JP2009121774A - Composite bulletproof plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composite bulletproof plate, easily formed, light-weighted and having excellent impact resistance in the case of impact. <P>SOLUTION: A high strength fiber reinforced plastic member, a plurality of ceramic sheet members stuck to the surface thereof without a clearance, and a sheet member covering the whole surfaces of the ceramic members are sequentially stack to form the composite bulletproof plate. In the composite bulletproof plate, the peripheral part of the sheet member covers the peripheral part of the high strength fiber reinforced plastic member, or the peripheral part of the high strength fiber reinforced plastic member covers the peripheral part of the sheet member. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a composite bulletproof plate. More specifically, the present invention relates to a composite bulletproof plate that is easy to mold, lightweight, and excellent in impact resistance when hit.

First of all, composite bulletproof plates need to have excellent impact resistance against bullets with a large penetrating force such as rifles and rifles that collide at high speed, and conventional high-strength fibers are used as reinforcing materials. A normal configuration such as FRP is not sufficient. For this reason, metal plates are laminated on the surface of the FRP, or bulletproof plates made of only metal materials have been used. Alternatively, instead of metal, ceramics or ceramic styles have been formed into shapes arranged on the surface of FRP and used as bulletproof plates.
However, when trying to cope with bulletproof plates made of only metal materials, bulletproof steel plates with excellent bulletproof properties have a large specific gravity, and it is extremely heavy because it is necessary to thicken the steel plates to make rifle bullets resistant. Not practical. Therefore, it is conceivable to use a titanium alloy having a small specific gravity, but it is not sufficient in terms of weight reduction effect.
Therefore, a combination of FRP and ceramics is considered as a lighter and more bulletproof effect. In this combination, a ceramic member is provided on the landing side with an FRP made of ultra high strength fiber such as “Kevlar” as a back plate. The bulletproof steel plate, ceramics, and FRP can be fixed by mechanical methods such as bolts, nuts, rivets, etc., adhesive resin sheets used for FRP, and general synthetic rubber or epoxy adhesives. Although a physicochemical method of bonding is used, fixing with an adhesive resin sheet or an adhesive described later is preferable from the viewpoint of simplicity.
However, the fixing with the adhesive resin sheet or the adhesive is not sufficiently reliable with respect to the impact of a bullet or the like having a high penetrating force, and an improvement in performance is strongly demanded.
For this reason, it has been proposed to form a composite protective plate by providing a hollow layer between a metal plate and an aramid fiber woven fabric reinforced plastic sheet (Patent Document 1).
In addition, regarding the ceramic member, due to its extremely fragile nature, there is a problem that if the ceramic is a single piece, the entire protective plate is greatly broken by a single landing. In order to cope with such a problem, a ceramic member is provided with a groove portion so that damage is not widely propagated except for a landed portion (Patent Literature 2), a coating with a reinforcing fiber cloth (Patent Literature 3), and a high strength There has been proposed a composite (Patent Document 4) encased in a plastic member.
However, these materials are not practical because the strength does not increase to a satisfactory level, and when a ceramic member is to be enlarged, not only the manufacturing time increases but also the manufacturing itself becomes difficult.
From such a viewpoint, at present, a method of manufacturing a small ceramic style and laying it out without any gap is employed (Patent Documents 5 and 6).
The basic idea of this method was considered to be a highly probable method, including practical and performance aspects. However, it has been found that the method of arranging ceramic styles is a weak point because the joint portion of the ceramic style is easily broken.
In order to deal with such problems, it is required to lay the butt joints of the ceramic style end face without any gaps. However, the butt joint part of the ceramic style end face is displaced in the manufacturing process, or the ceramic style is separated from the end part. However, the total performance of the composite was still insufficient (see FIG. 3).

Japanese Utility Model Publication No. 1-144699 (No. 7-17990) Utility Model Registration No. 3132775 Japanese Utility Model Publication No. 1-94794 (No. 7-11346) Japanese Patent Laid-Open No. 8-72200 (Japanese Patent No. 3127947) JP 2002-326861 A JP 2005-247622 A

  An object of the present invention is to provide a composite bulletproof plate that is lightweight and excellent in impact resistance against bullets and the like in view of the background of the above-described conventional technology.

  The inventors of the present invention cover the ends of the ceramic members joined together, and the periphery of the sheet member covers the periphery of the high-strength fiber-reinforced plastic member, or the high-strength fiber-reinforced plastic member. It has been found that a composite bulletproof plate having a light weight and excellent impact resistance against bullets and the like can be obtained by making the peripheral portion cover the peripheral portion of the sheet member. The present invention has been completed based on such findings.

