JP2004143625A - High-strength fiber composite material processed with special resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a high-strength fiber composite material with high water resistance. <P>SOLUTION: The high-strength fiber composite material is characterized in that a thermosetting resin is stuck in the internal open structure of high-strength fibers. <P>COPYRIGHT: (C)2004,JPO

Description

【００３８】
【発明の効果】
本発明によって耐水性に優れた高強度繊維複合材料を提供できる。
【図面の簡単な説明】
【図１】高強度繊維の模式的断面図であって、本発明における内部オープン構造を示す。
【図２】高強度繊維の模式的断面図であって、本発明における熱硬化性樹脂を上記高強度繊維の内部オープン構造内に注入する前の水分を含んだ状態の高強度繊維を示す。
【図３】高強度繊維の模式的断面図であって、高強度繊維の内部オープン構造内に上記熱硬化性樹脂が注入された状態を示す。
【図４】高強度繊維の模式的断面図であって、図３の高強度繊維と熱硬化性樹脂とが熱処理され高強度繊維の内部オープン構造内に熱硬化性樹脂が固着した状態を示す。
【符号の説明】
１　　高強度繊維結晶
２　　高強度繊維結晶間間隙
３　　高強度繊維の外表面
４　　高強度繊維の内部オープン構造における高強度繊維の表面
５　　水分
６　　熱硬化性樹脂[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a high-strength fiber composite material whose internal structure is processed with a specific resin.
[0002]
[Prior art]
Conventionally, many high-strength fibers have a water-absorbing property, and due to the absorption of water, the tensile strength of the high-strength fiber is reduced due to water absorption over a long period of time, for example, for use as a fishery material such as a fishing line or a fishing net. Had a problem. Therefore, a high-strength fiber composite material that imparts water resistance to such high-strength fibers has been demanded. In recent years, methods for imparting water resistance to high-strength fibers have been studied (Patent Document 1). However, imparting water resistance is not always satisfactory because the strength of the high-strength fiber is reduced or the water resistance is not good.
[0003]
[Patent Document 1]
JP 2001-152407 A
[Problems to be solved by the invention]
An object of the present invention is to provide a high-strength fiber composite material having excellent water resistance.
[0005]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to solve the above problems, and as a result, succeeded in creating a high-strength fiber composite material in which a thermosetting resin is filled in the internal open structure of the high-strength fiber. We discovered that the thermosetting resin adhered to the surface of the internal open structure of the high-strength fiber in the material, and that the high-strength fiber composite material was excellent in water resistance, and at a glance And that such a high-strength fiber composite material is useful as various industrial products described below. The present inventors have further studied and found that the high-strength fiber composite material can be industrially advantageously produced by injecting the thermosetting resin into the internal open structure of the high-strength fiber.
The present inventors have further studied after obtaining such various findings, and completed the present invention.
[0006]
That is, the present invention
(1) A high-strength fiber composite material in which a thermosetting resin is fixed in an internal open structure of a high-strength fiber,
(2) The high-strength fiber according to (1), wherein the high-strength fiber is at least one member selected from the group consisting of wholly aromatic polyamide fibers, wholly aromatic polyester fibers, and heterocyclic aromatic fibers. Strength fiber composite material,
(3) The high-strength fiber according to claim 1 or 2, wherein the high-strength fiber is a fiber having a water content of 15% by mass or more and a crystal size (110 direction) in a range of 30 to 55 °. Fiber composite materials,
About.
[0007]
Also, the present invention
(4) The thermosetting resin is one or more selected from the group consisting of phenolic resins, epoxy resins, polyester resins, polyamide resins, polyimide resins, polyamideamino resins, PES resins, PEEK resins, and CP resins. The high-strength fiber composite material according to (1),
(5) The high-strength fiber composite material according to any one of (1) to (4), wherein the high-strength fiber is a fiber constituting a high-strength fiber product.
(6) A fiber product comprising a high-strength fiber composite material in which a thermosetting resin is fixed to an internal open structure of a high-strength fiber,
About.
[0008]
Also, the present invention
(7) The textile product according to (6), which is a protective clothing.
(8) A composite material reinforced resin obtained by processing the high-strength fiber according to (1) or the fiber product according to (6) with a resin,
(9) The method for producing a high-strength fiber composite material according to (1), wherein the internal open structure of the high-strength fiber is treated with a thermosetting resin.
(10) The method for producing a high-strength fiber composite material according to (1), wherein moisture in the internal open structure of the high-strength fiber is removed, and then the open structure is treated with a resin.
