JP6809200B2 - Epoxy resin, curable resin composition and its cured product - Google Patents

Description

The present invention provides an epoxy resin that has an excellent balance of low shrinkage and low elastic modulus during heat curing, has good flame retardancy of the cured product, and can be suitably used as a semiconductor encapsulating material, and the epoxy. The present invention relates to a curable resin composition containing a resin and a cured product thereof.

A curable resin composition using an epoxy resin and various curing agents is used as an adhesive, a molding material, a paint, a photoresist material, a coloring material, etc., and also has excellent heat resistance and moisture resistance of the obtained cured product. It is widely used in the electrical and electronic fields such as semiconductor encapsulants and insulating materials for printed wiring boards because of its excellent properties.

Among these various applications, with the trend toward miniaturization and weight reduction of electronic devices, there is a remarkable tendency for the density to increase due to the narrowing of the wiring pitch of semiconductor devices, and as a semiconductor mounting method corresponding to this, semiconductors are used with solder balls. A flip-chip connection method for joining a device and a substrate is widely used. This flip-chip connection method is a semiconductor mounting method based on the so-called reflow method in which solder balls are placed between the wiring board and the semiconductor and the whole is heated and fused and joined. Therefore, the wiring plate itself is exposed to a high thermal environment during solder reflow. As a result, warpage occurs due to heat shrinkage of the wiring board, and a large stress is generated in the solder balls connecting the wiring board and the semiconductor, which may cause a poor connection of the wiring. That is, in order to suppress the warp of the wiring board, the sealing resin is also required to have a low shrinkage rate and a low elastic modulus.

As an epoxy resin that can be suitably used as a semiconductor encapsulant, an epoxy resin having an allyl group as a substituent on the aromatic ring of the bisphenol skeleton is provided (see, for example, Patent Document 1). Alternatively, it is also known that a naphthylene ether skeleton-containing epoxy resin which may have a substituent on the aromatic ring is preferably used as a semiconductor encapsulant (see, for example, Patent Document 2).

As described above, by using an epoxy resin having a substituent on the aromatic ring as the main agent of the curable resin composition, the fluidity of the composition and the cured product are higher than those in the case of using a general bisphenol type epoxy resin. Although a certain effect on the strength can be obtained, the balance level of the molding shrinkage rate and the thermal elastic modulus during heat curing of the resin composition required in recent years cannot be sufficiently satisfied, and further improvement is required.

JP 2015-000952 Japanese Unexamined Patent Publication No. 2016-89096

Therefore, the problem to be solved by the present invention is an epoxy resin, which has an excellent balance of molding shrinkage and elastic modulus during heat curing of a composition containing an epoxy resin, and also has good flame retardancy of the obtained cured product. The purpose is to provide a composition and a cured product thereof.

As a result of diligent studies to solve the above problems, the present inventors have decided to use an epoxy resin having a specific structure having a t-butyl group or a t-octyl group as a substituent on the aromatic ring within a certain range. We have found that the balance between the molding shrinkage and the elastic modulus at the time of heat curing is excellent and the flame retardancy of the cured product is also good, and have completed the present invention.

That is, the present invention has the following general formula (1).

（式中、Ｇはグリシジル基であり、Ｒ^１はそれぞれ独立して水素原子又は炭素数１〜８のアルキル基であり、少なくとも１つはｔ−ブチル基又はｔ−オクチル基であり、ｐは１〜３の整数であり、ｑは１〜４の整数であり、ｍは０又は１であり、ｎは繰り返し数を示し、平均値で１〜１０であり、繰り返し毎にＲ^１は同一でも異なっていてもよい。）
で表されるエポキシ樹脂であって、ｔ−ブチル基又はｔ−オクチル基の導入率の合計が１０〜９５％であることを特徴とするエポキシ樹脂、およびこれ含む硬化性樹脂組成物とその硬化物を提供するものである。

(In the formula, G is a glycidyl group, R ¹ is an independent hydrogen atom or an alkyl group having 1 to 8 carbon atoms, at least one is a t-butyl group or a t-octyl group, and p is. It is an integer of 1 to 3, q is an integer of 1 to 4, m is 0 or 1, n indicates the number of repetitions, and the average value is 1 to 10, even if R ¹ is the same for each repetition. It may be different.)
The epoxy resin represented by the above, wherein the total introduction rate of the t-butyl group or the t-octyl group is 10 to 95%, and the curable resin composition containing the epoxy resin and its curing. It provides things.

According to the present invention, the resin composition has an excellent balance of molding shrinkage and elasticity at the time of heat curing, and also has good flame retardancy of the cured product, so that it can be suitably used as a semiconductor encapsulating material or the like. It is possible to provide a resin, a curable resin composition, a cured product having the above-mentioned performance, a semiconductor encapsulating material, a semiconductor device, a prepreg, a circuit board, a build-up film, a build-up board, a fiber-reinforced composite material, and a fiber-reinforced molded product. ..

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

（式中、Ｇはグリシジル基であり、Ｒ^１はそれぞれ独立して水素原子又は炭素数１〜８のアルキル基であり、少なくとも１つはｔ−ブチル基又はｔ−オクチル基であり、ｐは１〜３の整数であり、ｑは１〜４の整数であり、ｍは０又は１であり、ｎは繰り返し数を示し、平均値で１〜１０であり、繰り返し毎にＲ^１は同一でも異なっていてもよい。）
で表されるエポキシ樹脂であって、ｔ−ブチル基又はｔ−オクチル基の導入率の合計が１０〜９５％であることを特徴とする。

(In the formula, G is a glycidyl group, R ¹ is an independent hydrogen atom or an alkyl group having 1 to 8 carbon atoms, at least one is a t-butyl group or a t-octyl group, and p is. It is an integer of 1 to 3, q is an integer of 1 to 4, m is 0 or 1, n indicates the number of repetitions, and the average value is 1 to 10, even if R ¹ is the same for each repetition. It may be different.)
The epoxy resin represented by (1) is characterized in that the total introduction rate of t-butyl group or t-octyl group is 10 to 95%.

The introduction rate of the t-butyl group or t-octyl group in the epoxy resin was determined by the peak of the aromatic ring carbon having a hydroxyl group and the quaternary carbon of the t-butyl group or t-octyl group in the ¹³ C-NMR measurement. It can be obtained from the ratio with the peak (in the case of a t-octyl group, the one having a short distance from the aromatic ring is read). That is, when calculating the introduction rate of a t-butyl group or t-octyl group in the present invention, it is not calculated for all aromatic rings in the molecule, but is calculated based on the introduction rate for aromatic rings having a hydroxyl group. Is.

In the present invention, when a resin having an introduction rate within a certain range, specifically within a range of 10 to 95% is used as one component of the curable resin composition, it becomes bulky as a substituent on the aromatic ring. It has been found that by having a branched alkyl group having a high carbon number of 4 or 8, the balance between the molding shrinkage and the elastic modulus at the time of heat curing is excellent, and the flame retardancy of the cured product is good. .. If this introduction rate is less than 10%, the molding shrinkage and elastic modulus at the time of heat curing are insufficient as in the case of the epoxidized product of the so-called polycondensate of phenol and bischloromethylbiphenyl, and the molded product is likely to warp. .. Further, when this introduction rate exceeds 95%, the aliphatic hydrocarbon property becomes high, and the flame retardancy of the cured product becomes insufficient. It is more preferable that the total introduction rate of the t-butyl group or the t-octyl group is in the range of 25 to 85% because the balance is better in these performances. Further, from the viewpoint that the effect of the present application is more likely to be exhibited, it is preferable that R ¹ in the general formula (1) is a hydrogen atom, a t-butyl group or a t-octyl group.

