JP3250872B2 - Imide group-containing phenolic resin and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel imide group-containing phenol resin and a method for producing the same. These imide group-containing phenolic resins are also useful in applications such as casting, lamination, molding, and adhesion as epoxy resin curing agents,
In addition to providing a thermosetting resin with hexamine or the like in the same manner as a normal phenol resin, it can be used as an additive to various resins.

[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, by using a phenol resin having an amino group as a raw material for an imidized resin,
It is disclosed that the obtained imidized resin gives a thermosetting resin with hexamine or the like in the same manner as a usual 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. That is, the disadvantages of the phenol cured product include (1) that it is hard and brittle (2) that it has a high water-absorbing property due to its high hydroxyl group density and (3) that it has poor heat resistance for a long time due to poor oxidation resistance. As is generally known, these disadvantages cannot be ameliorated even in the above-mentioned modified phenolic resin. Further, in terms of workability, the kneading and casting of the raw material resin and various compounding agents and the like are easily performed, and in order to achieve an improvement in productivity, the softening point of the raw material resin is preferably not too high, preferably Although it is desired that the temperature is 140 ° C. or lower, there is a problem that the modified resin has a high softening point.

[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. The present invention provides a modified phenol resin which is used 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 provides a softening point represented by the general formula (1) (Chemical Formula 3) of 60 to 140 ° C. and an average molecular weight of 350 to 5
000, imide group / hydroxyl group molar ratio is 3: 97-8
It relates to an imide group-containing phenol resin in the range of 0:20. Further, an imide group-containing phenolic resin represented by the general formula (1) is obtained by reacting a dicarboxylic anhydride with an amino group-containing phenolic resin represented by the general formula (2), and dehydrating and ring-closing the compound. And a method for producing the same.

[0006]

Embedded image (Wherein, R ₁ and R ₂ represent a hydrogen atom, a halogen atom, a hydroxyl group, or a C ₁ -C ₁₂ alkyl group, an aryl group, a cycloalkyl group, an aralkyl group , an alkoxy group, an aryl group,
Represents an oxy group and may be the same or different, and R ₁ and R ₂
May form a ring. R ₃ and R ₄ represent a hydrogen atom, a halogen atom, a hydroxyl group, an imide group, a C ₁ -C ₁₂ alkyl group, an aryl group, a cycloalkyl group, an aralkyl group, an imide-substituted aralkyl group, a hydroxy-substituted aralkyl group, an alkoxy group. And an aryloxy group, an imide group-substituted aryloxy group, and a hydroxy group-substituted aryloxy group, which may be the same or different, and R ₃ and R ₄ may form a ring. A represents a phenylene group, an alkyl-substituted phenylene group, a diphenylene group, a diphenyl ether group or a naphthenyl group. Z is a C _{2 to} C ₂₄ unsaturated aliphatic group, a saturated monocyclic aliphatic group, an unsaturated monocyclic aliphatic group,
Unsaturated condensed polycyclic aliphatic group, saturated condensed polycyclic aliphatic group,
An aliphatic group having an unsaturated monocyclic aliphatic group as a substituent,
Has a monocyclic aromatic group or a linear aliphatic group as a substituent
Monocyclic aromatic group, a monocyclic aromatic group is directly or
Non-condensed polycyclic aromatic groups interconnected by
Having a cyclic aliphatic group as a cyclic aromatic group or a substituent
And a divalent group selected from the group consisting of condensed polycyclic aromatic groups . However, m and n represent 0 to 20, and the m + n ≠ 0 terminal is a phenol compound and / or an aromatic imide compound, and the bonding order of the phenol compound and the aromatic imide compound is not limited. )

[0007]

Embedded image (Wherein, R _{1 to} R ₄ , A, m and n represent the same meaning as in the case of formula (1))

