JP2009006012A - Lamination structure body for protective clothing, and protective clothing - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a handleable, flexible, and lightweight material for protective clothing which is excellent in harmful gas absorbing performance, harmful microorganism shielding performance, air permeability, vapor permeability, and activated carbon fall preventing performance, and to provide protective clothing made of the material. <P>SOLUTION: A lamination structure body for the protective clothing is obtained by laminating an outer layer, a middle layer, and an inner layer in this order, where the outer layer is configured of fabric with water-repelling and oil-repelling finishing; the middle layer is an activated carbon-containing complex layer containing activated carbon with the specific surface of 600-5,000m<SP>2</SP>/g and protecting the activated carbon by a nano fiber layer which is composed of nano fiber with the average fiber diameter of 10-1,000 nm and has the air permeability of ≥0.1 cc/cm<SP>2</SP>/sec, and the inner layer is configured of fabric. The protective clothing is made of the lamination structure body. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a laminated structure for protective clothing and protective clothing comprising the same. More specifically, the present invention has an intermediate layer in which the activated carbon layer is protected by a nanofiber layer between the outer layer and the inner layer, and is excellent in protection performance against harmful chemical substances and shielding performance against harmful microorganisms. It is composed of a laminated structure for protective clothing and a laminated structure excellent in permeability and water vapor permeability, having no activated carbon removal, and having excellent characteristics such as handleability, processability, wearability, lightness, and flexibility. Related to protective clothing.

  In recent years, there has been an increased risk that harmful chemical substances such as sarin and mustard gas and harmful microorganisms will be used in terrorism and conflict, which can protect the human body from harmful chemical substances and microorganisms. There is an urgent need to develop protective clothing. In addition to terrorism and conflict, protective clothing that protects the human body from various infectious diseases caused by harmful microorganisms such as bacteria and viruses, and people involved in the handling of harmful chemical substances are protected from harmful chemical substances. There is a growing need for protective clothing.

  As protective clothing that protects the human body from harmful chemical substances and microorganisms, protective clothing formed from a material (for example, rubberized cloth) having a rubber layer that does not allow harmful chemical substances and microorganisms to pass through is known. However, a material having a rubber layer does not allow harmful chemical substances or microorganisms to pass through, but at the same time does not allow air or water vapor to pass through at all. Diffused heat, water vapor, carbon dioxide, etc. accumulate in clothes and are not released to the outside, so that the feeling of wearing is extremely inferior. In severe cases, there is a risk of causing serious health damage due to heat stress, heat stroke, etc.

From the above points, protective clothing or materials for protective clothing that can shield harmful chemical substances and microorganisms while allowing air and water vapor to pass therethrough have been proposed.
As such prior art, (1) a protective material having a liquid impermeable layer and a second layer holding solid particles that absorb, adsorb or detoxify harmful gases (see Patent Document 1), ( 2) Laminated woven fabric for protective clothing in which activated carbon fiber fabric layer and aramid fiber fabric layer are laminated and bonded (refer to Patent Document 2), (3) Liquid toxic chemical substance protection consisting of water / oil repellency cut pile fabric Layer, a protective clothing material comprising a laminated structure in which a gaseous toxic chemical substance adsorbing layer and an adsorbent protective layer made of fibrous activated carbon fabric are laminated (see Patent Document 3), (4) against gaseous organic chemical substances The selective permeation layer having permeation suppression ability and the gas adsorption layer made of fibrous activated carbon and the like are bonded with a hot melt adhesive, and the non-adhesive side of the selective permeation layer and the adherent side of the gas adsorption layer Protective material with a protective layer on top (See Patent Document 4), (5) An adsorption layer made of activated carbon fiber fabric is interposed between the sheet-like first carrier layer and the sheet-like second carrier layer, and the adsorption layer is made to be the first carrier layer and the second carrier layer. An adsorption filter material (see Patent Document 5) in which a carrier layer is bonded and laminated by point bonding is known.

However, the conventional protective materials or protective materials of (1) to (3) described above cannot be said to have sufficient shielding performance against harmful microorganisms, and it is difficult to sufficiently protect the human body from harmful microorganisms. is there. In addition, the protective material (1) is easy to remove solid particles for absorbing, adsorbing or detoxifying harmful gases from the protective material, and the laminated fabric (2) has insufficient protection function against liquid chemical substances. In addition, the shielding performance of harmful microorganisms is not sufficient.
In addition, the conventional protective materials (4) and (5) are insufficient in breathability and water vapor permeability, have poor wearability when wearing clothes manufactured from the protective material, There is a risk of developing heat stroke.

JP-A-4-255342 JP-A-2-190328 JP-A-8-308945 JP 2005-271222 A JP-A-2005-324025 Japanese Patent Publication No. 3-79467

  The object of the present invention is excellent in the adsorption of harmful gases, can safely protect the human body from harmful gases, and has excellent shielding properties against harmful microorganisms, and can safely protect the human body from harmful microorganisms. In addition to being able to protect, it also has excellent protection performance against liquid chemicals, and also has excellent air and water vapor permeability, so it feels comfortable to wear and does not cause heat stress or heat stroke. An object of the present invention is to provide a material for a protective garment which does not drop off activated carbon used for absorption and adsorption, and a protective garment comprising the material.

  As a result of intensive studies by the present inventors to achieve the above-described object, the conventional protective materials (laminated materials) described in (1) to (3) above are materials such as fabrics used for forming the protective material. Thus, it was found that the size of the voids formed in the material is large, and therefore the ability to shield harmful microorganisms such as bacteria is low. In addition, it has been found that the protective material (1) is easy to drop off because solid particles used for absorption and adsorption of harmful gases pass through such large gaps in the fabric. Furthermore, in the conventional protective materials of the above (4) and (5), the air permeability and the water vapor permeability of the permselective membrane and the sheet-like material used in these materials are insufficient. It was found that the water vapor transmission performance was insufficient.

  Therefore, as a result of further investigations by the present inventors based on the above-described knowledge, a fabric subjected to water / oil repellency processing is used as an outer layer, a fabric is used as an inner layer, and the fabric and the inner layer forming the outer layer are used. When a layer of activated carbon having a large specific surface area, which is protected by a nanofiber layer having a high air permeability formed from nanofibers having a very small fiber diameter, is present as an intermediate layer between the formed fabrics, a laminated structure obtained thereby has the following structure: It not only excels in the adsorption performance of harmful gases, but also has excellent shielding performance against harmful microorganisms, has excellent air and water vapor permeability, has excellent protection against liquid chemicals, and is flexible and moldable. Furthermore, the present inventors have found that activated carbon does not fall off from the laminated structure, and have completed the present invention based on these various findings.

That is, the present invention
(1) A laminated structure for protective clothing in which an outer layer, an intermediate layer, and an inner layer are laminated in the order of outer layer / intermediate layer / inner layer;
-The outer layer is composed of a fabric with water and oil repellent finishes;
The intermediate layer includes activated carbon having a specific surface area of 600 to 3000 m ² / g, and the activated carbon is protected by a nanofiber layer having an air permeability of 0.1 cc / cm ² / sec or more made of nanofibers having an average fiber diameter of 10 to 1000 nm. Activated carbon-containing composite layer;
The inner layer is made of fabric;
It is the laminated structure for protective clothing characterized by the above-mentioned.

