JP3127947B2 - Composite molding - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite molded article made of ceramic and high-strength fiber reinforced plastic (hereinafter, referred to as ACM) when a high-speed flying object is received from the ceramic (plate or molded article) side. Hold the cracks appropriately, keep the broken pieces from scattering to the outside as much as possible, reduce the bulge of the ACM on the opposite side of the ceramic, and further remove the ACM from the ceramic as much as possible with the ACM. The present invention relates to a lightweight composite molded article having excellent impact resistance to high-speed flying objects by enclosing the composite molded article.

[0002]

2. Description of the Related Art A shock-resistant body against an object falling from a high place or flying at a high speed is a chemical method such as adhesion of ACM to the back surface of a single metal or its alloy or ceramic, or a mechanical method such as a bolt / nut. (A combination with a metal plate is disclosed in JP-A-3-58835-5).
No. 8837) is a known fact today. However, when the impact force is very strong, or when the impact force is repeatedly applied to the same portion several times or more, especially in a ceramic / ACM composite molded article, the ceramic around the impact site is broken by the first impact force, and the ACM When the impact force is repeatedly applied to the same part, the impact absorption force by the ceramic is rapidly reduced, and the impact force may be directly applied to the ACM on the back surface. A phenomenon has arisen, and it is necessary to improve this point.

[0003]

SUMMARY OF THE INVENTION The present invention is based on the finding that by fixing ACM on the back surface of ceramic (plate and molded product), a composite molded product having light weight and good impact resistance can be obtained. As a result of various investigations to increase the impact resistance when a repeated impact force is applied, ceramic / A
By further wrapping the CM composite molded product entirely or partially with ACM (same material or different material as the main body), when repeatedly subjected to strong and repeated impact force, it suppresses the breakage of ceramics and reduces the projection of fragments. This has led to the completion of a composite molded article having excellent impact resistance, in which the separation between the ceramic and the ACM is reduced and the bulge at the rear of the ACM is extremely reduced.

[0004]

SUMMARY OF THE INVENTION The present invention relates to a composite molded article comprising ceramic and high-strength fiber-reinforced plastic, wherein a composite molded article obtained by laminating ceramic and high-strength fiber-reinforced plastic is converted into a high-strength fiber-reinforced plastic. The present invention relates to a composite molded article characterized in that it is wrapped.

The ceramics used here are mainly called fine ceramics and include alumina (purity 90 to 99.9), silicon nitride, silicon carbide, and the like.
It does not matter in particular such as zirconia. Ceramic only and 2
More than two types of ceramics may be combined. The physical properties of the ceramic include a Vickers hardness of 1000 kg / mm ² or more, a bending strength of 30 kgf / mm ² or more, and an elastic modulus of 2.8 × 10 ^4.
kg / mm ² or more is preferred.

On the other hand, as high strength fibers used as ACM, specific tensile strength obtained by dividing tensile strength by density is 10 × 10 ⁶ c
m or more, and the specific elastic modulus obtained by dividing the elastic modulus by the density is 2.5
× 10 ⁸ cm or more. Specifically, high-strength glass fiber, carbon fiber, aramid fiber, aromatic polyester fiber, high-strength polyethylene fiber, high-strength nylon fiber, and the like. General glass fiber, nylon fiber, polyester fiber, etc. are not applicable. When fibers having a specific tensile strength or a specific elastic modulus of not more than the above values are used, the impact resistance of the composite molded product is not always sufficient.

On the other hand, the resin for impregnating or coating these high-strength fibers 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 resins include polyolefins such as polyethylene and polypropylene, polyamides, polyesters, polyvinyl acetates, polyether sulfides, polyphenyl sulfides, polyethers, ether ketones, and the like. (AS) Resin, synthetic rubber such as neoprene, or elastomer.

In order to obtain ACM, in the case of a thermosetting resin,
A prepreg is prepared by impregnating or coating a high-strength fiber with a thermosetting resin, a plurality of prepregs are stacked, and a compression molding method in which heat and pressure are applied, or a hand lay-up method in which a prepreg is not formed is used. The resin content is in the range of 5 to 80% (weight%, the same applies hereinafter), but is usually 5 to 50%, preferably 8 to 30%. On the other hand, in the case of thermoplastic resin, a compression molding method in which a plurality of high-strength fibers and a sheet-like material such as a thermoplastic resin film or a woven fabric are alternately laminated and heated and pressed, or the resin is melted in advance and the resin is melted. There is also a method of adhering to a high-strength fiber. The content of the thermoplastic resin is the same as that of the thermosetting resin.

