JP3250871B2 - Amino group-containing phenolic resin and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel amino group-containing phenol resin and a method for producing the same. These phenolic resins are useful in applications such as casting, laminating, molding and bonding as epoxy resin raw materials and epoxy resin curing agents, and are also reacted with maleic anhydride, nadic anhydride, phthalic anhydride, etc. It can be used as a functionalized resin. These imidized resins can be used as an epoxy resin raw material or a curing agent for an epoxy resin, or as an additive to various resins, in addition to providing a thermosetting resin with hexamine or the like in the same manner as a normal phenol resin. it can.

[0002]

2. Description of the Related Art Conventionally, a phenol resin obtained by reacting a phenol with formaldehyde has a heat resistance,
As a material that balances properties and price, such as flame retardancy, electrical insulation, dimensional stability, workability, etc., it occupies an important position in thermosetting resins. The industrial application range as various molding materials is very wide. However, in recent years, with the development of industry, it has been required to significantly improve workability, heat resistance, mechanical strength, oxidation resistance, water resistance, etc. of a phenol resin cured product obtained by thermosetting a phenol resin. I have. At present, attempts have been made to introduce an amino group into a phenol resin for the purpose of further improving a part of the properties of the cured phenol resin. For example, it is disclosed that by using a phenol resin having an amino group introduced therein as a raw material of an imidized resin, the obtained imidized resin gives a thermosetting resin with hexamine or the like, similarly 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 an epoxy resin raw material or as a curing agent for an epoxy resin (Japanese Patent Application Laid-Open Nos. H4-227624 and H5-105734).

[0003] However, the resin disclosed above is:
Each of them has a novolak type phenol structure and is effective in improving heat resistance, but it cannot be said that these phenolic resins having a formalin bond can satisfy other required performances. The disadvantages of the cured phenolic resin are that (1) it is hard and brittle; (2) it has high water absorption due to high hydroxyl group density; and (3) it lacks long-term heat resistance due to poor oxidation stability. It is a generally known fact that these disadvantages cannot be ameliorated even with the above-mentioned modified phenolic resin. Further, in terms of workability, to easily perform operations such as kneading and casting of the raw material resin and various compounding agents, and to improve productivity, the softening point of the raw material resin is preferably not too high, preferably It is desired that the softening point is 120 ° C. or less,
The modified resin has a disadvantage that the softening point is increased.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to remarkably improve heat resistance, mechanical strength, oxidation resistance, water resistance, workability, etc. without impairing various properties of a conventional phenol resin. Another object of the present invention is to provide a modified phenol resin useful as various resin raw materials.

[0005]

Means for Solving the Problems The present inventors have made intensive studies to solve the above problems, and as a result, completed the present invention. That is, the present invention relates to a phenol compound represented by the general formula (1) and a phenol compound represented by the general formula (2)
The molar ratio of the aromatic amine compound represented by the formula (0.97:
0.03) to 1 mol of a mixture of (0.2: 0.8) and an aralkyl compound represented by the general formula (3) 0.1 to 0.9.
A method for producing an amino group-containing phenolic resin represented by the general formula (4) (formula 6) by reacting 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 from 00 to 5000 and an amine value of from 150 to 2000 g / eq.

[0006]

Embedded image (Wherein, R _1, R ₂ is a hydrogen atom, a halogen atom, a hydroxyl group or an alkyl group of C ₁ ~ C _12, an aryl group, a cycloalkyl group, an aralkyl group, an alkoxy group, an aryl
Represents an oxy group and may be the same or different, and R ₁ and R ₂
May form a ring)

[0007]

Embedded image (Wherein, R ₃ and R ₄ represent hydrogen, a halogen atom, a hydroxyl group,
An amino group, an alkyl group having ₁ to ₁₂ carbon atoms, an aryl group,
A cycloalkyl group, an aralkyl group, an amino group substituted aralkyl group, hydroxy group-substituted aralkyl group, an alkoxy group, an aryloxy group, an amino group substituted aryloxy group, a hydroxy group-substituted aryloxy group, may R ₃ be the same or different , R ₄ is in may form a _{ring) 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 represents a halogen atom, a hydroxyl group, or an alkoxy group having 1 to 4 carbon atoms)

[0008]

Embedded image (Wherein, R _{1 to} R ₄ and A represent the same meaning as described above, m and n each represent an integer of 0 to 20, m and n are not simultaneously 0, and the terminal is a phenol compound and /
Alternatively, the binding order of the phenol compound and the aromatic amine compound is not limited.

