JP6394941B2 - Epoxy compound, phenolic hydroxyl group-containing compound, curable composition, cured product thereof, semiconductor sealing material, semiconductor device, prepreg, circuit board, buildup film, buildup board, fiber reinforced composite material, and fiber reinforced resin molded product - Google Patents

Description

  The present invention relates to an epoxy compound, a phenolic hydroxyl group-containing compound, a curable composition, a cured product thereof, and a semiconductor sealing material, and in particular, an epoxy compound having excellent heat resistance, a phenolic hydroxyl group-containing compound, and a curability in the cured product. The present invention relates to a composition, a cured product thereof, a semiconductor sealing material, a semiconductor device, a prepreg, a circuit board, a buildup film, a buildup board, a fiber reinforced composite material, and a fiber reinforced resin molded product.

  Epoxy compounds and compounds typified by phenolic hydroxyl group-containing compounds are generally cured with various curing agents, so that they generally have mechanical properties, water resistance, moisture resistance reliability, chemical resistance, heat resistance, and electrical properties. It becomes an excellent cured product. Therefore, it is widely used in the electric and electronic fields such as molding materials, paints, semiconductor sealing materials, printed wiring boards and the like.

  Among these various fields, in the field of power semiconductors typified by in-vehicle power modules, with the further increase in current, miniaturization, and efficiency of power semiconductors, conventional silicon (Si) semiconductors to silicon carbide ( The transition to SiC) semiconductors is ongoing. In addition, since a SiC semiconductor can operate | move on higher temperature conditions, it is calculated | required that the semiconductor sealing material used for a SiC semiconductor also has heat resistance higher than before. In addition to this, the semiconductor sealing material is conventionally required to be highly filled with a filler. Therefore, the development of a compound having excellent fluidity and high heat resistance in the cured product is required as a compound used for a semiconductor sealing material.

  As a compound corresponding to the above requirements, Patent Document 1 describes an epoxy compound obtained by reacting a polyhydric phenol and an aldehyde and having a rigid and symmetrical benzopyran skeleton.

JP 2003-201333 A

  However, the epoxy compound described in Patent Document 1 is not a compound having excellent fluidity, and the cured product thereof is not one having sufficient heat resistance to meet market needs.

  Accordingly, the problem to be solved by the present invention is an epoxy compound, a phenolic hydroxyl group-containing compound, a curable composition, a cured product thereof, a semiconductor having excellent fluidity and excellent heat resistance in the cured product. An object is to provide a sealing material, a semiconductor device, a prepreg, a circuit board, a buildup film, a buildup board, a fiber reinforced composite material, and a fiber reinforced resin molded product.

  As a result of intensive studies to solve the above problems, the present inventors have found that the epoxy compound of the present invention represented by the following structural formula (1) contains a low molecular weight compound and contains an epoxy group at a high concentration, and Since it has high symmetry, it has been found that it has excellent fluidity and excellent heat resistance in its cured product, and has completed the present invention.

However, represented in the formula ^{(1), R 1, R} 2 are each independently a hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group.

  Therefore, this invention relates to the epoxy compound characterized by having the molecular structure represented by following Structural formula (1).

However, represented in the formula ^{(1), R 1, R} 2 are each independently a hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group.

  The present invention further relates to a phenolic hydroxyl group-containing compound having a molecular structure represented by the following structural formula (4).

However, represented in the formula ^{(4), R 1, R} 2 are each independently a hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group.

  The present invention further relates to a curable composition comprising the epoxy compound and a curing agent.

  The present invention further relates to a curable composition containing the phenolic hydroxyl group-containing compound and a curing agent.

  The present invention further relates to a cured product obtained by reacting the curable composition.

  The present invention further relates to a semiconductor encapsulating material further containing an inorganic filler in addition to the curable composition.

  The present invention further relates to a semiconductor device obtained by heat curing the semiconductor sealing material.

  The present invention further relates to a prepreg obtained by impregnating a reinforcing substrate with a solution obtained by diluting the curable composition in an organic solvent and semi-curing the resulting impregnated substrate.

  The present invention further relates to a circuit board obtained by laminating the above prepreg shaped into a plate shape with a copper foil and heating and pressing.

  Furthermore, this invention relates to the buildup film obtained by apply | coating what dried the said curable composition in the organic solvent on a base film, and making it dry.

  The present invention further provides a build obtained by applying the build-up film to a circuit board on which a circuit is formed, forming irregularities on the circuit board obtained by heating and curing, and then subjecting the circuit board to plating. Related to the up board.

  The present invention further relates to a fiber-reinforced composite material containing the curable composition and reinforcing fibers.

  The present invention further relates to a fiber reinforced molded product obtained by curing the fiber reinforced composite material.

  According to the present invention, an epoxy compound, a phenolic hydroxyl group-containing compound, a curable composition, a cured product thereof, a semiconductor encapsulating material, a semiconductor device, and a prepreg having excellent fluidity and excellent heat resistance in the cured product. A circuit board, a build-up film, a build-up board, a fiber-reinforced composite material, and a fiber-reinforced resin molded product can be provided.

2 is a GPC chart of a phenolic hydroxyl group-containing compound (1) in Example 1. 2 is an MS spectrum of the phenolic hydroxyl group-containing compound (1) of Example 1. 3 is a GPC chart of the epoxy compound (2) of Example 2.

