JP2017101366A - Protective material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a protective material and a protective garment having a decomposition ability of an adverse chemical material in addition to a protective performance of a gaseous and liquid harmful chemical material, making a secondary contamination risk low, and having high air permeability to suppress heat stress of a wearer.SOLUTION: A protective material includes at least one layer each of an adverse chemical material decomposition layer which contains a manganese oxide or an iron oxide having a BET specific surface area of 0.1-1,000 m/g, and a gas adsorptive layer which contains active carbon.SELECTED DRAWING: None

Description

The present invention can effectively protect workers from gaseous and liquid harmful chemicals that are absorbed from the skin such as organophosphorus compounds and have an adverse effect on the human body. It relates to protective materials with a low risk of contamination.
The protective material of the present invention is particularly suitable for shelters, clothes, gloves, shoes, covers and the like.

Various protective materials have been proposed as protective materials for protecting the human body from harmful chemical substances. For example, a protective cloth made of an adsorbent material such as activated carbon or the like that is made of a material that does not allow any harmful chemical substances to permeate, such as a rubber cloth, is exemplified.
However, since these protective materials are not degradable to harmful chemicals, a fatal accident can occur if a wearer comes into contact with or inhales harmful chemicals that remain or are adsorbed on clothes. May lead to

  In recent years, various techniques for imparting degradability of hazardous chemicals by imparting a metal compound or the like to a synthetic fiber or natural fiber sheet material have been proposed.

For example, Patent Document 1 proposes a fabric in which a semiconductor material having photocatalytic properties is provided on the fiber surface.
However, since photocatalysts that decompose harmful chemicals require visible or ultraviolet light irradiation, there is a problem that sufficient decomposability of harmful compounds cannot be obtained in indoor or night use. Furthermore, fabric degradation due to the influence of active oxygen species generated by the photocatalyst is also a problem.

Patent Document 2 proposes an electrospun fiber obtained by kneading metal oxide halogen adduct particles in an adsorbing polymer.
However, since these electrospun fibers are provided by kneading metal oxide halogen adduct particles into the fiber, there are few metal oxide halogen adduct particles on the fiber surface that contribute to the reaction, and sufficient harmful chemistry is achieved. There is a concern that the material cannot be decomposed.

Patent Document 3 proposes a protective material including a nucleophilic polymer that is advantageous for forming a covalent bond with a harmful chemical substance on a base material and reactive particles that decompose the harmful chemical substance.
However, since the nucleophilic organic polymer is coated on the surface of the base material, the air permeability is reduced, and it is expected that a great thermal stress is applied to the worker.

Special table 2011-517295 gazette Special table 2010-526941 gazette JP 2010-131971 A

  The present invention has been made against the background of such prior art problems. That is, the object of the present invention is to have a degradability of harmful chemical substances in addition to the protective performance of gaseous and liquid harmful chemical substances, has a low risk of secondary contamination, and further suppresses heat stress of the wearer, The object is to provide protective materials and protective clothing having high breathability.

As a result of intensive studies, the present inventors have found that the above problems can be solved by the following means, and have reached the present invention. That is, this invention consists of the following structures.
1. A protective material having at least one harmful chemical substance decomposition layer containing manganese oxide or iron oxide having a BET specific surface area of 0.1 to 1000 m ² / g and a gas adsorption layer containing activated carbon.
2. 2. The protective material according to 1 above, wherein the activated carbon contained in the gas adsorption layer is fibrous activated carbon.
3. A protective garment using the protective material according to 1 or 2 above.

The protective material of the present invention is a protective material that has a high permeation-inhibiting ability against gaseous and liquid hazardous chemicals and has a low risk of secondary contamination by decomposing harmful chemicals. It is a very suitable protective material.
In addition, since manganese oxide or iron oxide is used as a hazardous chemical substance decomposing agent, it does not require external energy such as sunlight like photocatalyst to decompose harmful chemical substances, and it is also harmful chemical substances at night or indoors. Can be disassembled.

It is the figure which showed one example of the protective material of this invention. It is the figure which showed the container used for the decomposability | decomposability test with respect to a hazardous | toxic chemical substance. It is the figure which showed the container used for a gas permeability test.

