JPH0762110A - Polynorbornene resin molded product - Google Patents

Abstract

PURPOSE:To provide an organic fiber composite material having excellent mechanical properties by imparting good physical and chemical adhesiveness to the interface between an organic fibrous material and a polynorbornene resin. CONSTITUTION:The product is obtained by bulk-polymerizing a norbornene monomer in the presence of an organic fiber material surface-treated with a coating monomer and/or a surface modifier which do not inhibit the metathesis polymerization of the monomer and having a void fraction of 5vol.% or below.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polynorbornene-based resin molded article, and more specifically, to reaction injection molding (RIM) using bulk polymerization of a norbornene-based monomer with a metathesis catalyst system in the presence of an organic fiber material. The present invention relates to a polynorbornene-based resin molded product having a small void fraction obtained by a method.

[0002]

2. Description of the Related Art As a conventional organic fiber material / thermoplastic resin composite material, JP-A-63-30209 and JP-A-63-30209 are known.
-87228, JP-A-1-280199, JP-A-2
-144901, JP-A-3-76614, JP-A-3
-121135, JP-A-3-130118 and JP-A-3-161331 disclose aramid fiber materials /
A thermoplastic resin composite material is disclosed. JP-A-59-
207966, JP-A-1-43532, JP-A-2-
No. 1,249,56, JP-A-3-76614 and JP-A-3-130118 disclose a nylon fiber material or a polyester fiber material / thermoplastic resin composite material.

Further, Japanese Unexamined Patent Publication No. 62-57429 discloses a highly elastic and rigid fiber material / polymer liquid crystal composite material, and Japanese Unexamined Patent Publication No. 4-44834 discloses a heat resistant fiber material / thermoplastic resin composite material. Has been done.

On the other hand, as a combination of organic fiber materials / thermoplastic resins other than the above, Japanese Patent Laid-Open No. 1111037
No. 2-110140 and 2-124.
No. 956 describes a polyethylene fiber material, a polyolefin fiber material / ethylene propylene rubber (EPR), or a thermoplastic resin such as cross-linked polyethylene. Furthermore, JP-A-3-30916 describes a polyarylate fiber material or a vinylon fiber material / thermoplastic resin composite material.

On the other hand, as the conventional organic fiber material / thermosetting resin composite material, aramid fiber material, ultra high molecular weight polyethylene fiber material, vinylon fiber material, PPS fiber material and the like and unsaturated polyester resin or Epoxy resin composites are being manufactured. These composite materials are manufactured by laminating a prepreg impregnated with a resin in advance in a mold, and then curing the resin by heating and pressurizing or impregnating a bag-shaped woven fabric with the resin. Further, JP-A-3-30916 discloses a polyarylate fiber material and a vinylon fiber material / thermosetting resin composite material. In this published patent publication,
A composite sheet is obtained by impregnating a mat made of fibers with a thermosetting resin.

Reinforcing a polynorbornene resin molded article with an organic fiber material is disclosed in JP-A-3-146517 and JP-A-4-357010, and surface treatment using a silane coupling agent is disclosed. The method is disclosed in Japanese Patent Laid-Open No. 3-146517.

On the other hand, in Japanese Patent Laid-Open No. 147822/1993, in producing a composite norbornene-based resin molded product containing an insert body, as a measure against the polymerization inhibition by the insert body, the insert body is made of a polymer having no polymerization inhibiting property. A method of surface treatment is disclosed. This method is mainly applied to a sheet-shaped or plate-shaped insert body, and a coating layer of the above-mentioned polymer is formed on the surface thereof, whereby a composite material in which the insert body and the polynorbornene resin are well adhered can be obtained.

[0008]

However, in the above-mentioned organic fiber material / thermoplastic resin composite material, the void content is reduced or the resin is evenly distributed because the molten resin is forcibly impregnated into the fiber or the woven fabric. Impregnation was not possible easily. In addition, since the molding temperature is high, an organic fiber material having excellent heat resistance such as aramid fiber material and vectran fiber material is used, or the glass transition point (T _g ) and crystal melting point (T _m ) of the organic fiber material used are also used. Since it was limited to using a thermoplastic resin having a lower flow temperature than that, it was difficult to form a composite with an organic fiber material having low thermal stability while having high mechanical properties. In addition, as an organic fiber material having low thermal stability, a high molecular weight polyethylene fiber (T _g : 120
℃, T _m : 147 ℃) and strong vinylon fiber (T _g : 60
-80 ° C, T _m : 230 ° C).

On the other hand, even in the above-mentioned organic fiber material / thermosetting resin composite material, there is room for improvement in the impregnation property of the resin into the fiber and the adhesive property of the fiber / resin interface, and the reinforcing effect of the organic fiber material is maximized. It cannot be said that it is utilized for.

Further, in the above-mentioned prior art, the method of reinforcing a polynorbornene-based resin molded article with an organic fiber material and the surface treatment method using a silane coupling agent often cause polymerization inhibition, and the polymerization inhibition may occur. Even if it does not exist, it is still not sufficient for the recent severe performance requirements.

As an example, the present inventors have tried to apply the method described in JP-A-3-147822 in order to reinforce the organic fiber material. However, when this method is applied as it is, polymerization inhibition is caused. Although the prevention effect was obtained, the improvement of mechanical properties was not always sufficient, and a molded product having the expected performance could not be obtained.

Therefore, an object of the present invention is to use an organic fiber material having a surface that inhibits ring-opening polymerization of a norbornene-based monomer or an organic fiber material having poor adhesion to a polynorbornene-based resin. / Providing good physical and chemical adhesiveness to the interface of polynorbornene resin, and providing an organic fiber composite material having excellent mechanical properties.

[0013]

Therefore, as a result of further investigations by the present inventors regarding the reason why the mechanical properties cannot be improved, in the case of the conventional molded product, the performance is not always sufficiently improved because the void fraction is relatively high. Based on the finding that it does not, it was found that the voids can be reduced by changing the concentration conditions of the fiber surface coating polymer solution or the fiber surface modifier solution used for the surface treatment of the organic fiber material. Does not hinder the metathesis polymerization of norbornene-based monomers,
Fiber surface coating is obtained by bulk polymerization of norbornene-based monomers in the presence of an organic fiber-based material surface-treated with a polymer and / or a fiber surface modifier, and a void fraction of 5% or less While improving the wettability between the norbornene-based monomer and the organic fiber material by polymer treatment or fiber surface modifier treatment, it prevents polymerization inhibition on the surface of the organic fiber, and at the interface between the fiber material and the polynorbornene-based resin, A strong physical adhesive layer, or
It has been found that the above object can be achieved by providing a strong chemical adhesion structure by a chemical reaction. The present invention has been completed based on these findings.

(Fiber surface coating polymer) In the present invention, the fiber surface coating polymer used for coating the organic fiber material, including those disclosed in the above (JP-A-3-147822), is highly Density polyethylene, linear low density polyethylene, low density polyethylene, olefin polymers such as polypropylene and ethylene-propylene rubber, diene polymers such as polybutadiene, ester polymers such as polyethylene terephthalate, polycarbonate, polysulfone or polyether sulfone, polyether It is a polyimide such as imide, a water-soluble or hydrophilic polymer such as polyvinyl alcohol, polypyrrolidone or polyvinyl butyral, or a mixture of two or more of the above polymers.

By coating the fiber surface with the fiber surface coating polymer, the wettability of the reaction liquid described later with respect to the fiber surface is improved and the generation of voids is suppressed. Further, since the contact between the reaction inhibiting solution and the fiber having the polymerization inhibiting property is cut off, the norbornene-based monomer is not hardened in the vicinity of the fiber surface. Furthermore, such polymers evaporate the solvent,
Since the film is formed with unevenness on the surface during removal,
The unevenness is impregnated with the reaction liquid, and the adhesion rate is given by the anchor effect. Some polymers, such as polyimide, have adhesiveness to organic fiber materials, and some polymers, such as polyolefin, fuse with norbornene-based monomers when they cure. Fiber surface coating polymer, by imparting such physical adhesion,
Improves mechanical strength.

Further, in order to enhance the adhesive strength due to the unevenness of the polymer layer, clay compounds such as kaolinite or bentonite, and inorganic fine particle fillers such as talc, colloidal silica and carbon black adversely affect the polymerizability and wettability. You may add in the range which does not exist. In addition, a colorant such as various pigments or dyes, an anti-deterioration agent such as an antioxidant or an ultraviolet absorber, an antifogging agent, an antistatic agent, etc., to the extent that polymerizability and wettability are not adversely affected You may add to a solution as needed.

(Fiber Surface Modifying Agent) Furthermore, the present inventors do not inhibit ring-opening polymerization of norbornene-based monomers and have adhesiveness with either or both of an organic fiber material and a polynorbornene-based resin. An organic fiber having excellent mechanical properties by chemically treating the organic fiber material with a norbornene-based resin by surface-treating the organic fiber material with a low molecular weight compound (hereinafter referred to as a fiber surface modifier) It was found that a composite material could be obtained. As the fiber surface modifier, allyl glycidyl ether or glycidyl methacrylate, a double bond and a glycidyl group such as vinyl cyclohexene monoepoxide or vinyl monoepoxide, or a compound having an epoxy group, an allyl group such as allyl isocyanate and an isocyanate group And a compound having a vinyl group such as acrylic acid or methyl acrylate and a carboxyl group or an ester group are preferred. These modifiers are chemically bonded to an organic fiber material having a polar functional group such as an OH group of a high-strength vinylon fiber material by an addition reaction, a transesterification reaction, or various condensation reactions at the same time as being chemically bonded to the organic fiber material. Since a double bond such as an allyl group or a vinyl group contained in the modifier participates in the metathesis-catalyzed polymerization reaction of the norbornene-based monomer, it is effective in improving the interfacial adhesion of the fiber material / polynorbornene-based resin. . The treatment improves the wettability of the reaction solution to the fiber, suppresses the generation of voids, and reduces the polymerization inhibitory property as described for the fiber surface coating polymer. If necessary, these fiber surface modifiers and the fiber surface coating polymer may be used in combination of several kinds.