And this invention,
(2) The laminated structure for protective clothing of (1) above, wherein the water repellency of the fabric constituting the outer layer is 80 or more and the oil repellency is 4 or more;
(3) The laminated structure for protective clothing of (1) or (2) above, wherein the fabric constituting the outer layer is a flame-retardant and heat-resistant fabric:
(4) The laminated structure for protective clothing according to any one of (1) to (3), wherein the nanofiber layer in the intermediate layer is composed of a nonwoven sheet made of organic polymer nanofibers;
(5) Any of the above (1) to (4), wherein the intermediate layer is bonded to the fabric constituting the outer layer and the fabric constituting the inner layer by point bonding or line bonding with a hot melt adhesive or by a hot melt nonwoven fabric Laminated structures for protective clothing;
It is.
Furthermore, the present invention provides
(6) A protective garment comprising the laminated structure according to any one of (1) to (5).

The laminated structure for protective clothing of the present invention is excellent in harmful gas adsorption performance. Therefore, the protective clothing comprising the laminated structure of the present invention can safely protect human bodies and the like from harmful gases.
Moreover, the laminated structure for protective clothing of the present invention is excellent in protective performance against liquid chemical substances.
In addition, since the laminated structure for protective clothing of the present invention protects the activated carbon contained in the intermediate layer with a nanofiber layer having a small gap size, the activated carbon does not fall off from the laminated structure and has excellent durability. ing.

The laminated structure for protective clothing according to the present invention has a small size capable of sufficiently shielding harmful microorganisms such as viruses because the size of the voids in the nanofiber layer used in the intermediate layer is sufficient to shield harmful microorganisms. Is excellent.
Furthermore, the laminated structure for protective clothing of the present invention is lightweight and flexible, and also has excellent air permeability and water vapor permeability. It does not cause wearer's health damage due to heat stress such as sickness.
Moreover, since the laminated structure for protective clothing of the present invention is flexible and excellent in moldability, it is excellent in workability when producing protective clothing.

The present invention is described in detail below.
The present invention relates to a laminated structure for protective clothing and protective clothing comprising the laminated structure.
Here, the term “protective clothing” in the present invention refers to humans and sometimes animals (pet animals, disaster rescue dogs, guide dogs, police dogs, etc.) for the purpose of protection from harmful gaseous substances, liquid substances, microorganisms, and the like. The protective clothing of the present invention includes clothing, gloves, socks, a hat, a mask, a collar, a feather, etc., and the laminated structure for protective clothing of the present invention includes A laminated structure used for manufacturing the protective clothing described above.
Representative examples of the laminated structure for protective clothing of the present invention and harmful gaseous substances intended to be protected by protective clothing are harmful gaseous substances having one or more carbon atoms and a molecular weight of 50 or more. It is a gaseous substance that can be adsorbed by a gas adsorbing substance such as activated carbon. Specific examples of such harmful gaseous substances include organophosphorus compounds used in agricultural chemicals, insecticides, herbicides, paints, adhesives, and other commonly used toluene, methylene chloride, chloroform. General organic solvents such as chlorine gas, phosgene, mustard, leucite, chloropicrin, cyanide, arsenic, agent V (VE, VG, VM, VX), agent G (tabung, sarin, soman) and other military gases The laminated structure for protective clothing of the present invention and the protective clothing comprising the same can be effectively used for protecting these harmful gases.
Biological poisons and harmful substances include viruses, bacteria, bacteria, other harmful microorganisms, anthrax, smallpox, Ebola, plague, Marburg virus and other biological biological weapons. The laminated structure for protective clothing of the invention and the protective clothing comprising the same can be effectively used for protection from these harmful substances.

  The laminated structure for protective clothing of the present invention (hereinafter sometimes simply referred to as “laminated structure”) includes an outer layer made of fabric, an intermediate layer containing activated carbon, and an inner layer made of fabric in the order of outer layer / intermediate layer / inner layer. Are stacked.

The outer layer is a layer that becomes the outer side (surface) of the garment when the protective garment is produced from the laminated structure. The outer layer needs to be made of a fabric subjected to water / oil repellent finish. Since the outer layer is made of a fabric subjected to water / oil repellent finish, the laminated structure is provided with a protective function against water, liquid chemical substances, and oil.
The fabric constituting the outer layer preferably has a water repellency of 80 or more, particularly 85 or more, and an oil repellency of 4 or more, particularly from the viewpoint of higher protection against water, liquid chemicals and oil. It is preferably 5 or more.
In this specification, “water repellency” refers to the water repellency measured according to JIS L 1092 5.2 spray test, and “oil repellency” refers to the oil repellency measured according to AATCC Test Method 118. Say.

The water / oil repellency treatment for the fabric constituting the outer layer (hereinafter sometimes referred to as “outer layer fabric”) is preferably performed using an organic fluorine compound having both water repellency and oil repellency. Examples of the organic fluorine compound water / oil repellent preferably used for the water / oil repellent processing of the outer fabric include “Scorch Guard” (registered trademark) manufactured by Minnesota Mining.
For the water / oil repellent finish of the outer fabric, a treatment method conventionally employed in the water / oil repellent finish of the fabric (for example, spray coating method, dipping method, coating method, etc.) can be employed.

As an outer layer fabric, water-repellent and oil-repellent processing has been applied, and it does not hinder the harmful gas adsorption performance, harmful microorganism shielding performance, air and water vapor transmission performance of the intermediate layer made of activated carbon-containing composite layer, Any fabric may be used as long as it has a reinforcing effect on the laminated structure, and any of a woven fabric, a knitted fabric, and a nonwoven fabric may be used. Among them, a woven fabric is preferable in terms of strength, uniformity, and the like. .
Further, as the fibers forming the outer layer cloth, polyethylene terephthalate, polybutylene terephthalate, aliphatic polyester, polyester fibers made of polyester such as aromatic polyester, nylon 6, nylon 66, nylon 610, nylon 11, aramid (totally fragrant) Polyamide fibers made of polyamide such as aromatic polyamides), synthetic fibers such as polyvinyl alcohol fibers, acrylic fibers, polyvinylidene chloride fibers, polypropylene fibers, ethylene-vinyl alcohol copolymer fibers, semi-synthetic fibers such as rayon, cupra and acetate Any of natural fibers such as cotton, wool and hemp, or a combination of two or more of the above fibers may be used. Moreover, the outer layer fabric may be manufactured from any of spun yarn, filament yarn, and short fiber.

In particular, if a flame retardant fabric (especially a woven fabric) is used as the outer layer fabric, the laminated structure of the present invention is imparted with water repellency and oil repellency as well as flame retardant, causing a fire or high temperature When a protective garment often used in is manufactured, it is possible to further improve the safety of the wearer.
As a flame retardant material effective as an outer layer fabric, it is important not to melt-drip from the viewpoint of preventing burns. Therefore, a flame retardant material made of a carbonized polymer such as vinylon, rayon, acrylic fiber, or phenol fiber is preferable. Specific examples of the flame retardant fabric include a woven fabric manufactured using a spun yarn obtained by mixing a flame retardant vinylon and a flame retardant rayon, and a woven fabric manufactured using a spun yarn obtained by mixing a flame retardant vinylon and an aramid fiber. Cloth etc. can be mentioned.

