JP4869915B2 - Compound bulletproof board - Google Patents

Description

  The present invention relates to a composite bulletproof plate that is lightweight and excellent in impact resistance such as a bullet.

  Unlike pistols, rifles and rifles have a much higher bullet penetration, so conventional FRPs that use high-strength fibers as a reinforcing material cannot be bulletproof in normal configurations. Therefore, metal has been laminated on the surface, or the structure of a single metal has been supported. Alternatively, instead of metal, ceramics and further ceramic styles have been formed on the surface and used as bulletproof plates.

  However, when trying to cope with metal, in a bulletproof steel plate having excellent bulletproof properties, the specific gravity is large, and if the rifle bullet is made bulletproof, it becomes extremely heavy and is not practical. Then, although application of titanium alloy etc. with a small ratio is considered, it is still not sufficient in terms of weight and has a problem. Therefore, a combination with ceramics has been considered as a lighter and more resilient material.

  In this combination, a ceramic member is provided on the landing side of an FRP made of ultrahigh-strength fibers such as “Kevlar” as a back plate, and a method of fixing the ceramic member and the FRP. For example, mechanical methods such as bolts and rivets, or the resin itself used for FRP, or chemical methods of bonding with general synthetic rubber and epoxy resin adhesives are used. From the viewpoints of optimization and simplicity, fixing with an adhesive described later is preferable.

  However, the fixing with 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.

  In addition, the ceramic member has the disadvantage that, due to its extremely fragile nature, if a single ceramic piece is used, it will be greatly broken by a single impact. In addition, when trying to enlarge the ceramic member, the manufacturing time increases and the manufacturing itself becomes difficult, which is not practical. From this point of view, at present, a method of manufacturing a small ceramic style and spreading it without gaps is employed.

  As a basic idea, this method was considered to be a highly practical method, including the performance aspect. However, the method of arranging ceramic styles has been found to be a weak point in the ceramic style joints due to the tendency of ceramics to break.

In order to cope with such a problem, a composite body in which a ceramic member is wrapped with a high-strength plastic member has been proposed, but the reliability of joining with the ceramic member is still insufficient (see Patent Document 1). ). Moreover, although the proposal of the shape improvement in a ceramic member is also made | formed, it is still inadequate in terms of the total performance as a composite (refer patent document 2).
JP-A-8-72200 JP 2002-326861 A

  In view of the background of such prior art, the present invention is intended to provide a composite bulletproof plate that is light and excellent in impact resistance against bullets.

  The present invention employs the following means in order to solve such problems. That is, the composite bulletproof board of the present invention has the following features.

1) A composite bulletproof plate comprising a ceramic member, a high-strength fiber reinforced plastic member, and a resin sheet for joining the ceramic member and the high-strength fiber reinforced plastic member. 2) The resin sheet has an elastomer. Including a thermosetting resin composition;
3) The thermosetting resin composition includes (A) at least one epoxide compound, (B) an epoxy curing agent, (C) an epoxy effect accelerator, (D) an elastomer, and (E) an inorganic filler. The content of the elastomer (D) is 40 to 80% by weight with respect to the total resin composition, and the elastic deformation rate in the cured state of the resin sheet is 20 to 60%.
The compressive elastic modulus is 10 ⁸ to 10 ¹⁰ Pa , and the adhesive strength with the ceramic member is 1.0 kN / m or more.

4) The (D) elastomer is a synthetic rubber or rubber-modified polymer compound having rubber elasticity at room temperature.

5) The synthetic rubber is at least selected from the group consisting of acrylic rubber, acrylonitrile butadiene rubber, styrene butadiene rubber, butadiene methyl acrylate acrylonitrile rubber, butadiene rubber, carboxyl-containing acrylonitrile butadiene rubber, silicone rubber, urethane rubber, and polyvinyl butyral. It is a kind of rubber.

6) The synthetic rubber contains a hydroxyl group and a carboxy group as functional groups.

7) The synthetic rubber has a glass transition temperature (Tg) of −30 to 20 ° C., a weight average molecular weight (Mw) of 200,000 to 800,000, and an acid value of 5 to 12 KOHmg / g. And

8) The (A) at least one epoxide compound is a biphenyl type epoxy resin.

9) The (B) epoxy curing agent is dihydroxydiphenyl sulfone.

10) The (E) inorganic filler is aluminum hydroxide.

