JPH072979A - Aminated phenolic resin and production thereof - Google Patents

Abstract

PURPOSE:To obtain an aminated phenolic resin effective in improving heat resistance, etc., and useful as the material of various resins by reacting a specific phenolic compound with a specific aromatic amine compound and a specific aralkyl compound. CONSTITUTION:A phenolic compound represented by formula I (wherein R1 and R2 each is H, halogen, OH, a 1-12C alkyl, an aryl, a cycloalkyl, or an aralkyl or they may form a ring) is mixed with an aromatic amine compound represented by formula II [wherein R3 and R4 each is the same as R1 or amino, an aminoaralkyl, a hydroxyaralkyl, an alkoxy, or an (amino- or hydroxy- substituted aryloxy or they may form a ring] in a given molar proportion. The mixture is reacted with an aralkyl compound represented by formula III [wherein A is an (alkyl-substituted) phenylene, diphenylene, naphthylenyl, or diphenyl ether and X is a halogen, OH, or a 1-4C alkoxy] in a given proportion to obtain the objective resin represented by formula IV (wherein m and n each is 0-20, provided that at least either is not 0).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel amino group-containing phenolic resin and a method for producing the same. These phenolic resins are useful as an epoxy resin raw material and an epoxy resin curing agent in applications such as casting, lamination, molding, and adhesion, and are reacted with maleic anhydride, nadic acid anhydride, phthalic acid anhydride, etc. It can be used as a chemical resin. These imidized resins can be used as a thermosetting resin with hexamine or the like like ordinary phenol resins, and can be used as a raw material for epoxy resins or a curing agent for epoxy resins, and as an additive to various resins. it can.

[0002]

2. Description of the Related Art Conventionally, phenolic resins obtained by reacting phenols with formaldehyde have
As a material that balances properties such as flame retardancy, electrical insulation, dimensional stability, and processability, and price, it occupies an important position among thermosetting resins. The range of industrial application as various molding materials is very wide. However, in recent years, with the development of industry, it has been required to significantly improve workability and heat resistance, mechanical strength, oxidation resistance, water resistance and the like of a phenol resin cured product obtained by thermosetting a phenol resin. There is. At present, it is attempted to introduce an amino group into a phenol resin for the purpose of further improving some of the properties of the cured product of the phenol resin. For example, it is disclosed that by using a phenol resin having an amino group introduced therein as a raw material for an imidized resin, the resulting imidized resin gives a thermosetting resin with hexamine or the like, similar to a normal phenol resin. (JP-A-3-275708). It is also disclosed that a phenol resin having an amino group introduced therein can be used as a raw material for an epoxy resin or as a curing agent for an epoxy resin (JP-A-4-276624, JP-A-5-105734).

However, the above disclosed resins are
All of them are composed of a novolac type phenolic structure and are effective in improving heat resistance, but it is hard to say that these phenolic resins having a formalin bond can satisfy other required performances. That is, the disadvantages of the cured phenolic resin are (1) hard and brittle, (2) high water absorption due to high hydroxyl group density, and (3) lack of long-term heat resistance due to poor oxidation resistance stability. It is a generally known fact, and even in the above-mentioned modified phenolic resin, these drawbacks cannot be remedied. Further, in terms of workability, the softening point of the raw material resin is not too high, in order to achieve the improvement in productivity by easily performing the work such as kneading and casting of the raw material resin and various compounding agents, preferably, Although it is desired that the softening point be 120 ° C. or lower,
The modified resin has a drawback that it has a high softening point.

[0004]

The object of the present invention is to significantly improve heat resistance, mechanical strength, oxidation resistance, water resistance, workability, etc. without impairing the various properties of conventional phenolic resins. The purpose of the present invention is to provide a modified phenolic resin which is useful as various resin raw materials.

[0005]

[Means for Solving the Problems] The present inventors have completed the present invention as a result of intensive studies for solving the above problems. That is, the present invention provides a phenol compound represented by the general formula (1) (chemical formula 4) and a general formula (2) (chemical formula 5).
The molar ratio of the aromatic amine compound represented by (0.97:
0.03) to (0.2: 0.8) mixture (1 mol) and the aralkyl compound represented by the general formula (3) 0.1 to 0.9.
A method for producing an amino group-containing phenol resin represented by the general formula (4) (Chemical Formula 6), which is reacted with 5 mol, and a softening point of 40 ° C to 120 ° C and an average molecular weight of 3 obtained by this method.
The present invention relates to an amino group-containing phenol resin having an amine value of 00 to 5000 and an amine value of 150 to 2000 g / eq.

