JP5385734B2 - Impact resistant composite - Google Patents

Description

  The present invention relates to a composite excellent in impact resistance, and particularly to a composite excellent in impact absorption and highly effective in suppressing scattering of a material even when subjected to a strong impact.

  High-speed moving objects such as automobiles, railways, and airplanes generate enormous destructive force and break the objects at the time of collision by kinetic energy derived from the moving speed. In many cases, the broken pieces are scattered along with the breakage of the object, causing a great deal of damage to objects and humans existing around the broken pieces. For this reason, it is an important safety issue to reduce the scattering of an object that accompanies destruction and to prevent the penetration of a flying object such as a broken piece.

  In order to solve such a problem, Patent Document 1 discloses a fiber-reinforced resin molded article obtained by impregnating a fabric composition with a resin composition, and the fabric article contains 0.01 to 10 wt% of a fluorine compound. An impact plate is disclosed. This document describes that the reinforcing effect of FRP used as an impact plate, for example, a bulletproof plate or a blade-proof plate, can be further improved by containing a fluorine compound in the fabric.

  However, the use of fluorine is restricted due to environmental problems, and technical development that does not use fluorine is required.

JP 2002-316319 A (claims, paragraph number [0012])

  An object of the present invention is to provide an impact-resistant composite that not only has high impact resistance without using a fluorine compound, but also has an excellent effect of preventing fragment scattering during crushing.

  Another object of the present invention is to provide a composite that is not only excellent in unity but also capable of being reduced in weight.

  Still another object of the present invention is to provide an impact resistant material formed from such a composite having excellent impact resistance.

  The present inventors have examined a material having impact resistance. When a composite is formed by combining fully aromatic polyester fibers and polyvinyl butyral, the impact resistance of the composite is improved without using a fluorine compound. The present invention has been completed.

That is, the present invention is a composite comprising a high-strength fiber group composed of high-strength fibers having a tensile strength of 10 cN / dtex or more and a matrix resin,
The high-strength fiber group includes at least a wholly aromatic polyester fiber,
The matrix resin is an impact-resistant composite containing at least polyvinyl butyral.

In the composite, at least a part of the high-strength fiber group may form a fabric, and the basis weight per fabric is about 50 to 500 g / m ² , and the thickness is 0.00. It may be about 1 to 2 mm.

  The high-strength fiber group is at least one fabric selected from the group consisting of a unidirectional woven fabric, a bi-directional woven fabric, a triaxial woven fabric, a multiaxial woven fabric, and a non-crimped fabric with respect to the wholly aromatic polyester fiber. May be included.

The matrix resin may be composed of polyvinyl butyral and a phenol resin. The basis weight of the composite may be about 1000 to 7000 g / m ² .
In the composite of the present invention, the fluorine compound may not be substantially applied to the high-strength fiber group.

  Furthermore, the present invention also includes an impact resistant material formed from the composite.

  In the present specification, “substantially no fluorine compound is applied to the high-strength fiber group” means that the high-strength fiber group does not contain 0.01% by weight or more of the fluorine compound. ing.

  According to the present invention, since a composite is formed by combining a wholly aromatic polyester fiber and a matrix resin containing polyvinyl butyral, the impact resistance of the composite is improved and strong without using a fluorine compound. Even when an impact is applied, the damage resistance of the object can be improved and the crushed material can be prevented from scattering.

  Furthermore, since the composite of the present invention is excellent in impact resistance even if it is lightweight, it can be used for various applications that require weight reduction of the composite.

  The impact resistant composite of the present invention is a composite containing a high-strength fiber group and a matrix resin, and is excellent in impact resistance.

[High-strength fiber group]
The high-strength fiber group is composed of high-strength fibers having a tensile strength of 10 cN / dtex or more, and includes at least wholly aromatic polyester fibers. The high strength fiber needs to have a tensile strength of 10 cN / dtex or more, preferably about 10 to 100 cN / dtex, and more preferably about 15 to 80 cN / dtex.

