JP4921198B2 - Protective material and protective clothing using the same - Google Patents

Description

  The present invention relates to protective materials and protective clothing for protecting workers handling hazardous chemical substances. Specifically, protective materials and protective clothing that can effectively protect workers from gaseous and liquid organic chemicals that are absorbed from the skin and are harmful to the human body, such as organophosphorus compounds, and are lightweight, and The present invention relates to a protective material for clothes and protective clothing, which can suppress heat stress of the wearer due to high moisture permeability and has excellent washing durability.

  Conventionally, various protective clothing that protects the human body from harmful chemical substances has been proposed (see Patent Document 1). For example, there is a material made of a material that does not allow permeation of harmful chemical substances, such as a rubber cloth, and has excellent protection performance. However, in this case, since the material (fabric) is heavy, handling and workability are poor, and if it is made into clothes, there is no breathability and moisture permeability, so it is used for work in extreme heat or harsh physical work environment. Workers are subjected to a great deal of heat stress and are at risk of serious health problems.

  On the other hand, a protective laminated fabric made of an adsorbent material such as activated carbon is disclosed (for example, Patent Document 2). When the concentration of harmful chemical substances in the environment is high, the adsorption performance due to the gas adsorbing substance approaches a saturated state in a relatively short time and the protective performance decreases. Can effectively release sweat and water vapor emanating from the body and suppress thermal stress, but in order to maintain the protective performance for a long time, a relatively large amount of adsorbent material is required, As a result, the mass of the protective material and protective clothing increases, which causes heat stress.

  Further, a protective material having selective permeability due to a cellulose-based polymer is known (for example, Patent Document 3). Such a polymer has a permeation suppressing ability and a moisture permeation performance for gaseous organic chemicals. However, in the case of a protective material made of the polymer alone, it may be bent, worn, scratched, or used as protective clothing. Once permeation of gas occurs due to deterioration of the permselective layer due to bending or the like received by washing, there is a risk that the concentration of the permeating gas rapidly increases. Therefore, if the thickness of the permselective layer is increased in order to reduce deterioration such as bending, abrasion, and scratches, the flexibility is low and the material becomes heavy and cannot be a desired protective material or protective clothing.

JP-A-9-651 Japanese Unexamined Patent Publication No. 57-156036 Japanese National Patent Publication No. 11-505775

  The present invention has been made against the background of the problems of the prior art, and is a protective material that has high protection against gaseous organic chemicals and liquid organic chemicals, is lightweight and flexible, and has excellent handling properties. In addition, when it is used as a garment, it is lightweight, flexible and highly breathable so as to suppress the heat stress of the wearer. To provide clothes.

As a result of intensive studies to solve the above problems, the present invention has been completed. That is, the present invention is as follows.
1. A protective material having at least one gas adsorption layer and at least one protective film layer described below, and having at least one protective film layer disposed on the outer layer side of the gas adsorption layer.
1. Protective membrane layer: a layer in which a moisture permeable membrane layer containing a moisture permeable adhesive is laminated on both surfaces of a permselective layer having organic chemical permeation inhibiting properties and water vapor permeability. 2. The protective material according to 1 above, wherein the permselective layer is composed of cellulose or a cellulose derivative.
3. 3. The protective material according to any one of 1 to 2 above, wherein the moisture permeable membrane layer constituting material is a material containing moisture permeable polyurethane.
4). 4. The protective material according to any one of 1 to 3, wherein the moisture-permeable adhesive constituting material is a material containing curable moisture-permeable polyurethane.
5. 5. The protective material according to any one of 1 to 4 above, wherein the moisture permeable membrane layer constituting material is a material in which 5% by mass or more of a curable moisture permeable polyurethane adhesive is mixed with moisture permeable polyurethane.
6). 6. The protective material according to any one of 1 to 5 above, wherein a protective film protective layer is laminated on at least one side of the protective film layer.
7). The protective material for clothes according to any one of 1 to 6, wherein the moisture permeability of the protective film layer is 50 to 625 g / m ² · h.
8). The protective material for clothes according to any one of 1 to 7 above, wherein the permselective layer has a moisture permeability of 60 to 850 g / m ² · h.
9. 9. A protective garment formed by sewing using the protective material according to any one of 1 to 8 above, wherein the seam is sealed with a resin that inhibits permeation of organic chemicals.

  When the above-mentioned protective material is further used as a garment, it is more preferable that an outer layer additional layer is provided in the outermost layer (outer layer when the garment is used as a garment) and an inner layer additional layer is provided in the innermost layer.

  The protective material having the protective film layer of the present invention and the protective garment formed by the protective material can protect the wearer from invasion of organic chemical substances caused by bending, wear, scratches, etc. that occur during use. . Moreover, since the durability of the permselective layer is improved, it is lightweight, flexible, and has high moisture permeability, it has the effect of suppressing thermal stress when it is made into clothes. Since the moisture permeable membrane layer has a curable moisture permeable adhesive, it will remain at the interface between the selectively permeable layer and the moisture permeable membrane layer even when exposed to liquid organic chemicals such as water and sweat for a long time or when washed. The effect that peeling does not occur is obtained.

  Furthermore, since the protective material of the present invention and the protective clothing formed of the protective material use a nonporous or microporous film or coating as the protective film layer, liquid harmful chemical substances or harmful substances are used. Excellent protection against aerosols such as fine dust, bacteria and viruses.