Hereinafter, the protective material of the present invention will be described in detail.
As shown in FIG. 1, the protective material of the present invention is composed of a sheet material having at least one harmful chemical substance decomposition layer and a gas adsorption layer. Or it is comprised from the layer in which the iron oxide is contained.

  The sheet base material used for the hazardous chemical substance decomposition layer of the present invention is a material such as a woven fabric, a knitted fabric, a non-woven fabric, and an apertured film, and is not particularly limited. A knitted fabric or a non-woven fabric is preferred.

  The material used for the sheet base material used in the harmful chemical substance decomposition layer of the present invention is not particularly limited, and natural fibers such as cotton, hemp, hair, silk; rayon, polynosic, cupra, reyocell, etc. Recycled fibers; Semi-synthetic fibers such as acetate fibers and triacetate fibers; Polyamide fibers such as nylon 6, nylon 66, and aramid fibers; Polyester fibers such as polyethylene terephthalate fibers, polybutylene terephthalate fibers, polylactic acid fibers, and polyarylate; Polyacrylonitrile fibers Acrylic fibers such as polyacrylonitrile-vinyl chloride copolymer fibers and modacrylic fibers; polyolefin fibers such as polyethylene fibers and polypropylene fibers; polyvinyl alcohol fibers such as vinylon fibers and polyvinyl alcohol fibers; polyvinyl chloride fibers and vinylide Polyvinyl chloride fibers such as fibers and polyclar fibers; synthetic fibers such as polyurethane fibers; polyphenylene sulfide fibers; polybenzazole fibers (PBZ), polyparaphenylene benzobisoxazole (PBO), polybenzimidazole (PBI) fibers, polyimide Examples thereof include heterocyclic polymer fibers such as fibers; polycarbonate fibers; polysulfone fibers; polyether fibers such as polyethylene oxide fibers and polypropylene oxide fibers; These fibers may be used by mixing and blending a plurality of types.

50-300 g / m < ² > is preferable and, as for the mass of the sheet | seat base material used for a hazardous | toxic chemical substance decomposition layer, 80-250 g / m < ² > is more preferable. When the mass of the sheet base material is less than 50 g / m ² , it is difficult to withstand from an external force such as friction. Moreover, when the mass of a sheet base material exceeds 300 g / m < ² >, the thickness of the protective material obtained will also increase, and when it is set as protective clothing, mass will become large.

Air permeability of the sheet substrate used in hazardous chemicals decomposition layer is preferably 5~500cm ³ / cm ² · s, and more preferably 10~350cm ³ / cm ² · s. When the air permeability of the sheet base material is less than 5 cm ³ / cm ² · s, it is expected that the air permeability of the protective material is deteriorated. On the other hand, if the air permeability of the sheet base material exceeds 500 cm ³ / cm ² · s, the fiber porosity increases and the material strength decreases.

  The thickness of the sheet base material used for the harmful chemical substance decomposition layer is preferably 0.1 to 0.5 mm, and more preferably 0.15 to 0.45 mm. If the thickness of the sheet base material is less than 0.1 mm, the mechanical strength may be inferior. In addition, if the thickness of the sheet base material exceeds 0.5 mm, the protective clothing may become stiff when used as protective clothing, which may hinder the work of the wearer of the protective clothing.

  Catalysts that show the decomposability of harmful compounds used in the hazardous chemical decomposition layer include metals, metal oxides, gold, silver, copper, platinum, palladium, iridium, tin, antimony, bismuth, zinc, silver oxide, Examples include magnesium oxide, calcium oxide, nickel oxide, manganese oxide, copper oxide, selenium oxide, zinc oxide, iron oxide, aluminum oxide, tungsten oxide, and titanium oxide. Among these, metal oxides can be suitably used because they are relatively inexpensive and stable.

The hazardous chemical substance decomposing layer of the present invention is one that provides a sheet base material with a metal oxide to give decomposability of harmful chemical substances. Among metal oxides, metal oxides such as manganese oxide, iron oxide, aluminum oxide, and titanium oxide are preferable.
As a method for containing the metal oxide in the sheet substrate, a known method such as a padding method, an impregnation method, a spray method, a coating method, and kneading during spinning can be employed.

