JP2018100320A - Epoxy resin, curable resin composition and cured product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: an epoxy resin which has an excellent balance between a mold shrinkage factor and an elastic modulus during heat curing and gives a cured product having good flame retardancy; a composition and a cured product thereof.SOLUTION: There are provided: an epoxy resin represented by the formula (1) in which the total of the introduction rate of a t-butyl group or a t-octyl group is 10 to 95%; a curable resin composition using the epoxy resin; and a cured product thereof. (G is a glycidyl group; Reach independently is H, an alkyl group having 1 to 8 carbon atoms, at least one of which is a t-butyl group or a t-octyl group; p is an integer of 1 to 3; q is an integer of 1 to 4; m is 0 or 1; n is a repeating number of 1 to 10 on average.)SELECTED DRAWING: None

Description

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

  Curable resin compositions using epoxy resins and various curing agents are used in adhesives, molding materials, paints, photoresist materials, color developing materials, etc., and the resulting cured products have excellent heat resistance and moisture resistance. It is widely used in the electrical and electronic fields such as semiconductor sealing materials and printed wiring board insulating materials.

  Among these various applications, along with the trend toward smaller and lighter electronic devices, the trend toward higher density due to the narrower wiring pitch of semiconductor devices is remarkable. A flip chip connection method in which the device and the substrate are joined is widely used. In this flip-chip connection method, a solder ball is placed between a wiring board and a semiconductor, and the whole is heated and melt bonded to form a so-called reflow semiconductor mounting method. Therefore, the wiring plate itself is exposed to a high heat environment during solder reflow. In some cases, warping occurs due to thermal contraction of the wiring board, and a large stress is generated in the solder balls connecting the wiring board and the semiconductor, resulting in poor connection of the wiring. That is, for the purpose of suppressing warping of the wiring board, a low shrinkage rate and a low elastic modulus are required for the sealing resin.

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

  As described above, by using an epoxy resin having a substituent on the aromatic ring as a main component of the curable resin composition, the fluidity of the composition and the cured product can be obtained more than when a general bisphenol-type epoxy resin is used. Although a certain effect on strength can be obtained, it does not sufficiently satisfy the balance level of molding shrinkage ratio and heat elastic modulus at the time of heat curing of a resin composition required in recent years, and further improvement is required.

JP2015-000952A Japanese Patent Laid-Open No. 2006-89096

  Therefore, the problem to be solved by the present invention is an epoxy resin that has an excellent balance of molding shrinkage and elastic modulus at the time of heat curing of a composition containing an epoxy resin, and also has good flame retardancy of the resulting cured product, It is in providing a composition and its hardened | cured material.

  As a result of intensive studies to solve the above problems, the present inventors have used an epoxy resin having a specific structure having a t-butyl group or a t-octyl group within a certain range as a substituent on the aromatic ring. The present inventors have found that the molding shrinkage ratio and the elastic modulus at the time of heat-curing are excellent and that the cured product has good flame retardancy, and have completed the present invention.

  That is, the present invention provides 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, each R ¹ is independently a 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 1 is an integer of 1 to 3, q is an integer of 1 to 4, m is 0 or 1, n is the number of repetitions, an average value is 1 to 10, and R ¹ is the same for each repetition May be different.)
And an epoxy resin characterized in that the total introduction rate of t-butyl group or t-octyl group is 10 to 95%, and a curable resin composition containing the epoxy resin and its curing It provides things.

  According to the present invention, the resin composition has excellent balance of molding shrinkage and elastic modulus at the time of heat curing, and the cured product has good flame retardancy, and can be suitably used for semiconductor sealing materials and the like. A resin, a curable resin composition, a cured product having the above-mentioned performance, a semiconductor sealing material, a semiconductor device, a prepreg, a circuit board, a buildup film, a buildup board, a fiber reinforced composite material, and a fiber reinforced molded product can be provided. .

<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, each R ¹ is independently a 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 1 is an integer of 1 to 3, q is an integer of 1 to 4, m is 0 or 1, n is the number of repetitions, an average value is 1 to 10, and R ¹ is the same for each repetition May be different.)
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 is 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 ¹³ C-NMR measurement. It can be determined from the ratio to the peak (in the case of a t-octyl group, the one having a short distance from the aromatic ring is read). That is, in calculating the introduction rate of the t-butyl group or t-octyl group in the present invention, it is not performed for all aromatic rings in the molecule, but calculated with the introduction rate for the aromatic ring having a hydroxyl group. It is.

In the present invention, when a resin having this 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 has been found that, due to having a branched alkyl group having 4 or 8 carbon atoms, it has an excellent balance of molding shrinkage and elastic modulus during heat curing, and the flame retardancy of the cured product is improved. . When the introduction ratio is less than 10%, the molding shrinkage rate and the elastic modulus at the time of heat curing are insufficient and the molded product is likely to warp, similarly to the epoxidized product of the polycondensation product of phenol and bischloromethylbiphenyl. . On the other hand, if the introduction rate exceeds 95%, the aliphatic hydrocarbon property becomes high, and the flame retardancy of the cured product becomes insufficient. In these performances, since the balance becomes better, the total introduction rate of t-butyl group or t-octyl group is more preferably in the range of 25 to 85%. Moreover, it is preferable that R < ¹ > in the said General formula (1) is a hydrogen atom, a t-butyl group, or a t-octyl group from the viewpoint which the said effect of this application tends to be expressed more.

