JP2014024236A - Protective material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a protective material as a material exhibiting excellent protective performances against gases, liquid chemical substances and particulate substances, above all excellent liquid osmosis inhibitory functions under pressure, permeating air, light in weight, and affording excellent comfort.SOLUTION: In a protective material 6 provided by laminating at least one layer each of: protective sheet layer 4 wherein at least three layers of upper layer 1, intermediate layer 2 consisting of a non-woven fabric with a mean single fiber diameter of 10 nm or above and 2000 nm or below, and lower layer 3 are laminate; and gas adsorption layer 5, the air permeability of the protective material is 5 cm/cmsec or above, and the oil repellency of the lower-layer sheet of the protective sheet layer stipulated by AATCC Test Method 118-2002 is Grade 3 or above.

Description

  The present invention can effectively protect a worker from liquid, gaseous organic chemicals, and particulates that are absorbed from the skin such as organophosphorus compounds and adversely affect the human body, and is lightweight and breathable. Therefore, the present invention relates to a protective material having excellent comfort. The protective material of the present invention is particularly suitable for shelters, clothes, gloves, shoes, covers and the like.

  Conventionally, various protective materials for protecting the human body from harmful chemical substances have been proposed. For example, in order to suppress the falling off and scattering of activated carbon, an adsorption sheet in which activated carbon is sandwiched or wrapped with a woven fabric or non-woven fabric has been proposed. In addition, a protective material that is lightweight and retains breathability and has excellent comfort has not yet been proposed.

For example, Patent Document 1, a support web, 1.0 diameter of less than microns, at least 145cm hydrocephalus and at least 0.3m ³ / ^{m 2} - of fibers having a minute Frazier air permeability and a hydrophobic barrier web Nonwoven materials comprising it have been proposed. Since this nonwoven fabric material has a very high water head, it is excellent in protective performance, but there is a concern that air permeability and flexibility are low.

  Patent Document 2 includes a liquid toxic chemical substance protective layer, a gaseous toxic chemical substance adsorption layer, and an adsorbent protective layer, which penetrates liquid and gaseous toxic chemical substances, particularly droplets under pressure. A material for protective clothing that prevents permeation of water and has excellent breathability and moisture permeability even when worn has been proposed. Although this protective clothing material is excellent in suppressing penetration of liquid droplets, air permeability, and moisture permeability, there is a concern that the ability to suppress penetration of particulate matter is low.

  Patent Document 3 proposes a protective clothing material having one or more particle removal layers and gas adsorption layers each having a collection efficiency of 90% or more for particulate matter. In this protective material, there is no detailed description regarding the suppression of the penetration of droplets under pressure.

  Patent Document 4 proposes a face mask composed of a spunbond / meltblown / spunbond (SMS) laminate and excellent in prevention of liquid penetration, resistance to invasion of microorganisms, air permeability, and the like. Regarding the material for the face mask, no consideration is given to the suppression of the permeation of liquid droplets under pressure. Furthermore, it contains an electret material, and the performance maintainability when using oil, solvent, etc. is not taken into consideration.

  Patent Document 5 discloses a nonwoven fabric composed of two or more layers of a synthetic fiber layer and a hydrophilic fiber layer, wherein a nonwoven fabric layer containing at least 50% by weight of ultrafine fibers having a single fiber fineness of 0.5 dtex or less exists in at least a part of the nonwoven fabric. Although materials have been proposed, this document does not take into consideration the suppression of droplet permeation under pressure, and is shown only by an index based on a water pressure resistance coefficient.

Patent Document 6 discloses that at least one surface of a synthetic resin sheet having an oxygen permeability coefficient of 500 cm ³ / m ² · 24 hr · atm or less, such as a polyacrylonitrile-based resin or an ethylene / vinyl alcohol copolymer, has a porosity of 10% or more. A protective clothing material in which one or more auxiliary sheets are laminated is proposed. Although the protective clothing material using this synthetic resin sheet has high permeation suppression and protection performance against particulate matter, it is inferior in breathability and moisture permeability, and there is a concern about wearing feeling.

JP 2005-539157 A Japanese Patent Laid-Open No. 08-308945 JP 2007-063353 A JP-T-2005-531361 JP 2003-20554 A JP 2003-166106 A

  The present invention was devised in view of the problems of the prior art, and its purpose is excellent in the protective performance of gaseous, liquid chemical substances and particulate substances, and particularly has excellent liquid permeation suppression ability under pressure. Furthermore, the present invention provides a protective material that is breathable, lightweight, and comfortable.

As a result of intensive studies on the protective material in order to achieve this object, the present inventor has completed the present invention. That is, the present invention is as follows.
1. A protective material in which an upper layer, an intermediate layer made of a nonwoven fabric having an average single fiber diameter of 10 nm or more and 2000 nm or less, and a protective sheet layer in which at least three layers of lower layer sheet materials are laminated, and one or more gas adsorbing layers are laminated. A protective material having an air permeability of 5 cm ³ / cm ² · sec or more and an oil repellency of AATCC Test Method 118-2002 under the protective sheet layer of 3 or more.
2. 2. The protective material according to 1 above, wherein the oil resistance of AATCC Test Method 118-2002, which is an upper layer of the protective sheet layer, is 2 or less.
3. A protective garment using the protective material according to 1 or 2 above.

  The protective material of the present invention has a high permeation suppressing ability with respect to gaseous and liquid organic chemical substances and particulate substances, and is also a breathable, lightweight and comfortable material. Very suitable for use on clothes.

It is the schematic of the cross-section of the protection material of this invention. It is the schematic which showed the pressurized liquid penetration test method. It is the schematic which showed the gas-penetration resistance test method. It is the schematic which showed the particle-permeation resistance test method.

Hereinafter, the protective material of the present invention will be described in detail.
As shown in FIG. 1, the protective material of the present invention is formed by laminating one or more protective sheet layers, each of which is a laminate of at least three sheet materials of an upper layer, an intermediate layer, and a lower layer, and a gas adsorption layer. About the intermediate | middle layer of a protective sheet layer, it consists of a structure containing the nonwoven fabric with an average single fiber diameter of 10 nm or more and 2000 nm or less.

