after thermal history; a hardening resin composition containing the epoxy resin and its hardened material; a semiconductor sealing material; Printed wiring board.

Epoxy resin is used for adhesives, molding materials, coatings, and other materials. In addition, it is widely used in semiconductor sealing materials or insulation materials for printed wiring boards because of the excellent heat resistance and humidity resistance of the hardened material obtained. Electrical and electronic fields.

Among them, power semiconductors represented by power modules for vehicles are the key and important technology to master the energy saving of electrical and electronic equipment. As power semiconductors further increase the current, miniaturization, and efficiency, self-learning silicon (Si) The transition from semiconductors to silicon carbide (SiC) semiconductors continues. The advantages of SiC semiconductors are that they can operate at higher temperatures. Therefore, semiconductor sealing materials are required to have higher heat resistance than in the past, and the physical properties change under high temperature environments are small. In addition, as an important property of resins for semiconductor sealing materials, it is also required to show high flame retardancy, low viscosity, excellent fluidity, and high filling of fillers even without the use of halogen-based flame retardants. A resin material that has all these properties.

As a resin material for responding to these various required characteristics, for example, it is known to contain the following structural formula

(Wherein G represents a glycidyl group)

The epoxy resin of the epoxy compound shown (refer patent document 1). Although this epoxy resin has the characteristics of excellent heat resistance, it has high melt viscosity. Therefore, a novel epoxy resin material with high heat resistance and low viscosity is sought.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2004-339371

Therefore, the problem to be solved by the present invention is to provide an epoxy resin with low melt viscosity, high heat resistance of hardened material, and small change in heat resistance after thermal history, and a curable resin composition containing the epoxy resin. Materials and hardened materials thereof, semiconductor sealing materials, printed wiring boards.

In order to solve the above-mentioned problems, the present inventors have made intensive research and found that Epoxy resin, which has a triphenylmethane skeleton, the epoxy equivalent of the epoxy resin is set to (α), and the epoxy group of the epoxy resin will be reacted with the corresponding molar amount of phenol When the hydroxyl equivalent of the obtained reaction product is set to (β), the value of 1000 × [(β-α) / α] is 480 or less. The epoxy resin has low melt viscosity and heat resistance of the cured product. Low, the change in heat resistance after its thermal history is small, so that the present invention is completed.

That is, the present invention relates to an epoxy resin having a structural portion (I) represented by the following structural formula (1) as a repeating structural unit, and is characterized in that the value of the epoxy equivalent of the epoxy resin is set Is (α), when the value of the hydroxyl equivalent of the reaction product obtained by reacting the epoxy group possessed by the epoxy resin with the corresponding molar amount of phenol is set to (β), 1000 × [(β-α ) / α] has a value of 480 or less.

[Wherein R ¹ and R ² are each independently 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 structural formula (1) Part (I) is any one of the bond nodes connected via a methylene group with an * symbol, 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 hardener.

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 using the curable resin composition.

The present invention further relates to a semiconductor sealing material containing the aforementioned epoxy resin, hardener, and inorganic filler.

The present invention further relates to a method for manufacturing an epoxy resin, which is characterized in that a triphenylmethane type resin is reacted with epihalohydrin in the presence of water and alcohols, and the triphenylmethane type resin has the following structure The phenolic hydroxyl group-containing compound (A) represented by the formula (2) is obtained by reacting the phenolic hydroxyl group-containing phenolic compound (B) represented by the following structural formula (3).

[Wherein R ³ and R ⁴ are each independently a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, and m is an integer of 1 to 3 , N is an integer from 1 to 4]

According to the present invention, it is possible to provide an epoxy resin having low melt viscosity, high heat resistance of a cured material, and small change in heat resistance after a thermal history; a curable resin composition containing the epoxy resin and a cured product thereof; and a semiconductor seal. Material; printed wiring board.

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

Hereinafter, the present invention will be described in detail.

The epoxy resin of the present invention has a structural site (I) represented by the following structural formula (1) as a repeating structural unit.

