JP2014227624A - Protection material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a protection material which has excellent protection performance from liquid chemical substances and particulate substances, especially has excellent suppressibility of liquid penetration under pressure, further has excellent air permeability, and is lightweight and provides comfort, and to provide a protection product usable for a long period which, when the protection material is used to form a protective clothing having an outer added layer and an inner added layer where the outer added layer is refabricated by a fluorine resin-based water repellant treatment agent, does not change characteristics of the protection material which is disposed as an inner layer.SOLUTION: Provided is a protection material comprising at least three layers of sheet materials laminated including an upper layer, an intermediate layer composed of a nonwoven fabric having an average single fiber diameter of 10 nm or more and 2000 nm or less, and a lower layer. The upper layer of the protection material is coated by a non-fluorine-based water repellant treatment agent, and the intermediate and lower layers are coated with a fluorine-based water repellant treatment agent. The protection material has an oil repellency grade of 3 or higher as determined by the AATCC Test Method 118-2002.

Description

  The present invention can effectively protect workers from liquid organic chemicals that are absorbed from the skin, such as organophosphorus compounds, and have an adverse effect on the human body, and particulate matter, and is lightweight and breathable. It is related with the protective material which is excellent also in comfort. The protective material of the present invention is particularly suitable for shelters, protective clothing, gloves, shoes, covers and the like.

  Various protective materials for protecting the human body from harmful chemical substances have been proposed. For example, in order to suppress falling off and scattering of activated carbon, adsorption sheets that have been sandwiched or wrapped with woven fabric or nonwoven fabric have been proposed. In particular, the ability to suppress penetration into liquid and particulate organic chemicals has been improved. In addition, a material that is lightweight and retains air permeability and has excellent comfort has not yet been proposed. In addition, material design considering repeated use has not been studied in detail.

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 liquid-proof 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 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. The material for the face mask includes the suppression of the permeation of liquid droplets under pressure, and further includes an electret material, and does not take into consideration performance maintainability when an oil, a solvent, or the like is used. .

  In Patent Document 4, a nonwoven fabric comprising two or more layers of a synthetic fiber layer and a hydrophilic fiber layer, and a nonwoven fabric layer in which at least a portion of the nonwoven fabric contains 50% by weight or more of ultrafine fibers having a single fiber fineness of 0.5 dtex or less exists. 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.

In Patent Document 5, the porosity is 10% or more on 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 resin or an ethylene / vinyl alcohol copolymer. 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-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 a material that has excellent liquid chemical substance and particulate matter protection performance, particularly excellent liquid permeation suppression ability under pressure. Furthermore, another object is to provide a protective material that is breathable, lightweight and excellent in comfort. In addition, in consideration of repeated use in protective clothing with the outer layer additional layer and the inner layer additional layer using the above protective material, reprocessing with a fluororesin-based water-repellent processing agent is applied to the outer layer additional layer. In other words, the characteristic of the protective material arranged in the inner layer is not changed.

As a result of intensive studies on the protective material in order to achieve the above object, the present inventors have 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 lower layer of at least three layers of sheet materials are laminated, and the upper layer of the protective material is a water-repellent finishing agent other than a fluororesin type A protective material in which an intermediate layer and a lower layer of the protective material are coated with a fluororesin-based water repellent, and the oil repellency of AATCC Test Method 118-2002 is 3 or more.
2. 2. The protective material according to 1 above, wherein the water-repellent agent other than the fluororesin-based agent is at least one water-repellent agent selected from silicon-based, wax-based or natural water-repellent agents.
3. A protective garment using the protective material according to 1 or 2 above.

  The protective material of the present invention is a material that has a high permeation suppressing ability for liquid organic chemical substances and particulate substances, and is breathable, lightweight and comfortable, and used for protective clothing. It is very suitable to do. Further, it is intended for repeated use in protective clothing having an outer layer additional layer and an inner layer additional layer.

It is the schematic of the cross-section of the protective material of this invention. It is the schematic which showed the pressurized liquid penetration 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 composed of a sheet material of at least three layers comprising an upper layer, an intermediate layer, and a lower layer, and at least the intermediate layer has an average single fiber diameter of 10 nm to 2000 nm. It is comprised from the nonwoven fabric of this.

  The material of the nonwoven fabric used for the intermediate layer of the protective material of the present invention is not particularly limited, and rayon, polynosic, cupra, lyocell, acetate, triacetate, nylon, aramid, vinylon, vinylidene, polyvinyl 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, PVD , PPS and the like.

