JPH0959333A - Phenol compound and its production and thermosetting resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a phenol compound having a specific structural unit, free from occurrence of volatile content in curing, excellent in flame retardance, toughness, fast-setting property, low hygroscopic property and heat resistance and useful for composite molding materials, etc. SOLUTION: This phenol compound has a structural unit expressed by the formula [R<1> is methyl, cyclohexyl or a (substituted)phenyl, with the proviso that H on aromatic ring may be replaced with an arbitrary substituent group, excepting one hydrogen atom at ortho position of hydroxyl group]. Furthermore, the phenol compound is obtained by reacting a phenol compound having two or more active hydrogen atoms at ortho or para position of phenolic hydroxy groups with a primary amine such as methylamine and formaldehydes in 0.75 to 1.25 molar ratio of the primary amine to hydroxyl group of the phenol compound and in >=2 molar ratio of formaldehydes to the primary amine. This thermosetting resin composition is preferably produced by blending the phenol compound having a structural unit of the formula with an epoxy compound.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention can be cured with an epoxy resin or the like, which is useful for an interlayer insulating film for semiconductors, a protective film, or a sealing material, a vacuum impregnated varnish for heavy electrical equipment, a printed wiring board and the like. TECHNICAL FIELD The present invention relates to a phenol compound, a method for producing the same, a curable resin composition that can form a cured product using the phenol compound and that has low hygroscopicity and excellent heat resistance, a composite molding material, and a laminate and a wiring board using the same. .

[0002]

Thermosetting resins such as phenolic resins, melamine resins, epoxy resins, unsaturated polyester resins and bismaleimide resins are widely used in many industrial fields due to their heat resistance and reliability due to their thermosetting properties. It is used. However, the phenol resin and the melamine resin have a problem that voids are formed in the molded product due to the volatile components generated at the time of curing and the properties of the molded product are significantly deteriorated. Epoxy resin and unsaturated polyester resin do not generate by-products during curing, but have inferior flame retardancy and bismaleimide resin is extremely expensive, and each has its own problems. It is used as a compromise.

The novolac type phenol resin is also useful as a curing agent for epoxy resins and is widely used as a sealing material for semiconductors. However, it is improved in terms of moisture absorption rate, flame retardancy, glass transition point and the like. It has been demanded.

Therefore, the development of a novel thermosetting resin which does not have these drawbacks has been advanced. As one of them, a method utilizing a ring-opening polymerization reaction of a dihydrobenzoxazine compound is known. For example, JP-A-49-
No. 47387 and U.S. Pat. No. 5,152,939, a dihydrobenzoxazine compound is synthesized by reacting various phenols with a primary amine and formaldehyde, and this substance is heated with almost no generation of volatile components. It has been shown to cure.

A curable composition of a dihydrobenzoxazine compound or its prepolymer and an epoxy resin is also disclosed in JP-A-49-47378 and JP-B-63-4608.
No. 8 and Japanese Patent Laid-Open No. 4-227922.

However, the compound having a dihydrobenzoxazine ring is described in Polym. Sci. Tech
nol. , Vol. 31, 27-49 (1985), there is a problem that the degree of extension of the molecular chain during the ring-opening polymerization reaction is small, and the molecular weight of the polymer is not sufficient.
Therefore, although the properties of the polymer are good from room temperature up to about 200 ° C., there is a problem that in the temperature range higher than that, softening and thermal deterioration occur due to the small crosslink density. Further, this ring-opening polymerization reaction has a drawback that it takes a long time to cure as compared with a usual curing reaction of a phenol resin, and it is known that industrial applications are limited in terms of productivity.

The composition of a compound having a dihydrobenzoxazine ring and an epoxy resin also has a problem that the curing rate is slow because the rate-determining step of curing is the ring-opening reaction of the dihydrobenzoxazine ring.

[0008] Further, along with the miniaturization of electronic / electrical devices, the demand for thermosetting films having high toughness as insulating adhesives is rapidly increasing. No product is obtained, and it is difficult to obtain a film-like product.