(Totally aromatic polyester fiber)
The wholly aromatic polyester fiber used in the present invention is formed from a wholly aromatic polyester polymer.
The wholly aromatic polyester polymer is obtained by polymerizing from an aromatic diol, aromatic dicarboxylic acid, aromatic hydroxycarboxylic acid, etc. Among them, a melt anisotropic polyester exhibiting optical anisotropy when melted is preferable. . The melt-anisotropic polyester referred to in the present invention is an aromatic polyester that exhibits optical anisotropy (liquid crystallinity) in the melt phase. For example, a sample is placed on a hot stage and heated in a nitrogen atmosphere, and the light transmitted through the sample is transmitted. It can be recognized by observing

  For example, the wholly aromatic polyester polymer used in the present invention is composed of, for example, combinations of structural units represented by the following chemical formulas 1 and 2.

  Of these, a polymer comprising (5), (6), (7) and (9) among the combinations of repeating structural units represented by Chemical Formula 1 and Chemical Formula 2 is preferable.

More preferably, the portion consisting of repeating structural units (A) and (B) shown in the following chemical formula 3 is 50 mol% or more (for example, about 55 to 95 mol%, preferably 60 to 90 mol%). Aromatic polyesters are preferred.
Furthermore, the molar ratio of the repeating unit of (B) to the repeating unit of (A) is (A) :( B) = 100: 1-50, preferably (A) :( B) = 100: 1-45, More preferably, (A) :( B) = about 100: 1 to 40 may be used.

  The melting point of the wholly aromatic polyester polymer suitably used in the present invention is preferably 250 to 360 ° C, more preferably 260 to 320 ° C. The melting point referred to here is the main absorption peak temperature measured and observed with a differential scanning calorimeter (DSC; “TA3000” manufactured by METTLER) according to the JIS K7121 test method.

The wholly aromatic polyester-based polymer has a thermoplasticity such as polyethylene terephthalate, modified polyethylene terephthalate, polyolefin, polycarbonate, polyamide, polyphenylene sulfide, polyetheretherketone, fluororesin and the like within a range not impairing the effects of the present invention. A polymer may be added.
For example, such a wholly aromatic polyester fiber is marketed as “Vectran (registered trademark)” by Kuraray Co., Ltd.

(Other fibers)
Other fibers forming the high-strength fiber group are not particularly limited as long as the tensile strength is 10 cN / dtex or more. For example, the other high-strength fibers include inorganic high-strength fibers such as carbon fibers and glass fibers; Examples thereof include organic high-strength fibers such as aramid fibers, PBO fibers, ultrahigh molecular weight polyethylene fibers, and high-strength PVA fibers. Among these high-strength fibers, inorganic high-strength fibers are preferable from the viewpoint of having an effect complementary to the wholly aromatic polyester fibers that are organic fibers.

(Shape of high strength fiber group)
As the high-strength fiber group used in the present invention, either long fibers or short fibers can be used. For example, as a chopped strand, it may be applied by directly mixing with a matrix resin, or once a fabric such as a woven or knitted fabric, a nonwoven fabric, or a stitching sheet (for example, a non-crimped fabric) is formed and then applied to the fabric. It may be applied by impregnating with a matrix resin.

  Among these, from the viewpoint of increasing the strength and elastic modulus, it is preferable that at least a part of the high-strength fiber group forms a fabric, and among the fabrics, a woven or knitted fabric or a stitching sheet is more preferable.

  When forming a woven or knitted fabric or stitching sheet, the high-strength fibers forming the high-strength fiber group are usually filament yarns (monofilaments, multifilaments), spun yarns, etc. Of these, the viewpoint of improving impact resistance Therefore, a multifilament yarn is preferable.

  The high-strength fiber may have a single fiber fineness of about 0.1 to 600 dtex, preferably about 0.25 to 500 dtex, and a total fiber fineness of about 100 to 5000 dtex, preferably about 500 to 3000 dtex. Also good.

  The structure of woven or knitted fabrics and stitching sheets that use high-strength fibers as woven or knitted yarns or fiber bundles are unidirectional fabrics, bidirectional fabrics, triaxial fabrics, multiaxial fabrics, non-crimped fabrics, etc. Any of these may be used.

