JPH0369373B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a novel composite-structure wholly aromatic polyamide molded product and a method for producing the same. More specifically, it relates to a surface-modified wholly aromatic polyamide molded article having a layer containing a compound having a functional group such as an epoxy group on the surface of the wholly aromatic polyamide molded article, and a method for producing the same. The present invention provides aromatic polyamide molded products, such as fully aromatic polyamide fibers with improved adhesion to matrix resins, or aromatic polyamide films or sheets with improved adhesion to adhesives, and methods for producing them. be. (Prior art) Conventionally, fully aromatic polyamide fibers have high specific strength, specific modulus, and excellent heat resistance.
It is being added to rubber, thermosetting, and thermoplastic resins to improve the mechanical properties, heat resistance, etc. of the resin compositions. (Problems to be Solved by the Invention) However, in a fiber-reinforced resin composite material made of wholly aromatic polyamide fibers having such performance,
Since the adhesion between the wholly aromatic polyamide fiber and the matrix resin is poor, and the fiber is poorly dispersible in the matrix resin, it does not exhibit good mechanical properties. Similarly, when using this fiber for rubber reinforcement, it has poor adhesion to resorcinol-formalin-latex (RFL), and methods have been proposed in which it is coated with epoxy resin and then treated with RFL. However, the adhesion between the wholly aromatic polyamide fiber and the epoxy resin interface cannot be said to be sufficient as in the above-mentioned fiber-reinforced resin composite material. Similarly, wholly aromatic polyamide films and other molded products have the problem of insufficient adhesion with varnishes, adhesives, and the like. Various studies have been made to overcome these drawbacks. For example, some methods using plasma show good adhesion, but these methods are considered to have industrial problems in terms of reproducibility, uniformity, and the like. On the other hand, there are examples of improved adhesion due to the chemical bonding force between the epoxy groups formed on the surface of the fully aromatic polyamide molded product through chemical treatment and the matrix resin (Japanese Patent Application Laid-Open No.
No. 57-195136, No. 59-74157 and
59-184234), the improvement of adhesion by these methods is not necessarily satisfactory, and due to the low reaction activity of wholly aromatic polyamides, severe reaction conditions are required, resulting in poor quality of molded products. Disadvantages include the destruction of higher-order structures and the cleavage of molecular chains, which often reduce the mechanical performance of molded products, or the need for expensive chemicals, which creates significant cost pressure. It was hot. (Means for Solving the Problems) In order to solve the above problems, the present inventors have conducted extensive research and found that after swelling only the surface layer of a wholly aromatic polyamide molded product using a special method, epoxy groups etc. By treating the wholly aromatic polyamide molded product with a compound having a functional group of 1 to form a layer containing a compound having a functional group such as an epoxy group on the surface of the fully aromatic polyamide molded product, the relationship between the fully aromatic polyamide molded product and the matrix resin is It was discovered that the adhesiveness was improved, and the present invention was achieved. That is, the object of the present invention is to provide the general formula -NH- _Ar1 -NH-CO- _Ar2 -CO- and/or
or -NH- _Ar3 -CO- (in the formula, _Ar1 , _Ar2 , and _Ar3 each independently represent a divalent aromatic cyclic group), which is a wholly aromatic polyamide molded product. , a compound having on its surface one or more functional groups selected from the group consisting of an epoxy group, a blocked isocyanate group, an amino group, a hydroxyaryl group, and an unsaturated bonding group (hereinafter referred to as an epoxy group, etc.). This has been achieved by providing a wholly aromatic polyamide molded product with a novel composite structure characterized by having a layer containing a compound having the general formula -NH-Ar ₁ - NH−CO−Ar ₂ −CO− and/