The amino-containing phenolic resin of the present invention comprises
Both are new compounds. The amino group-containing phenolic resin of the present invention is characterized in that aromatic amines are introduced into the structure of the phenolic resin, and an aralkyl group is used to link these. As a result, these phenolic resins have significantly lower softening points and melt viscosities than those based on formalin bonds, and can improve workability. Moreover, since the cured composition using these phenolic resins has an aralkyl group in the 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 an amino group, heat resistance can be improved in various uses.

Hereinafter, the method for obtaining the phenolic resin of the present invention will be specifically described. Examples of the phenol compound that can be used in the present invention include monohydric or dihydric phenol, and bisphenol and trisphenol.
Specifically, phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, p-ethylphenol, o-isopropylphenol, p-s
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-methoxyphenol resorcinol, catechol,
Hydroquinone, 2,2-bis (4-hydroxyphenyl) propane, di-hydroxy diphenyl methane, alpha-naphthol, beta-naphthol, and the like.

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'-hydroxydiphenylether, 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-resorcinol, 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. Preferred 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 naphthenyl group, and X is a chlorine atom, a bromine atom,
A halogen atom such as a fluorine atom, a hydroxyl group, or 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
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 '
-Diethoxymethyl diphenyl ether, 4,4'-diisopropoxymethyl diphenyl, 4,4'-diisobutoxymethyl diphenyl 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'-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 phenolic resin of the present invention, a mixture of a phenolic compound represented by the general formula (1) and an aromatic amine compound represented by the general formula (2) is prepared by the following method. The aralkyl compound represented by (3) is reacted with an acid catalyst. As the acid catalyst, an inorganic or organic acid, for example, hydrochloric acid, phosphoric acid, sulfuric acid or nitric acid, or zinc chloride, stannic chloride, aluminum chloride, Friedel-Crafts-based catalyst such as ferric chloride, methanesulfonic acid, Super strong acids such as Nafion H (trade name: manufactured by DuPont) and the like can be mentioned. These may be used alone or in combination. Activated clay, zeolite solid acid catalysts and heteropolyacids can also be used. Industrially preferred is inexpensive hydrochloric acid. The amount of the catalyst used is 3 mol% or more, preferably 5 to 80 mol%, based on the total of the phenol compound and the aromatic amine compound. In the case of a solid acid catalyst, 1 to 100 wt.
%, 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 performed 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 aforementioned acid catalysts can be used, and industrially preferred is inexpensive hydrochloric acid.

In the method of the present invention for introducing an aromatic amine component into a phenolic resin structure, the reaction between the aromatic amine component and the aralkyl compound of the formula (3) is obtained by a two-step reaction. That is, in the first-stage reaction, a resin containing a secondary amine is generated, and this secondary amine is led to the primary amine resin by the second-stage reaction (transfer reaction). This transfer reaction is achieved using the above-mentioned acid as a catalyst, but when a bishalogenomethyl derivative is used as the aralkyl compound, this transfer reaction involves hydrogen halide generated when a secondary amine resin is formed. Achieved as a catalyst.
In order to accelerate the 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., compared to the reaction conditions under which the secondary amine resin is formed. This is done by means. Even when a bishalogenomethyl derivative is used as the aralkyl compound and the reaction is carried out by an autocatalyst, as described above, the reaction can be accelerated by using the acid catalyst. In the method of the present invention, a reaction between the phenol compound and the aralkyl compound simultaneously occurs during the reaction of the first and second steps. As a result, useful resins of the present invention are 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 mixture ratio is (0.97: 0.0
3) to (0.2: 0.8).

