JPWO2021039558A1 - Phenol resin, curable resin composition and its cured product - Google Patents

Abstract

Provided are a phenol resin, a composition, and a cured product thereof, which are excellent in fluidity, have an excellent balance of thermal elasticity, low moisture absorption, and dielectric properties of the cured product, and can be suitably used as a semiconductor encapsulating material or the like. It is a reaction product of a monophenol compound and an aromatic carboxylic acid having a hydroxy group, and is represented by an ester compound represented by the following formula (1) and a following formula (2) in GPC measurement. Provided is a phenol resin characterized in that the total peak area with the ketone compound (2) is 70 to 99%. (In the formula, R1 to R17 are independently hydrogen atoms, alkyl groups having 1 to 4 carbon atoms, or alkoxy groups having 1 to 4 carbon atoms.)

Description

The present invention contains a phenol resin that is excellent in fluidity, has an excellent balance of thermal elasticity, low moisture absorption, and dielectric properties of the cured product, and can be suitably used as a semiconductor encapsulating material, and the phenol resin. The present invention relates to a curable resin composition and a cured product thereof.

Phenol resin is used as a curable resin composition in combination with, for example, an epoxy resin, and 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.

Among these various applications, in the field of semiconductor encapsulant materials, technological innovations such as shift to surface mount packages such as BGA and CSP, support for lead-free solder, and elimination of halogen-based flame-retardant materials are being promoted. In order to suppress the warp of the package, the resin material is required to have a low viscosity so that a filler such as silica can be highly filled. In addition, many electronic components have come to be used in the automatic driving and driving support systems of various automobiles in recent years, and the demand for reliability of the encapsulant material and the demand for high-speed communication are increasing. Encapsulating resins are required to have low hygroscopicity, low elastic modulus during heat, low dielectric loss tangent in the high frequency region, and high flame retardancy without halogen.

Dicyclopentadienephenol resin and α-naphthol are esterified with phthalate chloride as a resin that can be suitably used to meet the demands of low moisture absorption, low elasticity during heat, and low dielectric loss tangent in the high frequency region. Examples thereof include active ester resins (see, for example, Patent Document 1). The active ester resin described in Patent Document 1 has improved properties as compared with the case of using a conventional curing agent such as a phenol novolac resin, but does not satisfy the level required in recent years and is highly melted. Due to its viscosity, it is difficult to apply to semiconductor encapsulant materials.

International Publication No. 2018/008410

Therefore, the problem to be solved by the present invention is that phenol is excellent in fluidity, has an excellent balance of thermal elastic modulus, low moisture absorption property, and dielectric property of the cured product, and can be suitably used for semiconductor encapsulation materials and the like. The purpose of the present invention is to provide a resin, a composition, and a cured product thereof.

As a result of diligent studies, the present inventor used a specific phenolic resin which is a reaction product of a monophenol compound having one hydroxy group as a substituent on the aromatic ring and an aromatic carboxylic acid having a hydroxy group. , The present invention has been completed by finding that the above-mentioned problems can be solved.

That is, the present invention is a reaction product of a monophenol compound (A) having one hydroxy group on the aromatic ring and an aromatic carboxylic acid (B) having a hydroxy group and a carboxy group on the aromatic ring. In GPC measurement, the total peak area of the ester compound represented by the following structural formula (1) and the ketone compound (2) represented by the following structural formula (2) is 70 to 99%. The present invention provides a phenol resin, a curable resin composition containing the same, and a cured product thereof.

（式中、Ｒ^１〜Ｒ^１７はそれぞれ独立して水素原子、炭素原子数１〜４のアルキル基又は炭素原子数１〜４のアルコキシ基である。）

(In the formula, R ^{1 to} R ¹⁷ are independently hydrogen atoms, alkyl groups having 1 to 4 carbon atoms, or alkoxy groups having 1 to 4 carbon atoms.)

According to the present invention, a phenol resin having a low viscosity and excellent fluidity, an excellent balance of thermal elastic modulus, low hygroscopicity, and dielectric properties of a cured product, and which can be suitably used as a semiconductor encapsulating material, curable. It is possible to provide a 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.

