JP2008190085A - Protective material and protective clothes - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a protective material and protective clothes each protecting the human body from a toxic chemical substance, and having high heat, fire protecting properties without greatly increasing mass. <P>SOLUTION: This protective material has at least one layer each of a heat resistant layer and an activated carbon layer. At least one heat resistant layer is arranged on the outside of the activated carbon layer, on seeing from the inside of clothes. The heat resistant layer is made of a flame resisting fiber fabric. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a protective material and protective clothing having the performance of protecting workers handling hazardous chemical substances. More particularly, the present invention relates to protective materials and protective clothing that effectively protects workers from gaseous or liquid organic chemicals that are absorbed from the skin and have an adverse effect on the human body, such as organic phosphorus compounds. -It relates to lightweight protective materials and protective clothing that have flame protection performance.

  Various types of protective clothing that protects the human body from harmful chemical substances have been proposed, and there are protective clothing that protects gaseous chemical substances using an adsorbent material such as activated carbon. Some of these protective garments are provided with flame retardancy that suppresses the increase in temperature of the back surface when flame is applied to the material surface assuming the use of fire.

  A technique for imparting flame retardancy by imparting a flame retardant to an adsorbing material such as activated carbon or impregnating the flame retardant is disclosed (for example, Patent Document 1). However, these methods cause the gas adsorbability of the adsorbing material to deteriorate, and a relatively large amount of adsorbing material is required to compensate for this, resulting in an increase in the mass of the protective material and protective clothing, resulting in a physiological burden. There is a problem of increasing.

  In addition, as a layer other than the adsorbent material such as activated carbon, for example, a flame-proof cotton cloth or wool fabric, or an aramid fiber (for example, Patent Document 2) in which the material itself has flame retardancy, flame-retardant rayon fiber ( For example, a technique of laminating a woven fabric made of Patent Document 3), a flame-retardant vinylon fiber (for example, Patent Document 4), and the like is also used.

  However, when using a cotton fabric or wool fabric that has been subjected to flameproofing, it is flame retardant, but when it is applied from the surface of the material, it will carbonize and cracks will be allowed to enter, allowing the inside of the clothing to enter. There is a problem that the temperature of the back surface rises.

  In addition, flame retardant fibers such as aramid fibers can be dyed very expensive (kneading, electron beam crosslinking, etc.), but liquid dyeing, dip dyeing and printing dyeing cannot be performed. Productivity is very bad. Similarly, flame retardant vinylon fibers and the like are also highly likely to cause wet heat embrittlement and acid / alkali decomposition, so that they are difficult to mix and fiber with other fibers and have very poor productivity. In such a case, a method can be considered in which dyeable fibers are laminated on the outermost layer. However, as a result, the mass of the entire protective material increases, and there is a problem that a physiological burden increases when the protective clothing is used.

JP 2006-21535 A Japanese Unexamined Patent Publication No. 63-1996741 JP 2003-27383 A JP-A-2-154084

  The present invention has been made against the background of the problems of the prior art. A protective material and a protective garment that protect the human body from harmful chemical substances and the like, and have high thermal / flame protection performance without significantly increasing the mass. It is to provide.

In order to solve the above problems, the present invention has been completed as a result of intensive studies. That is, the present invention is as follows.
1. A protective material having at least one heat-resistant layer and at least one activated carbon layer, wherein at least one heat-resistant layer is disposed outside the activated carbon layer as viewed from the inside of the garment, wherein the heat-resistant layer is a flame-retardant fiber fabric Is a protective material.
2. ^2. The protective material according to 1 above, wherein the heat-resistant layer has a mass of 20 g / m ² or more and 100 g / m ² or less.
3. 3. The protective material according to 1 or 2 above, wherein the mass of the activated carbon layer is 30 g / m ² or more and 200 g / m ² or less.
4). 4. The protective material according to any one of 1 to 3, wherein the activated carbon layer is made of fibrous activated carbon.
5. The protective clothing using the protective material in any one of said 1-4.

  According to the present invention, a protective material and protective clothing that protects the human body from harmful chemical substances and the like and has high heat / flame protection performance without significantly increasing the mass are provided. It can be suitably used for applications such as protective materials for hazardous chemical substances and protective clothing that can suppress the temperature rise on the back surface against flame contact from the material surface, which is considered when an accident is assumed.

