阅读说明：本技术 无溶剂型芳纶防弹预浸料及其复合材料 (Solvent-free aramid bulletproof prepreg and composite material thereof ) 是由 余丽娇 张华川 李晓阳 李淑文 王培勇 于 2019-10-18 设计创作，主要内容包括：本发明公开了无溶剂型芳纶防弹预浸料,涉及高性能纤维复合材料,尤其涉及人体防护材料。所述的无溶剂型芳纶防弹预浸料由改性环氧树脂、热熔纤维载体与芳纶织物组成,改性环氧树脂与热熔纤维载体先制成胶膜,胶膜单面部分浸渍芳纶织物,所述胶膜在芳纶预浸料中所占质量比为10～20％,所述芳纶织物在芳纶预浸料中所占质量比为80～90％。所述的改性环氧树脂由环氧树脂、增韧树脂、双氰胺固化剂、有机脲促进剂、增韧剂、消泡剂组成,所述的热熔纤维载体是在高温下可熔融的热塑性纤维织物、无纺布或毡,其面密度为15～30g/m<Sup>2</Sup>。该改性环氧树脂具有良好的韧性,对芳纶织物具有合适的粘结强度,采用该树脂制备的芳纶复合材料具有优异的防弹性能。(The invention discloses a solvent-free aramid bulletproof prepreg, relates to a high-performance fiber composite material, and particularly relates to a human body protection material. The solvent-free aramid bulletproof prepreg is composed of modified epoxy resin, a hot-melt fiber carrier and an aramid fiber fabric, wherein an adhesive film is prepared from the modified epoxy resin and the hot-melt fiber carrier, the aramid fiber fabric is partially impregnated in a single surface of the adhesive film, the mass ratio of the adhesive film to the aramid fiber prepreg is 10-20%, and the mass ratio of the aramid fiber fabric to the aramid fiber prepreg is 80-90%. The modified epoxy resin is composed of epoxy resin, toughening resin, dicyandiamide curing agent, organic urea accelerator, toughening agent and defoaming agent, the hot-melt fiber carrier is a thermoplastic fiber fabric, non-woven fabric or felt which can be melted at high temperature, and the surface density of the hot-melt fiber carrier is 15-30 g/m 2 . The modified epoxy resin has good toughness, has proper bonding strength to aramid fabrics, and the aramid fiber composite material prepared by the resin has excellent bulletproof performance.)

1. The solvent-free aramid bulletproof prepreg is characterized by comprising solvent-free modified epoxy resin and aramid fabric or solvent-free modified epoxy resin, a hot-melt fiber carrier and aramid fabric, wherein the modified epoxy resin or the modified epoxy resin and the hot-melt fiber carrier are firstly prepared into an adhesive film, and then the single surface of the aramid fabric is covered with the adhesive film to prepare the aramid prepreg.

2. The solvent-free aramid bulletproof prepreg according to claim 1, wherein the adhesive film is composed of modified epoxy resin and a hot-melt fiber carrier, and the adhesive film accounts for 10-20% of the aramid prepreg by mass.

3. The solvent-free aramid bulletproof prepreg according to claim 1, wherein the aramid fabric is one of plain weave fabric and Banama weave fabric, and the areal density of the aramid fabric is 200-600 g/m²The mass ratio of the aramid fiber fabric in the aramid fiber prepreg is 80-90%.

4. The solvent-free aramid bulletproof prepreg according to claim 1, wherein the modified epoxy resin is composed of epoxy resin, toughening resin, a curing agent, an accelerator, a plasticizer and a defoaming agent, and the mass ratio of the modified epoxy resin in an adhesive film is 60-100%.

5. The solvent-free aramid bulletproof prepreg according to claim 4, wherein the epoxy resin is a liquid epoxy resin with medium and low molecular weight, the epoxy resin is one or a combination of bisphenol A type epoxy resin, bisphenol F type epoxy resin and novolac epoxy resin, the epoxy equivalent is 160-250 g/eq, and the mass ratio of the epoxy resin to the modified epoxy resin is 0-25%.

