JP3485721B2 - Surface treated aramid fiber material and epoxy resin composite - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a surface-treated aramid fiber material and an epoxy resin composite using the same. More specifically, it relates to an aramid fiber material surface-treated with an epoxidized aromatic polyamide resin, and an epoxy resin composite using the same.

[0002]

2. Description of the Related Art Since aramid fibers are excellent in tensile strength, tensile modulus and heat resistance, they are used as a base material for composite materials.
Used in aircraft, automobiles, boats, sports equipment, etc. In particular, para-oriented aramid fibers are expected as an electric circuit wiring board material because they have insulating properties, have a low dielectric constant, and have a negative coefficient of thermal expansion.

On the other hand, in a composite material composed of fibers and a resin matrix, the quality of the adhesiveness between the fibers and the resin matrix depends on the mechanical strength and elastic modulus of the composite material composed of both.
In order to improve the physical properties of the composite material, it is extremely important to improve the adhesiveness between the fiber and the resin matrix, since the fatigue resistance is greatly affected. Against this background, in a composite material using an aramid fiber and an epoxy resin as a matrix according to a conventional technique, the aramid fiber is a rigid polymer and has high crystallinity. Since it is inactive, the adhesiveness between the fiber and the epoxy resin is not sufficient. Further, even if an epoxy resin having a relatively good adhesiveness with an aramid fiber is used as a resin matrix, there is a problem that the interfacial adhesion is insufficient.
For such problems, a method of hydrolyzing the aramid fiber surface with an acid or a base to introduce an epoxy group by reacting with an amino group, and further with epichlorohydrin, or a chemical method similar to that of a matrix resin on the aramid fiber surface. A method of introducing a chemical species of structure, a method of performing a plasma treatment, a method of using a coupling agent, etc. have been proposed, but a sufficient effect has not been obtained yet, and a problem that the cost becomes very high There is also.

[0004]

With respect to such a problem, the present inventors have found that the phenolic hydroxyl group-containing aromatic polyamide resin can be used for the surface treatment of various materials, whereby the above problems are remarkably improved. It has been found to do so and has already proposed (Japanese Patent Publication No. 7-42359). However, in this method, when a compound having a group other than a phenolic hydroxyl group is used as a curing agent for an epoxy resin for the treatment of an aramid fiber, due to the difference in reactivity between these groups and the epoxy group, There was a problem that a uniform cured product could not be obtained and a sufficient strength could not be obtained as a whole system.

The present invention has been made in view of the above problems in the prior art. That is, an object of the present invention is to provide a surface-treated aramid fiber having excellent adhesiveness. Another object of the present invention, when used in the production of an epoxy resin composite, does not cause a difference in the reactivity between the aramid fiber and the epoxy resin with the curing agent for the epoxy resin, and the epoxy resin having improved properties. It is an object of the present invention to provide a surface-treated aramid-based fiber capable of producing a composite.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventor has conducted surface treatment of aramid fiber materials with a treatment liquid containing a specific epoxidized aromatic polyamide resin. And forming an epoxidized aromatic polyamide resin layer on the surface of the aramid-based fiber and the epoxy resin, without causing a difference in reactivity between the epoxy resin and the curing agent for the epoxy resin. It was found that a fiber-based epoxy resin composite was obtained, and the present invention was completed.

Therefore, the surface-treated aramid fiber material of the present invention contains 5 to 100 mol% of repeating units represented by the following general formula (1) and 95 to 0 mol% of repeating units represented by the following general formula (2). Intrinsic viscosity value including 0.1-3.
It is characterized by being surface-treated with a treatment liquid containing an epoxidized aromatic polyamide resin having 0 dl / g.

[Chemical 2] (In the formula, R is a monocyclic aromatic group or a plurality of aromatic rings is an oxygen atom, a sulfur atom, a CO group, an SO ₂ group or a carbon number 1
~ 3 represents a polycyclic aromatic hydrocarbon group which may be linked via a hydrocarbon group, and R'represents a divalent aromatic, alicyclic or heterocyclic dicarboxylic acid residue. ) Further, the aramid-based fiber / epoxy resin composite of the present invention is formed from the above-mentioned surface-treated aramid-based fiber material and an epoxy resin composition containing an epoxy resin and a curing agent for an epoxy resin as a main component. It is characterized by