It is a GPC chart of the phenol resin obtained in Example 1. ^{It is a 13} C-NMR spectrum of the phenol resin obtained in Example 1. 6 is an MS spectrum of the phenol resin obtained in Example 1. It is a GPC chart of the phenol resin obtained in Example 2. ^{It is a 13} C-NMR spectrum of the phenol resin obtained in Example 2. 6 is an MS spectrum of the phenol resin obtained in Example 2. It is a GPC chart of the phenol resin obtained in Example 3. ^{It is a 13} C-NMR spectrum of the phenol resin obtained in Example 3. 6 is an MS spectrum of the phenol resin obtained in Example 3. It is a GPC chart of the phenol resin obtained in Example 4. ^{It is a 13} C-NMR spectrum of the phenol resin obtained in Example 4. 6 is an MS spectrum of the phenol resin obtained in Example 4. 6 is a GPC chart of the phenol resin obtained in Example 5. ^{It is a 13} C-NMR spectrum of the phenol resin obtained in Example 5. 6 is an MS spectrum of the phenol resin obtained in Example 5. 6 is a GPC chart of the phenol resin obtained in Example 6. ^{It is a 13} C-NMR spectrum of the phenol resin obtained in Example 6. 6 is an MS spectrum of the phenol resin obtained in Example 6. 6 is a GPC chart of the phenol resin obtained in Example 7. ¹³ C-NMR spectrum of the phenol resin obtained in Example 7. 6 is an MS spectrum of the phenol resin obtained in Example 7. 6 is a GPC chart of the phenol resin obtained in Example 8. ^{It is a 13} C-NMR spectrum of the phenol resin obtained in Example 8. 6 is an MS spectrum of the phenol resin obtained in Example 8.

<Phenol resin>
Hereinafter, the present invention will be described in detail.
The phenolic resin of the present invention is a reaction product of a monophenol compound (A) having one hydroxy group on the aromatic ring and an aromatic carboxylic acid (B) having a hydroxy group and a carboxy group on the aromatic ring. , The total peak area of the ester compound represented by the following structural formula (1) and the ketone compound (2) represented by the following structural formula (2) in the GPC measurement is 70 to 99%. And.

（式中、Ｒ^１〜Ｒ^１７はそれぞれ独立して水素原子、炭素原子数１〜４のアルキル基又は炭素原子数１〜４のアルコキシ基である。）

(In the formula, R ^{1 to} R ¹⁷ are independently hydrogen atoms, alkyl groups having 1 to 4 carbon atoms, or alkoxy groups having 1 to 4 carbon atoms.)

^{R 1 to} R ¹⁷ in the phenol resin are independently hydrogen atoms, alkyl groups having 1 to 4 carbon atoms, or alkoxy groups having 1 to 4 carbon atoms, and in particular, hydrogen atoms and 1 to 2 carbon atoms. It is preferably an alkyl group, preferably a hydrogen atom or a methyl group.

In the present invention, a monophenol compound (A) having one hydroxy group on the aromatic ring and an aromatic carboxylic acid (B) having a hydroxy group and a carboxy group on the aromatic ring are used as raw materials. However, the hydroxy group in the monophenol compound (A) and the carboxy group in the aromatic carboxylic acid (B) are esterified and form a ketone. In the present invention, since the resin contains a certain amount of an ester compound and a ketone compound in which two aromatic rings are linked, the molecular weight is low and crystallization is unlikely to occur, so that the ester compound and the ketone compound are easy to handle and have a hydroxy group. By coexisting with the ester group, the ester group, which is generally considered to have a slow curing reaction, has a fast-curing property, and can be suitably used as a curable composition. In particular, when the total of these is 70% or more in terms of area% in GPC measurement, the balance between fluidity and curability as a resin is good, and when it is 99% or less, the melting point temperature of the crystal is low. Good handling.

In particular, when the ratio of the ester group to the ketone group in the phenol resin is in the ^{range of 1: 0.01 to 1: 0.20 as measured by 13} C-NMR, the moisture absorption rate is low and the curability is more excellent. .. In particular, when used as a curing agent for epoxy resins, the curing reaction easily proceeds even if a relatively mild catalyst such as triphenylphosphine is used as the curing catalyst, and it is affected by the curing catalyst remaining in the obtained cured product. It also has the characteristic of being difficult. More preferably, the ester group: ketone group is in the range of 1: 0.01 to 1: 0.15.