[0009]

DISCLOSURE OF THE INVENTION The present invention is a novel thermosetting resin having flame retardance which does not accompany volatile components during curing, which cannot be achieved by conventional phenolic resins and epoxy resins. An object of the present invention is to provide a phenolic compound having higher toughness and faster curability than a compound having a dihydrobenzoxazine ring known so far, and a suitable production method thereof. The present invention is also capable of changing the softening temperature of the resin in a wide range by changing the molecular weight, and can be used in various forms from a liquid thermosetting composition to a film-forming material such as a thermoplastic resin. The object is to provide a phenol compound capable of

The present invention also provides a curable resin composition which can be cured to form a cured product having low hygroscopicity and excellent heat resistance.
An object is to provide a composite molding material, and a laminated board and a wiring board using the same.

[0011]

Means for Solving the Problems The inventors of the present invention have made extensive studies in order to solve the above problems, and as a result, have reached the following inventions.

That is, the present invention provides a phenol compound having a structural unit A represented by the following formula (A). .

[0013]

Embedded image (However, R ¹ is a methyl group, a cyclohexyl group, a phenyl group or a substituted phenyl group, and the hydrogen atom of the aromatic ring of the structural unit A is an arbitrary substituent except one of the ortho positions of the hydroxyl group of the structural unit A. It may be substituted with a group.)

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION When R ¹ in the structural unit A of the phenol compound of the present invention is a substituted phenyl group, the substituent of the substituted phenyl group is, for example, halogen, an alkyl group, for example, having 1 to 30 carbon atoms. Alkyl groups of In addition, examples of the substituent that may substitute hydrogen on the aromatic ring of the structural unit A include an alkyl group such as an alkyl group having 1 to 30 carbon atoms, a phenyl group, and a halogen.

The number of structural units of the phenol compound of the present invention is at least 3, preferably 5 to 100. The upper limit of the structural unit depends on the use of the phenol compound,
There is no particular limitation, and n is tens of thousands, for example, 4 to 4, depending on the use.
It may be 50,000.

The phenol compound of the present invention comprises a phenol compound having at least two or more active hydrogens at the ortho or para position of the phenolic hydroxyl group, a primary amine and formaldehyde in 1 mol of the hydroxyl group of the phenol compound. In contrast, 0.75 primary amine
1.25 mol, and the ratio of formaldehydes to 1.6 to 3.0 times the molar amount of primary amine, preferably 1.8 to 2.
It is produced by reacting in a 5-fold molar amount.

Specifically, a mixed solution of a phenol compound having at least two or more active hydrogens at the ortho or para position of a phenolic hydroxyl group and a primary amine,
Add to formaldehyde heated to 70 ° C. or higher to 50 to 100 ° C., preferably 60 to 90 ° C.
The desired phenol compound can be obtained by reacting for 0 minutes to several tens of hours, for example, for 10 minutes to 50 hours.

Although various kinds of reaction solvents can be used, when the reaction is carried out in a polar solvent such as alcohol,
It is preferable because a desired phenol compound can be obtained without forming a cyclic compound such as dihydrobenzoxazine described later.

Further, as a method for synthesizing the phenol compound of the present invention, there is a method in which the compound is once passed through a benzoxazine compound and then subjected to ring-opening polymerization after purification. Although this method requires more steps, it can avoid a decrease in the molecular weight due to a side reaction in the initial stage of the reaction between phenol, amine and formaldehyde, and is therefore preferable for obtaining a high molecular weight compound. In this case, it is preferable to use a relatively nonpolar solvent such as MEK (methyl ethyl ketone) or toluene as the reaction solvent. The synthesis temperature of benzoxazine compounds is 5
The reaction time is 0 to 100 ° C, preferably 60 to 90 ° C, and the reaction time is preferably 10 minutes to several hours, for example, about 10 minutes to 50 hours. If the reaction is carried out at a high temperature for a long time, the dihydrobenzoxazine ring once formed is opened and the yield of the cyclic product is reduced, which is not preferable.

In the production method via this dihydrobenzoxazine compound, the desired phenol compound is obtained by ring-opening polymerization after purification of the dihydrobenzoxazine compound, but when the phenol compound is added at this time, it becomes a stopper to control the molecular weight. It will be possible.

