JP2011132618A - Head part-protecting gear - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a head part-protecting gear equipped jointly with excellent impact absorbing property and penetration resistance. <P>SOLUTION: This head part-protecting gear comprising a fiber-reinforcing material and a resin is characterized in that the fibrous reinforcing material is a para-type aromatic polyamide fiber consisting of a polypara-phenylene terephthalamide or a copolyparaphenylene 3,4'-oxydiphenylene terephthalamide having 10 to 45 dtex single fiber fineness, 55 to 70% crystallinity, ≥2,000 MPa tensile strength and 50 to 150 GPa tensile elastic modulus. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a head protector that mitigates an impact applied to the head of a human body and protects it from an obstacle. In particular, the head protector is made of a composite material that is lightweight, shock-absorbing, and has high protection properties with excellent rigidity. It is about.

  Glass fiber reinforced thermosetting resin (hereinafter referred to as GFRP) is widely used as a safety protector, especially for passenger car head protectors. There is a tendency to gradually increase in size with the expectation of improving safety and improving safety. However, since GFRP is relatively heavy, there is a limit to increasing the size. Further, GFRP is brittle with respect to impact and easily propagates to cracks to reach complete destruction. On the other hand, fiber reinforced composite materials using high-strength, high-modulus organic polymer fibers such as aramid fiber and ultrahigh molecular weight polyethylene fiber as a reinforcing material have excellent impact resistance. A head protector made of FRP, which is used in combination as a reinforcing material and is reduced in weight and size by reducing the amount of glass fiber used, is already on the market. These head protectors are excellent in impact resistance and penetration resistance (Patent Documents 1 and 2). However, the manufacturing process becomes complicated, and since different materials are combined, usable resins and adhesives are limited, and the interlaminar adhesion is poor, resulting in a problem of reduced impact resistance. Further, as fiber-reinforced plastics made of the same high-strength fibers, those using a high-strength polyethylene fiber woven fabric as an outer layer and a non-woven fabric as an inner layer and those having a uniform resin amount have been proposed (Patent Documents 3 and 4). The fiber reinforced plastic of Patent Document 3 has a problem inferior in impact resistance because a nonwoven fabric in which fibers are randomly arranged is used, and the fiber reinforced plastic of Patent Document 4 is inexpensive but has an impact resistance. There was a problem of inferiority. In order to increase the impact resistance, it is necessary to increase the thickness of the layer, which increases the weight and reduces the functionality as a head protector.

JP-A-7-189010 JP 2003-269898 A JP-A-8-276523 Japanese Patent Publication No. 6-4705

  An object of the present invention is to provide a head protector having excellent shock absorption and penetration resistance.

  As a result of intensive studies to achieve the above object, the present inventors have found that this object is a head protector made of a fiber reinforcing material and a resin, and the fiber reinforcing material has a single fiber fineness of 10 to 45 dtex, The present inventors have found that this can be achieved by a head protector characterized by comprising a para-type aromatic polyamide fiber having a crystallinity of 55 to 70%, and have reached the present invention.

  The head protector of the present invention can have both excellent shock absorption and penetration resistance by including para-type wholly aromatic polyamide fibers having specific single fiber fineness and crystallinity.

  Hereinafter, embodiments of the present invention will be described in detail. The head protector of the present invention is a head protector made of a fiber reinforcing material and a resin, and the fiber reinforcing material has a para-fragrance having a single fiber fineness of 10 to 45 dtex and a crystallinity of 55 to 70%. It consists of a group polyamide fiber.

  The para-type aromatic polyamide used in the present invention is obtained by polycondensing aromatic dicarboxylic acid, aromatic diamine, aromatic aminocarboxylic acid, etc. at a ratio such that the carboxyl group and amino group are approximately equimolar. And polyamides whose chain bonds are coaxial or parallel and are oriented in opposite directions. Specific examples of the para-type wholly aromatic polyamide fiber include polyparaphenylene terephthalamide fiber and copolyparaphenylene 3,4'-oxydiphenylene terephthalamide fiber, and the latter is a copolymer type. Is preferable because it has high mechanical strength, particularly impact strength, when used as a head protector.

  In the present invention, it is important that the para-type aromatic polyamide fiber has a single fiber fineness of 10 to 45 dtex and a crystallinity of 55 to 70%. Thereby, it can be set as the head protector which has the outstanding shock absorption property and penetration resistance. The details will be described below.