About.
[0009]
BEST MODE FOR CARRYING OUT THE INVENTION
The present invention is a high-strength fiber composite material in which a thermosetting resin is fixed in an internal open structure of a high-strength fiber. A feature is that a thermosetting resin is filled or injected into the internal open structure of the high-strength fiber. The form of the high-strength fiber composite material is not particularly limited, and may be a fibrous form, a film form, or a pellet form.
[0010]
The high-strength fiber used in the present invention is not particularly limited, but a fiber having a strength of about 8 g / D or more is preferable, and a fiber having a strength in a range of about 15 g / D to 50 g / D is more preferable. “Strength” is determined by measuring according to JIS L 1013: 1999 Chemical Fiber Filament Yarn Test Method 8.5.1. As the high-strength fiber used in the present invention, for example, a wholly aromatic polyamide fiber, an aromatic polyester fiber, a heterocyclic aromatic fiber or the like can be mentioned, and a mixed fiber or a composite fiber obtained by combining these fibers can also be used. .
[0011]
The wholly aromatic polyamide fiber is a fiber having at least one divalent aromatic group which may be usually substituted, and may be any fiber as long as it has at least one amide bond. Known materials called polyamide fibers may be used. In the above, the divalent aromatic group which may be substituted means a divalent aromatic group which may have the same or different one or more substituents, and such a "substituent" is For example, a halogen atom (for example, fluorine, chlorine, bromine or iodine), a nitro group, a cyano group, a hydroxy group, a thiol group, a sulfo group, a sulfino group, a mercapto group, a phosphono group, for example, a linear or branched alkyl Groups (e.g., methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, Decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group or A A silyl group), a hydroxyalkyl group (e.g., a hydroglycimethyl group, a hydroxyethyl group, a 1-hydroxyisopropyl group, a 1-hydroxy-n-propyl group, a 2-hydroxy-n-butyl group or a 1-hydroxy-isobutyl group), Halogenoalkyl groups (e.g., chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, 2-bromoethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 3,3,3-trifluoro Propyl, 4,4,4-trifluorobutyl, 5,5,5-trifluoropentyl or 6,6,6-trifluorohexyl or the like, a cycloalkyl group (for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl) Etc.), alkenyl Groups (such as vinyl, crotyl, 2-pentenyl or 3-hexenyl), cycloalkenyl groups (such as 2-cyclopentenyl, 2-cyclohexenyl, 2-cyclopentenylmethyl or 2-cyclohexenylmethyl), alkynyl groups (such as Ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-pentynyl, 3-hexynyl, etc.), oxo group, thioxo group, amidino group, imino group, alkylenedioxy group (for example, methylenedioxy or ethylenedioxy etc.) ), For example, a monocyclic or condensed cyclic hydrocarbon group such as phenyl and biphenyl, a hydrocarbon group such as a bridged cyclic hydrocarbon group such as 1-adamantyl group and 2-norbornanyl, and an alkoxy group (for example, methoxy, ethoxy, Propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, neopentyloxy or hexyloxy, etc., alkylthio groups (eg, methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, pentylthio or hexylthio, etc.), carboxyl groups, alkanoyl groups ( For example, formyl; acetyl, propionyl, butyryl, isobutyryl, etc.), alkanoyloxy group (eg, formyloxy; alkyl-carbonyloxy group, such as acetyloxy, propionyloxy, butyryloxy, isobutyryloxy, etc.), alkoxycarbonyl group (eg, methoxycarbonyl) , Ethoxycarbonyl, propoxycarbonyl or butoxycarbonyl, etc.), aralkyloxycarbonyl groups (eg benzyloxycarbo) Thiocarbamoyl group, alkylsulfinyl group (eg, methylsulfinyl or ethylsulfinyl), alkylsulfonyl group (eg, methylsulfonyl, ethylsulfonyl, butylsulfonyl, etc.), sulfamoyl group, mono-alkylsulfamoyl group (eg, methyl Sulfamoyl or ethylsulfamoyl, etc.), di-alkylsulfamoyl group (eg, dimethylsulfamoyl or diethylsulfamoyl), arylsulfamoyl group (eg, phenylsulfamoyl or naphthylsulfamoyl) An aryl group (eg, phenyl or naphthyl), an aryloxy group (eg, phenyloxy or naphthyloxy), an arylthio group (eg, phenylthio or naphthylthio), an arylsulfinyl group (eg, Phenylsulfinyl or naphthylsulfinyl, etc.), arylsulfonyl group (eg, phenylsulfonyl or naphthylsulfonyl), arylcarbonyl group (eg, benzoyl or naphthoyl), arylcarbonyloxy group (eg, benzoyloxy or naphthoyloxy), halogenated they may