The ¹³ C-NMR in the present invention is carried out by the following measurement method.
Equipment: AL-400 manufactured by JEOL Ltd.
Measurement mode: Decoupling with reverse gate Solvent: Deuterated chloroform Pulse angle: 30 ° pulse Sample concentration: 30 wt%
Accumulation number: 4000 times

The epoxy resin of the present invention has the following general formula (2).

（式中、Ｇはグリシジル基であり、Ｒ²は水素原子又はｔ−ブチル基であり、ｍは０又は１であり、ｎは繰り返し数を示し、平均値で１〜１０であり、繰り返し毎にＲ^２は同一でも異なっていてもよい。）
で表されるものを例示することができる。即ち、芳香環上の置換基は、エポキシ基に対してパラ位であることが、硬化反応が良好に進行する観点、原料の工業的入手が容易である観点、加熱硬化時の成形収縮率、弾性率のバランスがより優れる観点から好ましいものである。更に、ｍは１であることが好ましく、ｎで示される繰り返し数の平均値としては、１〜８の範囲であることがより好ましい。

(In the formula, G is a glycidyl group, R ² is a hydrogen atom or a t-butyl group, m is 0 or 1, n indicates the number of repetitions, and the average value is 1 to 10 for each repetition. R ² may be the same or different.)
An example of what is represented by. That is, the fact that the substituent on the aromatic ring is in the para position with respect to the epoxy group is from the viewpoint that the curing reaction proceeds well, from the viewpoint that the raw material is easily industrially available, and the molding shrinkage during heat curing. It is preferable from the viewpoint of having a better balance of elastic modulus. Further, m is preferably 1, and the average value of the number of repetitions represented by n is more preferably in the range of 1 to 8.

The viscosity of the epoxy resin is preferably in the range of 0.01 to 15.0 dPa · s at 150 ° C. from the viewpoint that it can be suitably used as a semiconductor encapsulant. The epoxy equivalent of the epoxy resin is preferably in the range of 300 to 500 g / eq.

In addition, n in the general formula (1) in the present invention can be obtained by GPC measurement under the following conditions.
<GPC measurement conditions>
Measuring device: "HLC-8320 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 Workstation EcoSEC-WorkStation" 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 the above-mentioned "GPC workstation EcoSEC-WorkStation".
(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 of 1.0% by mass in terms of resin solid content in tetrahydrofuran filtered with a microfilter (50 μl).

<Epoxy resin manufacturing method>
As described above, the epoxy resin of the present invention is characterized in that the total introduction rate of the t-butyl group or the t-octyl group is 10 to 95% as described above. As a method for obtaining such an epoxy resin, an alkylphenol (I) having at least a t-butyl group or a t-octyl group as a substituent on the aromatic ring is used to react with the (bi) phenyl-based condensing agent (II). Then, after obtaining a precursor phenol resin, a method of epoxidizing this can be mentioned.

Examples of the alkylphenol (I) having the t-butyl group or t-octyl group as a substituent on the aromatic ring include t-butylphenol, di-t-butylphenol, t-octylphenol and the like, and only one of them can be used. However, two or more of them may be mixed and used. Among these, from the viewpoint of the heat shrinkage rate of the curable resin composition using the obtained epoxy resin, it is preferable that the curable resin composition has an alkyl group having a bulkier structure, and further, the availability of raw materials and the obtained resin From the viewpoint of the curing characteristics of the composition, it is preferable to use pt-butylphenol, ot-butylphenol, 2,4-di-t-butylphenol, pt-octylphenol, and pt-butylphenol. Most preferably used.

Further, as a method for adjusting the introduction rate of the t-butyl group or the t-octyl group in the epoxy resin of the present invention, another phenol compound (I') having no of these groups is used in combination.

Examples of the other phenol compound (I') that can be used together at this time include alkylphenols having an alkyl group having 1 to 8 carbon atoms other than phenol, t-butyl group or t-octyl group as a substituent on the aromatic ring. Specific examples thereof include cresol, xylenol, ethylphenol, diethylphenol, propylphenol, n-butylphenol, pentylphenol, hexylphenol, n-octylphenol, nonylphenol and the like, which may be used alone or in combination of two or more. ..

From the viewpoint of preferably obtaining the epoxy resin of the present invention, the ratio of the above-mentioned alkylphenol (I) to the other phenol compound (I') is represented by alkylphenol (I) / other phenol compound (I'). The molar ratio to be obtained is preferably in the range of 0.1 to 95, and particularly preferably in the range of 0.2 to 85.

The (bi) phenyl-based condensing agent (II) includes an alkylphenol (I) or another phenol compound (I') and methylene by a condensation reaction with the above-mentioned alkylphenol (I) and other phenol compound (I'). Any material may be used as long as it can form a precursor phenolic resin in which the -OG portion of the epoxy resin having the structure represented by the general formula (1) in which an aromatic ring is bonded via a group is -OH. For example, the following Examples thereof include those represented by the general formula (3).

（式中、ｍは又は１であり、Ｘは塩素原子、臭素原子、水酸基又は炭素数１〜６のアルコキシ基である。）

(In the formula, m is or 1, and X is a chlorine atom, a bromine atom, a hydroxyl group, or an alkoxy group having 1 to 6 carbon atoms.)

Examples of the compound represented by the general formula (3) include 4,4'-bis (hydroxymethyl) biphenyl, 4,4'-bis (methoxymethyl) biphenyl, and 4,4'-bis (ethoxymethyl). Biphenyl, 4,4'-bis (isopropoxymethyl) biphenyl, 4,4'-bis (chloromethyl) biphenyl, 4,4'-bis (bromomethyl) biphenyl, 1,4-bis (hydroxymethyl) benzene, 1 , 4-Bis (chloromethyl) benzene and the like, and may be used alone or in combination of two or more.

The reaction of the above-mentioned alkylphenol (I) and other phenol compounds (I') with the (bi) phenyl-based condensing agent (II) can be carried out under an acid catalyst, if necessary. Specifically, various catalysts can be used, but organic or inorganic acids such as sulfuric acid, p-toluenesulfonic acid and oxalic acid, Friedel-Crafts type catalysts such as ferric chloride, zinc chloride and ferric chloride can be used. These may be mentioned alone or in combination of two or more. Among these, sulfuric acid and p-toluenesulfonic acid are preferably used from the viewpoint of reactivity. The amount of these acid catalysts used varies depending on the type of catalyst, but is preferably in the range of 0.0005 to 5% by mass with respect to the (bi) phenyl-based condensing agent (II).

The ratio of the alkylphenol (I) and the other phenol compound (I') to the (bi) phenyl-based condensing agent (II) can be appropriately adjusted according to the physical properties of the target resin, etc., but will be described later. From the viewpoint that an epoxy resin having excellent curability when prepared into a curable resin composition can be easily obtained, (bi) phenyl is relative to the total mass of the alkylphenol (I) and the other phenol compound (I'). The system condensing agent (II) is preferably used in the range of 0.1 to 5, and more preferably in the range of 0.1 to 1.

