JP6958898B2 - Heat-resistant high-strength film material and its manufacturing method - Google Patents

Description

The present invention relates to a heat-resistant high-strength film material for structures. Specifically, the present invention is a film having an elastomer coated on a cloth made of aromatic heterocyclic polymer fibers and having excellent heat resistance and mechanical properties. The present invention relates to flexible film materials for building structures, which are particularly excellent in heat-resistant bending durability and peeling strength, and flexible film materials for protection and explosion-proof, and their manufacturing methods.

The applicant has previously applied for organic fibers having a melting point of 300 ° C. or higher or a thermal decomposition point as a sheet material having excellent flame retardancy, stain resistance, weather resistance, sewing property, and bending resistance (aromatic polyamide, etc.). ), A flame-retardant silicone resin layer covering at least one surface of the base cloth, and a fluorine-containing resin layer covering the flame-retardant silicone resin (patented). Document 1) was proposed. Further, as a sheet material having excellent flame retardancy and heat resistance, and also having excellent stain resistance and weather resistance, a flame-retardant heat-resistant base cloth made of a flame-retardant heat-resistant organic fiber cloth and a flame-retardant heat-resistant base cloth formed on one surface thereof. We have proposed a flame-retardant heat-resistant sheet material (Patent Document 2) coated with a fluororesin layer and another synthetic resin layer formed on one surface. Both of these flame-retardant sheet materials and flame-retardant heat-resistant sheet materials can be produced by interposing an adhesive layer with an adhesive, but amino groups and iminos as disclosed in Patent Documents 1 and 2 can be produced. Bending of groups, acrylates containing ethyleneimine residues or alkylenediamine residues, acrylates containing azirinidyl groups, aminoester modified vinyl polymers, aromatic epoxy adhesives, aminonitrogen-containing methacrylate polymers, etc., especially in acrylate-based adhesives. Durability may be insufficient, and recently, a heat-resistant sheet material having excellent peel strength at 50 to 80 ° C. has been desired.

Japanese Patent No. 1769010 Japanese Patent No. 2085928

The present invention provides a film material having excellent heat resistance and mechanical physical properties, which is obtained by impregnating and coating a cloth made of aromatic heterocyclic polymer fibers as threads with an elastomer, and in particular, heat-resistant bending durability and 50 to 50 to It is intended to provide flexible membrane materials for building structures and mechanical structures having excellent peeling strength at 80 ° C. Specifically, tent structures, partitions, smoke-proof hanging walls, wall membranes, ceilings. Heat-resistant protective sheets used for building structures such as membranes, factories, energy facilities, etc., and flexible membrane materials suitable for rupture excavation, explosion-proof sheets used at rupture destruction sites, protective sheets, etc., as well as rockets and artificial It is intended to provide a flexible membrane material that can be applied to interior members of satellites, aircraft, motor boats, railway vehicles, automobiles, and the like.

As a result of repeated studies and studies in view of the above-mentioned current situation, the present invention uses a cloth made of an aromatic heterocyclic polymer fiber as a thread and a cloth subjected to a specific organic silane treatment as a base material, at least. In a flexible composite in which an elastomer coating layer is formed on one side, the elastomer coating layer contains reaction residues of a non-aromatic isocyanate compound and inorganic particles, and a crosslinked bond is formed at the interface between the elastomer coating layer and the base material. The present invention has been completed by finding that a film material having heat-resistant bending durability and excellent peeling strength at 50 to 80 ° C. can be obtained.

That is, the heat-resistant high-strength film material of the present invention is a cloth made of an aromatic heterocyclic polymer fiber as a thread, and is made of a cloth surface-treated with aminosilane and / or mercaptosilane as a base material, and at least one surface thereof. A flexible composite having an elastomer coating layer formed therein, wherein the elastomer coating layer contains reaction residues of a non-aromatic isocyanate compound and inorganic particles, and is formed at the interface between the elastomer coating layer and the base material. It is preferably formed by forming a crosslinked bond. As a result, a hydrolyzate (silanol group) of the alkoxy group of aminosilane and / or mercaptosilane is bonded to the surface of the aromatic heterocyclic polymer fiber of the fabric, while the amino group and / or mercapto group is contained in the elastomer coating layer. By reacting with a non-aromatic isocyanate compound to form a crosslinked bond, the interfacial adhesive strength between the aromatic heterocyclic polymer fiber fabric and the elastomer coating layer is improved, and the heat-resistant bending strength is further improved, and the peeling strength is improved. It is possible to obtain a heat-resistant and high-strength film material that is combined.

In the heat-resistant high-strength film material of the present invention, the aromatic heterocyclic polymer fibers are polybenzoimidazole-based, polybenzoxazole-based, polybenzothiazole-based, and copolymer polymers thereof (benzoimidazole-benzoxazole). Selected from the group of polymerization system, benzimidazole-benzothiazole copolymer system, benzoxazole-benzothiazole copolymer system, benzoimidazole-benzoxazole-benzothiazole copolymer system, the above-mentioned copolymer system containing aromatic polyamide component). It is preferable that the number is one or more. This makes it possible to obtain a heat-resistant high-strength film material having more excellent bending strength, tear strength, and breaking strength.

In the heat-resistant high-strength film material of the present invention, the elastomer is selected from the elastomer group of vinyl chloride-based, urethane-based, polyester-based, polyolefin-based, styrene-based copolymer, fluorine-based copolymer, and silicone-based elastomer. It is preferable that the number is one or more. This makes it possible to obtain a heat-resistant high-strength film material having excellent flexibility.

In the heat-resistant high-strength film material of the present invention, the non-aromatic isocyanate compound is hexamethylene diisocyanate [chemical 1], hydrogenated xylylene diisocyanate [chemical 2], isophorone diisocyanate [chemical 3], isocyanurate-modified triisocyanate (isocyanurate-modified triisocyanate). [Chemical 4-Chemical 7], [Chemical 4-Chemical 8], [Chemical 4-Chemical 9]), Bullet-modified triisocyanate ([Chemical 5-Chemical 7], [Chemical 5-Chemical 8], [Chemical 5-Chemical 5] Chemical 9]), trimethylol alkyl-modified triisocyanate ([Chemical 6-Chemical 7], [Chemical 6-Chemical 8], [Chemical 6-Chemical 9]). preferable. By using a non-aromatic isocyanate compound, aminosilane and / or mercaptosilane bind to the fiber surface of the fabric and inorganic particles, and the amino group and / or mercapto group react with the isocyanate compound contained in the elastomer coating layer to crosslink. By forming a bond, the interfacial adhesive force between the aromatic heterocyclic polymer fiber fabric and the elastomer-impregnated coating layer is improved, and it is possible to obtain a heat-resistant high-strength film material having more excellent heat-resistant bending strength.

In the heat-resistant high-strength film material of the present invention, the inorganic particles contain metals (including alloys), metal oxides, metal composite oxides, metal hydroxides, metal carbonates, metal sulfates, glass, silica, and the like. It is preferably at least one selected from zeolites, apatites, and minerals. By using the inorganic particles, a hydrolyzate (silanol group) of the alkoxy group of aminosilane and / or mercaptosilane is bonded to the surface of the inorganic particle, while the amino group and / or mercapto group is an isocyanate compound contained in the elastomer coating layer and. A heat-resistant high-strength film having a higher heat-resistant bending strength by further improving the interfacial adhesive force between the aromatic heterocyclic polymer fiber cloth and the elastomer coating layer by reacting with the fiber surface of the cloth to form a cross-linking bond. It makes it possible to obtain materials.

In the heat-resistant high-strength film material of the present invention, the basic structure of the cloth is plain weave, triaxial weave, triaxial basket weave, 2-5 × 2-5 oblique weave, 3/1 oblique weave (four-sheet twill). 3, 1 tearing plain weave (4 sheets Aya), 3/2 diagonal sentence (5 sheets Aya), 4/1 diagonal sentence (5 sheets Aya), 5/1 diagonal sentence (6 sheets Aya), 4/2 diagonal Sentence (6 sheets Aya), 1/3/1/1 diagonal sentence (6 sheets Aya), 2 jumps 4/1 Akiko (5 sheets Akiko), 3 jumps 4/1 Akiko (5 sheets Akiko), 2 jumps 3 / It is preferable that it is one selected from the group of 2 Akiko (5 sheets Akiko) and 3 jumping 3/2 Akiko (5 sheets Akiko). This makes it possible to obtain a heat-resistant high-strength film material having more excellent bending strength and breaking strength (tear strength).