be alkylcarbonylamino group (e.g. acetylamino or trifluoroacetylamino, etc.), in which may have a substituent carbamoyl group (e.g., the formula -CONR 3 ^R 4 ^(wherein, R ³ and R ⁴ each A hydrogen atom, a hydrocarbon group which may have a substituent or a heterocyclic group which may have a substituent, or R ³ and R ⁴ may form a ring together with an adjacent nitrogen atom. Good. A)), an amino group which may have a substituent (for example, amino, alkylamino, tetrahydropyrrole, piperazine, piperidine, morpholine, thiomorpholine, pyrrole or imidazole); Ureido group (eg, a group represented by the formula —NHCONR ³ R ⁴ (wherein, R ³ and R ⁴ have the same meanings as described above)), and a carboxamide group optionally having a substituent (For example, a group represented by the formula —NR ³ COR ⁴ (wherein, R ³ and R ⁴ have the same meanings as described above)), and a sulfonamide group which may have a substituent (for example, a formula —NR ³ SO 4) ₂ R ⁴ (wherein, R ³ and R ⁴ have the same meanings as described above), a hydroxyl group or a mercapto group which may have a substituent, or a group having a substituent. Good heterocycle (For example, as an atom (ring atom) constituting a ring system, an aromatic heterocyclic group containing at least one to three heteroatoms selected from oxygen, sulfur, and nitrogen atoms in addition to carbon atoms (eg, pyridyl , Furyl, thiazolyl, etc.) or a saturated or unsaturated aliphatic heterocyclic group, etc.), or a substituent obtained by substituting these substituents as long as they are chemically permissible. Examples of the “divalent aromatic group” include a p-phenylene group, an m-phenylene group, a naphthylene group, a biphenylene group, and the like.
[0012]
Further, the wholly aromatic polyamide fiber is also called an aramid fiber, and can be roughly classified into a para-aramid fiber or a meta-aramid fiber, and both are preferably used in the present invention. The para-aramid fiber used in the present invention may be any of the above wholly aromatic polyamide fibers, for example, the above-mentioned divalent aromatic group which may be substituted is a p-phenylene group which may be substituted. It may be a known one called a para-aramid fiber. The above-mentioned optionally substituted p-phenylene group means a p-phenylene group which may have the same or different one or more substituents, and such “substituent” has the same meaning as described above. is there. Further, as the para-aramid fiber, for example, polyparaphenylene terephthalamide fiber (manufactured by Dupont Co., Ltd., U.S.A., manufactured by Dupont Co., Ltd., trade name KEVLAR (registered trademark of Dupont Co., Ltd.)), or paraphenylene terephthalamide and 3,4 Commercial products such as copolymer fiber with '-oxydiphenylterephthalamide (manufactured by Teijin Limited, trade name Technora (registered trademark of Teijin Limited)) can be used. The meta-aramid fiber used in the present invention may be any of the above-described aromatic polyamide fibers in which the bond of the benzene ring which may be substituted in the molecular chain is a bond at the meta position, for example. A known material called meta-aramid fiber may be used. As the meta-aramid fiber, for example, a commercially available product such as polymetaphenylene isophthalamide fiber (manufactured by DuPont, USA, trade name NOMEX (registered trademark of DuPont)) can be used. In the present invention, the above-mentioned aramid fiber may be produced and used by a known method or a method analogous thereto.
[0013]
The wholly aromatic polyester fiber is a fiber having at least one divalent aromatic group which may ordinarily be substituted, and may be any fiber as long as it has at least one ester bond. Is not particularly limited. The above-mentioned "optionally substituted divalent aromatic group" is as defined above. The wholly aromatic polyester fiber may be a known fiber called a wholly aromatic polyester fiber, for example, a self-condensation polymer of parahydroxybenzoic acid, a polyester made of terephthalic acid and hydroquinone, or parahydroxy It may be a polyester fiber or the like comprising benzoic acid and 6-hydroxy-2-naphthoic acid. In the present invention, such a wholly aromatic polyester fiber can be produced and used by a known method or a method analogous thereto. In the present invention, as the wholly aromatic polyester fiber, for example, a commercially available product such as Vectran (R) (manufactured by Kuraray Co., Ltd.) can be used.