That is, the present invention provides the following (1) to (13).
(1) A high-strength fiber reinforced plastic member, a plurality of ceramic members affixed to the surface thereof without gaps, and a composite bulletproof plate formed by sequentially laminating a sheet member covering the entire surface of the ceramic member, the sheet member A peripheral part of the high-strength fiber-reinforced plastic member covers the peripheral part of the high-strength fiber-reinforced plastic member, or a peripheral part of the high-strength fiber-reinforced plastic member covers the peripheral part of the sheet member,
(2) The composite bulletproof plate according to (1), wherein the sheet member is any one of a metal foil, a reinforced fiber cloth, a reinforced fiber paper, and a fiber reinforced plastic sheet,
(3) The composite bulletproof plate according to (1) or (2), wherein the plurality of ceramic members are laminated with a high-strength fiber-reinforced plastic member via an adhesive layer,
(4) The composite bulletproof plate according to any one of (1) to (3), wherein the sheet member is laminated with the plurality of ceramic members via an adhesive layer,
(5) The composite bulletproof plate according to (3) or (4), wherein the adhesive layer is an adhesive resin sheet,
(6) The composite bulletproof plate according to any one of (3) to (5), wherein the adhesive layer is a sheet obtained from a thermosetting resin composition containing an elastomer.
(7) The composite bulletproof plate according to (6), wherein the elastomer is a synthetic rubber or rubber-modified polymer compound having rubber elasticity at room temperature,
(8) The above ceramic member comprising at least one selected from the group consisting of alumina, silicon nitride, silicon carbide, zirconia and boron carbide, having a Vickers hardness of 10 GPa or more, a bending strength of 300 MPa or more, and a bending elastic modulus of 200 GPa or more ( 1) A composite bulletproof board according to any one of (7),
(9) The composite bulletproof plate according to any one of (1) to (8), wherein the ceramic member has a square or hexagonal plate shape with a thickness of 1 to 15 mm and a main surface area of 400 to 25000 mm ^2. ,
(10) High strength in which the specific tensile strength of the high strength fiber contained in the high strength fiber reinforced plastic member is 0.1 × 10 ⁶ m or more and the specific tensile modulus is 3.0 × 10 ⁶ m or more. The above (1) to (9) which are at least one selected from the group consisting of glass fiber, high strength carbon fiber, high strength aramid fiber, high strength aromatic polyester fiber, high strength polyethylene fiber, high strength nylon fiber and PBO fiber. ) Composite bulletproof board according to any one of
(11) A sheet-like prepreg obtained by impregnating, applying or laminating a resin to a woven fabric in which the high-strength fiber-reinforced plastic member is made of high-strength fibers, or a sheet obtained by impregnating, applying or laminating a resin by drawing the high-strength fibers in parallel. The composite bulletproof plate according to any one of the above (1) to (10), which is a laminated plate formed by laminating using a prepreg
(12) The sheet member is a fiber-reinforced plastic sheet, and a woven fabric made of high-strength fibers is impregnated with resin, coated or laminated, or a sheet-like prepreg or the high-strength fibers are aligned in parallel to impregnate or laminate the resin. The composite bulletproof plate according to any one of the above (2) to (11), which is obtained using a sheet-like prepreg, and (13) the periphery of the sheet member is the periphery of the high-strength fiber-reinforced plastic member 1 to 10% of the total length of the parallel sides from the portion or the peripheral portion of the high-strength fiber reinforced plastic member is 1 to 10% of the total length of the parallel sides from the peripheral portion of the sheet member. The composite bulletproof plate according to any one of (1) to (12), which is to be covered, is provided.

  According to the present invention, it is possible to provide a novel composite bulletproof plate that is lightweight and excellent in impact resistance against bullets and the like. In the composite bulletproof plate of the present invention, it is possible to prevent the end face of the ceramic member from being peeled off or chipped.

Hereinafter, the present invention will be described in detail.
The composite bullet-proof plate of the present invention is a high-strength fiber reinforced plastic member or sheet member obtained by folding the periphery of a sheet member or a high-strength fiber reinforced plastic member respectively laminated on both surfaces of a plurality of ceramic members attached without gaps. Must be covered (see FIGS. 5 and 6).
Peripheral portions or sheets of the high-strength fiber reinforced plastic member are folded after the peripheral portions of the sheet member or the high-strength fiber reinforced plastic member laminated on both sides of the ceramic member are folded to cover the end surface of the ceramic member. By adopting a structure that covers up to the peripheral part of the member, it is possible to prevent the ceramic member from being displaced due to the pressure (about 0.5 to 4 MPa) applied at the time of forming the composite bulletproof plate and to prevent the ceramic member from protruding from the end. . Therefore, it is possible to obtain a composite bulletproof plate having no gap at the butt joint portions of the plurality of ceramic member end faces.
Length is folded long area 400cm ² ~10000cm ² about normal bulletproof plate used is sufficient if 1cm~10cm inside the respective peripheral portion (1-10% relative to the total length of the sides parallel Inside). If it is less than 1 cm, it is insufficient to prevent the ceramic member from protruding during molding, and if it exceeds 10 cm, the bulging part of the surface that overlaps with the folded part becomes large, and it is not possible to wrap and wrap it to a length exceeding 10 cm. This is not preferable because it causes a loss and a decrease in productivity.
The peripheral part must cover all four sides (see FIGS. 1 and 2). For example, when only two opposing sides are covered, even if the entire two sides are wrapped, the ceramic member protrudes from the other two opposing sides (see FIG. 4; see FIG. 3 for the protrusion of the ceramic member). (See the enlarged view).

If the edges of the two adjacent sides of the sheet member or the high-strength fiber-reinforced plastic member are cut diagonally and the cut surfaces are brought into contact with each other, the overlapping part of the two sides of the folded part disappears. Therefore, it is preferable because the surface bulge is reduced and the smoothness is further improved (see FIG. 2). When the folded portion is temporarily bonded to the ceramic member surface by heating with an iron or the like, it is possible to prevent displacement during operation. The end face may be temporarily fixed with a stapler or the like.
As the sheet member to be used, any of metal foil, reinforced fiber cloth, reinforced fiber paper, and fiber reinforced plastic sheet can be used.

As the metal foil, aluminum foil, copper foil, stainless steel foil or the like can be used. In the case of using a metal foil, a highly water-resistant composite bulletproof plate can be obtained.
The metal foil may have an adhesive layer on one side. When the metal foil does not have an adhesive layer, it is laminated on a ceramic member (described in detail later) through a separately prepared adhesive layer (described in detail later).
As the reinforcing fiber cloth, an aramid fiber cloth, a glass fiber cloth, a high stretch / high strength polyethylene fiber cloth, a carbon fiber cloth, a xylon cloth, a polyarylate fiber cloth, a PBO (polybenzoxazole) fiber cloth, and the like can be used. Any fiber reinforced paper may be used as long as it has a heat-resistant temperature that can maintain the tensile strength during molding, and aramid paper, polyarylate paper, and the like can be used.

