JPH0816151B2 - Aromatic amine resin and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel aromatic amine resin and a method for producing the same.

This aromatic amine resin is a curing agent for epoxy resin raw materials or other epoxy compounds, a curing agent for maleimide resin raw materials or other maleimide compounds, a curing agent for isocyanate resin raw materials or other isocyanate compounds, and a chelate resin. , Ion-exchange resins, molding materials, insulating coatings, adhesives, rubber modifiers, additives for various resins, deoxidizers and raw materials for polyimide, polyamide, polyamide-imide, etc.

[Conventional technology]

Aromatic amine resins have hitherto been known as condensation products of aromatic amines and formalin. For example, from aniline and formalin, the following general formula (d) An aniline-formalin resin represented by (K. Frey; Helvetica Himi Actor Vol. 18 481 (1
935)).

[Problems to be solved by the invention]

Conventional aromatic amino resins such as aniline-formalin resins composed of secondary amines represented by the general formula (d) are difficult to be maleimidized or isocyanated, so that they are used as raw materials for maleimide resins or isocyanate resins. Not suitable. Therefore, the conventional aromatic amino resin is
It was widely used as a curing agent. However, when used as a curing agent for a heat-resistant composite matrix resin or a heat-resistant adhesive, conventional aromatic amino resins have not been able to meet the recent high performance requirements.

Heat-resistant composite materials, heat-resistant adhesives, and the like are required to withstand instantaneous impacts such as stress concentration as external stress. For this reason, elastically deforming like rubber ideally attracts attention as an important factor. As a criterion for determining such elastic deformation, the elongation at break of the matrix resin is particularly important. The greater the elongation of the matrix resin, the more the drawbacks of reinforcing agents such as glass fibers and carbon fibers required for composite materials can be compensated. That is,
The overall strength of the composite material is improved.

Furthermore, in these matrix resins and the like, in addition to heat resistance and dimensional stability, long-term storage stability is important, and it is required that deterioration due to light and oxygen in the air is small. This oxidation resistance is mainly derived from the structure of the resin, and it is difficult for conventional aromatic amino resins to overcome various drawbacks caused by structural defects, together with the requirements for the mechanical strength and the like. there were.

Further, the aniline-formalin resin has a cross-linked structure if the molar ratio of formalin at the time of condensation is increased for the purpose of increasing the degree of condensation and improving the mechanical properties and the like. Therefore, in general, its molecular weight can only be increased to about 600 (Noda et al., Journal of Industrial Chemistry 55).
Volume 484-487 (1952)).

The inventors of the present invention found a novel aromatic amine resin capable of improving these drawbacks, and the applicant of the present invention, September 1987
Filed on 17th (Japanese Patent Laid-Open No. 64-74226). However, since this resin is composed of a secondary amine, it is difficult to form isocyanate or maleimid. Further, when used as a curing agent, there still remain problems such as a relatively large amount to be used and a relatively slow curing speed.

The present invention has been made in view of the above problems, and its object is to obtain excellent curing properties when used as a curing agent, such as heat resistance, mechanical strength, dimensional stability, and stability against light and oxygen in the air. An object of the present invention is to provide an aromatic amine resin which can be used as a raw material of an isocyanate resin, a maleimide resin and the like, which is capable of obtaining a resin and has excellent properties, and a method for producing the aromatic amine resin.

[Means for solving problems]

The present inventors have conducted intensive studies to achieve the above object, and as a result, completed the present invention.

That is, the present invention provides a compound represented by the general formula (a): (In the formula, A represents a phenylene group, an alkyl-substituted phenylene group, a diphenylene group, a diphenyl ether group or a naphthylenyl group, and R ¹ is a halogen atom, a hydroxyl group, a lower alkoxy group having 4 or less carbon atoms or a lower alkyl group having 5 or less carbon atoms. And R ¹ may be the same or different from each other and may form a ring, 1 represents 1 or 2, m represents an integer of 0 to 3, and n represents 0 to 300. An aromatic amine resin represented by the general formula (b) (In the formula, R ¹ represents a halogen atom, a hydroxyl group, a lower alkoxy group having 4 or less carbon atoms or a lower alkyl group having 5 or less carbon atoms, and R ¹ may be the same or different from each other,
You may form a ring. l represents 1 or 2, m is 0
Indicates an integer of 3. And an aromatic amine compound represented by the general formula (c) R ² OCH ₂ —A—CH ₂ OR ² (c) (wherein A is a phenylene group, an alkyl-substituted phenylene group, a diphenylene group, a diphenyl ether group or a naphthylenyl group). Group, wherein R ² represents a hydrogen atom, an acyl group or a lower alkyl group having 4 or less carbon atoms) in the presence of 10 mol% or more of an acid catalyst with respect to the aromatic amine compound. Is a method for producing an aromatic amine resin represented by the general formula (a).