  More specifically, as a woven or knitted fabric or stitching sheet using high-strength fibers as a woven or knitted yarn or fiber bundle, a unidirectional fabric in which high-strength fibers are arranged in one direction of warp or weft; high strength Bidirectional fabric with fibers arranged in both warp and weft; Triaxial fabric in which high-strength fibers are arranged in three directions, vertical, horizontal, and diagonal; Multiaxial in which high-strength fibers are arranged in more than four directions Woven fabric: Knitted fabric using high-strength fibers as knitting yarn (warp knitted fabric, weft knitted fabric, etc.); Unidirectional non-crimp using high-strength fibers as fiber bundles and fastening fiber bundles aligned in one direction with different yarns Any fabric such as a multi-directional non-crimped fabric in which high-strength fibers are used as fiber bundles, and fiber bundles aligned in a plurality of directions (for example, two directions) are stacked and fastened with separate yarns. Good.

  Among these, a unidirectional woven fabric, a bidirectional woven fabric, a unidirectional non-crimped fabric, and a bi-directional non-crimped fabric are preferable from the viewpoint of achieving both weight reduction and impact resistance. In addition, the composite_body | complex of this invention may be formed using a single or several fabric, and when using several fabric, the shape of each fabric may be the same and may differ.

  In the case of a unidirectional woven fabric and a bi-directional woven fabric, the woven fabric density is about 8 to 50 yarns / 2.5 cm and about 10 to 45 yarns / 2.5 cm. May be.

One per basis weight of the fabric formed by the high-strength fibers (woven or knitted fabric, stitching sheets, etc.) may be, for example, 50 to 500 g / ^{m 2} approximately, about 100 to 400 g / ^{m 2} is preferred. Moreover, about 0.1-2 mm may be sufficient as the thickness per sheet | seat, for example, and about 0.15-1.5 mm is preferable.

  The high-strength fiber group used in the present invention includes at least a wholly aromatic polyester fiber, and all of the high-strength fiber group may be formed of a wholly aromatic polyester fiber. High strength fiber groups may be formed by combining fibers.

  When other fibers are included, the wholly aromatic polyester fiber and the other fiber can be combined by various mixing methods by a known or commonly used method, for example, (i) wholly aromatic polyester fiber and others Mixing at the stage of kneading with resin as chopped strands formed from fibers of (ii) using filaments (monofilaments, multifilaments) and spun yarns using wholly aromatic polyester fibers and other fibers There are various modes such as mixing in the forming step, (iii) mixing in the step of forming various fabrics from the yarn, and (iv) mixing in the step of combining a plurality of fabrics. These mixing methods may be performed in various combinations.

  Among these, the high-strength fiber group is preferably in the form of (iii) or (iv), and particularly with respect to the fully aromatic polyester fiber, the unidirectional woven fabric, the bi-directional woven fabric, the triaxial woven fabric, the polyaxial It preferably includes at least one fabric selected from the group consisting of woven fabrics and non-crimp fabrics.

  Specifically, for example, (iii) includes forming a fabric by interweaving yarns formed from wholly aromatic polyester fibers and yarns formed from other fibers. . In addition, (iv) includes a method in which a fabric formed from wholly aromatic polyester fibers and a fabric formed from other fibers are superposed and impregnated into a resin to form a composite.

  When the high-strength fiber group includes both wholly aromatic polyester fibers and other high-strength fibers, the proportion of wholly aromatic polyester fibers and other high-strength fibers is 100 parts by weight of wholly aromatic polyester fibers. The other high-strength fibers may be about 10 to 300 parts by weight, preferably about 20 to 200 parts by weight, and more preferably about 30 to 150 parts by weight.

(Matrix resin)
The matrix resin contains at least polyvinyl butyral from the viewpoint of exhibiting impact resistance in combination with the wholly aromatic polyester fiber.

(Polyvinyl butyral)
Polyvinyl butyral can be produced by a known or conventional method. For example, first, a polyvinyl alcohol (PVA) resin is prepared by saponifying polyvinyl acetate and the like, and then, butyraldehyde is added to the obtained polyvinyl alcohol resin in water and / or an organic solvent in the presence of an acid catalyst. Polyvinyl butyral may be obtained by reaction.