(Types and Forms of Organic Fiber Materials) Organic fibers include aramid fiber, polyarylate fiber, ultra high molecular weight polyethylene fiber, polypropylene fiber, vinylon fiber, high strength vinylon fiber (polyvinyl alcohol fiber), polyester fiber, nylon. Examples thereof include fibers and a mixed weave of these fibers, and a mixed weave of the above fibers with inorganic fibers such as glass fibers or carbon fibers. The form of these fibers is not particularly limited, such as long fibers or chopped strands matted, cloth woven, chopped as they are, etc. Preferred are plain weaves, satin weaves, and three-dimensional woven fabrics. Further, inorganic fibers such as glass fibers or carbon fibers and the organic fibers may be mixed and woven, or the inorganic fiber woven fabric and the organic fiber woven fabric may be laminated and used.

(Preliminary Washing Treatment with Organic Solvent) In the case of organic fiber materials, especially woven fabrics, in order to prevent fiber buckling or surface protection, improve flexibility of fiber bundles, give flexibility, and prevent static electricity, in the fiber spinning step. The surface of the fiber is coated with a processing oil (oil agent) containing mineral oil as a component, a surfactant for softening processing, and an antistatic agent composed of an organic salt or an inorganic salt,
These fiber-processing agents often inhibit the metathesis polymerization of norbornene-based monomers because they release hydrogen ions or interact with the metathesis polymerization catalyst. In particular, in the case of organic fibers having high strength and high elastic modulus, fiber coating with an oil agent is indispensable in order to prevent damage to the fibers in the manufacturing process of fiber woven fabrics, but this oil agent is a metathesis catalyst system of norbornene-based monomers. Since it significantly inhibits the polymerization reaction of (1), it is necessary to remove the oil agent from the fiber fabric before the bulk polymerization. As the organic solvent for cleaning the oil solution, ketones such as acetone, esters such as ethyl acetate, alicycles such as cyclohexane, aromatics such as benzene, chlorine-based organic solvents such as dichloromethane or dichlorobenzene, and N- Aprotic solvents such as methylpyrrolidone are preferred. After using any one of these organic solvents, or a mixed solvent of two or more kinds, and washing the organic fiber material at a temperature from the boiling point of the solvent to room temperature or higher, the organic solvent is completely dried and removed. To do.

(Surface treatment of organic fiber material) In the present invention, the surface treatment with a fiber surface coating polymer or a fiber surface modifier which does not inhibit ring-opening polymerization on the reaction liquid contact surface of the organic fiber material coexisted during ring-opening polymerization. The organic fiber material is used. (Fiber Surface-Coating Polymer Treatment) In order to surface-treat an organic fiber material with a fiber surface-coating polymer, the polymer is mixed with an inorganic filler or various additives as necessary, and a solvent or a dispersant (hereinafter, both are It is carried out by dissolving or dispersing it in a "solvent"), immersing the organic fiber material in this, and then removing the solvent. At this time, when the polymer concentration of the solution or dispersion is high, the effect of improving the void fraction cannot be expected as shown in Comparative Examples described later, so
It is desirable to process in a dilute state of less than%.

When the fiber material is coated with these polymers, the polymer is dissolved or suspended in an appropriate solvent and applied to the fiber material, or the fiber material is dipped in the polymer solution. After that, the solvent is distilled off for coating. As the solvent of the polymer solution, water, alcohols such as methanol, ethanol or butyl alcohol, carboxylic acids such as formic acid or acetic acid, esters such as ethyl acetate, ketones such as acetone or methyl ethyl ketone, petroleum ether or dioxane. Ethers such as, benzene, aromatics such as toluene or xylene, chlorinated solvents such as chloroform, dichloromethane or dichlorobenzene, dimethylformamide,
An aprotic solvent such as N-methylpyrrolidone or dimethyl sulfoxide and a hydrocarbon-based compound such as a norbornene-based monomer described later are preferable.

In this polymer treatment, the adhesion rate of the polymer to the fiber fabric is

[Equation 1] Can be arbitrarily selected by changing the treatment conditions such as the solution concentration and the number of immersions.
-17% by weight, preferably 0.002-7% by weight. still,
If the adhesion rate is lower than 0.001% by weight, the coating polymer cannot cover the surface of the organic fiber material uniformly and sufficiently, so that the wettability of the reaction liquid to the fiber at the fiber material / resin interface and The effect of suppressing polymerization inhibition is not sufficiently exhibited. On the contrary, when the adhesion rate is larger than 17% by weight, the coated polymer adheres to the fiber bundle in a lump state,
It inhibits the fiber impregnation of the metathesis polymerization reaction liquid and also leaves voids in the composite material.

(Treatment of Fiber Surface Modifier) The present inventors have added a functional group which is added to the surface of an organic fiber material through a chemical reaction and is incorporated into a norbornene-based monomer reaction system without inhibiting metathesis polymerization. The present inventors have found a fiber surface modifier that improves the chemical adhesion between the fiber material and the resin when applied to the surface of the organic fiber material. When surface-treating an organic fiber with a fiber surface modifier, the surface modifier is dissolved or dispersed in a solvent or a dispersant (hereinafter, both are referred to as a “solvent”), and further, if necessary. The fiber surface coating polymer, the inorganic filler or various additives are also added and mixed before spraying the treatment liquid onto the organic fiber material or by dipping the fiber material directly into this solution. At this time, in order to accelerate the reaction between the organic fiber and the fiber surface modifier, the treatment temperature can be set from around the boiling point of the solvent to around room temperature. Then, after removing the excess treatment solution adhering to the treated fiber material, the solvent component is completely evaporated and removed. The solvent is benzene,
Toluene, aromatics such as dichlorobenzene or nitrobenzene, ketones such as acetone, methyl ethyl ketone or cyclohexanone, ethers such as ethyl ether, propyl ether, etc.
An acidic catalyst such as boron trifluoroether or p-toluene sulfonic acid or a basic catalyst such as sodium hydroxide or sodium ethoxide is added.

By changing the treatment conditions such as the solution concentration and the number of immersions, the adhesion rate of the fiber material of the fiber surface modifier

[Equation 2] Can be selected arbitrarily, but generally 0.0
The amount is 01 to 10% by weight, preferably 0.005 to 5% by weight.
When the adhesion rate is less than 0.001% by weight, the fiber surface modifier cannot sufficiently react and add to the surface of the organic fiber, so that the chemical adhesion of the fiber / resin interface cannot be sufficiently achieved. The wettability of the reaction solution with respect to the fiber surface is not improved. On the contrary, if the adhesion rate is more than 10% by weight,
Not only does the surface modifier react and adhere to the fiber bundle in a lump state to inhibit fiber impregnation of the metathesis polymerization reaction solution or to leave a void in the composite material,
It forms a brittle interfacial layer between the fiber / resin which leads to a deterioration of the mechanical properties of the composite material.

(Polynorbornene Resin) The composite material of the present invention is a polynorbornene obtained by bulk ring-opening polymerization of a reaction liquid containing a norbornene monomer and a metathesis catalyst system in a mold in the presence of another member. It is a composite material of resin.

Generally, a molded product made of a polynorbornene resin is prepared by mixing two or more low-viscosity raw materials that react with each other to quickly produce a polymer, and then supply the mixed reaction solution into a mold. Curing in the mold, so-called RI
It can be produced by the M method. For example, as the reaction liquid, a reaction liquid containing an activator and a norbornene-based monomer,
A polynorbornene-based resin molded product is obtained by using a metathesis catalyst and a reaction liquid containing a norbornene-based monomer, mixing both liquids and supplying them into a mold, and performing bulk ring-opening polymerization.

Molding of polynorbornene-based resin by the RIM method has a significantly lower injection pressure than injection molding of ordinary thermoplastic resin, so that an inexpensive and lightweight mold can be used, and a raw material in the mold can be used. Since it has good fluidity, it is preferable for producing an insert molded product, a large-sized molded product, or a molded product having a complicated shape.

Norbornene-based Monomer The polynorbornene-based resin used in the present invention may be any resin having a norbornene ring, but it is particularly preferable to use a polycyclic norbornene-based monomer having a tricyclic or higher ring. preferable. When the polymer has three or more rings, a polymer having a high heat distortion temperature can be obtained, and the heat resistance required as a composite material can be satisfied. Also,
In the present invention, the resulting ring-opening polymer can be a thermosetting type.
10% by weight, preferably 30% by weight or more of crosslinkable monomers may be used.

Specific examples of the norbornene-based monomer include bicyclic compounds such as norbornene and norbornadiene, tricyclic compounds such as dicyclopentadiene and dihydrodicyclopentadiene, tetracyclic compounds such as tetracyclododecene, and tricyclopentadiene. Etc., pentacyclic compounds such as tetracyclopentadiene, etc., 7-ring compounds such as tetracyclopentadiene, their alkyl-substituted products (eg, methyl, ethyl, propyl, butyl-substituted products, etc.), alkenyl-substituted products (eg, vinyl-substituted products, etc.), Examples thereof include alkylidene substituents (eg ethylidene substituents) and aryl substituents (eg phenyl, tolyl and naphthyl substituents). Among them, tricyclic or pentacyclic compounds are favored from the viewpoint of availability, reactivity, heat resistance and the like.