or a surface layer of a wholly aromatic polyamide molded product consisting of a repeating unit of -NH-Ar ₃ -CO- (in the formula, Ar ₁ , Ar ₂ , and Ar ₃ each independently represent a divalent aromatic cyclic group) The amide group of is alkyl metalated with a dimsyl alkali metal, and then, in a solvent capable of swelling the alkyl metalated wholly aromatic polyamide, an epoxy group, a blocked isocyanate group, an amino group, a hydroxyaryl group,
It can be produced by impregnating the surface layer of the molded article with a compound having one or more functional groups selected from the group consisting of unsaturated bond groups. The fully aromatic polyamide used in the present invention is
At least 85 mol% or more of the amide bond is obtained from an aromatic cyclic diamine or an aromatic cyclic dicarboxylic acid component. Examples of its structure include polyparabenzamide, polyparaphenylene terephthalamide, poly-4,4'-diaminobenzanilide terephthalamide, polyparaphenylene-2,6-
naphthalitukuamide, copolyparaphenylene/
4,4'(3,3'-dimethylbiphenylene)-terephthalamide, copolyparaphenylene/2,5-pyridylene-terephthalamide, polyorthophenylene phthalamide, polymetaphenylene phthalamide, polyparaphenylene Nylene phthalamide, polyorthophenylene isophthalamide, polymetaphenylene isophthalamide, polyparaphenylene isophthalamide, polyorthophenylene terephthalamide, polymetaphenylene terephthalamide, poly-1,5-naphthalene phthalamide, poly -4,4'-diphenylene-ortho-phthalamide, poly-4,4'-diphenylene isophthalamide, poly-1,4-naphthalene phthalamide, poly-1,4-naphthalene isophthalamide, poly-1,5 - Naphthalene isophthalamide, etc., and compounds in which part of the benzene nucleus of these aromatic diamines is substituted with halogen; , aromatic polyamide containing an alicyclic amine, such as a compound substituted with 5-diethylpiperazine, or where the aromatic diamine is 3,3'-oxydiphenylenediamine, 3,4'-oxydiphenylenediamine Ether groups, alkyl groups, -S-, -SO ₂ -, etc.

[Formula] An aromatic polyamide containing two phenyl groups bonded by groups such as -NH- or a copolymer of the above-mentioned aromatic polyamides, e.g.
Poly-3,3'-oxydiphenylene terephthalamide/polyparaphenylene terephthalamide copolymer, poly-3,4'-oxydiphenylene terephthalamide/polyparaphenylene terephthalamide copolymer, etc. be able to. The method for producing these wholly aromatic polyamides is not limited in carrying out the present invention, and for example, a low-temperature solution polymerization method known from Japanese Patent Publication No. 35-14399 etc. from the corresponding diamine and acid chloride can be used. It can be easily manufactured by The wholly aromatic polyamide molded product used in the present invention refers to the following molded products, and can be in various forms, such as filament, woven fabric, knitted fabric, fabric, spun yarn,
It is available in the form of fiber, pulp, film, sheet, powder, etc. Its effects are best exhibited especially when used in the form of fibers or fabrics. Known methods are used to produce the molded product of the present invention. For example, in the production of fibers, fibers soluble in organic solvents may be produced using conventional wet or dry spinning methods as described in the above-mentioned publications, or by special methods. Kosho 42-815
The fully aromatic polyamide, which is particularly important, can be produced by the method described in the publication, and 80 mol% of the divalent aromatic groups are in the para position (in the naphthalene group, 1,4-, 1,
It consists of an aromatic group bonded at the 5-, 2, 6-position) and a paraphenylene group in the middle.
Furthermore, the high montane fibers can be obtained by the methods described in various publications such as Japanese Patent Publication No. 1986-39458,
−12484, Special Publication No. 13365, Special Publication No. 13365, Special Publication No. 13365, No. 13365, Japanese Patent Publication No. 1972
It can be produced by the methods described in various publications such as No. 43419. Commercially available products include Kevlar 29 and Kevlar 49 (both trademarks of DuPont and called polyparaphenylene terephthalamide fibers). In addition, as a special wholly aromatic polyamide, there is a polyparaphenylene terephthalamide in which several tens of mole percent of the paraphenylenediamine component is replaced with 3,4'-diaminodiphenyl ether.