The total peak area of the ester compound represented by the structural formula (1) and the ketone compound (2) represented by the structural formula (2) in the present invention can be determined by GPC measurement under the following conditions. can.
<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 rate 1.0 ml / min Standard: Based on the measurement manual of the above-mentioned "GPC workstation EcoSEC-WorkStation", the following monodisperse polystyrene having a known molecular weight was used.
(Polystyrene used)
"A-500" manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
"F-1" manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
"F-4" manufactured by Tosoh Corporation
"F-10" manufactured by Tosoh Corporation
"F-20" manufactured by Tosoh Corporation
"F-40" manufactured by Tosoh Corporation
"F-80" manufactured by Tosoh Corporation
"F-128" manufactured by Tosoh Corporation
Sample: A solution obtained by filtering 1.0 mass% of a tetrahydrofuran solution in terms of resin solid content with a microfilter (50 μl).

Further, the ratio of the ester group to the ketone group in the phenol resin in the present invention is the sum of the sum of the peak area integral values between 147 and 154 ppm and the peak area integral between 191-205 ppm in the following ^{13 C-NMR measurement.} It is calculated as the ratio of the total values.

< ¹³ C-NMR measurement conditions>
Equipment: ECA500 manufactured by JEOL Ltd.
Measurement mode: Decoupling with reverse gate Solvent: Deuterated dimethyl sulfoxide Pulse angle: 30 ° pulse Sample concentration: 30 wt%
Accumulation number: 4000 times

The viscosity of the phenolic resin of the present invention is preferably in the range of 0.01 to 5 dPa · s at 150 ° C. from the viewpoint that it can be suitably used as a semiconductor encapsulant. Further, the melting point obtained when measured at a heating rate of 10 ° C./min using a DSC measuring device is preferably in the range of 30 to 180 ° C.

<Phenol resin manufacturing method>
As described above, the phenolic resin of the present invention comprises a monophenol compound (A) having one hydroxy group on the aromatic ring and an aromatic carboxylic acid (B) having a hydroxy group and a carboxy group on the aromatic ring. It is a reactant of.

The monophenol compound (A) having one hydroxy group on the aromatic ring has an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms as a substituent on the aromatic ring. You may. Among these, from the viewpoint of easy availability of raw materials and better curability of the obtained phenol resin, those having a hydrogen atom or an alkyl group having 1 to 2 carbon atoms as a substituent are preferable, and phenol is particularly preferable. , Cresol or xylenol is preferred. These monophenol compounds (A) may be used alone or in combination of two or more.

Further, as the aromatic carboxylic acid (B) having a hydroxy group and a carboxy group on the aromatic ring, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms is substituted on the aromatic ring. It may have as a group. Among these, from the viewpoint of easy availability of raw materials and better curability of the obtained phenol resin, those having a hydrogen atom or an alkyl group having 1 to 2 carbon atoms as a substituent are preferable, particularly p. -Hydroxybenzoic acid, salicylic acid, and m-hydroxybenzoic acid are preferable. These aromatic carboxylic acids (B) may be used alone or in combination of two or more.

Further, other phenol compounds and aromatic carboxylic acids may be used in combination as long as the effects of the present invention are not impaired. Examples of other phenolic compounds include dihydric phenols and trivalent phenols, and examples of other aromatic carboxylic acids include aromatic dicarboxylic acids, their anhydrides, and salicylic acids having an ester structure of carboxylic acids. Examples include methyl. When such other phenol compounds and other aromatic carboxylic acids are used in combination, it is preferable to use them in an amount of 10% by mass or less based on the total mass of the raw material.

The reaction between the monophenol compound (A) having one hydroxy group on the aromatic ring and the aromatic carboxylic acid (B) having a hydroxy group and a carboxy group on the aromatic ring in the present invention is carried out under an acid catalyst. It can be carried out. Specifically, various ones 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, it is preferable to use p-toluenesulfonic acid from the viewpoint of reactivity. The amount of these acid catalysts used varies depending on the type of catalyst, but is within the range of 0.0005 to 5% by mass with respect to the total mass of the monophenol compound (A) and the aromatic carboxylic acid (B). Is preferable.

The ratio of the monophenol compound (A) to the aromatic carboxylic acid (B) can be appropriately adjusted according to the physical properties of the target resin, etc., but it is more excellent in fluidity and is cured as described later. Equivalent ratio of hydroxy group in monophenol compound (A) to carboxy group in aromatic carboxylic acid (B) from the viewpoint that a phenol resin having excellent curability when made into a sex resin composition can be easily obtained. However, it is preferably used in the range of 0.95: 1 to 8: 1, and more preferably in the range of 0.97: 1 to 6: 1.