  As the material for the nonwoven fabric used for the intermediate layer, polyurethane, nylon, polyethylene terephthalate, polybutylene terephthalate, and the like are preferable from the viewpoint of comfort, flexibility, elongation, etc.

  The intermediate layer used for the protective material of the present invention is a nonwoven fabric. 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 is not particularly limited, and examples include known wet methods, dry methods, melt blown methods, spunbond methods, flash spinning methods, electrospinning methods, and composite fiber splitting methods. A melt blow method, an electrosping method, etc. are preferable from the point of obtaining high particle removal performance even without charging with the 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 present invention is 10 nm or more and 2000 nm or less. Preferably, they are 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 monofilament diameter exceeds 2000 nm, a large weight is required to satisfy the required particle removal performance and liquid protection performance, which provides a high level of protection and comfort for the wearer. It becomes difficult to achieve both. The required particle removal performance is 60% or more, more preferably 70% or more.

The mass of the nonwoven fabric used for the intermediate 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 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 such a range, the protective material excellent in the particle removal performance, the liquid resistance performance at the time of 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 material 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. In addition, it is also preferable to use a short fiber nonwoven fabric such as a spunlace nonwoven fabric or a thermal bond nonwoven fabric in consideration of flexibility.

In the lower layer, it is preferable to protect the upper layer and the intermediate layer with a highly flexible nonwoven fabric without impeding air permeability. 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 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, Polyesters such as cationic dyeable polyethylene terephthalate and polytrimethylene terephthalate, and other synthetic fibers (polyamide, polyacrylonitrile, polyurethane, acetate, polyvinyl chloride, polyethylene, polypropylene, polyimide, fluorine, polybenzazole, polylactic acid, etc.) Can be mentioned. 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.

  When the sheet material used for the upper layer in the present invention is used for protective clothing having camouflaged camouflage performance using an outer layer additional layer that has been camouflaged (wavelength controlled) in the near-infrared wavelength region to be described later, It is preferable that it consists of resin which can knead an absorber. Examples of resins that can be kneaded with infrared absorbers such as carbon black include polyethylene terephthalate, polybutylene terephthalate, polyamide, polyamideimide, polyurethane, silicon, polyacrylate, polyacrylonitrile, polyolefin, ethylene-vinyl alcohol copolymer, polyvinyl Examples include alcohol, cellulose, and cellulose derivative resin. By using a resin in which such an infrared absorber is kneaded, the performance can be satisfied with respect to camouflaged camouflage. In the case of using a sheet material made of a resin without kneading of an infrared absorbent, there is a concern that light reflection from the upper layer fabric occurs and the camouflaged camouflage is 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. On the other hand, when the content exceeds 10% by weight, it is difficult to produce a sheet material.

  Examples of materials that cannot be kneaded with infrared absorbers include natural fibers such as cotton, hemp, wool, and silk. After forming the raw material into a sheet material, an infrared absorbent is fixed through a binder resin or the like to obtain a sheet material in which the infrared absorbent is kneaded. 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). Examples include acrylic ester binder resins, silicon crosslinkable resins, epoxy crosslinkable resins, polyamide crosslinkable resins, polyester crosslinkable resins, polyvinyl alcohol resins, and the like. A combination of two or more types may be used, among these, those having an effect of fixing the washing durability, particularly a silicone-based cross-linking resin or a self-cross-linking type in terms of having both heat resistance and washing durability. Acrylic ester resins are preferred.

  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 each of the upper layer and the lower layer used in 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 the flexibility is poor.

  The thickness of each of the upper layer and the lower layer used in the present invention is 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 used in the present invention is 100 cm ³ / cm ² · sec or more and 500 cm in the air permeability test according to the method described in JIS L 1096 (2010) 8.26.1 A method (Fragile type method). ³ / cm ² · sec or less is preferable. More preferably, it is 150 cm ³ / cm ² · sec or more and 400 cm ³ / cm ² · sec or less. If the breathability is less than 100 cm ³ / cm ² · sec, wearing protective clothing that uses protective materials including the intermediate layer will lead to a feeling of stuffiness at the time of wearing, which may cause the feeling of use not being satisfied. . On the other hand, if it exceeds 500 cm ³ / cm ² · sec, there is a problem that the protective layer is not sufficient.