  The protective film protective layer preferably provided on at least one side of the protective material has an effect of protecting the protective film layer from a mechanical force applied from the outside and supplementing the mechanical strength. Furthermore, it is preferable to provide the outer layer addition layer and the inner layer addition layer, which are preferably provided on the outermost layer of the protective material, as well as the effect of protecting the protective film layer from the mechanical force applied from the outside, and in the case of clothing. Also has the effect of suppressing the sticky feeling of sweaters wearing sweat.

Hereinafter, the present invention will be described in detail.
As a material constituting the permselective layer, a material having moisture permeability after film formation and a permselectivity capable of suppressing permeation to organic chemical substances can be used without limitation. Specifically, cellulose, cellulose Derivatives, regenerated cellulose, ethylene-vinyl alcohol copolymer (EVA), polyvinyl alcohol, polyacrylate, polyacrylonitrile, polyamide, polyamideimide, polyurethane, polyester, copolymer polyester, polyolefin, and other polymers having film-forming performance are exemplified. Is done. These materials may be used alone or in combination of two or more. The film may be a single layer or may be formed by laminating two or more kinds.

  As the selective permeation layer constituting material, among the above-mentioned polymers, cellulose derivatives, regenerated cellulose or polyvinyl alcohol are excellent in balance between organic chemical permeation suppression and moisture permeability, more preferably cellulose diacetate, Particularly preferred is at least one selected from cellulose triacetate and regenerated cellulose (cellophane). The organic chemicals mentioned here are compounds that have one or more carbon elements. Toluene, methylene chloride, chloroform used for organic phosphorus compounds used in agricultural chemicals, insecticides, herbicides, and painting operations. General organic solvents such as are exemplified.

  The degree of acetylation of the cellulose derivative is 50% or more, preferably 55% or more. If it is less than 50%, effective permeation suppression may not be obtained depending on the target gaseous organic chemical.

The 6% viscosity, which is an index of the degree of polymerization of the cellulose derivative, is 50 × 10 ⁻³ Pa · s or more and 275 × 10 ⁻³ Pa · s or less, preferably 70 × 10 ⁻³ Pa · s or more and 140 × 10 ⁻³ Pa. -It is preferable that it is below s. If it is 50 × 10 ⁻³ Pa · s or less, effective permeation suppression ability for gaseous organic chemicals cannot be obtained, and if it is 275 × 10 ⁻³ or more, the material becomes stiff and unsuitable for clothing.

  The permselective layer composed of at least one selected from cellulose derivatives or regenerated cellulose preferably contains 60% by mass or more, more preferably 80% by mass or more of a cellulose polymer such as cellulose derivative or regenerated cellulose. When the content of the cellulose polymer is less than 60% by mass, it is impossible to obtain a highly moisture permeable material while maintaining the permeation suppressing property to the organic chemical substance. By blending a cellulosic polymer with a flexible polymer having resistance to permeation of, for example, gas and water vapor in the material of the above-described selective permeation layer, it is more flexible while maintaining the moisture permeability and permeation suppression ability of the permselective layer. A selective permeation layer can be produced. Examples of such a flexible polymer include polyvinyl alcohol, ethylene-vinyl alcohol copolymer (EVA), polyurethane, polyethylene terephthalate, and the like. Moreover, the softness | flexibility of a permselective layer can also be improved by adding a plasticizer to a polymer as needed. Such plasticizers include triethyl citrate, diaryl phthalate, dimethyl phthalate, diethyl phthalate, triethylene glycol, and the like.

  By blending an isocyanate compound with a cellulosic polymer, it is possible to increase adhesion with the moisture permeable membrane layer and suppress peeling at the interface. The addition amount is preferably 1% by mass or more and less than 10% by mass, and more preferably 2% by mass or more and less than 5% by mass. This is because if the amount is 10% by mass or more, the permeation suppression property for the organic chemical substance cannot be maintained.

  As a method for forming a permselective layer from a polymer, a method of once forming a polymer film by a casting method (casting method), an extrusion method, an injection molding method, a melt blown method, a flash spinning method, an electrospinning method, etc. A method of preparing a fine fiber nonwoven fabric by the above, then heat calendering it into a film, a method of drying or polymerizing and solidifying the polymer solution or reactive low polymer by coating on a moisture permeable membrane layer Can be mentioned.

  The thickness of the selectively permeable layer used in the present invention is preferably 3 μm or more and 100 μm or less, and more preferably 5 μm or more and 70 μm or less. If the thickness of the permselective layer is less than 3 μm, the protection against organic chemicals cannot be satisfied and sufficient strength cannot be obtained. When the thickness of the selectively permeable layer exceeds 100 μm, the moisture permeability decreases, and the material becomes stiff and the mass becomes heavy.

The mass of the selectively permeable layer is preferably 100 g / m ² or less, and more preferably 70 g / m ² or less. When the mass of the selectively permeable membrane layer exceeds 100 g / m ² , it cannot be a lightweight protective material that is the object of the present invention. The lower limit of the basis weight of the selectively permeable layer is not particularly limited as long as the above requirements for moisture permeability and gas permeability are satisfied, but is usually 5 g / m ² or more.