Hereinafter, the present invention will be described in detail.
The protective material according to the present invention preferably has at least one heat-resistant layer, and the heat-resistant layer is preferably composed of a flame-retardant fiber fabric. The flame retardant fiber used in the present invention is a fiber having flame retardancy having a critical oxidation index of about 25 or more and heat resistance having a thermal decomposition temperature of about 400 ° C. or more by a suggested scanning calorimetry method. Examples thereof include polybenzazole fibers, para-aramid fibers, wholly aromatic polyester fibers, and novoloid fibers composed of oxazole or polybenzothiazole or copolymers thereof. Moreover, what carbonized these fibers may be used. Among these flame retardant fibers, polybenzazole fibers having an excellent thermal decomposition temperature are very useful. In addition, using activated carbon fibers obtained by carbonizing novoloid fibers or the like is also useful in terms of protection against harmful chemical substances.
The flame-retardant fiber used for the protective material according to the present invention may be composed of one kind of the above-mentioned fibers, or may be composed of any two or more kinds.

  Examples of the form of the flame-retardant fiber fabric used for the protective material according to the present invention include a woven fabric, a knitted fabric, a nonwoven fabric, a felt shape, and a paper shape, but a low-mass production without using a resin such as a binder. From the point of being possible, it is preferable that it is a nonwoven fabric form.

The mass of the heat-resistant layer used in the protective material according to the present invention is preferably 20 g / m ² or more and 100 g / m ² or less. If it is less than 20 g / m ² , sufficient heat / flame protection cannot be obtained, and if it exceeds 100 g / m ² or less, the mass of the entire protective material increases, resulting in an increased physiological burden when used as protective clothing.

  Since the heat-resistant layer used in the protective material according to the present invention is a hardly dyeable fiber, it is more preferable to laminate a fiber assembly sheet that can be easily dyed on the outermost layer of the protective material.

  As the fiber assembly sheet of the outermost layer, natural fibers such as cotton, hemp, hair and silk, regenerated fibers such as rayon, polynosic, cupra and lyocell, semisynthetic fibers such as acetate and triacetate, nylon, polyester, polypropylene, polyethylene, Examples include woven fabrics, knitted fabrics, and nonwoven fabrics made of synthetic fibers such as vinylon, acrylic, acrylic, polyurethane, and polyclar. These fibers may be used alone or in combination by blending, union, union, etc. to form a fiber assembly sheet.

  The outermost fiber assembly sheet is preferably a woven fabric, a knitted fabric or a non-woven fabric imparted with water repellency and oil repellency. As the outermost layer, a woven fabric, a knitted fabric, or a nonwoven fabric having a water repellency of 4 or more when the 6.2 spray test described in JIS L-1092 is performed and an oil repellency by AATCC Test Method 118 of 4 or more. Can be preferably used, but those considering flexibility are recommended. The heat-resistant layer and the outermost layer are bonded in advance by bonding by adhesive application, thermal bonding by powder, granule, nonwoven fabric hot melt adhesive, etc., lamination by quilting, or a combination thereof. From the viewpoint of handleability, it is preferable.

  The protective material according to the present invention has at least one activated carbon layer. The main role of the activated carbon layer is to adsorb gaseous organic chemicals, but it also contributes to heat and flame protection due to the synergistic effect with the heat-resistant layer. As the types, granular or powdered activated carbon fixed to a sheet base material via an adhesive, woven fabric, knitted fabric or nonwoven fabric made of fibrous activated carbon, wet papermaking using fibrous or powdered activated carbon with base fiber and binder However, a woven fabric, a knitted fabric or a non-woven fabric made of fibrous activated carbon is preferable from the viewpoint of reduction of activated carbon falling and flexibility.

  The gaseous organic chemical substance in the present invention is a compound having one or more carbon elements. It is a gaseous chemical substance having a relatively large molecular weight of 50 or more and capable of adsorbing activated carbon as a gas adsorbing substance. For example, common organic solvents such as organic phosphorus compounds used for agricultural chemicals, insecticides and herbicides, and toluene, methylene chloride, chloroform used for painting work and the like can be mentioned.