In addition, this 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, toluene, xylene, methanol, ethanol, propanol, ethyl lactate, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1, 5-Pentane diol, 1,6-hexane diol, 1,7-heptane diol, 1,8-octane diol, 1,9-nonane diol, 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 Examples thereof include 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 15 to 250% by mass, based on the total mass of the monophenol compound (A) and the aromatic carboxylic acid (B). The reaction temperature is usually 40 to 150 ° C., and the reaction time is usually 1 to 24 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, but are not limited to, toluene, methyl ethyl ketone, acetone, methyl isobutyl ketone, n-hexane, methanol, ethanol and the like, 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.

<Curable resin composition>
The phenol resin of the present invention can be made into a curable resin composition by using another compound having a functional group that reacts with a hydroxyl 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.

Other compounds having a functional group that reacts with the hydroxyl group used in the present invention include, for example, a melamine compound, a guanamine compound, and a glycol uryl substituted with at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group. Examples thereof include compounds containing double bonds such as compounds, urea compounds, resole resins, epoxy resins, isocyanate compounds, azide compounds and alkenyl ether groups, acid anhydrides and oxazoline compounds.

The melamine compound is, for example, a compound in which 1 to 6 methylol groups of hexamethylol melamine, hexamethoxymethyl melamine, and hexamethylol melamine are methoxymethylated, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, and methylol of hexamethylol melamine. Examples thereof include compounds in which 1 to 6 groups are asyloxymethylated.

The guanamine compound is, for example, a compound in which 1 to 4 methylol groups of tetramethylol guanamine, tetramethoxymethyl guanamine, tetramethoxymethylbenzoguanamine, and tetramethylol guanamine are methoxymethylated, tetramethoxyethyl guanamine, tetraacyloxyguanamine, and tetra. Examples thereof include compounds in which 1 to 4 methylol groups of methoxyl guanamine are acyloxymethylated.

The glycoluril compound is, for example, 1,3,4,6-tetrakis (methoxymethyl) glycoluril, 1,3,4,6-tetrakis (butoxymethyl) glycoluril, 1,3,4,6-tetrakis (1,3,4,6-tetrakis). Hydroxymethyl) glycol uryl and the like can be mentioned.

Examples of the urea compound include 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetrakis (butoxymethyl) urea and 1,1,3,3-tetrakis (methoxymethyl) urea. Be done.

The resol resin is, for example, an alkaline compound containing phenol, an alkylphenol such as cresol or xylenol, a phenylphenol, a resorcinol, a biphenyl, a bisphenol such as bisphenol A or bisphenol F, a phenolic hydroxyl group-containing compound such as naphthol or dihydroxynaphthalene, and an aldehyde compound. Examples thereof include a polymer obtained by reacting under catalytic conditions.

Examples of the 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, diglycidyloxynaphthalene, naphthol aralkyl type epoxy resin, naphthol- Phenolic co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolak type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenol resin type epoxy resin, biphenyl modified novolac type epoxy resin, 1,1-bis (2,7-diglycidyl) Oxy-1-naphthyl) alkane, naphthylene ether type epoxy resin, triphenylmethane type epoxy resin, phosphorus atom-containing epoxy resin, polyglycidyl ether of cocondensate of phenolic hydroxyl group-containing compound and alkoxy group-containing aromatic compound, etc. Can be mentioned. 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 terms of obtaining a cured product having particularly excellent flame retardancy. A dicyclopentadiene-phenol addition reaction type epoxy resin is preferable in that a cured product having excellent dielectric properties can be obtained.

Examples of the isocyanate compound include tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate and the like.

Examples of the azide compound include 1,1'-biphenyl-4,4'-bis azide, 4,4'-methylidene azide, 4,4'-oxybis azide and the like.

Examples of the compound containing a double bond such as an alkenyl ether group include ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol divinyl ether, 1,4-butanediol divinyl ether, and tetramethylene glycol divinyl ether. , Neopentyl glycol divinyl ether, trimethylolpropantrivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, trimethylol propanetrivinyl ether And so on.

The acid anhydrides include, for example, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride, biphenyltetracarboxylic acid dianhydride, 4,4. Aromatic acid anhydrides such as'-(isopropyridene) diphthalic anhydride, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride; tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride , Alicyclic carboxylic acid anhydrides such as methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride dodecenylsuccinic anhydride, and trialkyltetrahydrophthalic anhydride.