Heat-resistant and high-strength film material of the present invention, the surface of the elastomers to be covered layer, titanium oxide, titanium peroxide, zinc oxide, tin oxide, strontium titanate, tungsten oxide, bismuth oxide, iron oxide, and these It is preferable that one or more photocatalytic substances selected from the group of doping substances are exposed. This makes it possible to obtain a heat-resistant high-strength film material having excellent self-cleaning antifouling properties.

The method for producing a heat-resistant high-strength film material of the present invention uses a cloth made of aromatic heterocyclic polymer fibers as threads, and in a step of forming an elastomer coating layer on one side or both sides of the cloth, aminosilane is applied to the cloth. And / or when a treatment for fixing mercaptosilane to the entire cloth is performed, and an elastomer composition containing a non-aromatic isocyanate compound and inorganic particles is applied or laminated on the cloth to form an elastomer coating layer. , 1) the non-aromatic isocyanate compound is reacted with the aminosilane and / or the mercaptosilane, and 2) the non-aromatic is formed at the interface between the cloth and the elastomer coating layer by reacting with the inorganic particles. It is preferable to introduce a crosslinked structure containing the reaction residue of the isocyanate compound. As a result, a crosslinked structure containing a reaction residue of a non-aromatic isocyanate compound and a reaction residue of aminosilane and / or mercaptosilane is introduced at the interface between the fabric and the elastomer coating layer, whereby an aromatic heterocyclic polymer is introduced. It is possible to improve the interfacial adhesive force between the fiber cloth and the elastomer coating layer, and to obtain a heat-resistant high-strength film material having more excellent heat-resistant bending strength.

In the method for producing a heat-resistant high-strength film material of the present invention, the aromatic heterocyclic polymer fiber is a polybenzoimidazole-based, a polybenzoxazole-based, a polybenzothiazole-based, and a copolymer polymer (benzoimidazole-) thereof. One or more selected from the group of benzoxazole copolymer system, benzoimidazole-benzothiazole copolymer system, benzoxazole-benzothiazole copolymer system, benzoimidazole-benzoxazole-benzothiazole copolymer system). preferable. This makes it possible to obtain a heat-resistant high-strength film material having more excellent bending strength, tear strength, and breaking strength.

In the method for producing a heat-resistant high-strength film material of the present invention, an elastomer group in which the elastomer is a vinyl chloride-based, urethane-based, polyester-based, polyolefin-based, styrene-based copolymer, fluorine-based copolymer, and silicone-based elastomer. It is preferable that it is one or more selected from. This makes it possible to obtain a heat-resistant high-strength film material having excellent flexibility.

In the method for producing a heat-resistant high-strength film material of the present invention, the non-aromatic isocyanate compound is hexamethylene diisocyanate [chemical 1], hydrogenated xylylene diisocyanate [chemical 2], isophorone diisocyanate [chemical 3], and isocyanurate-modified. Triisocyanate ([Chemical 4-Chemical 7], [Chemical 4-Chemical 8], [Chemical 4-Chemical 9]), Bullet-modified triisocyanate ([Chemical 5-Chemical 7], [Chemical 5-Chemical 8], [Chemical 5-Chemical 8], Chemical 5-Chemical 9]), Trimethylol alkyl-modified triisocyanate ([Chemical formula 6-Chemical formula 7], [Chemical formula 6-Chemical formula 8], [Chemical formula 6-Chemical formula 9]). It is preferable to have. By using a non-aromatic isocyanate compound, aminosilane and / or mercaptosilane binds to the fiber surface of the fabric and inorganic particles, and the amino group and / or mercapto group reacts with the isocyanate compound contained in the elastomer coating layer to form a non-aromatic isocyanate compound. Improves the interfacial adhesion between the aromatic heterocyclic polymer fiber fabric and the elastomer-impregnated coating layer by forming a cross-linked bond containing the reaction residue of the aromatic isocyanate compound and the reaction residue of aminosilane and / or mercaptosilane. This makes it possible to obtain a heat-resistant high-strength film material having more excellent heat-resistant bending strength.

In the method for producing a heat-resistant high-strength film material of the present invention, the inorganic particles contain a metal (including an alloy), a metal oxide, a metal composite oxide, a metal hydroxide, a metal carbonate, a metal sulfate, and glass. , Silica, zeolite, apatite, and one or more selected from minerals are preferable. By using the inorganic particles, a hydrolyzate (silanol group) of the alkoxy group of aminosilane and / or mercaptosilane is bonded to the surface of the inorganic particle, while the amino group and / or mercapto group is an isocyanate compound contained in the elastomer coating layer and. Aromatic heterocyclic polymer fiber fabric and elastomer coating by reacting with the fiber surface of the fabric to form a crosslinked bond containing the reaction residues of the non-aromatic isocyanate compound and the reaction residues of aminosilane and / or mercaptosilane. It is possible to further improve the interfacial adhesive force with the layer and obtain a heat-resistant high-strength film material having more heat-resistant bending strength.

According to the present invention, as a flexible film material formed by coating an elastomer on a cloth made of aromatic heterocyclic polymer fibers as threads, particularly for a building structure having excellent heat-resistant bending durability and peeling strength. And since flexible membrane materials for mechanical structures can be obtained, specifically for tent structures, partitions, smoke-proof hanging walls, wall membranes, ceiling membranes and other building structures, and in factories, energy facilities, etc. It can be applied to heat-resistant protective sheets used, explosion-proof sheets and protective sheets used at rupture excavation and rupture destruction sites, and also to interior members of rockets, artificial satellites, aircraft, motor boats, railway vehicles, automobiles and the like.

The heat-resistant high-strength film material of the present invention is a cloth made of an aromatic heterocyclic elastomer fiber as a thread, and is made of a cloth surface-treated with aminosilane and / or mercaptosilane as a base material, and has at least one surface thereof. A flexible composite in which an elastomer coating layer is formed, the elastomer coating layer containing reaction residues of a non-aromatic isocyanate compound and inorganic particles, and a non-aromatic isocyanate at the interface between the elastomer coating layer and the substrate. It is an embodiment in which a cross-linking including a reaction residue of a compound and a reaction residue of aminosilane and / or mercaptosilane is generated, and a photocatalytic substance is exposed on the surface of an elastomer coating layer, if necessary.

The basic structure of the fabric as the base material used in the present invention is plain weave, triaxial weave, triaxial basket weave, 2-5 × 2-5 diagonal weave (2 × 2, 3 × 3, 4 × 4 and the like. Regular weave, 3x2, 4x2, 4x3, 5x3, 2x3, 2x4, 3x4, 3x5, etc. Irregular weave), 3/1 weave (Four-sheet twill), 3/1 torn weave (four-sheet twill), three-two twill (five-sheet twill), four-one twill (five-sheet twill), five-one-thief (six-sheet twill) 4/2 woven fabric (6 sheets Aya), 1/3/1/1 woven fabric (6 sheets Aya), 2 jumps 4/1 Akiko (5 sheets Akiko), 3 jumps 4/1 Akiko (5 sheets Akiko) One type selected from 2, 2 jumps 3/2 Akiko (5 sheets Akiko), 3 jumps 3/2 Akiko (5 sheets Akiko), the sum of the warp and weft threads and the crossing gap between these threads. A woven fabric with an area ratio of 0 to 30% and a ^{woven fabric of 100 to 500 g / m 2} , a warp yarn group, and a bias yarn group, and a woven fabric having a total area ratio of 0 to 30% of the crossing gap between these yarn groups. It is a triaxial woven fabric of 100 to 750 g / m ^2. As the cloth (woven fabric), one or a plurality of known fiber treatment processes such as scouring, water repellent treatment, water absorption prevention, binder resin fixing, and adhesive application can be used.