  The material of the nonwoven fabric used for the intermediate layer of the protective sheet layer of the protective material of the present invention is not particularly limited, and rayon, polynosic, cupra, lyocell, acetate, triacetate, nylon, aramid, vinylon, vinylidene, poly Vinyl chloride, polyester, acrylic, acrylic, polyethylene, polyurethane, polyclar, polyarylate, polyimide, polyamideimide, polyphenylene sulfide, polyacrylonitrile, polysulfone, polycarbonate, polyparaphenylene benzoxazole, polybenzimidazole, polyvinyl alcohol, cellulose, polyethylene Oxide, Polypropylene oxide, Polyvinyl acetate, Polyethylene terephthalate, Polybutylene terephthalate, Polylactic acid, Polypropylene Pyrene, PVDF, PPS, and the like.

  As the nonwoven fabric material used for the intermediate layer of the protective sheet layer, polyurethane, nylon, polyvinyl alcohol, and the like are preferable from the viewpoint of comfort, flexibility, elongation, and the like, assuming use in clothing.

  A nonwoven fabric is used for the intermediate layer of the protective sheet layer of the protective material of the present invention. This is because if it is a non-woven fabric, excellent particle removal performance can be imparted, and the balance between flexibility and elongation is excellent. For example, when it is a protective garment, workability is good and stress can be reduced. In addition, it is one of preferable modes to form a film by individually or mixing these materials or sequentially laminating with other reinforcing materials.

  The method for producing the intermediate layer of the protective sheet layer is not particularly limited, and examples thereof include known wet methods, dry methods, melt blown methods, spunbond methods, flash spinning methods, electrospinning methods, and composite fiber splitting methods. However, the melt-blowing method, the electrosping method, and the like are preferable from the viewpoint that high particle removal performance can be obtained without charging with a fine fiber diameter. The electrospinning method referred to here is a kind of solution spinning, which is a technique of applying a positive high voltage to a polymer solution and causing fiberization in the process of being sprayed on a grounded or negatively charged surface. .

  The average single fiber diameter of the nonwoven fabric used for the intermediate layer of the protective sheet layer of the present invention is 10 nm or more and 2000 nm or less. More preferably, it is 50 nm or more and 1500 nm or less. When the average single fiber diameter is less than 10 nm, mechanical strength is not obtained, and furthermore, fiberization becomes difficult, physical properties close to a film shape are obtained, air permeability is reduced, and practical strength can be obtained. It becomes difficult. On the other hand, when the average single fiber diameter exceeds 2000 nm, a large weight is required to satisfy the required particle removal performance and liquid protection performance, and a high level of protection and wearer comfort. It becomes difficult to achieve both.

The mass of the nonwoven fabric used for the intermediate layer of the protective sheet layer of the present invention is preferably 0.1 g / m ² or more and 100 g / m ² or less. More preferably, it is 0.3 g / m ² or more and 80 g / m ² or less. If the mass is less than 0.1 g / m ² , the required particle removal performance and liquid protection performance cannot be satisfied, and further, the mechanical strength is insufficient and the material is not uniform, and the strength and particle removal performance. Are prone to problems. On the other hand, if it exceeds 100 g / m ² , the air permeability may be reduced.

  About the range of the value (A) which remove | divided the average single fiber diameter (D) in the nonwoven fabric used for the intermediate | middle layer of the protection sheet layer of this invention by mass (M), it is preferable that it is 10-500. More preferably, it is 30 or more and 400 or less. By setting it as this range, a protective sheet excellent in particle removal performance, liquid resistance performance during pressurization, air permeability, and mass balance can be obtained.

  Although it does not specifically limit as a sheet material used for the upper layer of the protective sheet layer of this invention, and a lower layer, It is preferable that it is a nonwoven fabric. Moreover, mechanical strength is given by using a long-fiber nonwoven fabric for the upper layer side, and also the protection performance with respect to a liquid substance improves. The long fiber nonwoven fabric may be formed by a known spunbond method or melt blow method, but is more preferably formed by a spunbond method having higher mechanical strength.

It is preferable that the upper layer and the intermediate layer of the protective sheet layer are protected by a non-woven fabric having high flexibility without disturbing the air permeability in the lower layer of the protective sheet layer. Although it will not specifically limit if it is a nonwoven fabric also about a lower layer, It is preferable to arrange | position highly flexible nonwoven fabric materials, such as a spunlace nonwoven fabric and a thermal bond nonwoven fabric.
In addition, about the number of layers of an upper layer and a lower layer, an optimal number can be suitably selected in terms of strength maintenance.

  The upper layer and lower layer sheet materials used in the protective sheet layer of the present invention are natural fibers such as cotton, wool, hemp (linen, ramie), regenerated cellulose fibers such as rayon, cupra, polynosic, purified cellulose, polyethylene terephthalate, Polybutylene terephthalate, cationic dyeable polyethylene terephthalate, polyesters such as polytrimethylene terephthalate, and other synthetic fibers (polyamide, polyacrylonitrile, polyurethane, acetate, polyvinyl chloride, polyethylene, polypropylene, polyimide, fluorine, polybenzazole, poly Lactic acid, etc.). It may be a non-woven fabric having a single structure, a mixture of two or more types (mixed fiber, mixed spinning), or a multilayer structure.

  The nonwoven fabric used for the upper layer of the protective sheet layer of the present invention is used for protective clothing having camouflaged camouflage performance using an outer layer additional layer that is camouflaged (wavelength controlled) in the near-infrared wavelength region described later. Is preferably made of a resin that can be kneaded with an infrared absorber. Examples of resins that can be kneaded with infrared absorbers such as carbon black include polyester, copolymer polyester, polyamide, polyamideimide, polyurethane, silicon, polyacrylate, polyacrylonitrile, polyolefin, ethylene-vinyl alcohol copolymer, polyvinyl alcohol. , Cellulose, cellulose derivative resin and the like. By using a resin in which such an infrared absorber is kneaded, the performance can be satisfied with respect to camouflaged camouflage. When using a non-woven fabric made of a resin with no kneading of an infrared absorbent, there is a concern that reflection of light from the upper layer fabric will occur and the camouflaged camouflage will be impaired.

  Moreover, as an amount which knead | mixes an infrared absorber, it is preferable that 0.2 to 10 weight% is contained normally. When the content of the infrared absorber is less than 0.2% by weight, sufficient infrared absorption performance is not exhibited, and when it exceeds 10% by weight, the production of the nonwoven fabric is deteriorated.