  The metal foil, the reinforcing fiber cloth and the fiber reinforced paper are usually laminated to a ceramic member (described in detail later) through an adhesive layer (described in detail later). The thickness of the metal foil, the reinforcing fiber cloth and the reinforcing fiber paper is usually 0.05 to 0.4 mm, preferably 0.1 to 0.2 mm. By setting the thickness to 0.05 mm or more, it is possible to prevent the ceramic member from slipping out of the peripheral portion, and to prevent the composite bulletproof plate from being hit and even if part of the ceramic member is cracked, it is scattered. Can do. By setting the thickness to 0.4 mm or less, light weight and ease of folding are ensured, and bulging of the part that is folded and covers the periphery of the high-strength fiber reinforced plastic member is reduced, and the overall smoothness of the composite bulletproof board is reduced. Sex is secured.

When a fiber-reinforced plastic sheet is used as the sheet member, the basic material may be the same as that of the high-strength fiber-reinforced plastic member (described in detail later), but the thickness is usually different. Specifically, when the peripheral portion of the fiber reinforced plastic sheet is folded back to the peripheral portion side of the high strength fiber reinforced plastic member, the thickness is preferably smaller than that of the high strength fiber reinforced plastic member. When the peripheral portion of the high-strength fiber reinforced plastic member is folded back to the peripheral portion of the fiber reinforced plastic sheet, the high-strength fiber reinforced plastic member is preferably thinner.
Furthermore, when the fiber reinforced plastic sheet peripheral side is folded back to the high strength fiber reinforced plastic member peripheral side, the high strength fiber reinforced plastic member is already cured (solidified in the case of thermoplastic resin, the same applies hereinafter) at the initial stage of the manufacturing stage. In contrast, fiber reinforced plastic sheets are not yet fully cured. Since the peripheral portion of the fiber reinforced plastic sheet needs to be folded back to the peripheral portion side of the high-strength fiber reinforced plastic member, it needs to have flexibility or flexibility at the initial stage of manufacturing (Example 2 described later). The prepreg 2 corresponds to a fiber-reinforced plastic sheet as a sheet member, and a laminated plate 2 obtained by laminating and curing 50 prepregs 2 corresponds to a high-strength fiber-reinforced plastic member).
This fiber-reinforced plastic sheet is also folded back to the periphery of the high-strength fiber-reinforced plastic member, and then cured by heating in the latter stage of the manufacturing stage, resulting in a similar cured product (thermoplasticity) having a thickness different from that of the high-strength fiber-reinforced plastic member. In the case of resin, it becomes a solidified product, and the same applies hereinafter.
The fiber material in the fiber-reinforced plastic sheet, the resin impregnated, coated or coated on it, the heat curing conditions, and the like are the same as in the case of the high-strength fiber-reinforced plastic member, and will be described in detail in the description section.
The thickness of the fiber reinforced plastic sheet may be the same as that of metal foil, reinforced fiber cloth or fiber reinforced paper for the same reason.

Next, the ceramic member in the composite bulletproof plate of the present invention will be described.
The ceramic member is generally called a fine ceramic and includes at least one of alumina, silicon nitride, silicon carbide, zirconia, boron carbide, boron nitride, aluminum nitride, etc., and has a Vickers hardness of 10 GPa or more. It is preferable that the bending strength is 300 MPa or more and the bending elastic modulus is 200 GPa or more.
By having such mechanical characteristics, the bulletproof characteristics of the target composite bulletproof plate can be sufficiently improved. On the other hand, when it does not have the above-mentioned mechanical characteristics, the reliability with respect to the ballistic resistance may be impaired. Specific examples of the ceramic member satisfying such mechanical characteristics include the following products.
1. Alumina: Trade name A-471 (manufactured by Kyocera Corporation): Vickers hardness 11.8 GPa, bending strength 390 MPa, bending elastic modulus 280 GPa
2. Silicon carbide: Trade name SC1000 (manufactured by Kyocera Corporation): Vickers hardness 23.0 GPa, bending strength 450 MPa, bending elastic modulus 440 GPa
3. Silicon nitride: trade name SN220 (manufactured by Kyocera Corporation): Vickers hardness 13.9 GPa, bending strength 610 MPa, bending elastic modulus 290 GPa
In addition, Vickers hardness, bending strength, and a bending elastic modulus are measured according to JIS-R1610.

