JP2024007435A - Protective material and protective garment - Google Patents

Abstract

To provide a protective material that can reduce the human labor and work time needed for decontamination.SOLUTION: A protective material 1A includes a rubber layer with water- and oil-repellency. On the surface of the rubber layer, the contact angle with water is 100° or more, the contact angle with decane is 35 or more, and the contact angle with 3-methoxybutyl acetate is 60°or more. This protective material 1B allows for reduction in the human labor and work time needed for decontamination.SELECTED DRAWING: Figure 8

Description

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

A technique related to a protective material that protects the human body from toxic gases, liquids, etc. is disclosed in, for example, Japanese Patent No. 5784812 (Patent Document 1). Such protective materials are required to have good water and oil repellency on the material surface against toxic liquids, etc., and techniques related to surface treatment of materials are disclosed, for example, in Japanese Patent Laid-Open No. 2003-2903 (Patent No. Document 2) and Japanese Patent Application Publication No. 2010-24279 (Patent Document 3).

Patent No. 5784812 Japanese Patent Application Publication No. 2003-2903 Japanese Patent Application Publication No. 2010-24279

For example, if a harmful liquid or the like adheres to protective clothing made of protective materials, decontamination work using a decontamination agent such as a bleaching powder aqueous solution is required. This work is carried out by multiple decontamination workers on people wearing protective clothing, but the problem is that the amount of human labor and work time required for decontamination work is large. .

The present disclosure aims to solve the above-mentioned problems, and to provide protective materials and protective clothing that can reduce the human labor and working time required for decontamination work.

[1] The protective material of the present disclosure is a protective material comprising a rubber layer having water and oil repellency, wherein the surface of the rubber layer has a contact angle of water of 100° or more and a contact angle of decane of 35° or more. , and the contact angle of 3-methoxybutyl acetate is 60° or more.

[2]: In the protective material described above, the surface of the rubber layer includes a fluorine coating made of a fluorine-based water and oil repellent.

[3]: Any of the protective materials described above, comprising an outer layer that is laminated on the rubber layer and located on the outer side, and the outer layer includes uneven shape imparting particles and a fluorine-based repellent. Contains water and oil repellent.

[4]: Any of the protective materials described above, in which the uneven shape imparting particles have a tetrapod shape, a needle shape, a polygonal shape, or a spherical shape.

[5]: Any of the protective materials described above, in which the uneven shape imparting particles are tetrapod-type zinc oxide.

[6]: Any of the protective materials described above, in which a fabric and a second rubber layer are laminated in the order listed on the opposite side of the rubber layer to the side on which the outer layer is laminated. There is.

[7]: Any of the protective materials described above, in which the fabric is a woven fabric, a knitted fabric, or a nonwoven fabric.

[8]: Any of the protective materials described above, in which the rubber layer and the second rubber layer use different types of rubber.

[9]: In the protective clothing of the present disclosure, the protective material according to any one of [1] to [8] is used.

According to the present disclosure, it is possible to provide protective materials and protective clothing that can reduce the human labor and work time required for decontamination work.

FIG. 2 is a cross-sectional structural diagram of a protective material according to an embodiment. FIG. 2 is a schematic diagram showing a method of fixing a fluorine-based water- and oil-repellent finishing agent. FIG. 3 is a cross-sectional structural diagram of another protective material according to the embodiment. FIG. 2 is an enlarged view showing the shape of tetrapod zinc oxide. This is an electron micrograph of a laminated structure of tetrapod zinc oxide. It is a schematic diagram showing a contact angle. It is a schematic diagram showing a sliding angle. It is a figure showing the evaluation result of a plurality of protective materials of an embodiment. FIG. 3 is a front view showing the configuration of a protective clothing according to a second embodiment.

Protective materials and protective clothing according to each embodiment based on the present disclosure will be described below with reference to the drawings. In the embodiments described below, when referring to the number, amount, etc., the scope of the present invention is not necessarily limited to the number, amount, etc. unless otherwise specified. Identical or equivalent parts will be given the same reference numbers, and duplicate descriptions may not be repeated. It has been planned from the beginning to use the configurations in the embodiments in appropriate combinations. For ease of understanding, the film thicknesses and layer thicknesses shown in the figures are shown in different proportions from the actual ratios.

In the specification, "outside" means the side that is exposed to toxic gases and liquids when the protective material is used, and "inside" means the side that is exposed to toxic gases and liquids when the protective material is used. means the side that is not exposed to Therefore, when this protective material is used in protective clothing, the side that touches the wearer is the "inside".