[Wherein R ¹ and R ² are each independently 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 structural site represented by structural formula (1) (I) Any one of the bond nodes connected via a methylene group with an asterisk, m is an integer of 1 to 3, and n is an integer of 1 to 4]

R ¹ and R ² in the above structural formula (1) are each independently 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 The structural site (I) shown is any one of the bond nodes connected via a methylene group with an * symbol. Examples of the hydrocarbon group having 1 to 4 carbon atoms include methyl, ethyl, propyl, and butyl. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Among these, in terms of an epoxy resin having excellent balance between melt viscosity and heat resistance of the cured product, it is preferable that R ¹ and R ² are hydrogen atoms or a structural site represented by the structural formula (1) ( I) Any one of the bonding nodes connected via a methylene group with an * symbol.

R ¹ and R ² are bonding points connected to the structural site (I) represented by the structural formula (1) via a methylene group with an asterisk (*), and specifically refer to a structural site (I) A state where the aromatic ring is connected to another structural site (I) via a methylene group with an * symbol. For example, when R ² is a bond point connected to the structural site (I) represented by the structural formula (1) via a methylene group with an * symbol, it becomes as shown in the following structural formula (1-1) The structure of the representation.

[Wherein R ¹ and R ² are each independently 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 structural site represented by structural formula (1) (I) Any one of the bond nodes connected via a methylene group with an asterisk, m is an integer of 1 to 3, and n is an integer of 1 to 4]

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

The epoxy resin of the present invention may have one or both of the two epoxy groups in the structural portion (I) in addition to the structural portion (I) represented by the structural formula (1). Structural site (I '). The proportion of the structural site (I) and the structural site (I ') is preferably such that the epoxy equivalent falls within the above range.

The epoxy resin of the present invention is characterized in that the epoxy equivalent of the epoxy resin is set to (α), and the epoxy group of the epoxy resin is reacted with a corresponding molar amount of phenol to obtain When the value of the hydroxyl equivalent of the obtained reaction product is (β), the value of 1000 × [(β-α) / α] is 480 or less. In the present invention, the value (α) of the epoxy equivalent of the epoxy resin is a value measured in accordance with JIS K 7236. The hydroxyl equivalent value (β) is a value measured in accordance with JIS K 0070 by the following procedure.

1. Under basic catalyst conditions, heat and stir the epoxy resin and excess phenol relative to the epoxy group in the epoxy resin at 150 ° C. for 6 hours.

2. Remove the unreacted phenol from the reaction mixture under reduced pressure at 180 ° C to obtain a reaction product.

3. The hydroxyl equivalent of the reaction product was measured based on JIS K 0070.

The above-mentioned value of 1000 × [(β-α) / α] is an epoxy resin having excellent balance between melt viscosity and heat resistance of the cured product. In this respect, it is more preferably in the range of 430 to 475, and even more preferably 450. The range of ~ 470.

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

[Wherein R ³ and R ⁴ are each independently a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, and m is an integer of 1 to 3 , N is an integer from 1 to 4]

R ³ and R ^{4 in} the structural formulae (2) and (3) are each independently a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom. . Examples of the hydrocarbon group having 1 to 4 carbon atoms include methyl, ethyl, propyl, and butyl. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Among these, in terms of an epoxy resin having excellent balance between melt viscosity and hardened heat resistance, it is preferable that both R ³ and R ⁴ are hydrogen atoms.

The hydroxyl group in the above structural formula (3) may be bonded to any one of the ortho, meta, and para positions of the methylamino group. Among these, in terms of excellent reactivity with the phenolic hydroxyl group-containing compound (A), it is preferred that the hydroxyl group is bonded to the ortho position of the methylamidino group.

The reaction ratio between the phenolic hydroxyl-containing compound (A) and the methylamino group-containing phenolic hydroxyl-containing compound (B) is an epoxy resin having excellent balance between melt viscosity and heat resistance of the cured product. From the aspect, it is preferable that the phenolic hydroxyl group-containing phenolic hydroxyl group-containing compound (B) is in the range of 0.01 to 0.9 mols relative to 1 mol of the phenolic hydroxyl group-containing compound (A).