  Furthermore, examples of materials that cannot be kneaded with infrared absorbers include natural fibers such as cotton, hemp, wool, and silk. With respect to the raw material, the nonwoven fabric material of the uppermost layer can be obtained by forming the sheet material and then fixing the infrared absorber via a binder resin or the like. In addition, about the raw material which an infrared absorber can knead | mix, you may fix an infrared absorber through a binder.

  The kneading of the infrared absorbent into the sheet material can be performed by means known in the art. For example, as a method of kneading an infrared absorbent into a nonwoven fabric that is one of the sheet materials, a masterbatch in which the infrared absorbent is kneaded by a known means is prepared, followed by dry spinning or processing by wet spinning or the like The method of doing is mentioned.

  In the case of fixing the infrared absorber, there are no particular limitations on the bonding method, the type of the adhesive, and the like, but examples of the adhesive to be fixed include polyurethane-based cross-linked resins and acrylic cross-linked resins (for example, self-cross-linked types). Acrylic ester binder resins, etc.), silicon crosslinkable resins, epoxy crosslinkable resins, polyamide crosslinkable resins, polyester crosslinkable resins, polyvinyl alcohol resins, and the like. These may be used alone. Two or more types may be used in combination. Among these, a silicone-based cross-linked resin or a self-cross-linked acrylic ester resin is preferable because it has an effect of fixing washing durability, and particularly has both heat resistance and washing durability.

  Examples of the method for fixing the infrared absorber include a method in which a working fluid having an infrared absorber is applied by a method such as a padding method, an impregnation method, a spray method, or a coating method, followed by drying and curing. The drying is preferably performed at a temperature of about 80 ° C. to 200 ° C. for 30 seconds to 60 seconds, particularly about 95 ° C. to 120 ° C. for 1 minute to 30 minutes. Also, after drying, it is desirable to carry out a curing process in order to firmly adhere. The curing is preferably performed at about 130 ° C. to 180 ° C. for 30 seconds to 10 minutes.

  The processed resin may contain a softening agent, a texture adjusting agent, a catalyst, a pH adjusting agent, a functional processing agent, a thickening agent, and the like. Two or more types may be used in combination.

The mass of the upper layer and the lower layer of the protective sheet layer of the present invention is preferably 10 g / m ² or more and 150 g / m ² or less. More preferably, it is 20 g / m ² or more and 120 g / m ² or less. When the mass is less than 10 g / m ² , the intermediate layer does not function sufficiently. On the other hand, if it exceeds 150 g / m ² , the material itself becomes hard and inferior in flexibility.

  The thicknesses of the upper and lower layers of the protective sheet layer of the present invention are preferably 0.05 mm or more and 0.8 mm or less. By setting it as such a range, the protective material which satisfy | fills the function as a protective layer of an intermediate | middle layer, and was excellent in air permeability and a feeling of use is obtained.

The air permeability of each of the upper layer and the lower layer of the protective sheet layer of the present invention is 100 cm ³ / cm ² · sec in the air permeability test according to the method described in JIS L1096 (2010) 8.26.1 A method (Fragile type method). It is preferably 500 cm ³ / cm ² · sec or less. More ^preferably, 150cm ^{3 /} cm 2 · sec or more 400cm is ³ / ^cm 2 · sec or less. If the breathability is less than 100 cm ³ / cm ² · sec, when wearing protective clothing using a protective sheet comprising a protective sheet layer including an intermediate layer and a gas adsorbing layer, it leads to a feeling of stuffiness during wearing, It becomes the cause which cannot satisfy a feeling of use. On the other hand, when it exceeds 500 cm ³ / cm ² · sec, there is a problem that the protective layer is not sufficient.

  The purpose of laminating the lower layer in the protective sheet layer of the present invention is to protect the upper layer and intermediate layer of the protective sheet layer as described above, and to provide liquid-proof protective properties. Therefore, about the lower layer, the oiliness degree of AATCC Test Method 118-2002 is 3rd grade or more, Preferably it is 4th grade or more. If the oil repellency of the lower layer is less than the third grade, the liquid-proof protective performance of the protective sheet cannot satisfy the required performance.

  The lower layer of the protective sheet layer of the present invention is coated with an oil processing agent such as a fluororesin system, a silicone resin system, a wax resin system, and a natural coconut oil system, preferably a fluororesin system is coated with an oil processing agent. The oiliness degree of AATCC Test Method 118-2002 can be made to be 3 or more. As a coating method, it can process by a well-known processing method, The spraying by a spray, an impregnation process, etc. are mentioned. The degree of oil repellency can be adjusted by appropriately adjusting the concentration of the oil repellant, the amount of adhesion, and the like.

  The main lamination purpose of the intermediate layer of the protective sheet layer of the present invention is to impart excellent particle removal performance. Therefore, the average single fiber diameter of the nonwoven fabric used for the intermediate layer is 10 nm or more and 2000 nm or less. Regarding the intermediate layer, it is preferable that the oiliness degree of AATCC Test Method 118-2002 is grade 3 or higher. This is because by providing the intermediate layer with liquid-proof protective properties, it is possible to give excellent liquid-proof protective performance to the protective material.

The purpose of layering the upper layer in the protective sheet layer of the present invention is to improve the liquid-proof protective performance under pressure. Therefore, as for the upper layer, the oiliness degree of AATCC Test Method 118-2002 is preferably 2nd grade or less, more preferably 1st grade or less.
The reason why it is preferable that the upper layer has a lower oil repellency is to increase the diffusibility of the liquid in the upper layer to disperse the liquid organic chemicals as uniformly as possible, and excessively in a part of the intermediate layer and the lower layer. This is to prevent the load from being applied.
That is, by sharing the role of diffusing the liquid in the upper layer and preventing the permeation of the liquid in the lower layer, the liquid-proof protective performance is improved particularly under pressure.

  The following method is mentioned as a lamination | stacking means of each layer of a protection sheet layer. As a first method, the intermediate layer is bonded to either the upper layer or the lower layer protective layer with an adhesive. As a second method, there is a method in which an intermediate layer is directly applied to either an upper layer or a lower layer prepared in advance by an electrospinning method or the like, and the other is laminated with an adhesive. Furthermore, as a third method, there is a method of laminating three layers by needle punch, hydroentanglement, ultrasonic waves, etc., and there is no particular limitation. A lamination method using the first and second adhesives, which can be laminated without destroying the material, is a preferable method. In addition, about the number of lamination | stacking of an upper layer and each lower layer, the optimal number can be suitably selected from the surface of strength maintenance, protection performance, etc. In consideration of destruction due to lamination of materials, durability in use, and the like, a method of bonding with the first adhesive is preferable.

