TWI855143B - Phenolic resin, hardening resin composition and hardened product thereof - Google Patents

Abstract

The present invention aims to provide a phenolic resin, a composition, and a cured product thereof which have excellent fluidity and a good balance of elastic modulus when heated, low hygroscopicity, and dielectric properties of the cured product and are suitable for use in semiconductor packaging materials, etc., and provides a phenolic resin which is a reaction product of a monophenol compound and an aromatic carboxylic acid having a hydroxyl group, wherein the total peak area of the ester compound represented by the following formula (1) and the ketone compound (2) represented by the following formula (2) in a GPC measurement is 70 to 99%. (wherein, R ¹ to R ¹⁷ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms).

Description

Phenolic resin, hardening resin composition and hardened product thereof

The present invention relates to a phenolic resin which has excellent fluidity and a well-balanced elastic modulus, low hygroscopicity, and dielectric properties of a cured product when heated and is suitable for use in semiconductor packaging materials, etc., and a curable resin composition containing the phenolic resin and a cured product thereof.

Phenolic resins are combined with epoxy resins to form curable resin compositions. In addition to being used as adhesives, molding materials, coatings, photoresist materials, and developer materials, the obtained cured products have excellent heat resistance and moisture resistance, and are widely used in the electrical and electronic fields such as semiconductor packaging materials and printed circuit board insulation materials.

Among these various uses, in the field of semiconductor packaging materials, the transition to surface mount packages such as BGA and CSP, the response to lead-free solders, and the elimination of halogen flame retardants are being promoted. For resin materials, in order to suppress the warping of the package, low viscosity is required so that fillers such as silica can be highly filled. In addition, in recent years, many electronic components have been installed in various types of automobiles such as automatic driving and driving support systems, and the requirements for the reliability of packaging materials and the corresponding requirements for high-speed communications are also gradually increasing. For encapsulation resins, it is required to have low moisture absorption, low elastic modulus when heated, low dielectric loss tangent in the high frequency region, and high flame retardancy while being halogen-free, which are difficult to achieve.

As for the requirements of low moisture absorption, low elastic modulus when heated, and low dielectric loss tangent in the high-frequency region, suitable resins include active ester resins obtained by esterifying dicyclopentadienol resin and α-naphthol with phthalic acid chloride (for example, see Patent Document 1). The active ester resin described in Patent Document 1 has improved properties when compared with the case of using a conventional hardener such as phenol novolac resin, but it does not meet the requirements of recent years. Due to its high melt viscosity, it is difficult to use it as a semiconductor packaging material. [Prior Art Document] [Patent Document]

[Patent Document 1] International Publication No. 2018/008410

[Problems to be solved by the invention]

Therefore, the problem to be solved by the present invention is to provide a phenolic resin, a composition, and a cured product thereof, wherein the phenolic resin has excellent fluidity, and the cured product has an excellent balance of elastic modulus, low hygroscopicity, and dielectric properties when heated, and can be suitable for use in semiconductor packaging materials, etc. [Means for solving the problem]

As a result of intensive research, the inventors of the present invention have found that the above-mentioned problems can be solved by using a specific phenolic resin which is a reaction product of a monophenol compound having one hydroxyl group as a substituent on an aromatic ring and an aromatic carboxylic acid having a hydroxyl group, thereby completing the present invention.

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

(In the formula, R ¹ to R ¹⁷ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms). [Effects of the Invention]

According to the present invention, a phenolic resin having excellent fluidity at low viscosity, and having an excellent balance of elastic modulus when heated, low hygroscopicity, and dielectric properties of the cured product can be provided, and the phenolic resin, a curable resin composition, a cured product having the above properties, a semiconductor packaging material, a semiconductor device, a prepreg, a circuit board, a build-up film, a build-up substrate, a fiber-reinforced composite material, and a fiber-reinforced molded product can be suitably used in semiconductor packaging materials, etc.

[Form used to implement the invention]

<Phenol resin> The present invention is described in detail below. The phenol resin of the present invention is a reaction product of a monophenol compound (A) having one hydroxyl group on an aromatic ring and an aromatic carboxylic acid (B) having a hydroxyl group and a carboxyl group on an aromatic ring, and is characterized in that 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%.

(wherein, R ¹ to R ¹⁷ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms).

In the aforementioned phenolic resin, R ¹ to R ¹⁷ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and hydrogen atom or an alkyl group having 1 to 2 carbon atoms is particularly preferred, and hydrogen atom or methyl group is particularly preferred.

In the present invention, a monophenol compound (A) having one hydroxyl group on an aromatic ring and an aromatic carboxylic acid (B) having a hydroxyl group and a carboxyl group on an aromatic ring are used as raw materials, but the hydroxyl group in the monophenol compound (A) and the carboxyl group in the aromatic carboxylic acid (B) are esterified to form a ketone. In the present invention, the ester compound and the ketone compound formed by linking two aromatic rings in a certain amount in the resin are easy to handle due to their low molecular weight and difficulty in crystallization. In addition, due to the coexistence of the hydroxyl group and 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 area percentage of these is 70% or more as measured by GPC, the balance between the fluidity and hardening properties of the resin is excellent, and when it is 99% or less, the melting point of the crystal becomes low, and the handling property becomes good.

In particular, if 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 curing property is more excellent. In particular, when used as a curing agent for epoxy resin, even if a relatively mild catalyst such as triphenylphosphine is used as a curing catalyst, the curing reaction is easy to proceed, and it also has the characteristic of being difficult to be affected by the residual curing catalyst in the obtained cured product. The more preferred range is 1:0.01 to 1:0.15 for the ester group:ketone group.

In addition, 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 obtained by GPC measurement using the following conditions. ＜GPC measurement conditions＞ Measurement device: "HLC-8320 GPC" manufactured by Tosoh Co., Ltd. Column: Protective column "HXL-L" manufactured by Tosoh Co., Ltd. ＋"TSK-GEL G2000HXL" manufactured by Tosoh Co., Ltd. ＋"TSK-GEL G2000HXL" manufactured by Tosoh Co., Ltd. ＋"TSK-GEL G3000HXL" manufactured by Tosoh Co., Ltd. ＋"TSK-GEL G4000HXL" manufactured by Tosoh Co., Ltd. Detector: RI (differential refractometer) Data processing: "GPC WorkStation EcoSEC-WorkStation" manufactured by Tosoh Co., Ltd. Measurement conditions: Column temperature 40℃ Development solvent Tetrahydrofuran Flow rate 1.0ml/min Standard: According to the above-mentioned "GPC WorkStation EcoSEC-WorkStation" measurement manual, using the following monodisperse polystyrene with known molecular weight. (Used polystyrene) Tosoh Co., Ltd. "A-500" Tosoh Co., Ltd. "A-1000" Tosoh Co., Ltd. "A-2500" Tosoh Co., Ltd. "A-5000" Tosoh Co., Ltd. "F-1" Tosoh Co., Ltd. "F-2" Tosoh Co., Ltd. "F-4" Tosoh Co., Ltd. "F-10" Tosoh Co., Ltd. "F-20" Tosoh Co., Ltd. "F-40" Tosoh Co., Ltd. "F-80" Tosoh Co., Ltd. "F-128" Sample: 1.0 mass% tetrahydrofuran solution converted to resin solid content, filtered with a microfilter (50μl).