11) The ceramic member contains at least one of alumina, silicon nitride, silicon band, zirconia, and boron carbide, has a Vickers hardness of 10 GPa or more, a bending strength of 300 MPa or more, and a bending elasticity of 200 GPa. It is the above.

12) The ceramic member has a rectangular or hexagonal plate shape with a thickness of 1 to 15 mm and a main surface area of 400 to 25000 mm ² .

13) The ceramic member has a surface roughness of 3 to 10 μm, and a corner portion of a non-joint surface with the resin sheet is a C-plane or R-plane of 0.1 to 0.5. .

14) The high-strength fiber contained in the high-strength fiber-reinforced plastic member 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 at least one selected from the group consisting of high-strength glass fiber, carbon fiber, aramid fiber, aromatic polyester fiber, high-strength polyethylene fiber, and high-strength nylon fiber.

15) The high-strength fiber-reinforced plastic member is a sheet obtained by impregnating or laminating a resin made of high-strength fiber with a resin, and forming a sheet-like prepreg, or by drawing the high-strength fibers in parallel and impregnating or laminating the resin. It is the laminated board which carried out the lamination | stacking shaping | molding using the prepreg made into the shape.

16) The laminate is formed by laminating the prepreg so that the directions of the high-strength fibers contained therein are orthogonal to each other.

  The feature 1) described above is an essential requirement of the present invention, and the features 2) to 16) show preferred embodiments (features) of the present invention. That is, by adding the features 2) to 16) to the feature 1), the above-described object of the present invention can be achieved more effectively.

  As described above, according to the features of the present invention described above, it is possible to provide a novel composite bulletproof plate that is light and excellent in impact resistance against bullets.

The resin sheet used for the composite bulletproof plate of the present invention is required to have an elastic deformation rate of 20 to 60% and a compression elastic modulus of 10 ⁸ to 10 ¹⁰ Pa in its cured state. When the elastic deformation rate and the compression elastic modulus are smaller than the above-described ranges, the adhesive strength, particularly the adhesive strength after moisture absorption is greatly impaired. Further, if the elastic deformation rate and the compression elastic modulus are larger than the above-mentioned ranges, it is not preferable because the ballistic resistance, particularly the reliability of the ceramic joint portion, is impaired.

  Moreover, the adhesive strength with the ceramic member needs to be 1.0 kN / m or more. If the adhesive strength does not satisfy this requirement, the ceramic member will be greatly scattered when it is impacted, resulting in deterioration of the ballistic resistance.

  The elastic deformation rate and the compression elastic modulus are measured with a micro hardness meter. An example of the test apparatus is a dynamic ultra-small intensity meter DUH-201 manufactured by Shimadzu Corporation. As measurement conditions, standard methods such as a test mode and a load-unload test can be adopted. The adhesive strength can be confirmed by JlS-C6471.

  The resin sheet preferably contains a thermosetting resin composition having an elastomer. In particular, (A) at least one epoxide compound, (B) an epoxy curing agent, (C) an epoxy effect accelerator, ( It is preferable that the composition contains D) an elastomer and (E) an inorganic filler, and the content of the (D) elastomer is 40 to 80% by weight based on the total resin composition. If the above requirements are not satisfied, the impact resistance against 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 (D) elastomer particularly satisfies the requirement of 40 to 80% by weight with respect to the total resin composition.

  For the same reason, the (A) at least one epoxide compound is preferably a biphenyl type epoxy resin. The (B) epoxy curing agent is preferably dihydroxydiphenyl sulfone. Furthermore, the (E) inorganic filler is preferably aluminum hydroxide.

  The (D) elastomer is preferably a synthetic rubber or rubber-modified polymer compound having rubber elasticity at room temperature, and in particular, acrylic rubber, acrylonitrile butadiene rubber, styrene butadiene rubber, butadiene methyl acrylate acrylonitrile rubber, butadiene It is preferably at least one rubber selected from the group consisting of rubber, carboxyl-containing acrylonitrile butadiene rubber, silicone rubber, urethane rubber, and polyvinyl butyral. Moreover, it is preferable that the said synthetic rubber contains a hydroxyl group and a carboxy group as a functional group. As a result, the impact resistance against the shell can be increased, the adhesive strength can be increased, and the scattering of the ceramic member by the shell can be effectively suppressed.