Among these, epoxy resins are particularly preferable because they provide a curable composition that is more excellent in curability and heat resistance in the cured product and has good dielectric properties.

Further, when the epoxy resin is used, a curing agent for epoxy resin may be blended.

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 phenol-based 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 (polyvalent phenolic 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 (polyvalent phenolic hydroxyl group-containing compound in which a phenol nucleus and an alkoxy group-containing aromatic ring are linked with formaldehyde).

When an epoxy resin is used in combination to form a curable resin composition, a curing catalyst can be used in combination. In particular, since the phenol resin of the present invention has excellent curability, a cured product can be obtained without using a strong base catalyst such as dimethylaminopyridine, which is conventionally used when an active ester is used as a curing agent. By using a phosphorus compound such as phenylphosphine or a nitrogen-containing compound, the influence of the residual catalyst in the cured product can be suppressed.

Further, the curable resin composition of the present invention 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, 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 excellent in 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, but 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 and formalin and aniline, reaction product of dihydroxydiphenyl ether and formalin and aniline, reaction product of diaminodiphenyl ether and formalin and phenol, dicyclopentadiene-phenol addition type resin and formalin And aniline reaction products, phenolphthaline, 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 m-valent organic group, 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 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 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, dihydroxybenzophenol, 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 other than the phenol resin of the present invention, an addition polymer resin of an alicyclic diene compound such as dicyclopentadiene and a phenol compound, and a modified novolak resin of a phenolic hydroxyl group-containing compound and an alkoxy group-containing aromatic compound. , Phenol aralkyl resin (Zyroc resin), naphthol aralkyl resin, trimethylolmethane resin, tetraphenylol ethane resin, biphenyl-modified phenol resin, biphenyl-modified naphthol resin, aminotriazine-modified phenol resin, and various vinyl polymers in combination. May be good.

More specifically, the various novolak resins are acid catalysts of 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 (polynorbornene, polycyclodecene, polytetracyclododecene, polynortricyclene, and poly (polynorbornene, polycyclodecene, polytetracyclododecene). Examples thereof include homopolymers of vinyl compounds such as meth) acrylate and copolymers thereof.

When these other resins are used, the blending ratio of the phenol resin of the present invention and the other resin can be arbitrarily set according to the application, but the thermal elasticity and the dielectric property of the cured product exhibited by the present invention can be set arbitrarily. It is preferable that the ratio of the other resin to 100 parts by mass is 0.5 to 100 parts by mass with respect to 100 parts by mass of the phenol resin of the present invention.

Further, when the curable resin composition of the present invention is used in an application requiring high flame retardancy, a non-halogen flame retardant which does not substantially contain a 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. It may be used alone, a plurality of flame retardants of the same system may be used, and flame retardants of different systems 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 blended in the range of 0.1 parts 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 and nonylphenol, and melamines such as melamine, benzoguanamine, acetguanamine and formguanamine and formaldehyde cocondensate, (3) Examples thereof include a mixture of the cocondensate of (2) and phenolic resins such as phenol formaldehyde condensate, and (4) the above-mentioned (2) and (3) further modified with tung oil, isomerized flaxseed 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. And other fillers, additives, etc. are all blended in the range of 0.05 to 10 parts by mass, preferably in the range of 0.1 parts by mass to 5 parts by mass, out of 100 parts by mass of the resin composition. It is more preferable to do so.

When using the nitrogen-based flame retardant, 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-based flame retardant is appropriately selected depending on the type of the silicone-based flame retardant, other components of the resin composition, and the desired degree of flame retardancy. For example, a non-halogen-based 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. Further, 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 oxide includes, 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 includes, for example, Shipley (Boxy Brown Co., Ltd.), 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 boards, 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. High filling of silicon or the like, or molten silica, crystalline silica, alumina, silicon nitride or the like may be used. The filling rate is preferably in the range of 30 parts by mass to 95 parts by mass of the inorganic filler per 100 parts by mass of the curable resin composition. 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. 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, dimethyl formamide, 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. , It is preferable to use the non-volatile content at a ratio 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-bonding 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, a filler and the like 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, the 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. Concavities and convexities are 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 substrate 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 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 at the same time as laminating the circuit board, it is applied to the circuit board. It is important to show 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 the circuit board, it is desirable to fill about 1/2 of the through holes.

As a specific method for producing the above-mentioned build-up 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 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 and the like. 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 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, after peeling off the layers (X) of the resin composition, 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, 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 for 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 may be carried out to produce the material.