It can be manufactured according to Japanese Patent Publication No. 54-43612 and others. In addition, for example, as a method for producing a film, there are
No. 35088, Special Publication No. 59-5407, Japanese Patent Publication No. 54-132674
It can be manufactured by the methods described in each of the publications. The composite structure of the surface layer of the wholly aromatic polyamide molded product of the present invention includes a step of forming an alkali metal salt by abstracting hydrogen from an amide group with a dimsyl alkali metal, that is, a metalization step, and then a step of forming an epoxy group, etc. It consists of two steps: impregnating the swelling layer with a compound in a solvent capable of swelling the metalized wholly aromatic polyamide surface layer. The metalation step is carried out by the reaction of dimethyl sulfoxide (hereinafter abbreviated as DMSO) with an alkali metal or an alkali metal hydride using a dimsyl alkali metal in DMSO or a mixture of DMSO and a solvent that does not inhibit the metalation reaction. This is done by treating a wholly aromatic polyamide molded product. The alkali metal or alkali metal hydride used in the present invention includes sodium metal, lithium metal, potassium metal, sodium hydride, lithium hydride, potassium hydride, and the like. During the metalization process, the metalized wholly aromatic polyamide increases its solubility in organic solvents, so
The surface of the molded product may dissolve excessively in DMSO, and metallization may extend beyond the surface layer to undesirable inner layers. Therefore, solvents that do not inhibit the metallization reaction, such as diethyl ether,
DMSO containing up to 95% by weight of tetrahydrofuran, dioxane, 1,2-dimethoxyethane, etc.
It is also a preferred embodiment to carry out the process inside. Appropriate metalation reaction conditions include a temperature between 10° C. and the boiling point of the reaction system, and a reaction time of about 1 second to 2 hours. Preferably, the reaction temperature is 19 to 100°C and the time is 15 seconds to 30 minutes. The concentration of dimsyl alkali metal used is between 0.05 and 5% by weight in terms of alkali metal. The next step, impregnation treatment with a compound having epoxy groups, etc., can be done by adding a compound having epoxy etc. to the metallization bath, or by taking out the metalized molded product and placing it in a solution in which a compound having epoxy etc. is dissolved. Any method is fine. It is also possible to perform these processes continuously. This impregnation process is carried out in a solvent capable of swelling the metallized fully aromatic polyamide, preferably the same DMSO used for metallization.
or in a mixture of DMSO and other solvents. Here, there are no particular restrictions on the solvent used in combination with DMSO, such as water, alcohols, ketones, or ethers, etc.
Any material that has good compatibility with DMSO may be used. In particular, water is inexpensive, and also has the property of deactivating the metalized fully aromatic polyamide through a competitive reaction if a compound having an epoxy group or the like does not want to react with the metalized fully aromatic polyamide. It may be preferably used. That is, in the case of a compound having an epoxy group,
It has been observed that not only are they simply dispersed in the metalized wholly aromatic polyamide swelling layer, but some of them also undergo an N-substitution reaction with the amide groups activated by metalation. However, since the consumption of epoxy groups in the reaction with the wholly aromatic polyamide is undesirable, it is preferable to suppress the amount to half or less, preferably 1/10 or less, of the epoxy groups contained. The reaction can be suppressed by adding a small amount of water capable of decomposing the alkali metal salt, for example,
This can be easily achieved by allowing a trace amount of about 200 ppm or more to coexist during treatment with a compound having an epoxy group. However, the presence of an excessive amount of water is undesirable because it inhibits the swelling of the metalized wholly aromatic polyamide, and the recommended amount is approximately 20% by weight or less, preferably 10% by weight or less. The temperature of the impregnation treatment is between 10° C. and the boiling point of the treatment liquid, and the treatment time is also suitably 30 seconds to 2 hours.
The concentration of the compound having an epoxy group or the like can be arbitrarily selected, but it is preferably a concentration that does not make the solution too viscous, and is practically 70% by weight or less.
After the impregnation treatment, excess compounds having epoxy groups, etc. are washed away with water-containing acetone, etc., thereby obtaining a wholly aromatic polyamide molded product with a novel composite structure containing a compound having epoxy groups, etc. in the surface layer of the present invention. be able to. The thickness of the surface layer is approximately 0.05 to 2.0 μm,
Preferably, the thickness is selected to be about 0.1 to 1.0 μm, and the adjustment of this thickness is mainly performed by the conditions of the metallization treatment described above, and secondary adjustment is also possible depending on the conditions in the second impregnation step. It is.
If this thickness is too large, the fine structure and higher-order structure of the molded product are likely to be destroyed during swelling.