<Epoxy compound>
Hereinafter, the present invention will be described in detail.
The epoxy compound according to the present invention has a molecular structure represented by the following structural formula (1).

In the structural formula (1), R ¹ and R ² are each independently any one of a hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an aryl group.

  Examples of the hydrocarbon group having 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, butyl, t-butyl, pentyl, isopentyl, and t-pentyl. A chain alkyl group such as a group, a hexyl group, an isohexyl group and a t-hexyl group, a cyclic alkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group and a cyclohexyl group, and a phenyl group. Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a t-propyloxy group, a butoxy group, an isobutyloxy group, a t-butyloxy group, a pentyloxy group, Isopentyloxy group, t-pentyloxy group, hexyloxy group, isohexyloxy group, t-hexyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, phenyloxy group, etc. Can be mentioned. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.

  As described above, the epoxy compound of the present invention represented by the structural formula (1) has a plurality of substituents other than the epoxy group at specific positions on the aromatic ring. Therefore, the epoxy compound of the present invention has excellent fluidity. Furthermore, the epoxy compound of the present invention represented by the structural formula (1) has a molecular structure having a high symmetry and containing an epoxy group at a high concentration while being a low molecular weight compound. Therefore, the epoxy compound of the present invention has excellent heat resistance in the cured product.

In the structural formula (1), R ¹ and R ² are preferably each independently any of a methyl group, an ethyl group, a propyl group, an isopropyl group, and a t-butyl group. If comprised as mentioned above, the epoxy compound of this invention will have the further outstanding fluidity | liquidity, and the hardened | cured material will come to have the further outstanding heat resistance.

<Method for producing epoxy compound>
In order to produce such an epoxy compound of the present invention, it can be obtained through the following steps.
Step 1: A step of obtaining a phenolic hydroxyl group-containing compound by reacting a methylol group-containing phenol compound (P) with a phenol compound (Q).
Step 2: A step of glycidyl etherification of the obtained phenolic hydroxyl group-containing compound.

  Step 1 will be described.

  In Step 1, a phenolic hydroxyl group-containing compound is obtained by reacting a methylol group-containing phenol compound (P) represented by the following structural formula (2) with a phenol compound (Q) represented by the following structural formula (3). A compound is obtained.

However, in Structural Formulas (3) and (4), R ¹ and R ² are each independently any one of a hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an aryl group. It is.

  The hydrocarbon group having 1 to 6 carbon atoms is, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, butyl group, t-butyl group, pentyl group, isopentyl group, t-pentyl group. Chain alkyl groups such as hexyl group, isohexyl group and t-hexyl group, cyclic alkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group, phenyl group and the like. Examples of the alkoxy group having 1 to 6 carbon atoms include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, t-propyloxy group, butoxy group, isobutyloxy group, t-butyloxy group, pentyloxy group, Pentyloxy group, t-pentyloxy group, hexyloxy group, isohexyloxy group, t-hexyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, phenyloxy group, etc. It is done. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.

  Examples of the methylol group-containing phenol compound (P) represented by the structural formula (2) include (2-hydroxy-5-methyl-1,3-phenylene) dimethanol and (2-hydroxy-5-ethyl- 1,3-phenylene) dimethanol, (2-hydroxy-5-propyl-1,3-phenylene) dimethanol, (2-hydroxy-5-butyl-1,3-phenylene) dimethanol, (2-hydroxy- 5-methoxy-1,3-phenylene) dimethanol, (2-hydroxy-5-ethoxy-1,3-phenylene) dimethanol, (2-hydroxy-5-propoxy-1,3-phenylene) dimethanol, ( 2-Hydroxy-5-butoxy-1,3-phenylene) dimethanol and the like. These may be used alone or in combination of two or more.

  Examples of the phenol compound (Q) represented by the structural formula (3) include 2,3,5-trimethylbenzene-1,4 diol, 2,3,5-triethylbenzene-1,4 diol, , 3,5-tripropylbenzene-1,4 diol, 2,3,5-tributylbenzene-1,4 diol, 2,3,5-tritertiary butylbenzene-1,4 diol, 2,3,5 -Trimethoxybenzene-1,4diol, 2,3,5-triethoxybenzene-1,4diol, 2,3,5-tripropoxybenzene-1,4diol, 2,3,5-tributoxybenzene 1,4-diol, 2,3,5-tritertiary butoxybenzene-1,4 diol, 2,3,5-trimethoxybenzene-1,4 diol, 4,6-dimethyl- [1,1'- Biphenyl] -2,5-diol trimethoxybenzene-1,4 diol, 3,6-dimethyl- [1,1'-biphenyl] -2,5-diol trimethoxybenzene-1,4 diol, and the like. These may be used alone or in combination of two or more.

  The reaction of the methylol group-containing phenol compound (P) and the phenol compound (Q) can be prepared by a method of reacting in a temperature range of 100 ° C. to 140 ° C., preferably under no catalyst or acid catalyst conditions.

  In addition, although reaction with the said methylol group containing phenolic compound (P) and the said phenolic compound (Q) advances also on non-catalytic conditions, you may carry out using an acid catalyst suitably. Examples of the acid catalyst used here include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as methanesulfonic acid, p-toluenesulfonic acid, and oxalic acid, boron trifluoride, anhydrous aluminum chloride, and zinc chloride. And Lewis acid. When these acid catalysts are used, it is preferably used in an amount of 5.0% by mass or less based on the total mass of the methylol group-containing phenol compound (P) and the phenol compound (Q).