Moisture permeability of the permselective layer is preferably, more preferably 80g / ^{m 2} · h or more 750g / ^{m 2} · h or less or less 60g / ^{m 2} · h or more 850g / ^{m 2} · h. When the moisture permeability of the permselective layer is less than 60 g / m ² · h, when used as clothes, sweat and vapor emitted from the wearer cannot be effectively released to the outside, and exceeds 850 g / m ² · h. And the permeation suppression property to organic chemicals cannot be maintained.

  The permeation suppression property of the organic chemical substance in the permselective layer may be any permeation suppression property that can be practically used to protect the organic chemical substance as a protective material, but as shown in FIG. In the organic chemical substance permeability test, it is preferable that the organic chemical substance has a permeation suppressing property to such an extent that the organic chemical substance cannot be detected.

  The constituent material of the moisture permeable membrane layer for protecting the selectively permeable layer is not particularly limited as long as it is a moisture permeable material, but moisture permeable polyurethane is most preferable in terms of moisture permeability, flexibility, and workability. .

  As a method for forming a moisture permeable membrane layer for protecting the permselective layer, a polymer solution or a reactive low polymer is applied to the permselective layer by coating or the like, and then dried or polymerized, or a separately manufactured permeation layer. There is a method of adhering the wet film by a laminating method that prevents deterioration of moisture permeability and maintains the flexibility of the material, but the coating method is more preferable in terms of moisture permeability, flexibility, mass, and workability.

When laminating a moisture permeable membrane layer on the selectively permeable layer, in order to increase the peel strength at the interface between the two materials, a curable moisture permeable adhesive is used as the moisture permeable membrane layer constituting material. It is an effective means to contain 5 mass% or more with respect to it. If the content of the curable moisture-permeable adhesive is less than 5% by mass, sufficient adhesive strength cannot be obtained.
The curable moisture-permeable adhesive is not particularly limited as long as it is a material capable of obtaining moisture permeability, but polyurethane is most preferable in terms of moisture permeability, flexibility, and processability.
Note that the moisture permeability of the adhesive may be moisture permeability that does not inhibit the moisture permeability of the selectively permeable layer and the moisture permeable membrane layer, and is at least 60 g / m ² · h, more preferably 100 g / m ² · h. That's all you need.

  In addition, in order to increase the peel strength at the interface between the two materials, the polymer used in the selective permeable layer as the material to be the moisture permeable membrane layer is in a proportion of 5% by mass to 50% by mass with respect to the moisture permeable membrane layer constituting material. Mixing is also an effective means. When the mixing ratio of the polymer used in the permselective layer is less than 5% by mass, interfacial peeling is likely to occur, and when it exceeds 50% by mass, the moisture permeability of the moisture permeable membrane layer is reduced. Moreover, you may add the raw material used for a moisture-permeable membrane layer to the raw material used as a permselective layer.

The moisture permeability of the moisture permeable membrane layer is preferably 200 g / m ² · h or more, and more preferably 250 g / m ² · h or more. This is because when the moisture permeability of the moisture permeable membrane layer is less than 200 g / m ² · h, the moisture permeability of the protective membrane layer is lowered.

  Moreover, in order to maintain moisture permeability and to make a lightweight and flexible protective material, the thickness of the moisture permeable membrane layer is preferably 3 μm or more and 50 μm or less. When the thickness of the moisture permeable membrane layer is less than 3 μm, the durability of the moisture permeable membrane layer is insufficient, and bending, wear and the like are insufficient. Moreover, it is because the mass of the whole film | membrane becomes large when the film thickness exceeds 50 micrometers.

  Examples of the gas adsorbing substance in the gas adsorption layer used for the protective material of the present invention include carbon-based adsorbents such as activated carbon and carbon black, or inorganic adsorbents such as silica gel, zeolite-based adsorbent, silicon carbide, and activated alumina. It can select suitably according to the to-be-adsorbed substance made into object. Among them, activated carbon capable of dealing with a wide range of gases is preferable, and fibrous activated carbon is more preferable because it has a large adsorption rate and adsorption capacity and can effectively prevent permeation when used in a small amount.

The BET specific surface area of the activated carbon is preferably 700 m ² / g or more and 3000 m ² / g or less, and more preferably 1000 m ² / g or more and 2500 m ² / g or less in order to obtain sufficient permeation suppression ability with a small amount of use. If the BET specific surface area is less than 700 m ² / g, a large amount of activated carbon is required to obtain sufficient protection, and the protective material becomes heavy. On the other hand, if it exceeds 3000 m ² / g, a problem of desorbing the adsorbed organic chemical substance occurs.

The absolute dry mass of the activated carbon is preferably 5 g / m ² or more and 100 g / m ² or less, more preferably 10 g / m ² or more and 50 g / m ² or less. If it is less than 5 g / m ² , the capacity that can be adsorbed becomes small, and the use time is limited. On the other hand, if it exceeds 100 g / m ² , the protective material becomes heavy and causes heat stress.