The crosslinkable monomer has two reactive double bonds.
It is a polycyclic norbornene-based monomer having two or more thereof, and specific examples thereof include dicyclopentadiene, tricyclopentadiene, tetracyclopentadiene and the like. Therefore, when the norbornene-based monomer and the crosslinkable monomer are the same, it is not necessary to use any other crosslinkable monomer. In addition, a monocyclic cycloolefin such as cyclobutene that can undergo ring-opening polymerization together with one or more of the above norbornene-based monomers can be used together within a range not impairing the object of the present invention.

The catalyst used in the metathesis catalyst system may be any metathesis catalyst system comprising a metathesis catalyst known as a catalyst for ring-opening polymerization of norbornene monomers and an activator, and specific examples thereof include tungsten, molybdenum and tantalum. And the like, oxyhalides, oxides and metathesis catalysts such as organic ammonium salts.
Specific examples of the activator (cocatalyst) include alkylaluminum halides, alkoxyalkylaluminum halides, aryloxyalkylaluminum halides and organic tin compounds.

The metathesis catalyst is generally used in an amount of about 0.01 to 50 mmol, preferably 0.1 to 20 mmol, based on 1 mol of the norbornene-based monomer. The activator (cocatalyst) is preferably used in the range of 1 to 10 (molar ratio) with respect to the catalyst component.

Both the metathesis catalyst and the activator are preferably dissolved in the monomer before use, but may be suspended or dissolved in a small amount of solvent as long as the properties of the product are not substantially impaired. Good.

In a preferred method for producing a bulk ring-opening polymerized polynorbornene-based resin, the norbornene-based monomer is divided into two liquids and placed in separate containers, a metathesis catalyst is added to one of them, and an activator is added to the other. Prepare a stable reaction of the type. The two kinds of reaction liquids are mixed and then poured into a mold or a mold having a predetermined shape (both are collectively referred to as a mold), where ring-opening polymerization is performed in bulk.

The mold temperature is usually room temperature or higher, preferably
It is 40 to 200 ° C, particularly preferably 50 to 130 ° C. The components used in the polymerization reaction are preferably stored and manipulated under an atmosphere of an inert gas such as nitrogen gas. The material of the mold may be any of metal, resin, wood, plaster and the like.

In addition to organic fiber materials, polynorbornene resins include inorganic fibers such as glass fibers and carbon fibers, antioxidants, fillers, reinforcing materials, foaming agents, pigments, colorants and elastomers and other additives. It can be blended. These additives are usually dissolved or dispersed in the reaction solution and blended, but in some cases, they may be placed in a mold.

(Manufacture of norbornene-based resin molded article) An organic fiber woven fabric surface-treated with a fiber surface coating polymer or an organic fiber material surface-treated with a fiber surface modifier is placed in the mold in advance. The reaction liquid is supplied into the mold and bulk ring-opening polymerization is performed under the above-mentioned reaction conditions. When the organic fiber material is a woven fabric, usually 4 to 8 sheets are laminated. The various surface-treated fiber materials can be placed in close contact with the die surface in the die, or placed as a core in the space of the die.

Molding of the polynorbornene-based resin is carried out by the usual method.
It can be carried out by supplying the reaction solution containing the metathesis catalyst system to the RIM method into the mold and curing (bulk ring-opening polymerization). The reaction solution can be supplied by mixing two or more reaction solutions instantaneously with the mixing head of the RIM machine, and then
Pour into hot molds, or in the case of reaction liquids with long pot life, after mixing is complete in the mixer, then inject or pour once or several times into the preheated mold. You may. These operations are performed under an inert gas atmosphere as needed. Mold pressure is -1
kg / cm ² from 50 kg / cm ^2, preferably atmospheric pressure ~5kg / cm ^2.

The present invention will be described below with reference to the drawings. FIG. 1 shows a process chart showing the procedure of the fiber surface coating polymer treatment and the fiber surface modification treatment of the organic fiber according to the present invention.

The fiber surface coating polymer treatment of the organic fiber was performed by the procedure of A → B → C → D → F → G in FIG. Degreasing was performed in order to remove the oil and stains of the commercially available organic fiber fabric. In the degreasing process, an organic solvent 2 having a boiling point of 100 ° C. or less and which does not dissolve or modify the organic fiber fabric 1, for example, ketones such as acetone, alcohols such as ethanol, ethers such as ethyl ether, and alicyclic rings such as cyclohexane. It was carried out by dipping the woven fabric 1 for about 10 minutes at room temperature using aromatics such as benzene and benzene. The type of solvent, the solvent immersion temperature, and the time can be arbitrarily selected, so that the type of solvent and the range of conditions are not particularly limited. At the end of the degreasing step, the fiber fabric 1 was taken out of the organic solvent 2.

Next, the organic solvent attached to and absorbed in the degreased organic fiber is evaporated and dried. The drying condition is a temperature at which the organic fiber is not melted or altered (for example, room temperature to 100 ° C)
Then, it was enough to dry for 12 hours or more. Regarding the drying conditions of this organic solvent, any selection is possible depending on the type of organic fiber and the type of organic solvent, and the condition range thereof is not particularly specified. It should be noted that the above B and this processing are experimental conditions to the last, and may be omitted in the actual manufacturing process.

Next, a solution 3 prepared to have a predetermined polymer concentration
A step (referred to as a coating treatment) of immersing the dried textile fabric in (referred to as a coating solution) was performed. Also in this case, the organic solvent used did not dissolve or alter the fabric. The immersion temperature and time can be arbitrarily selected, and detailed conditions are described in Examples and Comparative Examples. By this step, a polymer coating is provided on the surface of the organic fiber. After the coating treatment was completed, the fiber fabric was taken out and, if necessary, lightly pressed with a roll to remove the excessively adhered and absorbed solution.

Next, the organic solvent attached to and absorbed in the degreased organic fiber is evaporated and dried. The drying conditions include a temperature at which the organic fiber is not melted and deteriorated (for example, room temperature to 100
It was sufficient to dry it for 12 hours or more. The drying conditions of this organic solvent are substantially the same as the conditions of C above, and can be arbitrarily selected depending on the type of organic fiber and the type of organic solvent, and the range of conditions is not particularly specified. Through the above steps, the surface-treated organic fiber woven fabric 5 was obtained.
The fiber surface modification treatment was performed in the order of A->B->C->E->F-> G in FIG. First, the organic fiber fabric was degreased and the organic solvent was evaporated and dried in the same manner as described above.

Solution 4 prepared to have a predetermined surface modifier concentration
A step (referred to as a surface modification treatment) of immersing the dried textile fabric in (a surface modifier solution) was performed. Also in this case, the organic solvent used did not dissolve or alter the fabric. The immersion temperature and time can be arbitrarily selected, and detailed conditions are described in Examples and Comparative Examples. By this step, the surface modifier component is added to the surface of the organic fiber by a chemical reaction. After the surface modification treatment was completed, the fiber woven fabric was taken out, and if necessary, lightly squeezed by a roll to remove the excessively adhered and absorbed solution. Then, the organic solvent was evaporated and dried in the same manner as described above to obtain the surface-treated organic fiber woven fabric 5.

[0045]

EXAMPLES The present invention will be described below with reference to examples, comparative examples and test examples, but the present invention is not limited to these examples. Throughout the following examples and comparative examples, "parts" and "%" are "parts by weight" unless otherwise specified.
And "% by weight" are shown.

Example 1 From a commercially available high-strength vinylon fiber plain woven fabric (weight per unit area of 180 g / m ² ), 20 pieces of 22 cm long × 22 cm wide sample were cut out, and a glass container (size: length 30 cm × width 40 cm × depth 30 cm, Hereinafter, it will be simply referred to as a "glass container".) Commercial grade acetone 1 put in a glass container
It was immersed in L at room temperature for 30 minutes. Then take out the sample,
After removing the adhered acetone sufficiently, clean large metal tray (size: 120 cm in length × 100 cm in width × 10 cm in depth.
It is simply called a "large metal tray". ) I arranged them so that they would not overlap. In this state, the sample was left in the fume hood at room temperature for one day and then dried under reduced pressure at 60 ° C. for 24 hours to obtain a washed treated fabric sample.

30 g of commercially available polyvinyl alcohol (PVA) (degree of suspension: 97 mol%, degree of polymerization: 2000) was weighed, and distilled water was added at a rate of 0.
The mixture was placed in a 2 L Erlenmeyer flask together with 7 L and 0.3 L of methanol, and stirred at room temperature for about 1 hour using a magnetic stirrer to dissolve uniformly. The solution composition ratio is P
VA / methanol / water = 3.1 / 24.5 / 72.4. This solution was poured into 20 pieces of the above-mentioned acetone-washed high-strength vinylon fiber plain weave (weight per unit area: 180 g / m ² ) sample (size: length 22 cm × width 22 cm) placed in a glass container and soaked at room temperature for 30 minutes. . Next, the samples were taken out, and after removing the excess PVA solution, they were arranged so as not to overlap with several clean large metal trays. In this state, the fiber surface-coated polymer-treated woven fabric prepared by leaving it in the fume hood at room temperature for one day and then dried under reduced pressure at 60 ° C. for 48 hours was used as a polymer-coated woven fabric sample. For this sample, the adhesion rate of the polymer to the fiber fabric was calculated by

[Equation 3] It was calculated by

Two molds and a spacer (for forming a thickness of 3 mm) forming a space of 22 cm in length × 22 cm in width × 3 mm in thickness are used, and the washed woven fabric is formed on one inner surface of the mold. Four to eight samples were stacked on the cavity side and placed in close contact with each other. The mold temperature was maintained at 70 ° C., and the bulk polymerization reaction solution was injected into the space of the mold. The bulk polymerization reaction liquid used here is a mixed solution of the following liquids A and B. To 100 parts of dicyclopentadiene (DCP), 6.5 parts of styrene-isoprene-styrene block copolymer (SIS: manufactured by Nippon Zeon Co., Ltd., trade name Quintac 3421) was added and mixed in two containers. Is 41 mmol of diethylaluminum chloride (DEAC) in DCP,
n-Propyl alcohol was added at a concentration of 41 mmol and silicon tetrachloride was added at a concentration of 21 mmol (A).
liquid). On the other hand, tri (tridecyl) ammonium molybdate was added to DCP so as to have a concentration of 10 millimoles, and a phenolic antioxidant (manufactured by Ethyl Corporation, trade name Ethanox) was added per 100 parts of DCP.
702) 4 parts were added (solution B). Both reaction solutions (mixing ratio of solution A: solution B 1: 1) were rapidly injected into the mold using a gear pump and a power mixer at about normal pressure.
Three minutes after the completion of the injection, the mold was opened, the molded product was taken out, and cooled to room temperature.

