Protective material and protective clothing

Abstract

To provide: a protective material capable of inhibiting an increase in internal temperature of a protective clothing by inhibiting an influence of radiant heat due to solar radiation; and the protective clothing.SOLUTION: A protective material of the invention includes an inner layer located on an inner side, and an outer layer laminated on the inner layer and located on an outer side. The inner layer includes a rubber layer, and the outer layer includes an infrared reflection agent.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present disclosure relates to protective materials and protective clothing.

Background Art

[0002] Techniques related to protective materials for protecting the human body are disclosed, for example, in Japanese Patent No. 5784812 (Patent Document 1).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] Protective clothing using a protective material covers the entire body. Therefore, when used outdoors, the inside of the protective clothing becomes hot due to the radiant heat from solar radiation. As a result, it is difficult to wear the protective clothing for a long time, and the work efficiency of the work performed while wearing the protective clothing decreases.

[0005] An object of the present disclosure is to solve the above problems and provide a protective material and protective clothing capable of suppressing an increase in the internal temperature of the protective clothing by suppressing the influence of radiant heat from solar radiation.

Means for Solving the Problems

[0006] [1] The protective material of the present disclosure is a protective material having an inner side and an outer side, and includes an inner layer located on the inner side and an outer layer laminated on the inner layer and located on the outer side. The inner layer includes a rubber layer, and the outer layer includes an infrared reflector.

[0007] [2]: The protective material according to [1], wherein the outer layer contains a fluorine-based water and oil repellent.

[0008] [3]: The protective material according to [1] or [2], wherein the outer layer contains particles for imparting uneven shapes.

[0009] [4]: The protective material according to [2], wherein the outer layer contains an infrared reflective agent in the same kind of rubber as the rubber of the rubber layer, and the fluorine-based water and oil repellent forms a fluorine film.

[0010] [5]: The protective material according to [3], wherein the shape of the particles for imparting uneven shapes is a tetra-pot shape, a needle shape, a polygonal shape, or a spherical shape.

[0011] [6]: The protective material according to [3] or [5], wherein the particles for imparting uneven shapes are tetra-pot type zinc oxide.

[0012] [7]: The protective material according to any one of [1] to [6], wherein a fabric and a second rubber layer are laminated in this order on the surface opposite to the surface on which the outer layer of the inner layer is laminated.

[0013] [8]: The protective material according to [7], wherein the fabric is a woven fabric, a knitted fabric, or a non-woven fabric.

[0014] [9]: The protective material according to [7] or [8], wherein different kinds of rubber are used for the rubber layer and the second rubber layer.

[0015]

[10] : The protective material according to any one of [3], [5] or [6], wherein the particles for imparting uneven shapes are contained in an amount of 40 wt% to 60 wt% based on the solid content excluding the infrared reflective agent in the total solid content of the outer layer.

[0016]

[11] : The protective material according to any one of [1] to

[10] , wherein the infrared reflecting agent is a pigment containing at least one kind of metal element of titanium, manganese, calcium, iron, bismuth, chromium, and nickel, and the infrared reflecting agent is contained in an amount of 5 wt% to 30 wt% based on the solid content excluding the infrared reflecting agent in the total solid content of the outer layer.

[0017]

[12] : The protective material according to any one of [1] to

[11] , wherein the average particle diameter of the infrared reflecting agent is 600 nm or more and 1500 nm or less.

[0018]

[13] : In the protective clothing of the present disclosure, the protective material according to any one of [1] to

[12] is used.

Effect of the Invention

[0019] According to the present disclosure, it is possible to provide a protective material and a protective clothing capable of suppressing an increase in the internal temperature of the protective clothing by suppressing the influence of radiant heat due to solar radiation.

Brief Description of the Drawings

[0020]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

Figure 9

Figure 10

Embodiments for Carrying out the Invention

[0021] Regarding the protective materials and protective clothing of each embodiment based on the present disclosure, they will be described below with reference to the drawings. In the embodiments described below, when referring to the number, amount, etc., unless otherwise specified, the scope of the present invention is not necessarily limited to the number, amount, etc. The same parts and corresponding parts are given the same reference numerals, and duplicate descriptions may not be repeated. It is initially planned to use the configurations in the embodiments in appropriate combinations. For ease of understanding, the film thickness and layer thickness shown in the figures are described differently from the actual ratios.

[0022] In the specification, "outer side" means the side exposed to harmful liquids, etc. when the protective material is used, and "inner side" means the side not exposed to harmful liquids, etc. when the protective material is used. Therefore, when this protective material is used in a protective clothing, the side that touches the wearer is the "inner side".