  Further, the synthetic rubber preferably has a glass transition temperature (Tg) of −30 to 20 ° C., a weight average molecular weight (Mw) of 200,000 to 800,000, and an acid value of 5 to 12 KOHmg / g. . When the glass transition temperature and the weight average molecular weight are smaller than the above ranges, the heat resistance is impaired, which is not preferable. On the other hand, if it is larger than the above range, the resin viscosity increases, and the workability during the production of the composite bulletproof plate is impaired, which is not preferable. In addition, when the acid value is within the above range, the adhesiveness and curability of the resin sheet containing the synthetic rubber can be set to a range that can be practically used as a bulletproof plate.

  Synthetic rubbers satisfying the above physical properties include, for example, acrylic synthetic rubber, SG-708-6T manufactured by Nagase ChemteX Corporation (glass transition temperature: 6 ° C., weight average molecular weight: 700,000, acid value: 8 0.0 KOHmg / g), acrylonitrile butadiene based synthetic rubber, Nipol 1072 manufactured by Nippon Zeon Co., Ltd. (glass transition temperature: −24 ° C., weight average molecular weight: 340,000, acid value: 12.0 KOHmg / g). .

  The resin sheet is prepared as a film-like adhesive by a normal method of diluting a raw material substance having the above-described material composition with a suitable organic solvent such as propylene glycol monomethyl ether, applying it on a carrier film, and drying by heating. Obtainable.

  In the present invention, the ceramic member contains at least one of alumina, silicon nitride, silicon zirconia, and boron carbide, has a Vickers hardness of 10 GPa or more, a bending strength of 300 MPa or more, The elasticity is preferably 200 GPa or more. In this case, the bulletproof property of the intended composite bulletproof plate can be sufficiently improved. On the other hand, if the above-described requirements are not satisfied, the reliability with respect to the ballistic resistance may be impaired. Specific examples of the ceramic member satisfying such requirements include the following.

1. Alumina: Product name A471 (manufactured by Kyocera Corporation); Vickers hardness 11.8Gpa, bending strength 390MPa, flexural modulus 280GPa
2. Silicon carbide: Trade name SC1OOO (Kyocera); Vickers hardness 23.0Gpa, bending strength 450MPa,
Flexural modulus 440GPa
3. Silicon nitride: Trade name SN220 (manufactured by Kyocera Corporation); Vickers hardness 13.9Gpa, bending strength 610MPa, flexural modulus 290GPa

  Vickers hardness, bending strength, and flexural modulus are determined according to JIS-R1610.

The ceramic member preferably has a quadrangular or hexagonal plate shape with a thickness of 1 to 15 mm and an area of the main surface of 400 to 25000 mm ² . The thickness is required to balance the bulletproof strength and the accompanying weight increase. More preferably, it is 3-10 mm.

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 size of the damaged area caused by the destruction of the ceramic member due to the landing of the ceramic member. Is taken into account. That is, when manufacturing a composite bulletproof plate, it is generally manufactured by bonding a plurality of ceramic members in a tile shape rather than from a single ceramic member, but the area of the main surface of the ceramic member is more than the range described above. Is too small, the number of ceramic members (tiles) to be used becomes extremely large, and the workability when manufacturing the composite bulletproof plate is extremely deteriorated. On the other hand, when the area of the main surface of the ceramic member becomes larger than the above-described range, when one of the ceramic members is destroyed by the first landing, the area of the defect portion becomes extremely large and continues. This is because a case in which a bullet is landed on the defect portion and the composite bulletproof plate cannot exhibit the characteristic of anti-elasticity is likely to occur.

  Note that the requirement that the ceramic member has a quadrangular or hexagonal shape is that when the ceramic member is arranged in a plurality of tiles as described above, it can easily be in a close-packed state. is there. That is, the ceramic member does not come off, 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 they are closely packed, for example, a maximum of 0.8 mm, preferably 0.8 mm. A gap of about 3 mm is generated.

  Further, when the ceramic member is hexagonal, there is only one type of close-packing method. However, when the ceramic member is quadrilateral, the close-packing method can be a lattice arrangement or a “cross” -shaped intersection. For example, a staggered arrangement in which the parts are slightly shifted can be used.

  Further, from the viewpoint of use of the 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 the resin sheet has a C surface of 0.1 to 0.5. Or it is preferable that it is a R surface.

