JP3214764B2 - Molding material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an imide group-containing phenol resin molding material excellent in heat resistance, oxidation stability, mechanical strength, water resistance and workability.

[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 imide 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 an imidized resin obtained by a reaction of phenols, formaldehyde, an aromatic amine, and an aromatic carboxylic anhydride gives a thermosetting resin with hexamine or the like in the same manner as an ordinary phenol resin ( JP-A-3-275708).

[0003] However, the resin disclosed above is:
Although it has a novolak-type phenol structure and is effective in improving heat resistance, it cannot be said that this phenolic resin 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.

[0004] In terms of workability, the softening point of the raw material resin is not too high in order to easily perform operations such as kneading and molding of the raw material resin and various compounding agents, and to improve productivity.
It is desired that the temperature is preferably 140 ° C. or lower,
The modified resin has a disadvantage that the softening point is increased.

[0005]

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. It is to provide a molding material.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, completed the present invention. That is, the present invention provides a compound represented by the general formula (1):

Embedded image(Where R₁, R_TwoIs hydrogen atom, halogen atom, hydroxyl
Group, or C₁~ C₁₂Alkyl group, cycloalkyl
Group, aralkyl group, alkoxy group, aryl group or
A reeloxy group, which may be the same or different;₁
And R_TwoMay form a ring. R_Three, R_FourIs a hydrogen source
Atom, halogen atom, hydroxyl group, imide group, C₁~ C ₁₂No
Alkyl, aryl, cycloalkyl, aralkyl
Group, imide group-substituted aralkyl group, hydroxy group-substituted ara
Alkyl group, alkoxy group, aryloxy group, imide group
Substituted aryloxy group, hydroxy-substituted aryloxy
And represents the same or a different group,_ThreeAnd R_FourIs a ring
May be formed. Z is C_Two~ C_{twenty four}Unsaturated fat
Group, saturated monocyclic aliphatic group, unsaturated monocyclic aliphatic group,
Saturated condensed polycyclic aliphatic group, saturated condensed polycyclic aliphatic group,
Aliphatic group having an unsaturated monocyclic aliphatic group as a substituent,
Monocyclic aromatics which may have chain aliphatic groups as substituents
Group or monocyclic aromatic group, directly or
Linked non-fused polycyclic aromatic group, chain-like fat as a substituent
Consists of fused polycyclic aromatic groups that may have aliphatic groups
Shows a divalent group selected from the group. However, m and n are 0 to 2
0, and m + n ≠ 0. Terminal is phenolic compound
And / or an aromatic imide compound,
The bonding order of the compound and the aromatic imide compound is not limited.
No. ), Average molecular weight 3
50-5000, the molar ratio of imide group / hydroxyl group is 3: 9
An imide group-containing phenol tree in the range of 7 to 80:20
Phenolic resin containing fat and inorganic and / or organic
Molded material with hexamine or resole resin added to filler
And cured products obtained from these materials.

The imide group-containing phenolic 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.

Hereinafter, a method for obtaining an imide group-containing phenol resin used in the molding material of the present invention will be described. The imide group-containing phenol resin is obtained by reacting a phenol with an aromatic amine to obtain an amino group-containing phenol resin, and then reacting the phenol resin with dicarponic anhydride.

First, a method for producing an amino group-containing phenol resin will be described. As a specific method for producing an amino group-containing phenol resin, general formula (2)

Embedded image (Wherein R ₁ and R ₂ have the same meanings as in the general formula (1)) and a phenol represented by the general formula (3)
(Formula 4)

Embedded image(Where R_Five, R₆Is hydrogen atom, halogen atom, hydroxyl
Group, amino group, C₁~ C ₁₂An alkyl group, an aryl group,
Cycloalkyl, aralkyl, amino-substituted arals
Kill group, hydroxy-substituted aralkyl group, alkoxy
Group, aryloxy group, amino group-substituted aryloxy
Group, a hydroxy-substituted aryloxy group,
May also be different, R_FiveAnd R₆May form a ring
No. ) And the aromatic amine represented by the molar ratio (0.9)
7: 0.03) to 1 mol of a mixture of (0.2: 0.8)
And the general formula (4)

Embedded image (Wherein, X represents a halogen atom, a hydroxyl group, or a C ₁ -C ₄ alkoxy group).
0.95 moles is reacted with an acid catalyst.