  The method of using fibrous activated carbon in order to obtain effective permeation suppression ability with a small amount of use is an effective means, but the raw material of fibrous activated carbon used at that time is natural cellulose fibers such as cotton and hemp Other examples include regenerated cellulose fibers such as rayon, polynosic, and solvent spinning, and synthetic fibers such as polyvinyl alcohol fibers, acrylic fibers, aromatic polyamide fibers, lignin fibers, phenol fibers, and petroleum pitch fibers. From the physical properties (strength etc.) and adsorption performance of the fibrous activated carbon obtained, regenerated cellulose fibers, phenolic fibers and acrylic fibers are preferred. After weaving, knitting, and nonwoven fabric using these short fibers or long fibers of the raw material fibers and containing an appropriate flameproofing agent as necessary, flameproofing treatment is performed at a temperature of 450 ° C. or lower, Subsequently, fibrous activated carbon can be manufactured by the well-known method of activating carbonization at the temperature of 500 degreeC or more and 1000 degrees C or less.

  As a method for forming a gas-adsorbing substance such as fibrous activated carbon into a sheet, a wet paper machine is a method in which a gas-adsorbing substance is adhered to a sheet base material with a binder, or the adsorbent is made into a slurry including an appropriate pulp and binder. An adsorbent sheet can be obtained by a method of making paper or a known method of carbonizing and activating the raw material fibers of activated carbon fibers in advance by weaving, knitting, or non-woven fabric, and flame-proofing as necessary.

  Therefore, as the form of the fibrous activated carbon sheet, woven, knitted, non-woven, felt, paper, film, etc. can be mentioned, but when it is in the form of clothes, exercise workability when worn, fit to the body From the viewpoint of property, flexibility, and ease of lamination, it is preferably a woven fabric or a knitted fabric.

  The following methods can be used as a means for laminating the protective film layer and the gas adsorption layer. As a first method, a sheet-like, granular, or powdery gas-adsorbing substance is bonded to the protective film layer with an adhesive. As a second method, there is a method in which either the protective film layer or the gas adsorption layer is prepared in advance and then the other is coated or dipped. The third method can also be made by sewing together without bonding. Lamination is possible without using an adhesive or the like, and lamination is preferably performed by the third method from the viewpoint of not reducing the adsorption capacity of the gas adsorption layer.

  Examples of the adhesive used include urethane-based, vinyl alcohol-based, ester-based, epoxy-based, vinyl chloride-based, and olefin-based adhesives. In order to suppress a decrease in moisture permeability due to lamination, the adhesive is a moisture-permeable adhesive. Urethane, vinyl alcohol, and ester are preferred.

  The melt index (MFR) of the adhesive to be used is 100 g / 10 min or less, preferably 80 g / 10 min or less. By using an adhesive of 100 g / 10 min or less, the area covering the surface of the gas adsorbing substance can be reduced, and a decrease in gas adsorption performance can be suppressed.

  At least one protective film layer and one gas adsorption layer are required, but for the purpose of increasing flexibility and when there are multiple target gases, select the required number of protective film layers and gas adsorption layers. It is an effective means to use in a superimposed manner.

  As the stacking order of the protective film layer and the gas adsorption layer, it is preferable that there is at least one protective film layer on the outer layer side of the gas adsorption layer in consideration of the life of the gas adsorption layer. When a plurality of protective film layers are used, a structure may be adopted in which the gas adsorption layer is sandwiched between the protective film layers in order to protect the gas adsorption layer.

The total mass obtained by adding the masses of the protective film layer and the gas adsorption layer is preferably 300 g / m ² or less, more preferably 250 g / m ² or less. When it exceeds 300 g / m ² , the handleability of the material is impaired, and when it is used as a garment, the load on the wearer is increased.

  FIG. 1 is a schematic cross-sectional view showing an example of a protective material including the protective film layer of the present invention as a laminate. The protective membrane layer 9 is formed by laminating moisture permeable membrane layers 2 and 4 on both surfaces of the selective permeable layer 3, the protective membrane protective layer 1 is laminated outside the protective membrane layer 9, and the gas adsorption layer 5 and A protective material 10 is configured by laminating inner layer additional layers 6.

  FIG. 2 is a schematic cross-sectional view showing an example of a protective material including the protective film layer of the present invention as a laminate. The protective membrane layer 9 is formed by laminating moisture permeable membrane layers 2 and 4 on both surfaces of the selectively permeable layer 3, and the protective membrane protective layer 1 is laminated outside the protective membrane layer 9 to form a protective material 10. The outer layer additional layer 8 is laminated on the outermost side, and the quilted layers of the gas adsorbing layer 5 and the inner layer additional layer 6 are laminated on the innermost side to constitute the protective material 11 for clothes.

  The purpose of the protective film protective layer is to protect the protective film layer from mechanical force applied from the outside and to supplement the mechanical strength. When the spray test described in JIS L1092 6.2 is performed, A woven fabric, knitted fabric, or non-woven fabric having a water degree of 4 or more and an oil repellency of AATCC Test Method 118 of 4 or more can be suitably used, but it is recommended to use one considering flexibility.

  When laminating the protective film layer and the protective film protective layer with an adhesive, examples of the adhesive used include urethane, vinyl alcohol, ester, epoxy, vinyl chloride, and olefin. In order to suppress the decrease in wettability, it is preferable to use a moisture-permeable adhesive such as urethane, vinyl alcohol, or ester.

  The melt index (MFR) of the adhesive used is preferably 100 g / 10 min or less, more preferably 80 g / 10 min or less. By using an adhesive having an MFR of 100 g / 10 min or less, the area covering the surface of the protective film layer is reduced, and a decrease in moisture permeability can be suppressed.