Since the aromatic amine resin of the present invention is a resin composed of a primary amine, isocyanate formation, maleimidization, epoxidation and the like are easy.

In addition, when the aromatic amine resin of the present invention is used as a curing agent for another resin (for example, an isocyanate compound, an epoxy compound, a bismaleimide compound, and the like), a resin having high performance can be obtained.

For example, when the resin of the present invention is used as a curing agent for a bismaleimide compound, the cured resin has excellent mechanical strength and dimensional stability, and there is no problem with heat resistance and stability against light and oxygen in the air. . As a specific example thereof, when the resin of the present invention is used as a curing agent for bismaleimide derived from methylenedianiline, bending strength of the cured resin, flexural modulus, thermal decomposition initiation temperature in air,
The expansion coefficient and moisture absorption rate are superior to those of Kerimide 1050 (trade name: molding grade, manufactured by Rhone-Poulenc) when methylenedianiline is used as the curing agent, and the glass transition temperature and heat distortion temperature are almost the same. Is equivalent.

Further, the prepolymer using the resin of the present invention is soluble in low boiling point solvents (dioxane, methylene chloride, etc.).

Conventionally, a prepreg has been produced by dissolving a prepolymer such as kelimide in a high-boiling point aprotic polar solvent (N-methylpyrrolidone or the like) and impregnating the solution into glass cloth or carbon cloth. In contrast to such a conventional method, when the resin of the present invention is used as a prepolymer, it can be dissolved in a low boiling point solvent, so that the solvent can be easily volatilized and removed, and an extremely good prepreg can be obtained.

Further, the resin of the present invention has a faster curing rate than the resins described in the above-mentioned specification filed previously by the applicant of the present invention, and is particularly preferable for use as a semiconductor encapsulating resin.

Next, a method for producing the aromatic amine resin of the present invention will be described.

The resin of the present invention can be produced by subjecting an aromatic amine compound represented by the general formula (b) and an aralkyl alcohol derivative represented by the general formula (c) to a cocondensation reaction. In the middle of the reaction, a resin containing a secondary amine is formed, and this secondary amine may be led to the primary amine resin of the present invention by a rearrangement reaction. In the condensation reaction, the rearrangement reaction is carried out by means such as (a) increasing the amount of catalyst (b) increasing the reaction temperature (c) making the reaction time longer than the reaction conditions for producing the secondary amine resin. Be done. In particular, increasing the amount of catalyst is effective.

In addition, conventionally known aniline-formalin resin,
As described above, while the molecular weight can be increased to about 600 at most, in the aromatic amine resin of the present invention, by changing the molar ratio of the aromatic amine compound and the aralkyl alcohol derivative, the general formula (a It is possible to arbitrarily select from a low molecular weight resin whose main component is n) of 0) to a high molecular weight resin whose n is up to about 300. Therefore, the production method of the present invention is also characterized in that various forms of aromatic amine resins can be produced depending on the intended use, from those that are liquid at room temperature to those that are resinous with a high softening point.

The liquid to low softening point resin of the present invention can be obtained by increasing the molar ratio of the aromatic amine compound to the aralkyl alcohol derivative during the condensation reaction. The liquid to low softening point resin thus obtained is excellent in workability such as melt blending, impregnation and coating, and is mainly used in the fields of adhesives, paints, urethanes and additives to other resins. You.