In the repeating unit represented by the above general formula (2), R is a monocyclic aromatic group or a plurality of aromatic rings having an oxygen atom, a sulfur atom, a CO group, an SO ₂ group or a carbon number of 1 to 3. Represents a polycyclic aromatic hydrocarbon group which may be linked via a hydrocarbon group of, more specifically, a phenylene group, a naphthalene group, a biphenylene group, a bisphenoxybiphenyl group, a diphenyl ether group, a diphenyl thioether group, Bisphenoxyphenyl ether group, benzophenone group, diphenylsulfone group, bisphenoxyphenylsulfone group, bisphenylpropane group, bisphenoxybenzene group, diphenylmethane group, bisphenylisopropylidenebenzene group, bisphenylhexafluoropropane group, bisphenoxyphenylhexa Fluoropropane groups, etc. Group and the like of the benzene ring in these groups, the alkyl, nitro, hydroxyl, halogen, alkoxy, optionally substituted by a trifluoromethyl group.

R'represents a divalent aromatic, alicyclic or heterocyclic dicarboxylic acid residue, specifically, a phenylene group, a naphthalene group, a biphenylene group, a diphenylmethane group, a diphenyl ether group, Diphenylthioether group, benzophenone group, diphenylsulfone group,
Examples thereof include divalent groups such as a bisphenylpropane group, a pyridine group, a bisphenylhexafluoropropane group, an N, N'-methylenephthalimide group, and a cyclohexane group.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, 5 to 100 mol% of the repeating unit represented by the general formula (1) used for the surface treatment of an aramid fiber material and the general formula (2)
The epoxidized aromatic polyamide resin having an intrinsic viscosity value of 0.1 to 3.0 dl / g containing 95 to 0 mol% of the repeating unit is represented by the aromatic group having a phenolic hydroxyl group represented by the following general formula (3). A dicarboxylic acid component containing 5 to 100 mol% of the total amount of dicarboxylic acid is condensed with at least an equivalent amount of aromatic diamine to synthesize a phenolic hydroxyl group-containing aromatic polyamide resin, and the hydroxyl group is epoxidized with epihalohydrin. By doing so, it can be easily manufactured.

[0011]

[Chemical 3]

The method for producing the epoxidized aromatic polyamide resin used in the present invention will be described in detail. The condensation reaction between the dicarboxylic acid component and the aromatic diamine is a known condensation reaction, for example, the nylon salt method, Acid chloride method,
Although an active esterification method, a direct method using a condensing agent, or the like can be used, in the case of producing an aromatic polyamide resin having a phenolic hydroxyl group, as in the present invention, a phenol is used by a direct method using a condensing agent. It is preferable to carry out without protecting the hydroxyl group of the dicarboxylic acid monomer containing a polymerizable hydroxyl group. One example is US Pat. No. 5,342,89.
No. 5 specification.

Examples of the condensing agent used for producing a phenolic hydroxyl group-containing polyamide resin without protecting the hydroxyl groups of the phenolic hydroxyl group-containing dicarboxylic acid monomer include, for example, "Polymer" published by The Society of Polymer Science, 1991. Functional Materials Series 2 Polymer Synthesis and Reactions ”18th
Although those described on page 3 can be used,
In the present invention, a condensing agent composed of a combination of a phosphite ester and a pyridine derivative is preferably used from the viewpoint of easiness of handling and cost.

The condensation reaction is carried out in an amide solvent typified by N-methyl-2-pyrrolidone, dimethylacetamide or the like under an inert atmosphere such as nitrogen at room temperature to 160 ° C. for 30 minutes to several hours. It can be easily carried out by stirring. Lithium chloride, calcium chloride or the like can be added as a stabilizer to this reaction, if necessary.

As the dicarboxylic acid containing a phenolic hydroxyl group represented by the above general formula (3), which is a raw material for producing a phenolic hydroxyl group-containing aromatic polyamide resin, 5-
Examples thereof include hydroxyisophthalic acid, 4-hydroxyisophthalic acid, 2-hydroxyphthalic acid, 3-hydroxyphthalic acid and 2-hydroxyterephthalic acid. It is also possible to use a mixture of two or more of these.