The phenol compound having at least two active hydrogens at the ortho or para position of the phenolic hydroxyl group is a monovalent phenol such as phenol, m- or p-cresol, m- or p-chlorophenol, m- or p such as m- or p-bromophenol, β-naphthol, salicylic acid, and arylphenol
-Substituted phenols are mentioned. These phenols are preferable because the reaction site is not blocked. Further, divalent phenols such as hydroquinone, resorcinol, biphenol, 3,3′-diarylbiphenol, 4,4′-dihydroxydiphenylmethane,
3,3'-diaryl-4,4'-dihydroxydiphenylmethane, 3,3'-dihydroxystilbene, 2,
2'-bis (hydroxyphenyl) propane, 4,4 '
-Dihydroxydiphenylmethane, 3,3'-dihydroxydiphenylmethane and the like.

To obtain a high molecular weight phenolic compound,
Compounds having two active hydrogens at the o- or p-position with respect to the phenolic hydroxyl group such as o-cresol, p-cresol and p-phenylphenol are preferred so that a branched structure is not formed.

Specific examples of primary amines include alkylamines such as methylamine and cyclohexylamine, aniline, benzylamine, substituted anilines such as p-bromoaniline and anisidine, and the like.

As formaldehyde, formalin,
Examples include paraformaldehyde and trioxane.

The present invention also includes (a) the above-mentioned phenol compound of the present invention, (b) an epoxy compound, (c) a curing agent for an epoxy resin optionally blended, and (d)
It is intended to provide a curable resin composition comprising a curing accelerator which is blended if necessary.

In the case of the conventional novolac resin-cured epoxy resin, the reason why the moisture absorption rate is high is that there are many hydroxyl groups which are hydrophilic. In comparison with this, the phenol compound of the present invention also has a hydroxyl group, although it is small in quantity, but it has a feature that its hygroscopicity is extremely small. The reason for this is not clear, but it is considered that water is unlikely to enter between the molecules due to the large intermolecular cohesive force. In the case of the reaction product of the phenol compound and the epoxy compound of the present invention, the crosslinking density becomes small because the amount of the phenolic hydroxyl group is small, but a cured product having a low hygroscopic rate as well as the phenol compound with almost no decrease in heat resistance. Is obtained. It is speculated that this is also due to the strong intermolecular interaction due to the skeletal structure.

The cured product of the curable resin composition of the present invention is a cured product obtained by curing a conventional curable resin composition comprising a compound having a dihydrobenzoxazine ring and an epoxy compound, and the final chemical structure. Are similar, so Tg
And moisture absorption are similar. However, this conventional curable resin composition has a drawback in curability as described above. That is, the dihydrobenzoxazine ring does not directly react with the epoxy group, but the dihydrobenzoxazine ring once undergoes ring-opening polymerization and then reacts with the epoxy group. Therefore, since the dihydrobenzoxazine ring is a 6-membered ring with almost no strain in the ring, the reactivity is poor, and there is a practical problem in the field of semiconductor encapsulation and the like, which requires fast curing.

The epoxy compound used in the curable resin composition of the present invention is a glycidyl ether of a phenol compound having two or more phenolic hydroxyl groups in one molecule, for example, a diglycidyl ether of bisphenol A or a halogenated bisphenol A. And diglycidyl ether of phenol, polyglycidyl ether of phenol novolac, and the like. Further, an alicyclic epoxy compound is also used. Furthermore, monofunctional epoxy compounds can also be used as reactive diluents.

Examples of the curing agent for the epoxy resin used in the curable resin composition of the present invention include polyphenols, polycarboxylic acids, acid anhydrides, polyamines and polyamides.

The preferable blending ratio of the (a) phenol compound, the epoxy compound of (b) and the curing agent for the epoxy resin of (c) depends on the molecular weight of the raw materials used, but the ratio is The total equivalent amount of the functional groups of the phenol compound of the invention and the curing agent for epoxy resin is usually 0.2 to
It is 5 equivalents, preferably 0.5 to 2 equivalents, more preferably 0.8 to 1.2 equivalents, and the blending ratio of the phenol compound and the epoxy compound may not be equivalent.