  The polyvinyl butyral is composed of at least a vinyl butyral unit and a vinyl alcohol unit, and may contain a vinyl acetate unit depending on the degree of saponification of PVA.

  The PVA resin for reacting butyraldehyde can be copolymerized not only with PVA homopolymer but also with vinyl alcohol such as ethylene-vinyl alcohol copolymer, partially saponified ethylene-vinyl alcohol copolymer, and vinyl alcohol. A copolymer with a monomer may also be used, and modified polyvinyl alcohol in which a carboxylic acid or the like is partially introduced may also be used. PVA resins may be used alone or in combination of two or more.

  The PVA resin may be completely saponified or partially saponified. The saponification degree is preferably 80 mol% or more, more preferably 90 mol% or more, and further preferably 95 mol% or more.

  The hydroxyl group content of polyvinyl butyral may be, for example, 5 to 40 mol%, preferably 10 to 30 mol%.

  The solution viscosity measured according to DIN 53015 of polyvinyl butyral, that is, the viscosity of an ethanol solution having a resin concentration of 10% by weight measured at 20 ° C. using a Heppler viscometer is about 2 to 500 mPa × s, more preferably It may be about 2 to 200 mPa × s, more preferably about 2 to 125 mPa × s, and particularly preferably about 2 to 75 mPa × s.

(Other resins)
The matrix resin of the present invention may contain other resins as long as it is compatible with polyvinyl butyral. Such resins include phenolic resins (novolak type, resol type), epoxy resins (bisphenol A type, novolak type, brominated type, alicyclic type, etc.), vinyl ester resins (bisphenol A type, novolak type). Thermosetting resins such as unsaturated polyester resins, crosslinked methacrylic resins, urea resins, melamine resins, diallyl phthalate resins, furan resins, silicone resins; olefin resins (eg, polyethylene, polypropylene, Ethylene vinyl acetate copolymer, etc.), polyester resins (eg, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, etc.), polyamide resins (eg, aliphatic polyamides such as polyamide 6 and polyamide 66) Alicyclic polyamide, aromatic polyamide, etc.), styrene resin (for example, polystyrene), (meth) acrylic resin, polyether resin, polycarbonate resin, ionomer resin (for example, olefin ionomer, fluorine ionomer, etc.) ), Thermoplastic elastomers (such as styrene thermoplastic elastomers, urethane thermoplastic elastomers, olefin thermoplastic elastomers, vinyl chloride thermoplastic elastomers, polyester thermoplastic elastomers, polyamide thermoplastic elastomers, etc.) Can be mentioned.

  These resins may be used alone or in combination of two or more. Of these resins, thermosetting resins such as phenolic resins, epoxy resins, vinyl ester resins, unsaturated polyester resins, and cross-linked methacrylic resins are preferable, and phenolic resins are particularly preferable.

  The resin adhesion amount in the composite can be appropriately selected according to the shape of the high-strength fiber group. For example, when the high-strength fiber group forms a fabric, the resin adhesion amount is reduced in weight. From this viewpoint, the resin solid content may be, for example, about 10 to 60% by weight, preferably about 20 to 55% by weight.

  The ratio of polyvinyl butyral to other resins (for example, phenolic resin) is about 0 to 500 parts by weight, preferably about 20 to 400 parts by weight, more preferably about 100 parts by weight of polyvinyl butyral. May be about 40 to 300 parts by weight.

  The matrix resin may be a curing agent, a curing accelerator, a curing catalyst corresponding to the thermosetting resin, if necessary, a colorant such as a compatibilizer, a filler, a dye or a pigment, or an antioxidant. In addition, various additives such as an ultraviolet absorber and a light stabilizer may be contained.

[Complex]
As described above, the impact-resistant composite of the present invention may be a composite in which (i) a matrix resin is mixed with a group of high-strength fibers such as chopped strands, or (ii) It may be a composite formed by impregnating a dissolved matrix resin prepolymer with a high-strength fiber cloth, or (iii) a high-strength fiber cloth and a cloth-like or sheet-like matrix resin are laminated. Or (iv) a composite obtained by impregnating a high-strength fiber fabric with an emulsion containing a matrix resin prepolymer, drying it, and laminating it to form a composite by heating. May be.