In terms of efficiently reacting the phenolic hydroxyl group-containing compound (A) and the methylol group-containing phenolic hydroxyl group-containing compound (B), the reaction is preferably performed in the presence of an acid catalyst. Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as methanesulfonic acid, p-toluenesulfonic acid, and oxalic acid, and Lewis acids such as boron trifluoride, anhydrous aluminum chloride, and zinc chloride. . At this time, the amount of the polymerization catalyst used is preferably in a range of 0.1 to 5% by mass relative to the total mass of the reaction raw materials.

The reaction between the phenolic hydroxyl group-containing compound (A) and the methylol group-containing phenolic hydroxyl group-containing compound (B) is usually performed at a temperature of 100 to 200 ° C for 1 to 20 hours. This reaction can be carried out in an organic solvent if necessary. The organic solvent used here is not particularly limited as long as it is an organic solvent that can be used under the above-mentioned temperature conditions. Specific examples include methylcellulose, ethylcellulose, toluene, xylene, and methyl. Isobutyl ketone, etc. When using these organic solvents, it is preferable to use it in the range of 10-500 mass% with respect to the total mass of a reaction raw material.

In the reaction between the phenolic hydroxyl-containing compound (A) and the methylamino group-containing phenolic hydroxyl-containing compound (B), various antioxidants or reducing agents can be used in order to suppress the coloring of the reaction product. Examples of the antioxidant include a hindered phenol compound such as a 2,6-dialkylphenol derivative, a divalent sulfur compound, and a trivalent phosphorus atom-containing phosphite compound. Examples of the reducing agent include hypophosphite, phosphorous acid, thiosulfuric acid, sulfurous acid, bisulfite, such salts, and zinc.

After the reaction of the phenolic hydroxyl group-containing compound (A) and the methylol group-containing phenolic hydroxyl group-containing compound (B) is completed, unreacted reaction raw materials or by-products are distilled off to obtain an intermediate compound. Triphenylmethane type resin.

Then, the triphenylmethane type resin obtained previously is reacted with epihalohydrin to obtain the target epoxy resin. Examples of the reaction include a method of using both at a ratio of 1 mole of phenolic hydroxyl group and 1 to 10 mole of epihalohydrin in the triphenylmethane type resin, or Separately add a basic catalyst of 0.9 to 2.0 mol to 1 mol of phenolic hydroxyl group, and react at a temperature of 20 to 120 ° C for 0.5 to 10 hours.

Moreover, in industrial production, the epihalohydrins used for the addition of the first batch of epoxy resins are all new products, but it is preferred that the epihalohydrin recovered from the crude reaction product be equivalent to the equivalent after this batch. The amount of new epihalohydrin consumed in the reaction and the amount disappeared are used in combination. At this time, all The epihalohydrin to be used is not particularly limited, and examples thereof include epichlorohydrin, epibromohydrin, and β-methylepichlorohydrin. Among them, epichlorohydrin is preferred in terms of industrial availability.

Specific examples of the alkaline catalyst include alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides. Among them, an alkali metal hydroxide is preferred in terms of excellent catalyst activity, and specifically, sodium hydroxide or potassium hydroxide is preferred.

By performing the reaction of the triphenylmethane type resin and epihalohydrin in the presence of water and alcohols, the above-mentioned value of 1000 × [(β-α) / α] can be easily adjusted to 480 or less. Examples of the alcohol solvent include methanol, ethanol, 1-propanol, isopropanol, 1-butanol, second butanol, and third butanol. These can be used individually or in combination of 2 or more types. The mass ratio of water to alcohol (water) / (alcohol) 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 was washed with water, and then unreacted epihalohydrin or organic solvent was distilled off by distillation under heating and reduced pressure. In addition, in order to produce an epoxy resin having less hydrolyzable halogen, the obtained epoxy resin may be dissolved in an organic solvent again, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide may be added to further react. At this time, in order to increase the reaction speed, a related transfer catalyst such as a quaternary ammonium salt or a crown ether may be present. In the case of using a related transfer catalyst, the amount used is preferably 0.1 to 3.0 parts by mass relative 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, thereby obtaining the target epoxy resin of the present invention.

