JP7550208B2 - Protective Materials and Clothing - Google Patents

Description

This disclosure relates to protective materials and clothing for protecting the human body from toxic gases, liquids, etc.

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). Such protective materials require good gas permeability resistance and liquid protection resistance on 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).

Patent No. 5784812 JP 2003-2903 A JP 2010-24279 A

Protective materials are required to have improved resistance to gas permeation and liquid protection so that they can provide more reliable protection for the human body.

The present invention was made against the background of problems with the conventional technology, and aims to provide protective materials and clothing that have the ability to inhibit the penetration of gaseous and liquid organic chemicals, and that are lightweight, flexible, and have excellent peel strength.

[1] A protective material according to the present disclosure 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.

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

[3]: The protective material according to [1] or [2], in which a resin layer containing uneven-shape imparting particles 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.

[4]: The protective material described in [3], in which the shape of the unevenness-imparting particles is tetrapod-shaped, needle-shaped, polygonal, or spherical.

[5]: The protective material according to [3] or [4], wherein the irregularity-imparting particles are tetrapod-type zinc oxide.

[6]: A protective material according to any one of [1] to [5], wherein the reinforcing fabric is a woven fabric, a knitted fabric, or a nonwoven fabric.

[7] The protective clothing disclosed herein uses a protective material described in any one of [1] to [6].

This disclosure makes it possible to provide protective materials and 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.

1 is a cross-sectional structural diagram of a protective material according to a first embodiment. FIG. 5 is a cross-sectional structural diagram of a protective material according to a second embodiment. FIG. 11 is a cross-sectional structural diagram of a protective material according to a third embodiment. FIG. 2 is a schematic diagram showing a method for fixing a fluorine-based water- and oil-repellent processing agent. FIG. 2 is an enlarged view showing the shape of tetrapod-type zinc oxide. 1 is an electron microscope photograph of a layered structure of tetrapod-type zinc oxide. FIG. 11 is a diagram showing evaluation results of protective materials according to each embodiment. FIG. 2 is a schematic diagram showing a test vessel used in a gas permeability test. FIG. 1 is a schematic diagram of a liquid permeability test method. FIG. 13 is a front view showing the configuration of protective clothing according to a fourth embodiment.

The protective materials and protective clothing of each embodiment based on this 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 used for the same parts or corresponding parts, and duplicate descriptions may not be repeated. It is intended from the beginning that the configurations in the embodiments will be used in appropriate combinations. For ease of understanding, the film thicknesses and layer thicknesses shown in the figures are described at different ratios than the actual ratios.

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."

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

The protective material 1A of this embodiment has an inside and an outside, and is provided 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.

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 woven fabric, nonwoven fabric, etc. can also be used.

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

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 into 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.

(Method of manufacturing protective material 1A)
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 that are integrated with each other.

As a result of the above, protective material 1A is obtained, which has a three-layer structure consisting of a first rubber layer 11, a reinforcing fabric 13, and a second rubber layer 12.

[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.

Compared to protective material 1A of embodiment 1, protective material 1B of this embodiment uses the same materials for first rubber layer 11 and second rubber layer 12, but the arrangement is reversed.

The first rubber layer 11 is made of butyl rubber, and the second rubber layer 12 is made of acrylonitrile butadiene rubber (NBR). 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 woven fabric, nonwoven fabric, etc. can also be used.

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

(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 these 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.

As a result of the above, protective material 1B is obtained, which has a three-layer structure consisting of a first rubber layer 11, a reinforcing fabric 13, and a second rubber layer 12.

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

The basic configuration of the protective material 1C of this embodiment is the same as that of embodiment 1, and includes 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. 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 uneven shape-imparting particles in the resin, and the fluorine coating 15 is a coating made of a fluorine-based water- and oil-repellent agent.

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 woven fabric, nonwoven fabric, etc. can also be used.

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

A fluorine-based water- and oil-repellent agent is used for the fluorine coating 15. For example, the water- and oil-repellent agent disclosed in Japanese Patent No. 5784812 may be used as the fluorine-based water- and oil-repellent agent. A specific example of the fluorine-based water- and oil-repellent agent is 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 with 6 or more carbon atoms.

CH ₂ ═C(—Cl)-C(═O)-X—Y-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 manufacturing method of 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.

A method for fixing the fluorine-based water- and oil-repellent agent will be described with reference to Fig. 4. 20 cc/ ^m2 of a fluorine-based water- and oil-repellent agent with an apparent concentration of 7% is dropped onto the surface of the second rubber layer 12. Then, using a spatula L, the fluorine-based water- and oil-repellent agent is spread evenly over the surface of the resin layer 14. Then, a heat treatment (for example, 170°C, 5 minutes) is performed to complete the fluorine coating 15.

The resin layer 14 is preferably of the same type as the second rubber layer 12. It contains irregularity-imparting particles. In this specification, the irregularity-imparting particles refer to materials that can impart an irregular shape to the surface of the rubber layer. Examples of the shapes of the irregularity-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.

As shown in FIG. 5, the tetrapod-type zinc oxide crystals R have a "Tetrapod (registered trademark)" shape for revetments. Specifically, the crystals R are needle-shaped crystals that grow in the C-axis direction of hexagonal ZnO from the 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 each needle-shaped 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, multiple crystals R are layered on top of each other, and the resin layer 14 becomes a porous layered structure material with unevenness on the surface.