  In the present invention, the single fiber fineness of the aromatic polyamide fiber is 10 to 45 dtex, preferably 15 to 45 dtex, more preferably 20 to 45 dtex. In general, in order to increase the rigidity of the head protector, it is conceivable to employ a high-strength, high-modulus fiber having a single fiber fineness of 5 dtex or less drawn at a high magnification as a fiber for reinforcing the head protector. However, as a result of our investigation, if the single fiber fineness is made smaller than 10 dtex, the rigidity when used as a head protector is reduced, not only the impact absorption and penetration resistance are reduced, but also, for example, resin When forming a woven fabric with flattened threads to improve the impregnation property, even if a slight load is applied, the fibers may become fuzzy, single yarn breakage may occur, or the openability may be reduced. Similarly, it has been found that it becomes a cause of impairing shock absorption and penetration resistance. On the other hand, if the fiber is thicker than the single yarn fineness of 45 dtex, when the fibers having the same total weight are used, the number of fibers constituting the head protector is reduced, so that the fiber reinforced portion is non-uniform and the partial reinforcing effect is sufficient. You won't get. Further, conventionally, aromatic polyamide fibers having such a thick single fiber fineness are not common, and moreover, it is actually not proposed to be applied to the head protector application.

  Furthermore, in the present invention, the degree of crystallinity of the aromatic polyamide fiber needs to be 55 to 70%, preferably 57 to 63%. If the degree of crystallinity is less than 55%, the fiber is too soft to obtain a sufficient reinforcing effect. On the other hand, if the degree of crystallinity is greater than 70%, the fiber becomes hard and brittle and cracks, resulting in poor impact resistance.

  In the present invention, it is desirable that the para-type aromatic polyamide fiber has a tensile strength of 2000 MPa or more and a tensile modulus of 50 to 150 GPa. When the tensile strength of the para-type aromatic polyamide fiber is less than 2000 MPa, sufficient penetration resistance cannot be obtained, and the absolute amount of the organic fiber increases, so that the effect of weight reduction cannot be expected. Furthermore, when the modulus of elasticity of the para-type aromatic polyamide fiber is less than 50 GPa, sufficient reinforcement cannot be obtained. On the other hand, when the modulus of elasticity exceeds 150 GPa, stress at the interface with the resin increases due to impact deformation, thereby preventing peeling. The effect tends to decrease, and the effect of repeated impact resistance improvement tends to decrease.

  In the present invention, the para-type aromatic polyamide fiber satisfying both the single fiber fineness and the crystallinity at the same time is obtained by discharging a dope obtained by dissolving the para-type aromatic polyamide polymer in a solvent from a spinneret and passing through the air gap. After spinning into an aqueous solution, the solvent was further removed in a solvent removal tank provided with a concentration gradient of a plurality of tanks, followed by drying while stretching 1.2 to 1.4 times, and then at 450 to 550 ° C. for 8 to It can be manufactured by drawing after being stretched 15 times. Moreover, the para type | mold aromatic polyamide fiber which has said tensile strength and elastic modulus can also be easily manufactured by the said method.

  The fiber reinforcing material used in the present invention is desirably formed in the form of a fabric such as a woven fabric, a knitted fabric, a dry nonwoven fabric, or a wet nonwoven fabric. In particular, a woven fabric is preferable. By adopting such a configuration, excellent dimensional stability, strength, and impact resistance can be secured, and the curved structure of the head protector can be easily handled. As the woven fabric, plain woven fabric, twill woven fabric, satin weaving fabric, satin woven fabric, oblique weave fabric, cedar woven fabric, double woven fabric, etc. can be used, and in terms of bulk density, plain woven fabric or entangled woven fabric with high yarn shape retention It is desirable that In the case of a plain woven fabric, twisting may be added to each fiber as an effective means for reducing the bulk density. Such fibers and woven fabrics may contain various additives usually used for improving the productivity or properties in the production process and processing process of the raw yarn. For example, a heat stabilizer, an antioxidant, a light stabilizer, a smoothing agent, an antistatic agent, a plasticizer, a thickener, a pigment, a flame retardant, and an oil agent can be contained or adhered.

The fabric preferably has a basis weight of 150 g / m ² or more and 400 g / m ² or less. When the basis weight is less than 150 g / m ^2, the thickness of the fabric becomes thin and it is difficult to maintain rigidity. On the other hand, if it exceeds 400 g / m ² , the fabric thickness is more than necessary, and the thickness of the head protector is increased.