[0006]

[Chemical 4] (Wherein, R _1, R ₂ is hydrogen, an alkyl group of halogen, hydroxyl or until C ₁ -C _12,, an aryl group, a cycloalkyl group, an aralkyl group, which may be the same or different, R ₁ and R ₂ may form a ring)

[0007]

[Chemical 5] (In the formula, R ₃ and R ₄ are hydrogen, a halogen atom, a hydroxyl group,
Amino group, C _{1 to} C ₁₂ alkyl group, aryl group,
Cycloalkyl group, aralkyl group, amino group-substituted aralkyl group, hydroxy group-substituted aralkyl group, alkoxy group, aryloxy group, amino group-substituted aryloxy group, hydroxy group-substituted aryloxy group, which may be the same or different, R ₃ , R ₄ may form a ring) X—CH ₂ —A—CH ₂ —X (3) (In the formula, A represents a phenylene group, an alkyl-substituted phenylene group, a diphenylene group, a diphenyl ether group or a naphthylenyl group. , X represents a halogen atom, a hydroxyl group, or an alkoxy group having 1 to 4 carbon atoms)

[0008]

[Chemical 6] (In the formula, R _{1 to} R ₄ have the same meanings as described above, m and n represent an integer of 0 to 20, m and n do not become 0 at the same time, and the terminal is a phenol compound and / or (Aromatic amine compound, the order of bonding phenol compound and aromatic amine compound is not limited)

The amino group-containing phenol resin of the present invention is
All are novel compounds. The amino group-containing phenol resin of the present invention is characterized by introducing an aromatic amine into the structure of the phenol resin and using an aralkyl group for connecting them. As a result, the softening point and melt viscosity of these phenolic resins are remarkably lower than those obtained by formalin binding, and workability can be improved. In addition, since the cured composition using these phenolic resins has an aralkyl group as a linking group, the hydroxyl group density per unit molecule is reduced, the hydrophobicity is increased, and low water absorption is achieved. Further, as an effect of introducing the amino group, heat resistance can be improved in various applications.

The method for obtaining the phenol resin of the present invention will be specifically described below. Examples of the phenol compound that can be used in the present invention include monohydric or dihydric phenol, bisphenol, and trisphenol.
Specifically, phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, p-ethylphenol, o-isopropylphenol, ps
ec-butylphenol, p-cyclohexylphenol, p-chlorophenol, o-bromophenol, p
-Bromophenol, 2,4-xylenol, 2,6-
Xylenol, pt-butylphenol, p-octylphenol, p-nonylphenol, p-cumylphenol, p-phenylphenol, o-phenylphenol p-phenoxyphenol, o-methoxyphenol, p-methoxyphenolresorcin, catechol,
Examples thereof include hydroquinone, 2,2-bis (4-hydroxyphenyl) propane, 4,4′-thiodiphenol, dihydroxydiphenylmethane, α-naphthol and β-naphthol.