[0014]
The heterocyclic aromatic fiber may be any fiber as long as it has at least one divalent aromatic heterocyclic group which may ordinarily be substituted, and is not particularly limited in the present invention. In the above, the “optionally substituted divalent aromatic heterocyclic group” means a divalent aromatic heterocyclic group which may have the same or different one or more substituents, and “Substituent” is as defined above. The “divalent aromatic heterocyclic group” includes, for example, the same or different heteroatoms 1 selected from oxygen, sulfur, nitrogen, fluorine and the like as atoms (ring atoms) constituting a ring system. And an aromatic heterocyclic group having at least one of four to four types. As the aromatic heterocyclic ring in the divalent aromatic heterocyclic group, for example, an aromatic monocyclic heterocyclic ring (for example, furan, thiophene, pyrroline, oxazoline, isoxazoline, thiazoline, isothiazoline, imidazoline, pyrazoline, 1,2,3 -Oxadiazoline, 1,2,4-oxadiazoline, 1,3,4-oxadiazoline, furazanin, 1,2,3-thiadiazoline, 1,2,4-thiadiazoline, 1,3,4-thiadiazoline , 1,2,3-triazoline, 1,2,4-triazoline, tetrazoline, pyridine, pyridazine, pyrimidine, pyrazine or triazine, etc., or an aromatic condensed heterocyclic ring (for example, benzofuran, isobenzofuran, benzo [b] thiophene, Indoline, isoindoline, 1H-indazoline, benzindazoline, Zooxazoline, 1,2-benzisoxazoline, benzothiazoline, benzopyrazine, 1,2-benzoisothiazoline, 1H-benzotriazoline, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, phthalazine, naphthyridine, purine, buteridine, carbazoline, α-carboline, β-carboline, γ-carboline, acridine, phenoxazine, phenothiazine, phenazine, phenoxatin, thianthrene, phenatrene, phenatroline, indolizine, pyrrolo [1,2-b] pyridazine, pyrazolo [1,5-a Pyridine, imidazo [1,2-a] pyridine, imidazo [1,5-a] pyridine, imidazo [1,2-b] pyridazine, imidazo [1,2-a] pyrimidine, 1,2,4-triazolo [4,3- ] Pyridine, 1,2,4-triazolo [4,3-b] pyridazine and the like) and the like. In addition, a known material called a heterocyclic aromatic fiber may be used, such as a polyparaphenylene benzobisthiazole fiber, a polyparaphenylene benzobisoxazole fiber (hereinafter also referred to as a PBO fiber), a polybenzimidazole fiber, or the like. May be. Further, the heterocyclic aromatic fiber can be produced by a known method or a method analogous thereto. In the present invention, as the heterocyclic aromatic fiber, for example, a commercially available PBO fiber (manufactured by Toyobo Co., Ltd., product name: Zylon (R)) can be used.
[0015]
The high-strength organic fiber is appropriately selected according to the use of the final product, required performance, fiber production cost, product processing cost, and the like. Such a form is not particularly limited, either, and may be a short fiber or a long fiber. In the present invention, a mixed fiber or the like obtained by combining the high-strength organic fibers can be used. Further, in the present invention, the aramid fiber composed of a para-type homopolymer, which is known by the trade name of KEVLAR (registered trademark of DuPont) or Twaron (registered trademark of Teijin Twaron Co., Ltd.), particularly polyparaphenylene terephthalate It is preferable to use amide (hereinafter also referred to as PPTA) as the high-strength organic fiber.
[0016]
In the present invention, particularly when an aramid fiber such as PPTA is used as the high-strength fiber, a para-aramid fiber having a water content of 15% by mass or more and having no history of drying to a water content of 15% by mass or less is used. It is preferable to use The para-aramid fiber such as PPTA fiber used in the present invention preferably has a water content of about 15 to 100% by mass, more preferably about 20 to 60% by mass, and about 25 to 50% by mass. % Is most preferred. The measurement of the water content can be easily calculated from the following equation according to JIS L 1013 Test Method for Chemical Fiber Filament Yarn 8.1.1 Water Content.
(Equation 1)
Moisture percentage (% by mass) = (W−W ′) × 100 / W ′ (Equation 1)
(In the formula, W represents the mass at the time of sampling, and W ′ represents the mass of the sample at the time of absolute drying.)