BET specific surface area of the metal oxide is a 0.1~1000m ² / g, preferably from 0.2~500m ² / g, more preferably 0.3~300m ² / g, 0.4~250m ² / G is more preferable, and 0.5 to ²⁰⁰ m ² / g is particularly preferable. When the BET specific surface area of the metal oxide is less than 0.1 m ² / g, sufficient decomposability of harmful chemical substances cannot be obtained, and when it exceeds 1000 m ² / g, gaseous harmful chemical substances once adsorbed on the metal oxide surface There is a risk of causing detachment or the like.

  The content of the metal oxide is preferably 0.01 to 20% and more preferably 0.1 to 15% with respect to the sheet base material. If the content of the metal oxide is less than 0.01%, sufficient decomposability of harmful chemical substances cannot be obtained, and if it exceeds 20%, the toxic chemical substance decomposition layer may be reduced in flexibility.

  It is possible to provide protection against gas by laminating a gas adsorption layer on one or both sides of the upper or lower layer of the hazardous chemical substance decomposition layer of the present invention.

  Examples of the gas adsorbing layer include carbon adsorbing materials such as activated carbon and carbon black, or gas adsorbing layers containing inorganic adsorbing materials such as silica gel, zeolite adsorbing material, silicon carbide, and activated alumina. It can be appropriately selected according to the substance to be adsorbed. Among them, it is preferable to include activated carbon that can deal with a wide range of gases, particularly fibrous activated carbon that has a large adsorption rate and adsorption capacity and can effectively suppress gas permeation when used in a small amount.

  The adsorption performance of the activated carbon contained in the gas adsorption layer is preferably 20 wt% or more, more preferably 25 wt% or more in terms of toluene adsorption performance. If the toluene adsorption performance is less than 20 wt%, the amount of activated carbon required to exhibit sufficient gas adsorption ability increases, and the protective clothing becomes heavy. Although an upper limit is not specifically limited, For example, 90 wt% or less is preferable.

  The average pore diameter of the activated carbon contained in the gas adsorption layer is preferably 5 to 200 nm. When the average pore diameter is less than 5 nm, the adsorption amount of the gaseous chemical substance is low, and sufficient gas permeation suppression ability cannot be obtained. When the average pore diameter exceeds 200 nm, the adsorbed gaseous harmful chemical substance is easily desorbed.

  The pore volume of the activated carbon contained in the gas adsorption layer is preferably 0.25 cc / g or more, and more preferably 0.3 cc / g or more. When the pore volume is less than 0.25 cc / g, the amount of activated carbon required to exert a sufficient gas adsorbing capacity increases, so that the protective clothing becomes heavy. Although an upper limit is not specifically limited, For example, 1.0 cc / g or less is preferable.

The BET specific surface area of the activated carbon contained in the gas adsorption layer is preferably ^{700~3000m 2 / g, 1000~2500m 2 /} g is more preferable. When the BET specific surface area is less than 700 m ² / g, the amount of activated carbon necessary for exerting sufficient gas adsorption capacity increases, and the protective clothing becomes heavy. On the other hand, if the BET specific surface area exceeds 3000 m ² / g, once adsorbed gaseous harmful chemical substances may be desorbed or become brittle.

Preferably 35~250g / m ² as a weight per unit area (absolute dry weight) of the gas adsorption layer, 70~200g / m ² is more preferable. If the basis weight is less than 35 g / m ² , the capacity that can be adsorbed is reduced, and the use time is limited. On the other hand, when it exceeds 250 g / m ² , it becomes heavy as protective clothing and causes heat stress.

  The gas adsorbing layer is preferably processed into a sheet in order to facilitate lamination. As a method for forming fibrous activated carbon into a sheet, a method in which a gas adsorbing substance (activated carbon) is fixed to a sheet base material via a binder; a gas adsorbing substance (activated carbon) is dispersed in a dispersion containing pulp and a binder to form a slurry. A sheet is prepared by making a sheet using a wet paper machine; fabric is produced using carbon-containing fibers, the fabric is subjected to flame resistance treatment as necessary, and then the sheets are carbonized and activated. A method for producing a fibrous activated carbon is preferred.