The curable resin composition of the present invention contains the epoxy resin and the hardener described above as essential components.

改質酚樹脂(酚核經三聚氰胺、苯胍胺等連結之多元苯酚化合物)或含有烷氧基之芳香環改質酚醛清漆樹脂(酚核及含有烷氧基之芳香環經甲醛連結之多元苯酚化合物)等多元苯酚化合物等。該等可分別單獨使用，亦可併用2種以上。 Examples of the curing agent used here include amine compounds, amidine compounds, acid anhydrides, phenol resins, and the like, and these may be used alone or in combination of two or more kinds. Examples of the amine compound include diaminodiphenylmethane, diethylene triamine, triethylene tetramine, diamino diphenylsulfonium, isophorone diamine, imidazole, and BF _3- Amine complexes, guanidine derivatives, etc. Examples of the amidine-based compound include dicyandiamide, a polyammine resin synthesized from an aliphatic diacid or dimer acid, a carboxylic acid compound of a fatty acid, and an amine such as ethylenediamine. Examples of the acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, Methyl phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and the like. Examples of the phenol resin include phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadiene phenol addition molding resin, phenol aralkyl resin (ZYLOCK resin), Polyhydric phenol novolac resin, naphthol aralkyl resin, trimethylol methane resin, tetraphenol ethane resin, naphthol synthesized by polyhydric hydroxy compounds represented by resorcinol novolac resin and formaldehyde Novolac resin, naphthol-phenol co-condensation novolak resin, naphthol-cresol co-condensation novolac resin, biphenyl modified phenol resin (polyphenol compound with phenolic core connected by bismethylene), biphenyl modification Naphthol resin (multi-naphthol compound with phenolic core connected by bismethylene), amine group

Modified phenol resin (polyphenol compound with phenolic core connected via melamine, benzoguanamine, etc.) or aromatic ring containing alkoxy group modified novolak resin (phenol core and polyphenol with aromatic ring containing alkoxy group connected via formaldehyde Compounds) and other polyphenol compounds. These can be used individually or in combination of 2 or more types.

The curable resin composition of the present invention may use an epoxy resin other than the epoxy resin of the present invention as an epoxy resin component. The blending ratio of the epoxy resin of the present invention to other epoxy resins is not particularly limited, and in terms of the effect fully exhibited by the present invention, The epoxy resin of the present invention is preferably used in combination with other epoxy resins in a range of 30% by mass or more, more preferably 40% by mass or more with respect to the total mass of the epoxy resin components.

As the other epoxy resins, various epoxy resins can be used, and examples thereof include 2,7-diglycidyloxynaphthalene, α-naphthol novolac epoxy resin, and β-naphthol novolac epoxy resin. Polyglycidyl ether of α-naphthol / β-naphthol co-condensation novolac, naphthol aralkyl epoxy resin, 1,1-bis (2,7-diglycidyloxy-1-naphthalene Base) epoxy resins containing a naphthalene skeleton; bisphenol epoxy resins such as bisphenol A epoxy resin and bisphenol F epoxy resin; biphenyl epoxy resin, tetramethylbiphenyl epoxy resin Biphenyl epoxy resin such as resin; novolac epoxy resin such as phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol A novolac epoxy resin, biphenol novolac epoxy resin Resin; Tetraphenylethane type epoxy resin; Dicyclopentadiene-phenol addition reaction type epoxy resin; Phenol aralkyl type epoxy resin; Epoxy resin containing phosphorus atom, etc. Examples of the phosphorus atom-containing epoxy resin include epoxides of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter referred to as "HCA"), and HCA. Epoxy resin of phenol resin obtained by reaction with quinones, epoxy resin obtained by modifying phenol novolac epoxy resin with HCA, ring obtained by modifying phenol novolac epoxy resin with HCA Oxygen resin, epoxy resin obtained by modifying bisphenol A epoxy resin with phenol resin obtained by reaction of HCA with quinones, and the like. These can be used alone or in combination of two or more.