[0009]

The ACM obtained by the above method is fixed to the back surface of the ceramic by a mechanical method such as a bolt or a rivet, a resin itself used for the ACM, or an adhesive such as a synthetic rubber or epoxy resin. Although there is a chemical method for bonding, the ACM / ceramic is preferably brought into close contact with a resin and an adhesive.

In the present invention, in order to further improve the impact resistance of the composite molded product thus produced, the composite molded product is wrapped in ACM. Specifically, the composite molded product is wrapped with a prepreg obtained from the high-strength fiber and resin used for the composite molded product or another high-strength fiber and resin having good adhesion to the composite molded product, and heated and pressed. A method of curing, a method of molding while wrapping the composite molded product by the hand lay-up method, a method of alternately wrapping a thermoplastic resin sheet and high-strength fibers, heating and melting and pressing, or a high-strength fiber with thermoplastic resin attached There is a method in which the composite molded body is wrapped and heated and pressed. It is preferable that the resin content is slightly higher than that of the composite molded article body. That is, in the range of 10 to 80%, usually 1
It is 5 to 70%, preferably 20 to 60%. The number of layers to be wrapped is 1 to 30 layers, usually 1 to 20 layers, and preferably 2 to 15 layers.

The ceramic / ACM composite molded article wrapped with ACM obtained in this way has a larger impact force and a higher-speed flying object, for example, when compared with the non-wrapped composite molded article alone. When the ceramic in the composite molded article is broken by the impact force, the fracture area and cracks of the ceramic are reduced, the peeling of the adhesive layer between the ceramic and the ACM is extremely reduced, and the bulge at the rear of the ACM is also reduced by the ACM. Because they are wrapped, they can be significantly reduced due to the mutual tensile effect. Even if the impact is repeatedly applied to the same part or its vicinity two or more times, it is wrapped, so the destruction does not proceed greatly and the AC by the impact force
It doesn't do much damage to M.

[0012]

The present invention will be specifically described below with reference to examples.

Example 1 Specific tensile strength is 16 × 10 ⁶ c
m, a plain woven fabric (basis weight: 230 g / m ² ) made of high-strength gasla fiber having a specific elastic modulus of 3.2 × 10 ⁸ cm, impregnated with a resol-type phenol resin and dried to obtain a prepreg having a resin content of about 20%. Obtained. Three prepregs are stacked at 150.degree.
An ACM plate was obtained by heating and pressing at 00 kg / cm ² . This A
CM board made of 92% pure alumina ceramic (thickness 3mm)
Was fixed with a phenol resin-based hand lay-up resin to obtain a composite molded body A shown in FIG. The composite prepreg A was heated at about 80 ° C., wound twice, placed in an autoclave, and heated and pressurized at 150 ° C. and 10 kg / cm ² to obtain a composite molded article B shown in FIG.

Example 2 Specific tensile strength is 29 × 10 ⁶ c
m, a woven fabric (basis weight: 350 g / m ² ) made of high-strength polyethylene fiber having a specific elastic modulus of 10 × 10 ⁸ cm, coated with a bisphenol A type epoxy resin on the surface, dried, and dried to a resin content of about 25%. I got a prepreg. 10 prepregs are stacked and heated at 110 ° C. and 50 kg / cm ² to obtain AC.
An M plate was obtained. This ACM plate was bonded to a silicon nitride ceramic (4 mm thick) with an epoxy resin to obtain a composite molded product C.
The composite molded article C was wound twice by hand lay-up molding using the polyethylene woven fabric and the vinyl ester resin and cured at room temperature to obtain a composite molded article D.

Example 3 Specific tensile strength is 21 × 10 ⁶ c
An aramid fiber woven cloth (basis weight: 450 g / m ² ) having a specific elastic modulus of 6.4 × 10 ⁸ cm is impregnated with an 18% MEK solution of ABS resin and dried to obtain a prepreg having a resin content of about 20%. Was. Three layers of this prepreg are stacked at 150 ° C. and 100 kg / cm
^An ACM plate was obtained by heating and pressing at ² . The ACM plate was bonded to a silicon carbide ceramic (thickness: 3 mm) with a synthetic rubber adhesive to obtain a composite molded body E. The aramid woven prepreg is wound twice around the composite molded body E and put into a vacuum press,
Heat and pressure were applied to obtain a composite molded product F.