  For example, when a thermosetting resin is used as the other resin, the method (i), (ii) or (iv) is preferable in order to easily produce a composite, and particularly (ii) or (iv) ) Is preferred.

In the present invention, since the wholly aromatic polyester fiber is used as the reinforcing fiber, it is possible to reduce the weight of the entire composite while having impact resistance, and the density per area, that is, the basis weight, may be 1000~7000g / ^{m 2} approximately, preferably about 1500~5000g / ^{m 2.}

  Further, the thickness of the composite can be set in a wide range depending on the application. For example, from the viewpoint of weight reduction, it may be about 0.5 mm to 10 mm, preferably about 1 to 8 mm. It may be.

  In the composite thus obtained, the shape as a whole is not particularly limited, and may be a two-dimensional shape or a three-dimensional shape.

  The present invention also includes an impact-resistant material in which the composite is partially or wholly applied, and such an impact-resistant material is used as an additional armor to an impact plate, a high-speed moving object, various buildings, or the like, or It can be used effectively as a helmet or bulletproof clothing.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited at all by this Example. In addition, the various physical properties in an Example are calculated | required with the following method.

[Logarithmic viscosity]
A polymer sample was dissolved in pentafluorophenol in an amount of 0.1% by weight (60 to 80 ° C.), and the relative viscosity (ηrel) was measured with a Ubbelohde viscometer in a constant temperature bath at 60 ° C., and calculated according to the following formula.
ηinh = ln (ηrel) / c
Where c is the polymer concentration (g / dl).

[Melting point]
The peak temperature of the main endothermic peak observed with a differential scanning calorimeter (Mettler DSC) was defined as the melting point Mp (° C.).

[Solution viscosity]
According to DIN 53015, the viscosity of an ethanol solution having a resin concentration of 10% by weight was measured at 20 ° C. using a Heppler viscometer.

[Fiber strength, elongation, initial elastic modulus]
It measured based on JISL1013.

[Surface impact test method]
Using a falling weight graphic impact tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.), measurement was performed based on the JIS K-7111 Plastic-Hard Plastic Puncture Impact Test Method. The measurement conditions were a striker diameter of 12.7 mm, a holder diameter of 76 mm, a drop height of 100 cm, a weight of 14.5 kg, and an impact speed of 4.4 m / sec. Moreover, the state of the laminated body of the Example and comparative example after a test was evaluated by visual observation.

Example 1
(1) The wholly aromatic polyester polymer whose structural units (A) and (B) are 73/27 (molar ratio) was used. The physical properties of this polymer were ηinh = 4.6 dl / g, melting point Mp = 280 ° C. The polymer was spun using a normal melt spinning apparatus to obtain a multifilament of 1670 dtex / 300 filament. This multifilament was heat-treated in a nitrogen atmosphere at 280 ° C. for 20 hours to obtain a wholly aromatic polyester polymer filament (strength 23 cN / dtex).

(2) A plain woven fabric having a weft density of 12 / 2.5 cm and a warp density of 12 / 2.5 cm was produced using this filament. The fabric weight was 167 g / m ² and the thickness was 0.31 mm.

(3) 8 sheets of this woven fabric were laminated, polyvinyl butyral (manufactured by Kuraray Co., Ltd., “Mowital B30H”, hydroxyl group content 20% by weight, solution viscosity 48 mPa × s measured according to DIN 53015), and a 10 wt% methyl ethyl ketone solution; A varnish was prepared by blending a resol type phenolic resin (manufactured by Sumitomo Bakelite Co., Ltd., “PR-51406”, number average molecular weight 300, resin content 50% by weight) in a weight ratio of 1: 1. . This varnish was impregnated with the plain fabric of (2), dried at 150 ° C. to form a prepreg, and laminated with 8 sheets, and then heat-pressed to produce a laminated molded plate (weight per unit area 2720 g / m ² , thickness 2 8 mm). The resin adhesion amount of this molded plate was 50.9% by weight. The surface impact test performance of this composite is shown in Table 1.