Further, this condensation reaction can be carried out in the absence of a solvent or in the presence of a solvent. When a solvent is used, for example, water; methanol, ethanol, propanol, ethyl lactate, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol. , 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, trimethylene glycol, diethylene glycol, polyethylene glycol, glycerin, 2-ethoxyethanol, ethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl methyl ether, ethylene glycol monophenyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, 1 , 3-Dioxane, 1,4-Dioxane, tetrahydrofuran, ethylene glycol acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, N-methylpyrrolidone, dimethylformamide, dimethylsulfoxide and the like. Each of these solvents may be used alone or as a mixed solvent of two or more kinds. The amount of the solvent used is usually 10 to 300% by mass, preferably 20 to 250% by mass, based on the total mass of the alkylphenol (I), the other phenol compound (I') and the (bi) phenyl-based condensing agent (II). Is. The reaction temperature is usually 40 to 150 ° C., and the reaction time is usually 1 to 10 hours.

After completion of the reaction, the acid catalyst is removed by neutralization, washing with water, etc., and then the solvent used as necessary and the unreacted raw material are removed under heating and reduced pressure. If necessary, purification such as reprecipitation can be performed. Examples of the solvent that can be used for reprecipitation include toluene, methyl ethyl ketone, acetone, methyl isobutyl ketone, n-hexane, methanol, ethanol and the like, but the solvent is not limited thereto, and various solvents may be mixed. For reprecipitation, a usual method of heating these solvents, dissolving the reaction mixture, and then cooling and filtering can be applied.

The method for producing an epoxy resin of the present invention is a method for producing an epoxy resin in which a precursor phenol resin is reacted with epihalohydrin to epoxidize as described above, and a known technique can be appropriately applied to the method for epoxidation. ..

For example, for epihalohydrin, 1 to 10 mol is added to 1 mol of the hydroxyl group contained in the precursor phenol resin, and 0.9 to 2.0 mol of the basic catalyst is collectively added to 1 mol of the raw material 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 or gradually adding. This basic catalyst may be solid or an aqueous solution thereof may be used. When an aqueous solution is used, water and epihalohydrins are continuously added from the reaction mixture under reduced pressure or under normal pressure. The epihalohydrins may be continuously returned to the reaction mixture after being discharged and further separated to remove water.

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, they are consumed in the reaction with the epihalohydrins recovered from the crude reaction product. It is preferable to use in combination with new epihalohydrins corresponding to the amount that disappears in a certain amount. At this time, impurities such as glycidol may be contained, which are induced by the reaction of epichlorohydrin with water, an organic solvent and the like. At this time, the epichlorohydrin used is not particularly limited, and examples thereof include epichlorohydrin, epibromohydrin, and β-methylepichlorohydrin. Among these, epichlorohydrin is preferable because it is industrially easily available.

Specific examples of the basic catalyst include alkaline earth metal hydroxides, alkali metal carbonates and alkali metal hydroxides. In particular, alkali metal hydroxides are preferable from the viewpoint of excellent catalytic activity in the epoxy resin synthesis reaction, and examples thereof include sodium hydroxide and potassium hydroxide. At the time of use, these basic catalysts may be used in the form of an aqueous solution of about 10% by mass to 55% by mass, or may be used in the form of a solid. Further, by using an organic solvent in combination, the reaction rate in the synthesis of the epoxy resin can be increased. Such an organic solvent is not particularly limited, but for example, ketones such as acetone and methyl ethyl ketone, alcohols such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, 1-butanol, secondary butanol and tertiary butanol, and methyl. Examples thereof include cellosolves such as cellosolve and ethyl cellosolve, ethers such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane and diethoxyethane, and aprotonic polar solvents such as acetonitrile, dimethylsulfoxide and dimethylformamide. Each of these organic solvents may be used alone, or two or more of them may be used in combination as appropriate to adjust the polarity.

Subsequently, the reaction product of the above-mentioned epoxidation reaction is washed with water, and then the unreacted epihalohydrin and the organic solvent to be used in combination are distilled off by distillation under heating and reduced pressure. Further, in order to obtain an epoxy resin having less hydrolyzable halogen, the obtained epoxy resin is dissolved again in an organic solvent such as toluene, methyl isobutyl ketone and methyl ethyl ketone, and alkali metal hydroxide such as sodium hydroxide and potassium hydroxide is used. The reaction can be further carried out by adding an aqueous solution of the substance. 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 in the range of 0.1% by mass to 3.0% by mass with respect to the epoxy resin used. After completion of the reaction, the produced salt is removed by filtration, washing with water, or the like, and further, a solvent such as toluene or methyl isobutyl ketone is distilled off under heating and reduced pressure to obtain a high-purity epoxy resin.

<Curable resin composition>
The epoxy resin of the present invention can be made into a curable resin composition by using various curing agents having a group having a reactivity with an epoxy group in combination. The curable resin composition can be suitably used for various electric / electronic member applications such as adhesives, paints, photoresists, printed wiring boards, and semiconductor encapsulant materials.

Examples of the curing agent that can be used here include various known curing agents for epoxy resins such as amine compounds, amide compounds, acid anhydride compounds, and phenol compounds.

Specifically, diaminodiphenylmethane as amine compound, diethylenetriamine, triethylenetetramine, diaminodiphenyl sulfone, isophoronediamine, imidazo - Le, BF 3 _- amine complex, guanidine derivatives and the like, Examples of the amide compounds include dicyandiamide , Polyamide resin synthesized by a dimer of linolenic acid and ethylenediamine, and the like. Examples of acid anhydride compounds include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methylhexahydro. Examples include phthalic anhydride. Examples of phenolic compounds include phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadienephenol-added resin, phenol aralkyl resin (Zyroc resin), naphthol aralkyl resin, and triphenylol methane resin. Tetraphenylol ethane resin, naphthol novolac resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolak resin, biphenyl-modified phenol resin (polyphenolic hydroxyl group-containing compound in which phenol nuclei are linked by bismethylene groups), biphenyl Modified naphthol resin (polyvalent naphthol compound in which phenol nuclei are linked by bismethylene group), aminotriazine-modified phenol resin (polyvalent phenolic hydroxyl group-containing compound in which phenol nuclei are linked by melamine, benzoguanamine, etc.) and alkoxy group-containing aromatic ring Examples thereof include polyhydric phenolic hydroxyl group-containing compounds such as modified novolak resin (polyhydric phenolic hydroxyl group-containing compound in which a phenol nucleus and an alkoxy group-containing aromatic ring are linked with formaldehyde).

Further, the curable resin composition of the present invention may be used in combination with other epoxy resins other than the epoxy resin specified above as long as the effects of the present invention are not impaired.

Examples of the other epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, polyhydroxynaphthalene type epoxy resin, phenol novolac type epoxy resin, and cresol novolac type. Epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol novolac type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol Examples thereof include a reduced novolak type epoxy resin, a naphthol-cresol co-reduced novolak type epoxy resin, an aromatic hydrocarbon formaldehyde resin modified phenol resin type epoxy resin, and a biphenyl modified novolak type epoxy resin. Among these epoxy resins, tetramethylbiphenol type epoxy resin, biphenylaralkyl type epoxy resin, polyhydroxynaphthalene type epoxy resin, and novolac type epoxy resin can be used in that a cured product having particularly excellent flame retardancy can be obtained. A dicyclopentadiene-phenol addition reaction type epoxy resin is preferable, and a cured product having excellent dielectric properties can be obtained. When other epoxy resins are used in combination, the effect of the present invention is that the epoxy resin of the present invention is contained in an amount of 30 to 90 parts by mass with respect to a total of 100 parts by mass of the epoxy resin of the present invention and the other epoxy resin. Is preferable from the viewpoint that can be easily expressed.