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. Tetrapod-type zinc oxide is mixed in an amount of 30% to 70% (preferably 40% to 60%) of the total solids (rubber, resin + tetrapod-type zinc oxide). This makes the resin layer 14 brittle, but by heating and vulcanizing it, 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, tetrapod-shaped single crystal powder made of zinc oxide (Panatetra WZ-0501 manufactured by Amtec Co., Ltd., average fiber length (needle-shaped part): approximately 10 μm) can be used.

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 processing agent, so that the fluorine coating 15 has good bonding to the resin layer 14. In addition, 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 appear on the surface of the fluorine coating 15 as well. These irregularities bring about good results in the evaluation results of the gas penetration resistance and liquid resistance protection properties of the protective material 1C, which will be described later.

[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 the gas permeability test, and Fig. 9 is a schematic diagram of the liquid permeability test method.

The gas permeability resistance (5 hr maximum permeation concentration/ppm) was evaluated using a gas permeability test, and the liquid protection resistance was evaluated using a liquid permeability test method. Referring to FIG. 8, the gas permeability test was performed by sandwiching the test sample 108 of the embodiment between the upper cell (150 cc) 105 and the lower cell (150 cc) 100. Test liquid 107 was dripped onto the top 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. The gas permeability was then evaluated using the sampling port 106.

9, in the liquid permeability test, filter paper 140 is placed on a glass plate 150, and the test piece 130 of the embodiment is placed on top of that. 20 μL of liquid chemical substance 120 (dipropyl phthalate with red dye dissolved therein) is then dropped on top of that. After that, a weight with a base area of ¹ cm2 is placed on top of that with a predetermined load 110 (1 kgf/ ^cm2 ), and the presence or absence of liquid permeation is judged based on the coloring of the filter paper after 6 hours.

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).

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 also 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 approximately 0.08 mm to 0.1 mm, the thickness of the second rubber layer 12 is approximately 0.08 mm to 0.1 mm, and the thickness when a woven base fabric is used for the reinforcing cloth 13 is approximately 0.1 mm. Note that when a knit fabric is used for the reinforcing cloth 13, the thickness of the reinforcing cloth 13 is approximately 0.2 mm to 0.3 mm.

The protective materials of Comparative Examples 1 and 2 both had unacceptable gas permeability resistance of 240 ppm.

Although the protective material 1A of embodiment 1 was thinner than the protective material of the comparative example, it achieved an excellent passing result of 50 ppm in gas permeability resistance.

As such, it can be seen that the protective material 1A of embodiment 1 is far superior in gas permeability resistance to the evaluations of each comparative example. As a result, even if harmful gases, liquids, etc. come into contact with the outside of the protective material 1A, it is possible to suppress the penetration of harmful gases, liquids, etc. into the inside of the protective material 1A.

Although the protective material 1B of embodiment 2 was thinner than the protective materials of each comparative example, it achieved an excellent passing result of 20 ppm in gas permeability resistance.

As such, it can be seen that the protective material 1B of embodiment 2 is far superior in gas permeability resistance to the evaluations of each comparative example. As a result, even if harmful gases, liquids, etc. come into contact with the outside of the protective material 1B, it is possible to suppress the penetration of harmful gases, liquids, etc. into the inside of the protective material 1B.

Although the protective material 1C of embodiment 3 was thinner than the protective materials of each comparative example, it achieved an excellent passing result of 40 ppm in gas permeability resistance.

As such, it can be seen that the protective material 1C of embodiment 3 is far superior in terms of gas permeability resistance compared to the evaluations of each comparative example. As a result, even if harmful gases, liquids, etc. come into contact with the outside of the protective material 1C, it is possible to suppress the penetration of harmful gases, liquids, etc. into the inside of the protective material 1C.

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.

[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.

As an example, when protective material 1C is used, 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, an uneven coating containing uneven shape-imparting particles is applied to the outer rubber surface and dried (step 2). Next, heated vulcanization is performed (step 3). Next, a water- and oil-repellent treatment (adhering method shown in FIG. 2 or immersion) is applied (step 4).

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

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

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).

In this way, the protective clothing 100 has improved gas permeability resistance and liquid resistance, and its protective function is further strengthened, so that the worker wearing it 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.

Although the protective clothing 100 is shown as an example of a protective garment having a top, bottoms, and a hood, the protective material disclosed herein can be widely applied to clothing worn when entering or exiting an area contaminated by harmful gases, liquids, etc.

Although the above shows 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 even 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.

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

1A, 1B, 1C protective material, 11 first rubber layer, 12 second rubber layer, 13 reinforcing fabric.

Claims (7)

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 rubber,
The acrylonitrile butadiene rubber has an acrylonitrile content of 36 wt % or more,
The first rubber layer is made of the acrylonitrile butadiene rubber,
The second rubber layer is made of butyl rubber.
Protective materials. 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 rubber,
The acrylonitrile butadiene rubber has an acrylonitrile content of 36 wt % or more,
The first rubber layer is made of butyl rubber,
The second rubber layer is the acrylonitrile butadiene rubber.
Protective materials. 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 rubber,
The acrylonitrile butadiene rubber has an acrylonitrile content of 36 wt % or more,
On the outside of the second rubber layer, a resin layer containing roughness-imparting particles and a fluorine coating made of a fluorine-based water- and oil-repellent agent are laminated in this order.
Protective materials. The protective material according to claim 3 , wherein the irregularity-imparting particles have a tetrapod-like, needle-like, polygonal, or spherical shape. The roughening particles are tetrapod-type zinc oxide.
The protective material of claim 3 . The reinforcing fabric is a woven fabric, a knitted fabric, or a nonwoven fabric;
The protective material according to any one of claims 1 to 5 . A protective garment using the protective material according to any one of claims 1 to 5 .

Images