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., and in particular, after curing at 50 to 100 ° C. to obtain a tack-free cured product, further , It is preferable to treat at a temperature condition of 120 to 200 ° C.

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 both the moldability and the mechanical strength of the fiber-reinforced plastic member are compatible. 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 for obtaining a fiber-reinforced molded product (a 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. The vacuum bag method, in which the airtightly sealed material is vacuum (decompressed) molded by covering it with a flexible mold that can be used, the 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 in which a prepreg in which reinforcing fibers are impregnated with the varnish is produced by an RTM method in which the varnish is injected into a mating mold, and the prepreg is baked and hardened in 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 rate 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 obtained by filtering 1.0 mass% of a tetrahydrofuran solution in terms of resin solid content 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 dimethyl sulfoxide Pulse angle: 30 ° pulse Sample concentration: 30 wt%
Accumulation number: 4000 times

Example 1
565 g (6 mol) of phenol, 207 g (1.5 mol) of p-hydroxybenzoic acid, p-toluenesulfonic acid dihydration while performing nitrogen gas purging on a flask equipped with a thermometer, a fractional distillation tube, a cooling tube, and a stirrer. 7.7 g of the product and 207 g of toluene were charged. The temperature was raised to 140 ° C. while collecting water with a fractional distillation tube, and the mixture was reacted for 12 hours. After completion of the reaction, 3.4 g of a 49% aqueous sodium hydroxide solution was added to confirm neutralization, 685 g of toluene was added, the mixture was cooled to 80 ° C., and washing with water was repeated 4 times with 207 g of water. Then, the inside of the system was dehydrated by azeotrope, and after microfiltration, the solvent and the unreacted monomer were distilled off under reduced pressure to obtain a phenol resin (1). The melting point of the obtained phenol resin (1) was 175 ° C. The GPC chart of the phenol resin (1) is shown in FIG. 1, the ¹³ C-NMR chart is shown in FIG. 2, and the MS spectrum is shown in FIG. The total peak area of the ester compound represented by the structural formula (1) and the ketone compound (2) represented by the structural formula (2) from GPC was 86%, and the monophenol residue was 1.7%. .. From ¹³ C-NMR, the ratio of ester group: ketone group was 1: 0.06.

Example 2
A phenol resin (2) was obtained in the same manner as in Example 1 except that the phenol was changed to 649 g (6 mol) of orthocresol and the reaction temperature was changed to 150 ° C. The melting point of the obtained phenol resin (2) was 135 ° C. The GPC chart of the phenol resin (2) is shown in FIG. 4, the ¹³ C-NMR chart is shown in FIG. 5, and the MS spectrum is shown in FIG. From GPC, the total peak area of the ester compound represented by the structural formula (1) and the ketone compound (2) represented by the structural formula (2) was 91%, and the monophenol residue was 0.1%. From ¹³ C-NMR, the ratio of ester group: ketone group was 1: 0.05.

Example 3
Phenol resin (3) was obtained in the same manner as in Example 1 except that the phenol was paracresol 649 g (6 mol) and the reaction temperature was changed to 150 ° C. The melting point of the obtained phenol resin (3) was 165 ° C. The GPC chart of the phenol resin (3) is shown in FIG. 7, the ¹³ C-NMR chart is shown in FIG. 8, and the MS spectrum is shown in FIG. From GPC, the total peak area of the ester compound represented by the structural formula (1) and the ketone compound (2) represented by the structural formula (2) was 88%, and the monophenol residue was 6.5%. From ¹³ C-NMR, the ratio of ester group: ketone group was 1: 0.02.

Example 4
A phenol resin (4) was obtained in the same manner as in Example 1 except that the phenol was changed to 649 g (6 mol) of metacresol and the reaction temperature was changed to 150 ° C. The melting point of the obtained phenol resin (4) was 130 ° C. The GPC chart of the phenol resin (4) is shown in FIG. 10, the ¹³ C-NMR chart is shown in FIG. 11, and the MS spectrum is shown in FIG. From GPC, the total peak area of the ester compound represented by the structural formula (1) and the ketone compound (2) represented by the structural formula (2) was 86%, and the monophenol residue was 6.2%. From ¹³ C-NMR, the ratio of ester group: ketone group was 1: 0.10.