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,
p-cyclohexylaniline, 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′-hydroxydiphenylpropane, 2-amino-1, 3-resorcinol, 4-amino-
1,3-resorcinol, 2-aminohydroquinone, 2-
Methoxyaniline, 4-methoxyaniline, 2-isopropoxyaniline, 2,4-dimethoxyaniline, p-
Phenoxyaniline, o-isopropylaniline, m-
Isopropyl aniline, p-isopropyl aniline, o
-N-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. A preferred compound is aniline.

The aralkyl compounds are compounds represented by the formula (4), wherein X is a halogen atom such as a chlorine atom, a bromine atom or 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 ′
-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, 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 and the like can be mentioned. Suitable compounds include α, α′-dihydroxy-p-xylene, α, α′-dichloro-p-xylene and the like. Note that R ₁ and R ₂ in the general formula (1) correspond to R ₅ and R ₆ in the general formula (4), and the imide terminal groups of R ₁ and R ₂ are derived from the amino groups of R ₅ and R _6. I do.

As the acid catalyst, an inorganic or organic acid, for example, hydrochloric acid, phosphoric acid, sulfuric acid or nitric acid, or a Friedel-Crafts catalyst such as zinc chloride, stannic chloride, aluminum chloride, ferric chloride, methane 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 (4), 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 (4) 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 the transfer reaction, (a) increase the amount of the same or different catalyst, (b) raise the reaction temperature, and (c)
Means such as increasing the reaction time may be employed. 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 which is a raw material of the imide group-containing phenol resin of the present invention is produced. The reaction temperature is 0 to 220 ° C. as a whole reaction, but is 0 to 130 ° C., preferably 20 to 110 ° C. in the first stage reaction, and 150 to 220 ° 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,
The second stage reaction is for 3-20 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 carried out without a solvent. After completion of 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 and aromatic amine compounds are distilled off under vacuum or by steam distillation. In addition, inorganic salts and the like by-produced by neutralization may be removed by adding a water-immiscible solvent such as benzene, toluene, and MEK to the reaction system, and washing with a water-liquid 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, the amino group-containing phenolic resin thus obtained is added to the phenol resin of the general formula (5).

Embedded image (Wherein, Z represents the same meaning as in the general formula (1)), a method for obtaining an imide group-containing phenol resin by reacting a dicarboxylic anhydride represented by the general formula (1) will be described. As the dicarboxylic anhydride used here, maleic anhydride, phthalic anhydride, 2,3-benzophenone dicarboxylic anhydride, 3,4-benzophenone dicarboxylic anhydride, 2,
3-dicarboxyphenylphenyl ether anhydride,
3,4-dicarboxyphenylphenyl ether anhydride, 2,3-biphenyldicarboxylic anhydride, 3,4-
Biphenyl dicarboxylic anhydride, 2,3-dicarboxyphenyl phenyl sulfone anhydride, 3,4-dicarboxyphenyl phenyl sulfone anhydride, 2,3-dicarboxyphenyl phenyl sulfide anhydride, 3,4-dicarboxyphenyl phenyl 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 maleic anhydride, phthalic anhydride and nadic anhydride.

In this production method, first, a dicarboxylic acid anhydride is reacted with an amino group-containing phenol resin, and the resulting adduct is subjected to dehydration ring closure or heating to reflux in a predetermined solvent in the presence of an acidic catalyst. In this way, dehydration condensation is performed. In the method of performing 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. In this method, any of the above carboxylic anhydrides can be used, but carboxylic anhydrides other than aliphatic carboxylic anhydrides having an unsaturated group are particularly preferred.