  Examples of the adhesive used in the protective sheet layer of the present invention include urethane-based, vinyl alcohol-based, ester-based, epoxy-based, vinyl chloride-based, olefin-based, amide-based, etc., flexibility after lamination, texture, In consideration of durability and the like, urethane, ester and amide are preferable. Note that the adhesive is preferably a solventless adhesive in consideration of gas adsorption performance, but is not particularly limited. In addition to the resinous adhesive, using a non-woven adhesive and laminating is a useful means in terms of cost and workability.

  In consideration of washing processability, it is preferable to use a moisture-curable polyurethane adhesive among the urethane-based adhesives described above. Also, in order to ensure breathability when a protective clothing material is used, it is preferable to apply partial adhesion in which an adhesive is partially applied and laminated instead of a method in which an adhesive is applied to the entire surface.

  The method of partial adhesion is not particularly limited, but in consideration of flexibility, air permeability, etc., the adhesive is applied to the entire surface in the form of dots, lattices, spirals, rods by gravure method, screen method, spray method, etc. Then, the method of adhering is preferable.

The application amount of the adhesive to be used is preferably 3 g / m ² or more and 30 g / m ² or less. More preferably, the 5 g / ^{m 2} or more 20 g / ^{m 2} or less. If the coating amount is less than 3 g / m ² , the adhesion to the intermediate layer is poor, and there is a concern that floating or the like may occur when washing, drying, or the like is performed. On the other hand, when it exceeds 30 g / m ² , there is a concern that the texture at the time of lamination becomes hard and the air permeability is also lowered.

  The melt flow rate (MFR value) of the adhesive used is preferably 150 g / 10 min or less, more preferably 100 g / 10 min or less. By setting the MFR value to less than 150 g / 10 min, the area where the surface of the core layer is covered with the adhesive is reduced, and deterioration in air permeability due to lamination can be suppressed.

The mass of the protective sheet layer of the present invention is preferably 30 g / m ² or more and 200 g / m ² or less. More preferably, it is 50 g / m ² or more and 150 g / m ² or less. When the mass is less than 30 g / m ² , the mechanical strength is insufficient. On the other hand, if it exceeds 200 g / m ² , the air permeability is lowered, and further, when it is used as a protective garment, the wearability, the motion following ability, and the feeling of use cannot be satisfied.

  The thickness of the protective sheet layer of the present invention is preferably 0.1 mm or more and 1.0 mm or less. By setting it as such a range, the protective sheet excellent in the balance of particle | grain removal performance, the liquid-proof performance at the time of pressurization, and also air permeability and a feeling of use is obtained.

The air permeability of the protective sheet layer of the present invention is 5 cm ³ / cm ² · sec or more and 80 cm ³ / cm ² · in the air permeability test according to the method described in JIS L1096 (2010) 8.26.1 (Fragile method). It is preferable that it is sec or less. More preferably, it is 7 cm ³ / cm ² · sec or more and 50 cm ³ / cm ² · sec or less. If the air permeability is less than 5 cm ³ / cm ² · sec, it leads to a feeling of stuffiness when wearing protective clothing, and causes a feeling of unsatisfactory use. On the other hand, if it exceeds 80 cm ³ / cm ² · sec, the particle removal performance and further the liquid resistance performance during pressurization will deteriorate.

  The waterproof property of the protective sheet layer of the present invention is preferably 70 mm or more and 1300 mm or less in a water pressure resistance test according to the method described in JIS L1092 (2009) 7.1 (hydrostatic pressure method). More preferably, it is 80 mm or more and 1200 mm or less. If the head is less than 70 mm, the liquid resistance performance and particle removal performance during pressurization may not be satisfied. On the other hand, if it exceeds 1300 mm, the protective performance will be high, but the breathability will be low and the protective clothing will be It should not be excellent in feeling during use.

  By stacking the gas adsorption layer on the upper layer and / or the lower layer of the protective sheet layer of the present invention, it is possible to provide protection against gas. Examples of the gas adsorption layer include carbon adsorbents such as activated carbon and carbon black, or gas adsorbents composed of inorganic adsorbents such as silica gel, zeolite adsorbent, silicon carbide, and activated alumina. It can be appropriately selected according to the adsorbed substance to be adsorbed. Among them, activated carbon that can deal with a wide range of gases is preferable, and fibrous activated carbon that has a large adsorption rate and adsorption capacity and can effectively suppress gas permeation when used in a small amount is more preferable.

  The gas as the adsorbed substance includes a gaseous compound having one or more carbon elements. For example, the gaseous compound includes a gaseous chemical substance having a relatively large molecular weight of 50 or more and capable of being adsorbed by a gas adsorption layer such as activated carbon. Specific examples include organic phosphorus compounds used for agricultural chemicals, insecticides and herbicides, and general organic solvents such as toluene, methylene chloride and chloroform used for painting work and the like.

When fibrous activated carbon is used for the gas adsorption layer, the BET specific surface area 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. If the BET specific surface area is less than the above range, a large amount of activated carbon is required to obtain sufficient protection, the material becomes heavy, and there is a concern that the flexibility is inferior. On the other hand, when it becomes larger than the above range, a problem of desorbing the adsorbed gaseous organic chemical substance may occur.

The mass of the fibrous activated carbon in the gas adsorption layer is preferably 50 g / m ² or more and 300 g / m ² or less, more preferably 70 g / m ² or more and 250 g / m ² or less. When the mass is less than the above range, the capacity that can be adsorbed is reduced, and the use time is limited. On the other hand, when it exceeds the above range, there is a concern that the flexibility of the material is inferior.