The imide group-containing phenol resin of the present invention comprises
Both are new compounds. The imide group-containing phenolic resin of the present invention is characterized by introducing an imide group into the structure of the phenolic resin and using an aralkyl group for linking these. As a result, these phenolic resins, compared to those with formalin bonds,
The softening point and melt viscosity are remarkably reduced, and workability can be improved. Further, since the cured composition using these imide group-containing phenol 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. Furthermore, the bond structure formed by the aralkyl group is superior to the structure having a formalin bond in mechanical strength such as oxidation resistance and impact resistance (JP-A-63-238122). Further, as an effect of introducing the imide group, heat resistance can be improved in various uses. In particular, in a phenol resin having an unsaturated group such as a maleimide group or a nadic imide group, the crosslink density increases due to the reaction between the imide groups, and as a result, a large improvement in hot strength is achieved.

The method for obtaining the phenolic resin of the present invention will be specifically described below. First, a method for obtaining a raw material amino group-containing phenol resin will be described. As a specific method for producing an amino group-containing phenol resin, there are two methods: a phenol represented by the general formula (3) (formula 5) and an aromatic amine represented by the general formula (4) (formula 5). 1 mol of a mixture having a molar ratio of (0.97: 0.03) to (0.2: 0.8) and 0.1 to 0.95 mol of an aralkyl compound represented by the general formula (5) Are reacted using an acid catalyst.

[0010]

Embedded image (In the formula, R _{1 to} R ₄ and A represent the same meaning as described above, and X represents a halogen atom, a hydroxyl group, or a C _{1 to} C ₄ alkoxy group.)

The phenols include monohydric or dihydric phenols, bisphenol, trisphenol and the like. Specifically, phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, p-ethylphenol, o-isopropylphenol, p-sec-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, dihydroxydiphenylmethane, α-naphthol, β-naphthol and the like.

As the aromatic amine, 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-resorcinol, 2-aminohydroquinone, 2-methoxyaniline, 4-methoxyaniline,
-Isopropoxyaniline, 2,4-dimethoxyaniline, o-isopropylaniline, m-isopropylaniline, p-isopropylaniline, on-propylaniline, o-tert-butylaniline, p-ter
t-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-resorcinol, 1,1
-Dimethyl-4-aminoindane, o-phenylenediamine, 2,4-diaminotoluene, 2,4-diaminoethylbenzene, 2,6-diaminoethylbenzene, 2,
4-diaminoisopropylbenzene, 2,4-diamino-tert-butylbenzene, 2,6-diamino-te
rt-butylbenzene, 2,4-diamino-1,3-dimethylbenzene, 1,1-dimethyl-4-aminoindan, 1,1-dimethyl-4,6-diaminoindan and the like. A preferred compound is aniline.

The aralkyl compounds are compounds represented by the formula (5), wherein A is a phenylene group, an alkyl-substituted phenylene group, a diphenylene group, a diphenyl ether group, a naphthenyl group, etc., and X is a chlorine atom, a bromine atom. , A halogen atom such as a fluorine atom, a hydroxyl group, having 1 to 1 carbon atoms
Up to 4 alkoxy groups. 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-sec-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.

Examples of the acid catalyst include 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; Sulfonic 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, solid acid catalysts such as zeolites and heteropolyacids can also be used. Industrially preferred is inexpensive hydrochloric acid. The amount of the catalyst to be used is 3 mol% or more, preferably 5 to 8%, based on the total of phenols and aromatic amines.
0 mol%. In the case of a solid catalyst, 1 to 1
It is 00 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 formula (5), 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 introducing an aromatic amine component into the phenolic resin structure, the reaction between the aromatic amine component and the aralkyl compound of the formula (5) can be 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 can be led to the primary amine resin by a transfer reaction (second-stage reaction). The transfer reaction is achieved using the above-mentioned acid as a catalyst, but when a bishalogenomethyl derivative is used as the aralkyl compound, the transfer reaction is performed using hydrogen halide generated when a secondary amine resin is formed as a catalyst. Achieved. In order to accelerate this transfer reaction, (a) increase the amount of the same or different type of catalyst, (b) raise the reaction temperature, (c) lengthen the reaction time, etc., compared with the reaction conditions under which the secondary amine resin is formed. Means are taken. Even when a reaction is carried out by a self-catalyst using a bishalogenomethyl derivative as an aralkyl compound, the reaction can be accelerated by using the above-mentioned acid catalyst as described above. In the method of the present invention, a reaction between a phenol and an aralkyl compound occurs simultaneously during the reaction of the first and second steps. as a result,
An amino group-containing phenol resin as a raw material of the imide group-containing phenol resin of the present invention is produced.