The ratio of the ester group to the ketone group in the phenolic resin ^of the present invention is calculated as the ratio of the total of the peak area integral values between 147 and 154 ppm to the total of the peak area integral values between 191 and 205 ppm in the following 13 C-NMR measurement.

< ¹³ C-NMR measurement conditions > Equipment: ECA500 manufactured by JEOL Ltd. Measurement mode: inverse gated decoupling Solvent: deuterated dimethyl sulfoxide Pulse angle: 30° Pulse sample concentration: 30wt% Accumulated times: 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 of suitability for use as a semiconductor encapsulant. The melting point obtained by measuring at a temperature increase rate of 10°C/min using a DSC measuring device is preferably in the range of 30 to 180°C.

<Method for producing phenolic resin> As mentioned above, the phenolic resin of the present invention is a reaction product of a monophenol compound (A) having one hydroxyl group on the aromatic ring and an aromatic carboxylic acid (B) having a hydroxyl group and a carboxyl group on the aromatic ring.

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

In addition, the aforementioned aromatic carboxylic acid (B) having a hydroxyl group and a carboxyl group on the aromatic ring may have 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. Among these, those having a hydrogen atom or an alkyl group having 1 to 2 carbon atoms as a substituent are preferred from the viewpoint of easy availability of raw materials and better curability of the obtained phenolic resin, and p-hydroxybenzoic acid, salicylic acid, and m-hydroxybenzoic acid are particularly preferred. These aromatic carboxylic acids (B) may be used alone or in combination of two or more.

Furthermore, other phenolic compounds and aromatic carboxylic acids may be used in combination within the scope that does not impair the effect of the present invention. For example, other phenolic compounds include divalent phenols and trivalent phenols, and for other aromatic carboxylic acids, aromatic dicarboxylic acids and their anhydrides, methyl salicylate in which carboxylic acids form ester bonds, etc. In the case of using other phenolic compounds and other aromatic carboxylic acids in combination, it is preferred to use them in an amount of 10% by mass or less of the total mass of the raw materials.

The reaction of the monophenol compound (A) having one hydroxyl group on the aromatic ring and the aromatic carboxylic acid (B) having a hydroxyl group and a carboxyl group on the aromatic ring in the present invention can be carried out under an acid catalyst. Specifically, various catalysts can be used, including organic or inorganic acids such as sulfuric acid, p-toluenesulfonic acid, and oxalic acid; Friedel-Crafts catalysts such as tin chloride, zinc chloride, and ferric chloride, etc., which can be used alone or in combination of two or more. Among these, p-toluenesulfonic acid is preferably used from the viewpoint of reactivity. The amount of the acid catalyst used varies depending on the type of catalyst, but is preferably in the range of 0.0005 to 5% by mass relative to the total mass of the monophenol compound (A) and the aromatic carboxylic acid (B).

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. However, from the viewpoint of easily obtaining a phenolic resin having better fluidity and better curability when prepared into a curable resin composition described later, the equivalent ratio of the hydroxyl group in the monophenol compound (A) to the carboxyl group in the aromatic carboxylic acid (B) 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-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, trimethylene glycol, diethylene glycol, polyethylene glycol, glycerol, 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-di Alkane, 1,4-di Alkane, tetrahydrofuran, ethylene glycol acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, N-methylpyrrolidone, dimethylformamide, dimethyl sulfoxide, etc. These solvents can be used alone or as a mixed solvent of two or more types. The amount of the solvent used is usually 10 to 300 mass%, preferably 15 to 250 mass%, relative to 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 the reaction is completed, the acid catalyst is removed by neutralization, water washing, etc., and then the used solvent and unreacted raw materials are removed as needed under heating and reduced pressure. Purification such as reprecipitation can also be performed as needed. As for the solvent that can be used for reprecipitation, toluene, methyl ethyl ketone, acetone, methyl isobutyl ketone, n-hexane, methanol, ethanol, etc. can be listed, but it is not limited to these, and various solvents can be mixed. Reprecipitation can be applied by the usual method of heating these solvents, dissolving the reaction mixture, cooling, and filtering.

<Curing resin composition> The phenolic resin of the present invention can be used in combination with other compounds having a functional group that reacts with a hydroxyl group to form a curable resin composition. The curable resin composition can be suitably used in various electrical and electronic component applications such as adhesives, coatings, photoresists, printed circuit boards, and semiconductor packaging materials.

Other compounds having a functional group reactive with a hydroxyl group used in the present invention include, for example, melamine compounds substituted with at least one group selected from hydroxymethyl, alkoxymethyl, and acyloxymethyl, guanamine compounds, glycoluril compounds, urea compounds, soluble phenolic resins, epoxy resins, isocyanate compounds, azide compounds, compounds containing double bonds such as alkenyl ether groups, acid anhydrides, Oxazoline compounds, etc.

Examples of the melamine compound include hexahydroxymethylmelamine, hexamethoxymethylmelamine, and compounds in which 1 to 6 hydroxymethyl groups of hexahydroxymethylmelamine are methoxymethylated; hexamethoxyethylmelamine, hexaacyloxymethylmelamine, and compounds in which 1 to 6 hydroxymethyl groups of hexahydroxymethylmelamine are acyloxymethylated.

Examples of the aforementioned guanamine compounds include tetrahydroxymethylguanamine, tetramethoxymethylguanamine, tetramethoxymethylbenzoguanamine, and tetrahydroxymethylguanamine compounds in which 1 to 4 hydroxymethyl groups are methoxymethylated; tetramethoxyethylguanamine, tetraacyloxyguanamine, and tetrahydroxymethylguanamine compounds in which 1 to 4 hydroxymethyl groups are acyloxymethylated.

Examples of the aforementioned glycoluril compounds include 1,3,4,6-tetrakis(methoxymethyl) glycoluril, 1,3,4,6-tetrakis(butoxymethyl) glycoluril, and 1,3,4,6-tetrakis(hydroxymethyl) glycoluril.

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.

The aforementioned soluble phenolic resins include, for example, polymers obtained by reacting alkylphenols such as phenol, cresol, xylenol, etc.; bisphenols such as phenylphenol, resorcinol, biphenyl, bisphenol A or bisphenol F, etc.; phenolic hydroxyl group-containing compounds such as naphthol and dihydroxynaphthalene, etc., with aldehyde compounds under alkaline catalyst conditions.

The epoxy resins mentioned above include, for example, bisphenol A type epoxy resins, bisphenol F type epoxy resins, biphenyl type epoxy resins, tetramethylbiphenyl type epoxy resins, polyhydroxynaphthalene type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, triphenylmethane type epoxy resins, tetraphenylethane type epoxy resins, dicyclopentadiene-phenol addition reaction type epoxy resins, phenol aralkyl type epoxy resins, naphthol novolac type epoxy resins, diglycidyloxynaphthalene, naphthol aralkyl type epoxy resins, phenolic resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenolic resin type epoxy resin, biphenyl modified novolac type epoxy resin, 1,1-bis(2,7-dihydroxipropyloxy-1-naphthyl)alkane, naphthyl ether type epoxy resin, triphenylmethane type epoxy resin, epoxy resin containing phosphorus atom, polyglycidyl ether of co-condensation product of compound containing phenolic hydroxyl group and aromatic compound containing alkoxy group, etc. Among these epoxy resins, tetramethylbiphenyl type epoxy resins, biphenyl aralkyl type epoxy resins, polyhydroxynaphthalene type epoxy resins, and novolac type epoxy resins are preferably used from the viewpoint of obtaining a cured product having particularly excellent flame retardancy, and dicyclopentadiene-phenol addition reaction type epoxy resins are preferably used from the viewpoint of obtaining a cured product having excellent dielectric properties.