In the present invention, in addition to the above dicarboxylic acid, other dicarboxylic acids can be used in combination in an amount of up to 95 mol% for polycondensation. Examples of such dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, 4,4'-biphenyldicarboxylic acid, 3,3'-
Methylene dibenzoic acid, 4,4'-methylene dibenzoic acid,
4,4'-oxydibenzoic acid, 4,4'-thiodibenzoic acid, 3,3'-carbonyldibenzoic acid, 4,4'-sulfonyldibenzoic acid, 1,4-naphthalenedicarboxylic acid,
1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-carbonyldibenzoic acid, 2,
2-bis (4-carboxyphenyl) propane, bis (4-carboxyphenyl) methane, 2,2-bis (4
-Carboxyphenyl) hexafluoropropane, 2,
Examples thereof include 6-dicarboxypyridine, N, N'-methylenephthalimide-3,3'-dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and derivatives thereof. It is not limited to. These dicarboxylic acids can be used as a mixture of two or more kinds.

Examples of the above-mentioned aromatic diamine, which is another raw material for producing an aromatic polyamide resin containing a phenolic hydroxyl group, include p-phenylenediamine, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, and 4 ，
4'-bis (4-aminophenoxy) biphenyl, 3,
3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminodiphenyl ether, bis [4- (4-aminophenoxy) phenyl] ether , Metatolylenediamine, 3,
3'-diaminodiphenyl thioether, 4,4'-diaminodiphenyl thioether, 3,3'-dimethyl-
4,4'-diaminodiphenyl thioether, 3,3 '
-Diethoxy-4,4'-diaminodiphenyl thioether, 4,4'-diaminobenzophenone, 3,3'-
Dimethyl-4,4'-diaminobenzophenone, 2,2
-Bis (3-aminophenyl) propane, 2,2-bis (4-aminophenyl) propane, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'-dinitro-4, 4'-diaminodiphenyl sulfone, 3,3'-diamino-4,4'-dichlorodiphenyl sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone , O-toluidine sulfone, benzidine, 3,3′-dimethylbenzidine,
3,3'-dimethoxybenzidine, 2,2'-bis (trifluoromethyl) benzidine, 3,3'-diaminobiphenyl, p-xylylenediamine, m-xylylenediamine, 3,3'-dihydroxy-4, 4'-diaminobiphenyl, 4,10-bis (4-aminophenyl) anthracene, 9,9-bis (4-aminophenyl) fluorene, 1,4-bis (4-aminophenylisopropylidene) benzene, 1,3 -Bis (4-aminophenylisopropylidene) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 2,2-bis (3-amino-4-) Methylphenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,
2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-hydroxy-3-aminophenyl) hexafluoropropane, 3,
3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-
Diaminodiphenylmethane, bis (4-amino-3-methylphenyl) methane, bis (4-amino-3,5-dimethylphenyl) methane, bis (4-amino-3-ethylphenyl) methane, bis (4-amino-) 3,5-diethylphenyl) methane, bis (4-amino-3-propylphenyl) methane, bis (4-amino-3,5-dipropylphenyl) methane, bis (4-amino-3-isopropylphenyl) methane , Bis (4-amino-3,5
-Diisopropylphenyl) methane, bis (3-methyl-4-aminophenyl) methane, bis (3-ethyl-4)
-Aminophenyl) methane, bis (3-propyl-4-)
Aminophenyl) methane, bis (3-isopropyl-4)
-Aminophenyl) methane, bis (3-methyl-5-ethyl-4-aminophenyl) methane, bis (3-methyl-5-propyl-4-aminophenyl) methane, bis (3-methyl-5-isopropyl- 4-aminophenyl) methane, bis (3-ethyl-5-propyl-4-aminophenyl) methane, bis (3-ethyl-5-isopropyl-4-aminophenyl) methane, bis (3-propyl-5-isopropyl) Examples include, but are not limited to, 4--4-aminophenyl) methane and the like. These may be used alone or in combination of two or more.

The hydroxyl groups of the phenolic hydroxyl group-containing aromatic polyamide produced as described above are then epoxidized. Examples of epihalohydrin used for epoxidation include epichlorohydrin and epibromohydride. Phosphorus, epiiodohydrin and combinations thereof. Further, the epoxidation can be carried out by a known method (for example, refer to “Epoxy Resin” edited by Hiroshi Kakiuchi, published by Shokoido, 1972 edition).
Generally, it is carried out under basic conditions at about 20 to 120 ° C. while appropriately removing the produced water. Examples of the base used at that time include alkali metal hydroxides such as sodium hydroxide and lithium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, pyridine, tetramethylammonium hydroxide, trimethylhydroxyammonium hydroxide aqueous solution, and hydrazine. , Pyridine and the like. In the epoxidation reaction, epihalohydrin itself serves as a reaction solvent, but if desired, an organic solvent such as alcohols, ethers, ketones and amides may be used.

