Protective clothing

Abstract

To provide a protective material and a protective clothing which have permeation inhibiting performance against gaseous and liquid organic chemicals and are lightweight and flexible and have excellent peeling strength.SOLUTION: There is provided a protective material 1A having an inner part and an outer part, which comprises a first rubber layer 11 located on the inner part, a second rubber layer 12 located on the outer part and a reinforcing fabric 13 laminated between the first rubber layer 11 and the second rubber layer 12, wherein at least one of the first rubber layer 11 and the second rubber layer 12 uses an acrylonitrile-butadiene rubber, the acrylonitrile-butadiene rubber has an acrylonitrile content of 36 wt.% or more and an area between the first rubber layer 11 and the reinforcing fabric 13 and an area between the second rubber layer 12 and the reinforcing fabric 13 are vulcanization-adhered via an adhesive rubber layer.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present disclosure relates to protective materials and clothing for protecting the human body from toxic gases, liquids, and the like. [Background technology]

[0002] Technology relating to protective materials that protect the human body from toxic gases, liquids, etc. is disclosed, for example, in Japanese Patent No. 5784812 (Patent Document 1). For such protective materials, good gas permeability resistance and liquid protection resistance are required for the material surface, and technology relating to surface treatment of materials is disclosed, for example, in Japanese Patent Laid-Open No. 2003-2903 (Patent Document 2) and Japanese Patent Laid-Open No. 2010-24279 (Patent Document 3). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent No. 5784812 [Patent Document 2] JP 2003-2903 A [Patent Document 3] JP 2010-24279 A Summary of the Invention [Problem to be solved by the invention]

[0004] Protective materials are required to have further improved gas permeability resistance and liquid resistance so as to more reliably protect the human body.

[0005] The present invention has been made against the background of problems in the prior art, and aims to provide a protective material and protective clothing that have the ability to inhibit the penetration of gaseous and liquid organic chemicals, and that is lightweight and has excellent flexibility and peel strength. [Means for solving the problem]

[0006] [1] The protective material disclosed herein is a protective material having an inner side and an outer side, comprising a first rubber layer located on the inner side, a second rubber layer located on the outer side, and a reinforcing cloth laminated between the first rubber layer and the second rubber layer, wherein at least one of the first rubber layer and the second rubber layer uses acrylonitrile butadiene rubber, and the acrylonitrile butadiene rubber has an acrylonitrile content of 36 wt% or more, and the first rubber layer and the reinforcing cloth, and the second rubber layer and the reinforcing cloth are vulcanization-bonded with adhesive rubber layers interposed therebetween.

[0007] [2]: The protective material according to [1], wherein the first rubber layer is made of acrylonitrile butadiene rubber, and the second rubber layer is made of butyl rubber.

[0008] [3]: The protective material according to [1] or [2], wherein the first rubber layer is butyl rubber, and the second rubber layer is acrylonitrile butadiene rubber.

[0009] [4]: The protective material according to any one of [1] to [3], wherein a resin layer having roughness-imparting particles contained in a resin and a fluorine coating made of a fluorine-based water- and oil-repellent agent are laminated in this order on the outside of the second rubber layer.

[0010] [5]: The protective material according to [4], wherein the unevenness-imparting particles have a tetrapod-like, needle-like, polygonal, or spherical shape.

[0011] [6]: The protective material according to [4] or [5], wherein the unevenness-imparting particles are tetrapod-type zinc oxide, and the reinforcing fabric is a woven fabric, knitted fabric, or nonwoven fabric.

[0012] [7]: A protective material according to any one of [1] to [6], wherein the reinforcing fabric is a woven fabric, a knitted fabric, or a nonwoven fabric.