The resin of the present invention having a high softening point can be obtained by making the molar ratio of the aralkyl alcohol derivative and the aromatic amine close to the theoretical amount during the condensation reaction. The resin having a high softening point thus obtained can be used in the fields of molding materials, ion exchange resins, laminating resins and the like.

The molecular weight range of the aromatic amine resin obtained by the production method of the present invention is about 300 to 60,000, and the softening point range of the resin is liquid at room temperature to about 250 ° C. (JIS-K-25
Ring and ball softening point by 48).

Hereinafter, specific examples of the method for producing an aromatic amine resin of the present invention will be described in detail.

First, the aromatic amine compound represented by the general formula (b) is added in an amount of 1 to 15 mol, preferably 1.1 to 10 mol, relative to 1 mol of the aralkyl alcohol derivative represented by the general formula (c), and the presence of an acid catalyst is present. The temperature is raised as it is, and the reaction is performed at the temperature described below. Water, alcohol or organic acids produced as the reaction proceeds is trapped outside the system.
If necessary, a small amount of volatile matter remaining in the system is removed from the system by nitrogen.

In addition, A of the aralkyl alcohol derivative represented by the general formula (c) used in the present invention is A phenylene group of An alkyl-substituted phenylene group of Diphenylene group of Diphenyl ether group, And a naphthylenyl group, and R ² is a hydrogen atom, an acyl group or an alkyl group. The acyl group and alkyl group of R ^{2 have} a rapid reaction when the number of carbon atoms is 4 or less, and the tert-butyl group tends to have a slow reaction when the number of carbon atoms is 4, that is, a butyl group. Therefore, those used in the present invention include α, α′-dihydroxy-o-xylene, α, α′-dihydroxy-m-xylene, α, α ′.
-Dihydroxy-p-xylene, α, α'-diacetoxy-o-xylene, α, α'-diacetoxy-m-xylene, α, α'-diacetoxy-p-xylene, α,
α'-dipropionoxy-p-xylene, α, α'-di-n-butyroxy-p-xylene, α, α'-dimethoxy-o-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-sec-butoxy-p-xylene,
α, α′-diisobutoxy-p-xylene, 4,4′-dihydroxymethyldiphenyl ether, 4,4′-dihydroxymethyldiphenyl, 2,6-dihydroxymethylnaphthalene, 4,4′-diacetoxymethyldiphenyl ether, 4,4 ′ -Diacetoxymethyldiphenyl, 2,6-diacetoxymethylnaphthalene, 4,4′-methoxymethyldiphenyl ether, 4,4′-methoxymethyldiphenyl, 4,4′-diethoxymethyldiphenylether, 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'-
Examples thereof include dimethoxy-2,4-dimethyl-1,5-xylene. In addition, the more preferable compound among them is
It is α, α'-dimethoxy-p-xylene.

R ¹ of the aromatic amine compound represented by the general formula (b) used in the present invention is a halogen atom, a hydroxyl group, a lower alkoxy group having 4 or less carbon atoms, or a lower alkyl group having 5 or less carbon atoms. ~ 3, which may be the same or different from each other, and may form a ring. The number of amino groups is 1 or 2. Specifically, aniline, o-toluidine, m-toluidine, p-toluidine, o-ethylaniline, m-ethylaniline, p-ethylaniline, o-
Isopropylaniline, m-isopropylaniline, p
-Isopropylaniline, on-propylaniline,
o-tert-butylaniline, p-tert-butylaniline, on-butylaniline, p-sec-butylaniline, 2,3-xylidine, 2,4-xylidine, 2,6-xylidine, 3,4- Xylidine, 3,5-xylidine, 2-methyl-3ethylaniline, 2-methyl-4-isopropylaniline, 2,6-diethylaniline, 2-ethyl-5-ter
t-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-chloro Aniline, o-
Aminophenol, m-aminophenol, p-aminophenol, 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, 2-aminohydroquinone, 2-methoxyaniline, 3-methoxyaniline, 4-methoxyaniline, 2-isopropoxyaniline, 2,4-dimethoxyaniline, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine , 2,4-diaminotoluene, 2,6-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-aminoindane, 1,1-dimethyl-4,6-diaminoindane and the like can be mentioned. In addition, preferable compounds are aniline, toluidines, xylidines, aminophenols and diamines, and particularly preferable one is aniline.