  When the fiber reinforcing material is a fabric, particularly a woven fabric, it is preferable to use a glass fiber mat, for example, a chopped strand mat. For example, if the above woven fabric and chopped strand mat are used in the order of chopped strand mat, woven fabric, chopped strand mat, woven fabric, chopped strand mat, etc., so that the chopped strand mat is the outermost layer, only the fabric is laminated. Thus, the surface smoothness is improved as compared with the case of using it, and the impact energy acting on the cap body can be easily dispersed. In addition, the fabric can be easily sheared and deformed so that it can be easily conformed to the cap body at the time of molding. At this time, for example, if the mat is formed in the shape of a cap in advance, the molding becomes easier.

  As the resin constituting the head protector of the present invention, a thermosetting resin or a thermoplastic resin can be used, and is not particularly limited. Examples of the thermosetting resin include a phenol resin and a melamine resin. Examples of thermoplastic resins such as urea resin, unsaturated polyester resin, epoxy resin, polyurethane resin, diallyl phthalate resin, silicon resin, polyimide resin, vinyl ester resin, and modified resins thereof include, for example, vinyl chloride resin, polystyrene, A B S resin, polyethylene, polypropylene, fluororesin, polyamide resin, polyacetal resin, polycarbonate resin, polyester, polyamide, etc., and further, synthetic polyurethane or elastomer such as thermoplastic polyurethane, butadiene rubber, nitrile rubber, neoprene, polyester, etc. are preferable. You can use. Among them, resins mainly composed of phenol resin and polyvinyl butyral resin, unsaturated polyester resin, vinyl ester resin, polyolefin resin such as polyethylene and polypropylene, polyester resin are impact resistance, dimensional stability, heat resistance, strength, price Etc. can be preferably used. Such thermosetting resins and thermoplastic resins may contain various additives which are usually used for industrial purposes, applications, productivity in production steps and processing steps, or improvement of properties. For example, a modifier, a plasticizer, a filler, a release agent, a colorant, a diluent, and the like can be included.

  The head protector of the present invention can be manufactured using a conventional manufacturing method as it is. For example, using a pressure back molding method, placing fiber reinforcement in a splittable female mold, injecting resin, injecting pressurized air into the rubber bag as a male mold, and inflating in the female mold to pressurize the material Can be manufactured. The filling amount of the resin is not particularly limited, but in the case of a thermoplastic resin, it is preferably 70 to 95% by volume, particularly preferably 80 to 90% by volume, based on the entire molded part of the mold. Thereby, it is possible to achieve both the productivity and strength of the head protector. Moreover, in the case of a thermosetting resin, 60 to 90 volume% of the whole molded object part of a metal mold | die is preferable, and 70 to 80 volume% is especially preferable. Thereby, especially the intensity | strength of a head protector can be improved.

  The head protector can also be formed by forming a prepreg, cutting it into a multi-leaf shape such as a strip shape or a six-leaf shape, etc., laminating a plurality of sheets, and then heating and pressing. In this case, although not particularly limited, in the case of a thermosetting resin, the thermosetting resin is dissolved in a solvent to prepare a varnish, the woven fabric is passed through a varnish scissor, and a surplus with a bar coater or a clearance roll. In general, a method of scraping off a resin, coating, or coating using a spray is performed. On the other hand, in the case of a thermoplastic resin, a method of coating with a resin emulsion, melting or solvent and coating with a knife or gravure, or a method of laminating a molten resin directly on a fabric is generally performed. Moreover, 3-30 weight% is preferable with respect to a fiber reinforcement, and, as for resin adhesion amount, 5-20 weight% is more preferable. If it is less than 3% by weight, when high-speed flying objects collide, the shape retention tends to be low due to low rigidity, and if it exceeds 30% by weight, the degree of freedom of the fiber is lost and impact resistance is reduced. Tend to.

  According to the present invention, when the head protector includes para-aromatic polyamide fibers having a high fineness and improved crystallinity as reinforcing fibers, the head protector can be used for the intended use of the head protector. It is possible to provide a head protector which is difficult to be deformed even by an external force applied thereto, maintains adhesion between the reinforcing fiber and the matrix resin, and has excellent shock absorption and penetration resistance at the same time.

Hereinafter, the present invention will be described in more detail with reference to examples. The evaluation methods used in the examples are as follows.
(1) Crystallinity of fiber Using a wide-angle X-ray diffraction method, a scattering intensity of Cu-Kα rays is measured using an X-ray diffractometer (D8 DISCOVER with RAD-3a RU-300 GADDS Super Speed) manufactured by Bruker AXS. The crystallinity was calculated by the following formula.
Crystallinity = Scattering intensity of crystal part / total scattering intensity × 100 (%)
(2) Tensile strength and tensile modulus of fiber Measured according to ASTM D 885.
(3) Fabric basis weight, woven density Measured according to JIS L 1096.
(4) Performance evaluation of the head protector The shock absorption and penetration resistance tests were measured according to JIS T 8133. In addition, the impact absorbability is excellent, so that this value is low.