In order not to impede the harmful gas adsorption performance, harmful microorganism shielding performance, air and water vapor transmission performance, etc. of the intermediate layer comprising the activated carbon-containing composite layer, the air permeability (air permeability) of the outer fabric is is preferably 8~100cc / cm ² / sec, more preferably 10~80cc / cm ² / sec. Further, the outer layer fabric moisture permeability (permeation degree of water vapor) is preferably 5000~100000g / m ² / 24hr, more preferably 9000~80000g / m ² / 24hr.
The “air permeability” (air permeability) (outer layer fabric, activated carbon nanofiber layer, fabric constituting the inner layer, and air permeability of the laminated structure) as used in this specification is measured in accordance with JIS L 1096 (Fragile method). Air permeability.
Further, “moisture permeability” (outer layer fabric, activated carbon nanofiber layer, fabric constituting the inner layer, moisture permeability of the laminated structure) referred to in the present specification is a moisture permeability measured according to the JIS L 1099 A-1 method. .

The basis weight of the outer layer fabric is preferably 100 to 500 g / m ² and preferably 150 to 300 g / m ² from the viewpoint of the strength, flexibility, handleability, lightness, shielding properties, etc. of the laminated structure. More preferred.
The thickness of the outer layer fabric is preferably 0.1 to 1 mm, more preferably 0.3 to 0.8 mm, from the viewpoint of the strength, flexibility, handleability, shielding properties, etc. of the laminated structure. .

The intermediate layer in the laminated structure for protective clothing of the present invention comprises activated carbon-containing composite layer containing activated carbon, and the nanofiber layer protecting the activated carbon.
Activated carbon used for the intermediate layer, the adsorption performance of the toxic gases to a specific surface area in the range of 600 to 3000 m ² / g, it is necessary in view of handling properties, the specific surface area is 800~2800m ² / g It is preferably within the range, and more preferably within the range of 1000 to 2500 m ² / g.
If the specific surface area of the activated carbon is too small outside the above range, the harmful gas adsorption performance of the laminated structure is lowered. On the other hand, if the specific surface area of the activated carbon is too large, the activated carbon becomes brittle and handling properties become poor.
Here, the specific surface area of the activated carbon in this specification refers to the specific surface area measured by the BET one-point method.

  The activated carbon contained in the intermediate layer is not particularly limited in form and shape as long as it has the above-described specific surface area, and is granular, powdery, fibrous (short fiber, long fiber), a mixture thereof, etc. Any of these may be used. Among them, fibrous (particularly short fiber) activated carbon is preferably used from the viewpoint of adsorption rate. The size of the activated carbon is not particularly limited, but generally a size of 0.1 to 3 mm is preferably used.

The content of the activated carbon in the intermediate layer is preferably about 20 to 200 g, particularly 40 to 150 g per unit area (1 m ² ) of the intermediate layer, from the viewpoint of the amount of adsorption of harmful gases and the like. If the content of the activated carbon in the intermediate layer is less than the above range, the harmful gas adsorption performance of the laminated structure tends to be low, while if it exceeds the above range, the flexibility, molding processability, and lightness of the laminated structure are low. , Air permeability and the like are reduced, and powder leakage is likely to occur.
In the intermediate layer, the activated carbon is present on the surface forming the intermediate layer with a uniform thickness.
In general, the activated carbon has a thickness of 0.1 to 2.5 mm, particularly 0.15 to 2 mm in the form of an activated carbon layer, and is present in the intermediate layer. This is preferable from the viewpoints of flexibility and moldability of the laminated structure.

The nanofiber layer in the activated carbon-containing composite layer forming the intermediate layer needs to be formed from nanofibers having an average fiber diameter in the range of 10 to 1000 nm, and is formed from nanofibers having an average fiber diameter of 20 to 900 nm. It is preferable that it is formed from nanofibers having an average fiber diameter of 40 to 800 nm.
If the average fiber diameter of the nanofibers forming the nanofiber layer is too small out of the above range, the air permeability is deteriorated. On the other hand, if the average fiber diameter is too large, the size of the voids in the nanofiber layer becomes large and harmful microorganisms to the laminated structure Thus, the activated carbon is easily removed from the laminated structure.
Here, the average fiber diameter of the nanofibers or non-nanofibers in this specification means that 50 fibers of the nanofibers or non-nanofibers are randomly sampled and other than the collected 50 nanofibers or nanofibers. For each of the fibers, the thickness of the central portion in the length direction was measured using a scanning electron microscope (for example, a scanning electron microscope “S-510 type” manufactured by Hitachi, Ltd.), and an average of 50 fibers was measured. The fiber diameter obtained as a value.

The nanofiber layer in the intermediate layer is preferably composed of a nanofiber sheet-like material, and particularly composed of a nanofiber nonwoven sheet, the ease of manufacture of the nanofiber nonwoven sheet, the availability, It is preferable from the viewpoints of uniformity and air permeability.
The nanofiber layer constituting the intermediate layer (especially made of nanofibers constituting the nanofiber layer) from the viewpoint of wearing feeling when wearing the protective clothing manufactured from the laminated structure of the present invention, prevention of thermal stress, shielding properties, etc. air permeability of the nonwoven sheet) (permeability of air) is preferably 0.1~50cc / cm ² / sec, more preferably 0.3~30cc / cm ² / sec. Also, nanofiber layer moisture permeability (particularly nanofiber nonwoven fabric sheet constituting the nanofiber layer) (transmission degree of water vapor) is preferably ^{4000~20000g / m 2 / 24hr, 6000~18000g} / m 2 / 24 hr is more preferable.

The basis weight of the nanofiber layer (especially nanofiber non-woven sheet) in the intermediate layer is the shielding performance of harmful fines, prevention of falling off of activated carbon, air and water vapor permeation performance, flexibility of the laminated structure, handleability, light weight, From the viewpoint of cost and the like, 1 to 10 g / m ² is preferable, and 3 to 8 g / m ² is more preferable.
In addition, the thickness of the nanofiber layer in the intermediate layer is based on the adsorption performance of harmful gases (toxic gas adsorption rate and life), harmful microorganism shielding performance, air and water vapor transmission performance, flexibility, handleability, and lightness. From the viewpoint of cost and the like, the thickness is preferably 0.01 to 0.5 mm, more preferably 0.05 to 0.4 mm.

  The nanofibers that form the nanofiber layer are better than the fiber-forming organic polymers in terms of the ease of nanofiber formation, the flexibility of the laminated structure, molding processability, lightness, uniformity, shielding properties, etc. The nanofiber is preferably used. Nanofibers that can be used in the present invention include, for example, polyesters such as polyurethane, polyacrylonitrile, polyethylene terephthalate, polybutylene terephthalate, aliphatic polyester, polyamides such as nylon 6, nylon 66, nylon 610, nylon 11, and dicarboxylic acid components. Nanofibers composed of semi-aromatic polyamide, polyvinyl alcohol, polyvinylidene chloride, polypropylene, ethylene-vinyl acetate copolymer, polystyrene-polyolefin block copolymer, rayon, cupra, acetate, etc. with 60% or more of aromatic dicarboxylic acid Can be mentioned. The nanofiber layer may be formed from one kind of the above-described nanofibers, or may be formed from two or more kinds. Among these, it is preferable that the nanofiber layer in the intermediate layer is formed of nanofibers made of polyurethane from the viewpoint of excellent followability when made into clothes with high elongation.