It is also possible to use a curing accelerator in combination to accelerate the reaction between the phenolic hydroxyl group of the phenol compound and the epoxy group of the epoxy compound.
The amount of the curing R ¹ accelerator used is preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the phenol compound. Examples of the curing accelerator include curing accelerators commonly used in phenol-cured epoxy resins, such as tertiary amines, imidazoles, phosphines such as triphenylphosphine, and polyphenols.

The resin composition of the present invention is heated to 150 ° C. or higher, preferably 170 to 220 ° C.
Compared with a functional dihydrobenzoxazine compound or a compound in which a dihydrobenzoxazine ring is introduced into 90% or more of reactive hydroxyl groups, a cured product having a high heat resistance and a strong crosslinked structure is promptly provided.

Further, if necessary, a reinforcing agent selected from an inorganic filler and a fiber agent, a release agent, a coloring agent, an adhesiveness-imparting agent, etc. are added to the composite molding to further enhance the strength and dimensional stability. It can be a material. When the reinforcing agent is mixed, the mixing ratio is 1 with respect to 100 parts by weight of the resin component.
It is preferably about 500 parts by weight.

The composition containing the phenol compound of the present invention is a high-performance molding material excellent in heat resistance and flame retardancy, a coating material, a coating material, an adhesive, an encapsulating material, a laminate, an FRP.
It can also be used as a raw material for carbon products.

Further, the curable resin composition of the present invention is dissolved in an organic solvent and impregnated into a fiber base material such as glass cloth, organic fiber cloth, glass non-woven fabric, organic fiber non-woven fabric, paper, etc. and dried to obtain a coated cloth. A copper clad laminate is obtained by heat-pressing and laminating several pieces cut into a predetermined size and a copper foil. When the copper foil of this copper clad laminate is patterned using a photolithography technique, a cured product of the curable resin composition is used as a matrix, and an inorganic filler or a fibrous agent is used as a reinforcing agent to form a conductive pattern on a substrate. A substrate is obtained.

[0036]

EXAMPLES Specific examples of the present invention are shown below, but the present invention is not limited thereto. In the examples, the characteristics of the cured product are JIS-K6 regarding mechanical characteristics.
According to 911, for heat resistance, thermogravimetric / thermo-mechanical property evaluation device TG / DTA / T manufactured by Seiko Denshi Kogyo Co., Ltd.
Evaluation was performed using MA200. Flame retardant is UL-94
It was evaluated according to.

Example 1 Synthesis of Phenol Compound (1) 108 g of p-cresol (corresponding to 1 mol of hydroxyl group), 93 g of aniline (corresponding to 1 mol) and 50 g of ethylene glycol monomethyl ether (abbreviated as EMG) were mixed, and the mixture was mixed at 80 ° C. for 5 hours. Stir to prepare a uniform mixed solution. 162 g of formalin in a 500 ml flask
(Equivalent to 2 mol of formaldehyde) and methanol 175
g was added and heated to 90 ° C., and an EMG solution of p-cresol / aniline was added thereto little by little over 30 minutes. After completion of the addition, the reaction was allowed to proceed for 4 hours while maintaining the reflux temperature. Precipitation occurs as the reaction progresses. After cooling to room temperature and standing for about 1 day, the precipitated polymer layer was separated. The precipitated polymer was heated to 100 ° C. and dried under reduced pressure to obtain the objective phenol compound. The obtained phenolic compound has the following structural unit, GPC
As a result of measuring the molecular weight using
It was 200. In addition, I of the obtained phenol compound
The R-spectrum is shown in FIG.