Example 2 The same acetone washing treatment as in Example 1 was performed. afterwards,
30 g of commercially available PVA (suspended degree: 97 mol%, degree of polymerization: 2000) was put into a 2 L Erlenmeyer flask together with 1 L of distilled water, and stirred at room temperature for about 1 hour to dissolve uniformly. Later, commercially available 20% colloidal silica (particle size:
10-20 nm) aqueous solution (10 g) and methanol (0.5 L) were added and mixed uniformly. The solution composition ratio was PVA / colloidal silica / methanol / water = 2.5 / 0.2 / 13.3 / 84.0.
This solution was placed in a glass container, and the acetone-washed high-strength vinylon fiber plain woven fabric of Example 1 (weight per unit weight: 180 g / m 2
² ) Pour 20 samples (size: 22 cm x 22 cm) at room temperature
Soaked for 30 minutes. Next, the sample was taken out, and after removing the excess PVA solution, it was arranged so as not to overlap with several large clean metal trays. In this state, the fiber surface-coated polymer-treated woven fabric prepared by leaving it in the fume hood at room temperature for one day and then dried under reduced pressure at 60 ° C. for 48 hours was used as a polymer-coated woven fabric sample. Next, after the adhesion rate was calculated as in Example 1, molding was performed as in Example 1.

Example 3 The same acetone washing treatment as in Example 1 was performed. afterwards,
30g of commercially available polyvinylpyrrolidone (PVP) (degree of polymerization: 2000)
It was weighed and put in a 2 L Erlenmeyer flask together with 1 L of methanol, and stirred at room temperature for about 1 hour using a magnetic stirrer to dissolve uniformly. The solution composition ratio is PVP /
Methanol = 3.7 / 96.3. This solution was placed in a glass container, and the acetone-washed high-strength vinylon fiber plain weave fabric of Example 1 (weight per unit area: 180 g / m ² ) sample (size: length 22
(cm x width 22 cm) was poured into 20 sheets and immersed at room temperature for 30 minutes. Next, the sample was taken out, and after removing the excess PVP solution, it was arranged so as not to overlap several large clean metal trays. In this state, leave it in the fume hood at room temperature for 1 day, then 60 ℃
The fiber surface-coated polymer-treated woven fabric prepared by drying under reduced pressure for 24 hours was used as a polymer-coated woven fabric sample. Next, after the adhesion rate was calculated as in Example 1, molding was performed as in Example 1.

Example 4 Acetone cleaning treatment was carried out in the same manner as in Example 1. afterwards,
30 g of commercially available PVP (degree of polymerization: 2000) is weighed and methanol 1
Put it in a 2 L Erlenmeyer flask together with L and stir at room temperature using a magnetic stirrer for about 1 hour to uniformly dissolve it, then add 2 g of bentonite (particle size: 4 to 10 μ) until it becomes uniform. Mixed. The solution composition ratio was PVP / bentonite / methanol = 3.6 / 0.2 / 96.2. This solution was poured into 20 pieces of acetone-washed high-strength vinylon fiber plain weave (weight per unit area weight: 180 g / m ² ) sample (size: length 22 cm × width 22 cm) in a glass container, and the mixture was kept at room temperature for 30 minutes. Soaked. Next, the samples were taken out, and after removing the excess PVP solution, they were arranged so as not to overlap with several large clean metal trays. In this state, the fiber surface-coated polymer-treated woven fabric prepared by leaving it in the fume hood at room temperature for one day and then dried under reduced pressure at 60 ° C. for 24 hours was used as a polymer-coated woven fabric sample. Next, after the adhesion rate was calculated as in Example 1, molding was performed as in Example 1.

Example 5 Acetone washing treatment was carried out in the same manner as in Example 1. afterwards,
30 g of commercially available ethylene propylene rubber (EPR) (HDPE fraction: 70%, molecular weight: 120,000) was weighed, and 1 L of toluene was added to 1
The mixture was placed in an L eggplant-shaped flask and stirred with a magnetic stirrer for about 1 hour while keeping the temperature at 100 ° C. in an oil bath to obtain a uniform solution, which was then cooled to room temperature. The solution composition ratio was EPR / toluene = 3.3 / 96.7. This solution
The acetone-washed high-strength vinylon fiber plain woven fabric (weight per unit area: 180 g / m ² ) of 20 samples (size: length 22 cm × width 22 cm) in a glass container were poured and immersed for 30 minutes at room temperature. Next, the sample was taken out, and after removing the excess EPR solution, it was arranged so as not to overlap with several large clean metal trays. In this state, the fiber surface-coated polymer-treated woven fabric prepared by leaving it in the fume hood at room temperature for one day and then dried under reduced pressure at 60 ° C. for 48 hours was used as a polymer-coated woven fabric sample. Next, after the adhesion rate was calculated as in Example 1, molding was performed as in Example 1.

Example 6 The same acetone washing treatment as in Example 1 was performed. afterwards,
Commercial linear low density polyethylene (LLDPE) (Molecular weight: 4000)
Weigh 20 g of the above and put it in a 3 L separable flask together with 2 L of xylene.
After stirring for a period of time using a magnetic stirrer to form a uniform solution, the mixture was kept at 90 ° C. The solution composition ratio is LLDP
E / xylene was 1.2 / 98.8. While keeping this solution at 90 ° C, the acetone-washed high-strength vinylon fiber plain weave fabric of Example 1 (weight per unit area of 180 g / m ² ) sample (size: 22 cm in length)
Twenty sheets were quickly put in and immersed at 90 ° C. for 3 minutes. Next, the sample was taken out, the excess LLDPE solution was quickly removed, and then the samples were arranged so as not to overlap with several large clean metal trays. In this state, the fiber surface-coated polymer-treated woven fabric prepared by leaving it in the fume hood at room temperature for one day and then dried under reduced pressure at 60 ° C. for 48 hours was used as a polymer-coated woven fabric sample. Next, after the adhesion rate was calculated as in Example 1, molding was performed as in Example 1.

Example 7 Acetone washing treatment was carried out in the same manner as in Example 1. afterwards,
8 g of a commercially available polyetherimide (PEI) (molecular weight: 14000) was placed in a 2 L Erlenmeyer flask together with 1 L of methylene chloride, and stirred at room temperature with a magnetic stirrer for about 1 hour to be uniformly dissolved. The solution composition ratio was PEI / methylene chloride = 0.6 / 99.4. This solution was placed in a glass container, and the acetone-washed high-strength vinylon fiber plain weave fabric of Example 1 (weight per unit area of 180 g / m ² ) sample (size: length 22 cm × width 22)
cm) 20 sheets, and soaked at room temperature for 30 minutes. Next, the samples were taken out, and after removing the excess PEI solution, they were arranged so as not to overlap with several large clean metal trays. In this state,
After leaving it in the fume hood at room temperature for one day, at 60 ℃ for 24 hours,
The fiber surface-coated polymer-treated woven fabric prepared by drying under reduced pressure was used as a polymer-coated woven fabric sample. Next, after the adhesion rate was calculated as in Example 1, molding was performed as in Example 1.

Example 8 Acetone washing treatment was carried out in the same manner as in Example 1. afterwards,
Put 30 g of commercially available polyether sulfone (PES) (molecular weight: 24000) in a 2 L Erlenmeyer flask together with 1 L of chloroform,
Using a magnetic stirrer at room temperature, the mixture was stirred for about 1 hour to uniformly dissolve it. The solution composition ratio was PES / chloroform = 3.2 / 96.8. This solution was placed in a glass container, and the acetone-washed high-strength vinylon fiber plain weave fabric of Example 1 (weight per unit area of 180 g / m ² ) sample (size: length 22 cm × width 22)
cm) 20 sheets, and soaked at room temperature for 30 minutes. Next, the samples were taken out, and after removing the excess PES solution, they were arranged so as not to overlap with several large clean metal trays. In this state,
After leaving it in the fume hood at room temperature for one day, at 60 ℃ for 24 hours,
The fiber surface-coated polymer-treated woven fabric prepared by drying under reduced pressure was used as a polymer-coated woven fabric sample. Next, after the adhesion rate was calculated as in Example 1, molding was performed as in Example 1.

