JPS635937A - Member for protection tool and manufacture thereof - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a novel member for protective equipment and a method for manufacturing the same, and more particularly, it relates to a novel member for protective equipment and a method for manufacturing the same. The present invention relates to members suitable for use in protective equipment such as belly pads, shin pads, and shoulder pads in shields or bulletproof clothing, and a method for manufacturing the same.

(Prior Art) Conventionally, protective equipment or its components for protecting the body from weapons such as bullets and knives, or fragments of explosives, have been used.
Metal plates, ceramic plates, high-strength nylon fabrics, or para-aromatic polyamide (eg, Du Pont Kevlar@) fabrics, or combinations thereof have been used. However, metals such as iron and aluminum alloys and ceramics have the disadvantage of being heavy and lack mobility, and high-strength nylon fabrics have the disadvantage of having a high number of laminated layers due to poor ballistic resistance. On the other hand, para-aromatic polyamide fiber fabrics are preferred as materials for bulletproof vests because of their high strength and high impact resistance, making it possible to reduce the laminated weight compared to strong nylon. However, para-aromatic polyamide fabrics can also be used to obtain bulletproof clothing that is flexible, comfortable to wear, and has good bulletproof performance.
It has the disadvantage that it is surprisingly easy to penetrate when pierced with an awl or the like. Furthermore, although it does not allow bullets to penetrate, the fabric is flexible, so the amount of deformation toward the back side, that is, the human body side, is large, and it has the drawback that accidents such as rib fractures are likely to occur even if it does not result in death. Ta.

On the other hand, in order to improve the above drawbacks, high-strength nylon fabric,
Protective equipment or members for protective equipment have also been proposed in which a multi-layered para-aromatic polyamide fiber fabric is impregnated with a thermosetting resin and cured. In this case, the fabric is filled and fixed with resin. Therefore, it is resistant to being pierced by a knife, and can also be given structural strength, making it useful as a helmet or Ishikawa. However, it has the disadvantage that it is 30 to 40% heavier than a laminate made of woven fabric alone, and if the amount of resin impregnated exceeds 40%, bullets tend to penetrate more easily, so the amount of resin impregnated is There is also the problem that unless sufficient control is taken to ensure uniformity, local variations in bulletproof performance will occur.

(Problems to be Solved by the Invention) The present inventors have solved the problems found in conventional protective equipment or members for protective equipment as described above, namely, fabrics such as high-strength nylon fabrics and para-aromatic polyamide fiber fabrics. Poor dirt resistance and large deformation when hit by bullets in soft-type protective equipment (components) made of wood, and excessive weight in hard-type protective equipment (components) such as metal plates, ceramic plates, or thermosetting resin-impregnated fabrics. As a result of intensive research to provide a new protective equipment component that is lightweight, has improved ballistic resistance, and has good ballistic resistance and load resistance, we have found that a multilayer laminate of high-strength organic synthetic fiber fabric has a heat-resistant material. When impregnating and curing with a curable resin, even if the impregnation and curing with the resin is limited to only the surface layer of the laminate, the remaining fabrics are bonded to each other on their entire surfaces, giving them appropriate rigidity. By suppressing the occurrence of displacement of the fabric structure such as misalignment, sufficient strength can be obtained without impregnating and curing the entire laminate with resin, and weight reduction can be achieved due to partial impregnation. Not only that, but also in terms of bullet resistance, the presence of the non-impregnated layer with the above-mentioned moderate rigidity (in other words, moderate flexibility) reduces the amount of resin as in the case of hard type resin-impregnated fabrics. We found that there was no problem such as bullet penetration caused by a partial excess of bullets, and that the amount of deformation when hit was significantly reduced.Based on this knowledge, we conducted further studies and completed this research. I ended up doing it.

(Means for Solving the Problems) That is, first of all, the present invention consists of a multi-layer laminated structure of fabrics made of high-strength organic synthetic fibers having a tensile strength of 20 g/d or more, and both the front and back outer layers of the fabric are laminated. A protective equipment member characterized in that at least one of the fabrics is impregnated and cured with a thermosetting resin, and the remaining fabrics are bonded to each other and substantially over their entire surface with an adhesive, Second, a plurality of fabrics made of high-strength organic synthetic fibers with a tensile strength of 20 g/d or more are laminated with a film adhesive interposed therebetween, or on one or both of them.
Similarly, a prepreg made by impregnating a thermosetting resin with a high-strength organic synthetic fiber fabric with a tensile strength of 20 g/d or more is layered, and this is heated and pressed to harden the prepreg and thermally bond with a film adhesive. This is a method of manufacturing a member for protective equipment, characterized by carrying out the following steps.