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

Examples of the aforementioned bis-nitride compounds include 1,1'-biphenyl-4,4'-bis-nitride, 4,4'-methylene bis-nitride, and 4,4'-oxybis-nitride.

Examples of the aforementioned double-bonded compounds containing alkenyl ether groups include ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propylene glycol divinyl ether, 1,4-butylene glycol divinyl ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, trihydroxymethylpropane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, and trihydroxymethylpropane trivinyl ether.

Examples of the acid anhydrides include aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride, pyrophyllite anhydride, 3,3',4,4'-diphenyl ketone tetracarboxylic anhydride, biphenyltetracarboxylic anhydride, 4,4'-(isopropylidene)diphthalic anhydride, and 4,4'-(hexafluoroisopropylidene)diphthalic anhydride; and alicyclic carboxylic acid anhydrides such as tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, dodecenylsuccinic anhydride, and trialkyltetrahydrophthalic anhydride.

Among these, epoxy resin is particularly preferred because it has excellent curability, heat resistance of the cured product, and can form a curable composition with good dielectric properties.

Furthermore, when the aforementioned epoxy resin is used, a hardener for epoxy resin may be mixed therein.

As the hardener that can be used here, for example, there can be cited various well-known hardeners for epoxy resins such as amine compounds, amide compounds, acid anhydride compounds, and phenol compounds.

Specifically, as amine compounds, there can be listed diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF ₃ -amine complex, guanidine derivatives, etc., and as amide compounds, there can be listed polyamide resins synthesized from dicyandiamide, a dimer of perilla oil acid and ethylenediamine, etc. As anhydride compounds, there can be listed phthalic anhydride, trimellitic anhydride, pyrophyllitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc. As for the phenolic compounds, there can be mentioned phenol novolac resins, cresol novolac resins, aromatic hydrocarbon formaldehyde resin modified phenol resins, dicyclopentadienol addition type resins, phenol aralkyl resins (Xylok resins), naphthol aralkyl resins, triphenylol methane resins, tetraphenylol ethane resins, naphthol novolac resins, naphthol-phenol co-phenol novolac resins, naphthol-cresol co-phenol novolac resins, biphenyl modified phenol resins (compounds containing polyvalent phenolic hydroxyl groups connected to a phenol nucleus by a dimethylene group), biphenyl modified naphthol resins (polyvalent naphthol compounds connected to a phenol nucleus by a dimethylene group), aminotriphenylene glycol resins, and phenolic compounds. Compounds containing polyvalent phenolic hydroxyl groups, such as modified phenolic resins (melamine, compounds containing polyvalent phenolic hydroxyl groups linked to a phenolic nucleus by benzoguanamine, etc.), and aromatic ring-modified novolac resins containing alkoxy groups (compounds containing polyvalent phenolic hydroxyl groups linked to a phenolic nucleus by formaldehyde and an aromatic ring containing alkoxy groups).

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

Furthermore, the curable resin composition of the present invention may also be used in combination with other thermosetting resins.

As for other thermosetting resins, for example, cyanate resins, benzoic acid resins, Structured resins, maleimide compounds, active ester resins, vinyl benzyl compounds, acrylic compounds, copolymers of styrene and maleic anhydride, etc. When other thermosetting resins are used in combination, the amount used is not particularly limited as long as it does not hinder the effect of the present invention, but is preferably in the range of 1 to 50 parts by weight per 100 parts by weight of the curable resin composition.

As for the aforementioned cyanate resin, for example, bisphenol A type cyanate resin, bisphenol F type cyanate resin, bisphenol E type cyanate resin, bisphenol S type cyanate resin, bisphenol thioether type cyanate resin, phenylene ether type cyanate resin, naphthylene ether type cyanate resin, biphenyl type cyanate resin, tetramethylbiphenyl type cyanate resin, polyhydroxynaphthalene type cyanate resin, phenol novolac type cyanate resin, cresol novolac type cyanate resin, triphenylmethane type cyanate resin, The cyanate ester resins include cyanate ester resins of the type described herein, such as cyanate ester resins of the type described herein, tetraphenylethane cyanate ester resins, dicyclopentadiene-phenol addition reaction cyanate ester resins, phenol aralkyl cyanate ester resins, naphthol novolac cyanate ester resins, naphthol aralkyl cyanate ester resins, naphthol-phenol co-phenol novolac cyanate ester resins, naphthol-cresol co-phenol novolac cyanate ester resins, aromatic hydrocarbon formaldehyde resin-modified phenol resin-type cyanate ester resins, biphenyl-modified novolac cyanate ester resins, anthracene-type cyanate ester resins, etc. These may be used alone or in combination of two or more.

Among these cyanate resins, bisphenol A type cyanate resin, bisphenol F type cyanate resin, bisphenol E type cyanate resin, polyhydroxynaphthalene type cyanate resin, naphthyl ether type cyanate resin, and novolac type cyanate resin are particularly preferred from the viewpoint of obtaining a cured product having excellent heat resistance. From the viewpoint of obtaining a cured product having excellent dielectric properties, dicyclopentadiene-phenol addition reaction type cyanate resin is preferred.

Benzo The structural resin is not particularly limited, but examples thereof include: the reaction product of bisphenol F with formalin and aniline (Fa-type benzo Resin), diaminodiphenylmethane, formalin and phenol (Pd-type benzo Resin), reaction products of bisphenol A with formalin and aniline, reaction products of dihydroxydiphenyl ether with formalin and aniline, reaction products of diaminodiphenyl ether with formalin and phenol, reaction products of dicyclopentadiene-phenol addition type resin with formalin and aniline, reaction products of phenolphthalein with formalin and aniline, reaction products of diphenyl sulfide with formalin and aniline, etc. 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).

(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 greater than or equal to 1.)

(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 repeated units of 0 to 10.)

(wherein 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 repeated units of 0 to 10.) These may be used alone or in combination of two or more.

Although not particularly limited, the active ester resin is preferably a compound having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxylamine esters, and esters of heterocyclic hydroxyl compounds. The active ester resin is preferably obtained by a condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxyl 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 its halides and a hydroxyl compound is preferred, and an active ester resin obtained from a carboxylic acid compound or its halides and a phenol compound and/or a naphthol compound is 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, pyrophyllic acid, and the like, or halides thereof. As the phenolic compound or naphthol compound, hydroquinone, resorcinol, 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, dihydroxydiphenyl ketone, trihydroxydiphenyl ketone, tetrahydroxydiphenyl ketone, phloroglucin, benzenetriol, dicyclopentadiene-phenol addition resin, etc. can be listed.