The BET specific surface area of the activated carbon according to the present invention is preferably 700 m ² / g or more and 3000 m ² / g or less, and in order to obtain a sufficient permeation suppressing ability with a small amount of use, 1000 m ² / g or more and 2500 m ² / g or less. Further preferred. If the BET specific surface area is less than 700 m ² / g, a large amount of activated carbon is required to obtain sufficient protection, and the protective material becomes heavy. On the other hand, when it exceeds 3000 m ² / g, there arises a problem that the adsorbed gaseous organic chemical substance is separated.

The mass of the activated carbon layer is preferably 30 g / m ² or more and 200 g / m ² or less. If it is less than 30 g / m ² , the capacity that can be adsorbed becomes small and the use time is limited, and sufficient heat / flame protection cannot be achieved. On the other hand, when it exceeds 200 g / m ² , the protective material becomes heavy, which causes an increase in physiological burden. More preferably, it is 40 g / m ² or more and 150 g / m ² or less.

  The method of using fibrous activated carbon to obtain effective permeation suppression with a small amount of use is an effective procedure, but the raw material for the fibrous activated carbon used is natural cellulose fibers such as cotton and hemp Besides, regenerated cellulose fibers such as rayon, polynosic, solvent spinning, and further synthetic fibers such as polyvinyl alcohol fibers, acrylic fibers, aromatic polyamide fibers, lignin fibers, phenol fibers, petroleum pitch fibers, From the physical properties (strength etc.) and adsorption performance of the obtained fibrous activated carbon, regenerated cellulose fiber, phenol fiber, and acrylic fiber are preferable. After weaving, knitting, and nonwoven fabric using these short fibers or long fibers of raw materials, impregnating with an appropriate flameproofing agent as necessary, flameproofing treatment is performed at a temperature of 450 ° C. or less, Subsequently, fibrous activated carbon can be manufactured by the method of activating carbonization at the temperature of 500 degreeC or more and 1000 degrees C or less.

  The activated carbon layer used in the protective material according to the present invention may be subjected to water / oil repellent finishing. By imparting a water / oil repellent treatment to the activated carbon layer, it is possible to suppress the wet performance of the activated carbon by the wearer of the protective clothing and the deterioration of the adsorption performance for the gaseous organic chemical substance. The processing agent is not particularly limited. However, since the processing agent may block the pores of the activated carbon and the adsorption performance to the gaseous organic chemical substance may be lowered, it is desirable that the amount of attachment is as small as possible.

  In order to prevent the falling off of powdered or granular activated carbon forming the activated carbon layer in the protective material according to the present invention, or to supplement the mechanical strength of the fibrous activated carbon, both sides of the activated carbon layer may be laminated with a protective sheet. preferable. As the protective sheet, it is preferable to use a fiber assembly sheet, and the form thereof can be any suitable form such as a woven, knitted, non-woven, or paper form, but it is necessary to select according to the application. .

  Substances such as organophosphorus compounds have a relatively high boiling point and are present in the form of droplets or mist in addition to gas at room temperature. In order to prevent these liquid substances from penetrating and adhering to the skin, liquid organic chemistry can be obtained by laminating with the constitution of (a) liquid organic chemical protective layer, (b) activated carbon layer, (c) activated carbon protective layer. It is possible to protect against substances, which is a preferred embodiment as a protective material.

  (A) The liquid organic chemical protective layer is not particularly limited as long as it is a liquid-resistant sheet, but non-woven fabric and oil-absorbing paper are preferable from the viewpoint that a low mass can be produced. The material of the nonwoven fabric to be used is not particularly limited, such as polyolefin, polyester, polylactic acid, polycarbonate, polyvinyl chloride, and polyvinylidene chloride. Further, these materials may be made into paper and used in a paper form.

  As the activated carbon protective layer of (c), a woven or knitted fabric woven or knitted with a thin and coarse density made of hydrophobic fibers is used, but a tricot knitted fabric is preferable from the viewpoint of flexibility. It is possible to suppress the sweating of the wearer of the protective clothing from remarkably causing the sweat to wet the activated carbon and lowering the adsorption performance to the gaseous organic chemical substance.

  In order to easily pass the sweat vapor to the outside of the protective material, it is desirable to use a hydrophobic fiber fabric as the activated carbon protective layer of (c). If it is composed of hydrophilic fibers, the activated carbon protective layer itself is in a state of moisture absorption and water absorption by sweat, and the function of effectively transferring moisture in the clothes to the outside and dehumidifying it is not preferable. The hydrophobic fiber here is a fiber having a moisture content of 3% or less at 20 ° C. and 65% RH, and examples thereof include synthetic fibers such as polyethylene, polypropylene, and polyester.