In the curable resin composition of the present invention, the blending amount of the epoxy resin and the curing agent is a total of 1 equivalent of the epoxy groups in the epoxy resin and other epoxy resins used in combination with the epoxy resin from the viewpoint of excellent curability. On the other hand, it is preferable that the total number of active groups in the curing agent is 0.8 to 1.2 equivalents.

In addition, other thermosetting resins may be used in combination with the curable resin composition.

Examples of other thermosetting resins include cyanate ester resins, resins having a benzoxazine structure, maleimide compounds, active ester resins, vinylbenzyl compounds, acrylic compounds, copolymers of styrene and maleic acid anhydride, and the like. .. When the other thermosetting resin described above is used in combination, the amount used is not particularly limited as long as the effect of the present invention is not impaired, but is in the range of 1 to 50 parts by mass out of 100 parts by mass of the curable resin composition. It is preferable to have.

Examples of the cyanate ester resin include bisphenol A type cyanate ester resin, bisphenol F type cyanate ester resin, bisphenol E type cyanate ester resin, bisphenol S type cyanate ester resin, bisphenol sulfide type cyanate ester resin, and phenylene ether type cyanate ester resin. , Naftyrene ether type cyanate ester resin, biphenyl type cyanate ester resin, tetramethylbiphenyl type cyanate ester resin, polyhydroxynaphthalene type cyanate ester resin, phenol novolac type cyanate ester resin, cresol novolac type cyanate ester resin, triphenylmethane type cyanate Ester resin, tetraphenylethane type cyanate ester resin, dicyclopentadiene-phenol addition reaction type cyanate ester resin, phenol aralkyl type cyanate ester resin, naphthol novolac type cyanate ester resin, naphthol aralkyl type cyanate ester resin, naphthol-phenol co-condensed novolak Examples thereof include type cyanate ester resin, naphthol-cresol co-condensed novolak type cyanate ester resin, aromatic hydrocarbon formaldehyde resin modified phenol resin type cyanate ester resin, biphenyl modified novolak type cyanate ester resin, and anthracene type cyanate ester resin. Each of these may be used alone, or two or more types may be used in combination.

Among these cyanate ester resins, bisphenol A type cyanate ester resin, bisphenol F type cyanate ester resin, bisphenol E type cyanate ester resin, and polyhydroxynaphthalene type cyanate ester resin are particularly effective in obtaining a cured product having excellent heat resistance. , Naftylene ether type cyanate ester resin and novolak type cyanate ester resin are preferably used, and dicyclopentadiene-phenol addition reaction type cyanate ester resin is preferable in that a cured product having excellent dielectric properties can be obtained.

The resin having a benzoxazine structure is not particularly limited, and for example, a reaction product of bisphenol F, formalin and aniline (Fa type benzoxazine resin) or a reaction product of diaminodiphenylmethane, formalin and phenol (P-). d-type benzoxazine resin), reaction product of bisphenol A, formalin and aniline, reaction product of dihydroxydiphenyl ether, formalin and aniline, reaction product of diaminodiphenyl ether, formalin and phenol, dicyclopentadiene-phenol addition type resin and formalin And aniline reaction products, phenolphthalein, formalin and aniline reaction products, diphenylsulfide, formalin and aniline reaction products, and the like. Each of these may be used alone, or two or more types may be used in combination.

Examples of the maleimide compound include various compounds represented by any of the following structural formulas (i) to (iii).

（式中Ｒはｍ価の有機基であり、α及びβはそれぞれ水素原子、ハロゲン原子、アルキル基、アリール基の何れかであり、ｓは１以上の整数である。）

(In the formula, R is an organic group having an m valence, α and β are any of a hydrogen atom, a halogen atom, an alkyl group and an aryl group, respectively, and s is an integer of 1 or more.)

（式中Ｒは水素原子、アルキル基、アリール基、アラルキル基、ハロゲン原子、水酸基、アルコキシ基の何れかであり、ｓは１〜３の整数、ｔは繰り返し単位の平均で０〜１０である。）

(In the formula, R is any of a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a halogen atom, a hydroxyl group, and an alkoxy group, s is an integer of 1 to 3, and t is an average of 0 to 10 in repeating units. .)

（式中Ｒは水素原子、アルキル基、アリール基、アラルキル基、ハロゲン原子、水酸基、アルコキシ基の何れかであり、ｓは１〜３の整数、ｔは繰り返し単位の平均で０〜１０である。）これらはそれぞれ単独で用いても良いし、２種類以上を併用しても良い。

(In the formula, R is any of a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a halogen atom, a hydroxyl group, and an alkoxy group, s is an integer of 1 to 3, and t is an average of 0 to 10 in repeating units. .) Each of these may be used alone, or two or more types may be used in combination.

The active ester resin is not particularly limited, but generally contains an ester group having high reactive activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds in one molecule. A compound having two or more is preferably used. The active ester resin is preferably obtained by a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester resin obtained from a carboxylic acid compound or a halide thereof and a hydroxy compound is preferable, and an active ester resin obtained from a carboxylic acid compound or a halide thereof and a phenol compound and / or a naphthol compound is preferable. More preferred. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid and the like, or halides thereof. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, dihydroxydiphenyl ether, phenol phthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m. -Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglusin , Benzintriol, dicyclopentadiene-phenol-added resin and the like.

Specific examples of the active ester resin include an active ester resin containing a dicyclopentadiene-phenol addition structure, an active ester resin containing a naphthalene structure, an active ester resin which is an acetylated product of phenol novolac, and an activity which is a benzoyl product of phenol novolac. Ester resins and the like are preferable, and among them, an active ester resin containing a dicyclopentadiene-phenol addition structure and an active ester resin containing a naphthalene structure are more preferable in that they are excellent in improving peel strength. Specific examples of the active ester resin containing a dicyclopentadiene-phenol addition structure include compounds represented by the following general formula (iv).

However, in the formula (iv), R is a phenyl group or a naphthyl group, u represents 0 or 1, and n is an average of 0.05 to 2.5 in repeating units. From the viewpoint of reducing the dielectric loss tangent of the cured product of the resin composition and improving the heat resistance, R is preferably a naphthyl group, u is preferably 0, and n is preferably 0.25 to 1.5. ..

Further, various novolak resins, addition polymerization resins of alicyclic diene compounds such as dicyclopentadiene and phenol compounds, modified novolak resins of phenolic hydroxyl group-containing compounds and alkoxy group-containing aromatic compounds, phenol aralkyl resins (Zyroc resin). ), Naftor aralkyl resin, trimethylolmethane resin, tetraphenylol ethane resin, biphenyl-modified phenolic resin, biphenyl-modified naphthol resin, aminotriazine-modified phenolic resin, and various vinyl polymers may be used in combination.