Undesirable phenomena such as loss of mechanical properties of these wholly aromatic polyamide molded products are observed, which is often undesirable. The amount of compounds containing epoxy groups, etc. contained in this surface layer varies depending on the purpose, use, and type of molded product, but the amount of functional groups such as epoxy groups per 1 kg of the total weight of the molded product is In many cases, it is sufficient if it is about 10 to 1000meq. Examples of the compound having an epoxy group used in the present invention include low molecular weight monoepoxy compounds such as glycidyl ethers such as phenyl glycidyl ether and para-tolyl glycidyl ether;
Butadiene dioxide, 2-(2,3-epoxypropyl)phenyl glycidyl ether, vinylcyclohexene-3-diepoxide, 2,6
- Low molecular weight polyepoxy such as (2,3-epoxypropyl)phenyl glycidyl ether, diglycidyl ether, cyclopentadiene oxide, dipentene dioxide, triglycidyl isocyanurate, diglycidyl-5,5-dimethylhydantoin, glycerin triglycidyl ether, etc. Compounds and general formulas (wherein n is 0 or a positive integer) Bisphenol A type epoxy resin, general formula (In the formula, n is 0 or a positive integer) Novolak type epoxy resin, general formula (wherein R is an alkyl group and n is 0 or a positive integer) polyglycol type epoxy resin, cresol novolac type epoxy resin, bisphenol F type epoxy resin, triglycidyl-p-aminophenol type epoxy resin resin,
High molecular weight polyepoxy compounds such as polynuclear phenol/glycidyl ether type epoxy resin, tetraglycidyl methylene dianiline type epoxy resin, and triazine type epoxy resin can be mentioned. The compound having a blocked isocyanate group used in the present invention includes tolylene diisocyanate,
The isocyanate group of a diisocyanate compound such as 4,4'-diphenylmethane diisocyanate,
It is a compound blocked by reacting with phenol, diethyl ester of malonic acid, acetoacetate, acetylacetone, etc. These compounds are stable at room temperature, but when heated during use, they regenerate isocyanate groups and exhibit the effect of increasing the surface reaction activity of wholly aromatic polyamide molded articles. The compound having an amino group used in the present invention is
These include aliphatic polyamines represented by diethylenetriamine and polyethyleneimine, initial condensates thereof such as allyl glycidyl ether and diethylenetriamine adducts, aromatic diamines, and low molecular weight aliphatic polyamides. Further, the above-mentioned initial condensate of a polyepoxy compound and a polyamine is a typical example of a compound having both an epoxy group and an amino group. Compounds with hydroxyaryl groups used in the present invention include bisphenols such as bisphenol A and phenolic resin initial polymers,
As the phenolic resin initial polymer, either novolak resin or resol resin polymerized from phenols and formaldehyde can be used.
It is preferable that the metalized wholly aromatic polyamide molded product is subjected to the treatment in an uncured state, but crosslinking and curing may be optionally performed once it is included in the surface layer of the molded product. In some cases, favorable effects can be expected in terms of fixing the resin to the surface layer. Examples of compounds having an unsaturated bond group used in the present invention include dibasic acids having an unsaturated bond such as maleic anhydride, fumaric acid, itaconic acid, tetrahydrophthalic anhydride, and 3,6-endomethylenetetrahydrophthalic anhydride. Unsaturated polyester resin precursor polymers produced by condensation of dibasic acids and glycols, diallyl phthalate or its prepolymers, vinyl ester resins, bismaleimide compounds synthesized from maleic anhydride and various diamines, etc. are used. . Which of these compounds to use should be selected depending on the intended use of the wholly aromatic polyamide molded product containing the compound in the surface layer. Specifically, if the molded product is a fiber and is not reinforced with resin, Or, in various usage forms such as being used as a rubber reinforcing material, forming a resin layer on the surface of a molded product, or bonding with an adhesive.