The high-strength organic synthetic fibers with a tensile strength of 20 g/d or more referred to in the present invention include para-aromatic polyamides [for example, Du P
Kevlar 0 manufactured by Ont, HM-50 manufactured by Kijin ■] and aromatic polyesters [such as Econol 0 manufactured by Sumitomo Chemical ■]
etc.] etc. can be mentioned as preferable ones.

The structure of the woven fabric using these high-strength organic synthetic fibers used in the present invention is not particularly limited.
A 00d filament yarn is used, which is made into a plain weave or a diagonal weave. In this case, it is desirable that the weaving density (fabric weight) be close to the critical density for each weave design, for example 1.500.
If it is a 2×2 basket weave using thread d, the weft density in the warp and weft is about 34×34 yarns/25 yarns (the weight of the fabric is 46
0 g/m), and 1,000
If it is plain weave using thread d, it is the same <31 x 31 pieces / 25
A material having a weight of about 1 s (about 280 g/rd in terms of fabric weight) is preferably used. There is a tendency for ballistic resistance to decrease as the driving density decreases.

The protective equipment member of the present invention has a basic structure composed of multiple layers of high-strength organic synthetic fiber fabrics as described above, and the outer layer of the fabric is impregnated with a thermosetting resin and cured (hereinafter, in such a case, The remaining laminated fabric is bonded on its entire surface with adhesive (sometimes it is simply hardened), and the remaining laminated fabric is completely bonded with adhesive. This varies depending on the use of the (component), but for example, it is suitable for use with 380 diameter or 450 diameter handguns. If the purpose is protection, the total weight is 3,500 to 5,000 g.
/n? It is desirable that the thickness be within the range of 100 to 1000, and sufficient resistance to puncture by a knife can be provided if the range is within this range.

The extent to which the outer layer of this woven fabric laminate is hardened with thermosetting resin varies depending on the purpose of use of the protective equipment (member), etc.;
The outer layer portion may be cured in an amount corresponding to 000 g/n, and an appropriate amount is selected from this range depending on the above-mentioned purpose of use.

Suitable thermosetting resins used for curing the outer layer portion of the laminate include thermosetting resins commonly used for laminates, such as epoxy resins, unsaturated polyester resins, vinyl ester resins, and phenol resins.

The amount of thermosetting resin used (impregnated amount) is 30 to 60% of the weight of the cured layer (total weight of fabric and resin).
A range of weight percent is suitable. It was observed that when the amount of resin used was less than 30% by weight, the stain resistance tended to be insufficient.
If the amount exceeds 0% by weight, the ballistic resistance will decrease.

The above-mentioned hardened layer of thermosetting resin is usually formed on either the front or back outer layer of the textile laminate (the side that will be hit by a deadly weapon when used as a protective device), but in some cases it may be formed on both the front and back. You can also force it. In addition, the fabric to be cured with the thermosetting resin may have either a single layer or multiple layers, and the key point is that the above-mentioned portion of the fabric to be cured outside the weight of the fabric is bonded with adhesive. This structure provides appropriate rigidity (in other words, appropriate flexibility). In this case, it is important that the fabrics are joined to each other substantially over their entire surface;
This not only gives uniform rigidity to the entire structure, but also suppresses the occurrence of misalignment when being hit by a bullet or being pierced by a knife, resulting in significantly improved ballistic resistance and strength. do. In addition, from the perspective of imparting rigidity and preventing misalignment, adhesives are applied not only to substantially the entire surface of the fabric, but also to a certain extent to penetrate into the yarns that make up the fabric. It is desirable to use this method to force a stalemate.