[0023] [Embodiment 1: Protective Material 1] Next, with reference to FIGS. 1 to 3, the protective material 1 of this embodiment will be described. FIG. 1 is a cross-sectional structure diagram of the protective material 1, FIG. 2 is a schematic diagram showing the fixing method of a fluorine-based water and oil repellent, FIG. 3 is an enlarged view showing the shape of tetrapod-shaped zinc oxide, and FIG. 4 is an electron micrograph of the laminated structure of the protective material 1.

[0024] As shown in FIG. 1(A), the protective material 1 is a protective material having an inner side and an outer side, and includes an inner layer 11 located on the inner side and an outer layer 13 laminated on the inner layer 11 and located on the outer side. The outer layer 13 contains an infrared reflector.

[0025] The inner layer 11 contains a rubber layer, and the types of rubber used in the rubber layer include nitrile rubber (NBR), epichlorohydrin rubber (CO, ECO), chlorinated butyl rubber (CIIR), butyl rubber (IIR), brominated butyl rubber (BrIIR), fluororubber, chloroprene rubber (CR), chlorosulfonated polyethylene rubber (CSM), urethane rubber, etc. The thickness of the inner layer 11 may be about 0.1 mm to 0.3 mm, but is not limited thereto.

[0026] The outer layer 13 is preferably made of the same material as the inner layer 11, and more preferably contains an infrared reflective agent in the same kind of rubber or resin as the inner layer 11. In this specification, the infrared reflective agent means a material capable of reflecting light in the near-infrared region (780 nm to 2500 nm) contained in natural light. As the infrared reflective agent, a pigment containing one or more metal elements such as titanium, manganese, calcium, iron, bismuth, chromium, nickel, etc. can be used. For example, metal oxides (TiO2, Fe2O3, Mn3O4, MnO2, Cr2O3, CoO, CuO, CaO) etc. can be used. In this embodiment, the content of the infrared reflective agent contained in the outer layer 13 is 5 wt% to 30 wt%, preferably about 15 to 20 wt% with respect to the solid content excluding the infrared reflective agent in the total solid content of the outer layer 13 (here, rubber + tetrapod zinc oxide). The average particle size of the infrared reflective agent is preferably 600 nm or more and 1500 nm or less, but is not limited thereto.

[0027] The infrared reflective agent can increase the solar reflectance of the outer layer 13. As a result, it can be expected to suppress the temperature rise inside the protective material 1. Details will be described later with reference to FIG. 8.

[0028] A fabric or a second rubber layer may be laminated in this order on the surface of the inner layer 11 opposite to the surface on which the outer layer 13 is laminated. As the fabric, a woven fabric, a knitted fabric, or a non-woven fabric can be used. The rubber layer of the inner layer 11 and the second rubber layer may be different types of rubber or the same type of rubber.

[0029] The outer layer 13 may further contain a fluorine-based water and oil repellent. As shown in Fig. 1(B), a fluorine film 12 may be included as the fluorine-based water and oil repellent. Regarding the fluorine film 12, the solid content adhesion amount of the fluoropolymer is 0.01 g / m 2 ~10.5 g / m 2 , preferably 0.05 g / m 2 ~5 g / m 2 , more preferably 0.1 g / m 2 ~2 g / m 2 . It may be diluted with water to adjust the concentration so that it becomes such.

[0030] As the fluorine-based water and oil repellent, for example, a water and oil repellent processing agent disclosed in Japanese Patent No. 5784812 may be used. As an example of a specific fluorine-based water and oil repellent processing agent, a repeating unit derived from α-chloroacrylate (A) having a fluoroalkyl group represented by the following formula (1), and a non-fluorine monomer (B) having no fluoroalkyl group and having a hydrocarbon group with 6 or more carbon atoms A fluoropolymer containing a repeating unit derived from may be used.

[0031] CH2=C(-Cl)-C(=O)-X-Y-Rf ··· Formula (1) [In the formula, 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.] With reference to Fig. 2, the method of fixing the fluorine-based water and oil repellent to the outer layer 13 will be described. A fluorine-based water and oil repellent with an apparent concentration of 7% is dropped onto the surface of the inner layer 11 at 20 cc / m 2 . Then, using a spatula L, the fluorine-based water and oil repellent is uniformly spread on the surface of the inner layer 11. Then, a heat treatment (for example, 170 degrees, 5 minutes) is performed to complete the fluorine film 12 (solid content adhesion amount 0.7 g / m 2 ). The evaluation of the water and oil repellency of the protective material 1 will be described later.

[0032] The fluorine film 12 laminated on the surface of the outer layer 13 is formed using the fixing method shown in FIG. 2. For the outer layer 13, by impregnating a fluorine-based water and oil repellent, the bonding property of the fluorine film 12 to the outer layer 13 becomes good.