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 preferably at least one selected from the group consisting of high-strength glass fiber, carbon fiber, aramid fiber, aromatic polyester fiber, high-strength polyethylene fiber, and high-strength nylon fiber. Thereby, the impact resistance of the composite bulletproof plate of the present invention including the high-strength fiber reinforced plastic member can be improved, and the bulletproof performance can be improved. In particular, when the above-mentioned numerical range requirements are not satisfied, sufficient bulletproof performance may not be obtained.

As such a high strength fiber,
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.

  On the other hand, the resin used to impregnate or coat these high-strength fibers used in the present invention is a thermosetting resin such as a phenol resin, an epoxy resin, a polyurethane resin, an unsaturated polyester resin, a vinyl ester resin, and a polyimide resin. Examples of thermoplastic resins include polyolefins such as polyethylene and polypropylene, polyamides, polyesters, polyvinyl acetates, polyether sulfides, polyphenyl sulfides, polyethers, industrial terketones, and the like, as well as thermoplastic polyurethane, styrene, butadiene rubber, nitrile rubber, Synthetic rubber such as acrylonitrile styrene (AS) resin, neoprene, or elastomer.

  The high-strength fiber reinforced plastic member is made by impregnating or laminating a cloth made of high-strength fibers with a resin, forming a sheet of prepreg, or by drawing the high-strength fibers in parallel and impregnating or laminating the resin into a sheet form. Using the prepreg thus prepared, it is possible to obtain a laminate formed by lamination. 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.

  In the case of a thermosetting resin, the above-mentioned high-strength fiber reinforced plastic member is produced by impregnating or applying high-strength fibers with a thermosetting resin to produce a prepreg, and a plurality of the prepregs are stacked and compressed by heating and pressing. There are molding methods and hand lay-up methods that do not make prepregs. The resin content is in the range of 5 to 80% (% by weight, hereinafter the same), but is usually 5 to 50%, preferably 8 to 30%.

  On the other hand, in the case of a thermoplastic resin, a compression molding method in which high-strength fibers and a sheet of a thermoplastic resin film or woven fabric are alternately put together and heated and pressed, or the resin is melted in advance. There is also a method of attaching the resin to high-strength fibers. The thermoplastic resin content is also the same as that of the thermosetting resin.

  In order to obtain a practical composite bulletproof plate using the ceramic member and the high-strength fiber reinforced plastic member described above, the ceramic member is disposed on the landing side, and the high-strength fiber-reinforced plastic member is disposed on the rear surface thereof. It is preferable to closely contact the sheet. Thereby, the bulletproof performance of the composite bulletproof plate can be improved. In addition, in order to prevent secondary disasters caused by the pieces of the rack member that scatters upon landing, a prepreg using high-strength fibers on the surface of the ceramic member provided on the surface side, a resin sheet as described above, etc. It is preferable to provide a protective sheet.

In order to make a bulletproof plate having the above-described structure, a composite molded body can be manufactured by using the resin sheet and subjecting it to hot pressure molding by a conventional method. Preferred production conditions are as shown below.
Molding temperature: 100-200 ° C
Molding pressure: 0.1-10MPa
Molding time: 1 to 200 minutes

 Hereinafter, the present invention will be specifically described with examples.

(Manufacture of resin sheets)
Resin sheet 1
234.93 parts by weight of synthetic rubber SG-708-6T (manufactured by Nagase ChemteX Corporation), 39.15 parts by weight of synthetic rubber rubber Nipol 1072 (manufactured by Nippon Zeon), 100 parts by weight of biphenyl type epoxy resin NC-3000-H (Nipponization) 34,26 parts by weight of flame retardant phenoxyphosphazene oligomer (manufactured by Otsuka Chemical Co., Ltd., melting point 100 ° C.), 4,4′-DDS (manufactured by Wako Pure Chemical Industries, Ltd.), 17.16 parts by weight of aromatic diamine as a curing agent As a curing accelerator, boron trifluoride monoethylamine (Hashimoto Kasei Co., Ltd.) 0.3 parts by weight, inorganic filler aluminum hydroxide, Hajirite H-42I (Showa Denko Co., Ltd.) 97.89 parts by weight as a solvent Propylene bricol monomethyl ether (PGM) and methyl ethyl ketone were added to prepare an adhesive having a solid content of 40% by weight. 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, whereby a resin sheet 1 was obtained.