Those skilled in the art will be able to easily select a resin depending on the type of resin to which the molded article is to be bonded, taking into account reactivity and affinity with the resin. (Function of the Invention) The method for producing a wholly aromatic polyamide molded article with a novel composite structure of the present invention is characterized by a metalized wholly aromatic product in which the hydrogen of the amide group is at least partially substituted with an alkali metal by a dimsyl alkali metal. Taking advantage of the fact that group polyamides swell in organic solvents such as DMSO, only the surface layer of the wholly aromatic polyamide molded product is selectively metalized, and then the surface layer is swollen, and then epoxy groups, etc. When the molding is resolidified, the compound penetrates into the swollen layer and the metalated amide groups return to amide groups in the post-treatment step, adding epoxy groups to the polyamide surface layer when the molding is resolidified. This is due to the fact that a layer containing compounds having the following properties is formed. Therefore, this compound can be present in the surface layer without forming a special chemical bond with the wholly aromatic polyamide, so any compound can be used depending on the purpose. It is characterized by the advantage of high applicability. For example, when an epoxy resin is used as the matrix resin, the fully aromatic polyamide molded product with the novel composite structure of the present invention has an anchoring effect due to the presence of epoxy groups or amino groups in the surface layer that react with the matrix resin. Therefore, it is presumed that the adhesiveness is improved. In addition, if the molded product is a fiber and is used to reinforce a thermoplastic resin,
Since the affinity of the surface of the polyamide molded article with the matrix resin increases, it is thought that the fibers are uniformly dispersed in the matrix resin without causing aggregation, and the reinforcing effect is also expected to be increased. (Examples) In order to further clarify the present invention, the present invention will be described below with reference to Examples, but it goes without saying that the scope of the present invention is not limited to these Examples.
In each example, unless otherwise specified, percentages or parts are based on weight. Example 1 1.25 g of sodium hydride was added to 500 ml of dimethyl sulfoxide (DMSO) and heated at 70°C for 40 minutes in a nitrogen stream to completely dissolve.
The solution was cooled to ℃ to prepare a dimsyl sodium solution. Plain weave of 1140 denier yarn of polyparaphenylene terephthalamide (PPTA) fiber (Kevlar 49, trademark of Dupont), 15 cm long and 10 cm wide, with a density of 17 threads/25 mm in both length and width. The structured woven fabric was added to the above DMSO system, and a sodium conversion reaction was performed at 35°C for 10 seconds. Then,
The above-mentioned sodified woven fabric was taken out of the dimsyl sodium solution, lightly drained, and immediately immersed in a solution consisting of 450 ml of DMSO, 50 ml of water, and 50 g of bisphenol type epoxy resin (DER383, Dow Chemical Company), and then soaked for 50 minutes. The reaction was allowed to take place at ℃ for 30 minutes. The woven fabric was washed five times with large amounts of acetone to remove unreacted epoxy resin, and then dried under vacuum. A portion of this sample was measured using neutralization titration to quantify sodium ions released by the reaction between sodium thiosulfate and epoxy groups.
It was found that 64 meq/Kg of epoxy groups were contained. This woven fabric is coated with bisphenol type epoxy resin (DE).
A resin composition consisting of 100 parts of R.383) and 13.5 parts of triethylenetetramine was applied, the two sheets were bonded together, and pressed at room temperature under reduced pressure for 3 hours.
Cure for 2 hours. This cured product was cut into 15 mm width and 150 mm length, and a T-peel test was performed using a universal tensile tester (AUTOGRAPH DSS-500 manufactured by Shimadzu) at a head speed of 100 mm/min. The T-peel strength was
It was 1.45Kg/15mm. Comparative Example 1 A woven fabric without surface modification was molded in the same manner as in Example 1 and subjected to a T-peel test, and the T-peel strength was 0.91 Kg/15 mm. Comparative Example 2 Contains the epoxy resin obtained in Example 1
A comparison sample was prepared by extracting the PPTA fiber fabric with acetone for 8 hours using a Soxhlet extractor and then drying it under vacuum. When the epoxy group content was quantified in the same manner as in Example 1,
3meq/Kg, which is thought to be because some epoxy compounds reacted with the amide group or remained unextracted, and it can be seen that most of the epoxy compounds did not react and were impregnated. . When this sample was subjected to a T-peel test in the same manner as in Example 1, it was found to be 1.16Kg/15mm.