[0038]

Embedded image Example 2 Synthesis of phenol compound (2) 108 g of p-cresol (corresponding to 1 mol of hydroxyl group), 93 g of aniline (corresponding to 1 mol) and MIBK1
25 g was mixed and stirred at 80 ° C. for 5 hours to prepare a uniform mixed solution. Formalin 16 in a 50 ml flask
2 g (equivalent to formaldehyde 2 mol) and MIBK10
Charge 0 g and heat to 90 ° C., and p-cresol /
The aniline MIBK solution was added in small portions over a period of 30 minutes. After the addition was completed, the mixture was kept at the reflux temperature for 30 minutes and then once cooled to room temperature. After standing for about 1 day, the aqueous phase and the organic phase were separated. After that, the organic phase was heated to 50 ° C. and distilled under reduced pressure at that temperature for 3 hours to remove condensed water. Then, the product was dissolved in ethyl ether, washed 4 times with distilled water, 3 times with a 3N aqueous solution of sodium hydroxide, and dried again under reduced pressure to give 3-phenyl-6-methyl-4H-2, which has the following structure.
3-dihydro-1,3-benzoxazine (hereinafter 6-
Methyldihydrobenzoxazine) was obtained. The IR spectrum of the product is shown in FIG.

[0039]

Embedded image Next, 200 g of 6-methylbenzoxazine and 9.6 g of p-cresol were reacted in MIBK at 100 ° C. for 5 hours to obtain the objective phenol compound (hydroxyl group equivalent 215). The obtained phenol compound had the following structural unit, and its molecular weight was measured by GPC, and as a result, it was about 3900 in terms of polystyrene. The IR spectrum of this phenol compound was almost the same as in FIG.

[0040]

Embedded image Even when this reaction was carried out in a molten state without using a solvent, almost the same product was obtained.

Example 3 Synthesis of phenol compound (3) 6-methyldihydrobenzoxazine 2 obtained in Example 2
00g and p-cresol 32g are 100 times in MIBK.
The reaction was carried out at 0 ° C for 5 hours to obtain the desired phenol compound. The molecular weight of the obtained phenol compound was about 900 in terms of polystyrene measured by GPC.

Even when this reaction was carried out in a molten state without using a solvent, almost the same product was obtained.

Example 4 Synthesis of phenol compound (4) 6-methyldihydrobenzoxazine 2 obtained in Example 2
00g and p-cresol 1.0g in MIBK 10
The reaction was carried out at 0 ° C for 5 hours to obtain the desired phenol compound. The molecular weight of the obtained phenol compound was about 8800 in terms of polystyrene measured by GPC.

Example 5 Synthesis of Phenolic Compound (5) In the same manner as in Example 2, p-cresol was used instead of p-cresol.
A dihydrobenzoxazine compound was synthesized using phenylphenol. The type of solvent used for synthesis is the same,
The amount was blended so that the solid content was 50%. The purification solvent of 3,6-diphenyl-4H-2,3-dihydro-1,3-benzoxazine (hereinafter abbreviated as 6-phenyldihydrobenzoxazine) obtained as an intermediate product is M
IBK was used.

Then, 200 g of the obtained 6-phenyldihydrobenzoxazine and p-phenylphenol 1.
3 g was reacted in MIBK at 100 ° C. for 8 hours to obtain the objective phenol compound. The obtained phenol compound had the following structural unit, and the molecular weight was measured by GPC, and as a result, it was about 6,500 in terms of polystyrene.

[0046]

[Chemical 6] Example 6 Synthesis of phenol compound (6) A dihydrobenzoxazine compound was synthesized in the same manner as in Example 2 except that phenol was used instead of p-cresol. The type of solvent for synthesis was the same, and the amount was such that the solid content was 50%. MIBK was used as a purification solvent for 4H-2,3-dihydro-1,3-benzoxazine (hereinafter abbreviated as dihydrobenzoxazine) obtained as an intermediate product.

Then, 100 g of the obtained dihydrobenzoxazine and 14.9 g of p-phenylphenol were mixed with M
The reaction was carried out in IBK at 100 ° C. for 8 hours to obtain the objective phenol compound. The obtained phenol compound had the following structural unit, and the molecular weight was measured by GPC, and as a result, it was about 3,200 in terms of polystyrene.