Further, the reaction between the hydroxyl group and epihalohydrin can easily proceed to convert the active hydrogen of the hydroxyl group contained in the resin into an epoxy group,
The reaction rate varies greatly depending on the reaction conditions and generally largely depends on the amount of epihalohydrin introduced. Large excess,
That is, by introducing epihalohydrin at a hydroxyl group concentration or higher, a reaction rate of 100% can be obtained. Therefore, the general formula (1) of the epoxidized aromatic polyamide in the present invention is
The content of the repeating unit represented by can be controlled by controlling the concentration of hydroxyl groups contained in the phenolic hydroxyl group-containing aromatic polyamide resin or by controlling the reaction rate with epihalohydrin. In the present invention, these selections are not limited, but it is preferable to control by the hydroxyl group concentration, which is preferable.

In the present invention, the epoxidized aromatic polyamide resin produced as described above must contain 5 to 100 mol% of the repeating unit represented by the general formula (1). When the content is less than 5 mol%, the epoxy group content is too small to achieve the above object of the present invention. The epoxidized aromatic polyamide resin has an intrinsic viscosity of 0.1
It is necessary to be in the range of ~ 3.0 dl / g. It is estimated that this intrinsic viscosity value corresponds to an average degree of polymerization of 2 to 100. When the intrinsic viscosity value is lower than 0.1 dl / g, it becomes difficult to form a resin film having sufficient mechanical properties, and when it is higher than 3.0 dl / g, the solvent solubility is deteriorated. . The degree of polymerization can be adjusted by changing the blending ratio of the aromatic diamine and dicarboxylic acid used, and the degree of polymerization can be reduced by using one of them in excess.

In order to surface-treat an aramid fiber material using the epoxidized aromatic polyamide resin produced as described above, a solution of the epoxidized aromatic polyamide resin is dissolved in the above-mentioned various solvents. The resin film may be formed on the fiber surface by removing the solvent of the solution adhering to the fiber material by, for example, drying the solution and impregnating it with the aramid fiber material. In the present invention, in the above case, since a general-purpose solvent having a low boiling point, low cost, and low toxicity can be used as a solvent, there is an advantage that the solvent can be easily removed.

The above treatment liquid may be added, if necessary.
Other components may be included. For example, a stress relaxation agent, a flame retardant, a curing accelerator, a coloring agent such as a dye or a pigment, an oxidation stabilizer, a light stabilizer, a coupling agent, a thermoplastic resin, a diluent, an antifoaming agent, etc. are mixed as described below. can do.

In the present invention, examples of the aramid fiber material to be surface-treated include woven cloth, non-woven cloth and chopped strands. These fiber materials may be composed of two or more kinds of aramid fibers, and include reinforcing materials for composite materials other than aramid fibers, such as carbon fibers, glass fibers, and alumina fibers. Good. However, the content of the reinforcing material other than the aramid-based fiber is preferably 30% by weight or less based on the weight of the fiber material in order to utilize the characteristics of the aramid-based fiber which is light and strong. Further, in the present invention, these aramid fiber materials may be subjected to acid or alkali treatment, plasma treatment or the like.

The aramid fibers constituting the aramid fiber material include fibers made of poly [3,4 '-(diaminodiphenyl) terephthalamide], poly (paraphenylene terephthalamide) and copolymers thereof. , These are Kepler, Kepler 2 made by DuPont
9, Kepler 68, Kepler 49, Kepler 129 and Kepler 149 etc., Teijin Connex and Technora, Akzo Twaron, Monsanto X
-500, X-702 and the like are commercially available, but the present invention is not limited to these.

The aramid fiber / epoxy resin composite of the present invention contains, as a main component, the aramid fiber material surface-treated with the epoxidized aromatic polyamide resin as described above, the epoxy resin and the curing agent for the epoxy resin. It can be produced from an epoxy resin composition. That is, the above-mentioned surface-treated aramid fiber material is dipped in a liquid or liquefied epoxy resin composition consisting of an epoxy resin, a curing agent for an epoxy resin and other desired components to be impregnated to form a composite. it can. As the impregnation method, in the case of a liquid epoxy resin composition, it may be immersed as it is, and when the epoxy resin composition is in a solid state, it is obtained by dissolving it in an organic solvent such as methyl ethyl ketone, acetone, or toluene. It may be immersed in a varnish for impregnation, or the epoxy resin composition may be heated by a hot melt method to reduce the viscosity, and immersed in the resin for impregnation. After further impregnation, by heating the treated aramid fiber material, a curing agent for the epoxy resin in the epoxy resin composition and an epoxy resin and an epoxidized aromatic polyamide resin layer formed on the aramid fiber surface. It is possible to obtain a aramid-based fiber / epoxy resin composite having desired properties by performing a reaction between the two.