  Further, the above reaction is preferably performed under solvent-free conditions, but may be performed in an organic solvent as necessary. Examples of the organic solvent used here include methyl cellosolve, isopropyl alcohol, ethyl cellosolve, toluene, xylene, and methyl isobutyl ketone. When using these organic solvents, since reaction efficiency improves, an organic solvent is 50-200 mass parts with respect to a total of 100 mass parts of the said methylol group containing phenolic compound (P) and the said phenolic compound (Q). It is preferable to use it in a ratio that falls within the range.

  In addition, after completion | finish of reaction with the said methylol group containing phenolic compound (P) and the said phenolic compound (Q), the target phenolic hydroxyl group containing compound can be obtained by drying under reduced pressure.

  According to the above method, the phenolic hydroxyl group-containing compound of the present invention can be produced with a high purity of 80% or more. In addition, purity here is the peak area ratio of the phenolic hydroxyl group containing compound with respect to the peak area of the whole reaction product computed from the GPC chart figure measured on the following conditions.

Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “HXL-L” manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ Tosoh Corporation “TSK-GEL G4000HXL”
Detector: RI (differential refraction diameter)
Data processing: “GPC-8020 Model II version 4.10” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate: 1.0 ml / min Standard: The following monodisperse polystyrene having a known molecular weight was used in accordance with the above-mentioned measurement manual “GPC-8020 Model II version 4.10”.
(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 1.0 mass% tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (50 μl).

  Next, step 2 will be described.

  In Step 2, 1 to 10 mol of epihalohydrin is added to 1 mol of the phenolic hydroxyl group-containing compound obtained in Step 1, and further 0.9 to 2.0 mol of base to 1 mol of the phenolic hydroxyl group-containing compound. The method of making it react at the temperature of 20-120 degreeC for 0.5 to 10 hours, adding a sex catalyst collectively or gradually is mentioned. The basic catalyst may be solid or an aqueous solution thereof. When an aqueous solution is used, it is continuously added and water and epihalohydrins are continuously distilled from the reaction mixture under reduced pressure or normal pressure. The solution may be taken out and further separated to remove water and the epihalohydrins are continuously returned to the reaction mixture.

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

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

  Subsequently, the reaction product of the epoxidation reaction is washed with water, and unreacted epihalohydrin and the organic solvent to be used in combination are distilled off by distillation under heating and reduced pressure. Furthermore, in order to obtain an epoxy compound with less hydrolyzable halogen, the obtained epoxy compound is again dissolved in an organic solvent such as toluene, methyl isobutyl ketone, methyl ethyl ketone, and alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. Further reaction can be carried out by adding an aqueous solution of the product. At this time, a phase transfer catalyst such as a quaternary ammonium salt or crown ether may be present for the purpose of improving the reaction rate. When the phase transfer catalyst is used, the amount used is preferably in the range of 0.1 to 3.0% by mass with respect to the epoxy compound used. After completion of the reaction, the produced salt is removed by filtration, washing with water, and a high-purity epoxy compound can be obtained by distilling off a solvent such as toluene and methyl isobutyl ketone under heating and reduced pressure.

<Curable composition>
Next, the curable composition using the epoxy compound will be described.
The curable composition of the present invention uses the epoxy compound described above in detail as a main component and a curing agent. Examples of the curing agent include various known curing agents such as an amine compound, an amide compound, an acid anhydride compound, and a phenol compound.

Examples of amine compounds include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF ₃ -amine complexes, guanidine derivatives, and the like. Examples of amide compounds include dicyandiamide and linolenic acid. Examples thereof include a polyamide resin synthesized from a monomer and ethylenediamine. Acid anhydride compounds include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydro And phthalic anhydride. Phenol compounds include phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadiene phenol addition resin, phenol aralkyl resin (Zylok resin), naphthol aralkyl resin, triphenylol methane resin, Tetraphenylolethane resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolak resin, biphenyl-modified phenol resin (polyphenolic hydroxyl group-containing compound in which phenol nuclei are linked by a bismethylene group), biphenyl Modified naphthol resin (polyvalent naphthol compound in which phenol nucleus is linked by bismethylene group), aminotriazine modified phenol resin (melamine, benzo Polyhydric phenolic hydroxyl group-containing compounds in which phenol nuclei are linked with anamin, etc.), alkoxy group-containing aromatic ring-modified novolak resins (polyhydric phenolic hydroxyl group-containing compounds in which phenol nuclei and alkoxy group-containing aromatic rings are linked with formaldehyde), etc. And a polyhydric phenolic hydroxyl group-containing compound.

  The mixing ratio of the epoxy compound and the curing agent described in detail above is such that the equivalent ratio (epoxy group / active hydrogen atom) between the epoxy group in the epoxy compound and the active hydrogen atom in the curing agent is 1 / 0.5 to 1. A ratio of /1.5 is preferable from the viewpoint of excellent heat resistance.

  The curable composition of the present invention may further contain an epoxy resin in addition to the epoxy compound.