In the curable resin composition of the present invention, the blend ratio of the epoxy resin component and the curing agent is preferably higher than that of epoxy in terms of obtaining a cured product having excellent curability, heat resistance, or toughness. The total of the epoxy groups in the resin component is 1 equivalent, and the active group in the hardener becomes 0.7 to 1.5 equivalents.

The curable resin composition of the present invention may contain various additives such as a hardening 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 hardening accelerator include phosphorus-based compounds, tertiary amines, imidazoles, metal salts of organic acids, Lewis acids, and amine salts. Among these, in terms of excellent hardenability, heat resistance, electrical characteristics, humidity resistance reliability, etc., the imidazole compound is preferably 2-ethyl-4-methylimidazole, and the phosphorus-based compound is preferably triphenylphosphine. The primary amine is preferably 1,8-diazabicyclo- [5.4.0] -undecene (DBU).

化合物、三聚氰酸化合物、異三聚氰酸化合物、啡噻

等氮系難燃劑；聚矽氧油、聚矽氧橡膠、聚矽氧樹脂等聚矽氧系難燃劑；金屬氫氧化物、金屬氧化物、金屬碳酸鹽化合物、金屬粉、硼化合物、低熔點玻璃等無機難燃劑等。於使用該等難燃劑之情形時，較佳為於硬化性樹脂組成物中為0.1~20質量%之範圍。 Examples of the flame retardant include red phosphorus, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, and ammonium polyphosphate, and other inorganic phosphorus compounds such as ammonium phosphate; phosphate compounds, phosphonic acid compounds, Phosphonic acid compound, phosphine oxide compound, phosphane compound, organic nitrogen-containing phosphorus compound, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5-di (Hydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,7-dihydroxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene-10 -Cyclic organic phosphorus compounds such as oxides, and organic phosphorus compounds such as derivatives obtained by reacting them with compounds such as epoxy resins or phenol resins; three

Compound, cyanuric acid compound, isocyanuric acid compound, phenanthrene

Isonitrogen-based flame retardants; polysiloxane-based flame retardants such as silicone oil, silicone rubber, and silicone resin; metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, Inorganic flame retardants such as low melting glass. When using such a flame retardant, it is preferable that it is the range of 0.1-20 mass% in a curable resin composition.

For example, when the curable resin composition of the present invention is used for a semiconductor sealing material, the above-mentioned inorganic filler is blended. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. among them, In terms of being capable of blending more inorganic fillers, the above-mentioned fused silica is preferred. The above-mentioned fused silica can be used in both crushed and spherical shapes. However, in order to increase the blending amount of the fused silica and suppress the increase in the melt viscosity of the curable resin composition, it is preferable to use mainly spherical ones. Furthermore, in order to increase the blending amount of the spherical silica, it is preferable to appropriately adjust the particle size distribution of the spherical silica. The filling rate is preferably blended in a range of 0.5 to 95 parts by mass in 100 parts by mass of the curable resin composition.

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

The curable resin composition of the present invention is obtained by uniformly mixing the aforementioned components. The curable resin composition of the present invention containing an epoxy resin component, a hardener, and optionally a hardening accelerator can be easily made into a hardened product by the same method as a conventional method. As this hardened | cured material, laminated hardened | cured material, a cast-molded object, an adhesive hardened layer, a coating film, a film, etc. are formed hardened | cured material, for example.