  The purpose of laminating the upper layer, the intermediate layer, and the lower layer in the protective material of the present invention is to reinforce and protect the intermediate layer, and to improve the liquid-proof protective performance under pressure. Examples of the stacking means include the following methods. As a first method, both the upper layer and the lower layer are bonded to the intermediate 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, the third method includes a method of laminating three layers by needle punching, hydroentanglement, ultrasonic waves, and the like, and is not particularly limited. 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 material of the present invention include urethane, vinyl alcohol, ester, epoxy, vinyl chloride, olefin, amide, etc., but flexibility, texture, durability after lamination In consideration of properties and the like, urethane, ester, and amide are preferable. The adhesive is preferably a solventless adhesive, 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, it is 5 g / m ² or more and 20 g / m ² or less. If the coating amount is less than 3 g / m ² , the adhesiveness with 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 decreases.

  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 150 g / 10 min or less, the area where the surface of the core layer is covered with the adhesive is reduced, and a decrease in air permeability due to lamination can be suppressed.

  The upper layer is coated with a non-fluorine resin water repellent. In the present invention, the non-fluorine resin-based water-repellent agent refers to a water-repellent agent other than a fluorine-resin agent. Although it is not particularly limited, it can be processed by known processing methods such as spraying by spraying or impregnation processing. The water repellency of the upper layer is preferably 2 or more and more preferably 3 or more in the spray test described in JIS L 1092 (2009) 7.2. The oil repellency of the upper layer is preferably 2 or less, more preferably 1 or less, according to AATCC Test Method 118-2002.

  The intermediate layer and the lower layer are coated with a fluororesin water repellent. About a processing method, it can process by a well-known processing method. As the water repellency of the intermediate layer and the lower layer, the water repellency is preferably 3 or more and more preferably 4 or more in the spray test described in JIS L 1092 (2009) 7.2. In addition, as the oil repellency, the oil repellency according to AATCC Test Method 118-2002 is preferably 3 or more, more preferably 4 or more.

The mass of the protective material 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 170 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 material 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 material 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 material 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 L 1096 (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, which may cause the feeling of use not being satisfied. 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 material of the present invention is preferably 70 mm or more and 1300 mm or less water head in a water pressure resistance test according to the method described in JIS L 1092 (2009) 7.1 (hydrostatic pressure method). More preferably, it is 80 mm or more and 1200 mm or less water head. If the water head is less than 70 mm, the liquid resistance performance and particle removal performance during pressurization cannot be satisfied. On the other hand, if it exceeds 1300 cm water head, the protective performance will be high, but the air permeability will be low. If worn, it will not have a good feeling during use.

  By providing a gas adsorbing layer on one or both sides of the upper layer or the lower layer of the protective material 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.

  In addition, a gas adsorbing layer may be provided on the protective material, and an outer layer additional layer may be provided on the outermost side of the protective material, and at least one inner layer additional layer may be provided on the innermost side as required. The purpose of the outer layer additional layer is to protect the protective material and gas adsorbing layer from mechanical force given from the outside, and to apply a woven fabric, knitted fabric or nonwoven fabric to which water repellency and oil repellency are applied, The liquid penetration resistance can be further improved.

  As the outer layer additional layer, a woven fabric having a water repellency of 2 or more when the spray test described in JIS L 1092 (2009) 7.2 is performed, and an oil repellency by AATCC Test Method 118-2002 of 3 or more, A knitted fabric or a non-woven fabric can be suitably used, but it is recommended to use a fabric considering flexibility. The protective material composed of the protective material and the gas adsorbing layer and the outer layer additional layer may be bonded in advance with an adhesive, or, in consideration of flexibility, sewed in a superposed state without being bonded and protected. You may make clothes.

  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 material 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 material and the gas adsorbing layer and the inner layer additional layer may be pre-adhered with an adhesive, or may be sewn in a superposed state without bonding in consideration of flexibility, or After the gas adsorbing layer and the quilting process in advance, the protective material may be laminated. 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 an oil-repellent sewing thread.

The mass of the protective clothing 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 the mass exceeds 700 g / m ² , the weight of the protective garment increases, causing 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 9 on the slide glass 10, place the inner layer additional layer, protective material, outer layer additional layer 7 in that order, and drop 5 μL of test solution 6 (dipropyl phthalate in which the red dye is dissolved) onto the outer layer additional layer. Then, a weight (1 kg / cm ² ) was placed on the test liquid and pressurized, and the permeability of the liquid was determined by the degree of coloration of the filter paper after 24 hours. No color was indicated by ◯, and there was no color by ×.