In the present invention, ¹³ C-NMR is performed by the following measurement method.
Device: AL-400 manufactured by JEOL Ltd.
Measurement mode: Decoupling with reverse gate Solvent: Deuterated chloroform Pulse angle: 30 ° pulse Sample concentration: 30 wt%
Integration count: 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 represents a glycidyl group, R ² represents a hydrogen atom or a t-butyl group, m represents 0 or 1, n represents the number of repetitions, and is an average value of 1 to 10; R ² may be the same or different.
What is represented by can be illustrated. That is, the substituent on the aromatic ring is in the para position with respect to the epoxy group, the viewpoint that the curing reaction proceeds favorably, the viewpoint that the raw material is easily industrially available, the molding shrinkage during heat curing, It is preferable from the viewpoint that the balance of elastic modulus is more excellent. Furthermore, m is preferably 1, and the average number of repetitions represented by n is more preferably in the range of 1-8.

  Moreover, as a viscosity of the said epoxy resin, it is preferable that the ICI viscosity in 150 degreeC is the range of 0.01-15.0 dPa * s from a viewpoint which can be used conveniently as a semiconductor sealing agent. Moreover, it is preferable that the epoxy equivalent of the said epoxy resin is the range of 300-500 g / eq.

In the present invention, n in the general formula (1) 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
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ Tosoh Corporation “TSK-GEL G4000HXL”
Detector: RI (differential refractometer)
Data processing: “GPC workstation EcoSEC-WorkStation” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate: 1.0 ml / min Standard: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC workstation EcoSEC-WorkStation”.
(Used 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 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids and filtered through a microfilter (50 μl).

<Method for producing epoxy resin>
As described above, the epoxy resin of the present invention is characterized in that the total introduction rate of t-butyl group or t-octyl group is 10 to 95% as described above. As a method for obtaining such an epoxy resin, at least a t-butyl group or t-octyl group is used as a substituent on the aromatic ring, and alkylphenol (I) is used to react with (bi) phenyl condensing agent (II). And a precursor phenol resin is obtained and then epoxidized.

  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. Even if it becomes, you may mix and use 2 or more types. Among these, from the viewpoint of the heat shrinkage rate of the curable resin composition using the resulting epoxy resin, it is preferable to have an alkyl group having a more bulky structure, and the availability of raw materials and the resulting resin From the viewpoint of the properties at the time of curing of the composition, it is preferable to use pt-butylphenol, ot-butylphenol, 2,4-di-tert-butylphenol, pt-octylphenol, Most preferably, it is used.

  In addition, as a method for adjusting the introduction rate of the t-butyl group or t-octyl group in the epoxy resin of the present invention, another phenol compound (I ′) having no such group is used in combination.

  Examples of the other phenol compound (I ′) that can be used at this time include alkylphenols having a C 1-8 alkyl group other than phenol, t-butyl group or t-octyl group as a substituent on the aromatic ring. Specific examples include cresol, xylenol, ethylphenol, diethylphenol, propylphenol, n-butylphenol, pentylphenol, hexylphenol, n-octylphenol, and nonylphenol, which may be used alone or in combination of two or more. .

  From the viewpoint of suitably obtaining the epoxy resin of the present invention, the use ratio of the aforementioned alkylphenol (I) and other phenol compound (I ′) is represented by alkylphenol (I) / other phenol compound (I ′). The molar ratio is preferably in the range of 0.1 to 95, particularly preferably in the range of 0.2 to 85.

  As the (bi) phenyl-based condensing agent (II), alkylphenol (I) or other phenolic compound (I ′) and methylene can be obtained by condensation reaction with the aforementioned alkylphenol (I) and other phenolic compound (I ′). Any epoxy resin may be used as long as it can form a precursor phenol resin in which the -OG portion of the epoxy resin having the structure represented by the general formula (1) having an aromatic ring bonded thereto via a group is -OH. The thing represented by General formula (3) can be mentioned.

（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 1 or X, 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 may be used alone or in admixture of two or more.

  The reaction of the aforementioned alkylphenol (I), other phenolic compound (I ') and (bi) phenyl condensing agent (II) can be carried out under an acid catalyst, if necessary. Specific examples include various organic or inorganic acids such as sulfuric acid, p-toluenesulfonic acid, and oxalic acid, Friedel-Crafts type catalysts such as stannic chloride, zinc chloride, and ferric chloride. These may be used alone or in combination of two or more. Among these, it is preferable to use a sulfuric acid and p-toluenesulfonic acid from a reactive viewpoint. 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 mass% with respect to (bi) phenyl-based condensing agent (II).