  A method of producing a sheet-like fibrous activated carbon by producing a fabric using carbon-containing fibers, flame-treating the fabric as necessary, and then carbonizing and activating the fibers includes, for example, raw fiber After forming various fabrics such as woven fabrics, knitted fabrics, and nonwoven fabrics through weaving, knitting, carding and wrapping processes, etc., the fabric is made to contain a flameproofing agent as necessary, and then heated to 450 ° C. or less. It can be produced by applying a flameproofing treatment at a temperature and then carbonizing and activating the fiber at a temperature of 500 ° C. or higher and 1000 ° C. or lower. Examples of raw material fibers used include natural cellulose fibers such as cotton and hemp; regenerated cellulose fibers such as rayon fibers and polynosic fibers; polyvinyl alcohol fibers, acrylic fibers, aromatic polyamide fibers, lignin fibers, and phenolic fibers. Examples thereof include synthetic fibers such as fibers and petroleum pitch fibers. Among these, the use of regenerated cellulose fiber, acrylic fiber, and phenol fiber is preferable because of the excellent physical properties (strength, etc.) and adsorption performance of fibrous activated carbon. The fiber length of the raw fiber is not limited, and either short fiber or long fiber can be used.

  Although the form of the sheet-like fibrous activated carbon is not particularly limited, examples thereof include a woven form, a knitted form, a non-woven form, a felt form, a paper form, and a film form. In particular, when making protective clothing, it is easy to handle lamination, water and oil repellency, and when wearing protective clothing, the workability of workers, fit to the body, and flexibility of protective clothing Since the property is good, the form of the sheet-like fibrous activated carbon is preferably woven, knitted or non-woven.

  The thickness of the fibrous activated carbon formed into a sheet is preferably from 0.1 to 3.0 mm, more preferably from 0.5 to 2.0 mm, and even more preferably from 0.7 to 1.5 mm. If the thickness of the sheet-like fibrous activated carbon is less than 0.1 mm, the adsorption amount of gaseous harmful chemical substances may be reduced. On the other hand, if the thickness of the fibrous activated carbon formed into a sheet exceeds 3.0 mm, it is not possible to satisfactorily finish the workability of the worker when wearing protective clothing, the fit to the body, and the like.

Air permeability of the sheeted fibrous activated carbon is preferably 50~550cm ³ / cm ² · s, more preferably from 100~500cm ³ / cm ² · s, more preferably 150~480cm ³ / cm ² · s. If the air permeability of the sheet-like fibrous activated carbon is less than 50 cm ³ / cm ² · s, the air permeability of the obtained protective material is lowered, and it becomes difficult to control the air permeability of the protective material within a predetermined range. . In addition, when the air permeability of the protective material exceeds 550 cm ³ / cm ² · s, there is a possibility that the amount of adsorption of gaseous harmful chemical substances may be reduced.

  In the present invention, it is also possible to laminate an inner cloth on the innermost side of the protective material. The inner cloth is a layer provided to reduce discomfort such as stickiness of the wearer when the protective clothing is used. Moreover, since the intensity | strength of protective clothing increases by laminating | stacking an inner cloth, since it becomes strong with respect to an external force, it is preferable.

  The material which comprises an inner fabric is not specifically limited, Each material described in the column of the sheet base material used for a decomposition layer can be used. Especially, since it is excellent in heat resistance, use of a polyamide fiber, a polyethylene terephthalate fiber, and a polybutylene terephthalate fiber is preferable.

  As the inner fabric, a woven fabric, a knitted fabric, a non-woven fabric, a porous film, or the like can be suitably used, and a woven fabric or a knitted fabric is preferably used from the viewpoint of air permeability and flexibility.

  When a knitted fabric is used as the inner fabric, the knitting structure of the knitted fabric is not particularly limited. For example, weft knitting (flat knitting, rib knitting, double-sided knitting, pearl knitting), warp knitting (tricot knitting, raschel), etc. Can be mentioned. In the present invention, it is particularly preferable to use warp knitting, particularly tricot knitting, because of the good touch.