More specifically, the various novolak resins are acid-catalyzed with phenol, phenylphenol, resorcinol, biphenyl, bisphenol such as bisphenol A and bisphenol F, phenolic hydroxyl group-containing compounds such as naphthol and dihydroxynaphthalene, and aldehyde compounds. Examples thereof include a polymer obtained by reacting under conditions.

The various vinyl polymers include polyhydroxystyrene, polystyrene, polyvinylnaphthalene, polyvinylanthracene, polyvinylcarbazole, polyinden, polyacenaftylene, polynorbornene, polycyclodecene, polytetracyclododecene, polynortricyclene, and poly (polynortricyclene, poly). Examples thereof include homopolymers of vinyl compounds such as meth) acrylates and copolymers thereof.

When these other resins are used, the blending ratio can be arbitrarily set according to the intended use, but the balance effect of the molding shrinkage rate at the time of heat curing and the elastic modulus at the time of heating exhibited by the present invention is more remarkable. Therefore, it is preferable that the ratio of other resins to 100 parts by mass of the epoxy resin of the present invention is 0.5 to 100 parts by mass.

A curing accelerator may be used in combination with the curable resin composition of the present invention. Curing accelerators include tertiary amine compounds such as imidazole and dimethylaminopyridine; phosphorus compounds such as triphenylphosphine; boron trifluoride amine complexes such as boron trifluoride monoethylamine complex; thiodipropion. Organic acid compounds such as acids; benzoxazine compounds such as thiodiphenol benzoxazine and sulfonylbenzoxazine; sulfonyl compounds and the like can be mentioned. Each of these may be used alone, or two or more types may be used in combination. The amount of these catalysts added is preferably in the range of 0.001 to 15 parts by mass in 100 parts by mass of the curable resin composition.

Further, when the curable resin composition of the present invention is used in an application requiring high flame retardancy, a non-halogen flame retardant substantially containing no halogen atom may be blended.

Examples of the non-halogen flame retardant include phosphorus-based flame retardants, nitrogen-based flame retardants, silicone-based flame retardants, inorganic flame retardants, organic metal salt-based flame retardants, and the like, and their use is also restricted. They may be used alone, a plurality of flame retardants of the same system may be used, or different flame retardants may be used in combination.

As the phosphorus-based flame retardant, either an inorganic type or an organic type can be used. Examples of the inorganic compound include ammonium phosphates such as red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate and ammonium polyphosphate, and inorganic nitrogen-containing phosphorus compounds such as phosphate amide. ..

Further, the red phosphorus is preferably surface-treated for the purpose of preventing hydrolysis and the like, and examples of the surface treatment method include (i) magnesium hydroxide, aluminum hydroxide, zinc hydroxide and water. A method of coating with an inorganic compound such as titanium oxide, bismuth oxide, bismuth hydroxide, bismuth nitrate or a mixture thereof, (ii) inorganic compounds such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide and titanium hydroxide, and Method of coating with a mixture of thermosetting resins such as phenol resin, (iii) Thermocurability of phenol resin or the like on a coating of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide Examples thereof include a method of double coating with a resin.

The organic phosphorus compounds include, for example, general-purpose organic phosphorus compounds such as phosphoric acid ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphoran compounds, and organic nitrogen-containing phosphorus compounds, as well as 9,10-dihydro. -9-Oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5-dihydrooxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,7-) Examples thereof include cyclic organophosphorus compounds such as dihydrooxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide and derivatives obtained by reacting the cyclic organophosphorus compounds with compounds such as epoxy resins and phenol resins.

The blending amount of these phosphorus-based flame retardants is appropriately selected depending on the type of the phosphorus-based flame retardant, other components of the resin composition, and the desired degree of flame retardancy. For example, a non-halogen flame retardant. When red phosphorus is used as a non-halogen flame retardant, it is mixed in the range of 0.1 part by mass to 2.0 parts by mass in 100 parts by mass of the resin composition containing all of the fillers and other additives. In the same way, when an organic phosphorus compound is used, it is preferably blended in the range of 0.1 parts by mass to 10.0 parts by mass, and blended in the range of 0.5 parts by mass to 6.0 parts by mass. It is more preferable to do so.

When the phosphorus-based flame retardant is used, hydrotalcite, magnesium hydroxide, boron compound, zirconium oxide, black dye, calcium carbonate, zeolite, zinc molybdate, activated charcoal, etc. may be used in combination with the phosphorus-based flame retardant. Good.

Examples of the nitrogen-based flame retardant include triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, and phenothiazine, and triazine compounds, cyanuric acid compounds, and isocyanuric acid compounds are preferable.

The triazine compound includes, for example, melamine, acetoguanamine, benzoguanamine, melon, melam, succinoguanamine, ethylenedimelamine, polyphosphate melamine, triguanamine and the like, and for example, (1) guanyl melamine sulfate, melem sulfate, melam sulfate. Aminotriazine sulfate compounds such as (2) Phenols such as phenol, cresol, xylenol, butylphenol, nonylphenol and melamines such as melamine, benzoguanamine, acetguanamine, formguanamine and formaldehyde, (3) the above. Examples thereof include a mixture of the cocondensate of (2) and phenolic resins such as phenol formaldehyde condensate, and (4) the above (2) and (3) further modified with tung oil, isomerized melamine oil and the like.

Examples of the cyanuric acid compound include cyanuric acid and melamine cyanuric acid.

The blending amount of the nitrogen-based flame retardant is appropriately selected depending on the type of the nitrogen-based flame retardant, other components of the resin composition, and the desired degree of flame retardancy. For example, a non-halogen flame retardant. It is preferable to mix in the range of 0.05 to 10 parts by mass, and in the range of 0.1 parts by mass to 5 parts by mass, out of 100 parts by mass of the resin composition containing all of the other fillers and additives. It is more preferable to do so.

When the nitrogen-based flame retardant is used, a metal hydroxide, a molybdenum compound, or the like may be used in combination.

The silicone-based flame retardant can be used without particular limitation as long as it is an organic compound containing a silicon atom, and examples thereof include silicone oil, silicone rubber, and silicone resin. The blending amount of the silicone flame retardant is appropriately selected depending on the type of the silicone flame retardant, other components of the resin composition, and the desired degree of flame retardancy. For example, a non-halogen flame retardant. It is preferable to blend in the range of 0.05 to 20 parts by mass in 100 parts by mass of the resin composition containing all of the other fillers and additives. When using the silicone flame retardant, a molybdenum compound, alumina or the like may be used in combination.

Examples of the inorganic flame retardant include metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and low melting point glass.

Examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, zirconium hydride and the like.

The metal oxides include, for example, zinc molybdate, molybdenum trioxide, zinc tinate, tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, zirconium oxide, zinc oxide, molybdenum oxide, cobalt oxide, and bismuth oxide. Examples thereof include chromium oxide, nickel oxide, copper oxide, and tungsten oxide.

Examples of the metal carbonate compound include zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, basic magnesium carbonate, aluminum carbonate, iron carbonate, cobalt carbonate, titanium carbonate and the like.

Examples of the metal powder include aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper, tungsten, tin and the like.

Examples of the boron compound include zinc borate, zinc metaborate, barium metaborate, boric acid, and borax.