  Specifically, the epoxy resin used here is 1,6-diglycidyloxynaphthalene, 2,7-diglycidyloxynaphthalene, α-naphthol novolak type epoxy resin, β-naphthol novolak type epoxy resin, α-naphthol / β-naphthol co-condensation type novolak polyglycidyl ether, naphthol aralkyl type epoxy resin, 1,1-bis (2,7-diglycidyloxy-1-naphthyl) alkane and other naphthalene skeleton-containing epoxy resin; bisphenol A type epoxy resin Bisphenol type epoxy resin such as bisphenol F type epoxy resin; Biphenyl type epoxy resin such as biphenyl type epoxy resin and tetramethylbiphenyl type epoxy resin; Phenol novolac type epoxy resin, Cresol novolak type epoxy resin, Bi Phenol A novolac type epoxy resin, bisphenol F novolac type epoxy resin, epoxidized product of condensation product of phenolic compound and aromatic aldehyde having phenolic hydroxyl group, novolac type epoxy resin such as biphenyl novolac type epoxy resin; triphenylmethane type Examples include epoxy resins; tetraphenylethane type epoxy resins; dicyclopentadiene-phenol addition reaction type epoxy resins; phenol aralkyl type epoxy resins; and phosphorus atom-containing epoxy resins.

  Among these epoxy resins, a naphthalene skeleton-containing epoxy resin is preferable because a cured product having better heat resistance can be obtained. Furthermore, a naphthol aralkyl type epoxy resin and a β-naphthol novolak type epoxy resin are more preferable because of excellent compatibility with the epoxy resin. In the present invention, when the epoxy resin is produced, a mixture containing a naphthol aralkyl resin or a β-naphthol novolak type epoxy resin as a cyclohexadienone skeleton-containing naphthol resin, which is a precursor thereof, is obtained and epoxidized to obtain the above epoxy. It is also possible to produce a mixture of the resin and a naphthol aralkyl type epoxy resin or a β-naphthol novolac type epoxy resin.

  When using an epoxy resin, the blending ratio of the epoxy compound and the epoxy resin is determined from the viewpoints of fluidity, heat resistance in a cured product, low thermal expansion, moisture solder resistance, flame resistance, and adhesion to a substrate. The mass ratio [(epoxy compound) / (epoxy resin)] of the two is preferably in the range of 5/95 to 95/5.

  Moreover, when using an epoxy resin, the mixture ratio with the said hardening | curing agent is equivalent ratio (epoxy group / active hydrogen atom) of the epoxy group in all the epoxy components in a curable composition, and the active hydrogen atom in a hardening | curing agent. ) Is preferably 1 / 0.5 to 1 / 1.5 from the viewpoint of curability and heat resistance of the cured product.

  Furthermore, a curing accelerator can be used in combination with the curable composition as necessary. Various types of curing accelerators can be used. Examples of the curing accelerator include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, amine complex salts, and the like. Especially when used as a semiconductor sealing material, imidazole compounds are 2-ethyl-4-methylimidazole, and phosphorus compounds are triphenylphosphine because they are excellent in curability, heat resistance, electrical properties, moisture resistance reliability, and the like. As the tertiary amine, 1,8-diazabicyclo- [5.4.0] -undecene (DBU) is preferable.

  Furthermore, according to a use and desired performance, the curable composition of this invention explained in full detail above may contain the other additive component. Specifically, for the purpose of further improving the flame retardancy, a non-halogen flame retardant containing substantially no halogen atom may be blended.

  Examples of the non-halogen flame retardants include phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, inorganic flame retardants, and organic metal salt flame retardants. The flame retardants may be used alone or in combination, and a plurality of flame retardants of the same system may be used, or different types of flame retardants may be used in combination.

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

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

  Examples of the organic phosphorus compound include, for example, general-purpose organic phosphorus compounds such as phosphate ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phospholane compounds, organic nitrogen-containing phosphorus compounds, and 9,10- Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5-dihydrooxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,7 -Dihydrooxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide and other cyclic organic phosphorus compounds, and derivatives obtained by reacting them with compounds such as epoxy resins and phenol resins.

  The blending amount thereof is appropriately selected depending on the type of the phosphorus-based flame retardant, the other components of the curable composition, and the desired degree of flame retardancy. For example, a phenyl group component, a curing agent, and In 100 parts by mass of the curable composition containing all other additives and fillers, when using red phosphorus as a non-halogen flame retardant, it may be added in the range of 0.1 to 2.0 parts by mass. Preferably, when an organic phosphorus compound is used, it is preferably blended in the range of 0.1 to 10.0 parts by mass, and particularly preferably in the range of 0.5 to 6.0 parts by mass.

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

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

  Examples of the triazine compound include melamine, acetoguanamine, benzoguanamine, melon, melam, succinoguanamine, ethylene dimelamine, melamine polyphosphate, triguanamine, and the like, for example, (i) guanylmelamine sulfate, melem sulfate, sulfate (Iii) co-condensates of phenolic compounds such as phenol, cresol, xylenol, butylphenol, and nonylphenol with melamines such as melamine, benzoguanamine, acetoguanamine, formguanamine and formaldehyde; ) A mixture of the co-condensate of (ii) above and a phenol resin such as a phenol formaldehyde condensate, (iv) The above (ii) and (iii) are further modified with paulownia oil, isomerized linseed oil, etc. It is done.

  Specific examples of the cyanuric acid compound include cyanuric acid and cyanuric acid melamine.

  The compounding amount of the nitrogen-based flame retardant is appropriately selected depending on the type of the nitrogen-based flame retardant, other components of the curable composition, and the desired degree of flame retardancy. For example, a phenyl group component, It is preferable to mix in the range of 0.05 to 10 parts by mass, particularly in the range of 0.1 to 5 parts by mass, in 100 parts by mass of the curable composition containing all of the curing agent, other additives and fillers. It is preferable to mix with.