  The thickness of the inner fabric is preferably 0.05 to 0.5 mm, and more preferably 0.1 to 0.4 mm. If the thickness of the inner fabric is less than 0.05 mm, the thickness of the inner fabric is not sufficient, which may cause a problem that the inner fabric is easily broken. Moreover, if the thickness of the inner cloth exceeds 0.5 mm, the protective clothing may become stiff and the wearer may feel uncomfortable.

Air permeability of the inner fabric, preferably 10~600cm ³ / cm ² · s, more preferably from 30~500cm ³ / cm ² · s, more preferably 50~400cm ³ / cm ² · s. When the air permeability of the inner cloth is within the above range, the air permeability of the protective clothing material is in a desired range.

  The order in which the layers are laminated is preferably the order of a harmful chemical substance decomposition layer, a gas adsorption layer, and an inner cloth as viewed from the outside of the protective clothing. By sandwiching the gas adsorption layer between the harmful chemical substance decomposition layer and the inner cloth, the gas adsorption layer can be effectively protected.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, but may be appropriately modified within a range that can meet the purpose described above and below. Of course, it is possible to implement them, and they are all included in the technical scope of the present invention.

(1) Mass per unit area: According to JIS L 1096.8.3.

(2) Thickness: According to JIS L 1096.8.4.

(3) Breathability: According to JIS L 1096.88.26.1 A method (fragile type method).

(4) Degradability to hazardous chemicals: Fig. 2 shows the container used for the test. Place a 5 cm square test piece in a 200 cc flask, drop 1 μL of malathion (manufactured by Wako Pure Chemical Industries, Ltd.) on the test piece, and extract into 10 mL of hexane solvent 2 hours after the drop. Measure the concentration reduction rate. Those having a reduction rate of malathion of 50% or more were determined to be effective.

(5) Gas permeability test: FIG. 3 shows a container diagram used in the test. The test product is sandwiched between two glass cells having an internal volume of 350 cc, and the periphery is sealed with paraffin. From the upper cell of the test vessel, 10 μL of 3 methoxybutyl acetate is dropped onto the test product. This is put in a constant temperature box set to 25 ± 2 ° C., the gas concentration on the lower cell side is sampled at regular intervals, and the gas concentration permeated through the test piece is measured by gas chromatography.

(6) Specific surface area: An adsorption isotherm of nitrogen is obtained and calculated by the BET method based on this.

<Creating a hazardous chemical substance decomposition layer>
The hazardous chemical substance decomposition layer was produced by the following method.
Nylon 66 filament yarn and cotton were blended at a blending ratio of 5/95, and a 40th blended yarn was produced by an electric opening method. Subsequently, weaving was performed by an ordinary method using an air jet loom, and a 2/1 twill woven fabric having a warp density of 140 yarns / 2.54 cm and a weft density of 108 yarns / 2.54 cm was used as a sheet base material. This was subjected to hair sinter, desizing, refining, bleaching, mercerization, dyeing, and soaping treatments in the usual manner.
Further, manganese dioxide (manufactured by Chuo Denki Kogyo Co., Ltd.) having a BET specific surface area of 171 m ² / g was used as the metal oxide. This manganese dioxide as a 20 wt% aqueous solution was immersed in a sheet base material, then squeezed so that the wet pickup was 50%, and dried at 120 ° C. for 1 hour.
The obtained hazardous chemical substance decomposition layer had a thickness of 0.23 mm, a basis weight of 175 g / m ² , and a gas permeability of 18 cm ³ / cm ² · s with a water level gauge of 1.27 cm.

<Gas adsorption layer>
Fibrous activated carbon in the form of a knitted fabric was produced as a gas adsorption layer by the following method. A circular knitted fabric having a single yarn fineness of 2.2 dtex and a No. 20 novolak phenol resin fiber spun yarn having a basis weight of 220 g / m ² is heated in an inert atmosphere at 410 ° C. for 30 minutes, and then contains 12% by volume of water vapor. It was activated in an atmosphere at a temperature of 890 ° C. for 2 hours. The obtained gas adsorption layer has an absolute dry mass of 103 g / m ² , a BET specific surface area of 1421 m ² / g, a thickness of 0.98 mm, and a gas permeability of 355 cm ³ / cm ² with a pressure difference of 1.27 cm in water level. S, toluene adsorption performance (toluene gas equilibrium adsorption amount) was 52 g / m ² .