Specifically, preferred active ester resins include active ester resins containing a dicyclopentadiene-phenol addition structure, active ester resins containing a naphthalene structure, active ester resins that are acetylated products of phenol novolacs, active ester resins that are benzoylated products of phenol novolacs, and the like. Among them, active ester resins containing a dicyclopentadiene-phenol addition structure and active ester resins containing a naphthalene structure are more preferred from the viewpoint of excellent improvement in the so-called peel strength. More specifically, the active ester resin containing a dicyclopentadiene-phenol addition structure includes compounds represented by the following general formula (iv).

However, in formula (iv), R is phenyl or naphthyl, u is 0 or 1, and n is 0.05 to 2.5 as the average of the repeating units. In addition, 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 naphthyl, u is preferably 0, and n is preferably 0.25 to 1.5.

Furthermore, various novolac resins other than the phenolic resins of the present invention, addition polymerization resins of alicyclic diene compounds such as dicyclopentadiene and phenolic compounds, modified novolac resins of compounds containing phenolic hydroxyl groups and aromatic compounds containing alkoxy groups, phenol aralkyl resins (Xylok resins), naphthol aralkyl resins, trihydroxymethylmethane resins, tetraphenol ethane resins, biphenyl modified phenol resins, biphenyl modified naphthol resins, aminotris(2-hydroxy- ... Modified phenolic resins and various vinyl polymers.

More specifically, the aforementioned various novolac resins include polymers obtained by reacting phenol, phenylphenol, resorcinol, biphenyl, bisphenol A, bisphenol F and other bisphenols, naphthol, dihydroxynaphthalene and other phenolic hydroxyl group-containing compounds with aldehyde compounds under acid-catalyzed conditions.

Examples of the aforementioned vinyl polymers include homopolymers of vinyl compounds such as polyhydroxystyrene, polystyrene, polyvinylnaphthalene, polyvinylanthracene, polyvinylcarbazole, polyindene, polyacenaphthene, polynorbornene, polycyclodecene, polytetracyclododecene, polynortricyclene, poly(meth)acrylate, and the like, or copolymers thereof.

When using these other resins, the blending ratio of the phenolic resin of the present invention and other resins can be arbitrarily set according to the application, but the balancing effect of the elastic modulus when heated, the dielectric properties of the cured product, etc. exerted by the present invention is more significantly manifested, and it is preferred that the ratio of other resins is 0.5 to 100 parts by mass relative to 100 parts by mass of the phenolic resin of the present invention.

Furthermore, when the curable resin composition of the present invention is used for applications requiring high flame retardancy, a non-halogen flame retardant containing substantially no halogen atoms may be blended.

The aforementioned non-halogen flame retardants include, for example, phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, inorganic flame retardants, organic metal salt flame retardants, etc. There is no restriction on their use. They can be used alone or in combination. In addition, it is also possible to use flame retardants of different series in combination.

The phosphorus-based flame retardant may be either inorganic or organic. Examples of the inorganic compounds include red phosphorus, ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate, and inorganic nitrogen-containing phosphorus compounds such as phosphamide.

In addition, the red phosphorus is preferably subjected to a surface treatment for the purpose of preventing hydrolysis, etc., and the surface treatment method includes, for example: (i) a coating treatment with an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, bismuth oxide, bismuth hydroxide, bismuth nitrate, or a mixture thereof; (ii) a coating treatment with hydrogen; (iii) a method of coating a film of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, etc. with a thermosetting resin such as a phenolic resin; (iv) a method of double coating a film of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, etc. with a thermosetting resin such as a phenolic resin, etc.

Examples of the aforementioned organophosphorus compounds include, in addition to general organophosphorus compounds such as phosphate compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, and organic nitrogen-phosphorus compounds, cyclic organophosphorus compounds such as 9,10-dihydro-9-oxo-10-phosphophanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-10H-9-oxo-10-phosphophanthrene-10-oxide, and 10-(2,7-dihydroxynaphthyl)-10H-9-oxo-10-phosphophanthrene-10-oxide, and derivatives thereof obtained by reacting the compounds with epoxy resins or phenol resins.

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

Furthermore, when the phosphorus-based flame retardant is used, the phosphorus-based flame retardant may be used in combination with hydrotalcite, magnesium hydroxide, boron compounds, zirconium oxide, black dye, calcium carbonate, zeolite, zinc molybdate, activated carbon, and the like.

The nitrogen flame retardant mentioned above can be exemplified by: Compounds, cyanuric acid compounds, isocyanuric acid compounds, thiophene etc., preferably three Compounds, cyanuric acid compounds, isocyanuric acid compounds.

The above three Compounds such as melamine, acetoguanamine, benzoguanamine, melon, melam, succinoguanamine, ethylenedimelamine, polyphosphate melamine, triguanamine, etc., and also include: (1) melamine sulfate, melem sulfate, melam sulfate, etc. Compounds; (2) condensation products of phenols such as phenol, cresol, xylenol, butylphenol, nonylphenol, etc., and melamines such as melamine, benzoguanamine, acetoguanamine, acetoguanamine (formguanamine), etc., and formaldehyde; (3) mixtures of condensation products of the above (2) and phenolic resins such as phenol formaldehyde condensation products; (4) the above (2) and (3) further modified with tung oil, isomerized linseed oil, etc.

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

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

Furthermore, when using the aforementioned nitrogen-based flame retardant, metal hydroxides, molybdenum compounds, etc. may also be used in combination.

The aforementioned polysilicone flame retardant can be used without particular limitation as long as it is an organic compound containing silicon atoms, and examples thereof include polysilicone oil, polysilicone rubber, polysilicone resin, etc. The amount of the aforementioned polysilicone flame retardant to be blended is appropriately selected according to the type of polysilicone flame retardant, other components of the resin composition, and the desired degree of flame retardancy, but for example, it is preferably blended in a range of 0.05 to 20 parts by mass in 100 parts by mass of the resin composition including the blended non-halogen flame retardant and other fillers or additives. Furthermore, when using the aforementioned polysilicone flame retardant, molybdenum compounds, aluminum oxide, etc. may also 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 hydroxides include aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, zirconium hydroxide, and the like.

Examples of the aforementioned metal oxides 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, chromium oxide, nickel oxide, copper oxide, and tungsten oxide.

The aforementioned metal carbonate compounds include, for example, zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, alkaline magnesium carbonate, aluminum carbonate, iron carbonate, cobalt carbonate, titanium carbonate, and the like.

The aforementioned metal powder may include, for example, aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper, tungsten, tin, etc.

The aforementioned boron compound may include, for example, zinc borate, zinc metaborate, barium metaborate, boric acid, borax, and the like.

The aforementioned low melting point glass includes, for example, glassy compounds such as Ceepree (Bokusui-Brown), hydrated glass SiO2- _MgO - _H2O , PbO- _{B2O3 series} , ZnO- _P2O5 - _MgO series, _P2O5 - _B2O3 -PbO- _{MgO series} , P-Sn-OF series, PbO- _{V2O5 - TeO2} series, _Al2O3 - _H2O series, and lead _borosilicate series.

The amount of the inorganic flame retardant blended is appropriately selected according to the type of the inorganic flame retardant, other components of the resin composition, and the desired degree of flame retardancy. For example, the amount of the inorganic flame retardant blended is preferably in the range of 0.05 to 20 parts by mass, and more preferably in the range of 0.5 to 15 parts by mass, based on 100 parts by mass of the total resin composition including the non-halogen flame retardant and other fillers or additives.