The low melting point glass is, for example, Shipley (Boxy Brown), hydrated glass SiO ₂ -MgO-H ₂ O, PbO-B ₂ O ₃ system, ZnO-P ₂ O _5- MgO system, P ₂ O ₅ -B ₂ O _3- PbO-MgO system, P-Sn-OF system, PbO-V ₂ O _5- TeO ₂ system, Al ₂ O _3- H ₂ O system, lead borosilicate glassy compounds, etc. Can be mentioned.

The blending amount of the inorganic flame retardant is appropriately selected depending on the type of the inorganic flame retardant, other components of the resin composition, and the desired degree of flame retardancy. For example, a non-halogen flame retardant. It is preferable to blend in the range of 0.05 parts by mass to 20 parts by mass, and in the range of 0.5 parts by mass to 15 parts by mass, out of 100 parts by mass of the resin composition containing all of the other fillers and additives. It is more preferable to mix with.

The organometallic salt-based flame retardant includes, for example, ferrocene, an acetylacetonate metal complex, an organometallic carbonyl compound, an organocobalt salt compound, an organosulfonic acid metal salt, a metal atom and an aromatic compound or a heterocyclic compound in an ionic bond or arrangement. Examples thereof include position-bonded compounds.

The blending amount of the organic metal salt-based flame retardant is appropriately selected depending on the type of the organic metal salt-based flame retardant, other components of the resin composition, and the desired degree of flame retardancy. It is preferable to blend in the range of 0.005 parts by mass to 10 parts by mass in 100 parts by mass of the resin composition containing all of the halogen-based flame retardant and other fillers and additives.

The curable resin composition of the present invention can be blended with an inorganic filler, if necessary. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide and the like. When the blending amount of the inorganic filler is particularly large, it is preferable to use fused silica. 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 molding material, it is preferable to mainly use a spherical one. 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 high in consideration of flame retardancy, and is particularly preferably 20% by mass or more with respect to the total mass of the curable resin composition. When used for applications such as conductive paste, a conductive filler such as silver powder or copper powder can be used.

In addition to this, various compounding agents such as a silane coupling agent, a mold release agent, a pigment, and an emulsifier can be added to the curable resin composition of the present invention, if necessary.

<Use of curable resin composition>
The curable resin composition of the present invention shall be applied to semiconductor encapsulant materials, semiconductor devices, prepregs, printed circuit boards, build-up substrates, build-up films, fiber-reinforced composite materials, fiber-reinforced resin molded products, conductive pastes, and the like. Can be done.

1. 1. Semiconductor encapsulation material As a method for obtaining a semiconductor encapsulation material from the curable resin composition of the present invention, the curable resin composition and a compounding agent such as an inorganic filler are used in an extruder or a feeder as necessary. , A method of sufficiently melting and mixing until uniform using a roll or the like can be mentioned. At that time, fused silica is usually used as the inorganic filler, but when used as a high thermal conductivity semiconductor encapsulant for power transistors and power ICs, crystalline silica, alumina, and silicon nitride having higher thermal conductivity than fused silica are used. It is preferable to use high-filling silicon or the like, or use molten silica, crystalline silica, alumina, silicon nitride, or the like. It is preferable to use an inorganic filler in the range of 30 parts by mass to 95 parts by mass per 100 parts by mass of the curable resin composition, and among them, improvement of flame retardancy, moisture resistance and solder crack resistance, wire In order to reduce the coefficient of expansion, 70 parts by mass or more is more preferable, and 80 parts by mass or more is further preferable.

2. 2. Semiconductor device As a method for obtaining a semiconductor device from the curable resin composition of the present invention, the semiconductor encapsulant material is cast or molded using a transfer molding machine, an injection molding machine, or the like, and further at 50 to 200 ° C. 2 A method of heating for 10 hours can be mentioned.

3. 3. Prepreg As a method for obtaining a prepreg from the curable resin composition of the present invention, a curable resin composition obtained by blending an organic solvent to form a varnish is used as a reinforcing base material (paper, glass cloth, glass non-woven fabric, aramid paper, aramid cloth). , Glass mat, glass roving cloth, etc.) and then heated at a heating temperature according to the type of solvent used, preferably 50 to 170 ° C., to obtain the method. The mass ratio of the resin composition and the reinforcing base material used at this time is not particularly limited, but it is usually preferable to prepare the resin content in the prepreg to be 20% by mass to 60% by mass.

Examples of the organic solvent used here include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether acetate, and the like. It can be appropriately selected depending on the application, but for example, when further producing a printed circuit board from prepylene as described below, it is preferable to use a polar solvent having a boiling point of 160 ° C. or lower, such as methyl ethyl ketone, acetone, or dimethylformamide. , The non-volatile content is preferably used in a proportion of 40% by mass to 80% by mass.

4. Printed circuit board As a method for obtaining a printed circuit board from the curable resin composition of the present invention, the prepregs are laminated by a conventional method, copper foils are appropriately laminated, and the temperature is 170 to 300 ° C. under a pressure of 1 to 10 MPa. Examples thereof include a method of heat-pressing for 10 minutes to 3 hours.

5. Build-up substrate As a method for obtaining a build-up substrate from the curable resin composition of the present invention, a method via steps 1 to 3 can be mentioned. In step 1, first, the curable resin composition in which rubber, filler, etc. are appropriately mixed is applied to a circuit board on which a circuit is formed by a spray coating method, a curtain coating method, or the like, and then cured. In step 2, if necessary, a circuit board coated with the curable resin composition is drilled with a predetermined through-hole portion or the like, treated with a roughening agent, and the surface thereof is washed with hot water. Unevenness is formed on the substrate, and a metal such as copper is plated. In step 3, the operations of steps 1 and 2 are sequentially repeated as desired, and the resin insulating layer and the conductor layer having a predetermined circuit pattern are alternately built up to form a build-up substrate. In the above step, the through-hole portion may be drilled after the resin insulating layer of the outermost layer is formed. Further, the build-up substrate of the present invention is roughened by heat-pressing a resin-containing copper foil obtained by semi-curing the resin composition on a copper foil onto a wiring board on which a circuit is formed at 170 to 300 ° C. It is also possible to produce a build-up substrate by omitting the steps of forming a chemical surface and plating.

6. Build-up film As a method of obtaining a build-up film from the curable resin composition of the present invention, for example, a curable resin composition is applied on a support film, dried, and a resin composition layer is placed on the support film. There is a method of forming. When the curable resin composition of the present invention is used as a build-up film, the film is softened under the temperature conditions of lamination (usually 70 ° C. to 140 ° C.) in the vacuum laminating method, and is applied to the circuit board at the same time as laminating the circuit board. It is important to exhibit fluidity (resin flow) capable of filling the existing via hole or through hole with resin, and it is preferable to blend each of the above components so as to exhibit such characteristics.

Here, the diameter of the through hole of the circuit board is usually 0.1 to 0.5 mm, and the depth is usually 0.1 to 1.2 mm, and it is usually preferable to enable resin filling in this range. When laminating both sides of a circuit board, it is desirable to fill about 1/2 of the through holes.

As a specific method for producing the build-up film described above, a resin composition varnished by blending an organic solvent is prepared, and then the composition is applied to the surface of the support film (Y) and further heated. Alternatively, a method of drying the organic solvent by blowing hot air or the like to form the layer (X) of the resin composition can be mentioned.

Examples of the organic solvent used here include ketones such as acetone, methyl ethyl ketone and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, cellosolve and butyl carbitol. Carbitols, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like are preferably used, and the non-volatile content is 30% by mass to 60% by mass. Is preferable.