  The proportion of the alkylphenol (I), the other phenolic compound (I ′) and the (bi) phenyl condensing agent (II) can be adjusted as appropriate according to the physical properties of the target resin. From the viewpoint of easily obtaining an epoxy resin having excellent curability when used as a curable resin composition, (bi) phenyl with respect 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 using a solvent, 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-methyl Examples include pyrrolidone, dimethylformamide, dimethyl sulfoxide and the like. These solvents may be used alone or in combination of two or more kinds. As a usage-amount of a solvent, it is 10-300 mass% normally with respect to the total mass of alkylphenol (I), other phenolic compounds (I '), and (bi) phenyl-type condensing agent (II), Preferably it is 20-250 mass%. It 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 and unreacted raw materials are removed as necessary 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. However, the solvent is not limited to these, and various solvents may be mixed. For reprecipitation, a normal method of heating these solvents and dissolving the reaction mixture, followed by cooling and filtration can be applied.

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

  For example, epihalohydrin is added in an amount of 1 to 10 mol based on 1 mol of hydroxyl group contained in the precursor phenol resin, and 0.9 to 2.0 mol of basic catalyst is collectively added to 1 mol of hydroxyl group of the raw material. The method of making it react for 0.5 to 10 hours at the temperature of 20-120 degreeC, adding or adding gradually is mentioned. The basic catalyst may be solid or an aqueous solution thereof. When an aqueous solution is used, it is continuously added and water and epihalohydrins are continuously distilled from the reaction mixture under reduced pressure or normal pressure. The solution may be taken out and further separated to remove water and the epihalohydrins are continuously returned to the reaction mixture.

  In the first batch of epoxy resin production, all of the epihalohydrins used for preparation are new in industrial production, but the subsequent batches are consumed by the reaction with epihalohydrins recovered from the crude reaction product. It is preferable to use in combination with new epihalohydrins corresponding to the amount disappeared. Under the present circumstances, the impurity induced | guided | derived by reaction with epichlorohydrin, water, an organic solvent, etc. may be contained, such as glycidol. At this time, the epihalohydrin used is not particularly limited, and examples thereof include epichlorohydrin, epibromohydrin, β-methylepichlorohydrin, and the like. Among these, epichlorohydrin is preferable because it is easily available industrially.

  Specific examples of the basic catalyst include alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides. In particular, alkali metal hydroxides are preferable from the viewpoint of excellent catalytic activity of the epoxy resin synthesis reaction, and examples thereof include sodium hydroxide and potassium hydroxide. In use, these basic catalysts may be used in the form of an aqueous solution of about 10% to 55% by weight or in the form of a solid. Moreover, the reaction rate in the synthesis | combination of an epoxy resin can be raised by using an organic solvent together. Examples of such organic solvents include, but are not limited to, 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, methyl Examples include cellosolves such as cellosolve and ethyl cellosolve, ethers such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane and diethoxyethane, and aprotic polar solvents such as acetonitrile, dimethyl sulfoxide and dimethylformamide. These organic solvents may be used alone or in combination of two or more as appropriate in order to adjust the polarity.

  Subsequently, the reaction product of the epoxidation reaction is washed with water, and 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 with less hydrolyzable halogen, the obtained epoxy resin is again dissolved in an organic solvent such as toluene, methyl isobutyl ketone, methyl ethyl ketone, and alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. Further reaction can be carried out by adding an aqueous solution of the product. At this time, a phase transfer catalyst such as a quaternary ammonium salt or 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 generated salt is removed by filtration, washing with water, and a high-purity epoxy resin can be obtained by distilling off a solvent such as toluene and methyl isobutyl ketone under heating and reduced pressure.

<Curable resin composition>
The epoxy resin of this invention can be made into a curable resin composition by using together the various hardening | curing agent which has a group reactive with an epoxy group. The curable resin composition can be suitably used for various electric / electronic member applications such as adhesives, paints, photoresists, printed wiring boards, and semiconductor sealing 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, examples of the amine compound include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF ₃ -amine complex, and guanidine derivative. Examples of the amide compound include dicyandiamide. And a polyamide resin synthesized from a dimer of linolenic acid and ethylenediamine. Acid anhydride compounds include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydro And phthalic anhydride. Phenol compounds include phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadiene phenol addition resin, phenol aralkyl resin (Zylok resin), naphthol aralkyl resin, triphenylol methane resin, Tetraphenylolethane resin, naphthol novolak 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 a bismethylene group), biphenyl Modified naphthol resin (polyvalent naphthol compound in which phenol nucleus is linked by bismethylene group), aminotriazine modified phenol resin (melamine, benzo Polyhydric phenolic hydroxyl group-containing compounds in which phenol nuclei are linked with anamin, etc.), alkoxy group-containing aromatic ring-modified novolak resins (polyhydric phenolic hydroxyl group-containing compounds in which phenol nuclei and alkoxy group-containing aromatic rings are linked with formaldehyde), etc. And a polyhydric phenolic hydroxyl group-containing compound.