[0048]

[Chemical 7] Example 7 Synthesis of phenol compound (7) In the same manner as in Example 2, p-cresol was used instead of p-cresol.
A dihydrobenzoxazine compound was synthesized using bromophenol. The type of solvent for synthesis was the same, and the amount was such that the solid content was 50%. 3-phenyl-6-bromo-4H-2,3 obtained as an intermediate product
MIBK was used as a solvent for producing -dihydro-1,3-benzoxazine (hereinafter abbreviated as 6-bromodihydrobenzoxazine).

Next, 200 g of the obtained 6-bromodihydrobenzoxazine and 1.3 g of p-bromophenol.
And were reacted in MIBK at 100 ° C. for 3 hours to obtain the objective phenol compound. The obtained phenol compound had the following structural unit, and the molecular weight was measured by GPC, and as a result, it was about 3100 in terms of polystyrene.

[0050]

Embedded image Example 8 Synthesis of phenol compound (8) In the same manner as in Example 2, instead of p-cresol, m- was used.
A dihydrobenzoxazine compound was synthesized using cresol. The type of solvent for synthesis was the same, and the amount was such that the solid content was 50%. Dichloromethane was used as a purification solvent for 3-phenyl-5-methyl-4H-2,3-dihydro-1,3-benzoxazine (hereinafter abbreviated as 5-methyldihydrobenzoxazine) obtained as an intermediate product. The IR spectrum of the product is shown in FIG.

Then, 200 g of the obtained 5-methyldihydrobenzoxazine and 1.3 g of m-cresol were mixed with M
The reaction was carried out in IBK at 100 ° C. for 3 hours to obtain the objective phenol compound. The obtained phenol compound had the following structural unit, and the molecular weight was measured by GPC, and as a result, it was about 10,000 in terms of polystyrene. The IR spectrum of the obtained phenol compound is shown in FIG.

[0052]

Embedded image Examples 9 to 11 Phenol compounds obtained in Example 2 (OH equivalent 215.
5) 50% MIBK solution (solid content 25 g), phenol novolac epoxy resin (epoxy equivalent 220) and brominated bisphenol A type epoxy resin (epoxy equivalent 4)
00, Br content 50% by weight) and 2-phenylimidazole (0.3% based on the resin solid content) and MI as a solvent.
Varnishes were prepared from BK with the compounding ratios shown in the table below. Oxazine in the table is an intermediate 6-methyldihydrobenzoxazine (OH equivalent 215). The novolak in the table is a novolac phenol resin curing agent (OH equivalent 105). Then, using this varnish, a glass cloth (0.2
mmt). The coating conditions differ slightly depending on the gelation time of the varnish and the progress of the reaction, but normally 14
0 ° C / 1.5 minutes + 170 ° C / 2 minutes + 175 ° C / 2 minutes + 1
50 ° C./1.5 minutes. The coated cloth and the copper foil thus obtained were superposed and laminated under heat and pressure under reduced pressure to obtain a double-sided copper-clad laminate. The pressure is 30 kg / cm ² , and the temperature is RT → 185 ° C. for 30 minutes and 185 ° C. for 90 minutes. The characteristics of the obtained copper clad laminate are as shown in the table. As shown in the table, it can be seen that the Tg is high, the moisture absorption rate is small, the flame retardancy is excellent, and the curability is excellent as compared with the phenol novolac resin-cured epoxy resin. Curability was measured by DSC heat generation (reaction rate after heating at 180 ° C./30 minutes).

[0053]

[Table 1]

[0054]

According to the present invention, there is provided a novel thermosetting resin having a flame retardant property that does not generate a volatile component during curing.
It has higher toughness and faster curability than compounds with dihydrobenzoxazine ring known so far, and it is possible to change the softening temperature of the resin in a wide range by changing the molecular weight. Phenol compounds have been obtained which can be used in various forms, from thermosetting compositions to those which can be filmed like thermoplastics.

Further, according to the present invention, it is cured to have low hygroscopicity,
A curable resin composition capable of forming a cured product having excellent heat resistance, a composite molding material, and a laminated board and a wiring board using the same were obtained.

[Brief description of drawings]

1 is the IR- of the phenolic compound obtained in Example 1. FIG.
Spectrum chart.