The reaction temperature is 0 to 220 for the whole reaction.
° C, in the first stage reaction, 0-130 ° C,
The reaction temperature is preferably from 20 to 110 ° C, and from 150 to 220 ° 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-stage reaction as much as possible. The reaction time of the first-stage reaction is 1 to 5 hours, and the reaction time of the second-stage reaction is 3 to 20 hours.

In this amino group-containing phenolic resin, various forms of phenolic resin from low molecular weight resin to high molecular weight resin can be used by changing the molar ratio of the aralkyl compound to the total of phenols and aromatic amines. Can be manufactured according to. That is, a liquid-low softening point phenol resin can be obtained by increasing the total molar ratio of phenols and aromatic amines to the aralkyl compound during the condensation reaction. On the other hand, an aromatic amine resin having a high softening point can be obtained by making the total molar ratio of phenols and aromatic amines to the aralkyl compound close to the theoretical amount during the condensation reaction. That is, by reacting the aralkyl compound in the range of 0.1 to 0.95 mole ratio with respect to the total mole ratio of phenols and aromatic amines, the molecular weight range of the obtained amino group-containing phenolic resin is about 300 to 5000. , Resin softening point range 4
0-120 ° C, amine value 150-2000 g / eq
An amino group-containing phenolic resin having a certain degree can be obtained. In this method, a solvent inert to the reaction may be used, but the reaction is usually performed without a solvent. After the reaction,
The acid used as a catalyst in the reaction or the acid generated in the reaction is neutralized with a dilute aqueous alkali solution such as aqueous ammonia. At this time, unreacted phenols,
Aromatic amine compounds etc. are distilled off under vacuum or
Alternatively, it is distilled off by steam distillation. In addition, inorganic salts and the like by-produced by the neutralization are converted to benzene, toluene, ME in the reaction system.
A solvent that is immiscible with water, such as K, 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.