As a form of protection of the activated carbon by the nanofiber layer in the activated carbon-containing composite layer forming the intermediate layer, a form in which the activated carbon is layered and the nanofiber layers are disposed on both sides (upper surface and lower surface) of the activated carbon layer is preferably employed.
In that case, it is preferable to adhere the activated carbon layer and the nanofiber layer so that delamination does not occur. As a method for adhering and fixing the activated carbon layer between the upper and lower nanofiber layers, for example, an adhesive is mixed with activated carbon, the mixture is applied to the surface of one nanofiber layer, and then the other nanofiber is applied to the application surface. A method of forming an activated carbon-containing composite layer by laminating and fixing the fiber layers and bonding and laminating in the order of nanofiber layer / activated carbon layer / nanofiber layer, and interposing a hot melt nonwoven fabric between the nanofiber layer and the activated carbon layer A method of bonding by thermocompression bonding with a calendar or the like in a state of being in contact.
As an adhesive mixed with activated carbon, it is necessary to use an adhesive that does not hinder the harmful gas adsorption performance of activated carbon. As an adhesive that does not inhibit the harmful gas adsorption performance of activated carbon, for example, polyurethane or acrylic ester And the like based on a polymer polymer emulsion.
In addition, the amount of adhesive mixed with activated carbon may vary depending on the type of adhesive and the type of nanofibers that form the nanofiber layer, but the activated carbon does not hinder the harmful gas adsorption performance of activated carbon. In order to make the layer adhere well to the nanofiber layer, generally 0.1 to 10 parts by mass, and further 0.5 to 5 parts by mass of the adhesive (in solid content) with respect to 100 parts by mass of the activated carbon. Part, particularly about 0.5 to 3 parts by mass.

From the viewpoints of wearing feeling when wearing protective clothing manufactured from the laminated structure of the present invention, prevention of thermal stress, shielding properties, and the like, the (air permeability) of the activated carbon-containing composite layer forming the intermediate layer is 0. is preferably 1~50cc / cm ² / sec, more preferably 0.3~30cc / cm ² / sec, also moisture permeability (permeation degree of water vapor) is, 4000~20000g / m ² / 24hr It is preferable that it is 5500-18000 g / m < ² > / 24hr.
Basis weight of the activated carbon-containing composite layer constituting the intermediate layer is preferably 22~220g / m ^2, and more preferably 40~150g / m ^2.
The thickness of the activated carbon-containing composite layer that forms the intermediate layer is preferably 0.1 to 3 mm, and more preferably 0.2 to 2 mm.

The manufacturing method of the nanofiber used for an intermediate | middle layer, especially a nanofiber nonwoven sheet is not restrict | limited. The nanofiber nonwoven sheet used in the laminated structure of the present invention can be produced, for example, by a so-called electrospinning method.
Specifically, the fiber-forming organic polymer solution described above is sprayed (sprayed) from a thin nozzle such as an injection needle toward the ground surface in a high voltage region, and the ground surface is made of the organic polymer. It can be produced by depositing nanofibers in a non-woven sheet. The manufacturing method of the organic polymer nanofiber by the electrospinning method is already known (for example, refer patent document 6).
When producing nanofibers by electrospinning, the fiber diameter of the nanofibers is adjusted by adjusting the concentration, voltage, degree of polymerization of the organic polymer, surface tension of the organic polymer solution, etc. be able to.

The inner layer is a layer that becomes the back surface (the surface located on the human body side) of the clothing when the protective clothing is produced from the laminated structure. As the fabric constituting the inner layer (hereinafter sometimes referred to as “inner layer fabric”), air and water vapor are permeated, and even if the human body comes into contact with the human body, the human body is not damaged or uncomfortable, and the reinforcing action is activated carbon. Any fabric may be used as long as it has a protective action, and any of a woven fabric, a knitted fabric, and a non-woven fabric may be used. Among them, a knitted fabric or a woven fabric is preferable from the viewpoint of strength and uniformity. Further, the inner layer fabric may be a raised fabric (pile fabric) or a non-raised fabric (fabric having no pile). Using a raised fabric as the inner layer fabric is advantageous in terms of texture and sweat absorption.
Further, the fibers forming the inner layer fabric include polyester fibers made of polyester such as polyethylene terephthalate, polybutylene terephthalate, aliphatic polyester, polyamide fibers made of polyamide such as nylon 6, nylon 66, nylon 610, nylon 11, and polyvinyl alcohol. Fiber, acrylic fiber, polyvinylidene chloride fiber, polypropylene fiber, synthetic fiber such as ethylene-vinyl acetate copolymer, semi-synthetic fiber such as rayon, cupra, acetate, natural fiber such as cotton, wool, hemp, etc. Any of a combination of more than two species may be used. Further, the inner layer fabric may be manufactured from any of spun yarn, filament yarn, and short fiber.

Air permeability of the inner layer fabric is preferably 8~100cc / cm ² / sec, more preferably 10~80cc / cm ² / sec. Further, the inner fabric moisture permeability (permeation degree of water vapor) is preferably 5000~100000g / m ² / 24hr, more preferably 10000~80000g / m ² / 24hr.

The basis weight of the inner layer fabric is preferably 30 to 300 g / m ² , and preferably 50 to 200 g / m ² in terms of the strength, flexibility, handleability, lightness, texture, etc. of the laminated structure. More preferred.
The thickness of the inner layer fabric is preferably 0.1 to 1 mm, more preferably 0.2 to 0.7 mm, from the viewpoint of the strength, flexibility, handleability, texture, etc. of the laminated structure. .

  In the present invention, the lower surface of the outer layer made of the fabric and one surface (upper surface) of the intermediate layer made of the activated carbon-containing composite layer are bonded together, and the other surface (lower surface) of the intermediate layer made of the activated carbon-containing composite layer and the inner layer fabric The upper surface may adhere to form the laminated structure of the present invention. Moreover, depending on the case, after laminating | stacking the outer layer cloth, the intermediate | middle layer which consists of activated carbon containing composite layers, and an inner layer cloth, the said 3 persons may be fixed by sewing and the laminated structure of this invention may be formed. Among them, it is preferable to bond and laminate the outer layer, the intermediate layer, and the inner layer using an adhesive because a strong laminated structure without delamination can be easily manufactured.

  When adhesive lamination is performed using an adhesive, the adhesion between the outer layer and the intermediate layer is the adhesion of the harmful gas possessed by the intermediate layer made of the activated carbon-containing composite layer that is firmly adhered to the outer layer and the intermediate layer without peeling. Adhesion method is employed so that the ability to block harmful microorganisms is not hindered, and the air and water vapor permeability of the outer layer and the intermediate layer are not hindered. In addition, for the adhesion between the intermediate layer and the inner layer, an adhesion method is preferably employed in which the intermediate layer and the inner layer are firmly bonded without peeling and the air and water vapor permeability of the intermediate layer and the inner layer are not hindered. Examples of such an adhesion method include point adhesion, line adhesion, and adhesion using a hot melt nonwoven fabric. The adhesion between the outer layer and the intermediate layer and the adhesion between the intermediate layer and the inner layer may be performed by using the same adhesive and adopting the same adhesive method, or using the same adhesive and adopting another adhesive method. Alternatively, the same adhesion method or different adhesion methods may be employed using different adhesives.