No favorable results were obtained. Example 2 A PPTA-treated fabric sample was prepared in exactly the same manner as in Example 1, except that the epoxy resin impregnated into the fiber in Example 1 was changed to the same amount of an initial condensation compound of diaminodiphenyl sulfone and tetraglycidyldiaminodiphenylmethane. I got it. Next, in the same manner as in Example 1, a sample for T-peel test was prepared using epoxy resin, and the T-peel strength was measured.
It showed 1.79Kg/15mm. Examples 3 to 6 and Comparative Examples 3 to 5 In the same manner as in Example 1, the PPTA fiber cloth was
DMSO with a moisture content of 1000 ppm after sodiumization with dimsyl sodium in the solvent listed in the table,
Mixtures of each solvent and mixing ratio in Table 1, and as a comparative example, 50 g of the bisphenol type epoxy resin used in Example 1 in 500 ml of a solvent that does not contain DMSO.
The specimens were immersed in a treatment solution containing dissolved at 50°C for 30 minutes. Thereafter, it was post-treated in the same manner as in Example 1, and the contained epoxy groups were measured and the T-peel test was conducted in the same manner. The results are shown in Table 1, and in Comparative Examples 3 and 4, which have no swelling ability for sodified PPTA, no improvement in peeling force was observed at all, as seen in comparison with Comparative Example 1. .

[Table] Example 7 A metalized PPTA fiber woven fabric was prepared in the same manner as in Example 1, and an aryl resin (manufactured by Showa Kobunshi Co., Ltd., Ripoxy R802) in which the terminal of bisphenol A type epoxy was converted to methacrylic acid ester was used. of
60g dissolved in 500ml DMSO in processing solution at 40°C.
After being immersed in water for 60 minutes, it was washed once with acetone, then washed under running water, and then vacuum dried at 60°C. To the treated fabric, add 1.5% methyl ethyl ketone peroxide and 0.5% cobalt naphthenate to the above aryl resin.
% was added, and four sheets were laminated and cured at room temperature under a press. A test piece was cut out from the obtained laminate and its bending stress strain characteristics were measured.The bending strength was 16Kg/ ^mm2 , and the bending modulus was 2090Kg/mm.
showed mm ² . This can be said to be a large improvement effect compared to the bending strength of 10 Kg/mm ² and bending modulus of 1100 Kg/mm ² obtained by repeating this example without applying the treatment of the present invention. Example 8 The PPTA cloth treated with the initial condensate of tetraglycidyldiaminodiphenylmethane and diaminodiphenyl sulfone of Example 2 was treated with the initial condensate of bismaleimide and diaminodiphenylmethane (manufactured by Nippon Polyimide Co., Ltd., Kerimide 601). ) in a 50% solution of N-methylpyrrolidone,
After drying at 150℃ for 15 minutes, stack the four treated cloths,
180℃ by vacuum press autoclave processing method
A 90 minute curing process was carried out. A test piece was cut out from the obtained laminate and JIS-
When a bending test was conducted according to K-6911, a bending strength of 17 Kg/mm ² and a bending modulus of 2300 Kg/mm ² were obtained. For comparison, a test piece treated in exactly the same manner but without the treatment of the present invention had a bending strength of 12
Kg/mm ² , and the bending modulus was only 950 Kg/mm ² . Example 9 PPTA metallized in the same manner as Example 1
Add textile fabric to 300ml of DMSO and 200ml of dioxane.
Add 30 g of novolak resin to the treatment solution.
℃ for 45 minutes, then washed with acetone and water, and then dried under reduced pressure at 60°C. Next, it was immersed in a resorcinol-formalin-latex (RF/L) treatment solution prepared with the following formulation, and after squeezing out the solution with a mangle, it was heated at 150°C.