Next, a method for obtaining an imide group-containing phenol resin by reacting the amino group-containing phenol resin thus obtained with a dicarboxylic anhydride will be described. Examples of the dicarboxylic anhydride that can be used here include maleic anhydride, phthalic anhydride, 2,3-benzophenone dicarboxylic anhydride, 3,4-benzophenone dicarboxylic anhydride, and 2,3-dicarboxylicoxyphenylphenyl ether anhydride. , 3,4-dicarboxyphenylphenyl ether, 2,3-biphenyldicarboxylic anhydride, 3,4-
Biphenyldicarboxylic anhydride, 2,3-dicarboxylic acid phenylphenylsulfone anhydride, 3,4-dicarboxyphenylphenylsulfone anhydride, 2,3-dicarboxyphenylphenylsulfide anhydride, 3,4-dicarboxyphenylphenyl Sulfide anhydride, 1,2-
Naphthalenedicarboxylic anhydride, 2,3-naphthalenedicarboxylic anhydride, 1,8-naphthalenedicarboxylic anhydride, 1,2-anthracenedicarboxylic anhydride, 2,
3-anthracene dicarboxylic anhydride, 1,9-anthracene dicarboxylic anhydride, cyclobutane-1,2-dicarboxylic anhydride, cyclobutane-1,3-dicarboxylic anhydride, 1,2-cyclopentane dicarboxylic anhydride , 1-methyl-1,2-cyclopentanedicarboxylic anhydride, 1,2-cyclohexanedicarboxylic anhydride,
1,3-cyclohexanedicarboxylic anhydride, 1-cyclohexene-1,2-dicarboxylic anhydride, 2-cyclohexene-1,2-dicarboxylic anhydride, 3-cyclohexene-1,2-dicarboxylic anhydride, 4 -Cyclohexene-1,2-dicarboxylic anhydride, 1-cyclohexene-1,3-dicarboxylic anhydride, 3-cyclohexene-1,3-dicarboxylic anhydride, 4-cyclohexene-
1,3-dicarboxylic anhydride, 1,3-cyclohexadiene-1,2-dicarboxylic anhydride, 1,4-cyclohexadiene-1,2-dicarboxylic anhydride, 2,4-cyclohexadiene-1, 2-dicarboxylic anhydride, 2,
5-cyclohexadiene-1,2-dicarboxylic anhydride, 2,6-cyclohexadiene-1,2-dicarboxylic anhydride, 3,5-cyclohexadiene-1,2-dicarboxylic anhydride, cyclohexenylsuccinic acid Anhydride, 5
-Bicyclo [2,2,1] heptene-2,3-dicarboxylic anhydride, bicyclo [2,2,1] heptane-2,3
-Dicarboxylic anhydride, 2-bicyclo [2,2,1] heptene-2,3-dicarboxylic anhydride, 2-bicyclo [2,2,2] octene-2,3-dicarboxylic anhydride 5-bicyclo [2,2,2] octene-2,3-dicarboxylic anhydride and the like. Preferred compounds are anhydrous Ma <br/> maleic acid, phthalic acid and 5-bicyclo anhydrous [2,2,
1] Heptene-2,3-dicarboxylic anhydride .

In this production method, first, a carboxylic acid anhydride is reacted with an amino group-containing phenol resin, and the resulting adduct is subjected to dehydration ring closure or is heated and refluxed in a predetermined solvent in the presence of an acidic catalyst. In this way, dehydration condensation is performed. In the method of heat dehydration ring closure without using a catalyst, heat dehydration is performed under normal pressure or reduced pressure. At this time, the reaction temperature is 150 to 200 ° C. The reaction is usually performed without a solvent, but a solvent inert to the reaction may be used.
This how-out <br/> use any of the above carboxylic acid anhydrides.

In the case of ring closure by dehydration using an acidic catalyst, examples of the acidic catalyst include mineral acids such as sulfuric acid, hydrochloric acid and phosphoric acid, heteropolyacids such as phosphotungstic acid and phosphomolybdic acid, p-toluenesulfonic acid and methanesulfonic acid. And organic acids such as organic sulfonic acids, halogenated carboxylic acids such as trichloroacetic acid and trifluoroacetic acid, solid acids such as silica alumina, and cationic ion exchange resins. Particularly, sulfuric acid, phosphoric acid, and p-toluenesulfonic acid are preferred. These acids may also be in the form of a salt with an amine. These acidic catalysts vary depending on the type thereof, but generally, it is desirable to use the acidic catalyst in an amount of 0.1 to 10% by weight based on the total amount of the dicarboxylic anhydride and the amino group-containing phenol resin. If the amount of the catalyst is less than 0.1% by weight, the desired catalytic effect cannot be achieved, and if it is used more than 10% by weight, the effect cannot be obtained more than a certain level, which is economically disadvantageous. Or, it becomes difficult to remove the remaining catalyst.

The solvent used in the condensation reaction includes aliphatic or alicyclic hydrocarbons such as hexane, heptane, decane and cyclohexane, aromatic hydrocarbons such as benzene, toluene and xylene and their halides, N, N-
Oxygen-containing or sulfur-containing polar solvents such as dimethylformamide, N-methylpyrrolidone, acetonitrile, N, N-dimethylacetamide, dimethyl sulfoxide, sulfolane, anisole, and n-butyl ether are used.
The amount of the solvent is generally 1 to 20 times, preferably 2 to 20 times the total amount of the amino group-containing phenol resin and the carboxylic anhydride.
Preferably it is in the range of 10 times.