[Embodiment 1: Protective material 1A]
The protective material 1A will be described with reference to FIGS. 1 and 2. FIG. 1 is a cross-sectional structural diagram of the protective material 1A, and FIG. 2 is a schematic diagram showing a method of fixing a fluorine-based water- and oil-repellent finishing agent.

This protective material 1A is a protective material having an inner side and an outer side, and includes a rubber layer 11 located on the inside, and a fluorine coating 12 as an outer layer laminated on the rubber layer 11 and located on the outside. The thickness of the rubber layer 11 is about 0.1 mm to 0.3 mm, and the fluorine-containing coating 12 has a solid content of 0.01 g/m ² to 10.5 g/m ² , preferably The concentration is adjusted by diluting with water to 0.05 g/m ² to 5 g/m ² , more preferably 0.1 g/m ² to 2 g/m ² .

The types of rubber used for the rubber layer 11 include nitrile rubber (NBR), epichlorohydrin rubber (CO, ECO), chlorinated butyl rubber (CIIR), butyl rubber (IIR), brominated butyl rubber (BrIIR), fluororubber, and chloroprene. Rubber (CR), chlorosulfonated polyethylene rubber (CSM), urethane rubber, etc. The fluorine coating 12 uses a fluorine-based water and oil repellent.

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

CH2=C(-Cl)-C(=O)-X-Y-Rf...Formula (1) [wherein, X is -O- or -NH-, and Y is a direct bond or a divalent It is an organic group, and Rf is a fluoroalkyl group having 1 to 20 carbon atoms. ]
Referring to FIG. 2, a method for fixing the fluorine-based water- and oil-repellent finishing agent to the rubber layer 11 will be described. On the surface of the rubber layer 11, 20 cc/m ² of a fluorine-based water- and oil-repellent finishing agent with an apparent concentration of 7% is dropped. Thereafter, using a spatula L, the fluorine-based water- and oil-repellent finishing agent is uniformly spread on the surface of the rubber layer 11. Thereafter, heat treatment (for example, 170 degrees, 5 minutes) is performed to complete the fluorine coating 12 (solid content adhesion amount: 0.7 g/m ² ). Evaluation of the water and oil repellency of the protective material 1A will be described later.

[Protective material 1B]
Next, the protective material 1B will be explained with reference to FIGS. 3 to 5. FIG. 3 is a cross-sectional structural diagram of the protective material 1B, FIG. 4 is an enlarged view showing the shape of the tetrapod zinc oxide, and FIG. 5 is an electron micrograph of the laminated structure of the tetrapod zinc oxide.

The difference between the protective material 1B and the protective material 1A is that a resin layer 13 is further laminated between the rubber layer 11 and the fluorine coating 12. The fluorine coating 12 and the resin layer 13 constitute an outer layer. The thickness of the rubber layer 11 is about 0.1 mm to 0.3 mm, and the fluorine-containing coating 12 has a solid content of 0.01 g/m ² to 10.5 g/m ² , preferably The concentration is adjusted by diluting with water to 0.05 g/m ² to 5 g/m ² , more preferably 0.1 g/m ² to 2 g/m ² .

Like the protective material 1A, the rubber layer 11 contains nitrile rubber (NBR), epichlorohydrin rubber (CO, ECO), chlorinated butyl rubber (CIIR), butyl rubber (IIR), brominated butyl rubber (BrIIR), and fluorine. rubber, chloroprene rubber (CR), chlorosulfonated polyethylene rubber (CSM), urethane rubber, etc. The fluorine coating 12 uses a fluorine-based water and oil repellent, similar to the protective material 1A.

The resin layer 13 of the protective material 1B is preferably of the same type as the rubber layer 11. Preferably, the same type of rubber as the rubber layer 11 contains the uneven shape imparting particles. In this specification, the term "irregularity imparting particles" refers to a material capable of imparting an uneven shape to the surface of a rubber layer. Examples of the shape of the uneven shape-imparting particles include tetrapod, needle, spherical, and polygonal shapes. 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; Examples include inorganic substances other than metals. Specific examples include tetrapod zinc oxide and spherical silica.