Dry at 180℃ for 3 minutes, then at 180℃ for 2 minutes, then
Curing was performed at 230°C for 2 minutes. The amount of the RF/L polymer composition deposited at this time is
It was 8.9% of fiber. (RF/L treatment agent formulation) Resorcinol 11.0 parts Water 238.4 Formalin (37% aqueous solution) 16.2 NaOH 0.3 Styrene/butadiene/vinylpyridine copolymer latex (solid content 41%) 244.0 Total 509.9 parts Next, treated fabric and thickness Unvulcanized rubber sheets of approximately 0.7 mm were combined and vulcanized at 140°C for 15 minutes using a pressure press. The resulting sample was cut into 3 cm wide pieces, and the adhesive strength between the rubber and the fabric was measured using the 180 peel method. The composition of the rubber sheet used is as follows. #1 (natural rubber) 70 parts Hiker #1502 (SBR copolymer rubber) 30 Carbon FEF 50 Stearic acid 2.0 Aromatic softener 10 Zinc white 5.0 Anti-aging agent AIV 1.5 Vulcanization accelerator DM 2.0 Sulfur Yellow 2.5 Total 173 The peel strength between the rubber and the fabric was 6.4 kg, and the peel exhibited the dark brown color of the RF/L polymer, and no fibers were exposed at all even when observed under a stereomicroscope. It was confirmed that this occurred between the material layer and the rubber. Comparative Example 6 The PPTA fiber fabric used in Example 1 was not subjected to the treatment of the present invention, but was subjected to epoxy treatment using a conventional method, and then subjected to RF/L treatment in the same manner as Example 1, and then treated with rubber. The adhesion force was measured. Here, the epoxy treatment liquid formulation was as follows, and after immersing the woven fabric in the liquid, it was heat-treated at 240°C for 3 minutes. (Epoxy treatment liquid formulation) Catalyst 95 (Teikoku Kagaku, water-soluble epoxy resin) 2.0% NaOH 0.1 Perex OTP (5% soln) 2.0 Water 95.9 Total 100.0% Amount of RF/L polymer composition layer attached to fiber teeth,
In Example 9, which is 6.1% based on the fiber, it can be seen that one of the effects of the present invention is good wetting with the treatment liquid. The peel strength was 2.8 kg, less than half of that in Example 9, and the fiber color on the peeled surface was contaminated with RF/L.
It exhibited a yellow-brown color, which is the color of PPTA fibers, and even when observed under a stereomicroscope, clear exposure of the fibers could be seen. Example 10 According to the description in Japanese Patent Publication No. 54-43612, 3.
50 each of 4′-diaminodiphenyl ether, paraphenylenediamine, and terephthaloyl chloride
The resulting polymerization mixture was neutralized and used as a spinning dope, wet-spun, washed with water, dried, and then hot-stretched 10 times. , a small quantity of single yarn denier 1.6 denier, 50 filament yarn was produced. This fiber was wound around a fluororesin frame, and metallization and epoxy resin impregnation treatments were performed under the same conditions as in Example 6. The obtained treated fibers were processed using the method of Takayanagi et al. [Reports on Progress in Polymer Physics in Japan, Vol. 28, p. 343 (1985
)], the single yarn was made using bisphenol type epoxy resin (DER383, Dow Chemical Company) 100%
and 13.5 parts of triethylenetetramine so that a length of about 0.1 to 1.0 mm is embedded in the mixture,
After curing, from a plot of the pulling force and the fiber embedding length, the embedding length that exhibited a pulling force equal to the fiber cutting strength was determined to be approximately 0.6 mm. On the other hand, it was about 0.2 mm for the untreated fiber of the present invention, which shows the effect of the adhesive strength of the sample of the present invention. (Effects of the Invention) When the surface-modified wholly aromatic polyamide molded product of the present invention is used as a reinforcing material in a composite material, it has excellent adhesion with the matrix resin, so that the fully aromatic polyamide molded product has excellent adhesive properties. It can be made into a composite material that fully takes advantage of characteristics such as high strength and high modulus of elasticity, and in the case of films etc., favorable adhesion can be obtained between films or between films and copper foil etc. A laminate etc. useful for various purposes can be provided.