In the method of dehydration ring closure using an acidic catalyst,
As acidic catalysts, mineral acids such as sulfuric acid, hydrochloric acid, and phosphoric acid; heteropolyacids such as phosphotungstic acid and phosphomolybdic acid;
-Organic sulfonic acids such as toluenesulfonic acid and methanesulfonic acid, halogenated carboxylic acids such as trichloroacetic acid and trifluoroacetic acid, solid acids such as silica alumina, and cation-type ion exchange resins can be used. Especially sulfuric acid, phosphoric acid,
p-Toluenesulfonic acid is 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 even if the amount exceeds 10% by weight, the effect cannot be obtained beyond 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. In general, the carboxylic acid anhydride may be charged so as to be 1.03 to 1.50 times the total amino groups in the amino group-containing phenol resin on a molar basis.

After completion of the condensation reaction, the reaction mixture is washed with water,
After removing the remaining catalyst and unreacted dicarboxylic anhydride,
The solvent is distilled off to obtain a concentrate. Thus, the imide group-containing phenol resin represented by the general formula (1) is obtained. In the imide group-containing phenol resin, in the general formula (1), m and n, which are the numbers of bonds between the phenol compound and the aromatic imide compound by the aralkyl group, are each from 0 to 20, but not both 0. In addition, the binding order of the aralkyl group between the phenol compound and the aromatic imide compound is not particularly limited and is not limited. The terminal of the molecule is derived from one or both of the phenol compound and the aromatic imide compound. The resulting imide group-containing phenol resin has an average molecular weight range of 350 to 5,000, a molar ratio of imide group / hydroxyl group of 3:97 to 80:20, and a softening point of 60.
~ 140 ° C.

Next, a molding material using this imide group-containing phenol resin will be described. This molding material contains the imide group-containing phenol resin of the present invention as an essential component, and if necessary, may be used in combination with another phenol resin. The phenolic resin is a novolak resin obtained by reacting a phenol and an aldehyde such as formalin, and a phenol and an aralkyl compound used in the production of the imide group-containing phenol resin of the present invention. Phenol aralkyl resins and phenol resins obtained by reacting phenols with dicyclopentadiene are used. The use ratio of these phenolic resins and the imide group-containing phenolic resin, which is an essential component of the present invention, is not particularly limited.However, if the amount of the imide groups occupying the entire matrix resin in the molding material is too small, heat resistance and heat strength, Since the effect of the present invention is no longer exhibited, it should be appropriately adjusted according to the content ratio of the imide group. This imide group should be at least 3 mol%, preferably at least 5 mol%, based on the phenolic hydroxyl groups of the entire matrix resin. The upper limit of the imide group is 80 mol% or less when used alone, and is generally lower when used in combination.

Next, the curing components used in the molding material of the present invention will be described. The imide group-containing phenolic resin of the present invention is characterized in that the maleimide group, nadic imide group and the like having an aliphatic unsaturated bond can be crosslinked by polymerization. Therefore, those having a high imide group content can be used as a self-curing molding material without adding another kind of curing component. However, from the viewpoint of improving heat resistance and mechanical strength, it is better to add a curing component to any kind or ratio of resin containing an imide group. As such a curing component, hexaminemethylenetetramine or a resolated product which usually cures a phenol resin is used.

In the case of hexamethylenetetramine, it is usually used in an amount of 2 to 18% by weight based on the total resin.
This is used after being appropriately adjusted according to the content of the imide group. That is, if the content of the imide group is large, the use amount of hexamethylenetetramine may be small, and if the content of the imide group is small, the use amount of hexamethylenetetramine may be increased. On the other hand, in the case of the resolated product, the cured product is provided irrespective of the usage amount, and thus the usage amount is not particularly limited. However, in order to obtain a cured product having good physical properties, the amount of the resolated product is suitably in the range of 10 to 500% by weight based on the imide group-containing phenol resin or the phenol resin containing the same. Examples of the resolated compound include generally known phenolic resole resins, for example, resol novolak, dimethylolated phenol compound, resylated compound of bisphenol, resolated compound of phenol aralkyl resin, resole compound of phenol-dicyclopentadiene resin, and the like. ,
Examples include resole compounds of aromatic hydrocarbons such as xylene and mesitylene. The meaning of resol as used herein means a methylol compound reacted with formalin, hexamine, or the like in the presence of an alkaline catalyst or an acidic catalyst, or a mixed system of a methylene bond, a dimethylene ether bond, a methylol group, a methyleneoxymethylol group, and the like. It consists of