Example 9 Commercially available ultra high molecular weight polyethylene fiber plain weave (weight per unit area 140 g
/ m ² ), 20 pieces of 22 cm long × 22 cm wide sample were cut out and immersed in 1 L of commercial grade acetone placed in a glass container at room temperature for 30 minutes. Next, the sample was taken out, after sufficiently removing the attached acetone, it was arranged so as not to overlap with several large clean metal trays. In this state, the fiber surface-covered polymer-treated woven fabric prepared by leaving it in the fume hood at room temperature for one day and then drying it under reduced pressure at 60 ° C. for 24 hours was used as a washing-treated woven fabric sample.
30 g of commercially available EPR (HDPE fraction: 70%, molecular weight: 120,000)
The mixture was weighed and placed in a 1 L eggplant-shaped flask together with 1 L of toluene. The mixture was stirred with a magnetic stirrer for about 1 hour while keeping the temperature at 100 ° C. in an oil bath to obtain a uniform solution, which was then cooled to room temperature. The solution composition ratio was EPR / toluene = 3.3 / 96.7. This solution was placed in a glass container, and the acetone-washed ultra-high-molecular-weight polyethylene fiber plain weave (weight per unit area 140 g / m ² ) sample (size: length 22 cm × width
22 cm) 20 pieces were poured and immersed at room temperature for 30 minutes. Next, the sample was taken out, and after removing the excess EPR solution, it was arranged so as not to overlap with several large clean metal trays. In this state, the fiber surface-coated polymer-treated woven fabric prepared by leaving it in the fume hood at room temperature for one day and then dried under reduced pressure at 60 ° C. for 48 hours was used as a polymer-coated woven fabric sample. Next, Example 1
After calculating the adhesion rate in the same manner as in (1), molding was performed in the same manner as in Example 1.

Example 10 The same acetone washing treatment as in Example 9 was performed. afterwards,
30 g of commercially available EPR (HDPE fraction: 70%, molecular weight: 120,000)
The mixture was weighed and placed in a 1 L eggplant-shaped flask together with 1 L of toluene. The mixture was stirred with a magnetic stirrer for about 1 hour while keeping the temperature at 100 ° C. in an oil bath to obtain a uniform solution, which was then cooled to room temperature. To the above solution, 2 g of commercially available carbon black (particle size: 100 to 300 mμ) was added and stirred and mixed until uniform. The solution composition ratio was EPR / carbon black / toluene = 3.3 / 0.2 / 96.5. This solution was poured into 20 pieces of the above-mentioned acetone-washed ultra-high-molecular-weight polyethylene fiber plain weave (weight per unit weight 140 g / m ² ) sample (size: length 22 cm × width 22 cm) placed in a glass container and soaked at room temperature for 30 minutes did. Next, the sample was taken out, and after removing the excess EPR solution, it was arranged so as not to overlap with several large clean metal trays. In this state, the fiber surface-coated polymer-treated woven fabric prepared by leaving it in the fume hood at room temperature for one day and then dried under reduced pressure at 60 ° C. for 48 hours was used as a polymer-coated woven fabric sample. Next, after the adhesion rate was calculated as in Example 1, molding was performed as in Example 1.

Example 11 Acetone cleaning treatment was carried out in the same manner as in Example 9. afterwards,
30 g of commercially available polybutadiene (PB) (molecular weight: 360,000) was weighed and put in a 1 L eggplant-shaped flask together with 1 L of benzene.
The mixture was stirred with a magnetic stirrer for about 2 hours while keeping the temperature at 60 ° C. in an oil bath to obtain a uniform solution, and then cooled to room temperature. The solution composition ratio is PB / benzene = 3.3 / 9
It was 6.7. This solution was placed in a glass container, and the acetone-washed ultra-high molecular weight polyethylene fiber plain weave (weight per unit area 140 g / m ² ) sample (size: length 22 cm × width 22 cm) 20
It was poured into a plate and soaked at room temperature for 30 minutes. Next, the samples were taken out, and after removing the excess PB solution, they were arranged so as not to overlap with several large clean metal trays. In this state, the fiber surface-coated polymer-treated woven fabric prepared by leaving it in the fume hood at room temperature for one day and then dried under reduced pressure at 60 ° C. for 48 hours was used as a polymer-coated woven fabric sample. Next, after the adhesion rate was calculated as in Example 1, molding was performed as in Example 1.

Example 12 Acetone cleaning treatment was carried out in the same manner as in Example 9. afterwards,
30 g of commercially available PEI (molecular weight: 14000) was placed in a 2 L Erlenmeyer flask together with 1 L of methylene chloride, and stirred at room temperature with a magnetic stirrer for about 1 hour to dissolve uniformly. The solution composition ratio was PEI / methylene chloride = 3.6 / 96.4. This solution was poured into 20 pieces of the above-mentioned acetone-washed ultra-high-molecular-weight polyethylene fiber plain weave (weight per unit weight 140 g / m ² ) sample (size: length 22 cm × width 22 cm) placed in a glass container and soaked at room temperature for 30 minutes did. Next, the samples were taken out, and after removing the excess PEI solution, they were arranged so as not to overlap with several large clean metal trays. In this state, the fiber surface-coated polymer-treated woven fabric prepared by leaving it in the fume hood at room temperature for one day and then dried under reduced pressure at 60 ° C. for 24 hours was used as a polymer-coated woven fabric sample. Next, after the adhesion rate was calculated as in Example 1, molding was performed as in Example 1.

Example 13 From a commercially available polyarylate fiber plain weave (weight per unit area 170 g / m ² ), 20 pieces of 22 cm × 22 cm were cut out and immersed in 1 L of commercially available special grade acetone in a glass container at room temperature for 30 minutes. did. Next, the sample was taken out, after sufficiently removing the attached acetone, it was arranged so as not to overlap with several large clean metal trays. In this state, the sample was left in the fume hood at room temperature for one day and then dried under reduced pressure at 60 ° C. for 24 hours to obtain a washed treated fabric sample. Commercially available PVA (saponification degree: 97 mol%, degree of polymerization: 2000) 30 g
Put 1 L of distilled water into a 2 L Erlenmeyer flask and stir at room temperature with a magnetic stirrer for about 1 hour to uniformly dissolve, and then commercially available 20% colloidal silica (particle size: 10 to 20 nm) aqueous solution 10 g And 0.5 L of methanol was added,
Mix evenly. The solution composition ratio was PVA / colloidal silica / methanol / water = 2.5 / 0.2 / 13.3 / 84.0. This solution was poured into 20 pieces of the above-mentioned acetone-washed polyarylate fiber plain weave (weight per unit area 170 g / m ² ) sample (size: length 22 cm × width 22 cm) placed in a glass container, and immersed at room temperature for 30 minutes. Next, the samples were taken out, and after removing the excess PVA solution, they were arranged so as not to overlap with several large clean metal trays. In this state, the fiber surface-coated polymer-treated woven fabric prepared by leaving it in the fume hood at room temperature for one day and then dried under reduced pressure at 60 ° C. for 24 hours was used as a polymer-coated woven fabric sample. Next, after the adhesion rate was calculated as in Example 1, molding was performed as in Example 1.

Example 14 From a commercially available aramid 4,9 fiber plain woven fabric (weight per unit area 170 g / m ² ), 20 samples of 22 cm in length × 22 cm in width were cut out and placed in 1 L of commercially available special grade acetone in a glass container at room temperature for 30 hours. Soaked for a minute. Next, the sample was taken out, after sufficiently removing the attached acetone, it was arranged so as not to overlap with several large clean metal trays. In this state, the sample was left in the fume hood at room temperature for one day and then dried under reduced pressure at 60 ° C. for 24 hours to obtain a washed treated fabric sample. 30 g of commercially available PVP (degree of polymerization: 2000) was weighed and placed in a 2 L Erlenmeyer flask together with 1 L of methanol, and stirred for about 1 hour at room temperature with a magnetic stirrer to dissolve uniformly, and then bentonite (particle size : 4-10μ) 2g
Add and mix until uniform. The solution composition ratio is PV
P / bentonite / methanol = 3.6 / 0.2 / 96.2.
This solution was poured into 20 pieces of the above-mentioned acetone-washed aramid 4,9 fiber plain weave (weight per unit area 170 g / m ² ) sample (size: length 22 cm x width 22 cm) in a glass container and soaked at room temperature for 30 minutes did. Next, the samples were taken out, and after removing the excess PVP solution, they were arranged so as not to overlap with several large clean metal trays. In this state, the fiber surface-coated polymer-treated woven fabric prepared by leaving it in the fume hood at room temperature for one day and then dried under reduced pressure at 60 ° C. for 24 hours was used as a polymer-coated woven fabric sample. Next, after the adhesion rate was calculated as in Example 1, molding was performed as in Example 1.

Example 15 The same acetone washing treatment as in Example 1 was performed. afterwards,
50g of commercial grade allyl glycidyl ether and commercial grade p-
2 g of toluenesulfonic acid was weighed and put in a 3 L separable flask together with 2 L of commercially available special grade acetone, and the mixture was kept at 50 ° C. in an oil bath while stirring with a magnetic stirrer. The solution composition ratio is allyl glycidyl ether / p-toluenesulfonic acid / acetone = 3.1 / 0.
It was 1 / 96.8. Then, promptly, 20 pieces of the acetone-washed high-strength vinylon fiber plain weave (weight per unit area: 180 g / m ² ) sample (size: 22 cm in length × 22 cm in width) were put into the solution in a separable flask at 50 ° C. After soaking for 3 hours, remove the fabric sample, remove the excess solution and
Clean with 500 mL and then clean with a small metal tray (size:
50cm x 40cm x 3cm depth, and later "small metal tray"
Call. ) I arranged them so that they would not overlap. In this state, a fiber surface-coated polymer-treated woven fabric prepared by drying under reduced pressure at 40 ° C. for 24 hours was used as a fiber surface-modified woven fabric sample. Next, after the adhesion rate was calculated as in Example 1, molding was performed as in Example 1.