The acid catalyst may be an inorganic or organic acid, especially a mineral acid such as hydrochloric acid, phosphoric acid, sulfuric acid or nitric acid, or a Friedel-Crafts type catalyst such as zinc chloride, stannic chloride, aluminum chloride or ferric chloride. Is used alone or in combination with an organic sulfonic acid such as methanesulfonic acid or p-toluenesulfonic acid, and further a super strong acid such as trifluoromethanesulfonic acid and Nafion H (trade name: manufactured by DuPont). Good. Industrially preferable is inexpensive hydrochloric acid. The amount of the catalyst used is 10 col% or more, preferably 20 to 100 mol%, based on the aromatic amine compound. Below this range, the reaction progresses slowly, and complete conversion to the primary amine is difficult to achieve. Above this range, there is no problem in the reaction, but it is not economical.

The reaction temperature must be 130 ° C or higher, and if it is lower than 130 ° C, the reaction becomes extremely slow. In order to shorten the reaction time as much as possible, a temperature range of about 170 to 240 ° C is desirable. The reaction time is between 10 and 40 hours.

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 catalyst. After completion of the reaction, the acid used as the catalyst is neutralized with a dilute alkaline aqueous solution such as an aqueous solution of caustic soda, an aqueous solution of potassium hydroxide and aqueous ammonia, and then separated.

When an unreacted aromatic amine compound remains in the following reaction, this is distilled off under vacuum or steam distillation.

The aromatic amino resin of the present invention is obtained as described above.

〔Example〕

 Hereinafter, the present invention will be described in more detail with reference to Examples.

Example 1 A reaction vessel equipped with a stirrer, a thermometer, and a Dean-Stark azeotropic distillation trap had 111.6 g (1.2 mol) of aniline as an aromatic amine compound represented by the general formula (b), and a general formula (c). Α, α'-dimethoxy-p-xylene 6 as an aralkyl alcohol derivative represented by
6.5 g (0.4 mol) and 35% aqueous hydrochloric acid solution 62.
6 g (0.6 mol) was charged and the temperature was raised while nitrogen gas was passed through. Since the internal temperature was about 110 ° C, water distilled in the trap was removed from the system. When the temperature was further raised, methanol was distilled off from about 130 ° C., and the temperature was raised while distilling off the generated methanol. After reaching 170 ° C., the temperature was kept constant for 3 hours. The generation of methanol almost disappeared, and then the temperature was raised and the reaction was carried out at 190 to 200 ° C for 12 hours. Then, the mixture was cooled to reduce the internal temperature to 95 ° C., 168 g of a 15% aqueous caustic soda solution was added, and the mixture was stirred and neutralized. After standing, the lower aqueous layer was separated and removed, and 300 g of saturated saline was added to carry out washing and separation. Next, after heat dehydration was performed under a nitrogen stream, pressure filtration was performed to remove inorganic salts and the like. This is 2-3mmHg
After vacuum concentration under vacuum, 51.9 g of unreacted aniline was recovered. The residue was discharged to obtain 94.5 g of a light yellowish brown aniline resin.

The aromatic amino resin of the present invention obtained as described above,
As a result of composition analysis by high performance liquid chromatography,
In the general formula (a), n = 0 is 28, n = 1 is 16.8, and n = 2 is 1
0.5, n = 3 was 7.8, and n ≧ 4 was 36.9 (mol%).

Also, the amino equivalent of this resin (perchloric acid-glacial acetic acid method)
Was 0.578 equivalents / (100 g), and the softening point measured by a ring and ball method softening point measuring apparatus according to JIS-K-2548 was 68 ° C.
Further, the average molecular weight was 960.

 The results of IR analysis of this resin are shown in FIG.

Example 2 As the aromatic amine compound represented by the general formula (b),
Example 1 except that 244.4 g (2.0 mol) of 4-diaminotoluene was used and 209 g (2.0 mol) of 35% hydrochloric acid was used as a catalyst.
The reaction was carried out in the same manner as described above to obtain 132 g of reddish brown oily diaminotoluene resin.