[0033] As shown in FIG. 1(C), the outer layer 13 may contain concavo-convex shape-imparting particles. In this specification, the concavo-convex shape-imparting particles refer to materials that can impart a concavo-convex shape to the surface of the inner layer 11. Examples of the shape of the concavo-convex shape-imparting particles include a tetrapod shape, a needle shape, a spherical shape, a polygonal shape, etc. Examples of the raw materials include inorganic oxides such as alumina, potassium titanate, wollastonite, zinc oxide, and aluminum borate; metals such as chromium, copper, iron, and nickel; and inorganic substances other than inorganic oxides and metals such as silicon carbide, graphite, and silicon nitride. Specific examples include tetrapod-type zinc oxide and spherical silica.

[0034] As shown in FIG. 3, the crystal R of tetrapod-type zinc oxide has the shape of a "tetrapod (registered trademark)" type for a seawall. Specifically, the crystal R is a needle-like crystal in which zinc metal vapor and oxygen react and grow in the C-axis direction of hexagonal ZnO from every other 4 sides of each regular octagon. 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. 4, in the laminated structure, a plurality of crystals R overlap and are laminated, so that the outer layer 13 becomes a porous layer structure material with concavities and convexities appearing on the surface.

[0035] The outer layer 13 preferably has a structure in which tetrapod-shaped zinc oxide and an infrared reflecting agent are dispersed in rubber or resin of the same type as the inner layer 11. In the outer layer 13, the tetrapod-shaped zinc oxide is contained in an amount of 30 wt% to 70 wt%, preferably 40 to 60 wt%, based on the solid content excluding the infrared reflecting agent (here, rubber or resin + tetrapod-shaped zinc oxide) of the total solid content. Then, the outer layer 12 becomes brittle, but by heating and vulcanizing, a crosslinked structure is formed between the inner layer 11 and the outer layer 13 of the same type, and they are firmly bonded to improve the film strength of the outer layer 13. As the tetrapod-shaped zinc oxide, for example, tetrapod-shaped single crystal powder made of zinc oxide ("Panatetra WZ-0501" manufactured by Amtech Co., Ltd., average fiber length (needle-like part): about 10 μm) can be used. When an additive is contained in the rubber or resin, the additive also enters the solid content excluding the infrared reflecting agent.

[0036] As shown in (D) of FIG. 1, the outer layer 13 contains concavo-convex shape-imparting particles, and a fluorine coating 12 may be provided. In this case, the concavo-convexities appearing on the surface of the outer layer 13 are also reflected on the surface of the fluorine coating 12, and fine concavo-convexities also appear on the surface of the fluorine coating 12. These concavo-convexities bring good results for the evaluation results of the water and oil repellency of the protective material 1 to be described later. The size of the fine concavo-convexities also appearing on the surface of the fluorine coating 12 is 1 to 50 μm, preferably 5 to 30 μm, more preferably about 8 to 20 μm, as the length of the needle-like crystals.

[0037] (Evaluation method of protective material) Next, with reference to FIGS. 5 to 7, the evaluation method of the protective material will be described. FIG. 5 is a schematic diagram showing the contact angle, FIG. 6 is a schematic diagram showing the sliding angle, and FIG. 7 is a schematic diagram showing the heat insulation test and the surface temperature measurement.

[0038] First, referring to FIGS. 5 and 6, the "θ: contact angle (static)" and "α: sliding angle (dynamic)" used to evaluate the droplets adhering to the material surface will be described. Referring to FIG. 5, the evaluation of the "θ: contact angle (static)" is to evaluate the adhesion state of the droplet W1 with respect to a horizontal surface. As shown in FIG. 5, the larger the angle θ formed between the tangent to the surface of the droplet W1 and the horizontal plane, the smaller the amount of adhesion of the droplet W1 to the horizontal surface. The droplet W1 maintains a shape close to a sphere and can be evaluated as a droplet W1 with good water and oil repellency. If the water repellency is such that θ is 150 degrees or more and the oil repellency is such that θ is 90 degrees or more, the droplet W1 will bounce on the horizontal surface and is in a state where it is easy to slide. However, if the water repellency is such that θ is 120 degrees and the oil repellency is such that θ exceeds 75 degrees, it has sufficient performance. Also, if the water repellency is such that θ is 100 degrees and the oil repellency is such that θ exceeds 50 degrees, it can be said to have water and oil repellency.

[0039] On the other hand, referring to FIG. 6, the evaluation of the "α: sliding angle (dynamic)" is to evaluate the inclination angle at which the droplet W1 starts to fall. As shown in FIG. 6, the smaller the adhesion force of the droplet W1 to the inclined surface, the smaller the inclination angle α at which the droplet W1 starts to fall. Therefore, the smaller the inclination angle α at which the droplet W1 starts to fall, the better the water and oil repellency of the droplet W1 can be evaluated. If α is 45 degrees or less, the droplet W1 will bounce on the horizontal surface and is in a state where it is easy to slide.