The aromatic amine compounds usable in the present invention include aniline, 2-methylaniline,
2-chloroaniline, 2-ethylaniline, m-phenylenediamine, p-phenylenediamine, 2,6-diaminotoluene, 3,5-diaminobiphenyl, 4,4 '.
-Diaminodiphenylmethane, 1,3,5-triaminobenzene, p-aminophenol, m-aminophenol, 4-amino-4'-hydroxydiphenyl ether, 4-amino-4'-hydroxypropane, 2-amino-1, 3-resorcin, 4-amino-1,3-resorcin, 2-aminohydroquinone, 2-methoxyaniline, 4-methoxyaniline, 2-isopropoxyaniline, 2,4-dimethoxyaniline, o-isopropylaniline, m-isopropyl Aniline, p-isopropylaniline, on-propylaniline, o-tert-
Butylaniline, p-tert-butylaniline, p-sec
-Butylaniline, 2,3-xylidine, 2,4-xylidine, 2,6-xylidine, 3,4-xylidine,
3,5-xylidine, 2-methyl-3-ethylaniline, 2-methyl-4-isopropylaniline, 2,6-
Diethylaniline, 2-ethyl-5-tert-butylaniline, 2,4-diisopropylaniline, 2,4
6-trimethylaniline, 4-chloroaniline, 4-bromoaniline, 4-fluoroaniline, 3-chloroaniline, 3-bromoaniline, 3,4-dichloroaniline, 3-chloro-o-toluidine, 3-chloro-p. -Toluidine, 2,6-dimethyl-4-chloroaniline, 2
-Amino-4-cresol, 4-amino-2-tert
-Butylphenol, 2,6-dimethyl-4-aminophenol, 2,6-dichloro-4-aminophenol,
2-amino-1,3-resorcin, 4-amino-1,3
-Resorcin, 1,1-dimethyl-4-aminoindan, o-phenylenediamine, 2,4-diaminotoluene, 2,4-diaminoethylbenzene, 2,6-diaminoethylbenzene, 2,4-diaminoisopropylbenzene, 2, 4-diamino-tert-butylbenzene,
2,6-diamino-tert-butylbenzene, 2,4
-Diamino-1,3-dimethylbenzene, 1,1-dimethyl-4-aminoindan, 1,1-dimethyl-4,6
-Diaminoindan and the like. Suitable compounds are
It is aniline.

The aralkyl compound is a compound represented by the general formula (3), wherein A is a phenylene group, an alkyl-substituted phenylene group, a diphenylene group, a diphenyl ether group or a naphthylenyl group, and X is a chlorine atom, a bromine atom,
A halogen atom such as a fluorine atom, a hydroxyl group, and an alkoxy group having 1 to 4 carbon atoms. For example, α, α′-dihydroxy-o-xylene, α, α′-dihydroxy-m-xylene, α, α′-dihydroxy-p-xylene, α,
α'-dimethoxy-m-xylene, α, α'-dimethoxy-p-xylene, α, α'-diethoxy-o-xylene, α, α'-diethoxy-m-xylene, α, α'-
Diethoxy-p-xylene, α, α′-diisopropoxy-o-xylene, α, α′-diisopropoxy-m-
Xylene, α, α′-diisopropoxy-p-xylene, α, α′-di-n-propoxy-p-xylene,
α, α′-di-n-butoxy-m-xylene, α, α ′
-Di-n-butoxy-p-xylene, α, α'-di-s
ec-butoxy-p-xylene, α, α′-diisobutoxy-p-xylene, 4,4′-dihydroxymethyldiphenyl ether, 4,4′-dihydroxymethyldiphenyl, 2,6-dihydroxymethylnaphthalene, 4,
4'-dimethoxymethyldiphenyl ether, 4,4 '
-Diethoxymethyldiphenyl ether, 4,4'-diisopropoxymethyldiphenyl, 4,4'-diisobutoxymethyldiphenyl ether, α, α'-dimethoxy-2-methyl-p-xylene, α, α'-dimethoxy-3 -Methyl-m-xylene, α, α'-dihydroxy-2,5-dimethyl-p-xylene, α, α'-dimethoxy-2,5-dimethyl-p-xylene, α, α'-dimethoxy-2, 4-dimethyl-1,3-xylene, α,
α'-dimethoxy-2,4-dimethyl-1,5-xylene, α, α'-dichloro-o-xylene, α, α'-dichloro-m-xylene, α, α'-dichloro-p-xylene, α, α'-dibromo-o-xylene, α, α'-
Dibromo-m-xylene, α, α′-dibromo-p-xylene, α, α′-difluoro-o-xylene, α,
α'-difluoro-m-xylene, α, α'-difluoro-p-xylene, α, α'-diiodo-o-xylene, α, α'-diiodo-m-xylene, α, α'-diiodo-p -Xylene, 4,4'-bis (chloromethyl) diphenyl ether, 4,4'-bis (chloromethyl) diphenyl, 2,6-bis (chloromethyl) naphthalene, 4,4'-bis (bromomethyl) diphenyl ether, 4 , 4'-bis (bromomethyl) diphenyl,
2,6-bis (bromomethyl) naphthalene, 4,4'-
Bis (fluoromethyl) diphenyl ether, 4,4 '
-Bis (fluoromethyl) diphenyl, 2,6-bis (fluoromethyl) naphthalene, 4,4'-bis (iodomethyl) diphenyl ether, 4,4'-bis (iodomethyl) diphenyl, 2,6-bis (iodomethyl)
Naphthalene, α, α′-dichloro-2-methyl-p-xylene, α, α′-dichloro-3-methyl-m-xylene, α, α′-dichloro-2,5-dimethyl-p-xylene, α , Α'-dibromo-2,5-dimethyl-p-xylene, α, α'-dichloro-2,4-dimethyl-1,
Examples thereof include 3-xylene and α, α′-dibromo-2,4-dimethyl-1,5-xylene. Suitable compounds include α, α′-dihydroxy-p-xylene, α, α′-dichloro-p-xylene and the like.