[0013] [8]: The protective clothing disclosed herein uses the protective material described in any one of [1] to [7]. Effect of the Invention

[0014] According to the present disclosure, it is possible to provide protective materials and protective clothing that have the ability to inhibit the penetration of gaseous and liquid organic chemicals, and that are lightweight and have excellent flexibility and peel strength. [Brief description of the drawings]

[0015] [Figure 1] 1 is a cross-sectional structural view of a protective material according to a first embodiment. [Diagram 2] FIG. 6 is a cross-sectional structural view of a protective material according to a second embodiment. [Diagram 3] FIG. 11 is a cross-sectional structural view of a protective material according to a third embodiment. [Figure 4] FIG. 2 is a schematic diagram showing a method for fixing a fluorine-based water- and oil-repellent processing agent. [Diagram 5] FIG. 2 is an enlarged view showing the shape of tetrapod-type zinc oxide. [Figure 6] 1 is an electron microscope photograph of a layered structure of tetrapod-type zinc oxide. [Figure 7] FIG. 13 is a diagram showing evaluation results of protective materials according to each embodiment. [Figure 8] FIG. 2 is a schematic diagram showing a test vessel used in a gas permeability test. [Figure 9] FIG. 1 is a schematic diagram of a liquid permeability test method. [Figure 10] FIG. 11 is a front view showing the configuration of protective clothing according to a fourth embodiment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] The protective material and protective clothing of each embodiment based on the present disclosure will be described below with reference to the drawings. In the embodiments described below, when numbers, amounts, etc. are mentioned, the scope of the present invention is not necessarily limited to those numbers, amounts, etc., unless otherwise specified. The same reference numbers are given to the same parts and corresponding parts, and duplicate descriptions may not be repeated. It is originally intended that the configurations in the embodiments will be used in appropriate combination. For ease of understanding, the film thicknesses and layer thicknesses shown in the drawings are described at different ratios from the actual ratios.

[0017] In the specification, "outer side" means the side that is exposed to toxic gases, liquids, etc. when the protective material is in use, and "inner side" means the side that is not exposed to toxic gases, liquids, etc. when the protective material is in use. Therefore, when this protective material is used in protective clothing, the side that comes into contact with the wearer is the "inner side."

[0018] [Embodiment 1: Protective Material 1A] A protective material 1A of the present embodiment will be described with reference to Fig. 1. Fig. 1 is a cross-sectional structural view of the protective material 1A.

[0019] The protective material 1A of this embodiment has an inside and an outside, and is equipped with a first rubber layer 11 located on the inside, a second rubber layer 12 located on the outside, and a reinforcing cloth 13 laminated between the first rubber layer 11 and the second rubber layer 12.

[0020] The first rubber layer 11 is made of acrylonitrile butadiene rubber (NBR), and the second rubber layer 12 is made of butyl rubber. The reinforcing fabric 13 is made of nylon woven fabric with a thread thickness of 70 decitex. The thread thickness is not limited to this thickness. The material is also not limited to nylon. For example, polyester, cotton, etc. can also be used. In addition to woven fabric, knit, thin fabric, nonwoven fabric, etc. can also be used.

[0021] The first rubber layer 11 has a thickness of about 0.08 mm to 0.2 mm, the second rubber layer 12 has a thickness of about 0.08 mm to 0.2 mm, and the thickness is about 0.1 mm when a woven base fabric is used for the reinforcing fabric 13. When a knit fabric is used for the reinforcing fabric 13, the thickness of the reinforcing fabric 13 is about 0.2 mm to 0.3 mm.

[0022] Acrylonitrile butadiene rubber (NBR) is a synthetic rubber, a copolymer of acrylonitrile and 1,3-butadiene. Although not strictly defined according to the content of acrylonitrile, it is generally classified as 24 wt% or less (low nitrile), 25 to 30 wt% (medium nitrile), 31 to 35 wt% (medium-high nitrile), 36 to 42 wt% (high nitrile), and 43 wt% or more (very high nitrile). The acrylonitrile butadiene rubber (NBR) of this embodiment is preferably high nitrile or more, and more preferably very high nitrile. In the protective material 1A of this embodiment, acrylonitrile butadiene rubber (NBR) classified as very high nitrile is used.

[0023] (Protective Material 1A Manufacturing Method) The manufacturing method of the protective material 1A is as follows: first, adhesive rubber layers (not shown) are interposed between the first rubber layer 11 and the reinforcing cloth 13, and between the second rubber layer 12 and the reinforcing cloth 13, and then the layers are bonded together by can vulcanization to obtain a laminated structure of the first rubber layer 11, the reinforcing cloth 13, and the second rubber layer 12, which are integrated with each other.

[0024] As a result of the above, a protective material 1A having a three-layer structure of the first rubber layer 11, the reinforcing fabric 13, and the second rubber layer 12 is obtained.