  As raw materials for fibrous activated carbon, in addition to natural cellulose fibers such as cotton and hemp, regenerated cellulose fibers such as rayon, polynosic and solvent spinning methods, polyvinyl alcohol fibers, acrylic fibers, aromatic polyamide fibers, lignin fibers, phenols Synthetic fibers such as system fibers and petroleum pitch fibers can be mentioned, but regenerated cellulose fibers, phenol fibers, and acrylic fibers are preferred from the physical properties (strength etc.) and adsorption performance of the obtained fibrous activated carbon. Fibrous activated carbon can be produced by a conventionally known method. For example, a fabric that has been woven, knitted, or non-woven using short fibers or long fibers of these raw material fibers can be appropriately flame-resistant as necessary. After containing an agent, it can be produced by applying a flameproofing treatment at a temperature of 450 ° C. or lower, and then carbonizing at a temperature of 500 ° C. or higher and 1000 ° C. or lower.

  As a method for forming the gas adsorption layer, a conventionally known method can be adopted. For example, a gas adsorbent is bonded to a sheet base material with a binder, or the gas adsorbent is made into a slurry including an appropriate pulp and binder. A method of making paper by a wet paper machine, or a method of carbonizing and activating the raw material fibers of the gas adsorbent in advance after weaving, knitting or non-woven fabric, and flame-proofing treatment as necessary can be employed.

  The gas adsorption layer preferably has any form of woven fabric, knitted fabric, non-woven fabric, or felt. Among these, the form of the woven fabric or the knitted fabric is preferable from the viewpoints of air permeability, ease of lamination, flexibility, and the like.

  As a means for laminating the protective sheet layer and the gas adsorbing layer, it is preferable that they are partially bonded in consideration of air permeability. Although it does not specifically limit as an adhesive agent used for partial adhesion | attachment, Solvent type or solventless adhesives, such as a synthetic rubber, a vinyl acetate resin, a urethane resin, an epoxy resin, an acrylic resin type, a polyester type, a vinyl chloride, are preferable. When using a solvent-based adhesive, the organic solvent contained in the adhesive may be adsorbed by the gas adsorption layer and gas adsorption performance may be reduced. It needs to be vaporized. The method for desorbing the solvent adsorbed on the gas adsorbing layer needs to be set according to the type of solvent used in the adhesive. The residual solvent ratio with respect to the gas adsorption layer is preferably 20% or less, more preferably 15% or less.

  The method of partial adhesion is not particularly limited, but in consideration of flexibility, air permeability, etc., the adhesive is applied in a non-whole dot, lattice, spiral, or rod shape by gravure method, screen method, spray coating, etc. A method of uniformly applying and adhering is preferable. The adhesive can be applied on either the protective sheet surface or the gas adsorption layer surface, but it is preferable to apply the adhesive to the protective sheet surface in consideration of gas adsorption performance.

The coating amount of the adhesive is preferably 5 g / m ² or more and 50 g / m ² or less. More preferably, the 10 g / ^{m 2} or more 40 g / ^{m 2} or less. When the coating amount is less than the above range, there is a problem that the adhesive strength is lowered. On the other hand, when the coating amount exceeds the above range, flexibility and air permeability are deteriorated.

  The ratio of the adhesion area at the time of partial adhesion (the ratio of the adhesive application area to the area of the gas adsorption layer) is preferably 5% or more and 80% or less, more preferably 10% or more and 70% or less. If the ratio is less than the above range, there is a problem that the adhesive strength is lowered. On the other hand, if the ratio is more than the above range, the amount of adhesive applied becomes large, partial adhesion hardly occurs, and flexibility and breathability are reduced. A problem that degrades occurs.

  In the case of partial adhesion by a gravure method, a screen method, or a spray method, the gravure roll, screen, or spray nozzle conditions to be used can be appropriately selected according to the adhesion area and the adhesive application weight. In the case of the gravure method, these can be arbitrarily set according to the number and depth of gravure lines, in the case of the screen method, mesh thickness and aperture ratio, in the case of the spray method, the nozzle shape, nozzle pressure, etc. Is possible.

  Further, the peel strength at the adhesive interface between the protective sheet layer and the gas adsorbing layer via the adhesive is preferably 30 gf / cm or more, more preferably 40 gf / cm in both the length direction and the width direction of the material. cm or more. When the peel strength is low, the protective sheet and the gas adsorbing layer are peeled off, which causes problems such as the strength of the gas adsorbing layer or the handleability when used as clothes. The upper limit of peel strength is practically 150 gf / cm.

As described above, the mass of the protective material including the protective sheet layer and the gas adsorbing layer is preferably 500 g / m ² or less, and more preferably 400 g / m ² or less. If the mass of the laminate exceeds the above range, the material becomes heavy and poor in flexibility, and when it is used as a protective garment, there is a problem that the wearability, the motion following ability, and the feeling of use cannot be satisfied. The lower limit of mass is practically 100 g / m ² .

  The thickness of the protective material composed of the protective sheet layer and the gas adsorbing layer is preferably 5.0 mm or less, and more preferably 4.0 mm or less. If the thickness exceeds the above range, the laminate becomes stiff and the workability to protective clothing is deteriorated. The lower limit of the thickness is actually 1.0 mm.

  The stiffness, which is an index of the flexibility of the protective material composed of the protective sheet layer and the gas adsorbing layer, is preferably 0.08 N · cm or less in both the length direction and the width direction of the material, more preferably 0.8. 05 N · cm or less. If the bending resistance exceeds the above range, the material becomes stiff and it becomes difficult to process as an adsorption sheet. The lower limit of the bending resistance is actually 0.002 N · cm.

The air permeability of the protective material composed of the protective sheet layer and the gas adsorbing layer is 5 cm ³ / cm ² · sec or more in the air permeability test according to the method described in JIS L1096 (2010) 8.26.1 (Fragile method). It is. It is preferably 7 cm ³ / cm ² · sec or more and 100 cm ³ / cm ² · sec or less, more preferably 10 cm ³ / cm ² · sec or more and 80 cm ³ / cm ² · sec or less. If the air permeability is less than the above lower limit, the air permeability is inferior, and if it exceeds the above range, the material becomes insufficiently bonded, causing a problem of peeling, and further, the particle resistance may be inferior.

The toluene adsorption performance (toluene gas equilibrium adsorption amount) of the protective material composed of the protective sheet layer and the gas adsorption layer is preferably 20 g / m ² or more. More preferably, it is 25 g / m ² or more. When the toluene adsorption performance is less than the above range, the adsorptivity is poor and the protection against gas is poor. The upper limit of toluene adsorption performance is practically 200 g / m ² .