As a specific method for producing the phenol resin of the present invention, a mixture of a phenol compound represented by the general formula (1) and an aromatic amine compound represented by the general formula (2) is prepared by the general formula The aralkyl compound represented by (3) is reacted with an acid catalyst. As the acid catalyst, an inorganic or organic acid such as hydrochloric acid, phosphoric acid, sulfuric acid or nitric acid, or a Friedel-Crafts catalyst such as zinc chloride, stannic chloride, aluminum chloride or ferric chloride, methanesulfonic acid, Ultra strong acids such as Nafion H (trade name: manufactured by DuPont) can be used. These may be used alone or in combination. In addition, activated clay, solid acid catalysts of zeolites and heteropolyacids can also be used. Industrially preferable is inexpensive hydrochloric acid. The amount of the catalyst used is 3 mol% or more, preferably 5 to 80 mol% based on the total amount of the phenol compound and the aromatic amine compound. In the case of solid acid catalyst, 1 to 100 wt% based on all raw materials
%, Preferably 5 wt% or more. Above this range, there is no problem in the reaction, but it is not economical. When a bishalogenomethyl derivative is used as the aralkyl compound represented by the general formula (3), the reaction can be carried out in the absence of a catalyst, but an acid catalyst may be used for the purpose of accelerating the reaction. As the acid catalyst, any of the above-mentioned acid catalysts can be used, and inexpensive hydrochloric acid is industrially preferable.

In the method of the present invention for introducing an aromatic amine component into the phenolic resin structure, the reaction between the aromatic amine component and the aralkyl compound of formula (3) is obtained by a two-step reaction. That is, in the first step reaction, a resin containing a secondary amine is produced, but this secondary amine is led to the primary amine resin by the second step reaction (transfer reaction). This transfer reaction is achieved by using the above-mentioned acid as a catalyst. However, when a bishalogenomethyl derivative is used as the aralkyl compound, this transfer reaction reduces the hydrogen halide generated when the secondary amine resin is generated. Achieved as a catalyst.
In order to accelerate this transfer reaction, (a) increase the amount of the same or different type of catalyst, (b) increase the reaction temperature, (c) increase the reaction time, etc., rather than the reaction conditions in which the secondary amine resin is produced. By means. Even when the reaction is carried out by autocatalysis using a bishalogenomethyl derivative as the aralkyl compound, the reaction can be accelerated by using the above-mentioned acid catalyst, as described above. In the method of the present invention, the reaction between the phenol compound and the aralkyl compound also occurs at the same time in the course of such first-stage and second-stage reactions. As a result, the useful resin of the present invention is produced. In order to obtain the amino group-containing phenol resin of the present invention, a mixture of a phenol compound and an aromatic amine compound is used, and the mixing ratio is (0.97: 0.0
3) to (0.2: 0.8).

The reaction temperature is 0 to 22 for the whole reaction.
0 ° C., but in the first stage reaction, 0 to 130
C., preferably 20 to 110.degree. C. and 150 to 220.degree. C. in the second stage reaction. A reaction temperature of 170 ° C. or higher is desirable in order to shorten the reaction time of the second step as much as possible. The reaction time is 1 to 5 hours in the first stage reaction and 3 to 20 hours in the second stage reaction.

In the phenol resin of the present invention, various forms of phenol resin, from low molecular weight resins to high molecular weight resins, can be used depending on the application by changing the molar ratio of the aralkyl compound to the total of the phenol compound and the aromatic amine compound. Can be manufactured. That is, during the condensation reaction,
By increasing the total molar ratio of the phenol compound and the aromatic amine compound with respect to the aralkyl compound, a liquid to low softening point phenol resin can be obtained. On the other hand, during the condensation reaction, an aromatic amine resin having a high softening point can be obtained by making the total molar ratio of the phenol compound and the aromatic amine compound to the aralkyl compound close to the theoretical amount. That is, by reacting the aralkyl compound in the range of 0.1 to 0.95 mol with respect to 1 mol in total of the phenol compound and the aromatic amine compound,
The molecular weight range of the present invention is 300 to 5000, the softening point range of resin is 40 to 120 ° C., and the amine value is 150 to 200.
An amino group-containing phenol resin having 0 g / eq can be obtained.