As a result of measuring the elastic deformation rate and the compression elastic modulus of the cured product of the resin sheet 1, it was confirmed that the elastic deformation rate was 40.3% and the compression elastic modulus was 1.2 × 10 ⁹ Pa.

Resin sheet 2
120.52 parts by weight of synthetic rubber SG-708-6T (manufactured by Nagase ChemteX), 20.08 parts by weight of synthetic rubber Nipol 1072 (manufactured by Nippon Zeon), 100 parts by weight of biphenyl type epoxy resin NC-3000-H (Nippon Kayaku) 34.26 parts by weight of flame retardant phenoxyphosphazene oligomer (manufactured by Otsuka Chemical Co., Ltd., melting point 100 ° C.), aromatic diamine 4,4'-DDS (manufactured by Wako Pure Chemical Industries, Ltd.) 17.16 parts by weight, cured As a promoter, boron trifluoride monoethylamine (Hashimoto Kasei Co., Ltd.) 0.3 parts by weight, inorganic filler aluminum hydroxide, Hajilite H-42I (Showa Denko Co., Ltd.) 97.89 parts by weight in a mixture of propylene glycol as a solvent Monomethyl ether (PGM) and methyl ethyl ketone were added to prepare an adhesive having a solid content of 40% by weight. 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, whereby a resin sheet 2 was obtained.

As a result of measuring the elastic change rate and the compression elastic modulus of the cured product of the resin sheet 2, it was confirmed that the elastic deformation rate was 57% and the compression elastic modulus was 8.8 × 10 ⁸ Pa.

Resin sheet 3
1398 parts by weight of synthetic rubber SG-708-6T (manufactured by Nagase ChemteX Corporation), 199.91 parts by weight of synthetic rubber Nipol 1072 (manufactured by Nippon Zeon), 100 parts by weight of biphenyl type epoxy resin NC-3000-H (Nippon Kayaku) 34.26 parts by weight of flame retardant phenoxyphosphazene oligomer (manufactured by Otsuka Chemical Co., Ltd., melting point 100 ° C.), aromatic diamine 4,4'-DDS (manufactured by Wako Pure Chemical Industries, Ltd.) 17.16 parts by weight, cured As a promoter, boron trifluoride monoethylamine (Hashimoto Kasei Co., Ltd.) 0.3 parts by weight, inorganic filler aluminum hydroxide, Hajilite H-42I (Showa Denko Co., Ltd.) 97.89 parts by weight in a mixture of propylene glycol as a solvent Monomethyl ether (PGM) and methyl ethyl ketone were added to prepare an adhesive having a solid content of 40% by weight. 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, whereby a resin sheet 3 was obtained.

As a result of measuring the elastic change rate and the compression elastic modulus of the cured product of the resin sheet 3, it was confirmed that the elastic deformation rate was 25% and the compression elastic modulus was 2.2 × 10 ⁸ Pa .

Resin sheet 4
274.08 parts by weight of synthetic rubber SG-280DR (manufactured by Nagase ChemteX Corporation, glass transition temperature -31 ° C., weight average molecular weight 900,000, acid value 30 KOH mg / g), 100 parts by weight of biphenyl type epoxy resin NC3000-H (Nipponization) Manufactured by Yakuhin Co., Ltd.), 34.26 parts by weight of flame retardant phenoxyphosphazene oligomer (manufactured by Otsuka Chemical Co., Ltd., melting point 100 ° C.), aromatic diamine as a curing agent, 4,4′-DDS (manufactured by Wako Pure Chemical Industries, Ltd.) 17.16 parts by weight, As a hardening accelerator, boron trifluoride monoethylamine (manufactured by Hashimoto Kasei Co., Ltd.) 0.3 parts by weight, inorganic filler aluminum hydroxide, Hajilite H-42I (manufactured by Showa Denko) 97.89 parts by weight propylene as a solvent Glycol monomethyl ether (PGM) and methyl ethyl ketone were added to prepare an adhesive having a solid content of 40% by weight. This adhesive composition was applied and dried on a release paper having a thickness of 30 μm with a roll coater so as to have a thickness of 20 μm, and a resin sheet 4 was obtained.

As a result of measuring the elastic deformation rate and the compression elastic modulus of the cured product of the resin sheet 4, it was confirmed that the elastic deformation rate was 35% and the compression elastic modulus was 8.9 × 10 ⁸ Pa.