Examples of adhesives used for point bonding or line bonding include hot melt adhesives, solution type adhesives in which a thermoplastic polymer or a thermosetting polymer is dissolved in an organic solvent, thermoplastic polymers or thermosetting polymers. Examples thereof include an aqueous adhesive dispersed or dissolved in water, and a reactive monomer type adhesive.
Among them, the adhesion between the outer layer and the intermediate layer and the adhesion between the intermediate layer and the inner layer are polyester, polyamide, ethylene-vinyl acetate copolymer depending on the material of the fabric constituting the outer layer and the material of the fabric constituting the inner layer. System, polyurethane-based hot-melt adhesives are used for point bonding or wire-bonding, or polyester hot-melt nonwovens, polyamide hot-melt nonwovens, polyurethane hot-melt nonwovens and other hot-melt nonwovens are used as adhesives However, the adhesive ability of the intermediate layer composed of the activated carbon-containing composite layer is not hindered by the adhesive, and the ability of the outer layer, intermediate layer and inner layer to transmit air and water vapor is not affected by the adhesive. Performs a drying process to remove the organic solvent and water after adhesion lamination without being disturbed Since there is no necessity preferable.

  In particular, when a hot melt nonwoven fabric is used, the hot melt nonwoven fabric is interposed between the outer layer fabric and the intermediate layer (activated carbon-containing composite layer), and further hot between the intermediate layer (activated carbon-containing composite layer) and the inner layer fabric. Create a laminate with the outer layer fabric / hot melt nonwoven fabric / intermediate layer (activated charcoal-containing composite layer) / hot melt nonwoven fabric / inner layer fabric in order, with the melt nonwoven fabric intervening. By heating and pressurizing at a temperature, the laminated structure of the present invention can be easily produced in a single bonding step, which is desirable.

When bonding the outer layer to the intermediate layer and / or the intermediate layer to the inner layer by point bonding or line bonding, the size of the point made of the adhesive, the thickness of the line, the number of points or lines per unit area The (density of dots or lines) and the like can be determined according to the type of adhesive, the type of outer layer cloth, the type of inner layer cloth, and the like.
In addition, when hot melt nonwoven fabric is used to bond the outer layer and the intermediate layer and / or the intermediate layer and the inner layer, the air and water vapor permeability, flexibility, handleability, and adhesiveness of the resulting laminated structure are obtained. The air permeability is 10 to 200 cc / cm ² / sec, particularly 15 to 150 cc / cm ² / sec, the basis weight is 10 to 50 g / m ² , particularly 15 to 35 g / m ² , and the thickness is 0.05 It is preferable to use a hot melt nonwoven fabric of ˜1 mm, particularly 0.1 to 0.7 mm.

  The conditions when the outer layer, the intermediate layer and the inner layer are bonded and laminated using a hot melt adhesive or a hot melt nonwoven fabric are as follows: the type of fabric constituting the outer layer and the inner layer, the melting point of the hot melt adhesive or the hot melt nonwoven fabric, the thickness of each layer It can be adjusted according to the situation. In general, a hot melt adhesive or a hot melt nonwoven fabric having a melting point of 180 ° C. or lower, preferably about 100 to 160 ° C., is used at a temperature equal to or higher than the melting point of the hot melt adhesive (hot melt nonwoven fabric). It is preferable to perform adhesive lamination by applying heat and pressure at a temperature in the range of melting point + 10 ° C. to melting point + 40 ° C. and applying a pressing pressure of 10 to 500 Pa, particularly 20 to 200 Pa.

The overall basis weight of the laminated structure of the present invention, which is laminated in the order of the outer layer / intermediate layer / inner layer, is 200 to 600 g in terms of the strength, flexibility, handleability, lightness, breathability, etc. of the laminated structure. preferably / a m ^2, and more preferably a 300 to 500 g / m ^2.
The total thickness of the laminated structure of the present invention is preferably 0.3 to 3 mm, and preferably 0.6 to 2 mm from the viewpoint of the strength, flexibility, handleability, air permeability, and the like of the laminated structure. It is more preferable.

  Using the above-described laminated structure of the present invention, various types of protective clothing such as clothing, gloves, socks, hats, masks, wraps, and feathers can be produced. The production method of the protective clothing using the laminated structure of the present invention is not particularly limited, and depending on the type, structure, shape, usage pattern, etc. of the protective clothing, conventionally used protective clothing or ordinary clothing can be used. It can be manufactured by employing a manufacturing method or the like.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples.
In the following examples, etc., the average fiber diameter of nanofibers and non-nanofibers, the specific surface area of activated carbon, the adsorbability of harmful gases of laminated structures, the shielding properties of bacteria, the air permeability and water vapor permeability, the laminated structures The ability to prevent the activated carbon from falling off and the feeling of wearing the protective clothing made from the laminated structure were measured or evaluated as follows.

(1) Average fiber diameter of nanofibers and non-nanofibers:
50 fibers were randomly sampled from a non-woven sheet made of nanofibers or non-nanofibers, and the thickness of the central portion in the length direction of each of the collected 50 fibers was measured using a scanning electron microscope ( It was measured using a scanning electron microscope “S-510 type” manufactured by Hitachi, Ltd., and an average value of 50 fibers was taken as an average fiber diameter of the fibers.

(2) Specific surface area of activated carbon fiber:
Using a non-woven sheet made of activated carbon fiber as a sample, 0.05 g of activated carbon fiber was sampled, and using the sample, a fully automatic surface area measuring device “Monosorb” manufactured by Yuasa Ionics Co., Ltd. according to the BET 1-point method was used. The specific surface area was measured.

(3) Hazardous gas adsorptivity of laminated structure:
The laminated structure obtained in the following examples or comparative examples is cut, and a test piece of length × width = 5 cm × 5 cm is collected, and the concentration of harmful gas (3-methoxybutyl acetate) is measured on the test piece. Arrange the outer layer of the laminated structure facing up on the bottom of the 350 cc container whose internal volume has been adjusted to 0.06 mg / cc in advance (place the inner layer of the laminated structure in contact with the bottom of the container) The container was immediately closed and sealed, allowed to stand in that state for 60 minutes, and then the gas in the container was collected, and the concentration of harmful gas in the collected gas was measured by gas chromatography.
When the concentration of harmful gas in the collected gas is reduced to less than 5% of the initial concentration (0.06 mg / cc), the adsorptivity of harmful gas is evaluated as good (O), When the concentration is 5% or more and less than 40%, the harmful gas adsorptivity is evaluated as slightly poor (△), and when the concentration is 40% or more of the initial concentration, the harmful gas adsorptivity is poor (×). As evaluated.