  The purpose of the outer layer additional layer is to protect the protective film layer from mechanical force applied from the outside. When the spray test described in JIS L1092 6.2 is performed, the water repellency is 4 or more, and AATCC Test. A woven fabric, a knitted fabric, or a nonwoven fabric having an oil repellency by Method 118 of 4th grade or higher can be suitably used, but it is recommended to use one considering flexibility.

  The protective material and the outer layer additional layer may be pre-adhered with an adhesive. In consideration of moisture permeability and flexibility, the protective material and the outer layer are sewn in a stacked state without bonding, and the protective clothing is made in the shape of a flash. You may use for. With this method, it is possible to laminate the protective material and the outer layer additional layer without using an adhesive or the like, and this lamination method is also used because the moisture permeability and flexibility of the protective material for clothing after lamination are not lowered. preferable.

Examples of the inner layer additional layer include materials such as a woven fabric, a knitted fabric, a nonwoven fabric, and an apertured film, but a woven fabric or a knitted fabric woven or knitted at a coarse density is preferable in terms of moisture permeability and flexibility.
The purpose of the inner layer additional layer is to protect the protective film layer from mechanical force applied from the outside and to suppress the feeling of stickiness caused by sweat of the wearer of the protective clothing.

  When the protective material, outer layer additional layer and inner layer additional layer are laminated with an adhesive, examples of the adhesive used include urethane, vinyl alcohol, ester, epoxy, vinyl chloride, and olefin. In order to suppress a decrease in moisture permeability due to the use of urethane, vinyl alcohol and ester which are moisture permeable adhesives are preferred.

  Further, the melt index (MFR) of the adhesive used is preferably 100 g / 10 min or less, and more preferably 80 g / 10 min or less. By using an adhesive having an MFR of 100 g / 10 min or less, the area covering the surface of the protective film layer is reduced, and a decrease in moisture permeability can be suppressed.

The mass of the laminate provided with at least one of the outer layer additional layer and the inner layer additional layer is preferably 350 g / m ² or less. When the mass of the laminated body exceeds 350 g / m ² , the mass of the protective garment becomes large, which causes thermal stress.

  When using the protective material described above to make protective clothing, it prevents the penetration of gaseous and liquid chemical substances from the seams and the entry of harmful fine dust, bacteria, viruses and other aerosols, and is also breathable and flexible. From the viewpoint of considering the performance, it is preferable to perform sewing by flash stitching, and it is more preferable to seal the seam in order to prevent penetration from the seam.

In the sealing process, the seam portion is covered with a resin that has a permeation suppressing property particularly for gaseous and liquid chemical substances, and is sealed. As a material used for processing, a solution of a resin having a permeation suppression property, a permeation-inhibiting and adhesive resin film, a seal tape using a permeation suppression resin film, and the like can be used. As the sealing tape, one having two or more layers including a gas permeation suppressing layer and an adhesive layer can be used. As the resin for the adhesive layer, a hot melt resin, a low temperature (150 ° C. or lower) curable adhesive, or a moisture curable adhesive is used. The adhesive can be used. In consideration of processability and peel resistance of the seal tape after processing, it is more preferable to use a curable adhesive. The type of the resin is not particularly limited as long as the seam can be sealed, but a polyurethane resin is preferable in terms of flexibility, adhesiveness, and moisture permeability, and among the polyurethane resins, a curable resin is preferable.
As the sealing method, a method of laminating after applying an adhesive to the seam portion can be adopted. However, a method of using a film or tape prepared in advance with the resin as a sealing material is preferable in terms of workability.

  In addition, when making protective clothing, the protective clothing upper garment, trousers, hood, protective mask, gloves, shoes, socks, etc., the shape of the protective clothing upper garment, trousers and hood integrated into one piece, protective clothing outer garment 2 pieces made of hood and hood, 2 pieces made of protective clothing and hood, 2 pieces made of trousers, protective clothing, trousers, 3 pieces made of hood, etc. It is necessary to have a design that considers airtightness that prevents entry from the joint.

  The weight of the protective clothing is preferably 3 kg or less. If it exceeds 3 kg, the burden at the time of wearing becomes large, which causes heat stress.

EXAMPLES Next, although this invention is demonstrated concretely using an Example and a comparative example, this invention is not restrict | limited by these Examples. The evaluation described in the examples is based on the method described below.
<Organic chemical substance permeability test>
A container diagram used in the test is shown in FIG. A test article 23 is sandwiched between two glass cells 21 and 22 having an internal volume of 150 cc, and the periphery is sealed with paraffin 24. 30 μL of a test solution (3-methoxybutyl acetate) 25 is dropped on the test product 23 from the upper cell 21 of the test container. This is put in a constant temperature box set at 25 ± 2 ° C., the gas concentration on the lower cell 22 side is sampled from the sampling port 26 at regular intervals, and the gas concentration permeated through the test article 23 is measured by gas chromatography.
<Moisture permeability>
Measured according to JIS L1099 4.1.1 calcium chloride method.
<mass>
It was measured according to JIS L1018 8.4 and JIS L1096 8.4.
<thickness>
It was measured according to JIS L1018 8.5 and JIS L1096 8.5.
<Peel test>
The protective material was immersed in the water of a beaker, and the peeling state of the interface between the selectively permeable membrane layer and the moisture permeable membrane layer after stirring with a 24 hr stirrer was visually observed.
<Flexibility>
It was measured according to JIS L1096 8.19.
<A feeling of wearing>
Heart rate, blood pressure, skin temperature, rectal temperature, inside clothes after walking on a treadmill at a speed of 5 km / h for 10 minutes in a constant temperature and humidity chamber at 32 ° C and 70% RH, wearing one-piece protective clothing A comprehensive evaluation was performed based on the measurement results of temperature and humidity and the questionnaire survey results.
<Laundry test>
The state of peeling at the interface when the JIS L1096 G method was washed 10 times was visually observed.