Example 5
Phenol resin (5) was obtained in the same manner as in Example 1 except that the phenol was changed to 733 g (6 mol) of 2,6-xylenol and the reaction temperature was changed to 160 ° C. The melting point of the obtained phenol resin (5) was 176 ° C. The GPC chart of the phenol resin (5) is shown in FIG. 13, the ¹³ C-NMR chart is shown in FIG. 14, and the MS spectrum is shown in FIG. From GPC, the total peak area of the ester compound represented by the structural formula (1) and the ketone compound (2) represented by the structural formula (2) was 93%, and the monophenol residue was 0.2%. From ¹³ C-NMR, the ratio of ester group: ketone group was 1: 0.03.

Example 6
Phenol resin (6) was obtained in the same manner as in Example 1 except that the phenol was changed to 733 g (6 mol) of 2,4-xylenol and the reaction temperature was changed to 160 ° C. The melting point of the obtained phenol resin (6) was 155 ° C. The GPC chart of the phenol resin (6) is shown in FIG. 16, the ¹³ C-NMR chart is shown in FIG. 17, and the MS spectrum is shown in FIG. From GPC, the total peak area of the ester compound represented by the structural formula (1) and the ketone compound (2) represented by the structural formula (2) was 97%, and the monophenol residue was 0.1%. From ¹³ C-NMR, the ratio of ester group: ketone group was 1: 0.03.

Example 7
Phenol in the same manner as in Example 1 except that p-hydroxybenzoic acid was changed to 207 g (1.5 mol) of salicylic acid, p-toluenesulfonic acid dihydrate was changed to 15.4 g, and the reaction temperature was changed to 180 ° C. Resin (7) was obtained. The melting point of the obtained phenol resin (7) was 40 ° C. The GPC chart of the phenolic resin (7) is shown in FIG. 19, the ¹³ C-NMR chart is shown in FIG. 20, and the MS spectrum is shown in FIG. From GPC, the total peak area of the ester compound represented by the structural formula (1) and the ketone compound (2) represented by the structural formula (2) was 98%, and the monophenol residue was 0.1%. From ¹³ C-NMR, the ratio of ester group: ketone group was 1: 0.01.

Example 8
Phenol in the same manner as in Example 2 except that p-hydroxybenzoic acid was changed to 207 g (1.5 mol) of salicylic acid, p-toluenesulfonic acid dihydrate was changed to 15.4 g, and the reaction temperature was changed to 180 ° C. Resin (8) was obtained. The melting point of the obtained phenol resin (8) was 83 ° C. The GPC chart of the phenol resin (8) is shown in FIG. 22, the ¹³ C-NMR chart is shown in FIG. 23, and the MS spectrum is shown in FIG. 24. From GPC, the total peak area of the ester compound represented by the structural formula (1) and the ketone compound (2) represented by the structural formula (2) was 97%, and the monophenol residue was 0.1%. From ¹³ C-NMR, the ratio of ester group: ketone group was 1: 0.02.

Examples 9 to 16, Comparative Example 1
A curable resin composition was obtained by blending with the compositions shown in Table 1. This was poured into a mold of 11 cm × 9 cm × 2.4 mm, molded by a press at a temperature of 175 ° C. for 1 hour, and then cured at a temperature of 175 ° C. for 5 hours to prepare a cured product. The elastic modulus at heat, dielectric loss tangent, and hygroscopicity of the obtained cured product were measured. The results are shown at the bottom of Table 1.

The raw materials used to prepare the composition are as follows.
HE100C-15: Phenylaralkyl type phenol resin, hydroxyl group equivalent: 174 g / eq (manufactured by Air Water Inc.)
N-655-EXP-S: Cresol novolac type epoxy resin, epoxy equivalent 201 g / eq (manufactured by DIC Corporation)
・ TPP: Triphenylphosphine

<Measurement of elastic modulus at heat>
The 2.4 mm thick cured product produced above was cut into a size of 5 mm in width and 54 mm in length, and this test piece was cut into a viscoelasticity measuring device (DMA: solid viscoelasticity measuring device "RSAII" manufactured by Leometric Co., Ltd., rectangular tension. Method: Using a frequency of 1 Hz and a heating rate of 3 ° C./min), the storage elastic modulus at 260 ° C. was measured as the thermal elastic modulus.

<Measurement of dielectric loss tangent>
The cured product obtained above was vacuum-dried by heating at 105 ° C. for 2 hours, and then stored in a room at a temperature of 23 ° C. and a humidity of 50% for 24 hours as a test piece. The dielectric loss tangent of the test piece at 1 GHz was measured by the cavity resonance method using a “network analyzer E8632C” manufactured by Agilent Technologies, Inc.