The thickness of the layer (X) of the resin composition to be formed usually needs to be equal to or larger than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, the thickness of the resin composition layer is preferably 10 to 100 μm. The layer (X) of the resin composition in the present invention may be protected by a protective film described later. By protecting with a protective film, it is possible to prevent dust and the like from adhering to the surface of the resin composition layer and scratches.

The support film and protective film described above include polyolefins such as polyethylene, polypropylene and polyvinyl chloride, polyethylene terephthalate (hereinafter, may be abbreviated as "PET"), polyesters such as polyethylene naphthalate, polycarbonate, polyimide, and further release. Examples include metal foils such as patterns, copper foils, and aluminum foils. The support film and the protective film may be subjected to a mold release treatment in addition to the mud treatment and the corona treatment. The thickness of the support film is not particularly limited, but is usually 10 to 150 μm, and is preferably used in the range of 25 to 50 μm. The thickness of the protective film is preferably 1 to 40 μm.

The support film (Y) described above is peeled off after being laminated on a circuit board or after forming an insulating layer by heat curing. If the support film (Y) is peeled off after the resin composition layer constituting the build-up film is heat-cured, it is possible to prevent the adhesion of dust and the like in the curing step. When peeling off after curing, the support film is usually subjected to a mold release treatment in advance.

A multilayer printed circuit board can be manufactured from the build-up film obtained as described above. For example, when the layer (X) of the resin composition is protected by a protective film, the layers (X) of the resin composition are peeled off, and then one side or both sides of the circuit board are brought into direct contact with the layer (X) of the resin composition. , For example, by the vacuum laminating method. The laminating method may be a batch method or a continuous method using a roll. If necessary, the build-up film and the circuit board may be preheated if necessary before laminating. As for the laminating conditions, the crimping temperature (lamination temperature) is preferably 70 to 140 ° C., and the crimping pressure is 1 to 11 kgf / cm ² (9.8 × 10 ^{4 to} 107.9 × 10 ⁴ N / m ² ). It is preferable to laminate under a reduced air pressure of 20 mmHg (26.7 hPa) or less.

7. Fiber-reinforced composite material As a method of obtaining a fiber-reinforced composite material (a sheet-like intermediate material in which a resin is impregnated in a reinforcing fiber) from the resin composition of the present invention, each component constituting the resin composition is uniformly mixed and varnished. Then, after impregnating the reinforcing base material made of reinforcing fibers with the reinforcing base material, a polymerization reaction is carried out to produce the resin.

Specifically, the curing temperature at the time of carrying out such a polymerization reaction is preferably in the temperature range of 50 to 250 ° C., in particular, after curing at 50 to 100 ° C. to obtain a tack-free cured product, further , 120 to 200 ° C. is preferable.

Here, the reinforcing fiber may be any of twisted yarn, untwisted yarn, untwisted yarn and the like, but the untwisted yarn and the untwisted yarn are preferable because they have both moldability and mechanical strength of the fiber reinforced plastic member. Further, as the form of the reinforcing fiber, one in which the fiber directions are aligned in one direction or a woven fabric can be used. For woven fabrics, plain weaves, satin weaves, and the like can be freely selected according to the part to be used and the intended use. Specific examples thereof include carbon fiber, glass fiber, aramid fiber, boron fiber, alumina fiber, and silicon carbide fiber because of their excellent mechanical strength and durability, and two or more of these can be used in combination. Among these, carbon fibers are particularly preferable from the viewpoint of improving the strength of the molded product, and various carbon fibers such as polyacrylonitrile-based, pitch-based, and rayon-based can be used. Of these, polyacrylonitrile-based ones, which can easily obtain high-strength carbon fibers, are preferable. Here, the amount of the reinforcing fiber used when impregnating the reinforcing base material made of the reinforcing fiber with the varnish to obtain the fiber-reinforced composite material is such that the volume content of the reinforcing fiber in the fiber-reinforced composite material is 40% to 85%. The amount is preferably in the range of.

8. Fiber-reinforced resin molded product As a method of obtaining a fiber-reinforced molded product (molded product in which a sheet-like member impregnated with resin impregnated in reinforcing fibers is cured) from the resin composition of the present invention, a fiber aggregate is laid on a mold and the varnish is applied. Using either the hand lay-up method, spray-up method, or male or female type, in which multiple layers are laminated, the base material made of reinforcing fibers is impregnated with varnish and stacked to form, and pressure is applied to the molded product. Vacuum bag method in which a flexible mold that can be used is covered and airtightly sealed is vacuum (decompressed) molded, SMC press method in which a sheet of varnish containing reinforcing fibers is previously compression-molded with a mold, and fibers are laid out. Examples thereof include a method of producing a prepreg in which reinforcing fibers are impregnated with the varnish by an RTM method in which the varnish is injected into a mating mold, and baking the prepreg with a large autoclave. The fiber-reinforced resin molded product obtained above is a molded product having a reinforcing fiber and a cured product of the resin composition. Specifically, the amount of the reinforcing fiber in the fiber-reinforced molded product is 40 mass. It is preferably in the range of% to 70% by mass, and particularly preferably in the range of 50% by mass to 70% by mass from the viewpoint of strength.

9. Conductive Paste As a method for obtaining a conductive paste from the resin composition of the present invention, for example, a method of dispersing fine conductive particles in the curable resin composition can be mentioned. The conductive paste can be a paste resin composition for circuit connection or an anisotropic conductive adhesive depending on the type of fine conductive particles used.

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 GPC and ¹³ C-NMR spectra were measured under the following conditions.

<GPC measurement conditions>
Measuring device: "HLC-8320 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 Workstation EcoSEC-WorkStation" 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 the above-mentioned "GPC workstation EcoSEC-WorkStation".
(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 of 1.0% by mass in terms of resin solid content in tetrahydrofuran filtered with a microfilter (50 μl).

< ¹³ C-NMR measurement conditions>
Equipment: AL-400, manufactured by JEOL Ltd.
Measurement mode: Decoupling with reverse gate,
Solvent: Deuterated chloroform,
Pulse angle: 30 ° pulse,
Sample concentration: 30 wt%,
Accumulation number: 4000 times.

Example 1
90 parts by mass (0.6 mol) of pt-butylphenol, 94 parts by mass (1.0 mol) of phenol, 4,4 in a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractional tube, and a stirrer. Add 100.5 parts by mass (0.4 mol) of'-bis (chloromethyl) biphenyl, 15 parts by mass of p-toluenesulfonic acid, and 300 parts by mass of toluene, raise the temperature from room temperature to 110 ° C. in 45 minutes, and hold for 8 hours. did. After completion of the reaction, a 49% aqueous sodium hydroxide solution was added for neutralization, and the unreactant was removed in the reaction system under heating and reduced pressure to obtain a precursor phenol resin. While performing nitrogen gas purging on a flask equipped with a thermometer, a cooling tube, and a stirrer, 108 parts by mass of the phenol resin, 278 parts by mass (3.0 mol) of epichlorohydrin, and 83 parts by mass of n-butanol obtained above were charged and dissolved. It was. After the temperature was raised to 50 ° C., 45 parts by mass (0.55 mol) of a 49% aqueous sodium hydroxide solution was added over 3 hours, and then the reaction was further carried out at 50 ° C. for 1 hour. After completion of the reaction, unreacted epichlorohydrin was distilled off under reduced pressure at 150 ° C. Next, 300 g of methyl isobutyl ketone and 50 g of n-butanol were added to the obtained crude epoxy resin and dissolved. Further, 15 parts of a 10 mass% sodium hydroxide aqueous solution was added to this solution and reacted at 80 ° C. for 2 hours, and then washing with 100 g of water was repeated 3 times until the pH of the washing solution became neutral. Next, the inside of the system was dehydrated by azeotrope, and after undergoing microfiltration, the solvent was distilled off under reduced pressure to obtain an epoxy resin (A-1). The epoxy equivalent of the obtained epoxy resin (A-1) was 321 g / eq, and the t-butyl group introduction rate was 28%.