[Production example]
(Example of protective film layer production)
The protective film layer was produced by the following method. As a moisture permeable membrane layer, a moisture permeable polyurethane resin having a solid content of 10% by mass (Samprene HMP17A manufactured by Sanyo Chemical Industries, Ltd.), cellulose acetate having a solid content of 10% by mass (Daicel Chemical Industries, Ltd. L-30), and a solid content of 30%. The dope solution mixed so that the mass mixing ratio of the mass% curable moisture-permeable polyurethane resin (Sanpuren LQ120 manufactured by Sanyo Chemical Industries, Ltd.) was 50:25:25 was used. This dope solution was cast on a release paper (manufactured by Lintec Corporation), applied while adjusting the film thickness with a coater, and dried with a hot air dryer at 100 ° C. The permselective layer uses cellulose acetate having a degree of acetylation of 55% and a viscosity of 70% 10 ⁻³ Pa · s (Daicel Chemical Industries, Ltd. L-30) as described above, and the solvent is methyl ethyl ketone and N, N dimethyl. A 50:50 (mass ratio) mixed solvent of formamide was used, and a cellulose acetate solution was prepared by mixing and stirring at room temperature so that the solid content concentration was 10% by mass. This solution was cast on the moisture permeable membrane layer prepared above, applied while adjusting the film thickness with a coater, and dried with a 130 ° C. hot air dryer. Then, the protective membrane layer was produced by producing the moisture permeable membrane layer again on the obtained laminated body of the moisture permeable membrane layer and the selective permeable layer by the same method as described above. The thickness of the produced protective membrane layer was 25 μm (the moisture permeable membrane layer was 5 μm each, the selectively permeable membrane layer was 15 μm), the mass was 34 g / m ² , and the moisture permeability was 169 g / m ² · h.

(Production example of gas adsorption layer)
A fibrous activated carbon fabric was produced as a gas adsorption layer by the following method. Single yarn 2.2 decitex 20th novolak phenol resin fiber spun yarn with a mass of 80 g / m ² is heated in an inert atmosphere at 400 ° C. for 30 minutes and then inerted to 870 ° C. for 20 minutes. It heated in atmosphere, carbonization was advanced, and it activated at the temperature of 870 degreeC in the atmosphere which contains water vapor | steam 12 volume% for 2 hours. The mass of the obtained woven fibrous activated carbon was 47 g / m ² , specific surface area 1430 m ² / g, thickness 0.40 mm, and air permeability was 52 cm ³ / cm ² · s with a pressure difference of 1.27 cm in water level. The water repellency was 5, and the oil repellency was grade 6.

(External layer additional layer production example)
The outer layer additional layer was produced by the following method. A plain woven fabric using 40 yarns of cotton yarn was subjected to fluorine-based water and oil repellency treatment, and 0.54% by mass was adhered as a resin solid content. The obtained woven fabric has a thickness of 0.30 mm, a mass of 118 g / m ² , a bending resistance of 0.56 gf · cm, and an air permeability of 80 cm ³ / cm ² · s with a water level gauge of 1.27 cm. The degree was 5 and the oil repellency was grade 6.

(Inner layer additional layer production example)
The inner layer additional layer was produced by the following method. Polyester filaments (33 dtex, 18 filaments) are knitted with a 2-0 / 1-3 structure using a half tricot machine, then scoured by a regular method, dyed with a disperse dye, and water- and oil-repellent with a fluorine-based processing agent. Processed. The knitted fabric thus obtained has a thickness of 0.20 mm, a mass of 44 g / m ² , and an air permeability of 700 cm ³ / cm ² · s with a water level gauge of 1.27 cm, water repellency of 5, oil repellency It was 6th grade.

[Example 1]
To the protective film layer obtained in the above production example, 40 g / m ² of ester taffeta (EL2244 manufactured by Toyobo Co., Ltd.) was bonded as a protective film protective layer with a basis weight of 10 g / m ² and a breathable non-woven hot melt adhesive. Next, the gas adsorption layer was laminated on the protective film layer side of the material to obtain a protective material. The mass of the protective material was 145 g / m ² , the thickness was 0.60 mm, and the moisture permeability was 155 g / m ² · h. Table 1 shows the results of organic chemical permeability tests using this protective material. In addition, Table 2 shows the peel test results of this protective material.