In the method of the present invention, a solvent inert to the reaction may be used, but the reaction is usually carried out without a solvent. After completion of the reaction, the acid used as a catalyst or the acid generated by the reaction is neutralized with a dilute aqueous alkaline solution such as aqueous ammonia. At this time, unreacted phenol compounds, aromatic amine compounds, etc. are distilled off under vacuum or by steam distillation. In addition, the inorganic salts and the like produced as a by-product of the neutralization are benzene, toluene, MEK, etc.
A solvent that is immiscible with water may be added and the liquid may be removed by a water separation method. After that, the solvent can be removed to obtain the desired product. When a solid acid catalyst is used, it can be removed by filtration.

[0018]

EXAMPLES Next, the present invention will be described in more detail by way of examples. However, the present invention is not limited to these examples. Example 1 A glass reaction vessel equipped with a stirrer, a thermometer and a reflux condenser was charged with 193.0 g (2.05 mol) of phenol and 181.5 g (1.95 mol) of aniline, and the internal temperature was adjusted. 1
The temperature was raised to 05 ° C. Next, 175.0 g (1.0 mol) of p-xylylene dichloride was charged, and stirring was continued for 2.5 hours while maintaining the internal temperature at the same temperature. Then, the internal temperature was raised to 180 ° C. and stirring was continued for 9.5 hours. After completion of the reaction, the internal temperature was gradually cooled to 60 ° C., and 280 g of 28% ammonia water was added for neutralization. Next, water, unreacted phenol and aniline were removed by vacuum distillation, toluene and water were added to the residue, and the mixture was washed with water to remove ammonium chloride. After washing with water, toluene and a small amount of water were removed by distillation under reduced pressure, and the obtained reddish brown transparent resin was discharged while hot. The yield was 215 g and had a softening point (JIS-K-254).
8) was 62.4 ° C. Hydroxyl equivalent of this resin (g
/ Eq) is 201 and the amine value (g / eq) is 82.
It was 0. The average molecular weight of the resin by GPC is 620
Met. The infrared absorption spectrum of this resin is shown in FIG.

Example 2 A glass reaction vessel equipped with a stirrer, a thermometer and a reflux condenser was charged with 259.6 g (1.8 mol) of α-naphthol and 111.7 g (1.2 mol) of aniline. The internal temperature to 9
The temperature was raised to 5 ° C. Then, 105.1 g (0.6 mol) of p-xylylene dichloride was charged and the reaction was carried out in the same manner as in Example 1. After the reaction was completed, the internal temperature was gradually cooled to 60 ° C., and 157.7 g of 28% aqueous ammonia was added to neutralize.
Next, water and toluene were added, liquid separation and water washing were performed to remove ammonium chloride. Toluene, residual unreacted α-naphthol and a trace amount of water were removed by vacuum distillation,
The resulting dark brown resin was discharged while hot. Yield 156g
The softening point (JIS-K-2548) was 94.0 ° C. The hydroxyl group equivalent (g / eq) of this resin was 390, and the amine value (g / eq) was 1190. GPC
This resin had an average molecular weight of 760. The infrared absorption spectrum of this resin is shown in FIG.

Example 3 In a glass reaction vessel equipped with a stirrer, a thermometer, a reflux condenser and a water separator, 138.1 g (1.0 mol) of α, α'-dihydroxy-p-xylene and 94 of phenol were added. .1
g (1.0 mol), p-aminophenol 109.1 g
(1.0 mol) and activated clay (Galeonite # 13)
6, Mizusawa Chemical Co., Ltd.) 68.3 g was charged, and the internal temperature was set to 1
The temperature was raised to 80 ° C. Keep the internal temperature at the same temperature and stir for 13
I continued for hours. Water produced during the reaction was removed by a water separator. After completion of the reaction, the reaction solution was gradually cooled to 110 ° C., activated clay was removed by filtration, and vacuum distillation was performed.
The residual phenol and p-aminophenol were removed, and the resulting dark brown resin was discharged while hot. The yield is 230g
The softening point (JIS-K-2548) was 81 ° C. The hydroxyl group equivalent (g / eq) of this resin was 175, and the amine value (g / eq) was 435. The average molecular weight of the resin by GPC was 2,300.