(2) Particle permeation resistance test: An explanatory diagram of this test is shown in FIG. The outer layer additional layer, the protective material, and the inner layer additional layer are installed in the duct 11, and the atmosphere is ventilated so that the air filtration speed becomes 5 cm / sec. The number of 0.3 to 0.5 μm particles upstream and downstream of the protective sheet The concentration was measured by a particle measuring device (particle counter) 16 and the collection efficiency was calculated by the following equation.
0.3 μm particle collection efficiency (%) = {1− (downstream concentration / upstream concentration)} × 100

(3) 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.

(4) Mass: Measured according to JIS L1096 (2010) 8.3.

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

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

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

(8) Oil repellency: According to AATCC Test Method 118-2002.

(9) Wearability test: As a wear monitor test, a protective clothing consisting of an outer layer additional layer, a protective material, and an inner layer additional layer was used to produce a protective clothing in the form of a tether, lower garment, and hood, and then the environmental temperature and humidity In an artificial climate room at 20 ° C and 65% RH, while blowing air to the front of the trunk at 3 m / sec with a blower, the treadmill was run at 5 km / hr for 30 minutes, and the eardrum temperature increased in 30 minutes The wearability was determined from thermal comfort based on the maximum heart rate and subjective report. The number of subjects was 10.

(10) Washing reworkability test: As a washing reworking test, a protective material comprising an outer layer additional layer, a protective material, and an inner layer additional layer was prepared, and then a fluororesin water-repellent finishing agent (Asahi Guard manufactured by Asahi Glass Co., Ltd.). AG7105) 1% solution pad, dehydrated in accordance with the electric washing machine method, dried at 100 ° C, cured at 180 ° C, pressure penetration resistance test on protective material, oil repellency of protective material (upper layer) A test was conducted to determine laundry reworkability.

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 obtained woven fabric has a thickness of 0.2 mm, a mass of 120 g / m ² , and a gas permeability of 60 cm ³ / cm ² · sec, a water repellency of 5 and an oil repellency of 6 grade with a water level gauge of 1.27 cm. It was.

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 , and a breathability of 700 cm ³ / cm ² · sec with a water level gauge of 1.27 cm, water repellency of 5, oil repellency It was 6th grade.

Example 1
For the production of the protective material, 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 ( Kureha Tech Co., Ltd. Dynac LNS0015) was superposed in advance, and the nanofiber nonwoven fabric made of polyurethane was produced on the adhesive surface by electrospinning so that the average single fiber diameter was 100 nm and the mass was 0.5 g / m ² . . Thereafter, the three layers including the adhesive layer are pressure-bonded by a heating roller, and then immersed in a processing bath of 3 wt% fluorine-based water repellent (Asahi Guard AG7105 manufactured by Meisei Chemical Co., Ltd.) and dried at 100 ° C. Then, the temperature was raised to 150 ° C. and cured. Both the spunlace nonwoven fabric side and the nanofiber nonwoven fabric side had a water repellency of 4 and an oil repellency of 5 grade.
Furthermore, as an upper layer, a spunbond nonwoven fabric (Ecule 3301AD manufactured by Toyobo Co., Ltd.) having a mass of 30 g / m ² was immersed in a processing bath of a 3 wt% silicone water repellent (Drypon 600E manufactured by Nikka Chemical Co., Ltd.). Drying was performed at 0 ° C., and the temperature was raised to 150 ° C. and curing was performed. The water repellency of this material was grade 4 and oil repellency was grade 0, and a protective material was prepared by adhering this layer onto nanofibers using the same adhesive as described above.
Furthermore, the outer layer additional layer on the spunbond nonwoven fabric side of the protective material, the pressure liquid penetration resistance test result, the particle permeability test result, the wearability test result of the protective material with the inner layer additional layer superimposed on the spunlace nonwoven fabric side, The results of washing reworkability and the physical property values of the protective material are shown in Tables 1 to 4, respectively.

(Example 2)
A protective 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 500 nm and a mass of 1 g / m ² was used in the intermediate layer. Tables 1 to 4 show the pressure liquid penetration resistance test results, particle permeation resistance test results, wearability test results, washing reworkability results, and physical properties of the protective materials obtained for the protective materials, respectively.

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 700 nm and a mass of 2 g / m ² was used for the intermediate layer. Tables 1 to 4 show the pressure liquid penetration resistance test results, particle permeation resistance test results, wearability test results, washing reworkability results, and physical properties of the protective materials obtained for the protective materials, respectively.