The thickness of the single (one piece) ceramic member before joining is usually about 1 to 15 mm, preferably about 3 to 10 mm. It is preferable that the area of the main surface is 400 to 25000 mm ² and presents a quadrangular or hexagonal plate shape. The thickness is required to balance the bulletproof strength and the weight increase accompanying the increase in thickness. The condition that the area of the main surface is 400 to 25000 mm ² is that the number of ceramic members constituting the composite bulletproof plate and the partial destruction of the ceramic member due to landing propagate to other parts. This is to prevent the damage area from expanding.
That is, when the composite bulletproof plate of the present invention is manufactured, it is manufactured not by a single ceramic member but by arranging a plurality of ceramic members in the plane direction and joining the end faces to each other. If the area of the main surface of the ceramic member is smaller than the above-described range, the number of ceramic members (tiles) to be used becomes extremely large, and the workability when manufacturing the composite bulletproof plate becomes extremely poor. On the other hand, when the area of the main surface of a single ceramic member becomes larger than the above-described range, if one of the ceramic members is destroyed and broken by the first landing, the area of the missing portion is extremely large. This is because when the subsequent bullets land on the chipped portion, the composite bulletproof plate may not be able to exhibit its characteristic of anti-elasticity.
Note that the requirement that a single ceramic member has a quadrangular or hexagonal shape is that, as described above, when a plurality of single ceramic members are used arranged in a tile wall shape, it can be easily packed in a close-packed state. This is because it can be done. That is, the absence of the ceramic member is eliminated, and the elasticity of the target composite bulletproof plate is not impaired. However, when a plurality of ceramic members are used in an array, it is practically difficult to eliminate gaps between adjacent ceramic members even when the ceramic members are closely packed, for example, a gap of about 0.8 mm at maximum occurs. End up. This gap is preferably about 0.3 mm or less.
It is an object of the present invention to minimize this gap as much as possible by preventing a part of the arranged ceramic members from sticking out, and as a means for that purpose, the peripheral portion of the sheet member is the above-mentioned high height. Folding is performed so as to cover the periphery of the strength fiber reinforced plastic member or so that the periphery of the high strength fiber reinforced plastic member covers the periphery of the sheet member.
Further, when the single ceramic member is hexagonal, there is only one arrangement form for close packing, but when it is quadrilateral, the arrangement form for close packing is “cross”. It is also possible to adopt a grid-like arrangement in which cross-shaped intersections are formed, or an arrangement in which a “T” -shaped cross section is formed, for example, slightly shifted so as not to form a “cross” -shaped cross section. You can also Further, when the quadrangular shape is a rectangle, the intersections may be arranged so as not to be continuously formed on a straight line like a mosaic pattern.
Further, from the viewpoint of use of a composite bulletproof plate, the ceramic member has a surface roughness of 3 to 10 μm, and a corner portion of a non-joint surface with an adhesive layer described later has a thickness of 0.1 to 0.5. A C-plane or R-plane is preferable.

Next, the high strength fiber reinforced plastic member in the composite bulletproof plate of the present invention will be described. The individual materials in the high-strength fiber-reinforced plastic member may be the same as the individual materials in the fiber-reinforced plastic sheet used as one of the sheet members, but have different thicknesses. It is preferable that the folding is thinner.
The high-strength fiber contained in the high-strength fiber-reinforced plastic member used in the present invention has a specific tensile strength of 0.1 × 10 ⁶ m or more and a specific tensile modulus of 3.0 × 10 ⁶ m or more. It is preferable that The material of the high-strength fiber is not particularly limited. For example, high-strength glass fiber, high-strength carbon fiber, high-strength aramid (aromatic polyamide) fiber, high-strength aromatic polyester fiber, high-strength aromatic poly At least one selected from the group consisting of etheramide fiber, high-strength polyethylene (ultra high molecular weight polyethylene) fiber, and high-strength nylon fiber, polyamideimide, polyetherketone, and the like, High strength carbon fiber, high strength aramid fiber, high strength aromatic polyester fiber, high strength polyethylene fiber, high strength nylon fiber and high strength PBO fiber are preferred.
By using these high-strength fibers, the impact resistance of the composite bulletproof plate of the present invention in which the high-strength fiber-reinforced plastic member is used can be improved, and the bulletproof performance can be improved. In particular, when the above-described numerical mechanical characteristics are not satisfied, there may be cases where sufficient bulletproof performance cannot be obtained.

As a product of high strength fiber used in the present invention,
1) Aramid fiber: DuPont brand name Kevlar 29, specific tensile strength 0.22 × 10 ⁶ m, specific tensile modulus 5.3 × 10 ⁶ m
2) Carbon fiber: trade name Torayca T300 manufactured by Toray Industries, Inc., specific tensile strength 0.22 × 10 ⁶ m, specific tensile elastic modulus 14.2 × 10 ⁶ m
3) High-strength polyethylene fiber: Dyneema manufactured by Toyobo Co., Ltd., specific tensile strength 0.29 × 10 ⁶ m, specific tensile modulus 13.5 × 10 ⁶ m
And so on.
The specific tensile strength and the specific tensile elastic modulus are measured based on JISK7073.

  Further, among the resins used in the present invention for impregnating, coating or laminating these high-strength fibers, examples of thermosetting resins include epoxy resins, epoxy acrylate resins, phenol resins, polyurethane resins, unsaturated polyester resins, vinyl esters. Examples of thermoplastic resins include polyolefins such as polyethylene and polypropylene, polyamides, polyesters, polyvinyl acetates, polyether sulfides, polyphenyl sulfides, polyethers, and ether ketones, and thermoplastic polyurethanes and styrenes. Butadiene rubber, nitrile rubber, acrylonitrile styrene (AS) resin, synthetic rubber such as neoprene, or elastomer.

When it is a thermosetting resin, examples of the curing agent include polyamine curing agents such as diethylenetriamine, tertiary amine compound curing agents such as benzyldimethylamine and 2- (dimethylaminomethyl) phenol, and phthalic anhydride. Anhydrides such as tetrahydrophthalic anhydride and tetrahydrophthalic anhydride, imidazole compound curing agents such as 2-methylimidazole and 2-phenylimidazole, peroxides such as benzoyl peroxide and dicumyl peroxide, phenol novolacs , Trioxane trimethylene mercaptan, compounds having isocyanate groups such as tolylene diisocyanate and hexamethylene diisocyanate, compounds having phenol groups such as phenol and cresol, compounds having hydrazide groups, or carboxyl groups A compound having the like.
A high-strength fiber reinforced plastic member is a sheet obtained by impregnating, applying or laminating a resin to a woven or non-woven fabric made of high-strength fibers, and impregnating or laminating the resin by aligning the high-strength fibers in parallel. The laminated prepreg can be used as a laminated plate. At this time, the laminate can be configured by laminating the prepreg so that the directions of the high-strength fibers contained therein are orthogonal to each other.