[0025] [Embodiment 2: Protective Material 1B] A protective material 1B of this embodiment will be described with reference to Fig. 2. Fig. 2 is a cross-sectional structural view of the protective material 1.

[0026] In the protective material 1B of this embodiment, the materials used for the first rubber layer 11 and the second rubber layer 12 are the same as those in the protective material 1A of embodiment 1, but the arrangement is reversed.

[0027] Butyl rubber is used for the first rubber layer 11, and acrylonitrile butadiene rubber (NBR) is used for the second rubber layer 12. Nylon fabric with a thread thickness of 70 decitex is used for the reinforcing cloth 13. The thread thickness is not limited to this thickness. The material is also not limited to nylon. For example, polyester, cotton, etc. can also be used. In addition to woven fabric, knit, thin fabric, nonwoven fabric, etc. can also be used.

[0028] The first rubber layer 11 has a thickness of about 0.08 mm to 0.2 mm, the second rubber layer 12 has a thickness of about 0.08 mm to 0.2 mm, and the thickness is about 0.1 mm when a woven base fabric is used for the reinforcing fabric 13. When a knit fabric is used for the reinforcing fabric 13, the thickness of the reinforcing fabric 13 is about 0.2 mm to 0.3 mm.

[0029] (Method of manufacturing protective material 1B) The manufacturing method of protective material 1B is similar to that of protective material 1A of embodiment 1, in that adhesive rubber layers (not shown) are interposed between first rubber layer 11 and reinforcing cloth 13 and between second rubber layer 12 and reinforcing cloth 13, and then the layers are bonded together by can vulcanization to obtain a laminated structure of first rubber layer 11, reinforcing cloth 13, and second rubber layer 12 that are integrated with each other.

[0030] As a result of the above, a protective material 1B having a three-layer structure of the first rubber layer 11, the reinforcing fabric 13, and the second rubber layer 12 is obtained.

[0031] [Embodiment 3: Protective material 1C] A protective material 1C of this embodiment will be described with reference to Fig. 3. Fig. 3 is a cross-sectional structural view of the protective material 1C.

[0032] The basic configuration of the protective material 1C of this embodiment, like that of embodiment 1, includes a first rubber layer 11 located on the inside, a second rubber layer 12 located on the outside, and a reinforcing fabric 13 laminated between the first rubber layer 11 and the second rubber layer 12. Furthermore, a resin layer 14 and a fluorine coating 15 are laminated in this order on the outside of the second rubber layer 12. The resin layer 14 contains unevenness-imparting particles in the resin, and the fluorine coating 15 is a coating made of a fluorine-based water- and oil-repellent agent.

[0033] The first rubber layer 11 is made of acrylonitrile butadiene rubber (NBR), and the second rubber layer 12 is made of butyl rubber. The reinforcing fabric 13 is made of nylon woven fabric with a thread thickness of 70 decitex. The thread thickness is not limited to this thickness. The material is also not limited to nylon. For example, polyester, cotton, etc. can also be used. In addition to woven fabric, knit, thin fabric, nonwoven fabric, etc. can also be used.

[0034] The first rubber layer 11 has a thickness of about 0.08 mm to 0.2 mm, the second rubber layer 12 has a thickness of about 0.08 mm to 0.2 mm, and the thickness is about 0.1 mm when a woven base fabric is used for the reinforcing fabric 13. When a knit fabric is used for the reinforcing fabric 13, the thickness of the reinforcing fabric 13 is about 0.2 mm to 0.3 mm.

[0035] A fluorine-based water- and oil-repellent agent is used for the fluorine coating 15. As a fluorine-based water- and oil-repellent agent, for example, the water- and oil-repellent agent disclosed in Japanese Patent No. 5784812 may be used. As a specific example of the fluorine-based water- and oil-repellent agent, a fluorine-containing polymer containing a repeating unit derived from α-chloroacrylate (A) having a fluoroalkyl group represented by the following formula (1), and a repeating unit derived from a non-fluorine monomer (B) having no fluoroalkyl group and a hydrocarbon group having 6 or more carbon atoms may be used.