In the present invention, the epoxy resin used in the epoxy resin composition has two or more epoxy groups in one molecule and is not limited in any way. For example, glycidyl ethers and glycidyl esters are included. ,
Examples thereof include compounds consisting of glycidyl amines, linear aliphatic epoxides, alicyclic epoxides, hydantoin type epoxides and the like.

As the glycidyl ethers, for example,
Examples thereof include diglycidyl ether of bisphenol, polyglycidyl ether of phenol novolac, alkylene glycol or diglycidyl ether of polyalkylene glycol. More specifically, examples of the diglycidyl ether of bisphenol include bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, and tetramethylbisphenol A.
Examples thereof include diglycidyl ethers of divalent phenols such as D, tetramethylbisphenol S, tetrachlorobisphenol A, and tetrabromobisphenol A. Examples of polyglycidyl ethers of phenol novolac include phenol novolac, cresol novolac, and brominated phenol. Examples thereof include polyglycidyl ethers of novolac resins such as novolac, and examples of diglycidyl ethers of alkylene glycols or polyalkylene glycols include polyethylene glycol,
Examples thereof include diglycidyl ethers of glycols such as polypropylene glycol and butanediol.

As the glycidyl esters, for example,
Examples thereof include diglycidyl ester of hexahydrophthalic acid and glycidyl ester of dimer acid. As the glycidyl amines, for example, triglycidyl aminodiphenylmethane, triglycidyl aminophenol,
Examples thereof include triglycidyl isocyanurate. Examples of linear aliphatic epoxides include epoxidized polybutadiene and epoxidized soybean oil,
Examples of the alicyclic epoxides include 3,4-epoxy-6-methylcyclohexylmethylcarboxylate, 3,4-epoxycyclohexylmethylcarboxylate, hydrogenated bisphenol epoxide and the like. Further, as hydantoin type epoxides,
Examples thereof include diglycidyl hydantoin and glycidyl glycidoxyalkyl hydantoin. These epoxy resins may be used alone or in combination of two or more.

In the present invention, the curing agent for epoxy resin used in the epoxy resin composition is, for example, bis (4
-Aminophenyl) sulfone, bis (4-aminophenyl) methane, 1,5-diaminonaphthalene, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 2,6-dichloro-1,4-phenylenediamine, 1,3-di (p-aminophenyl) propane,
Aromatic amine curing agents such as m-xylenediamine, ethylenediamine, diethylenetriamine, tetraethylenepentamine, diethylaminopropylamine, hexamethylenediamine, isophoronediamine, bis (4-amino-3-methyldicyclohexyl) methane, polymethylenediamine , Aliphatic amine compounds such as polyether diamine, polyaminoamide compounds, dodecyl succinic anhydride, polyadipic acid anhydride, polyazelaic acid anhydride and other aliphatic acid anhydrides, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride Alicyclic acid anhydrides such as acids, phthalic anhydride, trimellitic anhydride, benzophenone tetracarboxylic acid anhydride, aromatic acid anhydrides such as ethylene glycol bis trimellitate, glycerol tris trimellitate, pheno Le compounds and phenolic resins, amino resins, urea resins, melamine resins, dicyandiamide,
Examples thereof include dihydrazines, imidazoles, Lewis acids, Bronsted acid salts, polymercaptans, isocyanates and blocked isocyanates.