Resin sheet 5
189 parts by weight of synthetic rubber SG-708-6T (manufactured by Nagase ChemteX Corporation), 66.6 parts by weight of polyfunctional epoxy resin EPPN-501HY (manufactured by Nippon Kayaku Co., Ltd.), 33.4 parts by weight of biphenyl type epoxy resin NC-3000 -H (manufactured by Nippon Kayaku Co., Ltd.), 34.26 parts by weight of flame retardant phenoxyphosphazene oligomer (manufactured by Otsuka Chemical Co., Ltd., melting point 100 ° C.), 4.4′-DDS (manufactured by Wako Pure Chemical Industries, Ltd.) 17.16 A mixture consisting of 0.3 parts by weight of boron trifluoride monoethylamine (manufactured by Hashimoto Kasei Co., Ltd.), aluminum hydroxide as an inorganic filler, and 97.89 parts by weight of Hajilite H-42I (manufactured by Showa Denko KK) Propylene glycol monomethyl ether (PGM) and methyl ethyl ketone were added as solvents to prepare an adhesive having a solid content of 40% by weight. 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, whereby a resin sheet 5 was obtained.

As a result of measuring the elastic deformation rate and the compression elastic modulus of the cured product of the resin sheet 5, it was confirmed that the elastic deformation rate was 69% and the compression elastic modulus was 2.2 × 10 ¹⁰ Pa.

Resin sheet 6
790 parts by weight of synthetic rubber Nipol 1072 (manufactured by Zeon Corporation), 50 parts by weight of bisphenol A type epoxy resin Epicoat 1001 (manufactured by Japan Epoxy Resin Co., Ltd.), 50 parts by weight of biphenyl type epoxy resin NC-3000-H (Nippon Kayaku) 34.26 parts by weight flame retardant phenoxyphosphazene oligomer (manufactured by Otsuka Chemical Co., Ltd., melting point 100 ° C.), aromatic agent diamine 4.4'-DDS (Wako Pure Chemical Industries, Ltd.) 17.16 parts by weight, curing acceleration As a solvent, propylene glycol monomethyl as a solvent in a mixture comprising 0.3 part by weight of boron trifluoride monoethylamine (manufactured by Hashimoto Kasei Co., Ltd.) and 97.89 parts by weight of aluminum hydroxide hajilite H-42I (manufactured by Showa Denko KK) as an inorganic filler. Ether (PGM) and methyl ethyl ketone were added to prepare an adhesive having a solid content of 40% by weight. 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, whereby a resin sheet 6 was obtained.

As a result of measuring the elastic deformation rate and the compression elastic modulus of the cured product of the resin sheet 6, it was confirmed that the elastic deformation rate was 17% and the compression elastic modulus was 8.9 × 10 ⁸ Pa.

Example 1
UD prepreg of aramid fiber-polyurethane resin (manufactured by Honeywell) UD sheet product name: RS sheet basis weight 222 g / m ² , resin amount 30 wt%, aramid fiber specific tensile strength 0.22 × 10 ⁶ m, specific tensile modulus 5.3 × 10 ⁶ m) were alternately arranged in an orthogonal arrangement of 0 ° and 90 °, 50 sheets were overlaid, and molded under molding conditions, 130 ° C., 30 minutes, molding pressure 13 MPa, and laminate 1 was produced.

  A resin sheet 1 is laid on one side of the laminate, and an alumina ceramic plate A-471 (manufactured by Kyocera, 100 mm × 100 mm × thickness 8 mm, roughness of the joint surface with the laminate is 4.5 μm, with corner finish) The composite bulletproof plate 1 was produced by covering the resin sheet 1 with a gap of 0.3 mm and then press-molding the molding sheet under molding conditions of 160 ° C. for 60 minutes under a molding pressure of 4 MPa.

(Example 2)
Aramid fiber fabric (Fiber: DuPont brand name Kevlar 29, specific tensile strength 0.22 × 10 ⁶ m, specific tensile modulus 5.3 × 10 ⁶ m), epoxy resin impregnated varnish (TVB-2638, Kyocera Chemical Co., Ltd.) Impregnation and drying were performed to prepare prepreg 2 (weight per unit area 220 g / m ² , resin amount 30% by weight). 50 sheets of this prepreg were stacked and molded under molding conditions, 160 ° C., 60 minutes, and a molding pressure of 4 MPa to produce a laminate 2.