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

  The silicone flame retardant is not particularly limited as long as it is an organic compound containing a silicon atom, and examples thereof include silicone oil, silicone rubber, and silicone resin.

  The blending amount of the silicone flame retardant is appropriately selected according to the type of the silicone flame retardant, other components of the curable composition, and the desired degree of flame retardancy. For example, a phenyl group component, It is preferable to mix in the range of 0.05 to 20 parts by mass in 100 parts by mass of the curable composition containing all of the curing agent and other additives and fillers. Moreover, when using the said silicone type flame retardant, you may use a molybdenum compound, an alumina, etc. together.

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

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

  Specific examples of the metal oxide include, for example, zinc molybdate, molybdenum trioxide, zinc stannate, tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, zirconium oxide, zinc oxide, molybdenum oxide, and cobalt oxide. Bismuth oxide, chromium oxide, nickel oxide, copper oxide, tungsten oxide and the like.

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

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

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

Specific examples of the low-melting-point glass include, for example, Sheepley (Bokusui Brown), hydrated glass SiO ₂ —MgO—H ₂ O, PbO—B ₂ O ₃ system, ZnO—P ₂ O ₅ —MgO system, P ₂ O ₅ —B ₂ O ₃ —PbO—MgO, P—Sn—O—F, PbO—V ₂ O ₅ —TeO ₂ , Al ₂ O ₃ —H ₂ O, lead borosilicate, etc. The glassy compound 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 curable composition, and the desired degree of flame retardancy. It is preferable to mix in the range of 0.5 to 50 parts by mass, particularly in the range of 5 to 30 parts by mass, in 100 parts by mass of the curable composition in which all the additives and other additives and fillers are mixed. It is preferable to do.

  Examples of the organometallic salt flame retardant include ferrocene, acetylacetonate metal complex, organometallic carbonyl compound, organocobalt salt compound, organosulfonic acid metal salt, metal atom and aromatic compound or heterocyclic compound or an ionic bond or Examples thereof include a coordinated compound.

  The amount of the organometallic salt flame retardant is appropriately selected depending on the type of the organometallic salt flame retardant, the other components of the curable composition, and the desired degree of flame retardancy. For example, phenyl It is preferable to mix | blend in 0.005-10 mass parts in 100 mass parts of curable compositions which mix | blended all the base components, the hardening | curing agent, and other additives, fillers, etc.

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

  Furthermore, an inorganic filler can be mix | blended with the curable composition of this invention as needed. Since the epoxy compound of the present invention has excellent fluidity, it is possible to increase the blending amount of the inorganic filler, and such a curable composition can be suitably used particularly for a semiconductor sealing material application. .

  Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. Especially, since it becomes possible to mix | blend more inorganic fillers, the said fused silica is preferable. The fused silica can be used in either a crushed shape or a spherical shape, but in order to increase the blending amount of the fused silica and to suppress an increase in the melt viscosity of the curable composition, a spherical shape is mainly used. It is preferable. Furthermore, in order to increase the blending amount of the spherical silica, it is preferable to appropriately prepare the particle size distribution of the spherical silica. The filling rate is preferably in the range of 0.5 to 95 parts by mass in 100 parts by mass of the curable composition. Of these, flame retardancy, moisture resistance, and solder crack resistance are improved, and the linear expansion coefficient can be reduced. Therefore, it is preferably used in the range of 70 to 95 parts by mass, particularly in the range of 80 to 95 parts by mass. preferable.

<Use of curable composition>
The curable composition of the present invention is applied to semiconductor encapsulating materials, semiconductor devices, prepregs, printed circuit boards, build-up films, build-up boards, fiber reinforced composite materials, fiber reinforced molded products, conductive pastes, adhesive films, etc. it can.

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

2. Semiconductor sealing device As a method for obtaining a semiconductor device from the curable composition of the present invention, the composition is molded using a casting, a transfer molding machine, an injection molding machine, etc. The method of heating for 10 hours is mentioned.

3. Prepreg As a method for obtaining a prepreg from the curable composition of the present invention, a varnish-like curable composition containing the organic solvent is used as a reinforcing substrate (paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat). And a glass roving cloth, etc.), followed by heating at a heating temperature corresponding to the solvent type used, preferably 50 to 170 ° C. Although it does not specifically limit as a mass ratio of the curable composition used at this time and a reinforcement base material, Usually, it is preferable to prepare so that the resin part in a prepreg may be 20-60 mass%.

4). Printed Circuit Board As a method for obtaining a printed circuit board from the curable composition of the present invention, the above prepreg is laminated by a conventional method, and a copper foil is appropriately layered, and the pressure is increased from 170 to 300 ° C. under a pressure of 1 to 10 MPa. Examples include a method of heat-pressing for minutes to 3 hours.

5. Build-up film As a method for obtaining a build-up film from the curable composition of the present invention, for example, the curable composition is applied on a support film and then dried to form a curable composition layer on the support film. The method of forming is mentioned. When the curable composition of the present invention is used for a build-up film, it is important that the film is softened under the lamination temperature condition (usually 70 ° C. to 140 ° C.) in the vacuum laminating method, and such characteristics are exhibited. It is preferable to blend each of the above components.