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

  Examples of the other epoxy resins 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 novolak type. Epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol novolak type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol Condensed novolac epoxy resin, naphthol-cresol co-condensed novolac epoxy resin, aromatic hydrocarbon formaldehyde resin modified pheno Resin type epoxy resins, biphenyl-modified novolak type epoxy resins. Among these epoxy resins, tetramethylbiphenol type epoxy resin, biphenyl aralkyl type epoxy resin, polyhydroxynaphthalene type epoxy resin, and novolac type epoxy resin are used in that a cured product having excellent flame retardancy can be obtained. A dicyclopentadiene-phenol addition reaction type epoxy resin is preferable in that a cured product having excellent dielectric properties is obtained. Moreover, when using together another epoxy resin, it is the effect of this invention that the epoxy resin of this invention is included in 30-90 mass parts with respect to a total of 100 mass parts of the epoxy resin of this invention and another epoxy resin. Is preferable from the viewpoint that can be easily expressed.

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

  The curable resin composition may be used in combination with other thermosetting resins.

  Examples of other thermosetting resins include cyanate ester resins, resins having a benzoxazine structure, maleimide compounds, active ester resins, vinyl benzyl compounds, acrylic compounds, and copolymers of styrene and maleic anhydride. . When the other thermosetting resins described above are used in combination, the amount used is not particularly limited as long as the effects of the present invention are not impaired, but in the range of 1 to 50 parts by mass in 100 parts by mass of the curable resin composition. Preferably there is.

  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. , Naphthylene 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, Cyclopentadiene-phenol addition reaction type cyanate ester resin, phenol aralkyl type cyanate ester resin, naphthol novolak type cyanate ester resin, naphthol aralkyl type cyanate ester resin, naphthol-phenol co-condensed novolak type cyanate ester resin, naphthol-cresol co-condensed novolak type Examples include cyanate ester resins, aromatic hydrocarbon formaldehyde resin-modified phenol resin-type cyanate ester resins, biphenyl-modified novolac-type cyanate ester resins, and anthracene-type cyanate ester resins. These may be used alone or in combination of two or more.

  Among these cyanate ester resins, bisphenol A-type cyanate ester resins, bisphenol F-type cyanate ester resins, bisphenol E-type cyanate ester resins, and polyhydroxynaphthalene-type cyanate ester resins are particularly preferred in that a cured product having excellent heat resistance can be obtained. Naphthalene 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. 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 Reaction product of phenol and aniline, reaction product of phenolphthalein, formalin and aniline, reaction product of diphenyl sulfide, formalin and aniline. These may be used alone or in combination of two or more.

  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 m-valent organic group, α and β are each a hydrogen atom, a halogen atom, an alkyl group, or an aryl group, 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 one 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 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 one 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 repeating units. .) These may be used alone or in combination of two or more.

  Although there is no restriction | limiting in particular as said active ester resin, Generally ester group with high reaction activity, such as phenol ester, thiophenol ester, N-hydroxyamine ester, ester of heterocyclic hydroxy compound, is in 1 molecule. A compound having two or more is preferably used. The active ester resin is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and 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 preferred, 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 preferred. 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 a halide thereof. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, dihydroxydiphenyl ether, phenolphthalein, 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, phloroglucin , Benzenetriol, dicyclopentadiene-phenol addition 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 that is an acetylated product of phenol novolac, and an activity that is a benzoylated product of phenol novolac. An ester resin or the like is preferable, and an active ester resin including a dicyclopentadiene-phenol addition structure and an active ester resin including a naphthalene structure are more preferable because they are excellent in improving peel strength. More specifically, an active ester resin containing a dicyclopentadiene-phenol addition structure includes a compound represented by the following general formula (iv).

  However, in formula (iv), R is a phenyl group or a naphthyl group, u represents 0 or 1, and n is 0.05-2.5 on the average of a repeating unit. 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. .

  Furthermore, 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 (Xylok resins) ), Naphthol aralkyl resin, trimethylol methane resin, tetraphenylol ethane resin, biphenyl-modified phenol resin, biphenyl-modified naphthol resin, aminotriazine-modified phenol resin, and various vinyl polymers may be used in combination.

  More specifically, the above-mentioned various novolak resins are an acid catalyst for 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 polymers obtained by reacting under conditions.

  The various vinyl polymers include polyhydroxystyrene, polystyrene, polyvinyl naphthalene, polyvinyl anthracene, polyvinyl carbazole, polyindene, polyacenaphthylene, polynorbornene, polycyclodecene, polytetracyclododecene, polynortricyclene, poly ( A homopolymer of a vinyl compound such as (meth) acrylate or a copolymer thereof may be mentioned.

  The blending ratio in the case of using these other resins can be arbitrarily set according to the use, but the balance effect of the molding shrinkage ratio at the time of heat curing and the elastic modulus at the time of the present invention is more prominently exhibited. Therefore, it is preferable that the ratio of the other resin is 0.5 to 100 parts by mass with respect to 100 parts by mass of the epoxy resin of the present invention.

  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 and trifluoride monoethylamine complexes; thiodipropion Organic acid compounds such as acids; benzoxazine compounds such as thiodiphenol benzoxazine and sulfonyl benzoxazine; sulfonyl compounds and the like. These may be used alone or in combination of two or more. It is preferable that the addition amount of these catalysts is 0.001-15 mass parts in 100 mass parts of curable resin compositions.