[Example 2]
Recycled cellulose film (P-5 manufactured by Phthamura Chemical Co., Ltd.) having a mass of 28 g / m ² and a thickness of 19 μm is used as the selectively permeable membrane layer, and the moisture permeable polyurethane resin having a solid content of 10% by mass is used as the moisture permeable membrane layer. Dope mixed so that the mass mixing ratio of Sanprene Chemical Co., Ltd. (Samprene HMP17A) and solid content 30% by mass of curable moisture-permeable polyurethane resin (Sanyo Kasei Kogyo Co., Ltd., Samprene LQ120) is 75:25. The solution was used. This dope solution was cast on a regenerated cellulose film, applied while adjusting the film thickness with a coater, and dried with a hot air dryer at 100 ° C. This operation was repeated on both surfaces of the permselective membrane to form a protective membrane layer.
A protective material was produced in the same manner as in Example 1 using the protective film layer. The mass of the obtained protective material was 158 g / m ² , thickness 0.61 mm, and moisture permeability 148 g / m ² · h. Table 1 shows the results of organic chemical permeability tests using this protective material. In addition, Table 2 shows the peel test results of this protective material.

[Comparative Example 1]
In the above (protective membrane layer production example), the moisture permeable membrane layer has a moisture permeable polyurethane resin having a solid content of 10% by mass (Samprene HMP17A manufactured by Sanyo Chemical Industries, Ltd.) and cellulose acetate having a solid content of 10% by mass (Daicel Chemical Industries ( A protective film layer was prepared in the same manner except that the dope solution mixed so that the mass mixing ratio of L-30) was 75:25 was used, and the protective film layer was used, as in Example 1. Thus, a protective material was produced. The obtained protective material had a mass of 147 g / m ² , a thickness of 0.60 mm, and a moisture permeability of 157 g / m ² · h. Table 1 shows the results of organic chemical permeability tests using this protective material. In addition, Table 2 shows the peel test results of this protective material.

[Comparative Example 2]
A protective membrane layer was prepared in the same manner as described above (Example of production of protective membrane layer) except that a moisture-permeable polyurethane resin (Samprene HMP17A manufactured by Sanyo Chemical Industries, Ltd.) was used as the selective permeable layer constituting material. A protective material was prepared in the same manner as in Example 1 using The obtained protective material had a mass of 144 g / m ² , a film thickness of 0.60 mm, and a moisture permeability of 168 g / m ² · h. Table 1 shows the results of organic chemical permeability tests using this protective material. In addition, Table 2 shows the peel test results of this protective material.

  According to the results in Tables 1 and 2 above, Examples 1 and 2 are suitable protective materials with excellent organic chemical permeation suppression and adhesion of the protective film layer, while Comparative Example 1 is peeled off. The result was low adhesion in the test. As for Comparative Example 2, the permselectivity of the permselective layer was insufficient, and it was not sufficient for the purpose of the present invention.

Example 3
A melt blown non-woven fabric made of polybutylene terephthalate having a mass of 40 g / m ² and a thickness of 0.34 mm (manufactured by Tapirs Co., Ltd.) as a protective film protective layer obtained in the above production example is a hot melt type urethane. A protective material was prepared by bonding with an adhesive. Further, the inner layer additional layer and the gas adsorbing layer are quilted to form an integrated product, and the protective material is disposed between the integrated product and the outer layer additional layer with the protective film protective layer on the outside without bonding. A protective material was obtained. The mass of the protective material for clothes was 312 g / m ² , thickness 1.30 mm, and moisture permeability 115 g / m ² · h. Table 3 shows the organic chemical permeability test results using this protective material. Table 4 shows the results of the washing test of the protective material for clothes and the feeling of wearing the protective clothing formed of the protective material.

Example 4
Recycled cellulose film (P-5 manufactured by Phthamura Chemical Co., Ltd.) having a mass of 28 g / m ² and a thickness of 19 μm is used as the selectively permeable membrane layer, and the moisture permeable polyurethane resin having a solid content of 10% by mass is used as the moisture permeable membrane layer. (Samprene HMP17A manufactured by Sanyo Chemical Industries Co., Ltd.), cellulose acetate having a solid content of 10% by mass (Daicel Chemical Industries, Ltd. L-30), and a curable moisture-permeable polyurethane resin having a solid content of 30% by mass (Sanyo Chemical Industries, Ltd. The dope solution mixed so that the mass mixing ratio of SAMPLEN LQ120) was 50:25:25 was used. This dope solution was cast on a regenerated cellulose film, applied while adjusting the film thickness with a coater, and dried with a hot air dryer at 100 ° C. This operation was repeated on both surfaces of the permselective membrane to form a protective membrane layer.
A protective material is prepared by bonding a melt blown nonwoven fabric made of polybutylene terephthalate (manufactured by Tapirs Co., Ltd.) having a mass of 40 g / m ² and a thickness of 0.34 mm to the protective film layer with a hot melt type urethane adhesive. It was created. Further, the inner layer additional layer and the gas adsorbing layer are quilted to form an integrated product, and the protective material is disposed between the integrated product and the outer layer additional layer with the protective film protective layer facing outside without being bonded. A protective material was obtained. Mass of clothes protective material 318 g / ^{m 2,} and a thickness of 1.31 mm, moisture permeability 108g / ^{m 2} · h. Table 3 shows the organic chemical permeability test results using this protective material. Table 4 shows the results of the washing test of the protective material for clothes and the feeling of wearing the protective clothing formed of the protective material.