The reaction temperature under reflux under heating varies slightly depending on the solvent used and the like.
Particularly, the range of 100 to 160 ° C. is preferable. The pressure may be any of pressurized, normal or reduced pressure, and is appropriately selected according to the solvent used and the reaction temperature. The reaction time is generally 0.
The range is from 5 to 20 hours, especially from 1 to 15 hours. The amount of the dicarboxylic acid anhydride and the amino group-containing phenol resin to be charged is preferably such that the amount of the dicarboxylic acid anhydride is slightly excessive with respect to the amino group-containing phenol resin component.
Generally, on a molar basis, the carboxylic acid anhydride is present in an amount of 1.03 to 1.0 based on all amino groups in the amino group-containing phenol resin.
What is necessary is just to charge so that it may become 1.50 times. After the completion of the condensation reaction, the reaction mixture is washed with water to remove the remaining catalyst and unreacted carboxylic anhydride, and then the solvent is distilled off to obtain a concentrate. The imide group-containing phenolic resin thus obtained has an average molecular weight range of 350 to 5000, a molar ratio of imide group / hydroxyl group of 3:97 to 80:20, and a softening point of 60 to 1.
It is about 40 ° C.

[0023]

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. Then, the internal temperature is reduced to 1
The temperature was raised to 80 ° C., and stirring was continued for another 9.5 hours.
After completion of the reaction, the internal temperature was gradually 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, and toluene and water were added to the residue, followed by washing 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) was 201 and the amine value (g / eq) was 820. The average molecular weight of the resin measured by GPC is 62
It was 0. Next, 50 g of toluene and 0.8 g of p-toluenesulfonic acid were charged into a glass reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a water separator. Reflux dehydration was performed for 1 hour. Next, 7.75 g (0.08 mol) of maleic anhydride was added, and the mixture was further subjected to reflux dehydration for 1 hour. A solution prepared by previously heating and dissolving the above amino group-containing phenol resin in 50 g of toluene was added dropwise from a dropping funnel over 2 hours. After completion of the dropwise addition, the mixture was aged for 6 hours. During the period from the start of the dropping to the completion of ripening, water generated by the reaction was collected by a water separator provided in a reflux condenser. After completion of the reaction, the internal temperature was gradually cooled to 80 ° C, and water was added to remove p-toluenesulfonic acid and unreacted maleic anhydride by washing with water. The solvent was distilled off under reduced pressure, and the obtained reddish brown resin was discharged while hot. The yield was 54 g and the softening point (JIS-K-254)
8) was 71.5 ° C. In addition, the molar ratio of maleimide group / hydroxyl group of this resin was 19.7 / 80.3.
FIG. 1 shows the infrared absorption spectrum of this resin.

Example 2 A glass reactor equipped with a stirrer, thermometer and reflux condenser was charged with 9.03 g (0.061 mol) of phthalic anhydride and 50 g of the amino-containing phenol resin of Example 1. Then, stirring was continued for 1 hour while keeping the internal temperature at 150 ° C. Then, the internal temperature was kept at 180 ° C. and the mixture was kept under reduced pressure for 90 minutes, and then the obtained reddish brown resin was discharged while hot. Yield 5
The softening point (JIS-K-2548) was 75.0 ° C with 7 g. The phthalimide / hydroxyl molar ratio of this resin was 19.7 / 80.3. FIG. 2 shows the infrared absorption spectrum of this resin.