  Moreover, when using for the use as which the high flame retardance is calculated | required by the curable resin composition of this invention, you may mix | blend the non-halogen-type flame retardant which does not contain a halogen atom substantially.

  Examples of the non-halogen flame retardant include a phosphorus flame retardant, a nitrogen flame retardant, a silicone flame retardant, an inorganic flame retardant, an organic metal salt flame retardant, and the like. It is not intended to be used alone, and a plurality of the same type of flame retardants may be used, or different types of flame retardants may be used in combination.

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

  The red phosphorus is preferably subjected to a surface treatment for the purpose of preventing hydrolysis and the like. Examples of the surface treatment method include (i) magnesium hydroxide, aluminum hydroxide, zinc hydroxide, water A method of coating with an inorganic compound such as titanium oxide, bismuth oxide, bismuth hydroxide, bismuth nitrate or a mixture thereof; (ii) an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide; and A method of coating with a mixture of a thermosetting resin such as a phenol resin, (iii) thermosetting of a phenol resin or the like on a coating of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, or titanium hydroxide For example, a method of double coating with a resin may be used.

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

  The amount of these phosphorus-based flame retardants is appropriately selected depending on the type of phosphorus-based flame retardant, the other components of the resin composition, and the desired degree of flame retardancy. For example, non-halogen flame retardants And 100 parts by mass of resin composition containing all other fillers and additives, etc., when red phosphorus is used as a non-halogen flame retardant, it is blended in the range of 0.1 to 2.0 parts by mass. In the case of using an organophosphorus compound, it is preferably blended in the range of 0.1 to 10.0 parts by weight, and blended in the range of 0.5 to 6.0 parts by weight. More preferably.

  Also, when using the phosphorus flame retardant, the phosphorus flame retardant may be used in combination with hydrotalcite, magnesium hydroxide, boron compound, zirconium oxide, black dye, calcium carbonate, zeolite, zinc molybdate, activated carbon, etc. Good.

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

  Examples of the triazine compound include melamine, acetoguanamine, benzoguanamine, melon, melam, succinoguanamine, ethylene dimelamine, melamine polyphosphate, triguanamine, and the like, for example, (1) guanylmelamine sulfate, melem sulfate, melam sulfate (2) Cocondensates of phenols such as phenol, cresol, xylenol, butylphenol and nonylphenol with melamines such as melamine, benzoguanamine, acetoguanamine and formguanamine and formaldehyde, (3) (2) A mixture of a co-condensate and a phenol resin such as a phenol formaldehyde condensate, (4) those obtained by further modifying (2) and (3) above with paulownia oil, isomerized linseed oil or the like.

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

  The amount of the nitrogen-based flame retardant is appropriately selected depending on the type of the nitrogen-based flame retardant, the other components of the resin composition, and the desired degree of flame retardancy. For example, a non-halogen flame retardant And in 100 parts by mass of the resin composition in which all other fillers and additives are blended, it is preferably blended in the range of 0.05 to 10 parts by weight, and blended in the range of 0.1 to 5 parts by weight. More preferably.

  Moreover, when using the said nitrogen-type flame retardant, you may use together a metal hydroxide, a molybdenum compound, etc.

  The silicone flame retardant is not particularly limited as long as it is an organic compound containing a silicon atom, and examples thereof include silicone oil, silicone rubber, and silicone resin. The amount of the silicone-based flame retardant is appropriately selected according to the type of the silicone-based flame retardant, the other components of the resin composition, and the desired degree of flame retardancy. For example, a non-halogen flame retardant And it is preferable to mix | blend in the range of 0.05-20 mass parts in 100 mass parts of resin compositions which mix | blended all the other fillers, additives, etc. Moreover, when using the said silicone type flame retardant, you may use a molybdenum compound, an alumina, etc. together.

  Examples of the inorganic flame retardant include metal hydroxide, metal oxide, metal carbonate compound, metal powder, boron compound, and low melting point glass.

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

  Examples of the metal oxide include zinc molybdate, molybdenum trioxide, zinc stannate, tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, zirconium oxide, zinc oxide, molybdenum oxide, cobalt oxide, 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, and titanium carbonate.

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

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

Examples of the low-melting-point glass include Shipley (Bokusui Brown), hydrated glass SiO ₂ —MgO—H ₂ O, PbO—B ₂ O ₃ system, ZnO—P ₂ O ₅ —MgO system, and P ₂ O _5. Glassy compounds such as —B ₂ O ₃ —PbO—MgO, P—Sn—O—F, PbO—V ₂ O ₅ —TeO ₂ , Al ₂ O ₃ —H ₂ O, and lead borosilicate Can be mentioned.

  The blending amount of the inorganic flame retardant is appropriately selected according to the type of the inorganic flame retardant, the other components of the resin composition, and the desired degree of flame retardancy. For example, a non-halogen flame retardant And in 100 parts by mass of the resin composition in which all other fillers and additives are blended, it is preferably blended in the range of 0.05 to 20 parts by weight, and in the range of 0.5 to 15 parts by weight. It is more preferable to mix with.

  Examples of the organic metal salt flame retardant include ferrocene, acetylacetonate metal complex, organic metal carbonyl compound, organic cobalt salt compound, organic sulfonic acid metal salt, metal atom and aromatic compound or heterocyclic compound. And the like.