[Comparative Example 3]
In the above (protective membrane layer production example), the moisture permeable membrane layer has a moisture permeable polyurethane resin having a solid content of 10% by mass (Samprene HMP17A manufactured by Sanyo Chemical Industries, Ltd.) and cellulose acetate having a solid content of 10% by mass (Daicel Chemical Industries ( A protective film layer was prepared in the same manner except that the dope solution mixed so that the mass mixing ratio of L-30) was 75:25 was used, and the protective film layer was used, as in Example 1. Thus, a protective material for clothes was produced. The obtained protective material for clothes had a mass of 315 g / m ² , a thickness of 1.30 mm, and a moisture permeability of 120 g / m ² · h. Table 3 shows the organic chemical permeability test results using this protective material. Table 4 shows the results of the washing test of the protective material for clothes and the feeling of wearing the protective clothing formed of the protective material.

[Comparative Example 4]
A protective membrane layer was prepared in the same manner as described above (Example of production of protective membrane layer) except that a moisture-permeable polyurethane resin (Samprene HMP17A manufactured by Sanyo Chemical Industries, Ltd.) was used as the selective permeable layer constituting material. Was used in the same manner as in Example 1 to prepare a protective material for clothes. The obtained protective material for clothes had a mass of 313 g / m ² , a film thickness of 1.30 mm, and a moisture permeability of 130 g / m ² · h. Table 3 shows the organic chemical permeability test results using this protective material. Table 4 shows the results of the washing test of the protective material for clothes and the feeling of wearing the protective clothing formed of the protective material.

[Comparative Example 5]
In the above [Example 4], an ethylene vinyl copolymer film (Eval EF-XL manufactured by Kuraray Co., Ltd.) having a mass of 15 g / m ² and a thickness of 12 μm is used as the permselective membrane layer. The mass mixing ratio of a moisture permeable polyurethane resin having a solid content of 10% by mass (Samprene HMP17A manufactured by Sanyo Chemical Industries, Ltd.) and a curable moisture permeable polyurethane resin having a solid content of 30% by mass (Samprene LQ120 manufactured by Sanyo Chemical Industries, Ltd.). A protective film layer was prepared in the same manner as described above except that a dope solution mixed so as to be 75:25 was used, and a protective material for clothes was prepared in the same manner as in Example 1 using the protective film layer. The obtained protective material for clothes had a mass of 307 g / m ² , a film thickness of 1.30 mm, and a moisture permeability of 3 g / m ² · h. Table 3 shows the organic chemical permeability test results using this protective material. Table 4 shows the results of the washing test of the protective material for clothes and the feeling of wearing the protective clothing formed of the protective material.

  According to the results of Tables 3 and 4 above, Examples 3 and 4 are protective materials excellent in organic chemical permeation suppression ability, washing durability and wearing feeling, while Comparative Example 3 is washing. The result was low durability. In Comparative Example 4, the permselectivity of the selective permeation layer was poor, and Comparative Example 3 was not satisfactory for the purpose of the present invention because of poor wearing feeling.

  The protective material and protective garment of the present invention can protect organic chemicals from penetrating and bend, wear, and scratches that occur during use by laminating a moisture permeable membrane layer blended with a moisture permeable adhesive on a selectively permeable layer. The protective layer, protective tent, protective garment, protective gloves, protective sheet, protective tent, protective garment, It can be used for protective socks, protective shoes, protective storage bags, etc., and contributes greatly to the industry.

It is a schematic cross section which shows an example of the protective material of this invention. It is a schematic cross section which shows an example of the protective material for clothes of this invention. It is the schematic which shows the test container used for an organic chemical substance permeability test method.

Explanation of symbols

1: protective membrane protective layer, 2: moisture permeable membrane layer, 3: selective permeable layer, 4: moisture permeable membrane layer,
5: Gas adsorption layer, 6: Inner layer additional layer, 7: Quilted yarn, 8: Outer layer additional layer,
9: protective film layer, 10: protective material, 11: protective material for clothes,
21: Upper cell (150cc), 22: Lower cell (150cc), 23: Test product,
24: Paraffin sealing, 25: Test solution, 26: Sampling port

Claims (6)

A protective material having at least one gas adsorption layer and at least one protective film layer described below, and having at least one protective film layer disposed on the outer layer side of the gas adsorption layer.
Protective membrane layer: on both sides of the selective permeation layer having organic chemical permeation suppression and water vapor permeation,
A layer in which a moisture permeable membrane layer made of a moisture permeable membrane layer constituting material in which 5% by mass or more of a curable moisture permeable polyurethane adhesive is mixed with moisture permeable polyurethane is laminated.   The protective material according to claim 1, wherein the permselective layer is made of cellulose, a cellulose derivative, or regenerated cellulose. Protective material according to claim 1 or 2 by laminating at least one side protective film protective layer of the protective film layer. The protective material for clothes according to any one of claims 1 to 3 , wherein the protective membrane layer has a moisture permeability of 50 to 625 g / m ² · h. The protective material for clothes according to any one of claims 1 to 4, wherein the moisture permeability of the selectively permeable layer is 60 to 850 g / m ² · h. A protective garment formed by sewing using the protective material according to any one of claims 1 to 5 , wherein the seam is sealed with a resin having a permeation-inhibiting property against organic chemical substances.

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