6). Build-up Substrate As a method for obtaining a build-up substrate from the curable composition of the present invention, for example, the curable composition appropriately blended with rubber, filler, etc. is spray-coated on a printed circuit board on which a circuit is formed, curtain The method of hardening after apply | coating using the coating method etc. is mentioned. In addition, after drilling a predetermined through-hole or the like in the obtained build-up substrate as necessary, the surface thereof may be plated using copper or the like. As the plating method, electroless plating or electrolytic plating treatment is preferable, and examples of the roughening agent include an oxidizing agent, an alkali, and an organic solvent.

7). Fiber Reinforced Composite Material As a method for obtaining a fiber reinforced composite material from the curable composition of the present invention, each component constituting the curable composition is uniformly mixed to prepare a varnish, and then this is reinforced with reinforcing fibers. After impregnating the substrate, it can be produced by a polymerization reaction.

  Specifically, the curing temperature at the time of performing the polymerization reaction is preferably in the temperature range of 50 to 250 ° C., in particular, after curing at 50 to 100 ° C. to obtain a tack-free cured product, The treatment is preferably performed at a temperature of 120 to 200 ° C.

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

8). Fiber Reinforced Molded Article As a method for obtaining a fiber reinforced molded article from the curable composition of the present invention, a hand lay-up method or spray-up method in which a fiber aggregate is laid on a mold and the varnish is laminated in layers, a male mold, Using one of the female dies, forming a base material consisting of reinforcing fibers while impregnating the varnish, stacking and molding, covering with a flexible mold that can apply pressure to the molded product, and vacuum-tightening the one that is hermetically sealed Reinforced fibers by vacuum bag method for molding, SMC press method in which varnish containing reinforcing fiber is formed into a sheet shape by compression molding with a mold, RTM method in which the varnish is injected into a mating die laid with fibers Examples thereof include a method of producing a prepreg impregnated with the varnish and baking it in a large autoclave. In addition, the fiber reinforced resin molded product obtained above is a molded product having a reinforced fiber and a cured product of the curable composition. Specifically, the amount of the reinforced fiber in the fiber reinforced molded product is 40 It is preferably in the range of -70% by mass, and particularly preferably in the range of 50-70% by mass from the viewpoint of strength.

9. Electrically conductive paste As a method of obtaining an electrically conductive paste from the curable composition of this invention, the method of disperse | distributing fine electroconductive particle in this curable composition is mentioned, for example. 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.

10. Adhesive film As a method for obtaining an adhesive film from the curable composition of the present invention, for example, after preparing a varnish-like curable composition, the varnish-like composition is applied to the surface of the support film, and further heated. Alternatively, it can be produced by drying the organic solvent by blowing hot air or the like to form a curable composition layer. In general, the thickness of the curable composition layer is preferably equal to or greater than the thickness of the conductor layer. In addition, the curable composition layer may be protected with the protective film mentioned later. By protecting with a protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches.

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

  The above support film is peeled after laminating the adhesive film at a predetermined location. In addition, if a support film peels after the curable composition layer which comprises an adhesive film hardens | cures, it can prevent that a dust etc. adhere to a curable composition layer at a hardening process. In addition, when a support film peels after the curable composition layer hardens | cures, a mold release process is normally given to a support film normally.

  In addition, a printed circuit board can also be manufactured using the adhesive film obtained as mentioned above. As a method for producing a printed circuit board using an adhesive film, the adhesive film and the printed circuit board are bonded so that the curable composition layer of the adhesive film is in contact with the printed circuit board, and then laminated by, for example, a vacuum laminating method. To do. The laminating method may be a batch method or a continuous method using a roll. If necessary, the adhesive film or the printed circuit board may be heated (preheated) before lamination. The laminating conditions are preferably a pressure bonding temperature (lamination temperature) of 70 to 140 ° C., and a pressure bonding pressure of 1 to 11 kgf / cm 2 (9.8 × 10 4 to 107.9 × 104 N / m 2). Lamination is preferably performed under a reduced pressure of 20 mmHg (26.7 hPa) or less.

  Finally, an intermediate of the epoxy compound that can be used for the above various applications will be described.

  The intermediate of the epoxy compound is a phenolic hydroxyl group-containing compound represented by the following structural formula (4).

In the structural formula (1), R ¹ and R ² are each independently any one of a hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an aryl group.

  Examples of the hydrocarbon group having 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, butyl, t-butyl, pentyl, isopentyl, and t-pentyl. A chain alkyl group such as a group, a hexyl group, an isohexyl group and a t-hexyl group, a cyclic alkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group and a cyclohexyl group, and a phenyl group. Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a t-propyloxy group, a butoxy group, an isobutyloxy group, a t-butyloxy group, a pentyloxy group, Isopentyloxy group, t-pentyloxy group, hexyloxy group, isohexyloxy group, t-hexyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, phenyloxy group, etc. Can be mentioned. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.

  As described above, the phenolic hydroxyl group-containing compound represented by the structural formula (4) has a plurality of substituents other than hydroxyl groups at specific positions on the aromatic ring. Furthermore, the phenolic hydroxyl group-containing compound represented by the structural formula (4) has a molecular structure having a high symmetry and containing hydroxyl groups at a high concentration even though it is a low molecular weight compound. Therefore, the phenolic hydroxyl group-containing compound is an epoxy compound intermediate that is excellent in fluidity and can provide an epoxy compound having excellent heat resistance in the cured product.