[0017]
The para-aramid fiber such as PPTA used in the present invention also has a crystal size (110 directions) of usually about 30 to 55 °, preferably about 30 to 47 °, more preferably about 30 to 42 °, and most preferably about 30 to 42 °. Å40 °. The crystal size is determined by a known wide-angle X-ray diffraction (diffractometer) method. Specifically, for example, the crystal size is measured by the following apparatus according to a wide-angle X-ray diffraction (diffractometer) method.
X-ray diffractometer Rigaku Corporation 4036A2 type, X-ray source CuK α-ray (using Ni filter), output 35 kV, 15 mA
Goniometer Rigaku Corporation Slit 2mmφ-1 ° -1 °, detector Scintillation counter,
Count recording device RAD-C type manufactured by Rigaku Denki Co., Ltd.
The PPTA fiber is formed by, for example, dissolving PPTA in concentrated sulfuric acid, extruding a viscous solution from a spinneret, spinning into water through a small space to form a filament thread, and then adding a 10% by mass aqueous sodium hydroxide solution. It is obtained by drying and heat treatment at a temperature of about 120 to 500 ° C., if desired, after washing with water. The PPAT fiber before drying and heat treatment has a moisture content of about 15 to 200% by mass, a crystal size (110 directions) of less than about 55 °, and a moisture content of about 10% by mass or less after drying and heat treatment with a hot roller or the like. The crystal size (110 direction) is usually about 55 ° or more.
Thus, in the present invention, PPTA fibers having a water content of about 15 to 100% by mass and a fiber crystal size (110 direction) of about 30 to 55 ° are manufactured by appropriately changing the heat treatment conditions such as a hot roller. It is preferable to use such fibers. To achieve such a water content, it is preferable to dry the spun PPTA fiber at about 100 to 150 ° C. for about 5 to 20 seconds.
[0019]
More specifically, for such a fiber, for example, PPTA obtained by a usual method is dissolved in 99.9% by mass of concentrated sulfuric acid to obtain a spin dope having a polymer concentration of 19.0% by mass and a temperature of 80 ° C. , Extruded from a die having a number of pores of 1,000 with a hole diameter of 0.06 mm, passed through an air gap of about 6 mm from the die to the water surface, then led into water at about 4 ° C., solidified, and led to a Nelson roller, about 500 m / Minutes, and neutralized with about 10% by mass of sodium hydroxide aqueous solution, washed with water, slightly dried with a hot roller having a surface treatment temperature of about 110 ° C., and wound up on a water-resistant bobbin. A PPTA fiber yarn having a moisture content of about 46% by mass and a moisture-containing fineness of about 64 tex (absolutely dry 44 tex, absolutely dry single yarn fineness 0.167 tex) consisting of 263 filaments is obtained. The crystal size (110 direction) of the fibers is about 36 Å.
[0020]
The thermosetting resin used in the present invention may be any resin that exhibits thermosetting properties. For example, a phenol resin, an epoxy resin, a polyester resin, a melamine resin, a polyamide resin, a polyimide resin, a polyamide amino resin, a PES (polyethersulfone) resin, a PEEK (polyetheretherketone) resin, a CP resin (for example, a crosslinked polyesteramide or Crosslinked polyaminoamide), copolymer resins thereof, and / or modified resins obtained by modifying these resins. The thermosetting resin can be manufactured by using a known method such as radical polymerization. Many of the thermosetting resins are commercially available, and in the present invention, these commercially available products may be used. For example, Sumilite resin (R) (manufactured by Sumitomo Bakelite Co., Ltd.) or Rigolac (R) (manufactured by Showa Kobunshi Co., Ltd.) and the like can be mentioned.
[0021]
In the present invention, the high-strength fiber composite material can be manufactured by injecting the thermosetting resin into the internal open structure of the high-strength fiber. Hereinafter, the production of the preferred high-strength fiber composite material in the present invention will be described with reference to the drawings. In the high-strength fiber before the treatment with the thermosetting resin, moisture 5 is usually attached to the gap between the fiber crystals having the internal open structure as shown in FIG. When the high-strength fiber shown in FIG. 2 is treated with the above-described thermosetting resin, a state in which the thermosetting resin 6 is injected into and mixed with the outer surface of the high-strength fiber and its internal open structure as shown in FIG. Become. Then, when the permeated and impregnated high-strength fiber is heat-treated, the heat treatment causes the fiber crystal of the high-strength fiber to expand, thereby narrowing the gap between the fiber crystals. Then, as shown in FIG. 4, the thermosetting resin 6 in the inter-crystal gap is sandwiched between the crystals and fixed. As a result, the high-strength fiber composite material can be obtained.