[Example 1]
As the dope for spinning, an NMP solution having a concentration of 6% by weight of copolyparaphenylene 3,4'-oxydiphenylene terephthalamide (fully aromatic polyamide having a copolymerization molar ratio of 1: 1) was used. Using the obtained dope, it was discharged from a spinneret having a hole number of 300 holes, spun into an aqueous solution having an NMP concentration of 30% by weight through an air gap of about 10 mm, and then 15 tanks and a concentration gradient of 10% to 0%. After removing the solvent in a 0.001% by weight desolvation tank, the film was dried while being stretched 1.3 times, then stretched 10 times at a temperature of 500 ° C., and wound up to obtain a crystallinity of 70%. A copolyparaphenylene 3,4'-oxydiphenylene terephthalamide yarn having a single fiber fineness of 10 dtex and a total fineness of 3000 dtex was obtained.
A plain woven fabric was produced under the conditions shown in Table 1 using the copolyparaphenylene · 3,4'-oxydiphenylene · terephthalamide yarn obtained by the above yarn production. The obtained woven fabric was cut into 50 cm ² and placed in a head protector female mold, and then molded at 120 ° C. for 3 seconds to obtain a head protector shape. On the woven fabric, 200 g of unsaturated polyester resin (RMD-179, Japan Composite Co., Ltd.) was filled (filling amount: 75% by volume of the entire molded part of the mold).

On the other hand, glass fiber (RS240 F-562, manufactured by Nittobo Co., Ltd.) is installed in a preform machine (manufactured by Toho Electric Co., Ltd. and Hasegawa Seisakusho Co., Ltd.), cut to a length of 50 mm, and the head is cut. A preform was obtained by suction and bonding with a vinyl acetate resin (manufactured by Daido Kasei Kogyo Co., Ltd.) on a screen having a part protector shape.
The fabric filled with resin was placed on a preform formed by roving glass fibers and heated and pressed at a mold temperature of 120 ° C. and a clamping pressure of 40 t to obtain a head protector. The results are shown in Table 1. In the composition of the woven fabric in Table 1, the woven density indicates the number of yarns driven per inch (unit: yarn / inch) in each of the warp direction and the weft direction of the fabric.

[Examples 2-3, Comparative Examples 1-2]
The physical properties of the copolyparaphenylene 3,4'-oxydiphenylene terephthalamide yarn were adjusted as shown in Table 1. That is, in Comparative Examples 1 and 2, the draw ratio was changed from 10 times to 5 times. In each of the examples and comparative examples, the single fiber fineness and the total fineness are different from each other in the number of holes (for example, 150 holes in Example 2 and 34 holes in Example 3). The amount of polymer discharged was adjusted as shown in Table 1 by changing the polymer discharge amount. Further, in Example 3 and Comparative Example 2, the woven density (lines / inch) of the yarn in the woven fabric was changed. Except this, it implemented like Example 1 and obtained the head protector. The results are shown in Table 1.

[Reference example]
Copolyparaphenylene, 3,4'-oxydiphenylene, terephthalamide yarn with two yarns made by Teijin Techno Products Co., Ltd. with a total fineness of 1670 dtex and 1000 filaments (single fiber fineness of 1.67 dtex) The head protector was obtained in the same manner as in Example 1 except that. The results are shown in Table 1. Although this was used as a reference in the evaluation, Examples 1 to 3 all exhibited higher performance in impact resistance and penetration resistance.

  The head protector of the present invention relaxes the impact applied to the human head and protects it from obstacles, and is particularly lightweight and excellent in shock absorption and rigidity, such as various helmets for vehicles, construction, etc. Can be widely used.

Claims (4)

  A head protector made of a fiber reinforcing material and a resin, wherein the fiber reinforcing material is made of a para-type aromatic polyamide fiber having a single fiber fineness of 10 to 45 dtex and a crystallinity of 55 to 70%. Head protector.   The head protector according to claim 1, wherein the para-type aromatic polyamide fiber has a tensile strength of 2000 MPa or more and a tensile modulus of 50 to 150 GPa.   The head protector according to claim 1, wherein the para type aromatic polyamide fiber is a fiber made of polyparaphenylene terephthalamide or a fiber made of copolyparaphenylene 3,4'-oxydiphenylene terephthalamide.   The head protector according to claim 1, wherein the fiber reinforcement is a woven fabric.