(4) Bacterial shielding:
According to JIS L 1912 bacterial filtration efficiency, the degree to which bacteria in the air were filtered through the laminated structure was tested.
Specifically, using Staphylococcus aureus, a bacterial suspension is prepared so that the total number of colonies is 2,200 ± 500, and the bacterial suspension is 2.7 to 3.3 μm in size. A test piece (length × width = 15 cm × 15 cm) obtained by aerosolizing (gasifying) and cutting the aerosol at a rate of 28.3 L / min and cutting the laminated structure obtained in the following examples or comparative examples. ), The air that passed through the test piece (air filtered by the test piece) was passed through an under-sensor sampler in which a petri dish containing tryptosoy agar medium was set, and then the petri dish was taken out to 37 ± The cells were cultured at 2 ° C. for 48 hours.
Then, the bacterial collection efficiency (BFE) (%) of the test piece is obtained from the following mathematical formula (1), and when the BFE is 90% or more, the shielding property of the bacteria is evaluated as good (◯), and the BFE is 50%. The case where it was less than 90% was evaluated as slightly poor (Δ) for bacterial shielding, and the case where BFE was less than 50% was evaluated as poor (×) for bacterial shielding.

Bacteria collection efficiency (BFE) (%) = {(A−B) / A} × 100 (1)
In the formula, A = the total number of colonies of control (the same test is performed without setting a test piece)
B = Total number of colonies when the test piece is set

(5) Air permeability of laminated structure:
It measured according to JISL1906 (fragile method) using the test piece (length × width = 10 cm × 10 cm) obtained by cutting the laminated structure obtained in the following examples or comparative examples.

(6) Water vapor permeability of laminated structure:
It measured according to JISL1099A-1 method using the test piece (length x width = 10cmx10cm) obtained by cutting the laminated structure obtained by the following example or the comparative example.

(7) Prevention of falling off of activated carbon from the laminated structure:
A test piece (length × width = 10 cm × 10 cm) obtained by cutting the laminated structure obtained in the following examples or comparative examples is placed on the mesh of the sieve with the outer layer of the test piece (laminated structure) facing up. And the screen is vibrated in the horizontal direction for 20 minutes under the conditions of frequency = 100 times / min and amplitude = 50 cm, and then the test piece is taken out from the sieve and the outer layer side of the test piece (laminated structure) When the activated carbon does not leak out of the outer layer and the inner layer, the drop-off prevention is good (○), and when the activated carbon leaks slightly out of the outer layer and / or the inner layer The case where the prevention property was slightly poor (Δ), and the case where the activated carbon was leaked considerably outside the outer layer and / or the inner layer was evaluated as the failure prevention property (x).

(8) Wearing feeling of protective clothing made from the laminated structure:
Using the laminated structure obtained in the following examples or comparative examples, an outer garment in the form of being worn from the head (a cylindrical body having a length of 150 cm with a hole formed only in a portion through which the head is passed), The outer garment was worn and stayed in a room at a temperature of 30 ° C. for 30 minutes, and the wearing feeling at that time was evaluated according to the following evaluation criteria.
○: It does not feel steamed, there is almost no increase in body temperature, and the wearing feeling is good.
Δ: Slightly steamed, slightly increased body temperature, and slightly worn.
X: The feeling of steaming is strong, there is a rise in body temperature, and the wearing feeling is poor.

<< Reference Example 1 >> [Production of non-woven sheet made of polyurethane nanofiber]
(1) Thermoplastic polyurethane [“Kuramylon 1195” manufactured by Kuraray Co., Ltd.] was added to dimethylformamide so as to be 16% by mass, stirred and dissolved at 90 ° C., and completely dissolved, cooled to room temperature, and spun. Stock solutions were prepared. Electrospinning was performed using the spinning dope thus obtained. In electrospinning, a needle having an inner diameter of 0.9 mm was used as a die, and the distance between the die and the nanofiber deposition surface (conveyor) was 10 cm. The spinning dope was spun from the die at a predetermined supply amount, a 23 kV applied voltage was applied to the die, and polyurethane nanofibers were deposited on the conveyor to produce a nonwoven fabric sheet made of polyurethane nanofibers.
(2) The polyurethane nanofiber nonwoven sheet obtained in (1) above has a basis weight of 4 g / m ² , a thickness of 0.1 mm, an air permeability (air permeability) of 1 cc / cm ² / sec and water vapor. permeability was 6500g / m ² / 24hr.
Moreover, when the average fiber diameter of the polyurethane nanofiber which comprises this polyurethane nanofiber nonwoven sheet was measured by the above-mentioned method, the average fiber diameter was 250 nm.

<< Reference Example 2 >> [Production of material for activated carbon-containing composite layer (A)]
50 parts by mass of activated carbon (“Kuraray Coal” manufactured by Kuraray Chemical Co., Ltd .; specific surface area = 2000 m ² / g, average particle size = 100 μm) adhesive (“Nipol LX” manufactured by Nippon Zeon Co., Ltd.); acrylate latex adhesive, solid content concentration 45 mass%) After mixing 10 parts by mass, an activated carbon mixture was prepared, and this activated carbon mixture was applied to the surface of the polyurethane nanofiber nonwoven sheet obtained in Reference Example 1 to a thickness of about 1 mm. And dried at 140 ° C. for 10 minutes. Then, another polyurethane nanofiber nonwoven sheet obtained in Reference Example 1 above was applied to the coated surface and heated and pressurized under the conditions of a temperature of 120 ° C. and a pressure of 100 Pa to obtain a polyurethane nanofiber nonwoven fabric. An activated carbon-containing composite layer material (composite material for an intermediate layer) composed of a sheet layer / activated carbon layer / polyurethane nanofiber nonwoven sheet layer (hereinafter referred to as “active carbon-containing composite layer (A) material”) was produced.
The thickness of the activated carbon-containing composite layer (A) thus obtained is 0.3 mm, the basis weight is 108 g / m ² , the air permeability (air permeability) is 0.8 cc / cm ² / sec, and the water vapor transmission rate time was 6000g / m ² / 24hr. Further, in this activated carbon-containing composite layer (A) material, the activated carbon is 100 g per 1 m ² of area of the activated carbon-containing composite layer (A) material and has a uniform thickness between the upper and lower polyurethane nanofiber nonwoven sheet layers. That layer was formed.

<< Reference Example 3 >> [Production of material for activated carbon-containing composite layer (B)]
An active carbon mixture was prepared by mixing 10 parts by mass of the same adhesive used in Reference Example 2 with 50 parts by mass of the same activated carbon used in Reference Example 2, and this activated carbon mixture was made into a polyester spunbond nonwoven fabric [Toyobo. “Ecule” manufactured; average fiber diameter of polyester fiber = 1800 nm, nonwoven fabric thickness = 0.15 mm, basis weight = 20 g / m ² , air permeability (air permeability) = 95 cc / cm ² / sec, water vapor permeability = after coating to a thickness of about 1mm to 8500g / m ² / 24hr] surface, and dried for 10 minutes at 140 ° C.. Thereafter, another non-woven sheet made of the same polyurethane fiber on the coated surface is overlapped and heated and pressed under the conditions of a temperature of 120 ° C. and a pressure of 100 Pa to form a non-woven sheet layer made of polyurethane fiber / activated carbon layer / polyurethane fiber. An activated carbon-containing composite layer material (composite material for an intermediate layer) composed of a non-woven sheet layer (hereinafter referred to as “material for activated carbon-containing composite layer (B)”) was produced.
The thickness of the activated carbon-containing composite layer (B) thus obtained is 0.4 mm, the basis weight is 140 g / m ² , the air permeability (air permeability) is 35 cc / cm ² / sec, and the water vapor permeability is 7700 g. / m was ² / 24hr. In this activated carbon-containing composite layer (B) material, the activated carbon is 100 g per 1 m ² of the activated carbon-containing composite layer (B) material and has a uniform thickness between the upper and lower polyurethane fiber nonwoven sheet layers. Layer was formed.