When the curable resin composition of the present invention is used for a printed wiring board application or a build-up adhesive film application, an organic solvent is preferably blended. Examples of the organic solvent include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methylcellulose, and diethylene glycol monoamine. Diethyl ether acetate, propylene glycol monomethyl ether acetate, and the like. The type or blending amount of the organic solvent can be appropriately adjusted according to the use environment of the curable resin composition. For example, in printed wiring board applications, the boiling points such as methyl ethyl ketone, acetone, and dimethylformamide are preferably The polar solvent at 160 ° C or lower is preferably used at a ratio of 40 to 80% by mass of nonvolatile matter. For the application of the build-up adhesive film, ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone, ethyl acetate, butyl acetate, cellulose acetate, propylene glycol monomethyl ether acetate, and carbidine are preferably used Alcohol Acetate solvents such as acid esters, carbitol solvents such as cellulose, butyl carbitol, aromatic hydrocarbon solvents such as toluene and xylene, dimethylformamide, dimethylacetamide, N-formyl Pyrrolidone and the like are preferably used at a ratio of 30 to 60% by mass of nonvolatile matter.

In addition, as a method for manufacturing a printed wiring board using the curable resin composition of the present invention, for example, a method of impregnating a reinforcing substrate with an varnish-like hardening property including an epoxy resin component, a hardener, an organic solvent, and other additives may be mentioned. The resin composition is hardened to obtain a prepreg, and the prepreg and the copper foil are recombined and heated and pressure-bonded. Examples of the reinforcing substrate include paper, glass cloth, glass nonwoven cloth, aramid paper, aramid cloth, glass felt, and glass roving cloth. The impregnation amount of the curable resin composition is not particularly limited, and it is usually preferably prepared so that the resin component in the prepreg becomes 20 to 60% by mass.

When the curable resin composition of the present invention is used for a semiconductor sealing material, for example, an epoxy resin component, a curing agent, and a filler can be sufficiently blended by using an extruder, a kneader, a roll, or the like. A method of ground mixing to uniformity to obtain a semiconductor sealing material. The filler used here may include the above-mentioned inorganic filler. As described above, it is preferably used in a range of 0.5 to 95 parts by mass in 100 parts by mass of the curable resin composition. Among them, in terms of improvement in flame resistance, moisture resistance, and crack resistance and reduction in linear expansion coefficient, it is preferably used in a range of 70 to 95 parts by mass, and particularly preferably 80 to 95 parts by mass. Use range.

As a method of forming a semiconductor device using the obtained semiconductor sealing material, for example, the following methods can be used: the semiconductor sealing material is formed using a casting or transfer molding machine, an injection molding machine, and the like, and the temperature is 50 to 200 ° C. Heat for 2-10 hours. By this method, a semiconductor device as a molded article can be obtained.

[Example]

Next, the present invention will be specifically described with reference to examples and comparative examples. Unless otherwise specified below, "parts" and "%" are quality standards. The epoxy equivalent, 150 ° C melt viscosity, GPC, NMR, and MS spectra were measured under the following conditions.

◆ Determination of epoxy equivalent

The measurement was performed based on JIS K 7236.

◆ Determination of melt viscosity at 150 ℃

The measurement was performed using an ICI viscometer in accordance with ASTM D4287.

◆ GPC measurement conditions

Measuring device: "HLC-8220GPC" manufactured by Tosoh Corporation,

Column: Protective Column "HXL-L" manufactured by Tosoh Corporation + "TSK-GEL G2000HXL" manufactured by Tosoh Corporation + "TSK-GEL G2000HXL" manufactured by Tosoh Corporation + "TSK-GEL G3000HXL" + "TSK-GEL G4000HXL" manufactured by Tosoh Corporation

Detector: RI (differential refractometer)

Data processing: "GPC-8020 Model II Version 4.10" manufactured by Tosoh Co., Ltd.

Measurement conditions: column temperature 40 ° C, developing solvent, tetrahydrofuran flow rate, 1.0ml / min

Standard: According to the above-mentioned "GPC-8020 Model II Version 4.10" measurement guide, the following monodisperse polystyrene with a known molecular weight is used.

(Using polystyrene)

"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 filter (50 μl) obtained by filtering a 1.0% by mass tetrahydrofuran solution in terms of resin solid content by a microfilter.