In the structural formula (4), R ¹ and R ² are preferably each independently any of a methyl group, an ethyl group, a propyl group, an isopropyl group, and a t-butyl group. When configured as described above, the phenolic hydroxyl group-containing compound has a further excellent fluidity, and the cured product can give an epoxy compound having a further excellent heat resistance.

<Method for producing phenolic hydroxyl group-containing compound>
In order to produce such a phenolic hydroxyl group-containing compound, it can be obtained through the step 1 described above. That is, it can be obtained by reacting the methylol group-containing phenol compound (P) with the phenol compound (Q) to obtain a phenolic hydroxyl group-containing compound. The specific methylol group-containing phenol compound (P), the structure of the phenol compound (Q), the reaction conditions, and the like are as described above.

  The present invention will be specifically described with reference to examples and comparative examples. In the following, “part” and “%” are based on mass unless otherwise specified. The heat resistance, melt viscosity, and GPC of the compound or resin were measured under the following conditions.

1) Heat resistance measurement method:
Apparatus: Rheometric “Solid Viscoelasticity Measurement System RSAII”
Measurement mode: Rectangular tension method Frequency: 1Hz
Temperature increase rate: 3 ° C / min

  2) Melt viscosity measurement method: Conforms to ASTM D4287

Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “HXL-L” manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ Tosoh Corporation “TSK-GEL G4000HXL”
Detector: RI (differential refraction diameter)
Data processing: “GPC-8020 Model II version 4.10” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate: 1.0 ml / min Standard: The following monodisperse polystyrene having a known molecular weight was used in accordance with the above-mentioned measurement manual “GPC-8020 Model II version 4.10”.
(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 1.0 mass% tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (50 μl).

<Example 1>
1. Production of phenolic hydroxyl group-containing compound (1) A flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer was charged with 183 g (1.2 mol) of trimethylhydroquinone, 350 g of toluene, and paratoluenesulfonic acid. 5 g (0.04 mol) was charged, and the temperature was raised from room temperature to 120 ° C. with stirring. Subsequently, 101 g (0.6 mol) of paracresol dimethylol was added to the flask using a dropping funnel over 1 hour, and the mixture was stirred until a solid precipitated. After completion of the reaction, the precipitated solid was washed with 2-propanol and dried under heating and reduced pressure to obtain 220 g of a phenolic hydroxyl group-containing compound (1). The obtained hydroxyl group equivalent of the phenolic hydroxyl group-containing compound (1) was 87 g / eq. Next, it was confirmed from the GPC chart and MS spectrum that the target phenolic hydroxyl group-containing compound (1) was obtained. The results are shown in FIGS. 1 and 2, respectively. The content purity of the phenolic hydroxyl group-containing compound (1) calculated from the GPC chart shown in FIG. 1 was 89%.

<Example 2>
2. Production of Epoxy Compound (2) While purging a flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer with a nitrogen gas purge, 130 g (1.5 equivalents of hydroxyl group) of the phenolic hydroxyl group-containing compound (1) obtained above, Epichlorohydrin 1106 g (8.0 mol) and n-butanol 387 g were charged and dissolved. After raising the temperature to 50 ° C., 344 g (1.7 mol) of a 20% aqueous sodium hydroxide solution was added over 3 hours, and then further reacted at 50 ° C. for 1 hour. After completion of the reaction, unreacted epichlorohydrin was distilled off under reduced pressure at 150 ° C. Then, 363 g of methyl isobutyl ketone and 50 g of n-butanol were added to the obtained crude epoxy resin and dissolved. Further, 20 g of a 10% by mass aqueous sodium hydroxide solution was added to this solution and reacted at 80 ° C. for 2 hours. Next, the system was dehydrated by azeotropic distillation, and after passing through microfiltration, the solvent was distilled off under reduced pressure to obtain 190 g of the desired epoxy compound (2). The resulting epoxy compound (2) had a melt viscosity of 6.0 dPa · s and an epoxy equivalent of 166 g / eq. Next, it was confirmed from the GPC chart that the target epoxy compound (2) was obtained. The result is shown in FIG. The content purity of the epoxy compound (2) calculated from the GPC chart shown in FIG. 3 was 72%.

<Comparative Example 1>
1. Production of Phenol Resin (1 ′) The following experiment was conducted with reference to Synthesis Example 2 and Example 2 of JP-A-2003-201333. First, 152 g (1.0 mol) of trimethylhydroquinone was dissolved in a mixed solvent of 500 g of toluene and 200 g of ethylene glycol monoethyl ether in a 1-liter four-necked flask equipped with a stirrer and a heating device. Next, 4.6 g of paratoluenesulfonic acid was added to the solution in which trimethylhydroquinone was dissolved, and 64 g (0.6 mol) of benzaldehyde was added while paying attention to heat generation. Subsequently, it stirred at 100-120 degreeC for 15 hours, distilling the water | moisture content in a flask. Finally, after cooling, the precipitated crystals were filtered off, washed repeatedly with water until neutral, and then dried to obtain 175 g of a phenol resin (1 ′).