[0036] CH2=C(-Cl)-C(=O)-XY-Rf... formula (1) [wherein X is -O- or -NH-, Y is a direct bond or a divalent organic group, and Rf is a fluoroalkyl group having 1 to 20 carbon atoms.] (Method of manufacturing protective material 1C) In the method of manufacturing the protective material 1C, the steps up to obtaining the three-layer structure of the first rubber layer 11, the reinforcing fabric 13, and the second rubber layer 12 are the same as those of the protective material 1A of the first embodiment.

[0037] A method for fixing the fluorine-based water- and oil-repellent agent will be described with reference to Fig. 4. The fluorine-based water- and oil-repellent agent with an apparent concentration of 7% was applied to the surface of the second rubber layer 12 at a rate of 20 cc / m 2 Then, using a spatula L, the fluorine-based water- and oil-repellent processing agent is spread evenly on the surface of the resin layer 14. Then, a heat treatment (for example, 170 degrees, 5 minutes) is performed, and the fluorine coating 15 is completed.

[0038] The resin layer 14 is preferably of the same type as the second rubber layer 12. The unevenness-imparting particles are included. In this specification, the unevenness-imparting particles refer to materials that can impart an uneven shape to the surface of the rubber layer. Examples of the shapes of the unevenness-imparting particles include tetrapod-shaped, needle-shaped, spherical, and polygonal shapes. Examples of raw materials include inorganic oxides such as alumina, potassium titanate, wollastonite, zinc oxide, and aluminum borate; metals such as chromium, copper, iron, and nickel; inorganic oxides such as silicon carbide, graphite, and silicon nitride, and inorganic substances other than metals. Specific examples include tetrapod-type zinc oxide and spherical silica.

[0039] As shown in FIG. 5, the crystals R of tetrapod-type zinc oxide have a "Tetrapod (registered trademark)" shape for revetments. Specifically, the crystals R are needle-like crystals that grow in the C-axis direction of hexagonal ZnO from four alternating faces of each part of a regular octagonal shape as a result of a reaction between zinc metal vapor and oxygen. The length of one needle-like crystal is 1 to 50 μm, preferably 5 to 30 μm, and more preferably 8 to 20 μm. As shown in FIG. 6, in the layered structure of tetrapod-type zinc oxide, a plurality of crystals R are layered on top of each other, so that the resin layer 14 becomes a porous layered structure material with unevenness on the surface.

[0040] The resin layer 14 has a structure in which tetrapod-type zinc oxide is dispersed in the same type of rubber and resin as the second rubber layer 12. The tetrapod-type zinc oxide is mixed in an amount of 30% to 70% (preferably 40% to 60%) of the total solid content (rubber, resin + tetrapod-type zinc oxide). This makes the resin layer 14 brittle, but by heating and vulcanizing, a cross-linked structure is formed between the second rubber layer 12 and the resin layer 14 of the same type, resulting in a strong bond and improving the film strength of the resin layer 14. For example, a tetrapod-shaped single crystal powder made of zinc oxide ("Panatetra WZ-0501" manufactured by Amtec Co., Ltd., average fiber length (needle part): about 10 μm) can be used.

[0041] As a result, the fluorine coating 15 laminated on the surface of the resin layer 14 is formed using the fixing method shown in Fig. 4, and the resin layer 14 is impregnated with a fluorine-based water- and oil-repellent agent, which improves the bonding of the fluorine coating 15 to the resin layer 14. Furthermore, on the outside of the fluorine coating 15, the irregularities that appear on the surface of the resin layer 14 are reflected on the surface of the fluorine coating 15, and fine irregularities also appear on the surface of the fluorine coating 15. These irregularities bring about good results in the evaluation of the gas penetration resistance and liquid resistance protective properties of the protective material 1C, which will be described later.

[0042] [Evaluation results of protective materials 1A to 1C] Next, the evaluation results of protective materials 1A to 1C will be described with reference to Fig. 7 to Fig. 9. Fig. 7 is a diagram showing the evaluation results of protective materials 1A to 1C, Fig. 8 is a schematic diagram showing a test vessel used in a gas permeability test, and Fig. 9 is a schematic diagram of a liquid permeability test method.