The adhesive may be a thermoplastic (thermofusible) resin, a thermosetting resin, or an elastomer, but from the viewpoint of the manufacturing process of protective equipment members, thermoplastic (
A thermofusible) resin system is preferred because it is easy to handle.
In particular, if a thermosetting resin that plasticizes or melts at a temperature below the curing temperature of the thermosetting resin constituting the cured layer is used, curing of the cured layer, thermal adhesion by the adhesive, and further adhesion of the threads can be performed at the same time. It has the advantage of being possible.

Preferred adhesives from this point of view include polyethylene, polypropylene, low-melting copolymer polyester, and the like, and it is particularly desirable to use film-like materials of these adhesives since they can be easily bonded over the entire surface.

The amount of the adhesive to be used is preferably in the range of 5 to 15% by weight based on the weight of the fabric (the weight of one layer of the fabric to be laminated and bonded). If the amount of adhesive falls below 5% by weight, there is a risk that the bonding of the fabric, as well as the adhesion and fixation of the threads that make up the fabric, will be insufficient, and the amount of deformation when hit by a bullet will increase. - If the construction is made of earth with 15% by weight, the ballistic resistance is higher than that.
No improvement in strength is observed, and this is not preferable, as it simply causes an increase in weight.

There are various methods for manufacturing the member for protective equipment of the present invention having such a configuration, but considering the role of protective equipment to protect life and body from firearms and deadly weapons, there are various methods for manufacturing protective equipment and, in turn, Considering the fact that protective equipment components are particularly required to have consistent quality with no variation, and also considering the ease of operation and process control in the manufacturing process, The most preferred method is the method described above, in which a prepreg is placed on an alternate laminate of a high-strength organic synthetic fiber fabric and a film adhesive and then heated and pressurized.

In carrying out this method, as a prepreg,
Preferably, a single-layer fabric with the above-mentioned hardening layer is used, which is pre-impregnated with the above-mentioned thermosetting resin. This prepreg constitutes the hardened layer of the outer layer in the protective equipment member of the present invention, and by using such prepreg, for example, after forming a textile laminate, the outer layer can be impregnated with a thermosetting resin. Compared to the curing method, it is possible to make the distribution of the resin in the cured layer more uniform, and it is also easier to adjust the amount of resin impregnated.

Film adhesives used for forming the textile bonding layer include:
Thermoplastic resin films such as the above-mentioned polyethylene film, polypropylene film, and low melting point copolymerized polyester film are most suitable, but epoxy resin films may be used depending on the case. It is particularly desirable that these film adhesives have a softening point or melting point lower than the curing temperature of the prepreg.

In the method of the present invention, for example, high-strength organic synthetic fiber fabrics of appropriate weights and film adhesives as described above are alternately laminated, and prepreg is applied to the top surface of this laminate, or in some cases to both upper and lower surfaces. , - generally their total fabric weight is 3.50 Q ~ 5,000g/n? And the fabric weight of the prepreg (cured layer) is 200 to 1,000 g
/ffr,,! =2. (overlap them in a weight ratio such that
This is carried out by applying heat and pressure using a heat press machine or the like to harden the prepreg and thermally bond it with a film adhesive. The heat and pressure is usually 1 to 30 kg/cm at a temperature higher than the curing temperature of the prepreg (thermosetting resin) and the softening or melting temperature of the film adhesive.
This is done by holding under +il pressure for 10-60 minutes.

In this way, the protective equipment member of the present invention is obtained, which has a hardened fabric layer on the outer layer and a bonded fabric layer on the inner layer.
When this protective equipment member is applied to protective equipment with a cubic curved shape, such as a belly pad, shoulder pad, or shield, the above-mentioned heating and pressurizing process is performed using the mold of the protective equipment, and the outer layer is It is desirable to integrally mold the portion and the inner layer portion in the mold.

In addition to the methods described above, the member for protective equipment of the present invention can be produced by, for example, separately manufacturing a hardened fabric layer as an outer layer and a bonding layer of a fabric as an inner layer, and then bonding them together by appropriate means. Alternatively, it can be manufactured by a method in which woven fabrics are bonded and laminated in multiple layers using a film adhesive or the like, and the outer layer is impregnated with a thermosetting resin and cured. Yui,
In the case of the former post-adhesion method, it not only adds one step to the process, but also makes it difficult to mold protective gear with a shape with a cubic curved surface, and in the latter post-impregnation method, the distribution of the impregnated resin becomes difficult. Both methods are inferior to the previously detailed methods in terms of uniformity and the like.