<Comparative Example 2>
2. Production of epoxy resin (2 ′) While performing nitrogen gas purging on a flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer, 187 g of phenol resin (1 ′) obtained above (hydroxyl group 1.0 equivalent), Epichlorohydrin 463 g (5.0 mol), n-butanol 53 g, and tetraethylbenzylammonium chloride g were charged and dissolved. After raising the temperature in the system to 65 ° C., the pressure was reduced to an azeotropic pressure, and 82 g (1.0 mol) of a 49% aqueous sodium hydroxide solution was added dropwise over 5 hours. Stirring was continued for 5 hours. During this time, the distillate distilled azeotropically was separated with a Dean-Stark trap, the aqueous layer was removed, and the reaction was carried out while returning the oil layer to the reaction system. Thereafter, unreacted epichlorohydrin was distilled off under reduced pressure. To the crude epoxy resin obtained above, 550 g of methyl isobutyl ketone and 55 g of n-butanol were added and dissolved. Further, 15 g of a 10% aqueous sodium hydroxide solution was added to this solution and reacted at 80 ° C. for 2 hours, and then washing with 100 g of water was repeated three times until the pH of the washing solution became neutral. Finally, the system was dehydrated by azeotropic distillation, and after passing through microfiltration, the solvent was distilled off under reduced pressure to obtain 188 g of the desired epoxy resin (2 ′). The epoxy equivalent of the obtained epoxy resin was 262 g / eq.

<Example 3 and Comparative Example 3>
3. Measurement of fluidity of curable composition A curable composition was prepared with the formulation shown in Table 1. Details of each component are as follows. In addition, after completion | finish of preparation, the melt viscosity of the curable composition was measured. The melt viscosity was measured using an ICI viscometer. The results are shown in Table 1.
Epoxy compound (2): Epoxy compound of Example 2 Epoxy resin (2 ′): Epoxy resin of Comparative Example 2 Curing agent (1): Phenol novolac type phenol resin (“TD-2131” manufactured by DIC Corporation) , Hydroxyl equivalent: 104 g / eq)
Curing accelerator: triphenylphosphine Measurement of heat resistance of cured product Subsequently, the curable composition prepared at the ratio shown in Table 1 was poured into a mold of 11 cm × 9 cm × 2.4 mm and molded with a press at a temperature of 150 ° C. for 10 minutes. Thereafter, the molded product was taken out from the mold, and the molded product was heated at a temperature of 175 ° C. for 5 hours to obtain a cured product.
Using a viscoelasticity measuring device, the temperature at which the change in the elastic modulus of the cured product was maximized was measured as the glass transition temperature. The results are shown in Table 1.

Claims (14)

A reaction product of a methylol group-containing phenol compound (P) represented by the following structural formula (2) and a phenol compound (Q) represented by the following structural formula (3), which is represented by the following structural formula (4). An epoxy compound, which is a glycidyl etherified compound containing 80% or more of a phenolic hydroxyl group-containing compound having a molecular structure.
(Wherein R ¹ represents a hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group.)
(In the formula, each R ² independently represents any of a hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an aryl group.)
(In the formula, R 1 and R ² each independently represent any of a hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an aryl group.) R ¹ in the structural formulas (2) to (4) is any ^one of a methyl group, an ethyl group, a propyl group, an isopropyl group, and a t-butyl group, and R ² is a methyl group, an ethyl group, a propyl group, and an isopropyl group. The epoxy compound according to claim 1, which is any one of groups. A curable composition comprising the epoxy compound according to claim 1 or 2 and a curing agent. Hardened | cured material formed by hardening | curing the curable composition of Claim 3 . A semiconductor sealing material further containing an inorganic filler in addition to the curable composition according to claim 3 . A semiconductor device obtained by heat-curing the semiconductor sealing material according to claim 5 . A prepreg obtained by impregnating a reinforced composition obtained by diluting the curable composition according to claim 3 with an organic solvent into a reinforcing base material and semi-curing the resulting impregnated base material. A circuit board obtained by laminating a prepreg according to claim 7 in a plate shape with a copper foil, followed by heat and pressure molding. The buildup film obtained by apply | coating what dried the curable composition of Claim 3 in the organic solvent on a base film, and making it dry. A build-up film obtained by laminating the build-up film according to claim 9 on a circuit board on which a circuit is formed, heat-curing the circuit board, and then performing plating treatment on the circuit board. substrate. A fiber-reinforced composite material comprising the curable composition according to claim 3 and reinforcing fibers. A fiber-reinforced molded article obtained by curing the fiber-reinforced composite material according to claim 11 . After reacting the methylol group-containing phenolic compound (P) represented by the following structural formula (2) and the phenolic compound (Q) represented by the following structural formula (3) until a solid precipitates, A method for producing a compound, comprising drying to obtain a solid containing 80% or more of a phenolic hydroxyl group-containing compound having a molecular structure represented by the following structural formula (4).
(Wherein R ¹ represents a hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group.)
(In the formula, each R ² independently represents any of a hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an aryl group.)
(In the formula, R 1 and R ² each independently represent any of a hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an aryl group.) After reacting the methylol group-containing phenolic compound (P) represented by the following structural formula (2) and the phenolic compound (Q) represented by the following structural formula (3) until a solid precipitates, After drying, a solid containing 80% or more of a phenolic hydroxyl group-containing compound having a molecular structure represented by the following structural formula (4) is obtained, and then this is glycidyl etherified. The manufacturing method of the epoxy compound represented by this.
(Wherein R ¹ represents a hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group.)
(In the formula, each R ² independently represents any of a hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an aryl group.)
(In the formula, R 1 and R ² each independently represent any of a hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an aryl group.)
(In the formula, R ¹ and R ² each independently represents a hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group.)