<< Reference Example 4 >> [Production of activated carbon-containing composite layer (C) material]
An active carbon mixture was prepared by mixing 10 parts by mass of the same adhesive used in Reference Example 2 with 50 parts by mass of the same activated carbon used in Reference Example 2, and this activated carbon mixture was mixed with a commercially available porous film [Aussie film Corp. "Furekuron"; material polyester, the thickness of the porous film = 30 [mu] m, pore size = 0.5 [mu] m, (permeability of air) permeability = surface of unmeasurable, water vapor permeability = 3450g / m ² / 24hr] After coating to a thickness of about 1 mm, it was dried at 140 ° C. for 10 minutes. Thereafter, another same commercially available porous film is stacked on the coated surface, and heated and pressurized under the conditions of a temperature of 120 ° C. and a pressure of 100 Pa, and an activated carbon-containing composite layer comprising a porous film / activated carbon layer / porous film. A material (composite material for the intermediate layer) [hereinafter referred to as “active carbon-containing composite layer (C) material”] was produced.
The activated carbon-containing composite layer (C) material) thus obtained has a thickness of 0.2 mm, a basis weight of 110 g / m ² , an air permeability (air permeability) that cannot be measured, and a water vapor permeability of 3000 g / m. It was ² / 24hr. Further, in this activated carbon-containing composite layer (C) material, the activated carbon forms a layer having a uniform thickness between the upper and lower porous films in an amount of 100 g per 1 m ² area of the activated carbon-containing composite layer (C) material. Was.

<< Reference Example 5 >> [Manufacture of woven fabric for outer layer with water / oil repellent finish]
(1) Create a spun yarn (40th) by blending flame retardant vinylon (Kuraray Co., Ltd. “Vinard”) and aramid fiber at a mass ratio of 50:50, and twist the two spun yarns together. It is set as a double thread, and it is woven in a twill structure using the double thread, and a woven cloth for an outer layer [twill cloth; thickness = about 0.3 mm, basis weight = 180 g / m ² , air permeability (air permeability) = 18 cc / cm ² / sec, to produce a water vapor transmission rate ^{= 9010g / m 2 / 24hr]} .
(2) The woven fabric obtained in (1) above is sprayed with a water / oil repellent (“Scotchguard” manufactured by Minnesota Mining Co., Ltd .; fluorine-based organic compound) in an amount of 5 g / m ² to provide water / oil repellency. Oil processing was carried out to produce a flame retardant / heat resistant outer layer woven fabric (water repellency = 100, oil repellency = 5) subjected to water / oil repellency.

Example 1
(1) Tricot knitted fabric of 100% polyethylene terephthalate [thickness = about 0.3 mm, basis weight = 80 g / m ² , air permeability (air permeability) = 80 cc / cm ² / sec] is used as the fabric for the inner layer, A polyurethane hot melt nonwoven fabric [“Espassione FF” manufactured by KB Seiren Co., Ltd .; thickness = about 0.1 mm, basis weight = 25 g / m ² , air permeability (air permeability) = 80 cc / cm ² / sec], the material for the activated carbon-containing composite layer (A) obtained in Reference Example 2 above, and the same polyurethane hot-melt nonwoven fabric as above as an adhesive. The outer layer woven fabric / polyureta as shown in FIG. 1 is laminated on the melt nonwoven fabric with the water- and oil-repellent processed flame retardant / heat resistant outer layer woven fabric obtained in Reference Example 5 above. A laminate of the hot melt nonwoven fabric / active carbon-containing composite layer (A) / polyurethane hot melt nonwoven fabric / tricot knitted fabric for the inner layer in this order.
In FIG. 1, 1 is a woven fabric for the outer layer, 2a and 2b are polyurethane hot melt nonwoven fabrics, 3 is a material for the activated carbon-containing composite layer (A), 3a and 3b are polyurethane nanofiber nonwoven sheets, 3c is an activated carbon layer, 4 Indicates a tricot knitted fabric for the inner layer.

(2) The laminate obtained in the above (1) is heated and pressurized for 12 seconds under the conditions of a temperature of 120 ° C. and a pressure of 100 Pa to melt the polyurethane hot-melt nonwoven fabric, and the woven fabric for the outer layer and the activated carbon-containing composite layer (A) Adhesion with material, activated carbon-containing composite layer (A) material and inner layer tricot knitted fabric, outer layer (water- and oil-repellent flame retardant and heat-resistant woven fabric) / intermediate A laminated structure for protective clothing (thickness = 1.0 mm, basis weight = 418 g / m ² ) was produced by bonding layers in the order of layer [activated carbon-containing composite layer (A)] / inner layer (polyester tricot knitted fabric).
(3) Hazardous gas adsorption performance, bacteria shielding performance, air permeability and water vapor permeability, activated carbon fall-off prevention performance of the laminated structure for protective clothing obtained in (2) above, and protection produced from the laminated structure When the wear feeling of clothing was measured or evaluated by the method described above, it was as shown in Table 1 below.

<< Comparative Example 1 >>
(1) The same polyurethane hot melt as used in (1) of Example 1 on the same 100% polyethylene terephthalate tricot knitted fabric (inner layer fabric) as used in (1) of Example 1 After layering the nonwoven fabric, the water- and oil-repellent processed flame-retardant and heat-resistant outer layer woven fabric obtained in Reference Example 5 was layered thereon, and then at a temperature of 120 ° C. and a pressure of 100 Pa for 12 seconds. Polyurethane hot melt nonwoven fabric is melted by heating and pressurizing, and the outer layer woven fabric (water- and oil-repellent flame retardant and heat-resistant woven fabric) and the inner layer fabric (polyester tricot knitted fabric) are polyurethane hot melt. A laminated structure (thickness = 0.6 mm, basis weight = 285 g / m ² ) composed of an outer layer / inner layer bonded and laminated with a nonwoven fabric was produced.
(2) Hazardous gas adsorption performance (hazardous gas adsorption rate and harmful gas adsorption life), bacteria shielding performance, air permeability and water vapor permeability, activated carbon of the laminated structure for protective clothing obtained in (1) above As shown in Table 1 below, the drop-off prevention performance and the wearing feeling of protective clothing made from the laminated structure were measured or evaluated by the methods described above.