Example 4 Specific tensile strength is 20 × 10 ⁶ c
m, a woven fabric of aromatic polyester fibers having a specific elastic modulus of 4.9 × 10 ⁸ cm (basis weight: 260 g / m ² ) and seven highly stretched polyethylene films (thickness: 100 μm) are alternately laminated. Heating and pressing at 130 ° C. and 70 kg / cm ² yielded an ACM plate (both surfaces were polyethylene films). The ACM plate was fixed to a zirconia-based ceramic (2 mm thick) with an epoxy-based adhesive to obtain a composite molded body G. After laminating the above-mentioned polyethylene film and polyester woven fabric three times on this composite molded product G and heating and pressing it under the same conditions as above, a composite molded product H was obtained.

Example 5 Specific tensile strength is 32 × 10 ⁶ c
m, a unidirectional nonwoven fabric (basis weight: 130 g / m ² ) made of high-strength polyethylene fiber with a specific elastic modulus of 12 × 10 ⁸ cm, coated with a polyurethane-modified vinyl ester resin on the surface, and dried to prepare a prepreg having a resin content of about 30%. I got 10 prepregs are alternately stacked in the orthogonal direction at 120 ° C.
An ACM plate was obtained by heating and pressing at 60 kg / cm ² . This A
CM board made of 99% pure alumina ceramic (4mm thick)
Was bonded with a urethane-based adhesive to obtain a composite molded article I. The composite molded article I was wound around the composite molded article I four times by hand lay-up molding using the high-tensile high-elastic carbon woven fabric (weight per unit area: about 200 g / m ² ) and the same resin, and was cured.
I got

Comparative Example 1 Five prepregs and two prepregs obtained in Example 1 were separately heated and pressed at 150 ° C. and 100 kg / cm ² to obtain two kinds of A.
A CM board was obtained. Next, five ACMs were stacked on the back surface of the same 92% pure alumina ceramic (thickness: 3 mm) as in Example 1.
Was fixed on the surface with a phenol resin for hand lay-up, respectively, to obtain a composite molded product K shown in FIG.

COMPARATIVE EXAMPLE 2 Twelve prepregs obtained in Example 2 and two prepregs obtained in Example 2 were separately heated and pressed under the same conditions as in Example 2 to form two types of ACM plates. Obtained. 12 layers of ACM on the back and 2 layers of ACM on the back of silicon nitride ceramic (4mm thick)
Were bonded with an epoxy resin to obtain a composite molded product L.

Comparative Example 3 Five prepregs obtained in Example 3 and two prepregs obtained in Example 3 were separately heated and pressed under the same conditions as in Example 3 to obtain two types of AC.
An M plate was obtained. Five ACMs were adhered to the back surface of the silicon carbide ceramic (thickness: 3 mm), and two ACMs were adhered to the front surface with a synthetic rubber-based adhesive, respectively, to obtain a composite molding M.

Comparative Example 4 Ten high-stretched polyethylene films (thickness: 100 μm) and nine polyester woven fabrics alternately laminated in Example 4 and three polyethylene films and three polyester woven fabrics Were alternately heated and pressed separately under the same conditions as in Example 4 to obtain two types of ACM plates. Nine polyester woven fabric ACMs were fixed on the back surface of the zirconia ceramic (thickness: 3 mm), and three ACMs were fixed on the front surface with epoxy adhesives, respectively, to obtain a composite molded product N.

{Comparative Example 5} A obtained in Example 5
ACM made by hand lay-up molding on a CM board using four carbon woven fabrics and the same resin as in the example, on the back of a 99% pure aluminum ceramic (4 mm thick), and only four carbon woven fabrics on the front An ACM plate formed by hand lay-up molding with the above resin was adhered with a urethane-based adhesive to obtain a composite molded product P. According to MIL-STD-662
A penetration resistance test was performed at a speed of about 850 m / sec using a 1.1 g bullet. Table 1 shows the results.

[0023]

[Table 1]

[0024]

As is clear from the above results, the composite molded article of the present invention is excellent in impact resistance, has a small fracture area of the ceramic after the impact test, and has little peeling between the ACM plate and the ceramic. The bulge on the back of the molded product is also small.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view of a composite molded body A in Example 1.

FIG. 2 is a schematic sectional view of a composite molded product B in Example 1.

FIG. 3 is a schematic cross-sectional view of a composite molded product K in Comparative Example 1.

[Explanation of symbols]

 1 ceramic plate 2,3 ACM 4 ceramic plate 5,6 ACM

Claims (1)

(57) [Claims] 1. A composite formed from ceramic and high-strength fiber-reinforced plastic, wherein a composite formed by laminating ceramic and high-strength fiber-reinforced plastic is wrapped with high-strength fiber-reinforced plastic. Moldings.