[0043] As the evaluation objects, gas permeability resistance (5-hr maximum permeation concentration / ppm) was evaluated using a gas permeability test, and liquid protection resistance was evaluated using a liquid permeability test method. Referring to FIG. 8, in the gas permeability test, a test sample 108 of the embodiment is sandwiched between an upper cell (150 cc) 105 and a lower cell (150 cc) 100. A test liquid 107 was dropped onto the upper surface of the test sample 108. A dummy agent was used as the test liquid 107. The upper cell (150 cc) 105 and the lower cell (150 cc) 100 sandwiching the test sample 108 were sealed with a paraffin seal 109. Thereafter, the gas permeability was evaluated using a sampling port 106.

[0044] 9, in the liquid permeability test method, a filter paper 140 is placed on a glass plate 150, and a test sample 130 of the embodiment is placed on top of the filter paper 140. 20 μL of a liquid chemical substance 120 (dipropyl phthalate with red dye dissolved therein) is then dropped on top of the filter paper 140. Then, a sample with a base area of ​​1 cm2 is placed on top of the filter paper 140. 2 The weight is applied with a specified load of 110 (1kgf / cm 2 ) was placed on the filter paper, and the presence or absence of penetration of the liquid was determined by the color of the filter paper after 6 hours.

[0045] As the protective material in Comparative Example 1, inner and outer rubber layers using butyl rubber were arranged, and a reinforcing cloth was laminated between the inner and outer rubber layers. As the protective material in Comparative Example 2, the same composition as the protective material 1A was used, and 34 wt% (medium-high nitrile) was used as acrylonitrile butadiene rubber (NBR).

[0046] The reinforcing cloth 13 is made of nylon woven fabric with a thread thickness of 70 decitex. The thread thickness is not limited to this thickness. The material is also not limited to nylon. For example, polyester, cotton, etc. can be used. In addition to woven fabric, knit, thin woven fabric, nonwoven fabric, etc. can also be used. The thickness of the first rubber layer 11 is about 0.08 mm to 0.1 mm, the thickness of the second rubber layer 12 is about 0.08 mm to 0.1 mm, and the thickness when a woven fabric base fabric is used for the reinforcing cloth 13 is about 0.1 mm. When a knit fabric is used for the reinforcing cloth 13, the thickness of the reinforcing cloth 13 is about 0.2 mm to 0.3 mm.

[0047] In the protective materials of Comparative Examples 1 and 2, the gas permeability resistance was 240 ppm, which was unacceptable.

[0048] Although the protective material 1A of the first embodiment was thinner than the protective material of the comparative example, the gas permeability resistance was 50 ppm, which was an excellent passing result.

[0049] Thus, it is found that protective material 1A of embodiment 1 is far superior in gas permeability resistance to the evaluations of the comparative examples. As a result, even if harmful gases, liquids, etc. come into contact with the outside of protective material 1A, it is possible to suppress the penetration of harmful gases, liquids, etc. into the inside of protective material 1A.

[0050] Although the protective material 1B of embodiment 2 was thinner than the protective materials of the comparative examples, the gas permeability resistance was 20 ppm, which was an excellent passing result.

[0051] Thus, it is found that protective material 1B of embodiment 2 is far superior in gas permeability resistance to the evaluations of the comparative examples. As a result, even if harmful gases, liquids, etc. contact the outside of protective material 1B, it is possible to suppress the penetration of harmful gases, liquids, etc. into the inside of protective material 1B.

[0052] Although the protective material 1C of embodiment 3 was thinner than the protective materials of the comparative examples, the gas permeability resistance was 40 ppm, which was an excellent passing result.

[0053] Thus, it is found that protective material 1C of embodiment 3 is far superior in gas permeability resistance to the evaluations of the comparative examples. As a result, even if harmful gases, liquids, etc. come into contact with the outside of protective material 1C, it is possible to suppress the penetration of harmful gases, liquids, etc. into the inside of protective material 1C.

[0054] On the other hand, in Comparative Example 1, acrylonitrile butadiene rubber (NBR) was not used, and layers using butyl rubber were arranged on the front and back sides of the reinforcing fabric. As a result, the gas permeability resistance was evaluated as low at 240 ppm. In Comparative Example 2, 34 wt% (medium-high nitrile) acrylonitrile butadiene rubber (NBR) was also used. As a result, the gas permeability resistance was evaluated as low at 240 ppm.