The aromatic amino resin of the present invention obtained as described above,
As a result of composition analysis by high performance liquid chromatography,
In the general formula (a), n = 0 is 44.5, n = 1 is 29.7, and n = 2 is
14.6 and n ≧ 3 were 11.2 (mol%).

The amine equivalent of this resin was 1.204, the softening point was 46 ° C., and the average molecular weight was 550.

Example 3 121.1 g (1.3 mol) of aniline was used as the aromatic amine compound represented by the general formula (b), and α, α'-dihydroxy-m-xylene 138.2 was used as the aralkyl alcohol derivative represented by the general formula (c). g (1.0 mol),
The reaction was carried out in the same manner as in Example 1 except that 33 g (0.325 mol) of concentrated sulfuric acid was used as the catalyst, and a light yellowish brown aniline resin 15
1 g was obtained.

The aromatic amino resin of the present invention thus obtained has an amine equivalent of 0.496, a softening point measured by a ring and ball softening point measuring device according to JIS-K-2548 of 118 ° C., and an average molecular weight of 6500. there were.

Example 4 109 g (1.0 mol) of p-aminophenol as an aromatic amine compound represented by the general formula (b) and α, α′-diacetoxy as an aralkyl alcohol derivative represented by the general formula (c) were placed in a reaction vessel. -P-xylene 110.2g
(0.5 mol), zinc chloride as catalyst 6.8 g (0.05 mol)
And 19 g (0.1 mol) of p-toluenesulfonic acid were charged and the reaction was carried out under reduced pressure by a water-jet pump. The reaction started at around 130 ° C and was heated up to 170 ° C in 3 hours. On the way, acetic acid produced was collected by a cryogenic trap. After maintaining at the same temperature for 3 hours, the reaction temperature is further increased to 200 ° C and 200 to 210 ° C.
It was aged for 1 hour and finished. After cooling to 95 ° C, 300 ml of toluene was added and dissolved by stirring. To this, 20.2 g of triethylamine was added, and then 200 ml of water was added and after stirring,
The mixture was allowed to stand, and the lower aqueous layer was separated and removed. The liquid was washed once again with 200 ml of water for liquid separation, and concentrated in vacuo to remove toluene and unreacted p-aminophenol. As a residual brown resin thus obtained, 138 g of a co-condensation resin of p-aminophenol was obtained.

The aromatic amino resin of the present invention obtained as described above has an amine equivalent of 0.525, a softening point measured by a ring and ball softening point measuring device according to JIS-K-2548 of 94 ° C., and an average molecular weight of 2200. there were.

Examples 5 to 13 Types of aromatic amine compounds represented by the general formula (b),
The reaction was carried out in the same manner as in Example 1 except that the type and amount of the aralkyl alcohol derivative represented by the general formula (c), the type and amount of the catalyst, and the reaction conditions were as shown in Table 1.
Various aromatic amine resins of the present invention as shown in 1 were obtained.

Use Example 1 100 g of the aniline resin obtained in Example 1 was dissolved in 1400 g of dry orthodichlorobenzene. Next, at a temperature of 5 to 10 ° C., 253 g of phosgene was blown into the solution over 3 hours. After this, the temperature was raised by slowly blowing phosgene to 120
Aged at ~ 140 ° C for 2 hours. Then, ventilation of phosgene was stopped, and ventilation of nitrogen gas was switched to sufficient degassing, followed by cooling. The reaction solution was concentrated under vacuum to recover the solvent ortho-dichlorobenzene, and 111 g of a light brown oily isocyanate resin was obtained.

10.4 g of the isocyanate resin obtained as described above was dissolved in 400 g of methylene chloride to give “A liquid”. next,
DETDA (Ethyl Corporation) 2.2g / JEFFAMINE T
-5000 (manufactured by Texaco Chemical) 10 g / methylene chloride 25
A good polyurea film can be obtained by mixing the “solution B” composed of 00 g and the “solution A”, casting the mixture on a glass plate, leaving it to stand overnight, and post-curing at 120 ° C. for 2 hours. Was.

Use Example 2 40 parts by weight of the aniline resin obtained in Example 1 and 100 parts by weight of bismaleimide-s (manufactured by Daiwa Kasei Kogyo Co., Ltd.) were mixed to prepare 1
A prepolymer was prepared by heating and melting at 80 ° C. for 10 minutes.