[0022]
Examples of the method for producing the high-strength fiber composite material include, for example, a thermosetting resin injecting step of injecting the thermosetting resin into the internal open structure of the high-strength fiber, a production method including a post-treatment step, and the like. Can be In the present invention, as shown in FIG. 1, the internal open structure of the high-strength fiber includes not only the high-strength fiber crystal gap 2 between the high-strength fiber crystals 1 but also the fiber crystal surface and the outer surface of the fiber. The vicinity of the fiber crystal such as the surface 3 is also included.
Hereinafter, the above-described manufacturing method including the thermosetting resin injection step and the post-treatment step will be described more specifically.
[0023]
The thermosetting resin injection step is not particularly limited as long as the thermosetting resin can be injected into the internal open structure of the high-strength fiber. Examples of such injection means include known means such as immersion, spraying, coating, coating, hot melting, and heat compression. More specifically, for example, the above-mentioned thermosetting resin is dissolved in an organic solvent such as an alcoholic or etheric solvent or an inorganic medium such as concentrated sulfuric acid or concentrated hydrochloric acid or a thermosetting resin dispersion liquid dispersed in an aqueous phase. Means for immersing the high-strength fiber, means for applying, spraying or coating the solution or the dispersion on the fiber, or means for heat-melting the thermosetting resin or the thermosetting resin and the high-strength fiber Means for heating and compressing may be used. In the present invention, as the above means, the high-strength fiber is immersed in the thermosetting resin dispersion, and thereafter, the water adhering to the high-strength fiber is evaporated and removed by heating. It is preferable to use a means for fixing the above to the high-strength fiber. In the present invention, when the above solution is used, the above solution is preferably an aqueous solution, and when the above dispersion is used, the above dispersion is preferably the above-mentioned thermosetting resin dispersion liquid dispersed in water.
In the present invention, for example, fibrillation or the like of the high-strength fiber may be performed as a pretreatment before the thermosetting resin injecting step.
[0024]
The post-treatment step is not particularly limited as long as the solvent or the like attached to the high-strength fiber can be removed by the thermosetting resin injection step. Examples of such a removing means include known means such as heating with a heater or the like or drying with a dryer or the like. In the present invention, not only the solvent and the like attached to the high-strength fiber can be removed by the heating means, but also the high-strength fiber crystal is expanded and the thermosetting resin is cured to form an internal open structure of the high-strength fiber. It can be more firmly fixed inside. The heating temperature in the heating is not particularly limited as long as it is a temperature at which the crystal size of the high-strength fiber expands, but in the present invention, it is preferably in the range of about 50 to 300 ° C. , More preferably in the range of about 80C to 200C.
[0025]
The high-strength fiber composite material produced by the above production method is suitably used in various industrial fields (for example, the cooking field, the food processing field, the fishery field, the agricultural field, the medical field, or the industrial processing field). When the form of the high-strength fiber composite material is fibrous, a fiber product can be manufactured by using the high-strength fiber composite material as a fiber of the fiber product. As a method for producing such a fiber product, any method may be used as long as a fiber product can be produced using the high-strength fiber composite material. A known method may be used as appropriate. Hereinafter, a production method in the case where the above fiber product is a braid, a woven fabric, a knitted fabric, or a nonwoven fabric will be exemplified.
[0026]
When the fiber product is a braid, the fibrous high-strength fiber composite material is used as a raw material, using a known braiding machine (braiding machine), by a braiding method such as rounding, cornering or flat striking, A desired braid can be produced. More specifically, for example, a braid is obtained by preparing four filaments and alternately arranging the right or left yarns in the center and assembling them. The number of filaments used for the cord is not limited to four, and a desired number such as 8, 12, or 16 may be used.
When the fiber product is a woven fabric, for example, using a known loom (such as a jet loom or a sulzer loom), a desired woven fabric such as plain weave, twill weave, satin weave or oblique weave is formed into a fibrous high-strength fiber composite. It can be made from materials.
[0027]
When the fiber product is a knit, for example, a known knitting machine (such as a warp knitting machine or a flat knitting machine) can be used to produce a desired knit such as a flat knit, a flat knit, or a rubber knit.
When the fiber product is a nonwoven fabric, for example, using a known nonwoven fabric machine, a wet method, a dry method such as a tow opening method, a spunbond method, a melt blow method or a flash spinning method, etc. From the above high-strength fiber composite material. More specifically, for example, when the above-mentioned wet method is used, a wet-type nonwoven fabric can be produced by cutting the fibrous high-strength fiber into short pieces, making the paper with a paper machine, and then drying.