<Example 1>
The harmful chemical substance decomposition layer and gas adsorption layer obtained above were used as a protective material. Table 1 shows the results of the specific surface area of the metal oxide, the decomposability of harmful chemical substances, and the gas permeability of the protective material obtained.

<Example 2>
A protective material was produced in the same manner as in Example 1 except that the metal oxide used in the hazardous chemical substance decomposition layer was manganese dioxide (manufactured by Nippon Heavy Chemical Industry) having a BET specific surface area of 109 m ² / g. Table 1 shows the results of the specific surface area of the metal oxide, the decomposability of harmful chemical substances, and the gas permeability of the protective material obtained.

<Example 3>
Protect by the same method as in Example 1 except that the metal oxide used for the hazardous chemical substance decomposition layer is ferric trioxide (manufactured by Wako Pure Chemical Industries, Ltd.) with a BET specific surface area of 0.5 m ² / g. The material was made. Table 1 shows the results of the specific surface area of the metal oxide, the decomposability of harmful chemical substances, and the gas permeability of the protective material obtained.

<Example 4>
The protective material was prepared in the same manner as in Example 1 except that the metal oxide used in the hazardous chemical substance decomposition layer was ferric trioxide (manufactured by Wako Pure Chemical Industries, Ltd.) with a BET specific surface area of 100 m ² / g. Produced. Table 1 shows the results of the specific surface area of the metal oxide, the decomposability of harmful chemical substances, and the gas permeability of the protective material obtained.

<Comparative Example 1>
The metal oxide used in the hazardous chemical substance decomposition layer has a BET specific surface area of 0 m ² / g (the lower limit detection limit of the measuring instrument is 0.1 m ² / g and is lower than the detection limit). A protective material was prepared in the same manner as in Example 1 except that the product was manufactured by Kojun Pharmaceutical Co., Ltd. Table 1 shows the results of the specific surface area of the metal oxide, the decomposability of harmful chemical substances, and the gas permeability of the protective material obtained.

<Comparative example 2>
Only the hazardous chemical substance decomposition layer of Example 1 was used as a protective material. Table 1 shows the results of the specific surface area of the metal oxide, the decomposability of harmful chemical substances, and the gas permeability of the protective material obtained.

<Comparative Example 3>
Only the gas adsorption layer of Example 1 was used as a protective material. Table 1 shows the decomposability of harmful chemical substances and gas permeability of the obtained protective material.

<Comparative example 4>
A protective material was produced in the same manner as in Example 1 except that the metal oxide used for the harmful chemical substance decomposition layer was titanium oxide (manufactured by Nippon Aerosil Co., Ltd.) having a BET specific surface area of 53 m ² / g. Table 1 shows the results of the specific surface area of the metal oxide, the decomposability of harmful chemical substances, and the gas permeability of the protective material obtained.

  While the protective materials of Examples 1 to 4 are excellent in decomposability of harmful chemical substances and gas permeation suppression properties, the protective materials of Comparative Examples 1 to 4 are inferior to the examples in any of the evaluation items. Met.

  The protective material according to the present invention exhibits excellent protective performance against gaseous and liquid hazardous chemicals, has decomposability of hazardous chemicals, has a low risk of secondary contamination, and is Since it can provide protective materials and protective clothing with high breathability to suppress thermal stress, it can be used in shelters, clothing, gloves, socks, shoes, helmets, covers, etc. and contribute to the industry It ’s big.

1: Hazardous chemical substance decomposition layer 2: Gas adsorption layer 3: Protective material 4: Erlenmeyer flask (200 cc)
5: Malathion (1 μL)
6: Test piece 7: Upper cell (150cc)
8: Sampling port 9: Test solution 10: Test piece 11: Paraffin sealing 12: Lower cell (150 cc)

Claims (3)

A protective material having at least one harmful chemical substance decomposition layer containing manganese oxide or iron oxide having a BET specific surface area of 0.1 to 1000 m ² / g and a gas adsorption layer containing activated carbon.   The protective material according to claim 1, wherein the activated carbon contained in the gas adsorption layer is fibrous activated carbon.   A protective garment using the protective material according to claim 1.