The threads constituting the fabric are polybenzoimidazole type, polybenzoxazole type, polybenzothiazole type, and copolymer polymers thereof (benzoimidazole-benzoxazole copolymer type, benzoimidazole-benzothiazole copolymer type, One or more aromatic heterocyclic polymer fibers selected from the group of benzoxazole-benzothiazole copolymerization system, benzimidazole-benzoxazole-benzothiazole copolymerization system, copolymerization system with aromatic polyamide component). Yes, different types can be used for each warp and weft, or for each warp and bias, and different types of fiber threads can be arranged at specific driving intervals. The fabric as the base material used in the present invention is preferably a woven fabric made of drawn multifilament yarn or a short fiber spun fabric (spun), and the drawn multifilament yarn is 250 to 3000 denier (278 to 3333 dtex). ), Especially 500 to 2000 denier (555-2222dtex), 278dtex has 100 to 200 filaments, 1111dtex has 400 to 800 filaments, and if necessary, untwisted yarn (oval or flat cross section). , Or twisted yarn can be used. The short fiber spun yarns range from 10th (591dtex) to 60th (97dtex) cotton counts, especially 10th (591dtex), 14th (422dtex), 16th (370dtex), 20th (295dtex), and so on. These single yarns such as 24 count (246 dtex) and 30 count (197 dtex), or twin yarns (single twisted yarns), and twisted yarns made of two or more single yarns (multi-twisted yarns) are preferable. There is no limit to the driving density of the warp and weft, or the warp and bias yarn of these fabrics (woven fabrics), and any design is possible according to the thickness (denier, count) of the yarn used, but it depends on the yarn group. ^{A fabric having a depth of impact of 100 to 750 g / m 2} and a total area ratio of 0 to 30% of the crossing gap is most suitable as a base material for a high-strength heat-resistant sheet. The total area ratio of the intersection gap can be obtained as a value obtained by subtracting the area of the yarns occupied in the unit area of the fabric as a percentage.

The polybenzoimidazole-based fiber contains a diamine component of an aromatic tetraamine compound (which may be a hydrochloride) and a dicarboxylic acid such as an aromatic dicarboxylic acid, an aromatic dicarboxylic acid ester, an aromatic dicarboxylic acid dihalide, or a heterocyclic dicarboxylic acid. It is a fiber having an imidazole ring and an aromatic ring formed by a polycondensation reaction with an acid derivative to form an amide bond (prepolymer) and then a condensation reaction between an adjacent amino group and an amide bond. .. Polybenzoimidazole-based fibers are fibers that are dry-spun using a polycondensation solvent that produces polybenzoimidazole in a polycondensation solvent such as polyphosphoric acid, phosphorus pentoxide-methanesulfonic acid, and N-methyl-2-pyrrolidone as a spinning solvent. Alternatively, it may be any of the fibers obtained by dry-spinning the prepolymer and then heat-treating it to produce polybenzoimidazole. Specifically, drawn multifilament fibers obtained by dry-spinning polybenzobisimidazole obtained by a polycondensation reaction between 3,3'-diaminobenzidine (tetrachloride) and isophthalic acid diphenyl ester or terephthalic acid diphenyl ester are preferable. Further, a polybenzimidazole-based copolymer fiber containing an aromatic polyamide component obtained by substituting a part of the aromatic tetraamine compound with an aromatic diamine can also be used.

Polybenzoxazole-based fibers include aromatic diaminediols having an amino group and a hydroxyl group on adjacent carbon atoms in the aromatic ring, aromatic dicarboxylic acids, aromatic dicarboxylic acid esters, aromatic dicarboxylic acid dihalides, and heterocyclic fibers. A dicarboxylic acid derivative such as a dicarboxylic acid undergoes a polycondensation reaction to form an amide bond (prepolymer), and then an oxazole ring and an aromatic ring formed by a condensation reaction between an adjacent hydroxyl group and an amide bond are formed in the molecule. A polybenzo obtained by a polycondensation reaction between 3,3'-dihydroxybenzidine (which may be a hydrochloride) or 3,3'-diamino-4,4'-dihydroxybiphenyl and terephthalic acid. Stretched multifilament fibers obtained by dry-spinning bisoxazole are preferable. Polybenzoxazole-based fibers are fibers that are dry-spun using a polycondensation solvent that produces polybenzoxazole in a polycondensation solvent such as polyphosphoric acid, phosphorus pentoxide-methanesulfonic acid, and N-methyl-2-pyrrolidone as a spinning solvent. Alternatively, it may be any fiber obtained by dry-spinning the prepolymer and then heat-treating it to produce polybenzoxazole. Further, a polybenzoxazole-based copolymer fiber containing an aromatic polyamide component obtained by substituting a part of the aromatic diamine diol with an aromatic diamine can also be used.

Polybenzothiazole-based fibers include aromatic diamine dimercapto (aromatic diaminedithiol) having an amino group and a mercapto group on adjacent carbon atoms in the aromatic ring, aromatic dicarboxylic acid, aromatic dicarboxylic acid ester, and aromatic. A thiazole ring formed by a polycondensation reaction with a dicarboxylic acid derivative such as a group dicarboxylic acid dihalide or a heterocyclic dicarboxylic acid to form an amide bond (prepolymer), and then a condensation reaction between an adjacent mercapto group and an amide bond. A fiber having an aromatic ring and an aromatic ring in the molecule, specifically 3,3'-dimercaptobenzidine (which may be a hydrochloride), or 3,3'-diamino-4,4'-dimercaptobiphenyl, and terephthal. A drawn multifilament fiber obtained by dry-spinning polybenzobisthiazole obtained by a polycondensation reaction with an acid is preferable. Polybenzothiazole-based fibers are fibers that are dry-spun using a polybenzothiazole-generated polycondensation solvent in a polycondensation solvent such as polyphosphoric acid, phosphorus pentoxide-methanesulfonic acid, and N-methyl-2-pyrrolidone as a spinning solvent. Alternatively, it may be any fiber obtained by dry-spinning the prepolymer and then heat-treating it to produce polybenzothiazole. Further, a polybenzothiazole-based copolymer fiber containing an aromatic polyamide component obtained by substituting a part of the aromatic diamine dimercapto with an aromatic diamine can also be used.

The aromatic heterocyclic polymer fibers of the benzoimidazole-benzoxazole copolymer system are 3,3'-diaminobenzidine (which may be tetrachloride), 3,3'-dihydroxybenzidine (which may be hydrochloride), and iso. Alternatively, the copolymer fiber obtained by a polycondensation reaction with terephthalic acid diphenyl ester, and the aromatic heterocyclic polymer fiber of the benzoimidazole-benzothiazole copolymer system is 3,3'-diaminobenzidine (may be tetrahydrochloride). ) And 3,3'-dimercaptobenzidine (which may be a hydrochloride) and iso or terephthalic acid diphenyl ester are copolymerized fibers obtained by a polycondensation reaction. The aromatic heterocyclic polymer fibers of the benzoxazole-benzothiazole copolymer system are 3,3'-dihydroxybenzidine (which may be a hydrochloride) and 3,3'-dimercaptobenzidine (which may be a hydrochloride). , A copolymerized fiber obtained by a polycondensation reaction with an iso or terephthalic acid diphenyl ester. The aromatic heterocyclic polymer fibers of the benzimidazole-benzoxazole-benzothiazole copolymer system are 3,3'-diaminobenzidine (may be tetrachloride) and 3,3'-dihydroxybenzidine (may be hydrochloride). ) And 3,3'-dimercaptobenzidine (which may be a hydrochloride) and iso or terephthalic acid diphenyl ester are copolymerized fibers obtained by a polycondensation reaction. These copolymer fibers are fibers obtained by dry spinning using a polycondensation solvent in which a copolymer polymer is generated in a polycondensation solvent such as polyphosphoric acid, phosphorus pentoxide-methanesulfonic acid, and N-methyl-2-pyrrolidone as a spinning solvent. Alternatively, the prepolymer may be a fiber obtained by dry-spinning and then heat-treating to produce a copolymerized polymer. The copolymer fiber may be a copolymer fiber further containing an aromatic polyamide component.

The fabric used in the present invention is preferably one that has been surface-treated with aminosilane and / or mercaptosilane (silane coupling agent), whereby the fabric and elastomer (composition) made of aromatic heterocyclic polymer fibers. It exerts the effect of improving the adhesive force with the coating layer. Specifically, the cloth is treated with aminosilane and / or mercaptosilane to be fixed to the entire cloth, and an elastomer composition containing a non-aromatic isocyanate compound and inorganic particles is coated or laminated on the cloth to form an elastomer coating layer. Upon formation, aminosilane and / or mercaptosilane is reacted with 1) a non-aromatic isocyanate compound and 2) inorganic particles to react with the non-aromatic at the interface between the fabric and the elastomeric coating layer. A crosslinked structure containing the reaction residue of the isocyanate compound and the reaction residue of aminosilane and / or mercaptosilane is introduced, thereby strengthening the adhesive force at the interface between the aromatic heterocyclic polymer fiber cloth and the elastomer coating layer. By doing so, it is possible to obtain a heat-resistant high-strength film material having more excellent bending strength. An example of surface treatment of an aromatic heterocyclic polymer fiber fabric with aminosilane and / or mercaptosilane includes aminosilane and / or mercaptosilane at a concentration of 1 to 10% by mass, and a hydrolyzate of an alkoxy group (silanol group). The aromatic heterocyclic polymer fiber cloth is immersed in the containing aqueous solution, and the entire aromatic heterocyclic polymer fiber cloth is impregnated with the aqueous solution containing a hydrolyzate of an alkoxy group (silanol group), and the aromatic heterocyclic polymer fiber is impregnated. A method in which a hydrolyzate of an alkoxy group (silanol group) is attached to the surface of fibers constituting the cloth is squeezed with a nip roll to remove excess solution, and then heat treatment at 80 to 200 ° C. is performed. The method is not limited to this method.