[0040] As the evaluation targets, for the "θ: contact angle (static)", the water repellency (water), oil repellency (n-decane), and liquid repellency (3-methoxybutyl acetate) were evaluated. Similarly, for the "α: sliding angle (dynamic)", the water repellency (water), oil repellency (n-decane), and liquid repellency (3-methoxybutyl acetate) were evaluated. For the oil repellency (n-decane), grade 6 of the oil repellency reagent of AATCC 118 was used. Specifically, for the measurement methods of the contact angle and the sliding angle, with a dropping amount of 30 μL, using the Kyowa Interface Science DMo710 as the measuring device, the sliding angle determination is to measure when the advancing angle moves 1 mm.

[0041] The evaluation was as follows. Contact angle (water): Below 100° (×), with "wetting" (×), Above 100° to 120° or less (△), Above 120° (〇) Contact angle (n-decane, 3-methoxybutyl acetate): 50° or less (×), Above 50° to 75° or less (△), Above 75° (〇) Sliding angle (all): 45° or less (〇)

[0042] As evaluation items related to solar radiation countermeasures, each item of "color", "heat insulation rate", "surface temperature", and "solar radiation reflectance" was evaluated.

[0043] Based on the heat insulation test of the fabric (JIS L1951), the heat insulation rate was calculated. Using the test apparatus 10 shown in Figure 7, the ambient temperature was set to 20 degrees to 25 degrees, and a reflector lamp 110 (Iwaki Electric PRS-500W) was used as the light source. The output of the reflector lamp 110 is 500W. The distance from the reflector lamp 110 to the protective material sample S (between the sample and the light source) is 40 cm.

[0044] The irradiation time of the heat rays by the reflector lamp 110 is 15 minutes. A blank region R1 where the heat ray receiver 130 is not covered by the protective material sample S and a region R2 where the heat ray receiver 130 is covered by the protective material sample S were prepared. The temperature change of the heat ray receiver 130 was measured at multiple locations, and the average value of the temperature changes at each location was obtained. The temperature change of the protective material sample S was measured with a thermal camera 141, and the temperature change of the heat ray receiver 130 was measured with a thermal camera 142. As the judgment criteria, if the surface temperature after 15 minutes from light irradiation is less than 50°C, it is ◎; if it is 50°C or more and less than 60°C, it is 〇; if it is 60°C or more, it is ×.

[0045] Before the heat ray irradiation (irradiation time: 0 minutes), assuming that the average temperature of the heat ray receptor 130 in region R1 is 20 degrees and the average temperature of the heat ray receptor 130 in region R2 is 20 degrees, after the heat ray irradiation (irradiation time: 15 minutes), the average temperature of the heat ray receptor 130 in region R1 changes to 60 degrees, and the temperature of the heat ray receptor 130 in region R2 changes to 40 degrees. In this case, since the temperature change ΔT in region R1 is 40 degrees and the temperature change ΔT in region R2 is 20 degrees, the heat shielding rate (%) of the protective material sample S is ((40 - 20) / 40)×100 (%) = 50%.

[0046] Based on the above calculation formula of the heat shielding rate (%), the shielding rate of the protective material was calculated. The surface temperature in Fig. 8 indicates the surface temperature of the protective material.

[0047] Regarding the solar reflectance, using a spectrophotometer (manufactured by Shimadzu Corporation, UV-VIS-NIR spectrophotometer SolidSpec-3700), the spectral reflectance in the range of 300 - 2500 nm was measured, and based on JIS K 5602:2008 (Solar Reflectance of Paints), it was determined in the near ultraviolet and visible light region (300 - 780 nm) and the near infrared region (780 - 2500 nm). The judgment criteria were: for the solar reflectance in the near ultraviolet and visible light region, if it is less than 15%, it is marked as 〇, if it is 15% or more, it is marked as ×; for the solar reflectance in the near infrared region, if it is 40% or more, it is marked as 〇, if it is less than 40%, it is marked as ×.