The solubility of this prepolymer in various solvents was measured. The results are shown in Table 2 as Experimental Example 1. Further, the appearance, softening temperature, gelling time, and bulk specific gravity of this prepolymer are shown in Table 3 as Experimental Example 1. For comparison, Table 2 and Table 3 show, as Comparative Experimental Example 1, the same results as those of commercially available Kelimide-1050 (trade name: molding grade, manufactured by Nippon Polyimide Co., Ltd.).

Next, each of the prepolymer and Kelimide-1050 was compression-molded at a temperature of 200 ° C. under a pressure of 40 kg / cm ² for 1 hour and then post-cured at 250 ° C. for 4 hours to obtain a cured test piece. Created. The mechanical strength and thermophysical properties of this test piece were measured. The results are shown in Table 3 as Experimental Example 1 and Comparative Experimental Example 1, respectively.

[Effects of the Invention] As described above, since the aromatic amine resin of the present invention is a resin composed of primary amines, it is easy to undergo isocyanate formation, maleimidation formation, epoxidation formation, etc., and can be used as a raw material for polyamide and the like. Is.

Furthermore, when the aromatic amine resin of the present invention is used as a curing agent or as a raw material for other resins, the resulting cured resin has mechanical strength, dimensional stability, heat resistance, light and oxygen in the air. It has excellent stability to and has a fast curing speed.

Further, since the prepolymer using the aromatic amine resin of the present invention is soluble in the low melting point solvent, a good prepolymer can be easily obtained.

Furthermore, the aromatic amine resin of the present invention can be produced from an inexpensive raw material by a simple operation, and can be obtained by a pollution-free method with no by-products.

Since the aromatic amine resin of the present invention has the above effects, it is added to a curing agent, a raw material of the curing resin, a chelate resin, an ion exchange resin, a molding material, an insulating paint, an adhesive, a rubber modifier, and various resins. It can be used in various fields such as agents, deoxidizers, and raw materials for polyimide, polyamide, and polyamideimide.

[Brief description of drawings]

FIG. 1 is a graph showing the IR analysis result of the aromatic amine resin obtained in Example 1.

Claims (2)

[Claims] 1. A compound of the general formula (a) (In the formula, A represents a phenylene group, an alkyl-substituted phenylene group, a diphenylene group, a diphenyl ether group or a naphthylenyl group, and R ¹ is a halogen atom, a hydroxyl group, a lower alkoxy group having 4 or less carbon atoms, or a lower alkyl group having 5 or less carbon atoms. And R ¹ may be the same or different from each other and may form a ring, 1 represents 1 or 2, m represents an integer of 0 to 3, and n represents 0 to 300. An aromatic amine resin represented by an integer. 2. Formula (b) (In the formula, R ¹ represents a halogen atom, a hydroxyl group, a lower alkoxy group having 4 or less carbon atoms or a lower alkyl group having 5 or less carbon atoms, and R ¹ may be the same or different from each other,
You may form a ring. l represents 1 or 2, m is 0
Indicates an integer of 3. And an aromatic amine compound represented by the general formula (c) R ² OCH ₂ —A—CH ₂ OR ² (c) (In the formula, A is a phenylene group, an alkyl-substituted phenylene group, a diphenylene group, a diphenyl ether group or a naphthylenyl group. Group, wherein R ² represents a hydrogen atom, an acyl group or a lower alkyl group having 4 or less carbon atoms) in the presence of 10 mol% or more of an acid catalyst with respect to the aromatic amine compound. The general formula (a) is characterized in that (In the formula, A represents a phenylene group, an alkyl-substituted phenylene group, a diphenylene group, a diphenyl ether group or a naphthylenyl group, and R ¹ is a halogen atom, a hydroxyl group, a lower alkoxy group having 4 or less carbon atoms or a lower alkyl group having 5 or less carbon atoms. And R ¹ may be the same or different from each other and may form a ring, 1 represents 1 or 2, m represents an integer of 0 to 3, and n represents 0 to 300. A method for producing an aromatic amine resin represented by.