Example 16 The same acetone washing treatment as in Example 1 was performed. afterwards,
100 g of commercially available special grade allyl glycidyl methacrylate and 2 g of commercially available special grade p-toluenesulfonic acid were weighed and placed in a 3 L separable flask together with 2 L of commercially available special grade cyclohexanone, and stirred at 60 ° C. in an oil bath using a magnetic stirrer. Kept warm. The solution composition ratio was allyl glycidyl methacrylate / p-toluene sulfonic acid / cyclohexanone = 5.0 / 0.2 / 94.8. Then, promptly, the acetone-washed high-strength vinylon fiber plain weave (weight per unit area: 180 g / m ² ) sample (size: length 22 cm × width
(22 cm) 20 pieces were put into the above solution in a separable flask and immersed at 60 ° C. for 3 hours, and then a fabric sample was taken out,
The excess solution was removed, washed with 500 mL of cyclohexanone, and then lined up so as not to overlap several clean small metal trays. In this state, a fiber surface-coated polymer-treated woven fabric prepared by drying under reduced pressure at 40 ° C. for 24 hours was used as a fiber surface-modified woven fabric sample. Next, after the adhesion rate was calculated as in Example 1, molding was performed as in Example 1.

Example 17 The same acetone washing treatment as in Example 1 was performed. afterwards,
Vinyl norbornene monoepoxide 100g and commercial grade p-
2 g of toluenesulfonic acid was weighed and put in a 3 L separable flask together with 2 L of commercially available special grade acetone, and the mixture was kept at 60 ° C. in an oil bath while stirring with a magnetic stirrer. The solution composition ratio was vinylnorbornene monoepoxide / p-toluenesulfonic acid / acetone = 5.9 / 0.2 / 94.8. Next, promptly wash the acetone-washed high-strength vinylon fiber plain weave (weight per unit area: 180 g / m
² ) Twenty samples (size: 22 cm in length × 22 cm in width) were put into the solution in a separable flask and immersed at 60 ° C. for 3 hours, then the fabric sample was taken out, the excess solution was removed, and acetone was added. After washing with 500 mL, they were lined up so that they did not overlap with several clean small metal trays. In this state, the fiber surface-coated polymer-treated woven fabric prepared by drying under reduced pressure at 40 ° C. for 48 hours was used as a fiber surface-modified woven fabric sample. Next, Example 1
After calculating the adhesion rate in the same manner as in (1), molding was performed in the same manner as in Example 1.

Example 18 The same acetone washing treatment as in Example 1 was performed. afterwards,
200 g of commercially available special grade vinyl cyclohexene monoepoxide and 4 g of commercially available special grade p-toluene sulfonic acid were weighed and put in a 3 L separable flask together with 2 L of commercially available special grade cyclohexanone, and stirred in an oil bath while stirring with a magnetic stirrer. It was kept warm at ℃. The solution composition ratio was vinylcyclohexene monoepoxide / p-toluenesulfonic acid / cyclohexanone = 5.8 / 0.2 / 94.0. Then, immediately, the acetone-washed high-strength vinylon fiber plain weave (weight per unit area: 180 g / m ² ) sample (size: length 22
cm × width 22 cm) 20 pieces were put into the above solution in a separable flask and immersed at 60 ° C. for 3 hours, then the fabric sample was taken out, the excess solution was removed, and 500 mL of cyclohexanone
After cleaning with, they were lined up so that they would not overlap with several clean small metal trays. In this state, the fiber surface-coated polymer-treated woven fabric prepared by drying under reduced pressure at 60 ° C. for 48 hours was used as a fiber surface-modified woven fabric sample. Next, after the adhesion rate was calculated as in Example 1, molding was performed as in Example 1.

Example 19 The same acetone washing treatment as in Example 1 was performed. afterwards,
100 g of commercially available special grade methyl acrylate and 3 g of commercially available special grade p-toluene sulfonic acid were weighed and placed in a 3 L separable flask together with 2 L of commercially available special grade 1-butyl alcohol, and stirred in an oil bath with a magnetic stirrer. And kept at 80 ° C. The solution composition ratio was methyl acrylate / p-toluenesulfonic acid / 1-butyl alcohol = 5.8 / 0.2 / 94.0. Next, promptly wash the acetone-washed high-strength vinylon fiber plain weave (weight per unit area: 180 g / m
² ) Twenty samples (size: 22 cm in length × 22 cm in width) were put into the solution in a separable flask and soaked at 80 ° C. for 1 hour, and then the fabric sample was taken out to remove excess solution, and 1
-Washed with 500 mL of butyl alcohol and then lined up so that they do not overlap with several clean small metal trays. In this state,
The fiber surface-coated polymer-treated woven fabric prepared by drying under reduced pressure at 60 ° C. for 48 hours was used as a fiber surface-modified woven fabric sample. Next, after the adhesion rate was calculated as in Example 1, molding was performed as in Example 1.

Example 20 Acetone cleaning treatment was carried out in the same manner as in Example 1. afterwards,
100 g of commercially available special grade allyl isocyanate was weighed and put in a 3 L separable flask together with 2 L of commercially available special grade acetone, and the mixture was kept at 55 ° C. in an oil bath while stirring with a magnetic stirrer. The solution composition ratio was allyl isocyanate / acetone = 5.9 / 94.1. next,
Promptly, the acetone-washed high-strength vinylon fiber plain weave (weight per unit area: 180 g / m ² ) sample (size: length 22 cm x width 22 c
m) Add 20 pieces to the above solution in a separable flask,
After soaking at 5 ° C. for 3 hours, the fabric samples were removed, the excess solution was removed, washed with 500 mL of acetone and then lined up so that they did not overlap with several clean small metal trays. In this state, a fiber surface-coated polymer-treated woven fabric prepared by drying under reduced pressure at 40 ° C. for 24 hours was used as a fiber surface-modified woven fabric sample. Next, after the adhesion rate was calculated as in Example 1, molding was performed as in Example 1.

Comparative Example 21 Commercially available high-strength vinylon fiber plain weave (weight per unit area: 180 g / m ² ).
From this, cut out 20 unprocessed samples of 22 cm in length × 22 cm in width, 60
It was dried under reduced pressure at ℃ for 24 hours. Next, using two molds and a spacer (for forming a thickness of 3 mm) that forms a space of 22 cm in length × 22 cm in width × 3 mm in thickness, the above-mentioned untreated one inner surface of this mold is used. High-strength vinylon fabric sample 4
About 8 sheets were stacked on the cavity side and placed in close contact with each other. The mold temperature was maintained at 70 ° C., and the bulk polymerization reaction solution was rapidly injected into the space of the mold at about normal pressure using a gear pump and a power mixer. Three minutes after the completion of the injection, the mold was opened and the contents were taken out, but the norbornene-based monomer was hardly polymerized.

Comparative Example 22 Commercially available ultra high molecular weight polyethylene fiber plain weave (weight per unit area 140
20 pieces of 22 cm long × 22 cm wide untreated sample were cut out from g / m ² ) and dried under reduced pressure at 60 ° C. for 24 hours. Next, height 22 cm x width
Two molds and a spacer (for forming a thickness of 3 mm) forming a space of 22 cm × thickness of 3 mm were used, and one of the molds had an untreated ultra high molecular weight polyethylene fabric sample 4 described above. About 8 sheets were stacked on the cavity side and placed in close contact with each other. The mold temperature was maintained at 70 ° C., and the bulk polymerization reaction solution was rapidly injected into the space of the mold at about normal pressure using a gear pump and a power mixer. End of injection 3
After a minute, the mold was opened and the contents were taken out, but the norbornene-based monomer was hardly polymerized.

Comparative Example 23 Commercially available high-strength vinylon fiber plain weave (weight per unit area: 180 g / m ² ).
From the above, 20 samples each having a length of 22 cm and a width of 22 cm were cut out and immersed in 1 L of commercially available special grade methanol in a glass container at room temperature for 30 minutes. Next, the sample was taken out, and after adhering methanol was sufficiently removed, it was arranged so as not to overlap with several clean large metal trays. In this state, the sample was left in the fume hood at room temperature for one day and then dried under reduced pressure at 60 ° C. for 24 hours to obtain a washed treated fabric sample. Two molds and a spacer (for forming a thickness of 3 mm) that form a space of 22 cm in length × 22 cm in width × 3 mm in thickness are used, and one of the inner surfaces of this mold has a high strength treated with the methanol cleaning treatment. 4 to 8 vinylon fabric samples
It was placed on the cavity side in close contact with each other. The mold temperature was maintained at 70 ° C., and the bulk polymerization reaction solution was rapidly injected into the space of the mold at about normal pressure using a gear pump and a power mixer. Three minutes after the completion of the injection, the mold was opened and the contents were taken out, but the norbornene-based monomer was hardly polymerized.

Comparative Example 24 The same acetone washing treatment as in Example 1 was performed. afterwards,
Two molds and a spacer (for forming a thickness of 3 mm) that forms a space of 22 cm in length × 22 cm in width × 3 mm in thickness
Using the above, 4 to 8 samples of the high-strength vinylon woven fabric subjected to the acetone cleaning treatment were laminated and closely attached to the cavity side on one inner surface of this mold. The mold temperature was maintained at 70 ° C., and the bulk polymerization reaction solution was rapidly injected into the space of the mold at about normal pressure using a gear pump and a power mixer. Three minutes after the completion of the injection, the mold was opened, the composite material molded product was taken out, and cooled to room temperature.

Comparative Example 25 Commercially available ultra high molecular weight polyethylene fiber plain weave (weight per unit area 140
From g / m ² ), 20 pieces of 22 cm × 22 cm samples are cut out,
Put it in a 3L separable flask charged with 2L of commercially available special grade N-methylpyrrolidone while keeping it warm at 60 ° C in an oil bath.
Soak for 30 minutes. Next, the sample was taken out, after sufficiently removing excess N-methylpyrrolidone, it was arranged so as not to overlap several clean large metal trays. In this state, the sample was left in the fume hood at room temperature for one day and then dried under reduced pressure at 60 ° C. for 48 hours to obtain a washed sample. 22cm x 22cm x 3mm thickness
Using two molds and a spacer (for forming a thickness of 3 mm) that form the space of 4 to 8 sheets of the high molecular weight polyethylene fabric sample that has been subjected to the acetone washing treatment on one inner surface of the mold, It was placed on the cavity side in close contact with each other. The mold temperature was maintained at 70 ° C., and the bulk polymerization reaction solution was rapidly injected into the space of the mold at about normal pressure using a gear pump and a power mixer. Three minutes after the completion of the injection, the mold was opened, the composite material molded product was taken out, and cooled to room temperature.