As shown in FIG. 4, the tetrapod-type zinc oxide crystal R has a "tetrapod (registered trademark)" shape for use in seawalls. Specifically, the crystal R is an acicular crystal that grows in the C-axis direction of hexagonal ZnO from four alternate faces of each part of a regular octagon by reacting 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. 5, in the laminated structure of tetrapod zinc oxide, a plurality of crystals R are stacked one on top of the other, so that the resin layer 13 has a porous layered structure with unevenness on the surface. Becomes a material.

The resin layer 13 is made of the same type of rubber as the rubber layer 11, or has a structure in which tetrapod zinc oxide is dispersed in a resin. Tetrapod type zinc oxide is blended in an amount of 30 wt% to 70 wt% (preferably 40 wt to 60 wt%) based on the total solid content (rubber or resin + tetrapod type zinc oxide) of the resin layer 13. In this case, the resin layer 13 becomes brittle, but by heating and vulcanizing, a crosslinked structure is formed between the rubber layer 11 and the resin layer 13 of the same type to form a strong bond, thereby improving the film strength of the resin layer 13. For example, a tetrapod-like single crystal powder made of zinc oxide (“Pana Tetra WZ-0501” manufactured by Amtech Co., Ltd., average fiber length (acicular portion): about 10 μm) can be used.

As a result, the fluorine coating 12 laminated on the surface of the resin layer 13 is formed using the fixing method shown in FIG. This improves the bondability of the fluorine coating 12 to the resin layer 13. Further, on the outside of the fluorine coating 12, the irregularities appearing on the surface of the resin layer 13 are reflected on the surface of the fluorine coating 12, and fine irregularities also appear on the surface of the fluorine coating 12. This unevenness brings about good results in evaluating the water and oil repellency of the protective material 1B, which will be described later. The size of the fine irregularities appearing on the surface of the fluorine coating 12 is about 1 to 50 μm, preferably about 5 to 30 μm, and more preferably about 8 to 20 μm, in terms of the length of the needle-like crystals.

[Evaluation results of protective materials]
Next, evaluation results of the protective material 1A, the protective material 1Aa, the protective material 1B, and the protective material 1Bb will be described with reference to FIGS. 6 to 8. FIG. 6 is a schematic diagram showing the contact angle, FIG. 7 is a schematic diagram showing the sliding angle, and FIG. 8 is a diagram showing the evaluation results of the protective materials of each embodiment.

First, with reference to FIGS. 6 and 7, "θ: contact angle (static)" and "α: sliding angle (dynamic)" used to evaluate droplets attached to the material surface will be explained. Referring to FIG. 6, the evaluation of "θ: contact angle (static)" evaluates the adhesion state of the droplet W1 to a horizontal surface. As shown in FIG. 6, the larger the angle θ between the tangent to the surface of the droplet W1 and the horizontal plane, the less the droplet W1 adheres to the horizontal surface, and the more the droplet W1 maintains a shape close to a sphere. , it can be evaluated that the droplet W1 has good water repellency and oil repellency. If θ is 150 degrees or more, the droplet W1 is bounced off the horizontal surface and can be said to be in a slippery state.

On the other hand, referring to FIG. 7, the evaluation of "α: sliding angle (dynamic)" evaluates the inclination angle at which the droplet W1 starts falling. As shown in FIG. 7, the smaller the adhesion force of the droplet W1 to the slope, the smaller the droplet W1 starts falling at a smaller inclination angle α. Therefore, the smaller the inclination angle α at which the droplet W1 starts falling, the better the water repellency and oil repellency of the droplet W1 can be evaluated.

Next, evaluation results of the protective material 1A, the protective material 1Aa, the protective material 1B, and the protective material 1Bb will be described with reference to FIG. It is a figure showing the evaluation result of the protective material of each embodiment.

As evaluation targets, water repellency (water), oil repellency (n-decane), and liquid repellency (3-methoxybutyl acetate) were evaluated as "θ: contact angle (static)". "α: sliding angle (dynamic)" was similarly evaluated for water repellency (water), oil repellency (n-decane), and liquid repellency (3-methoxybutyl acetate). Note that for oil repellency (n-decane), AATCC118 oil repellent grade 6 was used. The same applies hereafter.

For the protective material in the comparative example, "θ: contact angle (static)" is 99° for water repellency (water), unmeasurable (<5°) for oil repellency (n-decane), and liquid repellency (3-methoxybutyl acetate) was 36°. "α: sliding angle (dynamic)" is 41° for water repellency (water), unmeasurable for oil repellency (n-decane) (oleophilic), and 7 for liquid repellency (3-methoxybutyl acetate). It was °.