6. The solvent-free aramid bulletproof prepreg according to claim 4, wherein the toughening resin is one or more of polyurethane modified epoxy resin, phenoxy resin, thermoplastic polyurethane elastomer, nitrile rubber, core-shell structure rubber, polyethylene oxide-polystyrene thermoplastic elastomer, polyvinyl formal and polyvinyl butyral, and the mass ratio of the toughening resin to the modified epoxy resin is 50-85%.

7. The solvent-free aramid bulletproof prepreg according to claim 4, wherein the accelerator is an organic urea accelerator, and the mass ratio of the accelerator to the modified epoxy resin is 1.5-4.5%.

8. The solvent-free aramid bulletproof prepreg according to claim 4, wherein the plasticizer is a phthalate compound, the plasticizer is dioctyl phthalate, and the mass ratio of the plasticizer in the modified epoxy resin is 1.6-6%.

9. The solvent-free aramid bulletproof prepreg according to claim 1, wherein the hot-melt fiber carrier is a thermoplastic fiber fabric, non-woven fabric or felt which can be melted at a high temperature, and the areal density of the hot-melt fiber carrier is 15-30 g/m²The hot-melt fiber is one of polyurethane fiber, polyester fiber, polyvinyl formal fiber and polyamide fiber, and the hot-melt fiber is polyurethane fiber, and accounts for 0-40% of the adhesive film by mass.

10. The solvent-free aramid bulletproof composite material is characterized in that: an aramid prepreg according to any one of claims 1 to 9, which is laminated 24 layers, and then pressed at 13bar and held at 150 ℃ for 20mm to obtain a composite material.

Technical Field

The invention belongs to the technical field of high-performance fiber composite materials, relates to a solvent-free aramid bulletproof prepreg and a composite material thereof, and further relates to a human body protection material technology.

Background

The bulletproof and stab-resistant composite material has been widely applied to the aspects of human body protection and protection of military instruments and equipment, such as bulletproof vests, helmets, and protection parts of tanks, airplanes, ships and warships. The bulletproof composite material has excellent physical and mechanical properties and chemical properties, has higher specific strength, specific modulus, fatigue resistance and shock absorption than metal materials, and also has excellent kinetic energy absorbability without secondary killing effect, thereby having excellent bulletproof property. Ballistic composites are essential life protection equipment for combat personnel, and the demand for ballistic helmets in particular has increased year by year.

In recent years, high-performance fiber materials such as aramid fibers are widely applied to preparing bulletproof products, and the aramid fibers have the advantages of high strength, high modulus and the like, so that the aramid fibers are mostly adopted as reinforcements for bulletproof composite materials. At present, the aramid fiber fabric of the high-performance aramid fiber composite material is generally bonded by adopting thermosetting resin, and two factors mainly influence the performance of the aramid fiber composite material: (1) the adhesion between the resin and the aramid fabric; (2) toughness of the resin. Therefore, the resin bonding layer between the aramid fabrics plays a key role in the bulletproof performance of the aramid bulletproof composite material.

For matrix resin, proper bonding strength and toughness are very important for improving the performance of the aramid fiber composite material. If the resin has poor toughness, brittle fracture tends to occur. The aramid fiber fabric is easy to delaminate and slide due to low bonding strength, and is not beneficial to bullet energy transfer; and if the bonding strength of the resin is too high, the resin can bind fibers, so that the product is easy to be subjected to brittle fracture, and the bonding strength of the resin needs to be moderate.

Currently, aramid bulletproof composite material products on the market and published patent documents and the like generally adopt modified phenolic resin as a resin bonding layer of aramid fabrics, and aramid prepregs prepared by using the modified phenolic resin adopt modified phenolic resin solutions containing solvents such as ethanol or toluene and the like. Chinese patent CN102604320A, CN102909920A, and U.S. patent US2016/0273884a1 disclose several methods for preparing aramid ballistic composites, in which the resins are all modified phenolic resins, the modifiers are mainly one or a combination of polyvinyl butyral, polyvinyl formal, and these modifiers are all dissolved in solvents such as ethanol or toluene to prepare solutions with low concentration, and then mixed with phenolic resins and other components to prepare aramid prepregs. Because the modified phenolic resin is solvent-based resin, the modified phenolic resin causes pollution to workshops and the environment when the prepreg is prepared, and is not beneficial to the health of workers; in addition, the volatile component content of the aramid prepreg is not easy to control, and voids are easily generated when a composite material product is manufactured, so that the material performance is influenced.