(Example 2)
(1) A plain woven fabric having a weft density of 12 / 2.5 cm and a warp density of 12 / 2.5 cm using carbon fiber (manufactured by Toho Tenax Co., Ltd., “BESFITE HTS40 3K”, strength 28 cN / dtex). Produced. The fabric weight was 200 g / m ² and the thickness was 0.25 mm.

(2) Four carbon fiber plain fabrics prepared in (1) above are superposed, and two plain fabrics obtained in (2) of Example 1 are superposed on the top and bottom, respectively, for a total of eight The woven fabric was laminated. The laminated fabric was impregnated with a matrix resin in the same manner as in (3) of Example 1 to prepare a laminated molded plate (weight per unit area 2840 g / m ² , thickness 2.8 mm). The resin adhesion amount of this molded plate was 48.3% by weight. The surface impact test performance of this composite is shown in Table 1.

(Example 3)
(1) Glass fiber plain fabric (manufactured by Nittobo Co., Ltd., “WF 230 100 BS6”, weft density 19 / 2.5 cm, warp density 18 / 2.5 cm, basis weight 200 g / m ² , thickness 0.25 mm ) Was prepared.

(2) Four glass fiber plain fabrics produced in (1) above are superposed, and two plain fabrics obtained in (2) of Example 1 are superposed on the top and bottom, respectively, for a total of eight The woven fabric was laminated. The laminated fabric was impregnated with a matrix resin in the same manner as in (3) of Example 1 to prepare a laminated molded plate (weight per unit area 2840 g / m ² , thickness 2.8 mm). The resin adhesion amount of this molded plate was 50.6% by weight. The surface impact test performance of this composite is shown in Table 1.

Example 4
(1) Carbon fiber (manufactured by Toho Tenax Co., Ltd., “Besfight HTS40 3K”, strength 28 cN / dtex) and wholly aromatic polyester polymer filament (strength 23 cN / dtex) obtained in (1) of Example 1 Were used as wefts and warps, respectively, to produce plain woven fabrics having a weft density of 12 / 2.5 cm and a warp density of 12 / 2.5 cm. The fabric weight was 184 g / m ² and the thickness was 0.28 mm.

(2) Eight mixed plain woven fabrics of wholly aromatic polyester fibers and carbon fibers prepared in the above (1) were laminated, and matrix resin was applied to the laminated woven fabrics in the same manner as (3) of Example 1. Was laminated to produce a laminated molded plate (weight per unit area 2970 g / m ² , thickness 2.8 mm). The resin adhesion amount of this molded plate was 47.1% by weight. The surface impact test performance of this composite is shown in Table 1.

(Comparative Example 1)
As a matrix resin, (1) 130 parts by weight of a polyfunctional epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., “YL6046B80”), (2) 70 wt. Except for preparing a varnish by mixing 0.3 part by weight of (3) imidazole type curing accelerator (manufactured by Japan Epoxy Resin Co., Ltd., “EMI24”), and (4) 130 parts by weight of methyl ethyl ketone. In the same manner as in Example 1, a molded plate (weight per unit area 2680 g / m ² , thickness 2.7 mm) was produced. The resin adhesion amount of this molded plate was 50.1% by weight. The surface impact test performance of this composite is shown in Table 1.

(Comparative Example 2)
(1) As a group of high-strength fibers, aramid fibers (manufactured by Toray DuPont Co., Ltd., “Kevlar 49”, strength 19 cN / dtex) are used, and the weft density is 13 / 2.5 cm, the warp density is 13/2. A 5 cm plain fabric was made. The fabric weight was 175 g / m ² and the thickness was 0.26 mm.

(2) Eight aramid plain fabrics prepared in (1) above were laminated, and the laminated fabric was impregnated with a matrix resin in the same manner as in (3) of Example 1 to form a molded plate (weight per unit: 2760 g / m ² , thickness 2.8 mm). The resin adhesion amount of this molded plate was 49.3% by weight. The surface impact test performance of this composite is shown in Table 1.