As a method for producing the high-strength fiber reinforced plastic member, in the case of a thermosetting resin, a resin composition obtained by dissolving a thermosetting resin in a solvent in the high-strength fiber is prepared, and after impregnation or coating Using a bar coater or a clearance roll, scrape off the excess resin composition to produce a prepreg, and then lay up multiple sheets of this prepreg to form a laminated plate. There are laws.
On the other hand, in the case of a thermoplastic resin, a compression molding method in which a plurality of sheets of high-strength fibers and thermoplastic resin films or woven fabrics are alternately stacked and heated and pressed, or the resin is previously melted, There is also a method of attaching the resin to high-strength fibers. The content of the thermoplastic resin is the same as that of the thermosetting resin.
The resin content in the member is usually in the range of 5 to 80% (mass%, the same applies hereinafter), preferably 5 to 50%, more preferably 8 to 30%.
By setting the resin content to 5% or more, even when a high-speed flying object collides, it has high rigidity and excellent shape retention. By setting it to 80% or less, the gap between the fibers becomes an appropriate interval and is necessary. Strength can be secured.
As described with respect to the sheet member, when a fiber reinforced plastic sheet is used in various sheet members, the high-strength fiber reinforced plastic member may be basically the same material as the fiber reinforced plastic sheet. The thickness is different.
Therefore, a fiber reinforced plastic sheet used as a sheet member (for example, a prepreg as used in the examples described later) is first heat-cured, and then the ceramic member is pasted in a finely packed state, and then the ceramic member A flexible high-strength fiber reinforced plastic member that has not yet been heat-cured is affixed to cover the periphery of the high-strength fiber reinforced plastic member by folding it back to the periphery of the fiber-reinforced plastic sheet. As such, heat curing may be performed. As described above, when the peripheral portion of the high-strength fiber reinforced plastic member is folded back to the peripheral portion side of the fiber reinforced plastic sheet, the bulge portion of the surface generated at the folded portion is prevented from becoming large. It is preferable to make the thickness thinner than that of the fiber-reinforced plastic sheet.
When the material other than the fiber-reinforced plastic sheet is used as the sheet member, it is preferable that the peripheral portion covers the peripheral portion of the high-strength fiber-reinforced plastic member.

Next, the adhesive layer will be described.
In the composite bulletproof plate of the present invention, the plurality of ceramic members arranged and joined so that the end surfaces are brought together are attached to the high-strength fiber reinforced plastic member via the adhesive layer, and then the plurality of attached pieces. It is preferable to laminate a sheet member on the ceramic member via an adhesive layer (when a fiber-reinforced plastic sheet is used as the sheet member, the order of application may be reversed). However, when the sheet member is a metal foil having an adhesive layer as described above, there is no need to newly laminate an adhesive layer.
The adhesive layer is preferably an adhesive resin sheet (that is, a sheet-shaped resin composition) from the viewpoint of processability or productivity, and the resin composition (adhesive composition) is a thermoset containing an elastomer. A functional resin composition is preferred. In the cured state, the adhesive resin sheet preferably has an elastic deformation rate of 20 to 60% and a compression elastic modulus of 10 ⁷ to 10 ⁸ Pa. When the elastic deformation rate and the compression elastic modulus are in the above ranges, the adhesive strength is not impaired, and the ballistic resistance and the reliability of the joint portion of the ceramic member are ensured. The adhesive strength with the ceramic member is preferably 1.0 kN / m or more.
The elastic deformation rate and the compression elastic modulus are measured using, for example, a microhardness meter. Examples of the micro hardness meter include a dynamic ultra micro hardness meter DUH-201 manufactured by Shimadzu Corporation.
When the adhesive strength is 1.0 kN / m or more, the ceramic member is less greatly scattered when it is hit. The adhesive strength is measured according to JISC6471.

As the thermosetting resin composition, a composition containing a resin used for a high-strength fiber-reinforced plastic member, that is, an epoxy resin composition, a phenol resin composition, an unsaturated polyester resin composition, or the like is used. From the viewpoint of heat resistance, an epoxy resin composition is preferred.
In particular, at least one epoxy compound, epoxy curing agent (various amines, acid anhydrides, etc.), epoxy curing accelerator (boron trifluoride monoethylamine, various imidazoles, etc.), elastomer and inorganic filler (hydroxylation) A thermosetting epoxy resin composition containing aluminum and the like and having an elastomer content of 40 to 80% by mass with respect to the total resin composition is preferable. If the elastomer content is outside the above range, the impact resistance to the shell may be impaired, and the ceramic member may be scattered by the shell due to insufficient adhesive strength. In this case, it is important that the content of the elastomer particularly satisfies the requirement of 40 to 80% by mass in the total resin composition.
As the epoxy compound, biphenyl type epoxy resin, bisphenol type epoxy resin, alicyclic epoxy resin and the like can be used without limitation, but biphenyl type epoxy resin is preferable from the viewpoints of film formability, moldability and economy.