Specific examples of the aminosilane include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, and 3- (2-aminoethyl) aminopropyltriethoxysilane. , 3- (2-Aminoethyl) Aminopropylmethyldimethoxyxysilane, 3- (2-Aminoethyl) Aminopropylethyldiethoxyxysilane, 3-Phenylaminopropyltrimethoxysilane, 3-Phenylaminopropyltriethoxysilane, 1,2-Ethandiamine N- [3- (trimethoxysilyl) propyl] -N-[(ethenylphenyl) methyl], N-2- (N-vinylbenzylaminoethyl) -3-aminopropyltrimethoxysilane , N-2- (N-vinylbenzylaminoethyl) -3-aminopropyltriethoxysilane, N-2- (N-benzylaminoethyl) -3-aminopropyltrimethoxysilane, N-2- (N-benzyl) Aminoethyl) -3-aminopropyltriethoxysilane and hydrochlorides thereof can be exemplified, but are not particularly limited as long as they are silane compounds having an amino group and a hydrolyzable group.

Specifically, the mercaptosilane is 3-mercaptotrimethoxysilane, 3-mercaptomethyltrimethoxysilane, 3-mercaptomethyltriethoxysilane, triethoxy (2-mercaptoethyl) silane, 3-mercaptopropyltrimethoxysilane, 3-mercapto. Propyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 4-mercaptobutyltrimethoxysilane, 10-mercaptodecyltriethoxysilane, 11-mercaptoundecyltrimethoxysilane, 11-mercapto Examples thereof include undecyltriethoxysilane, but the silane compound is not particularly limited as long as it has a mercapto group and a hydrolyzable group.

The elastomer coating layer shall be formed of one or more elastomers selected from the group of vinyl chloride-based, urethane-based, polyester-based, polyolefin-based, styrene-based copolymers, fluorine-based copolymers, and silicone-based elastomers. Can be done. The elastomer coating layer may be provided on only one side of the fabric or on both sides of the fabric, but the embodiment in which the elastomer coating layer is provided on both sides of the fabric is most preferable. In particular, the elastomer coating layer is preferably in a state in which the entire fabric is impregnated with the elastomer and has a coating layer covering the entire fabric, or a state in which the elastomer is impregnated in the vicinity of the surface of the fabric and has a coating layer covering the entire fabric. The amount of the elastomer coating layer (one side) is preferably ^{100 to 500 g / m 2.} The elastomer coating layer is formed by a) heat-melt laminating of a calendar-rolled molded film or sheet, b) heat-melt laminating of a T-die extrusion film or sheet, and c) coating or dipping of a liquid elastomer solubilized in an organic solvent. And the method by forming a coating film thereof, d) coating or dipping of an emulsified liquid elastomer and the method by forming a coating film thereof, and either c) or d) and either a) or b). The combination can be exemplified.

Examples of the vinyl chloride-based elastomer include soft vinyl chloride resin, vinyl chloride-ethylene copolymer resin, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl ether copolymer resin, vinyl chloride-vinylidene chloride copolymer resin, and the like. Vinyl chloride-maleic acid ester copolymer resin, vinyl chloride- (meth) acrylic acid copolymer resin, vinyl chloride- (meth) acrylic acid ester copolymer resin, vinyl chloride-urethane copolymer resin, etc. Two or more of these resins can be used in combination. A soft vinyl chloride resin-based elastomer is particularly preferable, and the composition is a vinyl chloride resin having a number average molecular weight of P = 700 to 3800 and containing a plasticizer. Plasticizers are phthalic acid dialkyl esters, adipic acid dialkyl esters, sebacic acid dialkyl esters, trimellitic acid dialkyl esters, pyromellitic acid dialkyl esters, polyester-based, phosphoric acid dialkyl esters, citric acid-based, ethylene CO. Examples thereof include plasticizers such as vinyl acetate ester type and ethylene CO acrylic acid ester type. Further, plasticizers such as isophthalic acid dialkyl esters, terephthalic acid dialkyl esters, 1,2-cyclohexanedicarboxylic acid dialkyl esters, and 4-cyclohexene-1,2-dicarboxylic acid dialkyl esters are particularly preferable.

The polyurethane-based elastomer is obtained by an addition polymerization reaction of one or more selected from a diisocyanate compound and a polyol compound having two or more hydroxyl groups in the molecular structure and a compound containing a functional group that reacts with the isocyanate group. The thermoplastic polyurethane resin to be used can be used. As the diisocyanate, aromatic, aliphatic diisocyanate compounds alicyclic (including hydrogenated product) is used, these are for example, tolylene diisocyanate, phenylene diisocyanate, 4,4 ^'- diphenylmethane diisocyanate, 3,3 ^{'- dimethyl-biphenyl-4,4'} - diisocyanate, xylylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, and isophorone diisocyanate. As the polyol compound having two or more hydroxyl groups, those containing an amount that reacts with the diisocyanate compound, for example, polytetramethylene ether glycol, dihydroxypolyethylene adipate, polyethylene glycol, polypropylene glycol and the like are used. As the polyurethane-based elastomer, any type having an ester bond, a type having an ether bond, a type having a carbonate bond, and a type having a caprolactone bond can be used, and these plurality of types may be used in combination.

Examples of the polyester-based elastomer include a block copolymer resin composed of a high melting point crystalline polyester segment (A) and a low melting point polymer segment (B) composed of an aliphatic polyether unit and / or an aliphatic polyester unit. , (A) segment is a polyester obtained by polymerization of dicarboxylic acid and diol, and examples of the dicarboxylic acid component include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, and diphenyl ether dicarboxylic acid. Examples thereof include alicyclic dicarboxylic acids such as acids, cyclohexanedicarboxylic acids and cyclopentanedicarboxylic acids, and aliphatic dicarboxylic acids such as adipic acid, sebacic acid and azelaic acid. Examples of the diol component include aliphatic or alicyclic diols having 2 to 12 carbon atoms, such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol. Can be mentioned. Examples of the aliphatic polyether unit constituting the (B) segment include polyethylene glycol, polypropylene glycol, poly (tetramethylene oxide) glycol, and glycols of copolymers thereof. Examples of the aliphatic polyester unit constituting the (B) segment include polyε-caprolactone, polyenant lactone, polycaprilolactone, polybutylene adipate, and polyethylene adipate.

Examples of the polyolefin-based elastomer include copolymer resins such as ethylene-α-olefin copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene- (meth) acrylic acid (ester) copolymer resin, and ethylene-propylene. Polymers, propylene-α-olefin copolymer resins, propylene / ethylene-propylene copolymers, propylene-ethylene / propylene / non-conjugated diene copolymers and the like. Examples of the styrene-based elastomer include ABA type styrene block copolymer resin (A is a styrene polymer block, B is a butadiene polymer block, an isoprene polymer block, or a vinyl isoprene polymer block), and A-. B-type styrene block copolymer resins (A and B are synonymous with the above), styrene random copolymer resins, hydrogenated resins of these styrene-based copolymer resins (double bonds substituted with hydrogen), and the like. These styrene-based elastomers are preferably used as a polymer alloy in combination with the above-mentioned polyolefin-based elastomers.

Examples of the fluoropolymer elastomer include vinyl fluoride (VF), vinylidene fluoride (VdF), trifluoroethylene (TrEE), tetrafluoroethylene (TFE), chlorotrifluoroethylene (CTFE), and hexafluoropropylene (HFP). ) And the like, obtained by copolymerizing two or more kinds of fluoroolefin monomers, such as VdF-TFE copolymer resin, VdF-CTFE copolymer resin, VdF-HFP copolymer resin, TFE-CTFE copolymer resin, TFE. -HFP copolymer resin, CTFE-HFP copolymer resin, VdF-TFE-CTFE copolymer resin, VdF-TFE-HFP copolymer resin, TFE-CTFE-HFP copolymer resin, VdF-CTFE-HFP It may be a copolymer resin, VdF-TFE-CTFE-HFP copolymer resin, etc., and a multi-polymer in which an ethylene monomer or a propylene monomer is further copolymerized with the above-mentioned copolymer resin, and it may be a fluorine-based copolymer. The polymer elastomer may be a combination of these two or more kinds of copolymer resins.