Reference Examples 1, 2 o-cresol novolac type epoxy resin (EOCN-
102S, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 214) 1
Amino group-containing phenolic resin and phenol novolac resin obtained in Example 1 (BRG # 558, Showa Highpolymer Co., Ltd.) obtained as in Example 1 were used as a curing agent, and spherical fused silica (Harmic S- was used as an inorganic filler). CO, Inc.
A mixture of Micron) and amorphous fused silica (Hugh Rex RD-8, manufactured by Tatsumori Co., Ltd.) in a ratio of 50/50 (weight ratio), and other additives (parts by weight) shown in (Table 1).
Then, the mixture was kneaded with a mixing roll machine at a temperature of 100 ° C. for 3 minutes to obtain an epoxy resin composition. This composition was cast, and the physical properties of the obtained cured product were measured. Test pieces for measuring physical properties are transfer molded (180 ° C, 30 Kg
/ Cm ² , 3 min), and post-cured under the conditions shown in (Table 1). Further, using the above epoxy resin composition, a semiconductor element (10 mm × 10 mm
After mounting the corner, transfer molding (180 ℃, 3
A semiconductor device was obtained at 0 Kg / cm ² , 3 min).
The evaluation results of the cured resin and the semiconductor device are shown in (Table 1). It can be seen that the one using the amino group-containing phenol resin of the present invention as a curing agent has excellent heat resistance and moisture resistance.

[0022]

[Table 1] ・ Glass transition temperature: TMA method (Shimadzu, TMA-DRW
(Measured by DT-30) -Boiled water absorption rate: Measure the weight increase after boiling for 2 hours in boiling water at 100 ° C-V. P. S test: Test semiconductor device at 65 ° C, 9
After leaving it in a 5% constant temperature and humidity chamber for 168 hours, immediately
40 ° C. Fronato liquid (Sumitomo 3M, FC-7
0), and the number of semiconductors having cracks in the package resin was counted. The test value is shown by a fraction, the numerator is the number of semiconductor devices in which a crack has occurred, and the denominator is the number of semiconductor devices used in the test. The additives, epoxidized products, and curing agents used in the test are as follows. -CIIZ: undecyl imidazole (manufactured by Shikoku Fine Chemicals) -Inorganic filler: spherical fused silica (Harimisk S-CO,
A mixture of 50 parts by weight of Micron Co., Ltd. and 50 parts by weight of amorphous fused silica (Hugh Rex RD-8, manufactured by Tatsumori Co., Ltd.) Silane coupling agent: (SZ-6083, manufactured by Toray Dow Corning Silicone)・ BRG # 558: Phenol Novolac Resin Co., Ltd.
Showa High Polymer, hydroxyl equivalent 102

[0023]

INDUSTRIAL APPLICABILITY The present invention is a very useful amino group-containing phenol which is useful as an epoxy resin raw material and an epoxy resin curing agent, and can also be used as an imidized resin by reacting with maleic anhydride or the like. Provide resin.

[Brief description of drawings]

FIG. 1 is an infrared absorption spectrum of the resin obtained in Example 1.

FIG. 2 is an infrared absorption spectrum of the resin obtained in Example 2.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] June 28, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 1

[Correction method] Change

[Correction content]

[Chemical 1] (Wherein, R _1, R ₂ is a hydrogen atom, an alkyl group having a halogen atom, a hydroxyl group or a C ₁ ~ C _12,, an aryl group, a cycloalkyl group, an aralkyl group, which may be the same or different, and R ₁ R ₂ may form a ring) Molar ratio (0.97: 0.03) to (0.2: 0.8) of the aromatic amine compound represented by the general formula (2) 1 mole of a mixture of