Example 2
An epoxy resin (A-2) was obtained in the same manner as in Example 1 except that the contents were changed to 210 parts by mass (1.4 mol) of pt-butylphenol and 19 parts by mass (0.2 mol) of phenol. The epoxy equivalent of the obtained epoxy resin (A-2) was 360 g / eq, and the t-butyl group introduction rate was 81%.

Comparative synthesis example 1
An epoxy resin (A'-1) was obtained in the same manner as in Synthesis Example 1 except that the pt-butylphenol was changed to 240 parts by mass (1.6 mol) and 0 part by mass (0 mol) of phenol. The epoxy equivalent of the obtained epoxy resin (A'-1) was 390 g / eq, and the t-butyl group introduction rate was 100%.

Comparative synthesis example 2
An epoxy resin (A'-2) was obtained in the same manner as in Example 1 except that the pt-butylphenol was changed to 0 parts by mass (0 mol) and 150 parts by mass (1.6 mol) of phenol. The epoxy equivalent of the obtained epoxy resin (A'-2) was 291 g / eq, and the t-butyl group introduction rate was 0%.

Examples 3 and 4, Comparative Examples 1 and 2
<Preparation of composition and cured product>
The following compounds were blended in the compositions shown in Tables 1 and 2, and then melt-kneaded at a temperature of 90 ° C. for 5 minutes using two rolls to prepare a curable resin composition. The abbreviations in Table 1 mean the following compounds.
The following compounds were blended in the compositions shown in Tables 1 and 2, and then melt-kneaded at a temperature of 90 ° C. for 5 minutes using two rolls to prepare a desired curable resin composition. The abbreviations in Table 1 mean the following compounds.
-Phenolic resin: Phenolic novolak resin "TD-2131" equivalent: 104 g / eq (manufactured by DIC Corporation)
・ TPP: Triphenylphosphine ・ Fused silica: Spherical silica "FB-560" manufactured by Denka Co., Ltd. ・ Silane coupling agent: γ-glycidoxytriethoxyxisilane "KBM-403" manufactured by Shin-Etsu Chemical Co., Ltd. ・ Carnauba wax : "PEARL WAX No.1-P" manufactured by Denka Co., Ltd. The obtained curable resin composition was pulverized and obtained by using a transfer molding machine at a pressure of 70 kg / cm ² , a temperature of 175 ° C., and a time of 180. It was formed into a disk shape of φ50 mm × 3 (t) mm in seconds, and further cured at 180 ° C. for 5 hours.

<Measurement of glass transition temperature and elastic modulus>
The cured product having a thickness of 0.8 mm produced above was cut into a size having a width of 5 mm and a length of 54 mm, and this was used as a test piece 1. Using this test piece 1 with 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), the change in elastic modulus is maximized. The temperature at which (tan δ change rate is the largest) was measured as the glass transition temperature, and the storage elastic modulus at 260 ° C. was measured as the thermal elastic modulus.

<Measurement of shrinkage rate during molding>
Using a transfer molding machine (Kotaki Seiki, KTS-15-1.5C), the resin composition was injection-molded under the conditions of a mold temperature of 150 ° C., a molding pressure of 9.8 MPa, and a curing time of 600 seconds. A test piece having a length of 110 mm, a width of 12.7 mm, and a thickness of 1.6 mm was prepared. After that, the test piece was post-cured at 175 ° C. for 5 hours, the inner diameter of the mold cavity and the outer diameter of the test piece at room temperature (25 ° C.) were measured, and the shrinkage rate was calculated by the following formula.
Shrinkage rate (%) = {(inner diameter dimension of mold)-(longitudinal dimension of cured product at 25 ° C)} / (inner diameter dimension of mold cavity at 175 ° C) x 100 (%)

<Evaluation of flame retardancy>
The cured product was used as a test piece, and five pieces were used to perform a combustion test in accordance with the UL-94 test method.
* 1: Total burning time (seconds) of 5 test pieces
* 2: Maximum combustion time (seconds) for one flame contact
These results are shown in Tables 1-2.

Claims (15)

The following general formula (1)

(In the formula, G is a glycidyl group, R ¹ is an independent hydrogen atom or an alkyl group having 1 to 8 carbon atoms, at least one is a t-butyl group or a t-octyl group, and p is. It is an integer of 1 to 3, q is an integer of 1 to 4, m is 0 or 1, n indicates the number of repetitions, and the average value is 1 to 10, even if R ¹ is the same for each repetition. It may be different.)
¹³ C-NMR measurement shows the ratio of the peak of aromatic ring carbon having a glycidyl ether group to the peak of quaternary carbon of t-butyl group or t-octyl group (t-). In the case of an octyl group, the total number of t-butyl groups and t-octyl groups is 10 to 95% of the number of aromatic rings having a glycidyl ether group, which is calculated from (reading the one that is closer to the aromatic ring). An epoxy resin characterized by being. The epoxy resin according to claim 1, wherein R ¹ in the general formula (1) is a hydrogen atom, a t-butyl group or a t-octyl group. The general formula (1) is the following general formula (2).

(In the formula, G is a glycidyl group, R ² is a hydrogen atom or a t-butyl group, m is 0 or 1, n indicates the number of repetitions, and the average value is 1 to 10 for each repetition. R ² may be the same or different.)
The epoxy resin according to claim 1, which is represented by The epoxy resin according to any one of claims 1 to 3, wherein the epoxy equivalent of the epoxy resin is in the range of 300 to 500 g / eq. A curable resin composition containing the epoxy resin according to any one of claims 1 to 4 and a curing agent as essential components. The curable resin composition according to claim 5, which contains an epoxy resin other than the epoxy resin. The curable resin composition according to claim 5 or 6, further comprising a curing accelerator for an epoxy resin. A cured product of the curable resin composition according to any one of claims 5 to 7. A semiconductor encapsulating material containing the curable resin composition according to any one of claims 5 to 7 and an inorganic filler. A semiconductor device containing a cured product of the semiconductor encapsulating material according to claim 9. A prepreg which is a semi-cured product of an impregnated base material having the curable resin composition according to any one of claims 5 to 7 and a reinforcing base material. A circuit board comprising a plate-shaped excipient of the curable resin composition according to any one of claims 5 to 7 and a copper foil. A build-up film comprising a cured product of the curable resin composition according to any one of claims 5 to 7 and a base film. A fiber-reinforced composite material containing the curable resin composition according to any one of claims 5 to 7 and reinforcing fibers. A fiber-reinforced molded product which is a cured product of the fiber-reinforced composite material according to claim 14.