[0055] [Embodiment 4: Protective clothing 100] The configuration of protective clothing 100 in this embodiment will be described with reference to Fig. 10. Fig. 10 is a front view showing the configuration of protective clothing 100. This protective clothing 100 is manufactured using protective material 1A, protective material 1B, or protective material 1C described in each of the above embodiments.

[0056] As an example, when using protective material 1C, the specific manufacturing method of the protective material for protective clothing 100 is as follows: first, rubber sheets are laminated on both sides of the fabric (step 1). Next, a concave-convex coating containing concave-convex shape imparting particles is applied to the outer rubber surface and dried (step 2). Next, heat vulcanization is performed (step 3). Next, a water- and oil-repellent treatment (adhering method shown in FIG. 2 or immersion) is performed (step 4).

[0057] Here, the outline of step 2 is as follows. Coating methods include kiss coating (gravure coating), knife coating, etc. The coating composition is a ratio of rubber:ZnO:solvent (toluene, ethyl acetate, etc.) mixed at 10:10:90 to 25:25:50.

[0058] Drying conditions are room temperature to about 170° C. The fabric may be woven, knitted, nonwoven, etc. The rubber of the rubber sheet on both sides may be the same or different types.

[0059] Protective clothing 100 manufactured using protective material 1A, protective material 1B, or protective material 1C can prevent harmful gases, liquids, etc. from passing through protective clothing 100 even if harmful gases, liquids, etc. come into contact with the surface (outside).

[0060] In this way, the protective clothing 100 has improved gas permeability resistance and liquid resistance, and the protective function is further strengthened, so that the worker wearing the protective clothing 100 can be reliably protected. Therefore, the worker wearing the protective clothing 100 can work with peace of mind, and can, for example, quickly scout contaminated interior and exterior areas and perform life-saving activities.

[0061] Although protective clothing 100 is shown as an example of protective clothing having a jacket, pants, and a hood, the protective material in this disclosure can be widely applied to clothing worn when entering or exiting an area contaminated by harmful gases, liquids, etc.

[0062] Although the above describes an example in which the protective material is applied to protective clothing, the protective material of the present invention can also be applied to other items, such as protective gloves, protective socks, protective hoods, protective covers, filters, protective tents, sleeping bags, and storage bags for storing these items. It can also be used as a sealing material such as packing and gaskets for protective containers and devices.

[0063] The embodiments disclosed herein should be considered to be illustrative and not restrictive in all respects. The scope of the present invention is defined by the claims, not the above description, and is intended to include all modifications within the meaning and scope of the claims. [Explanation of symbols]

[0064] 1A, 1B, 1C protective material, 11 first rubber layer, 12 second rubber layer, 13 reinforcing cloth.

Claims

1. A protective garment using a protective material having an inner side and an outer side, A first rubber layer located on an inner side; A second rubber layer located on the outer side; a reinforcing cloth laminated between the first rubber layer and the second rubber layer; Equipped with At least one of the first rubber layer and the second rubber layer is made of acrylonitrile butadiene Using rubber, The acrylonitrile butadiene rubber has an acrylonitrile content of 36 wt % or more. and Between the first rubber layer and the reinforcing cloth, and between the second rubber layer and the reinforcing cloth, adhesive rubber is provided. The material is vulcanized and bonded with a rubber layer in between. The first rubber layer is located on the outermost surface of one side of the protective material. Protective clothing.

2. The first rubber layer is made of the acrylonitrile butadiene rubber, The second rubber layer is made of butyl rubber.

2. The protective garment of claim 1.

3. The first rubber layer is made of butyl rubber, The second rubber layer is the acrylonitrile butadiene rubber.

2. The protective garment of claim 1.

4. The second rubber layer is further provided on its outer side with a resin layer containing roughness imparting particles in the resin. A fluorine coating made of a fluorine-based water and oil repellent is layered in this order:

2. The protective garment of claim 1.

5. The shape of the irregularity-imparting particles is tetrapod-like, needle-like, polygonal, or spherical.

5. Protective clothing according to claim 4.

6. The roughening particles are tetrapod-type zinc oxide.

5. Protective clothing according to claim 4.

7. The reinforcing fabric is a woven fabric, a knitted fabric, or a nonwoven fabric; 2. The protective garment of claim 1.

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