Examples of the aforementioned organic metal salt flame retardants include ferrocene, acetylacetonate metal complexes, organic metal carbonyl compounds, organic cobalt chloride compounds, organic sulfonic acid metal salts, and compounds in which metal atoms are ionically bonded or coordinatedly bonded with aromatic compounds or heterocyclic compounds.

The amount of the organic metal salt flame retardant to be blended is appropriately selected depending on the type of the organic metal salt flame retardant, other components of the resin composition, and the desired degree of flame retardancy. However, for example, it is preferably blended in a range of 0.005 to 10 parts by mass based on 100 parts by mass of the resin composition including the non-halogen flame retardant and other fillers or additives.

The curable resin composition of the present invention can be blended with an inorganic filler as needed. Examples of the aforementioned inorganic filler include molten silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, and the like. In the case of particularly increasing the blending amount of the aforementioned inorganic filler, it is preferred to use molten silica. The aforementioned molten silica can be used in either a crushed or spherical form, but in order to increase the blending amount of molten silica and suppress the increase in the melt viscosity of the molding material, it is preferred to mainly use spherical forms. Furthermore, in order to increase the blending amount of spherical silica, it is preferred to appropriately adjust the particle size distribution of the spherical silica. In consideration of flame retardancy, the filling rate is preferably high, and is particularly preferably 20% by mass or more relative to the total mass of the curable resin composition. In addition, when used in conductive pastes, conductive fillers such as silver powder and copper powder can be used.

The curable resin composition of the present invention may be added with various admixtures such as other silane coupling agents, release agents, pigments, emulsifiers, etc. as needed.

<Application of the curable resin composition> The curable resin composition of the present invention can be applied to semiconductor packaging materials, semiconductor devices, prepregs, printed circuit boards, build-up boards, build-up films, fiber-reinforced composites, fiber-reinforced resin molded products, conductive pastes, etc.

1. Semiconductor packaging material As for the method of obtaining a semiconductor packaging material from the curable resin composition of the present invention, there can be listed a method in which the curable resin composition and an inorganic filler are melt-mixed using an extruder, a kneader, a roller, etc. until they are uniform. At that time, molten silica was generally used as an inorganic filler, but when used as a high thermal conductivity semiconductor packaging material for power transistors and power ICs, it is preferable to use a high filler such as crystalline silica, alumina, silicon nitride, etc., which has a higher thermal conductivity than molten silica, or molten silica, crystalline silica, alumina, silicon nitride, etc. The filling rate is preferably 30 to 95 parts by mass of the inorganic filler per 100 parts by mass of the curable resin composition, and in order to improve flame retardancy, moisture resistance, and solder crack resistance and reduce the linear 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 for the method of obtaining a semiconductor device from the curable resin composition of the present invention, there can be cited a method of casting the aforementioned semiconductor packaging material, or using a transfer molding machine, injection molding machine, etc. to form it, and then heating it at 50 to 200°C for 2 to 10 hours.

3. Prepreg As for the method of obtaining the prepreg from the curable resin composition of the present invention, there can be cited a method in which the curable resin composition which is varnished by mixing an organic solvent is impregnated into a reinforcing substrate (paper, glass cloth, glass non-woven fabric, polyaramide paper, polyaramide cloth, glass felt, glass fiber yarn cloth, etc.), and then the prepreg is heated at a heating temperature of preferably 50 to 170°C depending on the type of solvent used. The mass ratio of the resin composition to the reinforcing substrate used at this time is not particularly limited, but it is generally preferred to prepare the prepreg so that the resin component in the prepreg is 20% to 60% by mass.

As for the organic solvent used here, methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellulose, ethyl diglycol acetate, propylene glycol monomethyl ether acetate, etc. can be listed. The selection and appropriate amount of use can be appropriately selected according to the purpose. However, for example, in the case of further manufacturing a printed circuit board from the prepreg as described below, it is preferred to use a polar solvent having a boiling point of 160°C or less such as methyl ethyl ketone, acetone, and dimethylformamide, and it is preferred to use it at a ratio of 40% to 80% by mass of the non-volatile component.

4. Printed circuit board As for the method of obtaining a printed circuit board from the curable resin composition of the present invention, there can be cited a method of laminating the aforementioned prepreg by a conventional method, appropriately stacking copper foil, and heat-pressing at 170-300°C for 10 minutes to 3 hours under a pressure of 1-10 MPa.

5. Stacking substrate As for the method of obtaining a stacking substrate from the curable resin composition of the present invention, the method through steps 1 to 3 can be listed. In step 1, first, the aforementioned curable resin composition appropriately mixed with rubber, filler, etc. is applied to the circuit substrate formed with the circuit by spray coating method, curtain coating method, etc., and then hardened. In step 2, as needed, after opening the designated through hole portion on the circuit substrate coated with the curable resin composition, it is treated with a roughening agent, and its surface is washed with hot water to form bumps on the aforementioned substrate, and a metal such as copper is plated. In step 3, the operations of steps 1 and 2 are repeated in sequence as needed, and the resin insulation layer and the conductor layer of the specified circuit pattern are alternately stacked to form a stacking substrate. In addition, in the aforementioned step, it is preferable to open the through hole portion after the formation of the outermost resin insulation layer. In addition, the stacking substrate of the present invention can also be made by heating and pressing the copper foil with the resin attached on the copper foil to form a wiring substrate for forming a circuit at 170 to 300°C to form a rough surface, omitting the step of plating treatment, and making a stacking substrate.

6. Deposited film As for the method of obtaining a deposited film from the curable resin composition of the present invention, for example, a method of coating the curable resin composition on a support film, drying it, and forming a resin composition layer on the support film can be cited. When the curable resin composition of the present invention is used for a deposited film, the film is softened by the temperature conditions of the deposition in the vacuum deposition method (usually 70°C to 140°C), and at the same time as the deposition of the circuit substrate, it is important to show the fluidity (resin flow) that allows the resin to fill the through holes or through-holes in the circuit substrate. In order to exhibit such characteristics, it is preferred to mix the aforementioned components.

Here, the diameter of the through hole of the circuit board is usually 0.1-0.5mm, and the depth is usually 0.1-1.2mm. It is usually better to fill the resin within this range. In addition, in the case of multilayer circuit board on both sides, it is expected to fill about 1/2 of the through hole.

As for the specific method of manufacturing the aforementioned stacked film, there can be cited a method in which a resin composition is prepared by mixing an organic solvent to form a varnish, the aforementioned composition is applied on the surface of a support film (Y), and the organic solvent is dried by heating or spraying hot air to form a layer (X) of the resin composition.

As the organic solvent used here, it is preferred to use ketones such as acetone, methyl ethyl ketone, cyclohexanone, etc.; acetates such as ethyl acetate, butyl acetate, cellosol acetate, propylene glycol monomethyl ether acetate, carbitol acetate, etc.; carbitols such as cellosol, butyl carbitol, etc.; aromatic hydrocarbons such as toluene, xylene, etc.; dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc., and it is preferred to use them at a ratio of 30% by mass to 60% by mass of non-volatile components.