As the silicone elastomer, silicone elastomers such as addition reaction curing type, condensation reaction curing type, and radical (peroxide crosslinked) reaction curing type can be used, and in particular, addition that can be diluted with toluene or the like for coating and can be cured at low temperature. The reaction curing type is preferable. In the addition reaction curing type, functional groups in two types of organopolysiloxanes are bonded by an addition reaction to crosslink and form an elastomer, and these contain an aliphatic unsaturated group such as a vinyl group or a hexenyl group. Examples thereof include a composition comprising an organopolysiloxane, an organohydrogenpolysiloxane, and a platinum group compound-based catalyst. Examples of the aliphatic unsaturated group-containing organopolysiloxane include both-terminal vinyl dimethylsiloxy group-blocking dimethylpolysiloxane, both-terminal vinyl dimethylsiloxy group-blocking dimethylsiloxane / methylvinylsiloxane copolymer, and both-terminal vinylmethylphenylsiloxy group-blocking dimethylsiloxane. -Methylphenylsiloxane copolymer can be mentioned. Organohydrogenpolysiloxane includes both-terminal trimethylsiloxy group-blocked methylhydrogenpolysiloxane, both-terminal trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, and both-terminal dimethylhydrogensiloxy group-blocked dimethylsiloxane / methylhydro. Examples thereof include gensiloxane copolymer and methylhydrogencyclopolysiloxane. The condensation reaction curing type is a type in which functional groups in two types of organopolysiloxanes or functional groups in an organopolysiloxane and a silicon compound such as silica or silane are bonded and crosslinked by a condensation reaction to form an elastomer, or radical reaction curing. The mold is elastomerized with organopolysiloxane, reinforcing filler and organic peroxide.

The coating layer made of the elastomer includes metals (including alloys), metal oxides, metal composite oxides, metal hydroxides, metal carbonates, metal sulfates, glass, silica, mica, zeolites, apatites, and minerals. It is preferable that one or more kinds of inorganic particles selected from the above are contained in an amount of 1 to 25% by mass, particularly 3 to 10% by mass, based on the mass of the elastomer coating layer. Examples of the metal include powders of aluminum, stainless steel, nickel, stainless steel, duralumin, brass and the like. Examples of the metal oxide include titanium oxide, tin oxide, zinc oxide, zirconium oxide, tungsten oxide, antimony trioxide, and molybdenum oxide. The metal composite oxide is a rutile-type composite particle or a spinel-type composite particle obtained by firing a plurality of metal oxides at a high temperature. Examples of the metal hydroxide include aluminum hydroxide and magnesium hydroxide, examples of the metal carbonate include calcium carbonate, barium carbonate and lithium carbonate, and examples of the metal sulfate include barium sulfate and magnesium sulfate. Examples of glass include glass powder, glass beads, hollow glass beads, and examples of minerals include mica and montmorillonite. The average particle size of these inorganic particles is preferably 0.1 μm to 20 μm. Further, on the coating layer made of the above elastomer, if necessary, pigments (organic pigments / inorganic pigments), flame retardants, stabilizers, lubricants, antistatic agents, surfactants, water repellents, oil repellents, cross-linking agents, etc. Any amount of known additives such as hardeners, fillers, foaming agents, ultraviolet absorbers, antioxidants, fungicides, and antibacterial agents can be blended.

Non-aromatic isocyanate compounds include hexamethylene diisocyanate [Chemical formula 1], isocyanurate-modified triisocyanate ([Chemical formula 4-Chemical formula 7], [Chemical formula 4-Chemical formula 8], [Chemical formula 4-Chemical formula 9]), and bullet-modified triisocyanate. ([Chemical 5-Chemical 7], [Chemical 5-Chemical 8], [Chemical 5-Chemical 9]), Trimethylol alkyl-modified triisocyanate ([Chemical formula 6-Chemical 7], [Chemical formula 6-Chemical formula 8], [Chemical formula 6-Chemical formula 8], [Chemical formula 6-Chemical formula 7], [Chemical formula 6-Chemical formula 8], [Chemical formula 6-Chemical formula 7] It is preferable that one or more selected from the 12 types of Ka 6-Ka 9]) is contained in an amount of 1 to 20 parts by mass, particularly 3 to 10 parts by mass, based on 100 parts by mass of the elastomer. Thereby, by reacting aminosilane and / or mercaptosilane with 1) a non-aromatic isocyanate compound, and 2) reacting with inorganic particles, the non-aromatic isocyanate compound is formed at the interface between the fabric and the elastomer coating layer. Introduce a crosslinked structure containing the reaction residue of aminosilane and / or the reaction residue of mercaptosilane, thereby strengthening the adhesive force at the interface between the aromatic heterocyclic polymer fiber fabric and the elastomer coating layer. Therefore, a heat-resistant high-strength film material having more excellent bending strength can be obtained. In the heat-resistant high-strength film material of the present invention, even if an isocyanate compound having an aromatic ring in its chemical structure is used, the same adhesive effect can be obtained at the interface between the aromatic heterocyclic polymer fiber cloth and the elastomer coating layer. However, when used outdoors, the elastomer coating layer may turn yellow or even brown due to the influence of ultraviolet rays in less than a year, resulting in a poor appearance.

Further, as one of the aspects of the heat-resistant high-strength film material of the present invention, titanium oxide, titanium peroxide, zinc oxide, tin oxide, strontium titanate, tungsten oxide, bismuth oxide, and iron oxide are formed on the surface of the elastomer coating layer. , And a heat-resistant high-strength film material that can have an antifouling layer to which one or more photocatalytic substances selected from these doping substances are exposed is preferable because it is accompanied by self-cleaning antifouling property. As the photocatalytic substance, titanium oxide, titanium oxide sol, and anatase-type peroxotitanic acid are preferable, and these titanium oxides can be any of anatase-type, rutile-type, and brookite-type, but hydrochloric acid-defoliing-type anatase-type titaniasol and nitrate solution. Glue-type anatase-type titania sol is preferable. In addition, a photocatalytic activity control type in which the surface of titanium oxide particles is partially coated with an inorganic compound such as silica, zirconium phosphate, calcium phosphate, calcium zinc phosphate, hydroxyapatite, silica alumina, calcium silicate, magnesium silicate, etc. It may be a titanium oxide composite particle. Further, it is preferable that the antifouling layer made of the photocatalytic substance has cerium oxide particles in order to prevent ultraviolet deterioration of the elastomer coating layer. Further, it is preferable to contain a surfactant as an antistatic agent, and particularly preferably to contain composite particles in which the surfactant is supported on inorganic porous fine particles such as silica, zeolite, and diatomaceous earth.

As long as the photocatalytic substance is exposed on the surface of the elastomer coating layer, the photocatalytic substance may be unevenly distributed only in the vicinity of the surface of the elastomer coating layer, or may be uniformly dispersed over the entire elastomer coating layer. The former is to form a photocatalytic substance-containing thin film by applying a coating solution containing a photocatalytic substance to the surface of an elastomer coating layer, for example, a coating agent containing particles or sol of a photocatalytic substance and a binder. Examples include coating and a sol-gel method from a solution of a photocatalytic substance. Examples of the binder include binders such as fluorine-based resin, silicone-based resin, acrylic fluorine copolymer resin, and acrylic silicone copolymer resin, polysilazane, organic silicate compounds, or hydrolyzate of a low condensate thereof (silanol group-containing silane compound). ) And the like, which can include silica sol, alumina sol, titanium sol and the like. The photocatalytic substance-containing thin film preferably contains 20 to 60% by mass of particles or sol of the photocatalytic substance. The latter can be formed by blending 5 to 30% by mass of a photocatalytic substance in an elastomer composition for forming an elastomer-impregnated coating layer.

Next, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to the scope of these examples. In the following Examples and Comparative Examples, the evaluation of the kneading bending strength of the heat-resistant high-strength film material is performed by the following test method.
Bending strength at room temperature (JIS L1096.8.19 B method)
The test film material piece was attached at a load of 500 gf in an atmosphere of 25 ° C., kneaded 500 times and 1000 times for heat-resistant bending, and the appearance of the film material was observed. Was judged.
1: No change in appearance
2: The elastomer coating layer is slightly peeled off or partially peeled off from the fabric.
3: The elastomer coating layer is conspicuously peeled off or partially peeled off from the fabric.
4: Elastomer coating layer falls off from the fabric (including partial peeling and falling off)
Bending strength in an atmosphere of 80 ° C (JIS L1096.8.19 B method)
The test film material piece was attached at a load of 500 gf in an atmosphere of 80 ° C., kneaded 500 times and 1000 times for heat-resistant bending, and the appearance of the film material was observed. Was judged.
1: No change in appearance
2: The elastomer coating layer is slightly peeled off or partially peeled off from the fabric.
3: The elastomer coating layer is conspicuously peeled off or partially peeled off from the fabric.
4: Elastomer coating layer falls off from the fabric (including partial peeling and falling off)
Evaluation of Light Resistance The obtained sheet was accelerated with a JIS K5600 xenon weather meter (black panel temperature 63 ° C.) for 500 hours, and the color difference ΔE value (JIS Z-8729) from the initial (blank) was evaluated. An optical color difference meter (JP7200F) manufactured by JUKI Co., Ltd. was used for the color difference measurement.