  Next, a resin sheet 1 is laid on one side of the laminate 2 and an alumina ceramic plate A-471 (manufactured by Kyocera, 100 mm × 100 mm × 8 mm thick, roughness of the joint surface with the laminate, 4.5 μm, corner finish) The composite bulletproof plate 2 was produced by covering the resin sheet 1 on top of it and press-molding it under molding conditions of 160 ° C. for 60 minutes under a molding pressure of 4 MPa.

(Example 3)
Resin sheet 1 is laid on one side of laminate 1 produced in Example 1, and silicon carbide ceramic plate SC1000 (manufactured by Kyocera, 100 mm × 100 mm × thickness 5 mm, joint surface roughness 4.5 μm with laminate, With a corner finish of 0.3 mm, the resin sheet 1 was further covered, and press molding was performed under molding conditions of 160 ° C. for 60 minutes at a molding pressure of 4 MPa to produce a composite bulletproof plate 3.

Example 4
An epoxy resin varnish (Kyocera Chemical TVB-2638) is applied to a high-strength polyethylene fiber (trade name Dyneema made by Toyobo Co., Ltd., specific tensile strength 0.29 × 10 ⁶ m, specific tensile modulus 13.5 × 10 ⁶ m), and dried. UD prepreg 3 (weight per unit area 220 g / m ² , resin amount 30% by weight) was produced. 50 sheets of this UD prepreg 3 were alternately arranged orthogonally at 0 degrees and 90 degrees, and the laminated sheets 3 were formed by molding them under molding conditions, 130 ° C., 30 minutes, and a molding pressure of 4 MPa.

  A resin sheet 1 is laid on one side of the laminate 3 and an alumina ceramic plate A-471 (manufactured by Kyocera, 100 mm × 100 mm × thickness 8 mm, roughness of the joint surface with the laminate is 4.5 μm, with corner finish) Was covered with 0.3 mm of hindrance, and the resin sheet 1 was further covered thereon, followed by press molding under molding conditions of 160 ° C. for 60 minutes and a molding pressure of 4 MPa, to produce a composite bulletproof plate 4.

(Example 5)
A composite bulletproof plate 5 was produced in the same manner as in Example 1 except that the resin sheet 1 used in Example 1 was used in place of the resin sheet 2.

(Example 6)
A composite bulletproof plate 6 was produced in the same manner as in Example 1 except that the resin sheet 1 used in Example 1 was used in place of the resin sheet 3.

(Example 7)
A composite bulletproof plate 7 was produced in the same manner as in Example 1 except that the resin sheet 1 used in Example 1 was used in place of the resin sheet 4.

(Comparative Example 1)
A composite bulletproof plate 8 was produced in the same manner as in Example 1 except that the resin sheet 1 used in Example 1 was replaced with the resin sheet 5 and used.

(Comparative Example 2)
A composite bulletproof plate 9 was produced in the same manner as in Example 1 except that the resin sheet 1 used in Example 1 was used in place of the resin sheet 6.

  Table 1 shows the characteristics of the resin sheets used in the above examples and comparative examples, Table 2 shows the characteristics of the ceramic members used in the above examples and comparative examples, and Table 3 shows the above examples and comparative examples. Various characteristics of the high-strength fiber reinforced plastic member used in the examples are shown. Table 4 shows the results of the adhesion strength and the antiballistic test of the composite bulletproof plates obtained in the above examples and comparative examples.

The characteristics of the composite bulletproof plate were measured by the following test method.
1) Adhesive strength (against ceramic): The adhesive strength after laminating and curing the resin sheet and ceramic was measured according to JIS-C6471.
Normal: No treatment, After treatment: 85 ℃ * 85RH% * hrs
2) Adhesive strength (vs. laminate): The adhesive strength of the resin sheet and laminate after lamination and curing was measured according to JIS-C6471.
Normal: No treatment, After treatment: 85 ℃ * 85RH% * hrs
3) Bulletproof test: A penetrating impact test was performed on the composite bulletproof plate from the ceramic side according to NTJ Standard0108.01 using 9.7g bullets at a speed of 838 ± 15m / sec. A bullet was hit at the center of the ceramic and the joint between the ceramics and evaluated. The evaluation items are as follows.
・ Peeling between ceramic and laminated board: ○: None, △: Slightly, ×: Peeling occurs frequently ・ Swelling on the surface of laminated board: ○: None, △: Slightly occurring, ×: Swelling occurs frequently ・ Existence of penetration : ○: None, △: Partially penetrated, ×: Completely penetrated

  As described above, as is clear from the examples and comparative examples, in the composite bulletproof plate in the examples according to the present invention, compared to the composite bulletproof plate in the comparative examples, the ceramic member of the resin sheet and the high-strength fiber reinforced plastic member It can be seen that the anti-elasticity is also improved.