In addition, the thickness of the resin composition layer (X) formed is usually necessary to be greater than the thickness of the conductor layer. The thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, so the thickness of the resin composition layer is preferably 10 to 100 μm. In addition, the resin composition layer (X) in the present invention can be protected by a protective film described later. By protecting with a protective film, dust and the like can be prevented from adhering to or damaging the surface of the resin composition layer.

The aforementioned support film and protective film can be polyolefins such as polyethylene, polypropylene, polyvinyl chloride, polyesters such as polyethylene terephthalate (hereinafter sometimes referred to as "PET"), polyethylene naphthalate, polycarbonate, polyimide, and further can be release paper, copper foil, aluminum foil, etc. In addition, the support film and protective film can also be subjected to release treatment in addition to matte treatment and corona treatment. The thickness of the support film is not particularly limited, but is usually 10 to 150 μm, preferably used in the range of 25 to 50 μm. In addition, the thickness of the protective film is preferably set to 1 to 40 μm.

The aforementioned support film (Y) is peeled off after being laminated on the circuit substrate or after being cured by heat to form an insulating layer. If the support film (Y) is peeled off after the resin composition layer constituting the deposited film is cured by heat, it is possible to prevent dust etc. from being attached during the curing step and peeling off after curing. Usually, the support film is subjected to a release treatment in advance.

Furthermore, a multi-layer printed circuit board can be manufactured from the stacked film obtained as described above. For example, in the case where the layer (X) of the resin composition is protected by a protective film, after peeling off the layer (X) of the resin composition, the layer (X) of the resin composition is directly contacted with the circuit board, and then laminated on one or both sides of the circuit board by, for example, a vacuum lamination method. The lamination method can be a batch method or a continuous roll method. Furthermore, if necessary, the stacked film and the circuit board can be preheated (preheated) as needed before lamination. The lamination conditions are preferably a compressive temperature (lamination temperature) of 70 to 140°C, a compressive pressure of 1 to 11 kgf/cm ² (9.8×10 ⁴ to 107.9×10 ⁴ N/m ² ), and lamination is preferably performed under reduced pressure with the air pressure being 20 mmHg (26.7 hPa) or less.

7. Fiber-reinforced composite material As for the method of obtaining a fiber-reinforced composite material (a sheet-shaped intermediate material in which a resin is impregnated with reinforcing fibers) from the resin composition of the present invention, there can be cited a method of uniformly mixing the components constituting the resin composition to prepare a varnish, then impregnating the varnish into a reinforcing matrix composed of reinforcing fibers, and then manufacturing the composite material by polymerization reaction.

Specifically, the curing temperature during the polymerization reaction is preferably in the range of 50 to 250°C. In particular, it is preferred to cure the material at 50 to 100°C to obtain a tack-free cured product and then further treat the product at 120 to 200°C.

Here, the reinforcing fiber may be twisted yarn, untwisted yarn, or untwisted yarn. However, from the viewpoint of having both formability and mechanical strength of fiber-reinforced plastic components, untwisted yarn and untwisted yarn are Better. Furthermore, as the form of reinforcing fibers, those with fiber directions aligned in one direction or fabrics can be used. The fabric can be freely selected from plain weave, satin weave, etc. according to the location and purpose of use. Specifically, since they are excellent in mechanical strength and durability, carbon fiber, glass fiber, aramid fiber, boron fiber, alumina fiber, silicon carbide fiber, etc. can be used, and two or more of these can also be used in combination. Among these, carbon fiber is particularly preferred because of its excellent strength in molded products. Various types of carbon fiber can be used, such as polyacrylonitrile, asphalt, and rayon. The amount of the reinforcing fiber used in the fiber-reinforced composite material formed by impregnating the varnish into the reinforcing matrix formed by the reinforcing fiber is preferably The volume content of the reinforcing fibers is in the range of 40% to 85%.

8. Fiber-reinforced resin molded product As for the method of obtaining a fiber-reinforced molded product (a molded product in which a sheet-like member of a resin impregnated with reinforcing fiber is hardened) from the resin composition of the present invention, there are exemplified the following methods: coating a fiber skeleton on a mold, applying multiple layers of the aforementioned varnish by hand, and then applying a plurality of layers of the varnish to the mold. The invention relates to a method of forming a prepreg made of reinforcing fibers by a lay-up method or a spray-up method; a method of forming a base material made of reinforcing fibers by impregnating the base material with a varnish using either a male or female mold, stacking the base material and forming the base material by vacuum (reduced pressure) by covering the base material with a flexible mold that can apply pressure to the molded product; an SMC pressing method in which a sheet of varnish containing reinforcing fibers is pre-formed by compressing the sheet with a mold; an RTM method in which the varnish is injected into a matching mold filled with fibers to produce a prepreg made of reinforcing fibers impregnated with the varnish and the prepreg is sintered in a large-scale high-pressure autoclave, etc. In addition, the fiber-reinforced resin molded product obtained above is a molded product having a hardened product of a reinforcing fiber and a resin composition. Specifically, the amount of reinforcing fiber in the fiber-reinforced molded product is preferably in the range of 40 mass % to 70 mass %, and from the point of view of strength, it is particularly preferably in the range of 50 mass % to 70 mass %.

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

Next, the present invention will be described in detail by way of Examples and Comparative Examples. In the following, "parts" and "%" are based on mass unless otherwise specified. In addition, GPC and ¹³ C-NMR spectra were measured under the following conditions.

<GPC measurement conditions> Measurement device: "HLC-8320 GPC" manufactured by Tosoh Co., Ltd. Column: Protective column "HXL-L" manufactured by Tosoh Co., Ltd. + "TSK-GEL G2000HXL" manufactured by Tosoh Co., Ltd. + "TSK-GEL G2000HXL" manufactured by Tosoh Co., Ltd. + "TSK-GEL G3000HXL" manufactured by Tosoh Co., Ltd. + "TSK-GEL G4000HXL" manufactured by Tosoh Co., Ltd. Detector: RI (differential refractometer) Data processing: "GPC WorkStation EcoSEC-WorkStation" manufactured by Tosoh Co., Ltd. Measurement conditions: Column temperature     40℃ Development solvent    Tetrahydrofuran Flow rate          1.0ml/min Standard: According to the above-mentioned "GPC WorkStation EcoSEC-WorkStation" measurement manual, using the following monodisperse polystyrene with known molecular weight. (Used polystyrene) Tosoh Co., Ltd. "A-500" Tosoh Co., Ltd. "A-1000" Tosoh Co., Ltd. "A-2500" Tosoh Co., Ltd. "A-5000" Tosoh Co., Ltd. "F-1" Tosoh Co., Ltd. "F-2" Tosoh Co., Ltd. "F-4" Tosoh Co., Ltd. "F-10" Tosoh Co., Ltd. "F-20" Tosoh Co., Ltd. "F-40" Tosoh Co., Ltd. "F-80" Tosoh Co., Ltd. "F-128" Sample: 1.0 mass% tetrahydrofuran solution converted to resin solid content, filtered with a microfilter (50μl).