<Measurement of hygroscopicity>
The mass change (wt%) before and after the cured product having a thickness of 2.4 mm produced above was cut into a size of 25 mm in width and 75 mm in length and treated in a constant temperature and humidity chamber at 85 ° C./85% RH for 300 hours. It was measured as a hygroscopicity.

Examples 17 to 24, Comparative Example 2
A composition was prepared by melt-kneading at a temperature of 90 ° C. for 5 minutes using two rolls at the composition ratios shown in Table 2. The obtained composition was evaluated for fluidity (spiral flow) and flame retardancy according to the following.

<Measurement of liquidity>
The curable resin composition was injected into a test mold, and the spiral flow value was measured under the conditions of a temperature of 175 ° C., an injection pressure of 70 kg / cm ^{2, and 300 seconds.}

<Evaluation of flame retardancy>
The curable resin composition was molded by a transfer molding machine at a sample having a width of 12.7 mm, a length of 127 mm, and a thickness of 1.6 mm at 175 ° C. for 5 minutes, and then cured at 175 ° C. for 5 hours to prepare an evaluation sample. .. A combustion test was conducted using the five samples according to the UL-94 test method.
* 1: Maximum combustion time (seconds) for one flame contact
* 2: Total burning time (seconds) of 5 test pieces

The raw materials used to prepare the composition are as follows.
HE100C-15: Phenylaralkyl type phenol resin, hydroxyl group equivalent: 174 g / eq (manufactured by Air Water Inc.)
N-655-EXP-S: Cresol novolac type epoxy resin, epoxy equivalent 201 g / eq (manufactured by DIC Corporation)
・ TPP: Triphenylphosphine ・ Fused silica: Spherical silica "FB-5604" 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.

Claims (16)

It is a reaction product of a monophenol compound (A) having one hydroxy group on the aromatic ring and an aromatic carboxylic acid (B) having a hydroxy group and a carboxy group on the aromatic ring.
In GPC measurement, the total peak area of the ester compound represented by the following structural formula (1) and the ketone compound (2) represented by the following structural formula (2) is 70 to 99%. Phenol resin.

(In the formula, R ^{1 to} R ¹⁷ are independently hydrogen atoms, alkyl groups having 1 to 4 carbon atoms, or alkoxy groups having 1 to 4 carbon atoms.) The phenolic resin according to claim 1, wherein ^{R 1 to} R ¹⁷ in the formulas (1) and (2) are hydrogen atoms or methyl groups. The phenol resin according to claim 1 or 2, wherein the ratio of the ester group to the ketone group in the phenol resin is in the range of 1: 0.01 to 1: 0.20 as the ratio measured by ^{13 C-NMR measurement.} The monophenol compound (A) having one hydroxy group on the aromatic ring is phenol, cresol or xylenol, and the aromatic carboxylic acid (B) having a hydroxy group and a carboxy group on the aromatic ring is monohydroxy. The phenolic resin according to any one of claims 1 to 3, which is a benzoic acid. The phenol resin according to any one of claims 1 to 4, which is a curing agent for an epoxy resin. A curable resin composition containing the phenolic resin according to any one of claims 1 to 4 and a resin having a functional group that reacts with a hydroxyl group as essential components. The curable resin composition according to claim 6, wherein the resin having a functional group that reacts with the hydroxyl group is an epoxy resin. The curable resin composition according to claim 7, further comprising a phosphorus compound and / or a nitrogen-containing compound as a curing catalyst. A cured product of the curable resin composition according to any one of claims 6 to 8. A semiconductor encapsulating material containing the curable resin composition according to any one of claims 6 to 8 and an inorganic filler. A semiconductor device that is a cured product of the semiconductor encapsulating material according to claim 10. A prepreg that is a semi-cured product of an impregnated base material having the curable resin composition according to any one of claims 6 to 8 and a reinforcing base material. A circuit board comprising a plate-shaped excipient of the curable resin composition according to any one of claims 6 to 8 and a copper foil. A build-up film comprising a cured product of the curable resin composition according to any one of claims 6 to 8 and a base film. A fiber-reinforced composite material containing the curable resin composition according to any one of claims 6 to 8 and reinforcing fibers. A fiber-reinforced molded product which is a cured product of the fiber-reinforced composite material according to claim 15.

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