2 is an IR-spectra chart of 3-phenyl-6-methyl-4H-2,3-dihydro-1,3-benzoxazine obtained in Example 2. FIG.

FIG. 3 is an IR-spectral chart of 3-phenyl-5-methyl-4H-2,3-dihydro-1,3-benzoxazine obtained in Example 8.

FIG. 4 shows IR- of the phenol compound obtained in Example 8.
Spectrum chart.

Continuation of front page (51) Int.Cl. ⁶ Identification number Internal reference number for FI Technical location H05K 1/03 610 7310-4F B29C 67/14 G // B29K 105: 08 (72) Inventor Yasuyuki Hirai Ibaraki Prefecture Shimodate City Oita 1500 Oita Hitachi Chemical Co., Ltd. Shimodate Plant (72) Inventor Hideo Nagase Ibaraki Shimodate Ogawa 1500 Ogawa Hitachi Chemical Co., Ltd. Shimodate Plant (72) Inventor Aihiko Sato Oita Shimodate Ogawa, Ibaraki Prefecture 1500 In Hitachi Chemical Co., Ltd. Shimodate Factory (72) Inventor Mitsuo Yokota 1500 Ogawa, Shimodate City, Ibaraki Prefecture In Hitachi Shiseido Co., Ltd. Shimodate Factory (72) Inventor Yoshihiro Nakamura 1500, Ogawa, Shimodate, Ibaraki Prefecture Hitachi Chemical Industrial Co., Ltd.Shimodate Factory (72) Inventor Yo Murai 1500 Ogawa, Shimodate, Ibaraki Hitachi Chemical Co., Ltd. Shimodate Factory (72) Inventor Yoshinori Sato 1500 Ogawa, Shimodate, Ibaraki Hitachi Chemical Co., Ltd.Shimodate In the factory (72 ) Inventor Shinichi Kamoshida 1500 Ogawa Oji, Shimodate City, Ibaraki Prefecture Inside Hitachi Chemical Co., Ltd. Shimodate Factory

Claims (7)

[Claims] 1. A phenol compound having a structural unit A represented by the following formula (A). Embedded image (However, R ¹ is a methyl group, a cyclohexyl group, a phenyl group or a substituted phenyl group, and the hydrogen atom of the aromatic ring of the structural unit A is an arbitrary substituent except one of the ortho positions of the hydroxyl group of the structural unit A. It may be substituted with a group.) 2. A phenolic compound having at least two or more active hydrogens at the ortho or para position of the phenolic hydroxyl group, a primary amine and formaldehydes are used per 1 mol of the hydroxyl group of the phenolic compound.
A method for producing a phenol compound, which comprises reacting a primary amine in an amount of 0.75 to 1.25 mol and a formaldehyde in a ratio of at least twice the molar amount of a primary amine. 3. A phenolic compound having at least two or more active hydrogens at the ortho or para position of a phenolic hydroxyl group, a primary amine and formaldehydes are added to 1 mole of the hydroxyl group of the phenolic compound, and the primary amine is 0. 0.75 to 1.25 mol and formaldehydes are reacted in an amount at least twice as much as the primary amine to synthesize a compound having a dihydrobenzoxazine ring, and then phenols are added or heated without addition. A method for producing a phenol compound, which comprises carrying out a reaction. 4. A phenol compound according to claim 1, (b) an epoxy compound, (c) a curing agent for an epoxy resin which is optionally blended, and (d) a curing accelerator which is optionally blended. A curable resin composition comprising an agent. 5. (a) The phenol compound according to claim 1, (b) an epoxy compound, (c) a curing agent for an epoxy resin optionally blended, and (d) a curing accelerator optionally blended. A composite molding material containing an agent and (e) a reinforcing agent selected from an inorganic filler and a fiber agent. 6. A laminate obtained by heat-molding the composite molding material according to claim 5, wherein the reinforcing material is glass cloth, organic fiber cloth, glass nonwoven fabric, organic fiber nonwoven fabric, or paper. 7. A wiring board in which a conductive pattern is formed on a substrate using the cured product of the curable resin composition according to claim 4 as a matrix and using an inorganic filler or a fiber material as a reinforcing agent.