[Example 1]
1) Treatment of silane coupling agent on fabrics Warp and weft of stretched multifilament fiber threads (1100dtex: number of filaments 664) of polybenzoxazole dry-spun from a polycondensate of 4,6-diaminoresorcinol and terephthalic acid. Cloth (1): Warp thread driving density 20 lines / 2.54 cm × Weft thread driving density 20 lines / 2.54 cm: Plain woven fabric with 0% void ratio: Weight 225 g / m ² as a silane coupling agent (aminosilane) , 3-Aminopropyltriethoxysilane is contained in a concentration of 10% by mass, the cloth is immersed in a normal temperature aqueous solution containing this hydrolyzate, and the entire cloth is impregnated with an aqueous solution containing a hydrolyzate of aminosilane to form a cloth. A cloth having an aminosilane hydrolyzate attached to the fiber surface (having an amino group and a silanol group) is squeezed with a nip roll to remove excess solution, and then dried with hot air at 100 ° C. for 3 minutes to cover the entire cloth with aminosilane. A treated adhesive-treated cloth (1) was obtained.
2) Formation of Elastomer Coating Layer As the base material of this adhesive-treated fabric (1), the composition (1) for forming the elastomer coating layer of the following [Formulation 1] is clearance-coated on both sides thereof, and this is applied at 180 ° C. for 2 minutes. To form an elastomer-impregnated coating layer having a thickness of 0.2 mm, a film material having ^{a thickness of 0.56 mm and a mass of 565 g / m 2 was obtained.} At this time, the silanol groups (hydrogenates of alkoxy groups) on the surface of the adhesive-treated cloth (1) are reacted with the inorganic particles (silica, antimony trioxide, titanium oxide) contained in the elastomer-impregnated coating layer, and at the same time, the elastomer-impregnated coating is applied. The non-aromatic isocyanate compound ([Chemical Formula 4]-[Chemical Formula 7]) contained in the layer is reacted with the amino group on the surface of the adhesive treated fabric (1), and the interface between the adhesive treated fabric (1) and the elastomer coating layer. A cross-linked adhesion containing a non-aromatic isocyanate compound residue and an aminosilane residue was formed.
[Formulation 1] Composition for forming an elastomer coating layer (1)
Vinyl chloride resin (degree of polymerization 1300) 100 parts by mass 4-cyclohexene-1,2-dicarboxylic acid bis (2-ethylhexyl)
60 parts by mass epoxidized soybean oil (plasticizer) 10 parts by mass zinc stearate (stabilizer) 2 parts by mass barium stearate (stabilizer) 2 parts by mass benzotriazole compound (ultraviolet absorber) 0.1 parts by mass silica ( (Inorganic particles) 10 parts by mass Antimon trioxide (inorganic particles) 10 parts by mass Titanium oxide (inorganic particles, white pigment) 5 parts by mass Non-aromatic isocyanate compound ([Chemical formula 4]-[Chemical formula 7]) 5 parts by mass
3) Formation of light-resistant antifouling antistatic layer A coating film is formed by the composition of [Formulation 2] by 80 mesh gravure roll transfer on the elastomer-impregnated coating layer (the surface side of the film material), and the temperature is 120 ° C. A film material having ^{a mass of 566 g / m 2} was obtained by drying in a hot air oven for 3 minutes to provide a light-resistant antifouling antistatic layer.
[Formulation 2] Light-resistant, antifouling, antistatic layer composition Nitrate-glutinous titanium oxide sol (particle size 20 to 30 nm) 50 parts by mass Silica sol (particle size 20 to 30 nm) 50 parts by mass Vinyl triethoxysilane (silane coupling agent) 20 Parts by mass Cerium oxide particles (particle size 15 nm: ultraviolet absorber) 5 parts by mass Polyethylene glycol type nonionic activator (antistatic agent) 1 part by mass Gel method silica (BET specific surface area 380 m ² / g) 5 parts by mass * Gel method Silica carries a polyethylene glycol type non-ionic activator 300 parts by mass of diluent (water)

[Example 2]
The fabric (1) of Example 1 was dry-spun from a polycondensate of 3,3'-diaminobenzidine and isophthalic acid diphenyl ester, and stretched multifilament fiber threads (1100 dtex: number of filaments 664) of polybenzoimidazole were applied. Cloth to be used as warp and weft (2): Warp driving density 20 / 2.54 cm × Weft driving density 20 / 2.54 cm: Plain woven fabric with 0% void ratio: Weight 235 g / m ² Similar to Example 1 except that the composition for forming an elastomer coating layer (1) of [1] was changed to the composition for forming an elastomer coating layer (2) of [Formulation 1], the thickness was 0.56 mm and the mass was 0.56 mm. A film material of 575 g / m ² (having a light-resistant antifouling antistatic layer) was obtained.
[Formulation 1] Composition for forming an elastomer coating layer (2)
Vinyl chloride resin (degree of polymerization 1300) 100 parts by mass 4-cyclohexene-1,2-dicarboxylic acid bis (2-ethylhexyl)
60 parts by mass epoxidized soybean oil (plasticizer) 10 parts by mass zinc stearate (stabilizer) 2 parts by mass barium stearate (stabilizer) 2 parts by mass benzotriazole compound (ultraviolet absorber) 0.1 parts by mass silica ( (Inorganic particles) 10 parts by mass Antimon trioxide (inorganic particles) 10 parts by mass Titanium oxide (inorganic particles, white pigment) 5 parts by mass Non-aromatic isocyanate compound ([Chemical formula 4]-[Chemical formula 8]) 5 parts by mass

[Example 3]
The fabric (1) of Example 1 was dry-spun polybenzothiazole from a polycondensate of 3,3'-dimercaptobenzidine and terephthalic acid, and stretched multifilament fiber threads (1100 dtex: number of filaments 664) were applied. Cloth to be used as warp and weft (3): Warp driving density 20 / 2.54 cm × Weft driving density 20 / 2.54 cm: Plain woven fabric with 0% void ratio: Weight 228 g / m ² Similar to Example 1 except that the composition for forming an elastomer coating layer (1) of [1] was changed to the composition for forming an elastomer coating layer (3) of [Formulation 1], the thickness was 0.56 mm and the mass was 0.56 mm. A film material of 568 g / m ² (having a light-resistant antifouling antistatic layer) was obtained.
[Formulation 1] Composition for forming an elastomer coating layer (3)
Vinyl chloride resin (degree of polymerization 1300) 100 parts by mass 4-cyclohexene-1,2-dicarboxylic acid bis (2-ethylhexyl)
60 parts by mass epoxidized soybean oil (plasticizer) 10 parts by mass zinc stearate (stabilizer) 2 parts by mass barium stearate (stabilizer) 2 parts by mass benzotriazole compound (ultraviolet absorber) 0.1 parts by mass silica ( (Inorganic particles) 10 parts by mass Antimon trioxide (inorganic particles) 10 parts by mass Titanium oxide (inorganic particles, white pigment) 5 parts by mass Non-aromatic isocyanate compound ([Chemical formula 4]-[Chemical formula 9]) 5 parts by mass

[Example 4]
The thickness is the same as that of Example 1 except that the elastomer coating layer forming composition (1) of [Formulation 1] of Example 1 is changed to the elastomer coating layer forming composition (1) of [Formulation 3]. A film material (having a light-resistant antifouling antistatic layer) having a mass of 0.56 mm and a mass of 544 g / m ^{2 was obtained.}
[Formulation 3] Composition for forming an elastomer coating layer (1)
* Addition reaction curable silicone elastomer (use the following two liquids)
Both-terminal vinyl dimethylsiloxy group-blocked dimethylpolysiloxane 50 parts by mass Both-terminal trimethylsiloxy group-blocked methylhydrogenpolysiloxane 50 parts by mass Platinum group compound (catalyst) 0.2 parts by mass Non-aromatic isocyanate compound ([Chemical formula 5]-[ 7]) 5 parts by mass silica (inorganic particles) 10 parts by mass titanium oxide (inorganic particles, white pigment) 5 parts by mass toluene (diluting agent) 100 parts by mass