Other components can be added to the epoxy resin composition used in the present invention, if necessary. For example, natural waxes, synthetic waxes and long-chain aliphatic acids and metal salts thereof, mold release agents such as acid amides, esters and paraffins, stress relaxation agents such as silicone rubber, nitrile rubber, butadiene rubber and polysiloxane. Flame retardants such as chlorinated paraffin, bromotoluene, hexabromobenzene, antimony trichloride, silane coupling agents, titanate coupling agents, aluminum coupling agents, fused silica, fused silica,
Crystalline silica, glass flakes, glass beads, glass balloons, talc, alumina, calcium silicate, calcium carbonate, barium sulfate, magnesia, silicon nitride,
Metal powder such as boron nitride, ferrite, rare earth cobalt, gold, silver, nickel, copper, zinc, lead, iron powder, iron oxide and iron sand,
Inorganic fillers or conductive particles such as graphite and carbon, curing accelerators, coloring agents such as dyes and pigments, oxidation stabilizers, light stabilizers, thermoplastic resins, reaction diluents for epoxy resins, humidity resistance improvers, thixotropy Additives, diluents, defoamers, other resins, etc. can be added.

Examples of the curing accelerator include triphenylphosphine, tertiary amine compounds such as triethylamine, triethanolamine, 1,8-diazabicyclo [5,4,0] -7-undecene, N, N. -Dimethylbenzylamine, 1,1,3,3-tetramethylguanidine, 2-ethyl-4-methylimidazole, N-
Examples thereof include boron-based compounds such as methylpiperazine and the like, such as 1,8-diazabicyclo [5,4,0] -7-undecenium tetrafluoroborate.

[0032]

EXAMPLES The present invention will be described in more detail below, but the present invention is not limited thereto. Synthesis Example 1 In a 1-liter three-necked round bottom flask equipped with a mechanical stirrer, a cooling tube, a calcium chloride tube, and a nitrogen introducing tube,
18.21 g (100 mmol) of 5-hydroxyisophthalic acid, 3,3 ', 5,5'-tetraethyl-4,4'
-Diaminodiphenylmethane 31.05 g (100 mmol), calcium chloride 10.10 g, lithium chloride 3.3 g, N-methyl-2-pyrrolidone 600 ml, pyridine 30 ml, triphenyl phosphite 62.05 g
(200 mmol) was added, and the mixture was stirred at 120 ° C. for 4 hours in a nitrogen atmosphere to synthesize an aromatic polyamide. The reaction solution was introduced into a water: methanol (8: 2) mixture,
The polymer was precipitated. Furthermore, the polymer was washed twice with this mixed solution and dried to obtain a phenolic hydroxyl group-containing aromatic polyamide. The intrinsic viscosity value of this resin was 0.60 dl / g. The intrinsic viscosity value is a value obtained by measuring the viscosity of a dimethylacetamide solution having a concentration of 0.5 g / dl at 30 ° C., and the same applies below.

Synthesis Example 2 25.59 g of the aromatic polyamide containing phenolic hydroxyl group obtained in Synthesis Example 1 was placed in a 1 liter three-necked round bottom flask equipped with a Dean-Stark type moisture meter, a reflux condenser and a mechanical stirrer. Then, 400 g of dimethylformamide, 100 g of benzene, and 3.5 g of sodium hydroxide were added, and the mixture was heated to 100 ° C. and refluxed until the produced water was removed. Hydrin 10.5 g (120 mmol)
And 10 g of pyridine were added, and the mixture was stirred and reacted for about 12 hours. The reaction solution was poured into a 10-liter water bath to obtain a crude product. Further, this was filtered and separated, and then washed twice with a mixed liquid of water and methanol (weight ratio 1: 1) to obtain 26.4 g of the desired epoxidized aromatic polyamide resin (yield: 9
2%) was obtained. NMR measurement of this resin (manufactured by JEOL Ltd.,
It was confirmed by PMX-60Si) that the addition rate of the epoxy group to the hydroxyl group was 90% and that the repeating unit represented by the general formula (1) was contained in 90%. The intrinsic viscosity of this resin was 0.59 dl / g.

Synthesis Example 3 5-hydroxyisophthalic acid used in Synthesis Example 1 18.
An aromatic polyamide containing a phenolic hydroxyl group was obtained by the same method except that 21 g (100 mmol) was changed to 13.66 g (75 mmol) and 4.16 g (25 mmol) of isophthalic acid. The intrinsic viscosity of this resin is 0.63d
It was 1 / g.

Synthetic Example 4 Furthermore, the phenolic hydroxyl group-containing aromatic polyamide obtained in Synthetic Example 3 was epoxidized by the same method as in Synthetic Example 2, and the target epoxidized aroma was obtained at a yield of 90%. A group polyamide resin was obtained. The addition rate of epoxy groups in this resin was about 95%. As a result, it was confirmed that the repeating unit represented by the general formula (1) was contained in about 71%. The intrinsic viscosity of this resin is 0.60d
It was 1 / g.