<< Comparative Example 2 >>
(1) In (1) of Example 1, the material for activated carbon-containing composite layer (B) produced in Reference Example 3 was used in place of the material for activated carbon composite-containing composite layer (A). Performed in the same manner as (1) and (2), outer layer (water- and oil-repellent flame-retardant and heat-resistant woven fabric) / intermediate layer [activated carbon-containing composite layer (B)] / inner layer (polyester tricot knitted fabric) ) Were laminated in the order of ( ¹ )) to produce a laminated structure (thickness = 1.1 mm, basis weight = 450 g / m ² ) for protective clothing.
(2) Hazardous gas adsorption performance, bacteria shielding performance, air permeability and water vapor permeability, activated carbon fall-off prevention performance of the laminated structure for protective clothing obtained in (1) above, and protection produced from the laminated structure When the wear feeling of clothing was measured or evaluated by the method described above, it was as shown in Table 1 below.

<< Comparative Example 3 >>
(1) In (1) of Example 1, instead of the material for activated carbon composite-containing composite layer (A), the material for activated carbon-containing composite layer (C) produced in Reference Example 4 was used. Performed in the same manner as (1) and (2), outer layer (water- and oil-repellent flame-retardant and heat-resistant woven fabric) / intermediate layer [activated carbon-containing composite layer (C)] / inner layer (polyester tricot knitted fabric) ) To produce a laminated structure for protective clothing (thickness = 0.9 mm, basis weight = 420 g / m ² ).
(2) Hazardous gas adsorption performance, bacteria shielding performance, air permeability and water vapor permeability, activated carbon fall-off prevention performance of the laminated structure for protective clothing obtained in (1) above, and protection produced from the laminated structure When the wear feeling of clothing was measured or evaluated by the method described above, it was as shown in Table 1 below.

<< Comparative Example 4 >>
(1) In Example 1 (1), instead of the activated carbon composite-containing composite layer (A) material, a commercially available activated carbon fiber woven fabric [“Kinol” manufactured by Nihon Kynol Co., Ltd .; average of activated carbon fibers constituting the woven fabric Fiber diameter = 14000 nm, specific surface area = 2500 m ² / g, woven fabric thickness = 0.44 mm, basis weight = 95 g / m ² , air permeability (air permeability) = 72 cc / cm ² / sec] Otherwise, the same operation as in (1) and (2) of Example 1 was carried out, and the outer layer (water- and oil-repellent flame-retardant and heat-resistant woven fabric) / intermediate layer (non-woven sheet made of activated carbon fiber) / A laminated structure (thickness = 1.1 mm, basis weight = 405 g / m ² ) for protective clothing, in which the inner layer (polyester tricot knitted fabric) was adhered and laminated in this order, was produced.
(2) Hazardous gas adsorption performance, bacteria shielding performance, air permeability and water vapor permeability, activated carbon fall-off prevention performance of the laminated structure for protective clothing obtained in (1) above, and protection produced from the laminated structure When the wear feeling of clothing was measured or evaluated by the method described above, it was as shown in Table 1 below.

As seen in Table 1 above, the laminated structure of Example 1 has an outer layer made of a fabric subjected to water / oil repellency, and has a specific surface area of 600 to 5000 m ² / g as an intermediate layer. An activated carbon-containing composite layer (A) in which the activated carbon is protected by a nanofiber layer having an air permeability of 0.1 cc / cm ² / sec or more comprising nanofibers having an average fiber diameter in the range of 10 to 1000 nm. ), The inner layer is made of fabric, and has a structure in which the outer layer / intermediate layer / inner layer are bonded and laminated in this order, so that it is excellent in harmful gas adsorption and bacteria shielding properties, and is permeable to air and water vapor. It has a high degree of strength, is excellent in the ability to prevent the activated carbon from falling off, and is excellent in a feeling of wearing when it is made into protective clothing, and is extremely useful as a laminated structure for protective clothing.

On the other hand, since the laminated structure of Comparative Example 1 does not have the activated carbon-containing composite layer, it does not have harmful gas adsorption ability and bacteria shielding ability and cannot be used for protective clothing.
In addition, the laminated structure of Comparative Example 2 has an intermediate layer made of an activated carbon-containing composite layer, but the protective layer of activated carbon in the intermediate layer is not a nanofiber layer, but has a normal fineness with an average fiber diameter exceeding 1000 nm. Therefore, it is inferior in bacteria shielding property and inferior in the ability of activated carbon to fall off.
Furthermore, although the laminated structure of Comparative Example 3 has an intermediate layer composed of an activated carbon-containing composite layer, the activated carbon protective layer in the intermediate layer is not a nanofiber layer but a porous film, and thus has a laminated structure. When wearing protective clothing made from the body, there is no permeation of air or water vapor, heat is accumulated in the clothing, and the feeling of wearing is inferior.
In the laminated structure of Comparative Example 4, since the intermediate layer is composed of a non-woven sheet made of activated carbon fiber having a normal fineness, the bacteria shielding ability is low and the ability to prevent the activated carbon from falling off is also poor.

  The laminated structure of the present invention is excellent in harmful gas adsorption performance and can safely protect the human body from harmful gases, and also has excellent shielding properties against harmful microorganisms, so that the human body is safe from harmful microorganisms. In addition, it has excellent protection performance against liquid chemicals, and also has excellent air and water vapor permeability, so that it is easy to wear and does not cause heat stress or heat stroke. Since activated carbon does not fall off, it can be used effectively for protective clothing.

The “woven fabric for outer layer / polyurethane hot melt nonwoven fabric / active carbon-containing composite layer (A) / polyurethane hot melt nonwoven fabric / tricot knitted fabric for inner layer” formed in Example 1 (1) before being heated and pressed. It is a figure which shows the laminated body which overlapped in order.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Woven cloth for outer layers 2a Polyurethane hot melt nonwoven fabric 2b Polyurethane hot melt nonwoven fabric 3 Material for activated carbon containing composite layer (A) 3a Nonwoven sheet made of nanofiber 3b Nonwoven sheet made of nanofiber 3c Activated carbon layer 4 Tricot knitted fabric for inner layer

Claims (6)

A laminated structure for protective clothing in which an outer layer, an intermediate layer and an inner layer are laminated in the order of outer layer / intermediate layer / inner layer;
-The outer layer is composed of a fabric with water and oil repellent finishes;
The intermediate layer includes activated carbon having a specific surface area of 600 to 3000 m ² / g, and the activated carbon is protected by a nanofiber layer having an air permeability of 0.1 cc / cm ² / sec or more made of nanofibers having an average fiber diameter of 10 to 1000 nm. Activated carbon-containing composite layer;
The inner layer is made of fabric;
A laminated structure for protective clothing characterized by the above.   The laminated structure for protective clothing according to claim 1, wherein the water repellency of the fabric constituting the outer layer is 80 or more and the oil repellency is 4 or more.   The laminated structure for protective clothing according to claim 1 or 2, wherein the fabric constituting the outer layer is a flame retardant fabric.   The laminated structure for protective clothing according to any one of claims 1 to 3, wherein the nanofiber layer in the intermediate layer is composed of a nonwoven sheet made of organic polymer nanofibers.   The intermediate layer is bonded to the fabric constituting the outer layer and the fabric constituting the inner layer by point bonding or line bonding with a hot melt adhesive or by a hot melt nonwoven fabric. Laminated structure for protective clothing.   The protective clothing which consists of a laminated structure of any one of Claims 1-5.

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