The elastomer is not particularly limited, and acrylic rubber, acrylonitrile butadiene rubber, styrene butadiene rubber, butadiene methyl acrylate acrylonitrile rubber, butadiene rubber, carboxyl group-containing acrylonitrile butadiene rubber, silicone rubber, urethane rubber, polyvinyl butyral, natural Synthetic rubber such as rubber and isoprene rubber, chloroprene rubber, hydrogenated nitrile rubber, butyl rubber, ethylene propylene rubber, ethylene vinyl acetate rubber, polyether urethane rubber, polyester urethane rubber, fluorine rubber, polyolefin thermoplastic elastomer, polyurethane heat Plastic elastomer, polyester thermoplastic elastomer, polyamide thermoplastic elastomer, epoxy-modified butadiene Such cross-linked product of acrylonitrile copolymer. Among them, an elastomer having a glass transition temperature of −30 to 20 ° C., a weight average molecular weight of 200,000 to 700,000, and an acid value of 5 to 12 KOHmg / g is preferable, and is relatively wide from around 0 ° C. to around 100 ° C. Since it can be used stably in a temperature range, at least one selected from acrylonitrile butadiene rubber, hydrogenated nitrile rubber, ethylene propylene rubber, silicone rubber, and fluoro rubber is preferably used.
Prepare a solution in which the above resin composition is dissolved in an inert solvent (eg, propylene glycol monomethyl ether, methyl ethyl ketone, etc.) and apply it to release paper or release film (carrier film) to evaporate the solvent. Thus, an adhesive resin sheet used as an adhesive layer having a thickness of about 10 to 50 μm, preferably about 20 μm can be obtained.
By making the thickness of the adhesive layer 10 μm or more, it is possible to ensure the adhesion of the ceramic members, and by making the thickness 50 μm or less, the ceramic generated when each member is laminated and then finally finished by pressing. The movement of the member can be suppressed.

In the composite bulletproof plate of the present invention manufactured using the above-described sheet member, ceramic member, and high-strength fiber reinforced plastic member, the sheet member is usually disposed on the landing side (front surface), and an adhesive layer is provided inside thereof. It is preferable that the ceramic member is disposed, and the high-strength fiber reinforced plastic member laminated via the adhesive resin sheet which is an adhesive layer on the rear surface thereof is used in a state of being closely disposed. Thereby, the bulletproof performance of the composite bulletproof plate of the present invention can be improved. The sheet member also has a role of preventing secondary disasters due to ceramic member fragments scattered upon landing.
In order to finally finish the composite bulletproof plate composed of each member as described above, the sheet member is laminated in the above order, and the periphery of the sheet member covers the periphery of the high-strength fiber reinforced plastic member. Alternatively, the high strength fiber reinforced plastic member is folded back so that the peripheral portion of the sheet member covers the peripheral portion of the sheet member, and compression-molded under heating by a conventional method. Preferred compression molding conditions are as shown below.
Molding temperature: 100-200 ° C
Molding pressure: 0.5-4MPa
Molding time: 1 to 200 minutes

Hereinafter, the present invention will be specifically described with reference to Examples.
[Production of adhesive resin sheet (adhesive layer)]
234.93 parts by mass of acrylic synthetic rubber [SG-708-6T, glass transition temperature 6 ° C., weight average molecular weight 700,000, acid value 8.0 KOHmg / g, manufactured by Nagase ChemteX Corporation], 39.15 parts by mass Acrylonitrile butadiene based synthetic rubber [Nipol 1072, glass transition temperature -24 ° C., weight average molecular weight 340,000, acid value 12.0 KOHmg / g, manufactured by Nippon Zeon Co., Ltd.], 100 parts by mass of biphenyl type epoxy resin [NC-3000-H , Manufactured by Nippon Kayaku Co., Ltd.], 34.26 parts by mass of a flame retardant (phenoxyphosphazene oligomer, melting point 100 ° C., manufactured by Otsuka Chemical Co., Ltd.), aromatic diamine [4,4′-DDS (4,4′- Diaminodiphenyl sulfone), manufactured by Wako Pure Chemical Industries, Ltd.] 17.16 parts by mass, boron trifluoride monoethylamine [manufactured by Hashimoto Kasei Co., Ltd.] 0 as a curing accelerator .3 parts by mass, aluminum hydroxide as an inorganic filler [Hidilite H-421, manufactured by Showa Denko KK] 97.89 parts by mass of a mixture of propylene glycol monomethyl ether and methyl ethyl ketone as a solvent (mass ratio) 1/1 A mixed solvent was added to prepare an adhesive composition having a solid content of 40% by mass. This adhesive composition was applied and dried on a release paper having a thickness of 30 μm with a roll coater so that the thickness after drying was 20 μm, to obtain “adhesive resin sheet 1 (adhesive layer)”.

[Example 1]
UD prepreg of aramid fiber-polyurethane resin [area: about 5000 cm ² , thickness: about 0.2 mm, manufactured by Honeywell, UD sheet (trade name: RS sheet), basis weight 222 g / m ² , resin amount 30% by mass, aramid The fiber has a specific tensile strength of 0.22 × 10 ⁶ m and a specific tensile modulus of 5.3 × 10 ⁶ m] so that the length direction of the fiber bundle is 0 degrees and 90 degrees, and the fibers are arranged orthogonally. 50 sheets are stacked and molded while being cured under molding conditions of 130 ° C., 30 minutes, molding pressure of 13 MPa, and the “laminated plate 1 (high strength fiber reinforced plastic member having an area of about 5000 cm ² and a thickness of about 8.7 mm” is obtained. ) ”.
Next, “adhesive resin sheet 1” having the same area and shape as “laminate plate 1” is laminated on one side (front surface) of “laminate plate 1”, and alumina ceramic plate (ceramic member) [A- 471 (manufactured by Kyocera), 100 mm × 100 mm × thickness 8 mm, average roughness of joint surface with laminated plate 4.5 μm, with corner finish], the gap between 10 sheets in the vertical and horizontal directions and 5 sheets in total is 50 as narrow as possible, In addition, an “aluminum sheet” having an area of 8024 cm ² and an adhesive layer with a thickness of 0.1 mm is attached to the upper surface of the bonded alumina ceramic plate. (Sheet member) "is laminated on the adhesive layer side, and the peripheral part of" aluminum sheet "is folded back by 70 mm from each side to cover all four sides of the back side peripheral part of" laminate 1 ", molding conditions, 160 ° C, 6 Min, to produce a "composite bulletproof plate" press molding to an area of about 5000 cm ² × thickness of about 17mm in the molding pressure 4 MPa. Note that the four corners of the peripheral portion of the “aluminum sheet” were cut out so that the folded portion had the shape shown in FIG.