  Further, in order to further improve the protection property of the protective sheet against the liquid chemical substance, a material that has been previously subjected to water-repellent and oil-repellent processing may be used for the gas adsorption layer. The water-repellent and oil-repellent processing may be any conventionally known method and is not particularly limited. The intermediate layer and the lower layer constituting the protective sheet layer of the protective material have a water repellency of 2 or more when the spray test described in JIS L1092 (2009) 7.2 is performed, according to AATCC Test Method 118-2002. The oiliness is preferably 3 or higher.

  Furthermore, the protective material consisting of the protective sheet layer and the gas adsorption layer is intended to greatly improve the mechanical strength, and when there are multiple target gases, the protective sheet layer and the gas adsorption layer are overlapped as many as necessary. It is effective to use.

  If necessary, at least one outer layer additional layer may be provided on the outermost side of the protective material composed of the protective sheet layer and the gas adsorbing layer, and one or more inner layer additional layers may be provided on the innermost side as required. The purpose of the outer layer additional layer is to protect the protective sheet layer and gas adsorbing layer from mechanical force given from the outside, and to apply woven fabric, knitted fabric or nonwoven fabric to which water repellency and oil repellency are imparted Thus, it is possible to further improve the liquid penetration resistance. As an outer layer additional layer, a woven fabric having a water repellency of 2 or more when the spray test described in JIS L1092 (2009) 7.2 is performed, and an oil repellency of 3 or more according to AATCC Test Method 118-2002. A knitted fabric, a non-woven fabric, or the like can be suitably used, but it is recommended to use a fabric considering flexibility. The protective material consisting of the protective sheet layer and the gas adsorbing layer and the outer layer additional layer may be pre-adhered with an adhesive, or, in consideration of flexibility, sewed in a stacked state without bonding, Protective clothing may be made. Examples of the inner layer additional layer include materials such as woven fabrics, knitted fabrics, nonwoven fabrics, and apertured films, but woven fabrics or knitted fabrics woven or knitted at a coarse density are preferable from the viewpoint of air permeability and flexibility. The purpose of the inner layer additional layer is to protect the protective sheet and the gas adsorbing layer from mechanical force applied from the outside and to suppress the sticky feeling caused by the sweat of the wearer of the protective clothing. The protective material consisting of the protective sheet and the gas adsorbing layer and the inner layer additional layer may be pre-adhered with an adhesive, or may be sewed in a stacked state without bonding, considering flexibility, or The protective sheet may be laminated after the gas adsorbing layer and the quilting process in advance. For the quilting process, a conventionally known method can be adopted, and a sewing thread such as polyester, nylon or cotton is preferably used. In view of protection against liquid substances, it is particularly preferable to use oil-repellent sewing thread.

The mass of the protective material layer provided with the outer layer additional layer and / or the inner layer additional layer is preferably 700 g / m ² or less, more preferably 600 g / m ² or less. If it exceeds 700 g / m ² , the weight of the protective garment will increase and cause heat stress.

  Next, the effects of the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The evaluation methods described in the examples are as follows.

(1) Pressurized liquid penetration resistance test: FIG. 2 shows an explanatory diagram of this test. Place the filter paper 11 on the slide glass 12 and place it on the inner layer additional layer, gas adsorption layer, protective sheet, outer layer additional layers 10 and 9 in that order, and test solution 8 (dipropyl phthalate in which red dye is dissolved) 5 μL Was added dropwise to the outer layer additional layer, a weight (1 kg / cm ² ) was placed on the test solution and pressurized, and the permeability of the solution was determined by the degree of coloration of the filter paper after 24 hours. No coloration was indicated by ○, slight coloration was indicated by Δ, and coloration was indicated by ×.

(2) Gas penetration resistance test: FIG. 3 shows an explanatory diagram of this test. An outer layer additional layer, a protective sheet, a gas adsorption layer, and an inner layer additional layer are sandwiched between two glass cells (upper cell 13 and lower cell 18) having an internal volume of 150 cc, and the periphery is sealed with paraffin 17. From the upper cell 13 of this test container, 10 μL of 3 methoxybutyl acetate as the test solution 15 is dropped on the outer layer additional layer. This is put in a constant temperature box set at 25 ± 2 ° C, the gas concentration on the lower cell 18 side is sampled every predetermined time (after 1, 3, 5, 7, 24 hours), and the sample is permeated by gas chromatography. Measure the gas concentration.

(3) Particle Permeation Resistance Test: An explanatory diagram of this test is shown in FIG. An outer layer additional layer, a protective sheet, a gas adsorbing layer, and an inner layer additional layer are installed in the duct 19, and the atmosphere is vented so that the air filtration speed becomes 5 cm / sec. The number concentration of 5 μm particles was measured by a particle measuring device (particle counter) 24, and the collection efficiency was calculated by the following equation.
0.3 μm particle collection efficiency (%) = {1− (downstream concentration / upstream concentration)} × 100

(4) Average single fiber diameter: A scanning electron micrograph was taken at an appropriate magnification, 100 or more fiber side surfaces were measured, and the average value was obtained from the average value.

(5) Mass: Measured in accordance with JIS-L1096 (2010) 8.3.

(6) Thickness: Measured according to JIS-L1096 (2010) 8.4.

(7) Breathability: Measured by JIS-L1096 (2010) 8.26.1 A method (fragile type method).

(8) Specific surface area: A nitrogen adsorption isotherm was determined and calculated by the BET method based on this.

(9) Gas equilibrium adsorption amount: measured by JIS-K1477 (2007).

(10) Peel strength: Peel strength at the interface between the protective sheet layer and the gas adsorption layer was measured according to JIS-L1089 (2007) 7.10.

(11) Water repellency: According to JIS-L1092 (2009) 7.2 spray test.

(12) Oiliness: According to AATCC Test Method 118-2002.

(13) Wearability test: As a wear monitor test, a protective garment in the form of a tether, in which the upper garment, the lower garment, and the hood were connected with a protective clothing material composed of an outer layer additional layer, a protective sheet, a gas adsorption layer and an inner layer additional layer, was prepared. Later, in an artificial climate room with an ambient temperature and humidity of 20 ° C and 65% RH, running on the treadmill at 5 km / hr for 30 minutes while blowing air to the front of the trunk with a blower at 3 m / sec for 30 minutes Wearability was judged from the thermal comfort feeling based on the increase in the eardrum temperature, the maximum heart rate and the subjective report. The number of subjects was 10.