[Example 5]
The thickness is the same as that of Example 1 except that the elastomer coating layer forming composition (1) of [Formulation 1] of Example 1 is changed to the elastomer coating layer forming composition (2) of [Formulation 3]. A film material (having a light-resistant antifouling antistatic layer) having a mass of 0.56 mm and a mass of 551 g / m ^{2 was obtained.}
[Formulation 3] Composition for forming an elastomer coating layer (2)
* Addition reaction curable silicone elastomer (use the following two liquids)
Both-terminal vinyl dimethylsiloxy group-blocked dimethylpolysiloxane 50 parts by mass Both-terminal trimethylsiloxy group-blocked methylhydrogenpolysiloxane 50 parts by mass Platinum group compound (catalyst) 0.2 parts by mass Non-aromatic isocyanate compound ([Chemical formula 5]-[ 8]) 5 parts by mass silica (inorganic particles) 10 parts by mass titanium oxide (inorganic particles, white pigment) 5 parts by mass toluene (diluting agent) 100 parts by mass

[Example 6]
The thickness is the same as that of Example 1 except that the elastomer coating layer forming composition (1) of [Formulation 1] of Example 1 is changed to the elastomer coating layer forming composition (3) of [Formulation 3]. A film material (having a light-resistant antifouling antistatic layer) having a mass of 0.56 mm and a mass of 555 g / m ^{2 was obtained.}
[Formulation 3] Composition for forming an elastomer coating layer (3)
* Addition reaction curable silicone elastomer (use the following two liquids)
Both-terminal vinyl dimethylsiloxy group-blocked dimethylpolysiloxane 50 parts by mass Both-terminal trimethylsiloxy group-blocked methylhydrogenpolysiloxane 50 parts by mass Platinum group compound (catalyst) 0.2 parts by mass Non-aromatic isocyanate compound ([Chemical formula 5]-[ 9]) 5 parts by mass silica (inorganic particles) 10 parts by mass titanium oxide (inorganic particles, white pigment) 5 parts by mass toluene (diluting agent) 100 parts by mass

[Example 7]
The silane coupling agent treatment of the fabric (1) of Example 1 was changed to 3-mercaptomethyltrimethoxysilane, and the composition (1) for forming an elastomer coating layer of [Formulation 1] of Example 1 was [blended. 4] Similar to Example 1 except that the composition (1) for forming an elastomer coating layer is changed, a ^{film material having a thickness of 0.56 mm and a mass of 566 g / m 2} (having a light-resistant antifouling antistatic layer). ) Was obtained.
Treatment of silane coupling agent on fabrics A stretched multifilament fiber yarn (1100dtex: number of filaments 664) of polybenzobisoxazole dry-spun from a polycondensate of 4,6-diaminoresorcinol and terephthalic acid is used as a warp and a weft. Cloth (1): Warp thread driving density 20 lines / 2.54 cm × Weft thread driving density 20 lines / 2.54 cm: Plain woven fabric with 0% void ratio: Weight 225 g / m ² as a silane coupling agent (aminosilane) The fabric is immersed in a normal temperature aqueous solution containing 3-mercaptomethyltrimethoxysilane at a concentration of 10% by mass, and the entire fabric is impregnated with the aqueous solution containing the hydrolyzate of mercaptosilane to form the fabric. A cloth having a mercaptosilane hydrolyzate attached to the fiber surface (having a mercapto group and a silanol group) is squeezed with a nip roll to remove excess solution, and then dried with hot air at 100 ° C. for 3 minutes to cover the entire cloth. An adhesive-treated cloth (4) subjected to a mercaptosilane treatment was obtained.
[Formulation 4] Composition for forming an elastomer coating layer (1)
Vinyl chloride resin (degree of polymerization 1300) 100 parts by mass 4-cyclohexene-1,2-dicarboxylic acid bis (2-ethylhexyl)
60 parts by mass epoxidized soybean oil (plasticizer) 10 parts by mass zinc stearate (stabilizer) 2 parts by mass barium stearate (stabilizer) 2 parts by mass benzotriazole compound (ultraviolet absorber) 0.1 parts by mass silica ( (Inorganic particles) 10 parts by mass Antimon trioxide (inorganic particles) 10 parts by mass Titanium oxide (inorganic particles, white pigment) 5 parts by mass Non-aromatic isocyanate compound ([Chemical formula 6]-[Chemical formula 7]) 5 parts by mass

[Example 8]
The silane coupling agent treatment of the fabric (2) of Example 2 was changed to 3-mercaptomethyltrimethoxysilane (the same procedure as in Example 7), and the entire fabric was subjected to the mercaptosilane treatment (5). ) Was used, and the same as in Example 2 except that the elastomer coating layer forming composition (2) of [Formulation 1] of Example 2 was changed to the elastomer coating layer forming composition (2) of [Formulation 4]. A film material having a thickness of 0.56 mm and a mass of 575 g / m ² (having a light-resistant antifouling antistatic layer) was obtained.
[Formulation 4] Composition for forming an elastomer coating layer (2)
Vinyl chloride resin (degree of polymerization 1300) 100 parts by mass 4-cyclohexene-1,2-dicarboxylic acid bis (2-ethylhexyl)
60 parts by mass epoxidized soybean oil (plasticizer) 10 parts by mass zinc stearate (stabilizer) 2 parts by mass barium stearate (stabilizer) 2 parts by mass benzotriazole compound (ultraviolet absorber) 0.1 parts by mass silica ( (Inorganic particles) 10 parts by mass Antimon trioxide (inorganic particles) 10 parts by mass Titanium oxide (inorganic particles, white pigment) 5 parts by mass Non-aromatic isocyanate compound ([Chemical formula 6]-[Chemical formula 8]) 5 parts by mass

[Example 9]
The silane coupling agent treatment of the cloth (3) of Example 3 was changed to 3-mercaptomethyltrimethoxysilane (the same procedure as in Example 7), and the entire cloth was subjected to the mercaptosilane treatment of the adhesive-treated cloth (6). ) Was used, and the same as in Example 3 except that the elastomer coating layer forming composition (3) of [Formulation 1] of Example 3 was changed to the elastomer coating layer forming composition (3) of [Formulation 4]. A film material having a thickness of 0.56 mm and a mass of 568 g / m ² (having a light-resistant antifouling antistatic layer) was obtained.
[Formulation 4] Composition for forming an elastomer coating layer (3)
Vinyl chloride resin (degree of polymerization 1300) 100 parts by mass 4-cyclohexene-1,2-dicarboxylic acid bis (2-ethylhexyl)
60 parts by mass epoxidized soybean oil (plasticizer) 10 parts by mass zinc stearate (stabilizer) 2 parts by mass barium stearate (stabilizer) 2 parts by mass benzotriazole compound (ultraviolet absorber) 0.1 parts by mass silica ( (Inorganic particles) 10 parts by mass Antimon trioxide (inorganic particles) 10 parts by mass Titanium oxide (inorganic particles, white pigment) 5 parts by mass Non-aromatic isocyanate compound ([Chemical formula 6]-[Chemical formula 9]) 5 parts by mass

[Comparative Example 1]
The silane coupling treatment is omitted from the cloth (1) used in Example 1, and an untreated cloth (consisting of polybenzoxazole fiber threads) is used, and further, for forming the [Compound 1] elastomer coating layer of Example 1. Similar to Example 1 except that 5 parts by mass of the non-aromatic isocyanate compound ([Chemical Formula 4]-[Chemical Formula 7]) was omitted from the composition (1), the thickness was 0.56 mm and the mass was 560 g / m ² . A film material was obtained. The flexibility of the obtained film material is inferior to that of the film material of Example 1 at room temperature and in an atmosphere of 80 ° C., and the elastomer layer is completely peeled off and separated in 500 bending tests. rice field.

[Comparative Example 2]
The same as in Example 1 except that the silane coupling treatment was omitted from the cloth (1) used in Example 1 and an untreated cloth (consisting of polybenzoxazole fiber threads) was used, the thickness was 0.56 mm. , A film material having a mass of 560 g / m ^{2 was obtained.} The obtained film material was inferior in flexibility in an atmosphere of 80 ° C. as compared with the film material of Example 1, and the elastomer layer was partially peeled off in 1000 times of bending tests.