Claims (1)

[Claims] 1 General formula -NH-Ar ₁ -NH-CO-Ar ₂ -CO-
and/or -NH- _Ar3 -CO- (in the formula, _Ar1 , _Ar2 , and _Ar3 each independently represent a divalent aromatic cyclic group). A layer containing a compound having one or more functional groups selected from the group consisting of an epoxy group, a blocked isocyanate group, an amino group, a hydroxyaryl group, and an unsaturated bond group is provided on the surface. A wholly aromatic polyamide molded product having a novel composite structure. 2. The novel composite according to claim 1, wherein the compound contained in the surface layer is one or a mixture of two or more selected from monoepoxy compounds and epoxy resins having two or more epoxy groups. Fully aromatic polyamide molded structure. 3. A wholly aromatic polyamide molded article with a novel composite structure according to claim 1, wherein the compound contained in the surface layer is an unsaturated polyester resin precursor. 4. The novel composite-structure wholly aromatic polyamide molded article according to claim 1, wherein the compound contained in the surface layer is diallyl phthalate, its prepolymer, or a vinyl ester resin precursor. 5. A wholly aromatic polyamide molded article with a novel composite structure according to claim 1, wherein the compound contained in the surface layer is a bismaleimide compound. 6. A wholly aromatic polyamide molded article with a novel composite structure according to claim 1, wherein the compound contained in the surface layer is an initial polymerization product of a phenolic resin. 7. The novel composite structure wholly aromatic polyamide molded article according to claim 1, wherein the compound contained in the surface layer is triethylenetetramine, polyethyleneimine or/and an aliphatic polyamide oligomer. 8. The novel composite structure according to any one of claims 1 to 7, wherein the wholly aromatic polyamide molded product is a polyparabenzamide fiber or film, or a polyparaphenylene terephthalamide fiber or film. Fully aromatic polyamide molded product. 9 General formula -NH-Ar ₁ -NH-CO-Ar ₂ -CO-
and/or -NH- _Ar3 -CO- (in the formula, _Ar1 , _Ar2 , and _Ar3 each independently represent a divalent aromatic cyclic group) of a wholly aromatic polyamide molded product. The amide groups in the surface layer are alkyl metallized with a dimsyl alkali metal, and then epoxy groups, blocked isocyanate groups, amino groups, and hydroxyaryl groups are added in a solvent capable of swelling the alkyl metallized wholly aromatic polyamide. A wholly aromatic polyamide molded article with a novel composite structure, characterized in that the surface layer of the molded article is impregnated with a compound having one or more functional groups selected from the group consisting of unsaturated bond groups. manufacturing method. 10. The novel composite structured wholly aromatic polyamide according to claim 9, wherein the alkyl metallization of the amide group of the wholly aromatic polyamide molded product with a dimsyl alkali metal forms a surface layer of about 2 μm or less of the molded product. A method for producing polyamide molded products. 11 When containing a compound having one or more functional groups selected from the group consisting of an epoxy group, a blocked isocyanate group, an amino group, a hydroxyaryl group, and an insoluble bonding group, the treatment is Claim 9 carried out in dimethyl sulfoxide or a mixture of 50% or more dimethyl sulfoxide and 50% or less of one or more compounds selected from water, alcohols, ketones and ethers. A method for producing a novel composite structure wholly aromatic polyamide molded article according to item 1 or item 10. 12. Claims 9 to 11, wherein the compound contained in the surface layer is one or a mixture of two or more selected from monoepoxy compounds and epoxy resins having two or more epoxy groups. A method for producing a wholly aromatic polyamide molded article having a novel composite structure according to any one of the above. 13. The method for producing a novel composite structure wholly aromatic polyamide molded article according to any one of claims 9 to 11, wherein the compound contained in the surface layer is an unsaturated polyester resin precursor. 14. A wholly aromatic compound with a novel composite structure according to any one of claims 9 to 11, wherein the compound contained in the surface layer is diallyl phthalate, a prepolymer thereof, or a vinyl ester resin precursor. A method for producing polyamide molded products. 15. The method for producing a novel composite structure wholly aromatic polyamide molded article according to any one of claims 9 to 11, wherein the compound contained in the surface layer is a bismaleimide compound. 16. The method for producing a novel composite structure wholly aromatic polyamide molded article according to any one of claims 9 to 11, wherein the compound contained in the surface layer is a phenolic resin initial polymer. 17. A wholly aromatic compound with a novel composite structure according to any one of claims 9 to 11, wherein the compound contained in the surface layer is triethylenetetramine, polyethyleneimine, or/and an aliphatic polyamide oligomer. A method for producing polyamide molded products. 18. The novel composite structure according to any one of claims 9 to 17, wherein the wholly aromatic polyamide molded product is a polyparabenzamide fiber or film, or a polyparaphenylene terephthalamide fiber or film. A method for producing a wholly aromatic polyamide molded article.