Production Example 1 Production of Triphenylmethane Type Resin (1)

Nitrogen flushing was performed on a flask equipped with a thermometer, a dropping funnel, a cooling tube, and a stirrer. 122 g of salicaldehyde, 370 g of phenol, and 2.4 g of p-toluenesulfonic acid were added. The temperature was raised to 100 ° C, and the mixture was stirred for 5 hours to react . After the reaction, the temperature was lowered to 80 ° C., and 1.4 g of a 49% by mass sodium hydroxide aqueous solution was added to neutralize the catalyst to completely stop the reaction. Thereafter, an excessive amount of phenol was distilled off under reduced pressure 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 equivalent of 97 g / equivalent.

Example 1 Manufacture of epoxy resin (1)

While flushing the flask equipped with a thermometer, a cooling tube, and a stirrer with nitrogen, 97 g of triphenylmethane resin (1) (hydroxyl content of 1 mole), 555 g of epichlorohydrin (6.0 moles), and n-butanol 111g and 17g of water were dissolved. After raising the temperature to 50 ° C., 220 g of a 20% by mass sodium hydroxide aqueous solution (sodium hydroxide amount 1.10 mol) was added over 3 hours, and the reaction was further performed at 50 ° C. for 1 hour. After the reaction was completed, unreacted epichlorohydrin was distilled off under reduced pressure at 150 ° C to obtain a crude product. 300 g of methyl isobutyl ketone and 50 g of n-butanol were added to the obtained crude product to dissolve them, 15 g of a 10% by mass sodium hydroxide aqueous solution was added, and the reaction was carried out at 80 ° C. for 2 hours. After the reaction was completed, 100 g of water was used each time and water washing was performed three times, and it was confirmed that the pH of the washing solution became neutral. Then, the system was azeotropically dehydrated, and after precise filtration, the solvent was distilled off under reduced pressure to obtain 150 g of an epoxy resin (1). The epoxy equivalent of the epoxy resin (1) was 167 g / equivalent. Fig. 1 shows a GPC chart of an epoxy resin (1).

Comparative Production Example 1 Production of Epoxy Resin (1 ')

烷111g，使之溶解。升溫至50℃後，一面於減壓條件下進行共沸脫水，一面歷時3小時添加20質量%氫氧化鈉水溶液220g(氫氧化鈉量1.10莫耳)，進而於50℃下反應1小時，而獲得粗產物。反應中係以如下方法進行反應：藉由共沸脫水而回收之水餾份於迪安-斯塔克分離器內經分離，使表氯醇返回至反應器內。又，適當測定反應溶液中之水分，確認到於反應結束時水分濃度為0.2質量%。繼而，對所獲得之粗產物添加甲基異丁基酮300g及正丁醇50g，使之溶解，添加10質量%氫氧化鈉水溶液15g，於80℃下反應2小時。反應結束後，每次使用水100g，重複進行3次水洗。繼 而，使系統內共沸而脫水，進行精密過濾後，於減壓條件下蒸餾去除溶劑，而獲得環氧樹脂(1')150g。環氧樹脂(1')之環氧當量為165g/當量。 While flushing the flask equipped with a thermometer, a cooling tube, and a stirrer with nitrogen, 97 g of triphenylmethane resin (1) (hydroxyl content 1 mol), 555 g of epichlorohydrin (6.0 mol), and two

111 g of alkane was dissolved. After raising the temperature to 50 ° C, while performing azeotropic dehydration under reduced pressure, 220 g of a 20% by mass sodium hydroxide aqueous solution (sodium hydroxide amount 1.10 mol) was added over 3 hours, and the reaction was further performed at 50 ° C for 1 hour. A crude product was obtained. During the reaction, the reaction was carried out in the following manner: The water fraction recovered by azeotropic dehydration was separated in a Dean-Stark separator to return epichlorohydrin to the reactor. Moreover, the water content in the reaction solution was appropriately measured, and it was confirmed that the water concentration was 0.2% by mass at the end of the reaction. Next, 300 g of methyl isobutyl ketone and 50 g of n-butanol were added to the obtained crude product to dissolve them, 15 g of a 10% by mass sodium hydroxide aqueous solution was added, and the reaction was carried out at 80 ° C. for 2 hours. After the reaction was completed, 100 g of water was used each time, and water washing was repeated three times. Then, the system was azeotropically dehydrated, and after precise filtration, the solvent was distilled off under reduced pressure to obtain 150 g of an epoxy resin (1 ′). The epoxy equivalent of the epoxy resin (1 ') was 165 g / equivalent.