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

In the phenolic resin of the present invention, by changing the molar ratio of the aralkyl compound to the total of the phenolic compound and the aromatic amine compound, various forms of the phenolic resin from the low molecular weight resin to the high molecular weight resin can be used according to the application. Can be manufactured. That is, during the condensation reaction,
By increasing the total molar ratio of the phenol compound and the aromatic amine compound to the aralkyl compound, a phenol resin having a liquid to a low softening point can be obtained. On the other hand, by making the total molar ratio of the phenol compound and the aromatic amine compound to the aralkyl compound close to the theoretical amount during the condensation reaction, an aromatic amine resin having a high softening point can be obtained. That is, by reacting the aralkyl compound in a range of 0.1 to 0.95 mol with respect to a total of 1 mol of the phenol compound and the aromatic amine compound,
The target molecular weight range of the present invention is 300 to 5000, the softening point of the resin is 40 to 120 ° C, and the amine value is 150 to 200.
An amino group-containing phenol resin having a concentration of 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, a method is employed in which the acid used as a catalyst or the acid generated by the reaction is neutralized with a dilute alkaline aqueous solution such as aqueous ammonia. At this time, unreacted phenol compounds, aromatic amine compounds and the like are distilled off under vacuum or by steam distillation. In addition, inorganic salts and the like by-produced by the neutralization, such as benzene, toluene, MEK, etc.
A solvent that is immiscible with water may be added and removed by a water separation method. Thereafter, the desired product can be obtained by removing the solvent. When a solid acid catalyst is used, it can be removed by filtration.

[0018]

Next, the present invention will be described in more detail by way of examples. However, the present invention is not limited by these examples. Example 1 193.0 g (2.05 mol) of phenol and 181.5 g (1.95 mol) of aniline were charged into a glass reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, and the internal temperature was reduced. 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. Thereafter, the internal temperature was raised to 180 ° C., and the stirring was further continued for 9.5 hours. After completion of the reaction, the internal temperature was cooled to 60 ° C., and 280 g of 28% aqueous ammonia was added to neutralize. Then, 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 trace amount of water were removed by distillation under reduced pressure, and the resulting red-brown transparent resin was discharged when hot. The yield was 215 g and the softening point (JIS-K-254)
8) was 62.4 ° C. The 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. FIG. 1 shows the infrared absorption spectrum of this resin.

Example 2 259.6 g (1.8 mol) of α-naphthol and 111.7 g (1.2 mol) of aniline were charged into a glass reactor equipped with a stirrer, a thermometer and a reflux condenser. And the internal temperature is 9
The temperature was raised to 5 ° C. Next, 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 completion of the reaction, the internal temperature was cooled to 60 ° C., and neutralized by adding 157.7 g of 28% aqueous ammonia.
Then, water and toluene were added thereto, and the mixture was separated and washed with water to remove ammonium chloride. Toluene, remaining unreacted α-naphthol and traces of water were removed by distillation under reduced pressure,
The resulting dark brown resin was discharged while hot. Yield 156g
And the softening point (JIS-K-2548) was 94.0 ° C. The hydroxyl equivalent (g / eq) of this resin was 390, and the amine value (g / eq) was 1190. GPC
The average molecular weight of this resin was 760. FIG. 2 shows the infrared absorption spectrum of this resin.

Example 3 138.1 g (1.0 mol) of α, α'-dihydroxy-p-xylene and phenol 94 were placed in a glass reactor equipped with a stirrer, thermometer, reflux condenser and water separator. .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 is charged, and the internal temperature is set to 1
The temperature was raised to 80 ° C. Keep the internal temperature at the same temperature and stir for 13 minutes.
Continued for hours. Water generated during the reaction was removed by a water separator. After completion of the reaction, the reaction solution was gradually cooled to 110 ° C., and then the activated clay was removed by filtration.
The remaining phenol and p-aminophenol were removed, and the resulting dark brown resin was discharged while hot. 230g yield
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 and 2 o-Cresol novolak epoxy resin (EOCN-
102S, Nippon Kayaku Co., Ltd., epoxy equivalent 214) 1
Using 00 parts, a phenolic resin containing an amino group and a phenol novolak resin (BRG # 558, manufactured by Showa Polymer Co., Ltd.) obtained in Example 1 as a curing agent, and spherical fused silica (Harimit S- CO, Inc.
50/50 (weight ratio) mixture of Micron) and amorphous fused silica (Hughes Rex RD-8, manufactured by Tatsumori), and other additives shown in Table 1 (parts by weight)
And kneaded for 3 minutes with a mixing roll machine at a temperature of 100 ° C. to obtain an epoxy resin composition. The composition was cast and the physical properties of the obtained cured product were measured. The test piece for measuring physical properties was transfer molded (180 ° C, 30 kg
/ Cm ² , 3 min) and post-cured under the conditions shown in (Table 1). Using the epoxy resin composition, a semiconductor element (10 mm × 10 mm) is mounted on the element mounting portion of a flat package type semiconductor device lead frame.
After mounting, transfer molding (180 ° C, 3
(0 Kg / cm ² , 3 min) to obtain a semiconductor device.
The evaluation results of the cured resin and the semiconductor device are shown in (Table 1). It can be seen that those using the amino group-containing phenolic resin of the present invention as a curing agent are excellent in heat resistance and moisture resistance.