Comparative Example 26 The same acetone washing treatment as in Example 13 was performed. afterwards,
Two molds and a spacer (for forming a thickness of 3 mm) that forms a space of 22 cm in length × 22 cm in width × 3 mm in thickness
Using the above, 4 to 8 samples of the polyarylate woven fabric subjected to the acetone cleaning treatment were laminated on the inner surface of one side of the mold and closely attached to the cavity side. The mold temperature was maintained at 70 ° C., and the bulk polymerization reaction solution was rapidly injected into the space of the mold at about normal pressure using a gear pump and a power mixer. Three minutes after the completion of the injection, the mold was opened, the composite material molded product was taken out, and cooled to room temperature.

Comparative Example 27 The same acetone washing treatment as in Example 14 was performed. afterwards,
Two molds and a spacer (for forming a thickness of 3 mm) that forms a space of 22 cm in length × 22 cm in width × 3 mm in thickness
4 to 8 aramid 4,9 woven fabric samples which had been subjected to the above-mentioned acetone cleaning treatment were laminated on one inner surface of this mold on the cavity side and placed in close contact with each other. The mold temperature was maintained at 70 ° C., and the bulk polymerization reaction solution was rapidly injected into the space of the mold at about normal pressure using a gear pump and a power mixer. Three minutes after the completion of the injection, the mold was opened, the composite material molded product was taken out, and cooled to room temperature.

Comparative Example 28 The same acetone washing treatment as in Example 1 was performed. afterwards,
Commercially available EPR (HDPE fraction: 70%, molecular weight: 120,000)
159 g was weighed and placed in a 1 L eggplant-shaped flask together with 1 L of toluene. The mixture was stirred with a magnetic stirrer for about 1 hour while keeping the temperature at 100 ° C. in an oil bath to obtain a uniform solution, and then cooled to room temperature. The solution composition ratio is EPR
/Toluene=15.5/84.5. This solution was poured into 20 pieces of the acetone-washed high-strength vinylon fiber plain weave sample (size: 22 cm in length × 22 cm in width) in a glass container, which was immersed in the glass container for 30 minutes at room temperature. Then take out the sample,
After removing the excess EPR solution, they were lined up so as not to overlap several clean large metal trays. In this state, the sample was allowed to stand at room temperature for one day in a draft and then dried under reduced pressure at 60 ° C. for 48 hours to obtain a polymer-coated woven fabric sample. Next, Example 1
After calculating the adhesion rate in the same manner as in Example 1, the composite material was molded in the same manner as in Example 1.

Comparative Example 29 The same acetone washing treatment as in Example 9 was performed. afterwards,
321 g of commercially available PEI (molecular weight: 14000) was weighed, put in a 2 L Erlenmeyer flask together with 1 L of methylene chloride, and stirred for about 1 hour using a magnetic stirrer to obtain a uniform solution. The solution composition ratio is PEI / methylene chloride = 19.5 / 8
It was 0.5. This solution was poured into 20 pieces of the acetone-washed ultra-high-molecular-weight polyethylene fiber plain weave sample (size: 22 cm in length × 22 cm in width) in a glass container, and the mixture was kept at room temperature for 30 times.
Soaked for a minute. Next, the samples were taken out, and after removing the excess PEI solution, they were arranged so as not to overlap several clean large metal trays. In this state, the sample was left in the fume hood at room temperature for one day and then dried under reduced pressure at 60 ° C. for 24 hours to obtain a polymer-coated woven fabric sample. Next, after the adhesion rate was calculated in the same manner as in Example 1, composite material molding was performed in the same manner as in Example 1.

Comparative Example 30 The same acetone washing treatment as in Example 1 was performed. afterwards,
840 g of commercially available special grade glycidyl methacrylate and 40 g of p-toluenesulfonic acid are weighed and placed in a 3 L separable flask together with 2 L of commercially available special grade cyclohexanone, and kept at 80 ° C in an oil bath while stirring with a magnetic stirrer. did. The solution composition ratio was glycidyl methacrylate / p-toluenesulfonic acid / cyclohexanone = 30.3 / 1.4 / 68.3. Next, a high strength vinylon fiber plain weave sample (size: warp 22
20 cm x 22 cm) is immediately added to this solution, and at 80 ℃
After soaking for 24 hours, the sample was taken out, the excess solution was removed, and after washing with 500 mL of cyclohexanone, they were arranged so as not to overlap with several large clean metal trays. In this state, the polymer-coated woven fabric sample was dried under reduced pressure at 60 ° C. for 48 hours. Next, after the adhesion rate was calculated as in Example 1, molding was performed as in Example 1.

Test Example The following measurements were carried out on the samples obtained in all Examples and Comparative Examples except Comparative Examples 21 to 23 in which the norbornene-based monomer was hardly polymerized. Density measurement of composite material At room temperature, it was calculated by the buoyancy method from the weight of the composite material piece in air and the weight in methanol. Void fraction

[Equation 4] Void fraction (volume%) = 100 [(theoretical density)-
(Measured density)] Tensile test Based on JIS K 7072, a test piece of a predetermined size was cut out parallel to the fiber direction in the molded product, and a tensile test was performed under predetermined conditions using a strograph (manufactured by Toyo Seiki). The results are shown in Table 1, Table 2 and Table 3.

[0079]

[Table 1] * 1 Various fibers: strong vinylon (density = 1.3 g / cm ³ ), polyarylate (density = 1.41 g / cm ³ ), aramid (density = 1.
45g / cm ³ , ultra high molecular weight polyethylene (ultra high molecular weight PE: density = 0.96g / cm ³ ) * 2 EPR: (HDPE fraction) 70% (molecular weight) 120,000, PE
I: (Molecular weight) 14,000 LLDPE: (Molecular weight) 4,000, PES: (Molecular weight) 24,000, PB:
(Molecular weight) 360,000, PVA: (Saponification degree) 97 mol%, (Polymerization degree) 2,000, PVP: (Polymerization degree) 2,000 Colloidal silica: (Particle size) 10 to 20 mμ, (Property) 20%
Aqueous solution, bentonite: (particle size) 4 to 10μ, carbon black: (particle size) 100 to 300mμ * 3 Solvent, the drying condition of the fiber fabric after solution treatment is 24 hours at 60 ℃, after leaving at room temperature for 24 hours. It is dried under reduced pressure for an hour. Adhesion rate (% by weight) = 100 (weight of treated fiber-weight of untreated fiber) / weight of untreated fiber * 4 Density measurement method: buoyancy method (solvent: methanol), fiber weight fraction: weight of woven fiber fabric And calculated from the weight of the material. Void fraction (volume%) = 100 [(theoretical density)-(measured density)] / (theoretical density), tensile test method: JIS K7073 * 5 Acetone cleaning conditions: various organic fiber fabrics before coating and surface modification At room temperature, soak for 30 minutes, wash

[0080]

[Table 2] * 1 Various fibers: strong vinylon (density = 1.3 g / cm ³ ), polyarylate (density = 1.41 g / cm ³ ), aramid (density = 1.
45g / cm ³ , ultra high molecular weight polyethylene (ultra high molecular weight PE: density = 0.96g / cm ³ ) * 2 EPR: (HDPE fraction) 70% (molecular weight) 120,000, PE
I: (Molecular weight) 14,000 LLDPE: (Molecular weight) 4,000, PES: (Molecular weight) 24,000, PB:
(Molecular weight) 360,000, PVA: (Saponification degree) 97 mol%, (Polymerization degree) 2,000, PVP: (Polymerization degree) 2,000 Colloidal silica: (Particle size) 10 to 20 mμ, (Property) 20%
Aqueous solution, bentonite: (particle size) 4 to 10μ, carbon black: (particle size) 100 to 300mμ * 3 Solvent, the drying condition of the fiber fabric after solution treatment is 24 hours at 60 ℃, after leaving at room temperature for 24 hours. It is dried under reduced pressure for an hour. Adhesion rate (% by weight) = 100 (weight of treated fiber-weight of untreated fiber) / weight of untreated fiber * 4 Density measurement method: buoyancy method (solvent: methanol), fiber weight fraction: weight of woven fiber fabric And calculated from the weight of the material. Void fraction (volume%) = 100 [(theoretical density)-(measured density)] / (theoretical density), tensile test method: JIS K7073 * 5 Acetone cleaning conditions: various organic fiber fabrics before coating and surface modification At room temperature, soak for 30 minutes, wash

[0081]

[Table 3] * 1 Various fibers: strong vinylon (density = 1.3 g / cm ³ ), ultra high molecular weight polyethylene (ultra high molecular weight PE: density = 0.96 g / c
m ³ ) * 2 EPR: (HDPE fraction) 70% (Molecular weight) 120,000, PEI
: (Molecular weight) 14,000 * 3 Drying condition of the fiber fabric after solvent and solution treatment is left at room temperature for 24 hours and then dried under reduced pressure at 60 ° C for 24-48 hours. Adhesion rate (weight%) = 100 (weight of treated fiber-weight of untreated fiber) / weight of untreated fiber * 4 Density measurement method: buoyancy method (solvent: methanol). * 5 Acetone cleaning conditions: Before coating and surface modification, various organic fiber fabrics were immersed and washed at room temperature for 30 minutes. Fiber weight fraction: Calculated from the weight of the charged fiber fabric and the weight of the material. Void fraction (volume%) = 100 [(theoretical density)-(measured density)] / (theoretical density) Tensile test method: JIS K7073 * 6 Methanol cleaning conditions: room temperature, 30 minutes immersion, cleaning * 7 N-methylpyrrolidone Cleaning conditions: 60 ° C, 30 minutes immersion, cleaning