[0048] As for chemical resistance, a gas permeability test (24-hour average penetration concentration / ppm) was carried out. Referring to Fig. 10, in the gas permeability test, the test piece 104 of the embodiment was sandwiched between the upper cell (150 cc) 100 and the lower cell (150 cc) 101. On the upper surface of the test piece 104, the test liquid 103 (2-chloroethyl ethyl sulfide, 3 μL) was dropped. The upper cell (150 cc) 100 and the lower cell (150 cc) 101 sandwiching the test piece 104 were sealed with a paraffin seal 105. Then, the gas in the lower cell was sampled from the sampling port 106, and the gas permeability was evaluated by gas chromatography. Judgment criteria: 24-hour average penetration concentration of the lower cell 〇: Below 50 ppm, ×: Exceeding 50 ppm Note that sampling was carried out every 1 hour from 1 to 6 hours, and then at the time point after 24 hours elapsed. 24-hour average penetration concentration ppm = (Integral value of penetration concentration ppm·hr from 1 to 24 hours) / 24 hours

[0049] (Examples and Comparative Examples) Next, as examples of Embodiment 1, the following protective materials 1A to 1D and 2A were manufactured and the above evaluations were performed. Also, the protective material of Comparative Example 1 was manufactured and the above evaluations were performed. Fig. 8 shows the evaluation results of the protective materials 1A to 1D, 2A, and the protective material of Comparative Example 1.

[0050] For the protective material 1A, butyl rubber was used for the inner layer 11, and a coating material was knife-coated on the outside thereof, dried, and heat-vulcanized to form the outer layer 13. The above coating material was mixed so that the mass ratio of butyl rubber : solvent (toluene) was 35:65, and further, as an infrared reflecting agent, "SG-101" manufactured by Ishihara Sangyo Co., Ltd. composed of metal elements of titanium, manganese, and calcium was used at 10 wt% with respect to the above solid content (butyl rubber). A fabric was laminated under the inner layer 11, and extremely high nitrile rubber was laminated under that. "θ: Contact angle (static)": For water repellency (water), it was 100°, for oil repellency (n-decane), it was wet (unmeasurable), and for liquid repellency (3-methoxybutyl acetate), it was 36°. "α: Sliding angle (dynamic)": For water repellency (water), it was 50°, for oil repellency (n-decane), it was wet (unmeasurable), and for liquid repellency (3-methoxybutyl acetate), it was 7°. Also, the "heat insulation rate" was 50%, the "surface temperature" was 59°C, the "solar reflectance" was 13.0% in the "near ultraviolet and visible light region (300 nm to 780 nm)" and 49.3% in the "near infrared region (780 nm to 2500 nm)". As described above, since the outer layer 13 of the protective material 1A contains an infrared reflecting agent, it can be expected to suppress the temperature rise inside the protective material 1A due to solar radiation.

[0051] The protective material 2A was formed by further forming a fluorine film 12 outside the outer layer 13 of the protective material 1A. For the fluorine film 12, a fluorine-based water and oil repellent was fixed to the outer layer 13 by the method described in FIG. 2. That is, a fluorine-based water and oil repellent with an apparent concentration of 7% was dropped onto the surface of the outer layer 13 at 20 cc / m 2 . Then, using a spatula L, the fluorine-based water and oil repellent was uniformly spread on the surface of the outer layer 13. Thereafter, heat treatment (for example, 170 degrees, 5 minutes) was performed to complete the fluorine film 12 (solid content adhesion amount 0.7 g / m 2 ). A fabric was laminated under the inner layer 11, and extremely high nitrile rubber was laminated under that. "θ: Contact angle (static)": For water repellency (water), it was 117°, for oil repellency (n-decane), it was 61°, and for liquid repellency (3-methoxybutyl acetate), it was 74°. "α: Sliding angle (dynamic)": For water repellency (water), it was 37°, for oil repellency (n-decane), it was 27°, and for liquid repellency (3-methoxybutyl acetate), it was 22°. Also, the "heat insulation rate" was 51%, the "surface temperature" was 58°C, the "solar reflectance" was 13.1% in the "near ultraviolet and visible light region (300 nm to 780 nm)" and 49.2% in the "near infrared region (780 nm to 2500 nm)". As described above, the protective material 2A contains an infrared reflective agent in the outer layer 13, and it can be expected to suppress the temperature rise inside the protective material 2A due to solar radiation.

[0052] For the protective material 1B, butyl rubber was used for the inner layer 11, and a coating material was knife-coated on the outside, dried, and heat-vulcanized to form the outer layer 13. The above coating material was mixed so that the mass ratio of butyl rubber:tetrapod-shaped ZnO:solvent (toluene) was 17.5:17.5:65, and further, as an infrared reflective agent, "SG-101" manufactured by Ishihara Sangyo Co., Ltd. composed of metal elements of titanium, manganese, and calcium was used at 10 wt% based on the solid content (butyl rubber and ZnO) of the above mixture. A fabric was laminated under the inner layer 11, and extremely high nitrile rubber was laminated under that. "θ: Contact angle (static)": The water repellency (water) was 145°, the oil repellency (n-decane) was wetting (not measurable), and the liquid repellency (3-methoxybutyl acetate) was wetting (not measurable). "α: Sliding angle (dynamic)": The water repellency (water) was 9°, the oil repellency (n-decane) was wetting (not measurable), and the liquid repellency (3-methoxybutyl acetate) was wetting (not measurable). Also, the "heat insulation rate" was 51%, the "surface temperature" was 58°C, and the "solar reflectance" was 13.2% in the "near ultraviolet and visible light region (300 nm to 780 nm)" and 49.1% in the "near infrared region (780 nm to 2500 nm)". As described above, since the protective material 1B contains tetrapod-shaped ZnO and an infrared reflecting agent in the outer layer 13, it is excellent in water repellency and it can be expected to suppress the temperature rise inside the protective material 1B due to solar radiation.