Production of gas adsorption layer As the gas adsorption layer, fibrous activated carbon in the form of a knitted fabric was produced by the following method. A circular knitted fabric having a single yarn fineness of 2.2 dtex and a 20th novolac phenol resin fiber spun yarn having a mass of 220 g / m ² is heated in an inert atmosphere at 410 ° C. for 30 minutes, and then contains 12% by volume of water vapor. It was activated in an atmosphere at a temperature of 890 ° C. for 2 hours. The obtained gas adsorption layer has an absolute dry mass of 100 g / m ² , a specific surface area of 1500 m ² / g, a thickness of 1.00 mm, and a gas permeability of 200 cm ³ / cm ² sec, toluene adsorption performance (toluene gas equilibrium adsorption amount) was 50 g / m ² .

The outer layer additional layer was produced by the following method. A plain woven fabric using 40 yarns of cotton yarn, pad-dried with a fluorinated water repellent oil processing agent (Asahi Guard AG7105 manufactured by Asahi Glass Co., Ltd.), cured at 180 ° C., and 2.0% by weight in terms of resin solids It was fixed. The resulting woven fabric has a thickness of 0.2 mm, a mass of 120 g / m ² , a breathability of 60 cm ³ / cm ² · sec with a water level gauge of 1.27 cm, water repellency of 5 and oil repellency of 6 Met.

The inner layer additional layer was produced by the following method. Using a 28-gauge 2-sheet tricot machine, set the polyester filament (82.5 dtex, 36 filament) on the front cage and the polyester filament (22 dtex, monofilament) on the back cage, respectively. A warp knitted fabric was knitted with a back 1-0 / 2-3 structure, refined by a conventional method, and further dyed with a disperse dye. The knitted fabric thus obtained has a thickness of 0.28 mm, a mass of 50 g / m ² , an air permeability of 700 cm ³ / cm ² · sec with a water level gauge of 1.27 cm, a water repellency of 5, The oiliness was grade 6.

Example 1
For the production of the protective sheet layer, a PET spunlace nonwoven fabric (manufactured by Yuho Co., Ltd.) having a mass of 40 g / m ² is used for the lower layer, and a polyester nonwoven fabric thermoplastic adhesive having a mass of 15 g / m ² is applied to the spunlace nonwoven fabric. (Dyac (registered trademark) LNS0015 manufactured by Kureha Tech Co., Ltd.) is superposed in advance, and the surface of the adhesive is made of polyurethane nanoparticle by electrospinning so that the average single fiber diameter is 100 nm and the mass is 0.5 g / m ^2. A fiber nonwoven fabric was prepared. Thereafter, the three layers including the adhesive layer are pressure-bonded with a heating roller, and then immersed in a processing bath of 3 wt% fluorine-based oil repellant (Asahi Guard AG970 manufactured by Meisei Chemical Industry Co., Ltd.) and dried at 100 ° C. Then, the temperature was raised to 150 ° C. and cured. The oiliness of these materials according to AATCC Test Method 118-2002 was grade 5 on both the spunlace nonwoven fabric side and the nanofiber nonwoven fabric side. Furthermore, as an upper layer, a protective sheet layer was prepared by adhering a spunbonded nonwoven fabric (Ecule (registered trademark) 3301AD manufactured by Toyobo Co., Ltd.) having a mass of 30 g / m ² onto nanofibers with the same adhesive.
Further, after applying a urethane-based reactive hot melt (manufactured by DIC Corporation, Tyforce H-1041) to the spunlace nonwoven fabric side of the protective sheet layer by a gravure method so that the amount of adhesive is 10 g / m ² , After superimposing on the gas adsorbing layer, all the materials were temporarily pressure-bonded with a roll, and then left for 24 hours in a constant temperature and humidity chamber at 30 ° C. and 65% RH, followed by curing treatment to obtain a protective material. In addition, pressure-resistant liquid penetration test results, gas penetration resistance test results, particle permeability resistance of protective clothing materials in which an outer layer addition layer on the spunbond nonwoven fabric side of the protection material and an inner layer addition layer on the gas adsorption layer side are overlaid Tables 1 to 5 show the test results, the wearability test results, and the physical property values of the protective sheet layer and the protective material, respectively.

(Example 2)
A protective clothing material was produced in the same manner as in Example 1 except that a polyurethane nanofiber nonwoven fabric having an average single fiber diameter of 100 nm and a mass of 2 g / m ² was used for the intermediate layer of the protective sheet layer. Table 1 shows the results of pressurized liquid penetration resistance test results, gas penetration resistance test results, particle penetration resistance test results, wear resistance test results, and physical properties of the protective sheet layer and the protective material of the obtained protective clothing materials. Table 5 shows.

(Example 3)
A protective clothing material was produced in the same manner as in Example 1 except that a polyurethane nanofiber nonwoven fabric having an average single fiber diameter of 200 nm and a mass of 0.5 g / m ² was used for the intermediate layer of the protective sheet layer. Table 1 shows the results of pressurized liquid penetration resistance test results, gas penetration resistance test results, particle penetration resistance test results, wear resistance test results, and physical properties of the protective sheet layer and the protective material of the obtained protective clothing materials. Table 5 shows.

Example 4
Meltblown nonwoven fabric made of polypropylene by weight 15 g / ^{m 2} (manufactured by Mitsui Chemicals, Inc. Syntex (TM) nano6; average single fiber diameter 600 nm) was used for the intermediate layer of the protective sheet layer, a polyester nonwoven fabric mass 15 g / ^{m 2} Except for adhering the lower layer mass of 40 g / m ² PET spunlace nonwoven fabric (manufactured by Yuho Co., Ltd.) with a sheet-like thermoplastic adhesive (Dynac (registered trademark) LNS0015 manufactured by Kureha Tech Co., Ltd.) A protective clothing material was produced. Table 1 shows the results of pressurized liquid penetration resistance test results, gas penetration resistance test results, particle penetration resistance test results, wear resistance test results, and physical properties of the protective sheet layer and the protective material of the obtained protective clothing materials. Table 5 shows.