  The protective sheet and the activated carbon layer are preferably a laminate in which the layers are in close contact with each other in order to facilitate the transfer of moisture when wearing protective clothing. Examples of the laminating means include bonding by applying an adhesive, thermal bonding using a powder, granule, or non-woven hot melt adhesive, lamination by quilting, and combinations thereof.

  It is preferable to have an intermediate layer between the heat-resistant layer and the activated carbon layer of the protective material according to the present invention. In order to develop a high level of heat / flame protection, it is necessary to form a large amount of air layer in the protective garment in order to delay the conduction of heat, and furthermore, between the heat-resistant layer and the activated carbon layer. It is useful to have an air layer. Therefore, it is most useful to form a laminated structure by inserting an intermediate layer between the heat-resistant layer and the activated carbon layer. However, when the intermediate layer is inserted, there is a disadvantage that the mass becomes heavy. In order to form an air layer without significantly increasing the mass of the intermediate layer, it is preferable to apply an intermediate layer having a small mass per unit volume.

  EXAMPLES Next, although this invention is demonstrated concretely using an Example and a comparative example, this invention is not restrict | limited by these Examples. In addition, evaluation described in an Example is based on the method described below.

(Organic chemical substance permeability test)
A container diagram used in the test is shown in FIG. The test product was sandwiched between two glass cells having an internal volume of 150 cc, and the periphery was sealed with paraffin. 10 μL of 3-methoxybutyl acetate was dropped from the upper cell of the test container onto the test product. This was placed in a constant temperature box set to 25 ± 2 ° C., the gas concentration on the lower cell side was sampled at regular intervals, and the gas concentration permeating the test sample was measured by gas chromatography.

(Heat and flame protection test)
The test product is placed so that the burner side is the outermost layer so as to be 50 mm above the gas burner having a diameter of 105 mm. Thereafter, the burner is removed from the apparatus, the flame is ignited with propane gas, and the flame length is adjusted to 5.5 cm. After the flame was stabilized, the burner was quickly returned to the predetermined position of the apparatus, and the rising temperature 10 mm above was measured from the test product on the back side of the test product 15 seconds after the burner was installed.

(A feeling of wearing)
Heart rate, blood pressure, skin temperature, rectal temperature, clothes after walking on a treadmill at a speed of 5 km / hr for 10 minutes in a constant temperature and humidity chamber at 32 ° C and 70% RH while wearing a one-piece type protective clothing The evaluation was based on the measurement of internal temperature and humidity and a comprehensive evaluation from a questionnaire survey.

(BET specific surface area)
An adsorption isotherm of nitrogen was obtained and calculated by the BET method based on this.

(mass)
According to JIS L-1018 8.4 and JIS L-1096 8.4.

[Example 1]
A nylon plain woven fabric (mass 50 g / m ² ) is used as the outermost layer, and a polybenzazole fiber nonwoven fabric (mass 30 g / m ² ) formed into a nonwoven fabric by the spunlace method is used as a heat-resistant layer, and these are breathable nonwoven hot-melt adhesives It was set as the outer-layer material by adhere | attaching by (mass 10g / m < ² >). Also, a woven fibrous activated carbon (mass 120 g / m ² ) having a BET specific surface area of 1400 m ² / g made of novolac phenol resin fibers was used as an activated carbon layer, and this was used as a polypropylene nonwoven fabric (mass 30 g / m ^2). ) And bonded with a breathable non-woven hot melt adhesive (mass 10 g / m ² ) to obtain an inner layer material. And the protective material was obtained by superimposing these. Table 1 shows the mass, heat / flame protection, gas permeability test results, and wearing feeling of this protective material.

[Example 2]
A woven fibrous activated carbon (mass 60 g / m ² ) having a BET specific surface area of 1400 m ² / g made of novolac phenol resin fiber is used as an activated carbon layer, and one side is a loop pile tricot cloth (mass 110 g / m ² ) made of nylon filaments, On the other side, a knitted fabric (mass 60 g / m ² ) made of polyester filaments was bonded with a breathable non-woven hot melt adhesive (mass 20 g / m ² ) to form an inner layer material. A protective material was obtained by overlapping this and an outer layer material having the same configuration as in Example 1 above. Table 1 shows the mass, heat / flame protection, gas permeability test results, and wearing feeling of this protective material.