Disclosure of Invention

The invention aims to overcome the defects of the conventional technology for preparing aramid bulletproof prepreg by using a solvent type resin formula, and provides the solvent-free aramid bulletproof prepreg and the composite material thereof, and the composite material has excellent bulletproof performance.

The technical scheme adopted by the invention is as follows: preparing a solvent-free high-toughness epoxy resin matrix and a hot-melt fiber carrier into an adhesive film, and covering the adhesive film on one side of the aramid fabric to prepare the aramid prepreg.

The solvent-free aramid bulletproof prepreg provided by the invention consists of solvent-free modified epoxy resin and an aramid fabric or consists of solvent-free modified epoxy resin, a hot-melt fiber carrier and an aramid fabric, wherein a glue film is prepared by the modified epoxy resin or the modified epoxy resin and the hot-melt fiber carrier, the aramid prepreg is prepared by covering a glue film on a single surface of the aramid fabric, the part of the glue film is impregnated in the aramid fabric, the content of the glue film is 10-20%, and the content of the aramid fabric is 80-90%.

The modified epoxy resin consists of epoxy resin, toughening resin, a curing agent, an accelerator, a plasticizer and a defoaming agent, and the mass ratio of the modified epoxy resin in a glue film is 60-100%.

The epoxy resin is liquid epoxy resin with medium and low molecular weight, such as one or a combination of bisphenol A epoxy resin, bisphenol F epoxy resin and novolac epoxy resin, the epoxy equivalent of the epoxy resin is 160-250 g/eq, and the mass ratio of the epoxy resin in the modified epoxy resin is 0-25%, preferably 10-25%.

The toughening resin is one or more of polyurethane modified epoxy resin, phenoxy resin, thermoplastic polyurethane elastomer, nitrile rubber, core-shell structure rubber, polyoxyethylene-polystyrene thermoplastic elastomer, polyvinyl formal and polyvinyl butyral. The mass ratio of the modified epoxy resin in the modified epoxy resin is 50-85%, and preferably 55-70%.

The curing agent is a latent amine curing agent, preferably dicyandiamide, and accounts for 1-4% by mass of the modified epoxy resin, preferably 2-3.5% by mass of the modified epoxy resin.

The accelerant is an organic urea accelerant, and the mass ratio of the organic urea accelerant in the modified epoxy resin is 1.5-4.5%, preferably 3-4%.

The plasticizer is a phthalate compound, preferably dioctyl phthalate, and accounts for 1.6-6% by mass, preferably 2.5-5% by mass of the modified epoxy resin.

The defoaming agent is an oligomer mixture containing a wetting agent, and the mass ratio of the defoaming agent in the modified epoxy resin is 0.5-2%.

The hot-melt fiber carrier is a thermoplastic fiber fabric, non-woven fabric or felt which can be melted at high temperature, and the surface density of the hot-melt fiber carrier is 15-30 g/m². The hot-melt fiber is one of polyurethane fiber, polyester fiber, polyvinyl formal fiber and polyamide fiber, and preferably is polyurethane fiber. At high temperature, the hot melt fiber is melted, and has a certain bonding effect on aramid fiber fabric, wherein the mass ratio of the hot melt fiber to the adhesive film is 0-40%.

The aramid fabric is one of plain weave fabrics and Banama weave fabrics, and the surface density of the aramid fabric is 200-600 g/m²The mass percentage of the aramid fabric in the aramid prepreg is 80-90%.

The invention also provides a solvent-free aramid bulletproof composite material, which is prepared by stacking 24 layers of the aramid prepreg, pressurizing to 13bar and preserving heat at 150 ℃ for 20 mmin.

In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that: tests prove that the solvent-free aramid bulletproof prepreg and the composite material thereof overcome the defects of the prior art and obtain an aramid bulletproof composite material product with excellent bulletproof performance. The brittleness of common epoxy resin is improved by the high-toughness resin and the thermoplastic fiber, so that a resin system has good toughness, and meanwhile, the aramid fiber fabric has proper bonding strength, and the requirements of the aramid fiber bulletproof composite material on the resin performance can be met.

Detailed Description

The invention will now be further illustrated, but not by way of technical limitation, with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.