  The present invention has been described in detail based on the above specific examples. However, the present invention is not limited to the above specific examples, and various modifications and changes can be made without departing from the scope of the present invention.

Claims (13)

A ceramic member, a high-strength fiber reinforced plastic member, and a resin sheet that joins the ceramic member and the high-strength fiber reinforced plastic member.
The resin sheet includes a thermosetting resin composition having an elastomer, and the thermosetting resin composition includes (A) at least one epoxide compound, (B) an epoxy curing agent, and (C) an epoxy effect enhancement. An agent, (D) an elastomer, and (E) an inorganic filler, wherein the content of the (D) elastomer is 40 to 80% by weight with respect to the total resin composition,
The elastic deformation rate of the resin sheet in a cured state is 20 to 60%, the compression elastic modulus is 10 ⁸ to 10 ¹⁰ Pa , and the adhesive strength with the ceramic member is 1.0 kN / m or more. A composite bulletproof board characterized by 2. The composite bulletproof plate according to claim 1 , wherein the elastomer (D) is a synthetic rubber or a rubber-modified polymer compound having rubber elasticity at room temperature. The synthetic rubber is at least one selected from the group consisting of acrylic rubber, acrylonitrile butadiene rubber, styrene butadiene rubber, butadiene methyl acrylate acrylonitrile rubber, butadiene rubber, carboxyl-containing acrylonitrile butadiene rubber, silicone rubber, urethane rubber, and polyvinyl butyral. The composite bulletproof plate according to claim 2 , wherein the composite bulletproof plate is rubber. The composite bulletproof plate according to claim 2 or 3 , wherein the synthetic rubber contains a hydroxyl group and a carboxy group as functional groups. The synthetic rubber has a glass transition temperature (Tg) of −30 to 20 ° C., a weight average molecular weight (Mw) of 200,000 to 800,000, and an acid value of 5 to 12 KOHmg / g. The composite bulletproof plate according to claim 4 . The composite bulletproof plate according to any one of claims 1 to 5 , wherein the (A) at least one epoxide compound is a biphenyl type epoxy resin. The composite bulletproof plate according to any one of claims 1 to 6 , wherein the (B) epoxy curing agent is dihydroxydiphenylsulfone.   The composite bulletproof plate according to any one of claims 1 to 7, wherein the (E) inorganic filler is aluminum hydroxide. The ceramic member includes at least one of alumina, silicon nitride, silicon band, zirconia, and boron carbide, has a Vickers hardness of 10 GPa or more, a bending strength of 300 MPa or more, and a bending elasticity of 200 GPa or more. The composite bulletproof plate according to any one of claims 1 to 8 , wherein the composite bulletproof plate is provided. 10. The composite bulletproof plate according to claim 9 , wherein the ceramic member has a quadrangular or hexagonal plate shape with a thickness of 1 to 15 mm and a main surface area of 400 to 25000 mm ² . The ceramic member has a surface roughness of 3 to 10 µm, and a corner portion of a non-joint surface with the resin sheet is a C-plane or R-plane of 0.1 to 0.5. Item 11. A composite bulletproof board according to Item 9 or 10 . The high-strength glass contained in the high-strength fiber-reinforced plastic 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 at least one selected from the group consisting of fiber, carbon fiber, aramid fiber, aromatic polyester fiber, high-strength polyethylene fiber, and high-strength nylon fiber, according to any one of claims 1 to 11, The composite bulletproof board described. The high-strength fiber reinforced plastic is made into a sheet by impregnating or laminating a resin made of a high-strength fiber with a resin and forming a sheet-like prepreg, or by drawing the high-strength fibers in parallel and impregnating or laminating the resin The composite bulletproof plate according to claim 12 , wherein the composite bulletproof plate is a laminated plate formed by lamination using a prepreg.