Determination of (β) value

For the above epoxy resin (1) and epoxy resin (1 '), the following procedures were used to determine the hydroxyl equivalent of the reaction product obtained by reacting the epoxy group of the epoxy resin with the corresponding molar amount of phenol. Value (β).

1. Under basic catalyst conditions, heat and stir the epoxy resin and excess phenol relative to the epoxy group in the epoxy resin at 150 ° C. for 6 hours.

2. Remove the unreacted phenol from the reaction mixture under reduced pressure at 180 ° C to obtain a reaction product.

3. The hydroxyl equivalent of the reaction product was measured based on JIS K 0070.

Calculation of 1000 × [(β-α) / α]

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

Determination of melt viscosity

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

Example 2 and Comparative Example 1

Curable resin for epoxy resin (1) and epoxy resin (1 ') according to the following procedure The composition and the cured product were evaluated for heat resistance. The results are shown in Table 2.

Manufacture of curable resin composition

Epoxy resin (1) or epoxy resin (1 ') and a phenol novolak-type resin ("TD-2131" hydroxyl equivalent produced by DIC Corporation) are blended in accordance with the composition shown in Table 2 below. 104 g / equivalent) and triphenylphosphine (hereinafter referred to simply as "TPP") as a curing accelerator to obtain a curable resin composition.

Manufacture of hardened materials

The previously obtained curable resin composition was poured into a mold frame of 11 cm × 9 cm × 2.4 mm, and pressed at a temperature of 150 ° C. for 10 minutes to be formed. The molded product was taken out from the mold frame and cured at a temperature of 175 ° C for 5 hours to obtain a cured product.

Evaluation of heat resistance

Using a viscoelasticity measuring device (DMA: solid viscoelasticity measuring device RSAII manufactured by Rheometrics, rectangular tension method; frequency 1 Hz, temperature increasing rate 3 ° C./min, and maximum measuring temperature 300 ° C.), the change in elastic modulus of the hardened material is The temperature at the maximum (the maximum change rate of tan δ) was evaluated as the glass transition temperature (Tg). The results are shown in Table 2.

Evaluation of heat resistance change (△ Tg) after thermal history

The previous measurement of the glass transition temperature (Tg) was repeated twice, and the difference (ΔTg) between the two was measured. The results are shown in Table 2.

Claims (6)

An epoxy resin having a structural portion (1) represented by the following structural formula (1) as a repeating structural unit, which is characterized in that the value of the epoxy equivalent of the epoxy resin is (α), When the value of the hydroxyl equivalent of the reaction product obtained by reacting the epoxy group possessed by the epoxy resin with the corresponding molar amount of phenol is set to (β), 1000 × [(β-α) / α] The value is below 480,

[Wherein R ¹ and R ² are each independently 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 structural site represented by structural formula (1) (I) Any one of the bond nodes connected via a methylene group with an * symbol, m is an integer of 1 to 3, and n is an integer of 1 to 4]. A hardening resin composition containing an epoxy resin and a hardener in the first scope of the patent application. A hardened product is obtained by hardening a hardenable resin composition according to item 2 of the patent application. A printed wiring board using a curable resin composition in the second patent application range Things. A semiconductor sealing material containing an epoxy resin, a hardening agent, and an inorganic filler in the first scope of the patent application. A method for producing an epoxy resin, which reacts a triphenylmethane type resin with epihalohydrin in the presence of water and alcohols. The triphenylmethane type resin is represented by the following structural formula (2) The phenolic hydroxyl group-containing compound (A) is obtained by reacting with a methylol group-containing phenolic hydroxyl group-containing compound (B) represented by the following structural formula (3),

[Wherein R ³ and R ⁴ are each independently a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, and m is an integer of 1 to 3 , N is an integer from 1 to 4].