  The amount of the organic metal salt flame retardant is appropriately selected depending on the type of the organic metal salt flame retardant, the other components of the resin composition, and the desired degree of flame retardancy. It is preferable to mix | blend in 0.005 mass part-10 mass parts in 100 mass parts of resin compositions which mix | blended all the halogenated flame retardants and other fillers and additives.

  The curable resin composition of this invention can mix | blend an inorganic filler as needed. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. When particularly increasing the blending amount of the inorganic filler, it is preferable to use fused silica. The fused silica can be used in either a crushed shape or a spherical shape. However, in order to increase the blending amount of the fused silica and suppress an increase in the melt viscosity of the molding material, it is preferable to mainly use a spherical shape. In order to further 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 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. Moreover, when using for uses, such as an electrically conductive paste, electroconductive fillers, such as silver powder and copper powder, can be used.

  In addition to the above, the curable resin composition of the present invention may contain various compounding agents such as a silane coupling agent, a release agent, a pigment, and an emulsifier, if necessary.

<Use of curable resin composition>
The curable resin composition of the present invention is applied to a semiconductor sealing material, a semiconductor device, a prepreg, a printed circuit board, a buildup board, a buildup film, a fiber reinforced composite material, a fiber reinforced resin molded product, a conductive paste, and the like. Can do.

1. Semiconductor encapsulating material As a method for obtaining a semiconductor encapsulating material from the curable resin composition of the present invention, the curable resin composition and a compounding agent such as an inorganic filler, if necessary, an extruder, a kneader. And a method of sufficiently melting and mixing until uniform using a roll or the like. At that time, fused silica is usually used as the inorganic filler, but when used as a high thermal conductive semiconductor encapsulant for power transistors and power ICs, crystalline silica, alumina, nitridation having higher thermal conductivity than fused silica. High filling such as silicon, or fused silica, crystalline silica, alumina, silicon nitride, or the like may be used. The filling ratio is preferably 30 to 95 parts by weight of an inorganic filler per 100 parts by weight of the curable resin composition. Among them, improvement in flame resistance, moisture resistance and solder crack resistance, wire In order to reduce the expansion coefficient, it is more preferably 70 parts by mass or more, and further preferably 80 parts by mass or more.

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

3. Prepreg As a method for obtaining a prepreg from the curable resin composition of the present invention, a curable resin composition blended with an organic solvent and varnished is used as a reinforcing substrate (paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth). And a glass mat, a glass roving cloth, etc.), followed by heating at a heating temperature corresponding to the solvent type used, preferably 50 to 170 ° C. The mass ratio of the resin composition and the reinforcing substrate used at this time is not particularly limited, but it is usually preferable that the resin content in the prepreg is adjusted to 20 mass% to 60 mass%.

  Examples of the organic solvent used here include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxy propanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether acetate, etc. For example, when a printed circuit board is further produced from a prepreg 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, dimethylformamide, etc. The nonvolatile content is preferably 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 prepreg is laminated by a conventional method, and a copper foil is appropriately laminated at 170 to 300 ° C. under a pressure of 1 to 10 MPa. The method of carrying out thermocompression bonding for 10 minutes-3 hours is mentioned.

5. Build-up substrate As a method for obtaining a build-up substrate from the curable resin composition of the present invention, a method through Steps 1 to 3 may be mentioned. In step 1, first, the curable resin composition appropriately blended with rubber, filler, and the like is applied to a circuit board on which a circuit is formed using a spray coating method, a curtain coating method, or the like, and then cured. In step 2, if necessary, after drilling a predetermined through-hole portion or the like on the circuit board coated with the curable resin composition, by treating with a roughening agent and washing the surface 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 to build up a resin insulating layer and a conductor layer having a predetermined circuit pattern alternately to form a build-up substrate. In the step, the through-hole portion is preferably formed after the outermost resin insulating layer is formed. In addition, the build-up board of the present invention is obtained by roughly pressing a resin-coated 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 forming the chemical surface and omitting the plating process.

6). Build-up film As a method for 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 and then dried, and then a resin composition layer is formed on the support film. The method of forming is mentioned. When the curable resin composition of the present invention is used for a build-up film, the film is softened under a lamination temperature condition (usually 70 ° C. to 140 ° C.) in a vacuum laminating method. It is important to show fluidity (resin flow) in which existing via holes or through holes can be filled with resin, and it is preferable to blend the above-described 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. It is usually preferable to allow resin filling in this range. When laminating both surfaces of the circuit board, it is desirable to fill about 1/2 of the through hole.

  As a specific method for producing the above-described buildup film, after preparing a varnished resin composition by blending an organic solvent, 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 resin composition layer (X) can be mentioned.

  Examples of the organic solvent used herein 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, butyl carbitol, and the like. Carbitols, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. are preferably used, and the nonvolatile content is used in a proportion of 30% to 60% by mass. It is preferable.

  In addition, the thickness of the layer (X) of the resin composition to be formed usually needs to be equal to or greater 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. In addition, 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 being attached to the surface of the resin composition layer and scratches.