[0053] A fluorine film 12 was formed on the outside of the outer layer 13 of the protective material 1B. Regarding the fluorine film 12, a fluorine-based water and oil repellent treating agent was fixed to the outer layer 13 by the method described in FIG. 2. That is, a fluorine-based water and oil repellent treating agent with an apparent concentration of 7% was dropped onto the surface of the outer layer 13 at 20 cc / m 2 . Then, using a spatula L, the fluorine-based water and oil repellent treating agent was uniformly spread on the surface of the outer layer 13. Then, heat treatment (for example, 170 degrees, 5 minutes) was performed to complete the fluorine film 12 (solid content adhesion amount 0.7 g / m 2 ). A fabric was laminated under the inner layer 11, and extremely high nitrile rubber was laminated under that. "θ: Contact angle (static)": The water repellency (water) was 148°, the oil repellency (n-decane) was 81°, and the liquid repellency (3-methoxybutyl acetate) was 92°. "α: Sliding angle (dynamic)": The water repellency (water) was 7°, the oil repellency (n-decane) was 41°, and the liquid repellency (3-methoxybutyl acetate) was 34°. Also, the "heat insulation rate" was 51%, the "surface temperature" was 58°C, and the "solar reflectance" was 13.1% in the "near ultraviolet and visible light region (300 nm to 780 nm)" and 49.0% in the "near infrared region (780 nm to 2500 nm)". As described above, since the protective material 1C contains tetrapod-shaped ZnO and an infrared reflecting agent in the outer layer 13 and further has a fluorine film 12 formed thereon, it is expected to be excellent in water repellency and oil repellency and to suppress the temperature rise inside the protective material 1C due to solar radiation.

[0054] The protective material 1D was produced in the same manner as the protective material 1C, except that an infrared reflecting agent (manufactured by Ishihara Sangyo Co., Ltd., product number SG101) was mixed at 15 wt% based on the solid content of the mixture (butyl rubber and ZnO). "θ: Contact angle (static)": The water repellency (water) was 142°, the oil repellency (n-decane) was 82°, and the liquid repellency (3-methoxybutyl acetate) was 92°. "α: Sliding angle (dynamic)": The water repellency (water) was 7°, the oil repellency (n-decane) was 43°, and the liquid repellency (3-methoxybutyl acetate) was 33°. Also, the "heat insulation rate" was 54%, the "surface temperature" was 57°C, the "solar radiation reflectance" was 12.8% in the "near ultraviolet-visible light region (300 nm to 780 nm)" and 50.8% in the "near infrared region (780 nm to 2500 nm)". As described above, since the protective material 1D contains tetrapod-shaped ZnO and an infrared reflecting agent in the outer layer 13 and further has a fluorine film 12 formed thereon, it is expected to be excellent in water repellency and oil repellency and to suppress the temperature rise inside the protective material 1D due to solar radiation.

[0055] The protective material 1E was produced in the same manner as the protective material 1C, except that an infrared reflecting agent (manufactured by Ishihara Sangyo Co., Ltd., product number SG101) was mixed at 20 wt% based on the solid content of the mixture (butyl rubber and ZnO). "θ: Contact angle (static)": The water repellency (water) was 140°, the oil repellency (n-decane) was 80°, and the liquid repellency (3-methoxybutyl acetate) was 90°. "α: Sliding angle (dynamic)": The water repellency (water) was 9°, the oil repellency (n-decane) was 42°, and the liquid repellency (3-methoxybutyl acetate) was 35°. Also, the "heat insulation rate" was 53%, the "surface temperature" was 58°C, the "solar radiation reflectance" was 10.6% in the "near ultraviolet-visible light region (300 nm to 780 nm)" and 49.6% in the "near infrared region (780 nm to 2500 nm)". As described above, since the protective material 1E contains tetrapod-shaped ZnO and an infrared reflecting agent in the outer layer 13 and the fluorine film 12 is further formed, it is excellent in water repellency and oil repellency, and it can be expected to suppress the temperature rise inside the protective material 1D due to solar radiation.