Next, an inorganic and / or organic filler is used in the molding material of the present invention. These include, for example, asbestos, mica, glass fiber, carbon fiber, aramid fiber, metal fiber, silica, alumina, calcium carbonate, magnesium oxide, aluminum hydroxide, wood flour, charcoal, kaolin,
Clay, diatomaceous earth, mica, carbon black and the like.
The ratio between the filler and the resin component is usually 0.3 to 6: 1 by weight.

The molding material of the present invention may contain, in addition to the above components, a curing accelerator, a pigment, a lubricant, a rust inhibitor, a stabilizer,
Flame retardants, antistatic agents and the like can be appropriately used according to the purpose. In particular, imidazole-based compounds such as 2-methylimidazole (2MZ) and 2-undecylimidazole (C17Z) -based phosphorus compounds, such as triphenyl, in terms of efficiently promoting the promotion of crosslinking of double bonds such as a maleimide group and a nadic imide group. The use of an accelerator such as phosphine (TPP), tetraphenylphosphonium tetraphenylborate or 1.8-diazabicyclo (5,4,0) undecene-7 in the range of 0.1 to 5% by weight based on the resin is rather. It is an effective means. The molding material of the present invention can be obtained by mixing and kneading the above components at, for example, about 80 to 140 ° C. by a roll mill to obtain a molding material. The molding material thus obtained can be cured by a method such as compression or extrusion, and then a cured product can be obtained.

[0030]

Next, the present invention will be described in more detail by way of examples. However, the present invention is not limited by these examples. Synthesis 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 the stirring was further continued for 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.

Synthesis Example 2 138.3 g (1.47 mol) of phenol, aniline 1
Synthesis Example 1 except that 175 g (1 mol) of P-xylylene dichloride was used for 42.4 g (1.53 mol).
The same procedure as described above was repeated to obtain a maleimide group-containing phenol resin 252.
g was obtained. The maleimide / hydroxyl molar ratio of this resin is 2
7.4 / 72.6, and the softening point was 84.5 ° C.

Synthesis Example 3 262.5 g of p-xylylene dichloride (1. mol of phenol and 94 g (1 mol) of phenol and 186 g (2 mol) of aniline).
290 g of an amino group-containing phenol resin was obtained in the same manner as in Synthesis Example 1 except that 5 mol) was used. The molar ratio of amino group / hydroxyl group of this resin was 53.2 / 46.8. Next, 118.4 g (0.8 mol) of phthalic anhydride was added to the amino group-containing phenol resin, and 18
The condensation reaction between the amino group and phthalic anhydride was performed under reduced pressure using an aspirator while melting and mixing at 0 ° C. Water generated on the way was collected by a cooling trap. The reaction was terminated when aging was carried out at the same temperature for 2 hours and no generation of water was observed. This molten resin was a phenol resin in which amino groups were phthalimidized, had a softening point of 126 ° C. and a yield of 388 g.

Examples 1 to 6, Comparative Examples 1 to 2 The imide group-containing phenolic resins obtained in Synthesis Examples 1 to 3 and a phenol novolak resin # 2000 for comparison
(Manufactured by Showa Polymer), general formula (6)

Embedded image A filler, a curing agent, and other additive components are blended as shown in Table 1 using a phenol ziloc resin (Mirex 225, manufactured by Mitsui Toatsu Chemicals, Inc., average molecular weight 2400) represented by To obtain a molding material composition. These compositions were compression molded at 190 ° C. for 5 minutes to obtain test pieces for evaluating physical properties. This test piece is 220 ° C / 4h
After 250 ° C./4 hr post-curing, physical properties were evaluated. As a curing agent, hexamethylenetetramine and resol type phenol resin (manufactured by Dainippon Ink and Chemicals, T
D-2040C solid content 100%) and a xylene resin (Nickanol-HH, manufactured by Mitsubishi Gas Chemical).