For protective material 1A, the water repellency (water) was 117°, the oil repellency (n-decane) was 61°, and the liquid repellency (3-methoxybutyl acetate) was 74°. "α: sliding angle (dynamic)" was 37° for water repellency (water), 27° for oil repellency (n-decane), and 22° for liquid repellency (3-methoxybutyl acetate). .

Thus, in the evaluation, the protective material 1A was evaluated higher than the evaluation of the comparative example. Therefore, it can be seen that the protective material 1A has excellent water repellency, oil repellency, and liquid repellency performance compared to the comparative example. As a result, even if harmful liquid etc. comes into contact with the outside of the protective material 1A, it becomes difficult for the harmful liquid etc. to stop on the surface of the protective material 1A, thereby suppressing the adhesion of the harmful liquid etc. to the surface of the protective material 1A. things become possible.

This makes it possible to reduce the labor required for decontaminating harmful liquids and the like adhering to the outside of the protective material. In addition, since it has excellent water repellency, oil repellency, and liquid repellency, it improves protection.

Next, for the protective material 1Aa, the water repellency (water) was 114°, the oil repellency (n-decane) was 37°, and the liquid repellency (3-methoxybutyl acetate) was 60°. "α: sliding angle (dynamic)" was 88° for water repellency (water), 36° for oil repellency (n-decane), and 28° for liquid repellency (3-methoxybutyl acetate). .

Thus, in the evaluation, the protective material 1Aa was evaluated higher than the evaluation of the comparative example. Therefore, it can be seen that the protective material 1Aa has excellent water repellency, oil repellency, and liquid repellency performance compared to the comparative example. As a result, even if harmful liquid etc. contacts the outside of the protective material 1Aa, it becomes difficult for the harmful liquid etc. to stop on the surface of the protective material 1Aa, thereby suppressing the adhesion of the harmful liquid etc. to the surface of the protective material 1Aa. things become possible.

This makes it possible to reduce the labor required for decontaminating harmful liquids and the like adhering to the outside of the protective material. In addition, since it has excellent water repellency, oil repellency, and liquid repellency, it improves protection.

Next, for protective material 1B, the water repellency (water) was 150°, the oil repellency (n-decane) was 109°, and the liquid repellency (3-methoxybutyl acetate) was 126°. "α: sliding angle (dynamic)" was 5° for water repellency (water), 22° for oil repellency (n-decane), and 14° for liquid repellency (3-methoxybutyl acetate). .

This protective material 1B received an even higher evaluation than the protective materials 1A and 1Aa. This shows that the protective material 1B has better water repellency, oil repellency, and liquid repellency than the protective material 1A and the protective material 1Aa. As a result, even if harmful liquid etc. comes into contact with the outside of protective material B, it becomes more difficult for the harmful liquid etc. to stop on the surface of protective material 1B, making it easier to prevent harmful liquid etc. from adhering to the surface of protective material 1B. It is possible to suppress it.

This makes it possible to further reduce the labor required for decontaminating harmful liquids and the like adhering to the surface of the protective material.

Next, the protective material 1Bb had water repellency (water) of 145°, oil repellency (n-decane) of 75°, and liquid repellency (3-methoxybutyl acetate) of 85°. "α: sliding angle (dynamic)" was 15° for water repellency (water), 44° for oil repellency (n-decane), and 35° for liquid repellency (3-methoxybutyl acetate). .

This protective material 1Bb had the same effect as the protective material 1B. This shows that the protective material 1Bb has excellent water repellency, oil repellency, and liquid repellency performance equivalent to that of the protective material 1B. As a result, even if harmful liquid etc. comes into contact with the outside of the protective material 1Bb, it becomes more difficult for the harmful liquid etc. to stop on the surface of the protective material 1Bb, making it easier to prevent the harmful liquid etc. from adhering to the surface of the protective material 1Bb. It is possible to suppress it.

This makes it possible to further reduce the labor required for decontaminating harmful liquids and the like adhering to the surface of the protective material.

Based on the evaluation results of the protective material 1A, the protective material 1Aa, the protective material 1B, and the protective material 1Bb explained above, the contact angle of water on the surface of the water- and oil-repellent rubber layer 11 is 100° or more, The contact angle is preferably 35° or more, and the contact angle of 3-methoxybutyl acetate is preferably 60° or more.