[0022]

[Table 1] -Glass transition temperature: TMA method (Shimadzu, TMA-DRW
(Measured by DT-30) Boiling water absorption: Measure the weight increase after boiling for 2 hours in boiling water at 100 ° C. P. S test: Test semiconductor device at 65 ° C, 9
Immediately after leaving for 168 hours in a 5% constant temperature and humidity chamber,
40 ° C Freonart liquid (manufactured by Sumitomo 3M, FC-7
0), and the number of semiconductors having cracks in the package resin was counted. The test value is indicated by a fraction, the numerator is the number of semiconductor devices having cracks, and the denominator is the number of semiconductor devices subjected to the test. The additives, epoxidized products, and curing agents used in the test are as follows. -CIYZ: undecyl imidazole (manufactured by Shikoku Fine Chemical)-Inorganic filler: spherical fused silica (Harimit S-CO,
Mixture of 50 parts by weight of Micron Corporation and 50 parts by weight of amorphous fused silica (Hughes Rex RD-8, manufactured by Tatsumori Co., Ltd.) • Silane coupling agent: (SZ-6083, manufactured by Toray Dow Corning Silicone)・ BRG # 558: Phenol Novolak Resin Co., Ltd.
Showa Polymer, hydroxyl equivalent 102

[0023]

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

[Brief description of the drawings]

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

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

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-1-95125 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 61/00-61/02

Claims (2)

(57) [Claims] 1. A phenol compound represented by the following general formula (1): (Wherein R ₁ and R ₂ represent hydrogen, halogen, hydroxyl, or an alkyl, aryl, cycloalkyl or aralkyl group from C _{1 to} C ₁₂ , which may be the same or different; 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 1 mol of a mixture of (0.2: 0.8); (Wherein, R ₃ and R ₄ represent hydrogen, a halogen atom, a hydroxyl group,
An amino group, an alkyl group having ₁ to ₁₂ carbon atoms, an aryl group,
A cycloalkyl group, an aralkyl group, an amino-substituted aralkyl group, a hydroxy-substituted aralkyl group, an alkoxy group, an aryloxy group, an amino-substituted aryloxy group, or a hydroxy-substituted aryloxy group, which may be the same or different; ₃ and R ₄ may form a ring. X-CH ₂ -A-CH ₂ -X (3) (where A represents a phenylene group or an alkyl-substituted phenylene) A group, a diphenylene group, a diphenyl ether group or a naphthylenyl group, and X represents a halogen atom, a hydroxyl group, or an alkoxy group having 1 to 4 carbon atoms.) A general formula (4) A method for producing an amino group-containing phenolic resin represented by the formula: Embedded image (Wherein, R _1, R ₂ is hydrogen, halogen, hydroxyl, or an alkyl group of up to 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, wherein R ₃ , R
₄ represents hydrogen, a halogen atom, a hydroxyl group, an amino group, C ₁ to
Alkyl group of up to C _12, aryl group, cycloalkyl group, aralkyl group, an amino group substituted aralkyl group, hydroxy group-substituted aralkyl group, an alkoxy group, an aryloxy group, an amino group substituted aryloxy group, a hydroxy group substituted aryloxy group And may be the same or different.
₃ and R ₄ may form a ring. m and n are from 0 to 20
Where m and n are not simultaneously 0, and the terminal is a phenol compound and / or an aromatic amine compound, and the bonding order of the phenol compound and the aromatic amine compound is not limited. ) 2. A softening point of 40 ° C. to 120 ° C. and an average molecular weight of 300 to 5000 obtained by the method according to claim 1.
An amino group-containing phenol resin having an amine value of 150 to 2000 g / eq.