< ¹³ C-NMR measurement conditions> Apparatus: AL-400 manufactured by JEOL Ltd. Measurement mode: reverse gate decoupling Solvent: deuterated dimethyl sulfoxide Pulse angle: 30° Pulse sample concentration: 30wt% Accumulated times: 4000 times

Example 1 In a flask equipped with a thermometer, a distillation tube, a cooling tube, and a stirrer, 565 g (6 mol) of phenol, 207 g (1.5 mol) of p-hydroxybenzoic acid, 7.7 g of p-toluenesulfonic acid dihydrate, and 207 g of toluene were fed while nitrogen was applied for purging. The temperature was raised to 140°C while water was collected with a distillation tube, and the mixture was reacted for 12 hours. After the reaction was completed, 3.4 g of a 49% aqueous sodium hydroxide solution was added and neutralization was confirmed. 685 g of toluene was added and the mixture was cooled to 80°C. The mixture was washed with 207 g of water four times. The system was then dehydrated by azeotropy, and after precision filtration, the solvent and unreacted monomers were distilled off under reduced pressure to obtain phenol resin (1). The melting point of the obtained phenolic resin (1) is 175°C. The GPC chart of the phenolic resin (1) is shown in FIG1 , the ¹³ C-NMR chart is shown in FIG2 , and the MS spectrum is shown in FIG3 . 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) is 86%, and the monophenol residue is 1.7%. In addition, from ¹³ C-NMR, the ratio of ester group: ketone group is 1:0.06.

Example 2 The same procedure as in Example 1 was followed except that phenol was replaced with 649 g (6 mol) of o-cresol and the reaction temperature was changed to 150°C to obtain phenol resin (2). The melting point of the obtained phenol resin (2) was 135°C. The GPC chart of the phenol resin (2) is shown in FIG4 , the ¹³ C-NMR chart is shown in FIG5 , and the MS spectrum is shown in FIG6 . 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%. Furthermore, from ¹³ C-NMR, the ratio of ester group:ketone group was 1:0.05.

Example 3 The same procedure as in Example 1 was followed except that phenol was replaced with 649 g (6 mol) of p-cresol and the reaction temperature was changed to 150°C to obtain phenol resin (3). The melting point of the obtained phenol resin (3) was 165°C. The GPC chart of the phenol resin (3) is shown in FIG7 , the ¹³ C-NMR chart is shown in FIG8 , and the MS spectrum is shown in FIG9 . 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%. Furthermore, from ¹³ C-NMR, the ratio of ester group:ketone group was 1:0.02.

Example 4 The same procedure as in Example 1 was followed except that phenol was replaced with 649 g (6 mol) of m-cresol and the reaction temperature was changed to 150°C to obtain phenol resin (4). The melting point of the obtained phenol resin (4) was 130°C. The GPC chart of the phenol resin (4) is shown in FIG10 , the ¹³ C-NMR chart is shown in FIG11 , and the MS spectrum is shown in FIG12 . 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%. Furthermore, from ¹³ C-NMR, the ratio of ester group:ketone group was 1:0.10.

Example 5 The same procedure as in Example 1 was followed except that phenol was replaced with 733 g (6 mol) of 2,6-dimethylphenol and the reaction temperature was changed to 160°C to obtain phenol resin (5). The melting point of the obtained phenol resin (5) was 176°C. The GPC chart of the phenol resin (5) is shown in FIG13 , the ¹³ C-NMR chart is shown in FIG14 , and the MS spectrum is shown in FIG15 . 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%. Furthermore, from ¹³ C-NMR, the ratio of ester group:ketone group was 1:0.03.

Example 6 Except that phenol was changed to 733 g (6 mol) of 2,4-dimethylphenol and the reaction temperature was changed to 160°C, the same procedure as in Example 1 was followed to obtain phenol resin (6). The melting point of the obtained phenol resin (6) was 155°C. The GPC chart of phenol resin (6) is shown in FIG16 , the ¹³ C-NMR chart is shown in FIG17 , and the MS spectrum is shown in FIG18 . From GPC, the total peak area of the ester compound represented by structural formula (1) and the ketone compound (2) represented by structural formula (2) was 97%, and the monophenol residue was 0.1%. Furthermore, from ¹³ C-NMR, the ratio of ester group:ketone group was 1:0.03.

Example 7 The same procedure as in Example 1 was followed except that p-hydroxybenzoic acid was replaced with 207 g (1.5 mol) of salicylic acid, p-toluenesulfonic acid dihydrate was replaced with 15.4 g, and the reaction temperature was changed to 180°C to obtain phenolic resin (7). The melting point of the obtained phenolic resin (7) was 40°C. The GPC chart of phenolic resin (7) is shown in FIG19 , the ¹³ C-NMR chart is shown in FIG20 , and the MS spectrum is shown in FIG21 . 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%. Furthermore, from ¹³ C-NMR, the ratio of ester group:ketone group was 1:0.01.

Example 8 The same procedure as in Example 2 was followed except that p-hydroxybenzoic acid was replaced with 207 g (1.5 mol) of salicylic acid, p-toluenesulfonic acid dihydrate was replaced with 15.4 g, and the reaction temperature was changed to 180°C to obtain phenolic resin (8). The melting point of the obtained phenolic resin (8) was 83°C. The GPC chart of phenolic resin (8) is shown in FIG22 , the ¹³ C-NMR chart is shown in FIG23 , and the MS spectrum is shown in FIG24 . From GPC, the total peak area of the ester compound represented by structural formula (1) and the ketone compound (2) represented by structural formula (2) was 97%, and the monophenol residue was 0.1%. Furthermore, 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 the composition shown in Table 1. It was poured into a mold of 11 cm × 9 cm × 2.4 mm, molded at 175°C for 1 hour with a press, and cured at 175°C for 5 hours to produce a cured product. The elastic modulus, dielectric loss tangent, and moisture absorption rate of the cured product were measured when heated. The results are shown in the lower half of Table 1.

In addition, the raw materials used in the preparation of the composition are as follows. ・HE100C-15: Phenyl aralkyl type phenol resin, hydroxyl equivalent: 174g/eq (manufactured by AIR WATER Co., Ltd.) ・N-655-EXP-S: Cresol novolac type epoxy resin, epoxy equivalent 201g/eq (manufactured by DIC Co., Ltd.) ・TPP: Triphenylphosphine

<Determination of elastic modulus when heated> The 2.4mm thick hardened material prepared above was cut into pieces with a width of 5mm and a length of 54mm. This test piece was used with a viscoelasticity measuring device (DMA: solid viscoelasticity measuring device "RSAII" manufactured by Rheometric, rectangular tension method: frequency 1Hz, heating rate 3℃/min), and the storage modulus at 260℃ was measured as the elastic modulus when heated.

<Measurement of dielectric loss tangent> The previously obtained hardened material was heated and vacuum dried at 105°C for 2 hours, and then stored in a room at 23°C and 50% humidity for 24 hours as a test piece. The dielectric loss tangent of the test piece at 1 GHz was measured using the cavity resonance method using the "Network Analyzer E8362C" manufactured by Agilent Technologies Co., Ltd.

<Measurement of moisture absorption> The 2.4mm thick hardened material prepared above was cut into pieces with a width of 25mm and a length of 75mm. The mass change (wt%) before and after treatment in a constant temperature and humidity device at 85℃/85%RH for 300 hours was measured as the moisture absorption.