[0028]
Further, using the above-prepared fiber product, a fiber product such as clothing can be further produced. Therefore, the form of the fiber product is not particularly limited. For example, primary processed yarns such as yarns obtained by drawing or twisting the fibers obtained from the high-strength fibers, cords such as braids, cotton, etc. And non-woven fabrics such as woven fabrics, knitted fabrics, felts and papers, and ropes or cords. Furthermore, the above-mentioned fiber products can be exemplified by the primary processed products alone or in combination, and even the secondary processed products obtained by processing with a combination containing other materials such as other resins and metals. Such secondary processed products are not particularly limited, and include, for example, bedding, clothing, miscellaneous goods, interiors, automobile interior products, products for industrial materials, and the like. More specifically, for example, beddings such as sheets, pillowcases, futons, futon cotton, futon covers or blankets, curtains, carpets, partitions, screens, goodwill, tablecloths, and other various interiors, coats, jackets, pants, and skirts , Shirts, knitted shirts, suits, trainers, blouses, nightwear, underwear, sweaters, supporters, socks, tights, stockings, gloves, hats, scarves, ties, lining of clothes, interlining of clothes, cotton filling, work clothes , Uniforms, school uniforms, firefighters or white garments, garments, purses, bags, handkerchiefs, tissue covers, towels, pot holders, rags or towels, etc., seats, seat covers or handle covers, etc. Products, or products for industrial materials such as wall cloth or floor lining. In the present invention, it is preferable that the textile is a protective garment. The protective clothing is not particularly limited as long as it is clothing intended to protect the body of a wearing person, and examples thereof include work clothes, firefighting clothes, and various sports clothes. Also, by knitting the fibrous high-strength fiber, a glove, particularly a waterproof glove, can be produced.
[0029]
In the present invention, a composite material reinforced resin can be produced by further processing the high strength fiber composite material or the fiber product with a resin. The resin used for the resin processing is not particularly limited. For example, the above-mentioned thermosetting resin, polyethylene terephthalate (PET) resin, polybutylene terephthalate (PBT) resin, polytrimethylene terephthalate (PTT) resin, polyethylene na Polyester resins such as phthalate (PEN) resin and liquid crystal polyester resin, polyolefin resins such as polyethylene (PE) resin, polypropylene (PP) resin and polybutylene resin, styrene resins, polyoxymethylene (POM) resins, polyamide (PA) Resin, polycarbonate (PC) resin, polymethylene methacrylate (PMMA) resin, polyvinyl chloride (PVC) resin, polyphenylene sulfide (PPS) resin, polyphenylene ether (PPE) resin, polyimide (P ) Resin, polyamide imide (PAI) resin, polyether imide (PEI) resin, polysulfone (PSU) resin, polyether sulfone resin, polyketone (PK) resin, polyetherketone (PEK) resin, polyetheretherketone (PEEK) Resin, polyarylate (PAR) resin, polyether nitrile (PEN) resin, phenol resin, phenoxy resin, fluororesin, polystyrene, polyolefin, polyurethane, polyester, polyamide, polybutadiene, polyisoprene, or fluorine And the like, or a thermoplastic resin such as a copolymer or a modified product thereof, a copolymer resin or a modified resin thereof, or a resin obtained by blending two or more kinds of these resins or / and elastomers. .
[0030]
The composite material reinforced resin can be produced, for example, by processing the high-strength fiber composite material and / or the fiber product with the resin. In order to process the high-strength fiber composite material and / or the fiber product with the resin, for example, when the resin is used, the resin is optionally melted, formic acid, cresol, cresol-substituted product, or hexafluoro, if desired. The high-strength fiber composite material or the fiber product is usually impregnated with the resin by dissolving it in an organic solvent such as isopropanol or an inorganic medium such as concentrated sulfuric acid or concentrated hydrochloric acid, and then curing the impregnated resin. Just fine. As a method of impregnation and curing, a known method such as a hand lay-up method, a preformed matched die molding method, a cold press method, a resin injection method, an SMC method, a BMC method, or a pultrusion method can be appropriately used.
[0031]
The composite material reinforced resin manufactured as described above can be used for various applications. Such "uses" are not particularly limited, and include, for example, marine materials such as fishing lines or fish nets, road pavement materials, concrete reinforcing materials, civil engineering and building materials such as anti-peeling agents or building members, and turbine wheels. It can be used as a member of a gas turbine, a member of a burner, a member of a nozzle, a member of a spacecraft or an aircraft, a part of a heat exchanger, a member of an automobile, a cargo ship or an industrial vehicle, or a member of a home appliance.