[0056] For the protective material of Comparative Example 1, only butyl rubber was used for the inner layer 11 and the outer layer 13 was not formed. For "θ: contact angle (static)", the water repellency (water) was 99°, the oil repellency (n-decane) was wet (unmeasurable), and the liquid repellency (3-methoxybutyl acetate) was 34°. For "α: sliding angle (dynamic)", the water repellency (water) was 66°, the oil repellency (n-decane) was wet (unmeasurable), and the liquid repellency (3-methoxybutyl acetate) was 9°. Also, the "heat shielding rate" was 38%, the "surface temperature" was 65°C, the "solar radiation reflectance" was 7.9% in the "near ultraviolet and visible light region (300 nm to 780 nm)" and 6.5% in the "near infrared region (780 nm to 2500 nm)". As described above, in Comparative Example 1, since the outer layer 13 and the fluorine film 12 were not formed, the contact angle, sliding angle, heat shielding rate, surface temperature, and solar radiation reflectance (near infrared region) were inferior compared to the protective materials 1A to 1E and 2A.

[0057] In the evaluation of "θ: contact angle (static)" and "α: sliding angle (dynamic)", the protective materials 1C to 1E received higher evaluations than the evaluation of the protective material of Comparative Example 1. Therefore, it can be seen that the protective materials 1C to 1E are excellent in water repellency and oil repellency compared to Comparative Example 1. As a result, even if a harmful liquid or the like comes into contact with the outside of the protective materials 1C to 1E, it becomes difficult for the harmful liquid or the like to stop on the surface of the protective materials 1C to 1E, and it is possible to suppress the adhesion of harmful liquids or the like to the surface of the protective materials 1C to 1E.

[0058] Thereby, it becomes possible to reduce the labor required for the decontamination work of harmful liquids or the like adhering to the outside of the protective materials 1C to 1E. Also, since the water repellency and oil repellency performances are excellent, the protection performance is improved.

[0059] In addition, in the evaluation of the "heat insulation rate", "surface temperature", and "solar reflectance", the protective materials 1A to 1E and 2A received higher evaluations than the evaluation of Comparative Example 1. Therefore, it can be seen that the protective materials 1A to 1E and 2A have superior performance in solar radiation countermeasures compared to Comparative Example 1. As a result, it becomes possible to suppress the temperature rise inside the protective materials 1A to 1E and 2A.

[0060] Note that the protective materials of the examples can be used according to the required performance. For example, Examples 1A and 2A are not problematic as protective materials when a high level of liquid repellency is not required.

[0061] [Embodiment 2: Protective Clothing 100] With reference to FIG. 9, the configuration of the protective clothing 100 in this embodiment will be described. FIG. 9 is a front view showing the configuration of the protective clothing 100.

[0062] As a specific manufacturing method of the protective material of this protective clothing 100, first, a rubber sheet is laminated on both sides of the fabric (Step 1). Next, a coating containing concavo-convex shaped particles and an infrared reflector is applied to the outer rubber surface and dried (Step 2). Next, heat vulcanization is performed (Step 3). Finally, a fluorine film is formed (Step 4).

[0063] The outline of Step 1 is as follows. An adhesive rubber layer (not shown) made of the same rubber material as the rubber sheet is interposed between both sides of the fabric and bonded by vulcanization adhesion to obtain a laminated structure of the rubber sheet, the fabric, and the rubber sheet integrated with each other.

[0064] The outline of Step 2 is as follows. Examples of the coating method include kiss coating (gravure coating), knife coating, etc. As the coating material, a mixture is prepared such that the mass ratio of rubber:ZnO:solvent (toluene, ethyl acetate, etc.) is 10:10:80 to 25:25:50, and further, an infrared reflector (such as "SG-101" manufactured by Ishihara Sangyo Co., Ltd.) is contained in an amount of 5 to 30 wt%, preferably 15 to 20 wt%, based on the solid content (rubber and ZnO) of the above mixture.

[0065] In this way, by manufacturing the protective clothing 100, even if a harmful liquid or the like comes into contact with the surface (outer side) of the protective clothing 100, it becomes difficult for the harmful liquid or the like to stop on the surface of the protective clothing 100, and it is possible to suppress the adhesion of the harmful liquid or the like to the surface of the protective clothing 100. As the fabric, woven fabrics, knitted fabrics, non-woven fabrics, etc. can be used, but a woven fabric is preferable because the thickness of the rubberized cloth can be made thin and the strength can be made high. As the material, nylon, polyester, cotton, etc. can be used.

[0066] This makes it possible to reduce the labor required for decontamination work on harmful liquids or the like adhering to the surface of the protective material. In addition, since the water repellency performance is excellent, the protection performance is improved.