Examples 1 to 20 are high-strength vinylon fiber plain weave (weight per unit area: 180 g / m ² ), ultrahigh molecular weight polyethylene fiber plain weave (weight per unit area: 140 g / m ² ), polyarylate fiber plain weave. (Weight per unit area: 170 g / m ² ) and aramid 4,9 fiber plain weave (weight per unit area: 170 g / m ² ) is a polymer coating method. As the polymer, polypinyl alcohol (abbreviation: PVA, saponification degree: 97 mol%, degree of polymerization: 2000), polyvinylpyrrolidone (abbreviation: PVP, degree of polymerization: 2000), ethylene-propylene rubber (abbreviation: EP)
R, HDPE fraction: 70%, molecular weight: 120,000), linear low density polyethylene (abbreviation: LLDPE, molecular weight: 4000),
Polyetherimide (abbreviation: PEI, molecular weight: 14000)
), Polyether sulfone (abbreviation: PES, molecular weight: 2)
4000) and polybutadiene (abbreviation: PB, molecular weight: 3)
60000). Also, Examples 2, 4, 10, 13, and 14
Then, in addition to the coating polymer, inorganic filler fine particles were added and used in combination to perform the polymer coating treatment. Here, as the inorganic filler fine particles, colloidal silica (particle size: 10 to 20
mμ), bentonite (particle size: 4-10 μm) and carbon black (particle size: 100-300 mμ).

In the polymer coating treatment, the organic polymer was coated with the coating polymer according to the treatment solvent composition and the treatment conditions described in Examples 1 to 14. The polymer solution concentration is
It is less than 15%. Adhesion rate of coating polymer is 0.004 to 6.0
% By weight. Then, the bulk fiber ring-opening polymerization of the norbornene-based monomer was used to obtain an organic fiber composite material. The characteristics of these composite materials are that the coverage of the coating polymer is 0.4 to 2.4% by weight, the density is 1.0 to 1.2 g / cm ³ , the fiber weight fraction is 23 to 53% by weight, and the void fraction is 0 to 0.5% by volume. As an example of mechanical properties, the tensile elastic modulus is 410-1300kg /
It was mm ² , and the tensile strength was 15 to 31 kg / mm ² . Here, it is not possible to directly compare the mechanical properties between various organic fiber materials / polynorbornene-based resin composite materials due to the difference in the fiber weight fraction, but in Comparative Examples 24 to 27, the coating polymer adhesion rate of 0% by weight ( When using untreated fiber), composite density 1.0-1.1, fiber weight fraction 28-44% by weight, void fraction 5.9-15.3% by volume, tensile modulus 330-940 kg / mm ² ,
Since the tensile strength is 12 to 22 kg / mm ² , it can be seen that the polymer coating treatment in Examples 1 to 20 described above reduces the void fraction of the composite material and significantly improves the mechanical properties. This is because the wettability between the norbornene-based monomer and the organic fiber material is improved, the void fraction is reduced, and at the same time polymerization inhibition is eliminated, and the coating polymer layer forms a complex structure with the norbornene-based polymer on the fiber surface. It is believed that this is due to the improvement of the physical adhesiveness at the interface of the fiber material / resin. In particular, Example 2,
4, 10, 13 and 14, by adding an inorganic filler to the coating polymer, depending on the surface properties, layered structure and microporous structure of said filler, said fibrous material /
It is also possible to improve the physical adhesiveness of the resin interface.
On the other hand, as in Comparative Examples 28 and 29, when a solution having a polymer concentration of 17% by weight or more was used and a treatment for excessively increasing the amount of the coating polymer attached was performed, the coating polymer did not form the fiber fabric in a lump form. The uniform coating prevents impregnation of the norbornene-based monomer-containing solution into the fiber fabric, or voids remain in the composite material to increase the void fraction, thereby improving the mechanical properties of the composite material. Spoil. Incidentally, as shown in Comparative Examples 21 to 23, on the surface of the organic fiber woven fabric, when water or an oil agent remains, the bulk ring-opening polymerization of the norbornene-based monomer is inhibited and a composite material cannot be obtained. It was

From the above, in order to obtain an organic fiber material / polynorbornene resin having excellent mechanical properties, the adhesion ratio of the fiber surface coating polymer to the organic fiber material is generally 0.0.
01 to 17% by weight, preferably 0.02 to 7% by weight is desirable.

On the other hand, Examples 15 to 20 are organic fiber materials / polynorbornene-based materials obtained by treating high-strength vinylon fiber plain weave (weight per unit area: 180 g / m ² ) with the low molecular weight compound (fiber surface modifier). It is an example of a resin composite material manufacturing method. here,
Allyl glycidyl ether, glycidyl methacrylate, vinyl norbornene monoepoxide, vinyl cyclohexene monoepoxide, methyl acrylate and allyl isocyanate were used as fiber surface modifiers.

As the method for treating the organic fiber material, the surface modifier was reacted and added to the high-strength vinylon fiber woven fabric according to the treatment solvent composition and treatment conditions shown in Table 2. The adhesion of the surface modifier to the fiber fabric is 0.002 to 3.5% by weight.
Met. Then, the bulk fiber ring-opening polymerization of the norbornene-based monomer was used to obtain an organic fiber composite material. The characteristics of these molded products are a density of about 1.1 g / cm ³ , a fiber weight fraction of 26 to 39% by weight, and a void fraction of 0 to 0.3% by volume. Examples of mechanical properties include tensile modulus of 400 to 610 kg /
mm ² and tensile strength were 14 to 21 kg / mm ² . Again, due to the difference in fiber weight fraction, it is not possible to directly compare the mechanical properties between various organic fiber materials / polynorbornene-based resin composite materials, but the untreated high strength vinylon fiber plain weave / poly In the norbornene-based resin molded product, the surface modifier adhesion rate is 0% by weight (when untreated fiber is used),
The composite material has a density of 1.00 g / cm ³ , a fiber weight fraction of 34.6% by weight, and a void fraction of 10.2% by volume.
Since the tensile modulus of elasticity is 325 kg / mm ² and the tensile strength is 12.4 kg / mm ² , by applying the fiber surface modification treatment to the high-strength vinylon fiber fabric, the wettability between the norbornene-based monomer and the organic fiber material is improved. Thus, it can be seen that the mechanical properties of the composite material are improved as the void fraction is significantly reduced.

However, as in Comparative Example 30, when a treatment for excessively increasing the amount of the surface modifier adhering was performed using a solution having a surface modifier concentration of more than 30% (adhesion rate 10.6%).
In addition, since the surface modifier adheres to the fiber woven fabric in a lump-like manner, the reaction solution containing the norbornene-based monomer may not sufficiently impregnate the fiber woven fabric, or voids may remain in the composite material. , As the void fraction increases,
A brittle layer is formed at the fiber material / resin interface, impairing the mechanical properties of the composite material. Therefore, the adhesion rate of the fiber surface modifier is generally 0.01 to 10% by weight, preferably 0.005 to 5% by weight.

[0088]

As described above, in the present invention, an organic fiber material having a surface that inhibits a ring-opening polymerization reaction of a norbornene-based monomer by a metathesis catalyst system or an organic fiber having poor adhesion to a polynorbornene-based resin By using the material, an organic fiber material / polynorbornene-based resin molded product having excellent mechanical properties can be obtained.

That is, the fiber surface is coated with a fiber surface coating polymer that imparts physical adhesion to the polynorbornene resin, and / or the fiber surface is imparted with chemical adhesion with the polynorbornene resin. By reacting and adding the fiber surface modifier, it is possible to easily produce an organic fiber composite material having excellent mechanical properties or various performances. In addition, by strengthening the adhesiveness at the interface of the organic fiber material / polynorbornene resin,
Since it is possible to prevent material deterioration from the interface, it is possible to obtain a structural resin material excellent in durability, fatigue characteristics or weight reduction.

This composite material is used for sports equipment such as skis, sailboards and canoes, electric parts such as speaker cones, marine transportation parts such as motor boat hulls, automobile parts such as bumpers, bumper beams and instrument cores.
It can be used for a wide range of applications such as construction parts such as soundproof panels.

[Brief description of drawings]

FIG. 1 is a process diagram showing a procedure of a fiber surface coating polymer treatment and a fiber surface modification treatment of an organic fiber according to the present invention.

[Explanation of symbols]

 1 Organic fiber woven fabric 2 Organic solvent 3 Coating solution 4 Surface modifier solution 5 Surface-treated organic fiber

Front page continuation (72) Inventor Jun Kato 2 Takaracho, Kanagawa-ku, Yokohama, Kanagawa Nissan Motor Co., Ltd.

Claims (3)

[Claims] 1. A bulk polymerization of a norbornene-based monomer in the presence of an organic fiber-based material which does not inhibit the metathesis polymerization of the norbornene-based monomer and which is surface-treated with a fiber surface coating polymer and / or a fiber surface modifier, A polynorbornene-based resin molded product having a void fraction of 5% by volume or less. 2. Obtained by surface-treating an organic fiber material with a low concentration fiber surface coating polymer solution of 15% or less,
Polymer attachment rate is 0.001 to 17% by weight, preferably 0.02 to
The polynorbornene-based resin molded article according to claim 1, wherein the organic fiber material is 7% by weight. 3. Obtained by surface-treating an organic fiber material with a low concentration fiber surface modifier solution of 30% by weight or less,
The polynorbornene-based resin molded article according to claim 1, characterized in that an organic fiber material having an adhesion rate of the fiber surface modifier of 0.001 to 10% by weight, preferably 0.005 to 5% by weight is used.