[Comparative Example 3]
The same as in Example 1 except that 5 parts by mass of the non-aromatic isocyanate compound ([Chemical Formula 4]-[Chemical Formula 7]) was omitted from the [Formulation 1] Elastomer Coating Layer Forming Composition (1) of Example 1. A film material having a thickness of 0.56 mm and a mass of 560 g / m ^{2 was obtained.} The flexibility of the obtained film material is inferior to that of the film material of Example 1 at room temperature and in an atmosphere of 80 ° C., and the elastomer layer is completely peeled off and separated in 1000 times of bending tests. rice field.

[Comparative Example 4]
Silica (10 parts by mass), antimony trioxide (10 parts by mass) and titanium oxide (5 parts by mass) were omitted from the composition (1) for forming the elastomer coating layer of Example 1 and contained inorganic particles. A film material having a thickness of 0.56 mm and a mass of 535 g / m ² was obtained in the same manner as in Example 1 except that the composition was not set. The flexibility of the obtained film material was inferior to that of the film material of Example 1 in an atmosphere of 80 ° C., and the elastomer layer was partially peeled off in a bending test of 500 times.

[Comparative Example 5]
^{A film material having a thickness of 0.56 mm and a mass of 560 g / m 2} was obtained in the same manner as in Example 1 except that the silane coupling agent treatment of the fabric (1) of Example 1 was completely changed to vinyltriethoxysilane. rice field. The flexibility of the obtained film material was inferior to that of the film material of Example 1 in an atmosphere of 80 ° C., and the elastomer layer was partially peeled off in a bending test of 500 times.

[Comparative Example 6]
5 parts by mass of the non-aromatic isocyanate compound ([Chemical formula 4]-[Chemical formula 7]) of the [Formulation 1] elastomer coating layer forming composition (1) of Example 1 was added to the aromatic isocyanate compound ([Chemical formula 10] *. ^{A film material having a thickness of 0.56 mm and a mass of 560 g / m 2} was obtained in the same manner as in Example 1 except that it was changed to 5 parts by mass of isocyanurate-modified triisocyanate, which is a trimeric of tolylene diisocyanate. The flexibility of the obtained film material was at the same level as that of the film material of Example 1 even at room temperature and in an atmosphere of 80 ° C. It was something to do.

As is clear from the above Examples and Comparative Examples, according to the present invention, as a flexible film material obtained by coating a fabric made of aromatic heterocyclic polymer fibers with an elastomer, particularly heat-resistant bending. Since flexible membrane materials for building structures and mechanical structures with excellent durability and peeling strength at 50 to 80 ° C can be obtained, specifically, tent structures, partitions, smoke-proof hanging walls, etc. Heat-resistant protective sheets used for building structures such as wall membranes and ceiling membranes, factories, energy facilities, etc., and explosion-proof sheets and protective sheets used at rupture excavation and rupture destruction sites, as well as rockets, artificial satellites, aircraft , Motor boats, railroad vehicles, automobiles, and other interior components.

Claims (12)

A flexible composite in which an elastomer coating layer is formed on at least one surface of a cloth made of aromatic heterocyclic polymer fibers and which has been surface-treated with aminosilane and / or mercaptosilane as a base material. The body is characterized in that the elastomer coating layer contains reaction residues of a non-aromatic isocyanate compound and inorganic particles, and a crosslinked bond is formed at the interface between the elastomer coating layer and the substrate. Heat resistant high strength film material. The aromatic heterocyclic polymer fibers are polybenzoimidazole type, polybenzoxazole type, polybenzothiazole type, and copolymer polymers thereof (benzoimidazole-benzoxazole copolymer type, benzoimidazole-benzothiazole copolymer type). , Benzoxazole-benzothiazole copolymerization system, benzimidazole-benzoxazole-benzothiazole copolymerization system, the above-mentioned copolymerization system containing an aromatic polyamide component), which is one or more selected from the group according to claim 1. Heat resistant high strength film material. Claim 1 or 2 in which the elastomer is at least one selected from the elastomer group of vinyl chloride-based, urethane-based, polyester-based, polyolefin-based, styrene-based copolymer, fluorine-based copolymer, and silicone-based. The heat-resistant high-strength film material described in. The non-aromatic isocyanate compound is hexamethylene diisocyanate [Chemical formula 1], hydrogenated xylylene diisocyanate [Chemical formula 2], isophorone diisocyanate [Chemical formula 3], isocyanurate-modified triisocyanate [Chemical formula 4-Chemical formula 7], [Chemical formula 4]. -Chemical 8], [Chemical 4-Chemical 9]), Bullet-modified triisocyanate ([Chemical 5-Chemical 7], [Chemical 5-Chemical 8], [Chemical 5-Chemical 9]), Trimethylol alkyl-modified triisocyanate ([Chemical 6-Chemical 7], [Chemical formula 6-Chemical formula 8], [Chemical formula 6-Chemical formula 9]). Heat resistant high strength film material.

The inorganic particles were selected from metals (including alloys), metal oxides, metal composite oxides, metal hydroxides, metal carbonates, metal sulfates, glass, silica, zeolites, apatites, and minerals. The heat-resistant high-strength film material according to any one of claims 1 to 4, which is more than a kind. The basic structure of the fabric is plain weave, triaxial weave, triaxial basket weave, 2-5 x 2-5 diagonal weave, 3/1 diagonal weave (four-sheet twill), and three-one tearing oblique pattern (four-sheet twill). ), 3/2 weave (five Aya), 4/1 twill (five Aya), 5/1 twill (six twill), 4/2 twill (six twill), 1.3 / 1.1 Weave (6 pieces Aya), 2 jumps 4/1 Akiko (5 sheets Akiko), 3 jumps 4/1 Akiko (5 sheets Akiko), 2 jumps 3/2 Akiko (5 sheets Akiko), and 3 jumps The heat-resistant high-strength film material according to any one of claims 1 to 5, which is one kind selected from the group of 3/2 Akiko (five sheets Akiko). The elastomers surface of the covering layer, titanium oxide, titanium peroxide, zinc oxide, tin oxide, strontium titanate, tungsten oxide, bismuth oxide, iron oxide, and one selected from the group of these doping substances, The heat-resistant high-strength film material according to any one of claims 1 to 6, wherein the above photocatalytic substance is exposed. In the step of forming an elastomer coating layer on one side or both sides of the fabric using an aromatic heterocyclic polymer fiber as a thread, a treatment of fixing aminosilane and / or mercaptosilane to the entire fabric is performed. When an elastomer composition containing a non-aromatic isocyanate compound and inorganic particles is applied or laminated on this fabric to form an elastomer coating layer, the aminosilane and / or the mercaptosilane and 1) the non-elastomer are used. By reacting with an aromatic isocyanate compound and 2) reacting with the inorganic particles, a crosslinked structure containing a reaction residue of the non-aromatic isocyanate compound is introduced at the interface between the fabric and the elastomer coating layer. A method for producing a heat-resistant high-strength film material. The aromatic heterocyclic polymer fibers are polybenzoimidazole type, polybenzoxazole type, polybenzothiazole type, and copolymer polymers thereof (benzoimidazole-benzoxazole copolymer type, benzoimidazole-benzothiazole copolymer type). The method for producing a heat-resistant high-strength film material according to claim 8, which is one or more selected from the group of benzoxazole-benzothiazole copolymerization system, benzimidazole-benzoxazole-benzothiazole copolymerization system). Claim 8 or 9 in which the elastomer is at least one selected from the elastomer group of vinyl chloride-based, urethane-based, polyester-based, polyolefin-based, styrene-based copolymer, fluorine-based copolymer, and silicone-based. A method for producing a heat-resistant high-strength film material according to. The non-aromatic isocyanate compound is hexamethylene diisocyanate [Chemical formula 1], hydrogenated xylylene diisocyanate [Chemical formula 2], isophorone diisocyanate [Chemical formula 3], isocyanurate-modified triisocyanate [Chemical formula 4-Chemical formula 7], [Chemical formula 4]. -Chemical 8], [Chemical 4-Chemical 9]), Bullet-modified triisocyanate ([Chemical 5-Chemical 7], [Chemical 5-Chemical 8], [Chemical 5-Chemical 9]), Trimethylol alkyl-modified triisocyanate ([Chemical 6-Chemical 7], [Chemical formula 6-Chemical formula 8], [Chemical formula 6-Chemical formula 9]). A method for producing a heat-resistant high-strength film material.

The inorganic particles were selected from metals (including alloys), metal oxides, metal composite oxides, metal hydroxides, metal carbonates, metal sulfates, glass, silica, zeolites, apatites, and minerals. The method for producing a heat-resistant high-strength film material according to any one of claims 8 to 11, which is more than one species.