[0032]
【Example】
Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to these Examples.
[0033]
(Example 1)
A phenol resin (Sumilite Resin (R) manufactured by Sumitomo Bakelite Co., Ltd.) was dissolved in ethanol at a ratio of 38% by mass as a thermosetting resin. The above-prepared solution is applied to aramid fiber (Kevlar (R), manufactured by Du Pont-Toray Co., Ltd.) having an internal open structure having a fiber diameter of 12 μm, a crystal size of the filament (110 direction) of 40 °, and a water content of 30% by mass. Thereafter, heat treatment was performed at 170 ° C. for 1 minute, and the film was wound by a winder to obtain a fibrous high-strength fiber composite material.
[0034]
(Example 2)
A single yarn of the obtained fibrous high-strength fiber composite material is taken out, and a polycaprolactone resin (Cell Green (R) manufactured by Daicel Chemical Industries, Ltd.) is attached to the fibers by heat melting (temperature: 70 ° C.). Then, the mixture was cooled and cured to obtain a composite material reinforced resin.
[0035]
(Example 3)
2 μl of pure water was dropped on the surface of the fibrous high-strength fiber composite material obtained in Example 1, and the contact angle was measured with a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.). The measurement results are shown in Table 1 below.
[0036]
(Comparative example)
As a comparative example, pure water was applied to the surface of an aramid fiber having an internal open structure (Kevlar (R) manufactured by Du Pont-Toray Co., Ltd.) having a fiber diameter of 12 μm, a crystal size of the filament (110 direction) of 40 °, and a water content of 30% by mass. Was dropped, and the contact angle was measured in the same manner as in Example 3. Table 1 shows the measurement results.
[0037]
[Table 1]

[0038]
【The invention's effect】
According to the present invention, a high-strength fiber composite material having excellent water resistance can be provided.
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view of a high-strength fiber, showing an internal open structure in the present invention.
FIG. 2 is a schematic cross-sectional view of the high-strength fiber, showing the high-strength fiber containing water before the thermosetting resin of the present invention is injected into the internal open structure of the high-strength fiber.
FIG. 3 is a schematic cross-sectional view of a high-strength fiber, showing a state in which the thermosetting resin is injected into an internal open structure of the high-strength fiber.
4 is a schematic cross-sectional view of the high-strength fiber, showing a state in which the high-strength fiber and the thermosetting resin of FIG. 3 are heat-treated and the thermosetting resin is fixed in the internal open structure of the high-strength fiber. .
[Explanation of symbols]
1 High-strength fiber crystal 2 High-strength fiber crystal gap 3 High-strength fiber outer surface 4 High-strength fiber surface in open structure of high-strength fiber 5 Water 6 Thermosetting resin

Claims (10)

A high-strength fiber composite material characterized in that a thermosetting resin is fixed in the internal open structure of the high-strength fiber. The high-strength fiber composite according to claim 1, wherein the high-strength fiber is one kind or two or more kinds selected from the group consisting of a wholly aromatic polyamide fiber, a wholly aromatic polyester fiber, and a heterocyclic aromatic fiber. material. The high-strength fiber composite material according to claim 1 or 2, wherein the high-strength fiber is a fiber having a water content of 15% by mass or more and a crystal size (110 direction) in a range of 30 to 55 °. . The thermosetting resin is a phenol resin, an epoxy resin, a polyester resin, a polyamide resin, a polyimide resin, a polyamide amino resin, a PES resin, a PEEK resin and a resin selected from the group consisting of two or more CP resins, The high-strength fiber composite material according to claim 1, wherein The high-strength fiber composite material according to any one of claims 1 to 4, wherein the high-strength fiber is a fiber constituting a high-strength fiber product. A fiber product comprising a high-strength fiber composite material in which a thermosetting resin is fixed to an internal open structure of a high-strength fiber. The textile product according to claim 6, which is a protective garment. A composite material reinforced resin obtained by subjecting the high-strength fiber according to claim 1 or the fiber product according to claim 6 to resin processing. The method for producing a high-strength fiber composite material according to claim 1, wherein the internal open structure of the high-strength fiber is treated with a thermosetting resin. The method for producing a high-strength fiber composite material according to claim 1, wherein moisture in the internal open structure of the high-strength fiber is removed, and then the open structure is treated with a resin.

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