(Function) The protective equipment member of the present invention has a structure in which the outer layer of a laminate of high-strength organic synthetic fiber fabric is hardened with a thermosetting resin, and the inner layer is fully bonded with an adhesive to have appropriate rigidity. This not only makes it possible to maintain penetration resistance at a sufficiently high level even though only a portion (the outer layer) of the laminate is cured, as in the case of full curing.
As for resistance to bullets, the synergistic effect of the surface hardening layer and the internal bonding layer prevents bullets from penetrating, and the bonding layer has an appropriate degree of rigidity (flexibility) to disperse and absorb bullet energy. However, it has the effect of reducing the amount of deformation toward the human body, and together with the weight reduction due to partial hardening, it is lightweight and has excellent ballistic resistance and strength. It has finally become possible to provide components for protective equipment.

Next, the present invention will be explained in detail with reference to Examples and Comparative Examples. In addition, in these cases, evaluation of the ballistic resistance and strength of the members for protective equipment was performed as follows.

Ballistic resistance: A 30 cI 11 square sample was affixed vertically to a 20-inch thick oil clay wall, and a 380 cm
Three shots each were fired from a 450-diameter and 450-diameter handgun, with the shooting points separated by at least lQc+a, and the bullet resistance was evaluated based on the degree of bullet penetration and the depth of the dent in the clay on the back of the sample.

Stain resistance: A Japanese sword and ice pink were pierced vigorously into the sample attached to the oil clay wall in the same manner as above using both hands, and the strength was evaluated by checking whether the cutting edge reached the oil clay wall. .

Production Example Kevlar 0 (manufactured by Du Pont), which is an aromatic polyamide fiber, was used as a high-strength organic synthetic fiber.
28 B, manufactured by Takeda Pharmaceutical Co., Ltd.], impregnated with a mixture of diallyl phthalate and benzoyl peroxide in a ratio of 100:15:2 (weight ratio) to a resin content of 40% by weight (based on the total amount of fabric and resin. An unsaturated polyester prepreg (hereinafter referred to as K735UP) of the same type was prepared.

Separately, K735 and polyethylene film (film adhesive) with a weight of 40 g/rtr were laminated alternately.
35. Create a laminate consisting of 8 sheets and 7 films,
A sheet of 735UP was layered on top of the above, and heated and pressure molded for 30 minutes at 130°C and 10 kg/cj using a heat press to obtain a plate-shaped protective common member (Inventive Example 1) ).

This protective equipment member was subjected to evaluation tests for ballistic resistance and stain resistance, and the results are shown in Table 2.

Table 2 shows each sample below (Comparative Example 1) for comparison.
The results of similar evaluation tests for items 5) to 5) are also listed.

Comparative example 1: Duraluminium: / (A-2024-T6),
Thickness: 2.71 〃 735.10 sheets stacked on 2:〃 1K
Ten sheets of 735UP were stacked and hot pressed under the same conditions as in Example 1 of the present invention.

〃 4: 8 sheets of 735UP were stacked on top of each other and hot pressed under the same conditions as in Example 1 of the present invention.

〃 5: 735 and polyethylene film (weight 40g
/r+f) to create a laminate consisting of 735.10 sheets and 9 films, which was then hot pressed under the same conditions as Example 1 of the present invention.

From the results in Table 2, the protective equipment member of the present invention (Invention Example 1
) is lightweight and has excellent ballistic resistance and stain resistance, whereas conventional protective equipment members (Comparative Examples 1 to 4) satisfy all of light weight, bullet resistance, and stain resistance. It turns out that it is difficult to enforce. Further, as is clear from the results of Comparative Example 5, effects similar to those of the present invention cannot be expected depending on the protective equipment member consisting only of a textile bonding layer and lacking a hardened layer.

Example 2 The following protective equipment members were prepared according to Invention Example 1 of Example 1.

(1) Protective equipment in the same manner as Example 1 of the present invention, except that the following epoxy prepreg (K735EP) was used instead of 735UP as the prepreg, and the heating and pressurizing conditions were 170°C, 20 +r/all, and 45 minutes. A member for use was obtained (Example 2 of the present invention).