[Example 3]
Nylon plain woven fabric (mass 50 g / m ² ) is used as the outermost layer, and a sheet (wet 30 g / m ² ) obtained by wet paper making of fibrous activated carbon with a BET specific surface area of 1400 m ² / g made of novolac phenol resin fiber is used as the heat-resistant layer. These were bonded to each other with a breathable non-woven hot melt adhesive (mass 10 g / m ² ) to obtain an outer layer material. And the protective material was obtained by superimposing the inner layer material which consists of the structure similar to the said Example 2. FIG. Table 1 shows the mass, heat / flame protection, gas permeability test results, and wearing feeling of this protective material.

[Comparative Example 1]
Cotton / nylon混糸(ratio: 23% nylon, nylon 77%) scouring in a conventional manner a twill by bleaching, dyeing, flame treatment, Water-repellent fabric (mass 180 g / ^{m 2)} and the outer layer material, which A protective material was obtained by superimposing an inner layer material having the same structure as in Example 1 above. Table 1 shows the mass, heat / flame protection, gas permeability test results, and wearing feeling of this protective material.

[Comparative Example 2]
A fabric (mass 125 g / m ² ) obtained by scouring, dyeing, and water-repellently treating a twill fabric (ratio: 30% nylon, 70% modacrylic) with nylon filament and weft modacrylic as a standard is used as an outer layer material. A protective material was obtained by superimposing an inner layer material having the same structure as in Example 1. Table 1 shows the mass, heat / flame protection, gas permeability test results, and wearing feeling of this protective material.

[Comparative Example 3]
A protective material was obtained by superimposing an outer layer material having the same configuration as in Comparative Example 1 and an inner layer material having the same configuration as in Example 2 above. Table 1 shows the mass, heat / flame protection, gas permeability test results, and wearing feeling of this protective material.

[Comparative Example 4]
A protective material was obtained by superimposing an outer layer material having the same configuration as in Comparative Example 2 and an inner layer material having the same configuration as in Example 2 above. Table 1 shows the mass, heat / flame protection, gas permeability test results, and wearing feeling of this protective material.

  Examples 1, 2, and 3 are suitable protective materials with excellent heat / flame protection, gas permeability and wearing feeling, while Comparative Examples 1 and 2 have a high temperature rise in heat / flame protection. became. Since the mass of Comparative Example 3 was heavy, the wearing feeling was poor. In Comparative Example 4, both the heat / flame protection and the feeling of wearing were somewhat bad.

  The protective material and protective garment of the present invention can protect gaseous organic chemicals by combining the heat-resistant layer and the activated carbon layer, and can have advanced heat / flame protection performance without significantly increasing the mass. , Which is related to protective materials that show excellent heat / flame protection against the contact of flames that can be considered in the event of accidents when using fire, etc., and can be used for protective clothing, protective tents, etc. It is important to contribute to the industry.

It is a cross-sectional schematic diagram which shows an example of the protective material of this invention. It is a cross-sectional schematic diagram which shows another example of the protective material of this invention. It is the schematic which shows the test container used for a gas-permeability test method.

Explanation of symbols

1: outermost layer 2: heat-resistant layer 3: activated carbon protective layer 4: activated carbon layer 5: liquid organic chemical protective layer 6: upper cell (150 cc)
7: Sampling port 8: Test solution 9: Test product 10: Paraffin sealing 11: Lower cell (150 cc)

Claims (5)

  A protective material having at least one heat-resistant layer and at least one activated carbon layer, wherein at least one heat-resistant layer is disposed outside the activated carbon layer as viewed from the inside of the garment, wherein the heat-resistant layer is a flame-retardant fiber fabric Is a protective material. The protective material according to claim 1, wherein the mass of the heat-resistant layer is 20 g / m ² or more and 100 g / m ² or less. The protective material according to claim 1 or 2, wherein the mass of the activated carbon layer is 30 g / m ² or more and 200 g / m ² or less.   The protective material according to claim 1, wherein the activated carbon layer is made of fibrous activated carbon. Protective clothing using the protective material according to claim 1.

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