(Comparative Example 3)
(1) As a high-strength fiber group, an aramid fiber (manufactured by Toray DuPont Co., Ltd., “Kevlar 49”, strength 19 cN / dtex) was used, and the fiber surface was subjected to a fluorine compound treatment. Specifically, first, Daikin Industries, Ltd., Unidyne TG510 (8% by weight), Kyokin Kasei Co., Ltd. EC243 (6% by weight), Sumitomo 3M Ltd. Sumitex Resin M3 (0.8% by weight) %), Catalyst ACX (0.5 wt%), isopropyl alcohol (6 wt%) and water (78.7 wt%) were prepared. And the aramid fiber was immersed in this aqueous solution for about 30 seconds, and then the aramid fiber was dried for 3 minutes in a drying furnace at 120 ° C. Further, heat treatment was performed in a baking furnace at 160 ° C. for 1 minute. Using this treated fiber, a plain woven fabric having a weft density of 13 / 2.5 cm and a warp density of 13 / 2.5 cm was produced. The fabric weight was 180 g / m ² and the thickness was 0.26 mm.

(2) Eight aramid plain fabrics prepared in (1) above were laminated, and the laminated fabric was impregnated with a matrix resin in the same manner as in (3) of Example 1 to form a molded plate (weight per unit: 2760 g / m ² , thickness 2.8 mm). The resin adhesion amount of this molded plate was 48.0% by weight. The surface impact test performance of this composite is shown in Table 1.

  As shown in Table 1, in Examples 1 to 4 in which polyvinyl butyral was applied as a matrix resin to the fully aromatic polyester fiber, high impact resistance was shown in the surface impact test, and penetration due to impact did not occur.

  On the other hand, in Comparative Example 1 in which an epoxy resin was applied as a matrix resin to a wholly aromatic polyester fiber, the impact resistance in the surface impact test was low, and the composite after the impact test penetrated by impact.

  In Comparative Example 2 using aramid fibers instead of wholly aromatic polyester fibers, even when polyvinyl butyral is used as the matrix resin, the impact resistance in the surface impact test is low, and the composite after the impact test is caused by impact. Penetrated.

  In Comparative Example 3, the composite after the impact test did not penetrate due to the impact, but in this Comparative Example, surface treatment of the fluorine compound on the aramid fiber was necessary.

  Since the impact-resistant composite of the present invention is excellent in impact resistance, it is used as an impact-resistant material to be added to high-speed moving objects such as impact plates, automobiles, railways, and airplanes, various buildings, or helmets or bulletproofs. It can be effectively used as a constituent material for clothing and the like.

Claims (8)

A composite comprising a high-strength fiber group composed of high-strength fibers having a tensile strength of 10 cN / dtex or more and a matrix resin,
The high-strength fiber group is at least one kind of fabric selected from the group consisting of a unidirectional woven fabric, a bi-directional woven fabric, a triaxial woven fabric, and a multiaxial woven fabric with respect to a wholly aromatic polyester fiber, and at least wholly aromatic Including polyester fiber,
The matrix resin is an impact-resistant composite containing at least polyvinyl butyral.   2. The composite according to claim 1, wherein at least a part of the high-strength fiber group forms a fabric. The composite according to claim 2, wherein the fabric weight per sheet is 50 to 500 g / m ² and the thickness is 0.1 to ² mm. The composite according to any one of claims 1 to 3, wherein the matrix resin includes polyvinyl butyral and, if necessary, other resin having compatibility with polyvinyl butyral, and polyvinyl butyral and other resin, Is a composite in which the other resin is 0 to 500 parts by weight with respect to 100 parts by weight of polyvinyl butyral .   5. The composite according to claim 1, wherein the matrix resin is composed of polyvinyl butyral and a phenol resin. In the complex of any one of claims 1 to 5, composite basis weight is 1000~7000g / ^{m 2.}   The composite according to any one of claims 1 to 6, wherein a fluorine compound is not substantially applied to the high-strength fiber group.   The impact-resistant material formed from the composite_body | complex as described in any one of Claims 1-7.