[Table 1] Table 1 Embodiment Comparison Example 9 10 11 12 13 14 15 16 1 Phenolic resin (1) 35 (2) 36 (3) 36 (4) 36 (5) 37 (6) 37 (7) 35 (8) 36 HE100C-15 46 Epoxy N-655-EXP-S 65 64 64 64 63 63 65 64 54 TPP 3 3 3 3 4 4 5 5 0.6 Test results Elastic modulus when heated (MPa) 20 14 15 16 7 8 8 6 40 Dielectric loss tangent @10GHz 0.019 0.017 0.017 0.014 0.016 0.015 0.019 0.018 0.030 Moisture absorption rate (%) 1.15 1.05 1.04 1.08 0.97 0.96 1.14 1.09 1.15

Examples 17 to 24, Comparative Example 2 The composition ratio shown in Table 2 was used to prepare the composition by melt kneading at 90°C for 5 minutes using 2 rolls. The fluidity (spiral flow) and flame retardancy of the obtained composition were evaluated as follows.

<Measurement of fluidity> The curable resin composition was injected into a test mold and the spiral flow value was measured at 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 into a sample with a width of 12.7 mm, a length of 127 mm, and a thickness of 1.6 mm using a transfer molding machine at 175°C for 5 minutes, and then cured at 175°C for 5 hours to prepare an evaluation sample. Five samples of the sample were used to conduct a combustion test according to the UL-94 test method. ※1: Maximum combustion time (seconds) after one contact with flame ※2: Total combustion time (seconds) of 5 test pieces

The raw materials used in the preparation of the composition are as follows. ・HE100C-15: Phenyl aralkyl type phenol resin, hydroxyl equivalent: 174 g/eq (manufactured by AIR WATER Co., Ltd.) ・N-655-EXP-S: Cresol novolac type epoxy resin, epoxy equivalent 201 g/eq (manufactured by DIC Co., Ltd.) ・TPP: Triphenylphosphine ・Fused silica: Spherical silica "FB-5604" manufactured by DENKA Co., Ltd. ・Silane coupling agent: γ-glycidyloxytriethoxysilane "KBM-403" manufactured by Shin-Etsu Chemical Co., Ltd. ・Palm wax: "PEARL WAX No.1-P" manufactured by DENKA Co., Ltd.

[Table 2] Table 2 Embodiment Comparison Example 17 18 19 20 twenty one twenty two twenty three twenty four 2 Phenolic resin (1) 16 (2) 16 (3) 16 (4) 16 (5) 17 (6) 17 (7) 16 (8) 16 HE100C-15 twenty one Epoxy N-655-EXP-S 29 29 29 29 28 28 29 29 twenty four TPP 1.35 1.35 1.35 1.35 1.8 1.8 2.25 2.25 0.27 Fused Silica 261 261 261 261 261 261 261 261 261 Silane coupling agent 0.45 0.45 0.45 0.45 0.45 0.45 0.45 0.45 0.45 Palm wax 0.68 0.68 0.68 0.68 0.68 0.68 0.68 0.68 0.68 Test results Spiral flow(cm) 103 114 121 140 110 109 118 121 81 Flame retardancy Fmax(sec)※1 30 20 twenty four twenty three twenty two twenty one 35 29 35 Flame retardancy ΣF(sec)※2 130 100 110 120 99 98 130 130 140

without.

[Figure 1] GPC chart of the phenolic resin obtained in Example 1. [Figure 2] ^{13 C-NMR spectrum of the phenolic resin obtained in Example 1. [Figure 3] MS spectrum of the phenolic resin obtained in Example 1. [Figure 4] GPC chart of the phenolic resin obtained in Example 2. [Figure 5] 13} C-NMR spectrum of the phenolic resin obtained in Example 2. [Figure 6] MS spectrum of the phenolic resin obtained in Example 2. [Figure 7] GPC chart of the phenolic resin obtained in Example 3. [Figure 8] ¹³ C-NMR spectrum of the phenolic resin obtained in Example ³ . [Figure 9] MS spectrum of the phenolic resin obtained in Example 3. [Figure 10] GPC chart of the phenolic resin obtained in Example 4. [Figure 11] ¹³ C-NMR spectrum of the phenolic resin obtained in Example 4. [Figure 12] MS spectrum of the phenolic resin obtained in Example 4. [Figure 13] GPC chart of the phenolic resin obtained in Example 5. [Figure 14] ¹³ C-NMR spectrum of the phenolic resin obtained in Example 5. [Figure 15] MS spectrum of the phenolic resin obtained in Example 5. [Figure 16] GPC chart of the phenolic resin obtained in Example 6. [Figure 17] ¹³ C-NMR spectrum of the phenolic resin obtained in Example 6. [Figure 18] MS spectrum of the phenolic resin obtained in Example 6. [Figure 19] GPC chart of the phenolic resin obtained in Example 7. [Figure 20] ¹³ C-NMR spectrum of the phenolic resin obtained in Example 7. [Figure 21] MS spectrum of the phenolic resin obtained in Example 7. [Figure 22] GPC chart of the phenolic resin obtained in Example 8. [Figure 23] ¹³ C-NMR spectrum of the phenolic resin obtained in Example 8. [Figure 24] MS spectrum of the phenolic resin obtained in Example 8.

without.

Claims (15)

A phenolic resin is a reaction product of a monophenol compound (A) having one hydroxyl group on an aromatic ring and an aromatic carboxylic acid (B) having a hydroxyl group and a carboxyl group on an aromatic ring, wherein 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 70-99% in GPC measurement, and the ratio of the ester group to the ketone group in the phenolic resin is in the range of 1:0.01-1:0.10 as measured by ¹³ C-NMR.

(In the formula, R ¹ to R ¹⁷ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). The phenolic resin of claim 1, wherein R ¹ to R ¹⁷ in the above formulas (1) and (2) are hydrogen atoms or methyl groups. The phenolic resin of claim 1 or 2, wherein the monophenol compound (A) having one hydroxyl group on the aromatic ring is phenol, cresol or xylenol, and the aromatic carboxylic acid (B) having a hydroxyl group and a carboxyl group on the aromatic ring is monohydroxybenzoic acid. If the phenolic resin in item 1 or 2 is requested, it is a hardener for epoxy resin. A curable resin composition, which contains as essential components a phenolic resin as described in any one of claims 1 to 3 and a resin having a functional group reactive with a hydroxyl group. The curable resin composition of claim 5, wherein the resin having a functional group reactive with a hydroxyl group is an epoxy resin. The curable resin composition of claim 6 further contains a phosphorus compound and/or a nitrogen-containing compound as a curing catalyst. A hardened product, which is a hardened product of a hardening resin composition as described in any one of claims 5 to 7. A semiconductor packaging material, comprising a curable resin composition as described in any one of claims 5 to 7 and an inorganic filler material. A semiconductor device, which is a hardened semiconductor packaging material as claimed in claim 9. A prepreg, which is a semi-cured material having an impregnated substrate having a curable resin composition as described in any one of claims 5 to 7 and a reinforcing substrate. A circuit substrate comprising a plate-shaped molding of a curable resin composition as described in any one of claims 5 to 7 and a copper foil. A build-up film comprising a cured product of a curable resin composition as described in any one of claims 5 to 7 and a substrate film. A fiber-reinforced composite material comprising a hardening resin composition as described in any one of claims 5 to 7 and reinforcing fibers. A fiber-reinforced molded product, which is a hardened product of the fiber-reinforced composite material as claimed in claim 14.