K735EP: 735 is impregnated with a 100:3.5:l (weight ratio) mixture of epoxy resin [bisphenol A epoxy resin with an epoxy equivalent weight of 450], curing agent (dicyandiamide), and curing accelerator (benzyldimethylamine). Epoxy prepreg with a resin content of 40% by weight.

(2) K73SEP (prepreg) is a laminate of K735 and polyethylene film (however, the number of layers is 735
A member for a protective equipment was obtained in the same manner as Example 2 of the present invention, except that one sheet was stacked on each of the front and back surfaces of 8 sheets of polyethylene film and 7 sheets of polyethylene film (Example 3 of the present invention).

(3) A protective equipment member was obtained in the same manner as Inventive Example 2 except that an epoxy resin film (weight 60 g/cd) was used instead of the polyethylene film as the film adhesive (Inventive Example 4).

Table 3 shows the results of performance evaluation of each of the protective equipment members thus obtained.

Example 3 As the prepreg for forming the hardened layer, the following two types of prepregs were used alone or in combination as shown in Table 4 instead of K735UP, but in the same manner as in Example 1 of the present invention Three types of protective equipment members having different weights of hardened surface layers were obtained.

(a) Unsaturated polyester prepreg (K289UP) with a resin content of 40% by weight, obtained by impregnating K289 with the same unsaturated polyester resin as in Example 1 of the present invention.

(b) Unsaturated polyester prepreg (K328UP) with a resin content of 40% by weight, obtained by impregnating K32B with the same unsaturated polyester resin as in Inventive Example 1.

Results of performance evaluation of each protective equipment member Example 4 In Invention Example 2 of Example 2, the composition of the inner layer KE735/polyethylene film laminate (number of laminated layers of KE735 and film) is shown in Table 5. Protective equipment members were obtained in the same manner as in Inventive Example 2 except as shown.

The performance evaluation results are shown in Table 5. In addition, as a prepreg for forming a surface hardening layer in Example 5, an unsaturated polyester prepreg (K10
33LIP) and K10 as the inner layer fabric.
A protective equipment member was prepared in the same manner as in Inventive Example 1 of Example 1, except that No. 33 was used (Inventive Example 10).

Claims (9)

[Claims] (1) It consists of a multilayered structure of fabrics made of high-strength organic synthetic fibers with a tensile strength of 20 g/d or more, and at least one of the outer layers of the fabric is impregnated and hardened with a thermosetting resin. . A member for protective equipment, characterized in that the remaining fabrics are joined to each other and substantially over the entire surface thereof by an adhesive. (2) The total weight of the laminated fabric is 3,500 to 5,000 g/
m^2, of which at least one of the front and back outer layer portions of the fabric equivalent to 200 to 1,000 g/m^2 is impregnated and hardened with a thermosetting resin.
Components for protective equipment as described in section. (3) The amount of thermosetting resin in the hardened portion of the outer layer is
The member for protective equipment according to claim 1 or 2, wherein the content is in the range of 30 to 60% by weight based on the total amount of the fabric and resin. (4) The protective equipment member according to any one of claims 1 to 3, wherein the thermosetting resin is an epoxy resin, an unsaturated polyester resin, a vinyl ester resin, or a phenol resin. (5) The member for protective equipment according to claim 1, wherein the woven fabrics are joined together by an adhesive in an amount corresponding to 5 to 15% by weight of the weight of one layer of woven fabric in the woven fabric joint portion. . (6) The member for protective equipment according to claim 1 or 5, wherein the adhesive is made of a low melting point thermoplastic resin. (7) The protective equipment member according to claim 6, wherein the low melting point thermoplastic resin is polyethylene. (8) The protective equipment member according to claim 1, wherein the high-strength organic synthetic fiber having a tensile strength of 20 g/d or more is a para-aromatic polyamide fiber. (9) Multiple sheets of fabric made of high-strength organic synthetic fibers with a tensile strength of 20 g/d or more are laminated via a film adhesive, and one or both of the top and bottom have a tensile strength of 20 g/d or more. A prepreg made by impregnating a thermosetting resin with a fabric made of high-strength organic synthetic fibers of /d or more is layered, and the prepreg is heated and pressed to harden the prepreg and thermally bond with a film adhesive. A method for producing a characteristic member for protective equipment.