[0034]

[Table 1]

As is clear from the results shown in Table 1, the water absorption of Examples 1 to 6 is about 50 to 90% as compared with Comparative Example 1, and the long-term thermal deterioration is 270 ° C. for Examples 1 to 6. × 31
Even after 2 hours, the strength is 40% or more before the treatment, but in Comparative Example 1, the strength is greatly reduced and the strength cannot be maintained. Further, Tg was 30 to 1 in Examples 1 to 6 compared to Comparative Example 2.
The temperature is higher by about 20 ° C., and the bending strength when heated is improved by about 2 to 3 times. In other words, in these examples, the molding material of the present invention exceeds the Xyloc resin with respect to the performance of Tg and flexural strength when heated, and maintains them at the same level as the Nopolak resin. Water absorption, which is a difficulty,
It shows that the performance of long-term thermal deterioration is improved more than that of Xylock resin.

[0036]

As described in detail above, the molding material of the present invention has good workability because the softening point is within an appropriate range, and the cured product has excellent heat resistance and mechanical strength, and low water absorption. Therefore, high reliability can be obtained when used in the advanced composite material field and the like.

Continuation of front page (72) Inventor Akihiro Yamaguchi 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Inside Mitsui Toatsu Chemicals Co., Ltd. (56) References JP-A-5-67706 (JP, A) (58) Fields investigated ( Int.Cl. ⁷ , DB name) C08G 61/02

Claims (4)

(57) [Claims] 1. A compound represented by the general formula (1):(Where R₁, R_TwoIs hydrogen atom, halogen atom, hydroxyl
Group, or C₁~ C₁₂Alkyl group, cycloalkyl
Group, aralkyl group, alkoxy group, aryl group or
A reeloxy group, which may be the same or different;₁
And R_TwoMay form a ring. R_Three, R_FourIs a hydrogen source
Atom, halogen atom, hydroxyl group, imide group, C₁~ C ₁₂No
Alkyl, aryl, cycloalkyl, aralkyl
Group, imide group-substituted aralkyl group, hydroxy group-substituted ara
Alkyl group, alkoxy group, aryloxy group, imide group
Substituted aryloxy group, hydroxy-substituted aryloxy
And represents the same or a different group,_ThreeAnd R_FourIs a ring
May be formed. Z is C_Two~ C_{twenty four}Unsaturated fat
Group, saturated monocyclic aliphatic group, unsaturated monocyclic aliphatic group,
Saturated condensed polycyclic aliphatic group, saturated condensed polycyclic aliphatic group,
Aliphatic group having an unsaturated monocyclic aliphatic group as a substituent,
Monocyclic aromatics which may have chain aliphatic groups as substituents
Group or monocyclic aromatic group, directly or
Linked non-fused polycyclic aromatic group, chain-like fat as a substituent
Consists of fused polycyclic aromatic groups that may have aliphatic groups
Shows a divalent group selected from the group. However, m and n are 0 to 2
0, and m + n ≠ 0. Terminal is phenolic compound
And / or an aromatic imide compound,
The bonding order of the compound and the aromatic imide compound is not limited.
No. ), Average molecular weight 3
50-5000, the ratio of imide group / hydroxyl group is 3: 97-
An imide group-containing phenolic resin in the range of 80:20 and
Inorganic and / or organic filler, hexamethylene tet
A molding material characterized by containing lamin. 2. A molding material comprising the imide group-containing phenol resin represented by the general formula (1) according to claim 1, an inorganic and / or organic filler, and a resol resin. 3. A molded cured product obtained from the molding material according to claim 1. 4. A molded cured product obtained from the molding material according to claim 2.