  The above-mentioned support film and protective film are made of polyolefin such as polyethylene, polypropylene and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyester such as polyethylene naphthalate, polycarbonate, polyimide, and further. Examples thereof include metal foil such as pattern paper, copper foil, and aluminum foil. In addition, the support film and the protective film may be subjected to a release treatment in addition to the mud treatment and the corona treatment. Although the thickness of a support film is not specifically limited, Usually, it is 10-150 micrometers, Preferably it is used in 25-50 micrometers. Moreover, it is preferable that the thickness of a protective film shall be 1-40 micrometers.

  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 after the resin composition layer constituting the build-up film is heat-cured, adhesion of dust and the like in the curing step can be prevented. In the case of peeling after curing, the support film is usually subjected to a release treatment in advance.

In addition, a multilayer printed circuit board can be manufactured from the buildup film obtained as mentioned above. For example, when the layer (X) of the resin composition is protected by a protective film, after peeling off these layers, one side or both sides of the circuit board so that the layer (X) of the resin composition is in direct contact with the circuit board For example, lamination is performed by a 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 heated (preheated) as necessary before lamination. The laminating conditions are preferably a pressure bonding temperature (laminating temperature) of 70 to 140 ° C. and a pressure bonding pressure of 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 pressure of 20 mmHg (26.7 hPa) or less.

7). Fiber Reinforced Composite Material As a method for obtaining a fiber reinforced composite material (a sheet-like intermediate material in which a resin is impregnated with a reinforced fiber) from the resin composition of the present invention, varnish is prepared by uniformly mixing the components constituting the resin composition. And then, impregnating a reinforcing substrate made of reinforcing fibers with this, followed by a polymerization reaction.

  Specifically, the curing temperature at the time of performing the 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, The treatment is preferably performed at a temperature of 120 to 200 ° C.

  Here, the reinforced fiber may be any of a twisted yarn, an untwisted yarn, or a non-twisted yarn, but an untwisted yarn or a non-twisted yarn is preferable because both the formability and mechanical strength of the fiber-reinforced plastic member are compatible. Furthermore, the form of a reinforced fiber can use what the fiber direction arranged in one direction, and a textile fabric. The woven fabric can be freely selected from plain weaving, satin weaving, and the like according to the site and use. Specifically, since it is excellent in mechanical strength and durability, carbon fiber, glass fiber, aramid fiber, boron fiber, alumina fiber, silicon carbide fiber and the like can be mentioned, and two or more of these can be used in combination. Among these, carbon fiber is preferable from the viewpoint that the strength of the molded product is particularly good. As the carbon fiber, various types such as polyacrylonitrile-based, pitch-based, and rayon-based can be used. Among these, a polyacrylonitrile-based one that can easily obtain a high-strength carbon fiber is preferable. Here, the amount of reinforcing fibers used when a reinforced varnish made of reinforcing fibers is impregnated into a fiber-reinforced composite material is such that the volume content of the reinforcing fibers in the fiber-reinforced composite material is 40% to 85%. It is preferable that the amount be in the range.

8). Fiber-reinforced resin molded article As a method of obtaining a fiber-reinforced molded article (molded article obtained by curing a sheet-like member impregnated with resin in a reinforcing fiber) from the resin composition of the present invention, a fiber aggregate is laid on a mold, and the varnish is used. Using multiple layers of hand lay-up, spray-up, and male / female types, the base material made of reinforcing fiber is stacked while being impregnated with varnish, and the pressure is applied to the molded product. A vacuum bag method that covers a flexible mold that can be sealed and vacuum-tightly seals what is hermetically sealed, a SMC press method that compresses a varnish containing reinforcing fibers in advance into a sheet, and spreads the fibers. A prepreg in which reinforcing fibers are impregnated with the varnish is manufactured by an RTM method in which the varnish is injected into a laminated mold, and this is baked in a large autoclave. The method of hardening is mentioned. In addition, the fiber reinforced resin molded product obtained above is a molded product having a reinforced fiber and a cured product of the resin composition. Specifically, the amount of the reinforced fiber in the fiber reinforced molded product is 40 mass. It is preferable that it is the range of%-70 mass%, and it is especially preferable that it is the range of 50 mass%-70 mass% from the point of intensity | strength.

9. Conductive paste Examples of a method for obtaining a conductive paste from the resin composition of the present invention include a method of dispersing fine conductive particles in the curable resin composition. 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. 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
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ Tosoh Corporation “TSK-GEL G4000HXL”
Detector: RI (differential refractometer)
Data processing: “GPC workstation EcoSEC-WorkStation” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate: 1.0 ml / min Standard: The following monodispersed polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC workstation EcoSEC-WorkStation”.
(Used 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 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids and filtered through a microfilter (50 μl).

<Measurement conditions for ¹³ C-NMR>
Apparatus: AL-400 manufactured by JEOL Ltd.
Measurement mode: decoupling with reverse gate,
Solvent: deuterated chloroform,
Pulse angle: 30 ° pulse,
Sample concentration: 30 wt%
Accumulation count: 4000 times.