(Example 5)
A PP meltblown nonwoven fabric having a mass of 18 g / m ² (SYNTEX (registered trademark) nano10, manufactured by Mitsui Chemicals, Inc .; average single fiber diameter: 900 nm) was used in the same manner as in Example 1 except that it was used as an intermediate layer of the protective sheet layer. A protective clothing material was produced. Table 1 shows the results of pressurized liquid penetration resistance test results, gas penetration resistance test results, particle penetration resistance test results, wear resistance test results, and physical properties of the protective sheet layer and the protective material of the obtained protective clothing materials. Table 5 shows.

(Example 6)
The same as in Example 1 except that the upper layer of the protective sheet layer was treated with a 0.5 wt% processing bath using the same fluorine-based oil-repellent agent (Asahi Guard AG970 manufactured by Meisei Chemical Co., Ltd.) as the lower layer. The protective clothing material was produced by the method described above. Table 1 shows the results of pressure-resistant liquid penetration test results, gas penetration resistance test results, particle penetration resistance test results, wear resistance test results, and physical properties of protective sheets and protective materials for the obtained protective clothing materials. As shown in FIG.

(Example 7)
In the upper layer of the protective sheet layer, protective clothing material was prepared in the same manner as in Example 1 except that it was treated with the same fluorine-based oil repellant (Asahi Guard AG970 manufactured by Meisei Chemical Co., Ltd.) as in the middle layer and lower layer. . Table 1 shows the results of pressure-resistant liquid penetration test results, gas penetration resistance test results, particle penetration resistance test results, wear resistance test results, and physical properties of protective sheets and protective materials for the obtained protective clothing materials. As shown in FIG.

(Comparative Example 1)
A protective clothing material was produced in the same manner as in Example 1 except that a PET spunlace nonwoven fabric (manufactured by Yuho Co., Ltd.) having an average single fiber diameter of 2500 nm and a mass of 30 g / m ² was used as an intermediate layer of the protective sheet layer. . Table 1 shows the results of pressurized liquid penetration resistance test results, gas penetration resistance test results, particle penetration resistance test results, wear resistance test results, and physical properties of the protective sheet layer and the protective material of the obtained protective clothing materials. Table 5 shows.

(Comparative Example 2)
A protective clothing material was produced in the same manner as in Example 1 except that the intermediate layer and the lower layer of the protective sheet layer as in Example 1 were not subjected to oil repellency. Table 1 shows the results of pressurized liquid penetration resistance test results, gas penetration resistance test results, particle penetration resistance test results, wear resistance test results, and physical properties of the protective sheet layer and the protective material of the obtained protective clothing materials. Table 5 shows.

(Comparative Example 3)
A protective clothing material was produced in the same manner as in Example 1 except that the intermediate layer was not laminated on the protective sheet layer. Table 1 shows the results of pressurized liquid penetration resistance test results, gas penetration resistance test results, particle penetration resistance test results, wear resistance test results, and physical properties of the protective sheet layer and the protective material of the obtained protective clothing materials. Table 5 shows.

(Comparative Example 4)
A protective clothing material was prepared in the same manner as in Example 4 except that a waterproof moisture-permeable fabric (Geovisor manufactured by Toyo Cloth Co., Ltd.) in which a polyurethane fabric was coated on a nylon fabric was used as an intermediate layer of the protective sheet layer. Table 1 shows the results of pressurized liquid penetration resistance test results, gas penetration resistance test results, particle penetration resistance test results, wear resistance test results, and physical properties of the protective sheet layer and the protective material of the obtained protective clothing materials. Table 5 shows.

(Comparative Example 5)
A protective clothing material was produced in the same manner as in Example 1 except that the mass of the intermediate layer of the protective sheet layer used in Example 1 was 20 g / m ² . Table 1 shows the results of pressurized liquid penetration resistance test results, gas penetration resistance test results, particle penetration resistance test results, wear resistance test results, and physical properties of the protective sheet layer and the protective material of the obtained protective clothing materials. Table 5 shows.

(Comparative Example 6)
A protective clothing material was produced in the same manner as in Example 1 except that the gas adsorption layer was not laminated. Table 1 shows the results of pressurized liquid penetration resistance test results, gas penetration resistance test results, particle penetration resistance test results, wear resistance test results, and physical properties of the protective sheet layer and the protective material of the obtained protective clothing materials. Table 5 shows.

  As is clear from the results of Tables 1 to 5, the protective clothing materials of Examples 1 to 5 are good in all of particle resistance, liquid penetration resistance, gas penetration resistance and wearability, The protective clothing materials of Comparative Examples 1 and 3 have low liquid penetration resistance and particle resistance, the protective clothing material of Comparative Example 2 has low liquid penetration resistance, and the protective clothing materials of Comparative Examples 4 and 5 are breathable. The protective clothing material of Comparative Example 6 has low gas permeation resistance, and the protective clothing materials of Comparative Examples 1 to 6 are inferior to the Examples in any of the evaluation items. It was.

The protective material of the present invention is a material having excellent protective performance against liquid chemical substances and particulate substances, and particularly having excellent liquid permeation suppressing ability under pressure, and further has air permeability, light weight and comfort. It is important to contribute to the industry by providing superior protective materials.

1: Upper layer 2: Intermediate layer 3: Lower layer 4: Protection sheet layer 5: Gas adsorption layer 6: Protection material 7: Weight (1 kg / cm ² )
8: test solution 9: outer layer additional layer 10: protective sheet layer + gas adsorption layer + inner layer additional layer 11: filter paper 12: glass slide 13: upper cell (150 cc)
14: Sampling port 15: Test solution 16: Outer layer additional layer + protective sheet layer + gas adsorption layer + inner layer additional layer 17: Paraffin sealing 18: Lower cell (150 cc)
19: Duct 20: Outer layer additional layer + Protective sheet layer + Gas adsorption layer + Inner layer additional layer 21: Flow meter 22: Valve 23: Blower 24: Particle counter 25: Sampling tube

Claims (3)

A protective material in which an upper layer, an intermediate layer made of a nonwoven fabric having an average single fiber diameter of 10 nm or more and 2000 nm or less, and a protective sheet layer in which at least three layers of lower layer sheet materials are laminated, and one or more gas adsorbing layers are laminated. A protective material having an air permeability of 5 cm ³ / cm ² · sec or more and an oil repellency of AATCC Test Method 118-2002 under the protective sheet layer of 3 or more.   The protective material according to claim 1, wherein the oiliness of the AATCC Test Method 118-2002 in the upper layer of the protective sheet layer is 2nd grade or less.   A protective garment using the protective material according to claim 1.