[Example 2]
Aramid fiber woven fabric [area approximately 8024 cm ² , thickness approximately 0.25 mm, fiber: manufactured by DuPont, trade name Kevlar 29, specific tensile strength 0.22 × 10 ⁶ m, specific tensile elastic modulus 5.3 × 10 ⁶ m ], Impregnated with an epoxy resin-based impregnated varnish (TVB-2638, solid concentration 80% by mass, manufactured by Kyocera Chemical Co., Ltd.) and dried to obtain “prepreg 2” [thickness of about 0.2 mm, basis weight 220 g / m ² , Resin amount 30% by mass] was prepared. This “prepreg 2” is cut into an area of about 5000 cm ² and 50 sheets are overlapped and press-molded while being cured under molding conditions of 160 ° C., 60 minutes, molding pressure 4 MPa, an area of about 5000 cm ² and a thickness of about An 8.6 mm “laminate 2 (high-strength fiber reinforced plastic member)” was produced.
Next, “adhesive resin sheet 1 (adhesive layer)” having the same area as “laminate plate 2” is laminated on one side (front surface) of “laminate plate 2”, and alumina ceramic plate (ceramic member) [A -471 (manufactured by Kyocera Corporation), 100 mm × 100 mm × thickness 8 mm, average roughness 4.5 μm of the joint surface with the laminated plate, with corner finish], 10 sheets in length and width and 5 sheets in total, the same as in Example 1. Further, the upper surface of the bonded alumina ceramic plate is covered with “prepreg 2 (sheet member)” having an area of about 8024 cm ² , and folded back by 70 mm from each side on the back surface side of “laminate plate 2”. "Compound bulletproof board" that covers all four sides of the back surface and is press-molded while being cured under molding conditions of 160 ° C, 60 minutes, molding pressure of 4 MPa, and has an area of about 5000 cm ² × thickness of about 17 mm. Was made.

[Example 3]
“Adhesive resin sheet 1 (adhesive layer)” having the same area as “laminate plate 1” is laminated on one side (surface) of “laminate 1 (high-strength fiber reinforced plastic member)” produced in Example 1, On top of that, 10 silicon carbide ceramic plates (ceramic members) [SC1000 (manufactured by Kyocera), 100 mm × 100 mm × thickness 5 mm, average roughness of joint surface with laminated plate 4.5 μm, with corner finishing] A total of 50 sheets were stuck in the same manner as in Example 1, and further covered with “aramid fiber woven fabric (sheet member)” having an area of about 7296 cm ² and a thickness of 0.2 mm, and four sides each on the back side. after folded from the side about 50mm increments covered a rear surface of the "laminate 1", 160 ° C., 60 min, area of about 5000 cm ² × thickness by press molding while curing the molding conditions of molding pressure 4MPa To produce a "composite bulletproof plate" of about 14mm. The “adhesive resin sheet 1 (adhesive layer)” having the same area as the “aramid fiber woven fabric” was laminated between the “aramid fiber woven fabric” and the silicon carbide ceramic plate.

[Comparative Example 1]
The same as in Example 1 except that the “aluminum sheet” used in Example 1 is cut so as to have the same size and shape as “Laminated plate 1” and formed without a folded portion (see FIG. 3). Thus, a “composite bulletproof plate” for comparison was produced.

[Comparative Example 2]
Similar to Example 2 except that the “prepreg 2” used in Example 2 is cut so as to have the same size and shape as “Laminate 2” and formed without a folded portion (see FIG. 3). Thus, a “composite bulletproof plate” for comparison was produced.

[Comparative Example 3]
Similar to Example 3 except that the aramid fiber woven fabric used in Example 3 is cut so as to have the same size and shape as “Laminate 1” and formed without a folded portion (see FIG. 3). Thus, a “composite bulletproof plate” for comparison was produced.

[Comparative Example 4]
A comparative “composite bulletproof plate” was prepared in the same manner as in Example 2 except that a prepreg having a width of 50 cm and a length of 304 cm was used and the peripheral portion of one side was wrapped and molded.

[Comparative Example 5]
A comparative “composite bulletproof plate” was prepared in the same manner as in Example 1 except that the prepreg 2 was the same as in Example 2 except that the width was 154 cm and the length was 304 cm.
Table 1 shows the member configuration, productivity, appearance, and antiballistic test results of the “composite bulletproof plate” obtained in the above example and the comparative “composite bulletproof plate” obtained in the comparative example.

Each characteristic was measured by the following test method.
(1) Productivity preparation time is a laminated plate (high-strength fiber reinforced plastic member), an adhesive resin sheet (adhesive layer), 50 ceramic members and a sheet member laminated to form 100 “composite bulletproof plates”. It was set as the time until 10 stages of products were finished in each stage, 10 sheets per stage.
The amount of sheet member used was as described in the above examples and comparative examples (Table 1), and was defined as the total area of the member used (unit cm ² ).
(2) Appearance The maximum protrusion length of the ceramic member was measured by measuring the maximum length of the ceramic member protruding from the laminated plate on the side surface of the “composite bulletproof plate” after molding (unit: mm).
The sheet member folding side surface appearance was evaluated visually by the following criteria for the smoothness of the laminated plate surface after molding.
○: Smooth, △: Slightly stepped (3) Bulletproof test From the sheet member side of the “composite bulletproof plate”, using 9.7 g bullets according to NTJ Standard 0108.01, 838 ± 15 m / sec from a distance of 5.0 m The penetration impact resistance test was conducted by firing at a speed of. Evaluation was made by hitting a bullet at the center part of the ceramic member and the joint part of the ceramic member.
Evaluation items and evaluation criteria are as follows.
a) Peeling between ceramic member and laminate (high-strength fiber reinforced plastic member) ○: No peeling, Δ: Some peeling, x: Many peelings occurred b) Swelling on the surface of the laminate ○: No swelling, Δ: Swelling There are a few, x: many occurrences of bulging c) Laminate side surface appearance (visual evaluation of the smoothness of the back side of the laminated plate after molding)
○: Smooth, △: Slightly stepped d) Presence of penetration ○: No penetration, △: Partial penetration