Example 1
In a flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube, and a stirrer, 90 parts by mass of pt-butylphenol (0.6 mol), 94 parts by mass of phenol (1.0 mol), 4, 4 '-Bis (chloromethyl) biphenyl 100.5 parts by mass (0.4 mol), p-toluenesulfonic acid 15 parts by mass, toluene 300 parts by mass were charged from room temperature to 110 ° C in 45 minutes and held for 8 hours did. After completion of the reaction, a 49% aqueous sodium hydroxide solution was added for neutralization, and unreacted substances were removed from the reaction system under heating and reduced pressure to obtain a precursor phenol resin. A flask equipped with a thermometer, a condenser tube, and a stirrer was charged with nitrogen gas purge and charged with 108 parts by mass of the phenol resin obtained above, 278 parts by mass of epichlorohydrin (3.0 mol), and 83 parts by mass of n-butanol. It was. After raising the temperature to 50 ° C., 45 parts by mass (0.55 mol) of a 49% aqueous sodium hydroxide solution was added over 3 hours, and the reaction was further continued 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% by mass aqueous sodium hydroxide solution was added to this solution and reacted at 80 ° C. for 2 hours. Then, washing with 100 g of water was repeated three times until the pH of the washing solution became neutral. Next, the system was dehydrated by azeotropic distillation, and after 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 content was 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 240 parts by mass (1.6 mol) of pt-butylphenol and 0 parts by mass (0 mol) of phenol were used. The epoxy resin (A′-1) obtained had an epoxy equivalent of 390 g / eq and a t-butyl group introduction rate of 100%.

Comparative Synthesis Example 2
An epoxy resin (A′-2) was obtained in the same manner as in Example 1 except that the content was changed to 0 parts by mass (0 mol) of pt-butylphenol 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
<Production of composition and cured product>
The following compounds were blended in the compositions shown in Tables 1 and 2, and then melt-kneaded for 5 minutes at 90 ° C. using two rolls to prepare a curable resin composition. In addition, the symbol in Table 1 means the following compound.
The following compounds were blended in the compositions shown in Tables 1 and 2, and then melt-kneaded for 5 minutes at a temperature of 90 ° C. using two rolls to prepare the desired curable resin composition. In addition, the symbol in Table 1 means the following compound.
Phenol resin: Phenol novolac 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-glycidoxytriethoxyxysilane “KBM-403” manufactured by Shin-Etsu Chemical Co., Ltd. ・ Carnauba wax : “PEARL WAX No. 1-P” manufactured by Denka Co., Ltd. A product obtained by pulverizing the obtained curable resin composition was subjected to a pressure of 70 kg / cm ² , a temperature of 175 ° C. and a time of 180 using a transfer molding machine. 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 of 5 mm in width and 54 mm in length, 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 Rheometric Co., Ltd., rectangular tension method: frequency 1 Hz, heating rate 3 ° C./min) The temperature (the 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 during molding>
Using a transfer molding machine (manufactured by Kotaki Seiki Co., Ltd., KTS-15-1.5C), the resin composition was injected and molded under 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 produced. Thereafter, the test piece was post-cured at 175 ° C. for 5 hours, the inner diameter size of the mold cavity and the outer diameter size 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.) × 100 (%)

<Evaluation of flame retardancy>
The cured product was used as a test piece, and five of them were used to conduct a combustion test based on the UL-94 test method.
* 1: Total burning time of 5 specimens (seconds)
* 2: Maximum burning time (seconds) in 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, each R ¹ is independently a 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 1 is an integer of 1 to 3, q is an integer of 1 to 4, m is 0 or 1, n is the number of repetitions, an average value is 1 to 10, and R ¹ is the same for each repetition May be different.)
An epoxy resin represented by the formula (1), wherein the total introduction rate of t-butyl group or t-octyl group is 10 to 95%. 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 represented by the following general formula (2)

(In the formula, G represents a glycidyl group, R ² represents a hydrogen atom or a t-butyl group, m represents 0 or 1, n represents the number of repetitions, and is an average value of 1 to 10; 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 an epoxy equivalent of the epoxy resin is in a range of 300 to 500 g / eq.   A curable resin composition comprising 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, comprising an epoxy resin other than the epoxy resin.   Furthermore, the curable resin composition of Claim 5 or 6 containing the hardening accelerator for epoxy resins.   Hardened | cured material of the curable resin composition of any one of Claims 5-7.   The semiconductor sealing material containing the curable resin composition and inorganic filler of any one of Claims 5-7.   A semiconductor device which is a cured product of the semiconductor sealing material according to claim 9.   A prepreg that is a semi-cured product of an impregnated base material comprising the curable resin composition according to any one of claims 5 to 7 and a reinforcing base material.   The circuit board which consists of a plate-shaped shaped thing and copper foil of the curable resin composition of any one of Claims 5-7.   A buildup film comprising a cured product of the curable resin composition according to claim 5 and a base film.   A fiber-reinforced composite material comprising the curable resin composition according to any one of claims 5 to 7 and reinforcing fibers.   A fiber-reinforced molded article, which is a cured product of the fiber-reinforced composite material according to claim 14.