Synthesis Example 5 5-hydroxyisophthalic acid used in Example 1 18.
An aromatic polyamide containing a phenolic hydroxyl group was obtained in exactly the same manner except that 21 g (100 mmol) was changed to 9.11 g (50 mmol) and isophthalic acid 8.31 g (50 mmol). The intrinsic viscosity of this resin is 0.63d
It was 1 / g.

Synthetic Example 6 Furthermore, the phenolic hydroxyl group-containing aromatic polyamide obtained in Synthetic Example 5 was epoxidized by the same method as in Synthetic Example 2, and the target epoxidized fragrance was obtained in a yield of 91%. A group polyamide resin was obtained. The addition rate of epoxy groups in this resin was about 96%. As a result, it was confirmed that about 48% of the repeating unit represented by the general formula (1) was contained. The intrinsic viscosity of this resin is 0.61d
It was 1 / g.

Synthesis Example 7 3,3 ', 5,5'-tetraethyl-4,4'-diaminodiphenylmethane used in Synthesis Example 1 31.05 g
Aromatic polyamide containing phenolic hydroxyl group was obtained by the same method except that (100 mmol) was changed to 20.03 g (100 mmol) of 3,4'-diaminodiphenyl ether. The intrinsic viscosity of this resin was 0.73 dl / g.

Synthetic Example 8 Furthermore, the phenolic hydroxyl group-containing aromatic polyamide obtained in Synthetic Example 7 was epoxidized by the same method as in Synthetic Example 2. The yield was 92%, and the desired epoxidized fragrance was obtained. A group polyamide resin was obtained. The addition rate of epoxy groups in this resin was about 93%. As a result, it was confirmed that the repeating unit represented by the general formula (1) was contained in an amount of about 93%. The intrinsic viscosity of this resin is 0.70d
It was 1 / g.

Example 1 Epoxidized aromatic polyamide resin 1 obtained in Synthesis Example 2
A solution of 0 g dissolved in 90 ml of methanol was dipped in a scouring cloth made of Kepler 49 (product number 352, manufactured by Clark Schwabel Co.) to impregnate it, and then heated at about 40 ° C. for 20 minutes to dry the epoxy. A Kepler cloth coated with a modified aromatic polyamide resin was obtained. The rate of sticking of this resin to the fibers was 1.5% by weight.

Example 2 Epoxidized aromatic polyamide resin 1 obtained in Synthesis Example 4
Kepler 49 was added to a solution of 0 g dissolved in 90 ml of a mixed solvent consisting of 10 ml of ethanol and 80 ml of toluene.
A cloth (product number 352, manufactured by Clark Schwabel Co.) consisting of
After heating for 0 minutes and drying, Kepler cloth coated with an epoxidized aromatic polyamide resin was obtained. The sticking rate of this resin to the fiber was 1.7% by weight.

Example 3 Epoxidized aromatic polyamide resin 1 obtained in Synthesis Example 6
A solution prepared by dissolving 0 g in 90 ml of dimethylformamide was dipped in a scouring cloth made of Kepler 49 (product number 352, manufactured by Clark Schebel) to impregnate it, and then heated at about 70 ° C. for 20 minutes to dry it, A Kepler cloth coated with an epoxidized aromatic polyamide resin was obtained.
The fixing rate of this resin to the fiber was 1.3% by weight.

Example 4 Epoxidized aromatic polyamide resin 1 obtained in Synthesis Example 8
A solution prepared by dissolving 0 g in 90 ml of dimethylformamide was dipped in a scouring cloth made of Kepler 49 (product number 352, manufactured by Clark Schebel) to impregnate it, and then heated at about 70 ° C. for 20 minutes to dry it, A Kepler cloth coated with an epoxidized aromatic polyamide resin was obtained.
The adhesion rate of this resin to the fiber was 1.6% by weight.

Comparative Example 1 10 g of the aromatic polyamide resin containing a phenolic hydroxyl group obtained in Synthesis Example 1 was dissolved in a mixed solvent of 45 ml of propanol and 45 ml of methyl ethyl ketone, and a cloth consisting of Kepler 49 (product number 352, Clark Schwebel) Approximately 7 after dipping the scouring cloth
It was heated at 0 ° C. for 20 minutes and dried to obtain Kepler cloth coated with a phenolic hydroxyl group-containing aromatic polyamide resin. The rate of sticking of this resin to the fibers was 1.5% by weight.