  The composite bulletproof plate of the present invention is lightweight, has excellent impact resistance against bullets, etc., has a beautiful surface appearance, and serves as a protective body against objects such as bomb fragments and bullets falling from high places or flying at high speed. Can be used.

It is a perspective view of the composite bulletproof board which shows that the periphery part 4 side of a sheet | seat member is turned up and has covered the periphery part 4 side of a high strength fiber reinforced plastic member. It is a perspective view of the compound bulletproof board which shows the state which the edge part of two adjacent sides of the folded sheet | seat member was cut | disconnected diagonally, and both the cut surfaces were faced | matched. FIG. 6 is a perspective view showing a state in which a high-strength fiber-reinforced plastic member, a ceramic member, and a sheet member are simply laminated and there is no folding (an enlarged view of arrows 4 and 5 shows a state in which the ceramic member protrudes). It is a perspective view which shows that only 2 sides of a sheet | seat member are return | folded and the peripheral part 2 sides of a high strength fiber reinforced plastic member are covered. FIG. 4 is a schematic cross-sectional view of a composite bulletproof plate showing a state in which a peripheral portion of a sheet member is folded and covers a peripheral portion of a high-strength fiber-reinforced plastic member. FIG. 3 is a schematic cross-sectional view of a composite bulletproof plate showing a state in which a peripheral portion of a high-strength fiber-reinforced plastic member is folded and covers a peripheral portion of a sheet member.

Explanation of symbols

1: Sheet member 2: Ceramic member 3: High-strength fiber reinforced plastic member 4: Projection of ceramic member 5: Projection of ceramic member

Claims (13)

  A high-strength fiber reinforced plastic member, a plurality of ceramic members affixed to the surface of the ceramic member without gaps, and a composite bulletproof plate formed by sequentially laminating sheet members covering the entire surface of the ceramic member, the peripheral portion of the sheet member Covers a peripheral part of the high-strength fiber-reinforced plastic member, or a peripheral part of the high-strength fiber-reinforced plastic member covers a peripheral part of the sheet member.   The composite bulletproof plate according to claim 1, wherein the sheet member is any one of a metal foil, a reinforced fiber cloth, a reinforced fiber paper, and a fiber reinforced plastic sheet.   The composite bulletproof plate according to claim 1 or 2, wherein the plurality of ceramic members are laminated with a high-strength fiber-reinforced plastic member via an adhesive layer.   The composite bulletproof plate according to any one of claims 1 to 3, wherein the sheet member is laminated with the plurality of ceramic members via an adhesive layer.   The composite bulletproof plate according to claim 3 or 4, wherein the adhesive layer is an adhesive resin sheet.   The composite bulletproof plate according to any one of claims 3 to 5, wherein the adhesive layer is a sheet obtained from a thermosetting resin composition containing an elastomer.   The composite bulletproof plate according to claim 6, wherein the elastomer is a synthetic rubber or rubber-modified polymer compound having rubber elasticity at room temperature.   The ceramic member includes at least one selected from the group consisting of alumina, silicon nitride, silicon carbide, zirconia, and boron carbide, and has a Vickers hardness of 10 GPa or more, a bending strength of 300 MPa or more, and a bending elastic modulus of 200 GPa or more. A composite bulletproof board according to any one of the above. Composite bulletproof plate according to any one of the claims 1-8 thickness of the ceramic member is 1 to 15 mm, a plate-shaped area of 400～25000Mm ² square or hexagonal major surface. A high strength glass fiber having a specific tensile strength of 0.1 × 10 ⁶ m or more and a specific tensile modulus of 3.0 × 10 ⁶ m or more of the high strength fiber contained in the high strength fiber reinforced plastic member; The high-strength carbon fiber, the high-strength aramid fiber, the high-strength aromatic polyester fiber, the high-strength polyethylene fiber, the high-strength nylon fiber, and the PBO fiber are at least one kind selected from any one of claims 1 to 9. Composite bulletproof board.   A sheet-like prepreg obtained by impregnating, applying or laminating a resin to a woven fabric in which the high-strength fiber-reinforced plastic member is made of high-strength fibers, or a sheet-like prepreg obtained by impregnating, applying or laminating the resin by drawing the high-strength fibers in parallel. The composite bulletproof plate according to any one of claims 1 to 10, wherein the composite bulletproof plate is a laminated plate formed by lamination using.   The sheet member is a fiber reinforced plastic sheet, and a sheet-like prepreg obtained by impregnating, applying or laminating a resin to a woven fabric made of high-strength fibers, or a sheet-like prepreg in which the high-strength fibers are aligned in parallel and impregnated or laminated with a resin. The composite bulletproof plate according to any one of claims 2 to 11, which is obtained using The peripheral part of the sheet member is from the peripheral part of the high-strength fiber-reinforced plastic member,
1 to 10% inner side with respect to the total length of parallel sides, or the peripheral part of the high-strength fiber reinforced plastic member covers 1 to 10% inner side with respect to the total length of parallel sides from the peripheral part of the sheet member. The composite bulletproof plate according to any one of claims 1 to 12.

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