[0067] Furthermore, the decontamination work involved in the entry and exit of the wearer wearing the protective clothing 100 into and out of the contaminated inside and outside areas is reduced or becomes unnecessary, and it becomes possible to perform rapid reconnaissance and rescue activities in the contaminated inside and outside areas. Furthermore, it is also possible to avoid the risk of contamination spread during the reconnaissance activity. Furthermore, the treatment of the decontamination liquid generated during the decontamination work can also be made unnecessary. Furthermore, it is also possible to give the wearer a mental sense of security.

[0068] Furthermore, when the protective clothing 100 is used in a solar radiation environment, the surface temperature rise is small, and it is possible to reduce the heat stress of the wearer. Therefore, it is possible to contribute to improving the work efficiency of the wearer.

[0069] Note that, as an example of the protective clothing 100, a protective clothing having an upper garment, a lower garment, and a headscarf is given, but the protective material in the present disclosure can be widely applied to clothes and the like worn when entering and leaving an area contaminated with a harmful liquid or the like.

[0070] As a modified example of the protective clothing 100, there is a protective clothing that is the same as the manufacture of the protective clothing 100, but does not contain concavo-convex shape-imparting particles in the coating in step 2. As another modification example of the protective garment 100, there is a protective garment manufactured in the same manner as the manufacture of the protective garment 100, but not including the concavo-convex shaped particles in the coating in step 2 and not performing the fluorine coating in step 4. As yet another modification example of the protective garment 100, there is a protective garment manufactured in the same manner as the manufacture of the protective garment 100, but not performing the fluorine coating in step 4. These protective garments are used according to the required performance. For example, if high water repellency is not required even without the fluorine coating, there is no problem as a protective garment.

[0071] Furthermore, although an example of applying the protective material to a protective garment has been shown, the protective material of the present invention can also be applied to, for example, protective gloves, protective socks, protective hoods, protective covers, filters, protective tents, sleeping bags, etc. Further, it can be applied to storage bags for storing these items, etc. Also, it can be used as a sealing material such as packing or gasket for containers, devices, etc. having protective properties. The protective material of the present invention may be used as an outdoor heat insulating sheet. The outdoor heat insulating sheet can be used, for example, for outdoor tools, awning materials, tent materials, tarps, umbrellas, wrapping materials, bodies of automobiles, etc., building materials, clothing, sports, and outdoor supplies, etc.

[0072] The embodiments disclosed this time should be considered as illustrative in all respects and not restrictive. The scope of the present invention is shown not by the above description but by the claims, and it is intended that all modifications within the meaning and scope equivalent to the claims are included.

Explanation of Reference Numerals

[0073] 1 Protective material, 11 Rubber layer, 12 Fluorine coating, 13 Outer layer, 100 Protective garment

Claims

1. A protective material having an inner side and an outer side, comprising: an inner layer located on the inner side; an outer layer laminated on the inner layer and located on the outer side; wherein the inner layer includes a rubber layer; the outer layer contains an infrared reflective agent, the protective material.

2. The protective material according to claim 1, wherein the outer layer contains a fluorine-based water and oil repellent.

3. The protective material according to claim 2, wherein the outer layer contains particles for imparting an uneven shape.

4. The protective material according to claim 2, wherein the outer layer contains the infrared reflective agent in the same kind of rubber as the rubber of the rubber layer, and the fluorine-based water and oil repellent forms a fluorine film.

5. The protective material according to claim 3, wherein the shape of the particles for imparting an uneven shape is a tetra-pot shape, a needle shape, a polygonal shape, or a spherical shape.

6. The protective material according to claim 3, wherein the particles for imparting an uneven shape are tetra-pot type zinc oxide.

7. On the surface of the inner layer opposite to the surface on which the outer layer is laminated, a fabric and a second rubber layer are laminated in the order described, the protective material according to claim 1.

8. The protective material according to claim 7, wherein the fabric is a woven fabric, a knitted fabric, or a non-woven fabric.

9. The protective material according to claim 7, wherein different types of rubber are used for the rubber layer and the second rubber layer.

10. The protective material according to claim 3, wherein the particles for imparting an uneven shape are contained in an amount of 40 wt% to 60 wt% with respect to the solid content excluding the infrared reflective agent in the total solid content of the outer layer.

11. The infrared reflective agent is a pigment containing at least one kind of metal element of titanium, manganese, calcium, iron, bismuth, chromium, and nickel, and the infrared reflective agent is contained in an amount of 5 wt% to 30 wt% with respect to the solid content excluding the infrared reflective agent in the total solid content of the outer layer, the protective material according to claim 1.

12. The average particle diameter of the infrared reflective agent is 600 nm or more and 1500 nm or less, the protective material according to claim 1.

13. A protective clothing using the protective material according to any one of claims 1 to 12.

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