Example 3 259.6 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, thermometer and 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 stirring was continued for 3 hours while maintaining the internal temperature at the same temperature, and then the internal temperature was raised to 180 ° C. Stirring was continued for another 10 hours. After the reaction,
The internal temperature was gradually cooled to 60 ° C., and 157.
7 g was added for neutralization. Then, water and toluene were added thereto, liquid separation was performed, and ammonium chloride was removed by washing with water. Then, toluene and remaining unreacted α-naphthol were removed by distillation under reduced pressure. Then, 23.0 g (0.16 mol) of phthalic anhydride was charged, the internal temperature was raised to 160 ° C., and stirring was performed for 1 hour. Next, after keeping the internal temperature at 180 ° C. under reduced pressure for 90 minutes, the black-brown resin was discharged while hot. The yield was 180 g. The softening point (JIS-K-2548) of this resin was 92 ° C. The phthalimide group / hydroxyl group molar ratio of this resin was 24.7 / 7 as a result of analysis of the amino group-containing resin in the middle.
5.3.

[0026]

The resin of the present invention is useful as a curing agent for an epoxy resin. In addition to providing a thermosetting resin with hexamine or the like in the same manner as an ordinary phenol resin, it can be used as an additive to various resins. Can be.

[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 a resin obtained in Example 2.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-5-39346 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 61/00-61/02

Claims (2)

(57) [Claims] 1. A softening point represented by the general formula (1) (Chemical formula 1) of 60 to 140 ° C., an average molecular weight of 350 to 5000, and a molar ratio of imide group / hydroxyl group of 3:97 to 80:20. Certain imide group-containing phenolic resins. 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, which may be the same or different, and R ₁ R ₂ may form a ring R ₃ , R ₄
Is a hydrogen atom, a halogen atom, a hydroxyl group, an imide group, C ₁
Alkyl -C _12, an aryl group, a cycloalkyl group,
Aralkyl group, an imido group-substituted aralkyl group, hydroxy group-substituted aralkyl group, an alkoxy group, an aryloxy group, an imido group substituted aryloxy group, a hydroxy group-substituted aryloxy group, which may be the same or different, R ₃ and R ₄ May form a ring. A represents a phenylene group, an alkyl-substituted phenylene group, a diphenylene group, a diphenyl ether group or a naphthenyl group. Z is C
Unsaturated unsaturated groups in which ₂ to ₂₄ unsaturated aliphatic groups, unsaturated monocyclic aliphatic groups, unsaturated condensed polycyclic aliphatic groups, and cycloaliphatic groups are directly or mutually linked by a bridge member. Condensed polycyclic aliphatic group, monocyclic aromatic group having a chain aliphatic group as a substituent, fused polycyclic aromatic group having a chain aliphatic group as a substituent, unsaturated monocyclic as a substituent Formula aliphatic group, fused polycyclic aromatic group having an unsaturated monocyclic aliphatic group as a substituent,
And a divalent group selected from the group consisting of: m and n are 0
２０20, and m + n ≠ 0. The terminal is a phenol compound and / or an aromatic imide compound, and the bonding order of the phenol compound and the aromatic imide compound is not limited. ) 2. The imide according to claim 1, wherein the phenolic resin having an amino group represented by the formula (2) is reacted with a dicarboxylic anhydride and dehydrated to effect ring closure to imidize the phenol resin. A method for producing a group-containing phenol resin. 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, which may be identical or different, R ₁ And R ₂ may form a ring, R ₃ and R ₄
Is a hydrogen atom, a halogen atom, a hydroxyl group, an imide group, C ₁
Alkyl -C _12, an aryl group, a cycloalkyl group,
Aralkyl group, an imido group-substituted aralkyl group, hydroxy group-substituted aralkyl group, an alkoxy group, an aryloxy group, an imido group substituted aryloxy group, a hydroxy group-substituted aryloxy group, which may be the same or different, R ₃ and R ₄ May form a ring. A represents a phenylene group, an alkyl-substituted phenylene group, a diphenylene group, a diphenyl ether group or a naphthenyl group. m, n
Represents 0 to 20 and m + n ≠ 0. The terminal is a phenol compound and / or an aromatic imide compound, and the bonding order of the phenol compound and the aromatic imide compound is not limited. )