[Chemical 2] (In the formula, R ₃ and R ₄ are a hydrogen atom , a halogen atom, a hydroxyl group, an amino group, a C ₁ to C ₁₂ alkyl group, an aryl group,
Cycloalkyl group, aralkyl group, amino group-substituted aralkyl group, hydroxy group-substituted aralkyl group, alkoxy group, aryloxy group, amino group-substituted aryloxy group, hydroxy group-substituted aryloxy group, which may be the same or different, R ₃ And R ₄ may form a ring) The aralkyl compound represented by the general formula (3) 0.1 to 0.9
And 5 moles, in _{X-CH 2 -A-CH 2} -X (3) ( wherein, A represents a phenylene group, an alkyl-substituted phenylene group, diphenylene group, diphenyl ether group, or a naphthylenyl group, X is a halogen atom, a hydroxyl group A C1-C4 alkoxy group is shown). The method for producing an amino group-containing phenol resin represented by the general formula (4) (Chemical Formula 3).

[Chemical 3] (In the formula, R _{1 to} R ₄ and A represent the same meaning as described above, m and n represent an integer of 0 to 20, m and n do not become 0 at the same time, and the terminal is a phenol compound and /
Or it is an aromatic amine compound, and the bonding order of the phenol compound and the aromatic amine compound is not limited)

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0008

[Correction method] Change

[Correction content]

[0008]

[Chemical 6] (In the formula, R _{1 to} R ₄ and A represent the same meaning as described above, m and n represent an integer of 0 to 20, m and n do not become 0 at the same time, and the terminal is a phenol compound and /
Or it is an aromatic amine compound, and the bonding order of the phenol compound and the aromatic amine compound is not limited)

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0010

[Correction method] Change

[Correction content]

The method for obtaining the phenol resin of the present invention will be specifically described below. Examples of the phenol compound that can be used in the present invention include monohydric or dihydric phenol, bisphenol, and trisphenol.
Specifically, phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, p-ethylphenol, o-isopropylphenol, ps
ec-butylphenol, p-cyclohexylphenol, p-chlorophenol, o-bromophenol, p
-Bromophenol, 2,4-xylenol, 2,6-
Xylenol, pt-butylphenol, p-octylphenol, p-nonylphenol, p-cumylphenol, p-phenylphenol, o-phenylphenol p-phenoxyphenol, o-methoxyphenol, p-methoxyphenolresorcin, catechol,
Hydroquinone, 2,2-bis (4-hydroxyphenyl) propane, di-hydroxy diphenyl methane, alpha-naphthol, beta-naphthol, and the like.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akihiro Yamaguchi 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd.

Claims (2)

[Claims] 1. A phenol compound represented by the general formula (1) (chemical formula 1) and: (Wherein, R _1, R ₂ is hydrogen, an alkyl group of halogen, hydroxyl or until C ₁ -C _12,, an aryl group, a cycloalkyl group, an aralkyl group, which may be the same or different, R ₁ and R ₂ may form a ring) General formula (2)
The molar ratio of the aromatic amine compound represented by Chemical formula 2 (0.
97: 0.03) to (0.2: 0.8) 1 mol of a mixture, (In the formula, R ₃ and R ₄ are hydrogen, a halogen atom, a hydroxyl group,
Amino group, C _{1 to} C ₁₂ alkyl group, aryl group,
Cycloalkyl group, aralkyl group, amino group-substituted aralkyl group, hydroxy group-substituted aralkyl group, alkoxy group, aryloxy group, amino group-substituted aryloxy group, hydroxy group-substituted aryloxy group, which may be the same or different, R ₃ , R ₄ may form a ring) 0.1 to 0.9 aralkyl compound represented by the general formula (3)
And 5 moles, in _{X-CH 2 -A-CH 2} -X (3) ( wherein, A represents a phenylene group, an alkyl-substituted phenylene group, diphenylene group, diphenyl ether group, or a naphthylenyl group, X is a halogen atom, a hydroxyl group A C1-C4 alkoxy group is shown). The method for producing an amino group-containing phenol resin represented by the general formula (4) (Chemical Formula 3). [Chemical 3] (In the formula, R _{1 to} R ₄ have the same meanings as described above, m and n represent an integer of 0 to 20, m and n do not become 0 at the same time, and the terminal is a phenol compound and / or (Aromatic amine compound, the order of bonding phenol compound and aromatic amine compound is not limited) 2. An amino group-containing phenol resin having a softening point of 40 ° C. to 120 ° C., an average molecular weight of 300 to 5000, and an amine value of 150 to 2000 g / eq, which is obtained by the method of claim 1.