Comparative Example 2 10 g of the phenolic hydroxyl group-containing aromatic polyamide resin obtained in Synthetic Example 3 was dissolved in a mixed solvent of 45 ml of propanol and 45 ml of methyl ethyl ketone, and a cloth consisting of Kepler 49 (product number 352, Clark Schwabel Company) was added. Approximately 7 after dipping the scouring cloth
It was heated at 0 ° C. for 20 minutes and dried to obtain Kepler cloth coated with a phenolic hydroxyl group-containing aromatic polyamide resin. The sticking rate of this resin to the fiber was 1.4% by weight.

Comparative Example 3 10 g of the phenolic hydroxyl group-containing aromatic polyamide resin obtained in Synthesis Example 5 was dissolved in a mixed solvent of 45 ml of propanol and 45 ml of methyl ethyl ketone, and a cloth consisting of Kepler 49 (product number 352, manufactured by Clark Schwebel) was used. Approximately 7 after dipping the scouring cloth
It was heated at 0 ° C. for 20 minutes and dried to obtain Kepler cloth coated with a phenolic hydroxyl group-containing aromatic polyamide resin. The adhesion rate of this resin to the fiber was 1.6% by weight.

Comparative Example 4 10 g of the aromatic polyamide resin containing a phenolic hydroxyl group obtained in Synthesis Example 7 was dissolved in a mixed solvent of 45 ml of propanol and 45 ml of methyl ethyl ketone, and a cloth consisting of Kepler 49 (product number 352, manufactured by Clark Schwebel). Approximately 7 after dipping the scouring cloth
It was heated at 0 ° C. for 20 minutes and dried to obtain Kepler cloth coated with a phenolic hydroxyl group-containing aromatic polyamide resin. The fixing rate of this resin to the fiber was 1.2% by weight.

Example 5 and Comparative Example 5 The Kepler cloth obtained in Examples 1 to 4 and Comparative Examples 1 to 4 was mixed with 100 parts of an epoxy resin (Epicoat 604,
(Shell Chemical Co., Ltd.), 40 parts curing agent: 4,4′-diaminodiphenyl sulfone, 1 part boron trifluoride monoethylamine complex, 50 parts methyl ethyl ketone, and after dipping in a solution consisting of hot air dryer at 140 ° C. Was dried for 10 minutes to prepare a prepreg. Four obtained prepregs were laminated and heated at 180 ° C. for 10K using a hot press machine.
It was cured at g / cm ² for 2 hours to prepare a composite material having a resin content of 50%. Furthermore, 50 × 1 from these composite materials
A test piece of 3 x 6 mm was prepared, and the distance between spans was 16 mm and the crosshead speed was 1 using an autograph.
A bending test was performed under the condition of 0 mm / min to measure the bending strength. The results are shown in Table 1.

[0049]

[Table 1]

[0050]

EFFECTS OF THE INVENTION The surface-treated aramid fiber material of the present invention exhibits excellent adhesiveness to epoxy resin and the like, and is mainly composed of the surface-treated aramid fiber material, epoxy resin and curing agent for epoxy resin. The composite with the epoxy resin composition is light and has excellent properties such as strength and elasticity, and is suitable for composite materials used in aircraft, space industry, automobiles, ships, sports equipment, electric circuit boards, etc. There is.

Claims (2)

(57) [Claims] 1. An intrinsic viscosity value of 0.1 to 5 including 5 to 100 mol% of a repeating unit represented by the following general formula (1) and 95 to 0 mol% of a repeating unit represented by the following general formula (2).
A surface-treated aramid fiber material, which has been surface-treated with a treatment liquid containing an epoxidized aromatic polyamide resin having 3.0 dl / g. [Chemical 1] (In the formula, R is a monocyclic aromatic group or a plurality of aromatic rings is an oxygen atom, a sulfur atom, a CO group, an SO ₂ group or a carbon number 1
~ 3 represents a polycyclic aromatic hydrocarbon group which may be linked via a hydrocarbon group, and R'represents a divalent aromatic, alicyclic or heterocyclic dicarboxylic acid residue. ) 2. An aramid-based material formed from the surface-treated aramid-based fiber material according to claim 1 and an epoxy resin composition containing an epoxy resin and a curing agent for an epoxy resin as a main component. Fiber / epoxy resin composite.