[Embodiment 2: Protective clothing 100]
With reference to FIG. 9, the configuration of protective clothing 100 in this embodiment will be described. FIG. 9 is a front view showing the configuration of the protective clothing 100.

As a specific method for manufacturing the protective material of this protective clothing 100, first, rubber sheets are laminated on both sides of the fabric (step 1). Next, a textured coating containing texture-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 (fixing method shown in FIG. 2 or dipping) is applied (step 4).

The outline of step 1 is as follows. Adhesive rubber layers (not shown) made of the same type of rubber material as the rubber sheet are interposed on both sides of the fabric, and the fabric is laminated and vulcanized to obtain a laminated structure of the rubber sheet, fabric, and rubber sheet that are integrated with each other.

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

As specific examples, in Example 1, the blending ratio was 5:5:90, in Example 2, 7.5:7.5:85, and in Example 3, the blending ratio was 17.5:17.5:65. And so. The drying conditions are room temperature drying to about 170°C. As the fabric, woven fabric, knitted fabric, non-woven fabric, etc. can be used. The rubber sheets on both sides may be of the same type or different types.

By manufacturing the protective clothing 100 in this way, even if the surface (outside) of the protective clothing 100 comes into contact with a harmful liquid, etc., it becomes more difficult for the harmful liquid to stop on the surface of the protective material 1B, and the protective material It becomes possible to suppress adhesion of harmful liquids, etc. to the surface of 1B. As the fabric, woven fabrics, knitted fabrics, non-woven fabrics, etc. can be used, but woven fabrics are preferable because they allow the rubberized fabric to be thin and have high strength. As the material, nylon, polyester, cotton, etc. can be used.

This makes it possible to reduce the labor required for decontaminating harmful liquids and the like adhering to the surface of the protective material. In addition, since it has excellent water repellency, oil repellency, and liquid repellency, it improves protection.

Further, decontamination work that involves the wearer wearing the protective clothing 100 going in and out of contaminated areas is reduced or becomes unnecessary, making it possible to perform prompt reconnaissance and life-saving activities in contaminated areas. Furthermore, it is also possible to avoid the risk of contamination spreading during reconnaissance activities. Furthermore, it is also possible to eliminate the need to process decontamination liquid generated during decontamination work. Furthermore, it is also possible to give the wearer a sense of mental security.

Although the protective clothing 100 includes a top coat, a bottom coat, and a hood, the protective material in the present disclosure may include clothing worn when going in and out of areas contaminated with harmful liquids, etc. It can be widely applied to

Further, although an example in which the protective material is applied to protective clothing has been shown, the protective material of the present invention can be used in other applications such as protective gloves, protective socks, protective hoods, protective covers, filters, protective awnings, sleeping bags, etc. , it can be applied to a storage bag for storing these items. It can also be used as a sealing material for packing, gaskets, etc. of containers and devices that have protective properties.

The embodiments disclosed this time should be considered to be illustrative in all respects and not restrictive. The scope of the present invention is indicated by the claims rather than the above description, and it is intended that all changes within the meaning and range equivalent to the claims are included.

1A, 1B Protective material, 11 Rubber layer, 12 Fluorine coating, 13 Resin layer, 100 Protective clothing.

Claims (9)

A protective material comprising a rubber layer having water and oil repellency,
The contact angle of water on the surface of the rubber layer is 100° or more, the contact angle of decane is 35° or more, and the contact angle of 3-methoxybutyl acetate is 60° or more.
Protective material. The surface of the rubber layer includes a fluorine coating made of a fluorine-based water and oil repellent.
Protective material according to claim 1. an outer layer laminated on the rubber layer and located on the outside;
Equipped with
The outer layer contains uneven shape imparting particles and a fluorine-based water and oil repellent.
Protective material according to claim 1. The shape of the uneven shape imparting particles is tetrapod, needle, polygon, or spherical.
Protective material according to claim 3. The uneven shape imparting particles are tetrapod zinc oxide,
Protective material according to claim 3. A fabric and a second rubber layer are laminated in the stated order on the opposite side of the rubber layer to the side on which the outer layer is laminated,
Protective material according to claim 3. The fabric is a woven fabric, a knitted fabric, or a nonwoven fabric,
Protective material according to claim 6. The rubber layer and the second rubber layer are made of different types of rubber,
Protective material according to claim 6. Protective clothing using the protective material according to any one of claims 1 to 8.

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