Example 4
A melt blown nonwoven fabric made of PP having a mass of 15 g / m ² (SYNTEX (registered trademark) nano6, manufactured by Mitsui Chemicals, Inc .; average single fiber diameter: 600 nm) is used as an intermediate layer, and a polyester nonwoven fabric thermoplastic adhesive having a mass of 15 g / m ² A protective material was produced in the same manner as in Example 1 except that the lower layer mass 40 g / m ² PET spunlace nonwoven fabric (manufactured by Yuhou Co., Ltd.) was adhered with (Dyac LNS0015, manufactured by Kureha Tech Co., Ltd.). Tables 1 to 4 show the pressure liquid penetration resistance test results, particle permeation resistance test results, wearability test results, laundry reworkability results, and physical properties of the protective material, respectively.

(Example 5)
A protective material was prepared in the same manner as in Example 1 except that a melt blown nonwoven fabric made of PP 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 for the intermediate layer. did. Tables 1 to 4 show the pressure liquid penetration resistance test results, particle permeation resistance test results, wearability test results, washing reworkability results, and physical properties of the protective materials obtained for the protective materials, respectively.

(Example 6)
A protective material was produced in the same manner as in Example 1 except that the mass of the intermediate layer used in Example 1 was 20 g / m ² . Tables 1 to 4 show the pressure liquid penetration resistance test results, particle permeation resistance test results, wearability test results, washing reworkability results, and physical properties of the protective materials obtained for the protective materials, respectively.

(Comparative Example 1)
A protective 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 for the intermediate layer. Tables 1 to 4 show the pressure liquid penetration resistance test results, particle permeation resistance test results, wearability test results, washing reworkability results, and physical properties of the protective materials obtained for the protective materials, respectively.

(Comparative Example 2)
A protective material was produced in the same manner as in Example 1 except that the same intermediate layer and lower layer sheet as in Example 1 were not subjected to water / oil repellent treatment. Tables 1 to 4 show the pressure liquid penetration resistance test results, particle permeation resistance test results, wearability test results, washing reworkability results, and physical properties of the protective materials obtained for the protective materials, respectively.

(Comparative Example 3)
A protective material was produced in the same manner as in Example 1 except that the intermediate layer was not laminated. Tables 1 to 4 show the pressure liquid penetration resistance test results, particle permeation resistance test results, wearability test results, washing reworkability results, and physical properties of the protective materials obtained for the protective materials, respectively.

(Comparative Example 4)
A protective material was produced in the same manner as in Example 4 except that a waterproof and moisture-permeable fabric (Geovisor manufactured by Toyo Cloth Co., Ltd.) in which a nylon fabric was coated with a polyurethane resin was used for the intermediate layer. Tables 1 to 4 show the pressure liquid penetration resistance test results, particle permeation resistance test results, wearability test results, washing reworkability results, and physical properties of the protective materials obtained for the protective materials, respectively.

(Comparative Example 5)
A protective material was produced in the same manner as in Example 1 except that the material was not subjected to water repellent processing on the upper layer as in Example 1. Tables 1 to 4 show the pressure liquid penetration resistance test results, particle permeation resistance test results, wearability test results, washing reworkability results, and physical properties of the protective materials obtained for the protective materials, respectively.

  As is clear from the results of Tables 1 to 4, the protective material using the protective material of Examples 1 to 6 is good in all of particle resistance, liquid penetration resistance, wearability, and washing reworkability. On the other hand, the protective materials of Comparative Examples 1 and 3 have low liquid permeation resistance and particle resistance, the protective material of Comparative Example 2 has low liquid permeation resistance, and the protective material of Comparative Example 4 is aerated. Since the property is low, the wearability is inferior, and the protective material of Comparative Example 6 has low washing reworkability, and the protective materials of Comparative Examples 1 to 5 are inferior to Examples in any of the evaluation items.

  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 suppression ability under pressure, and further has air permeability, light weight and comfort. It is to provide an excellent protective material. In addition, in consideration of long-term use in protective clothing with the outer layer additional layer and the inner layer additional layer using the above protective material, the outer layer additional layer may be reprocessed with a fluororesin-based water repellent agent. This is to keep the properties of the protective material arranged in the inner layer unchanged, and to provide a protective material that can be used for a long period of time, greatly contributing to the industry.

1: Upper layer 2: Intermediate layer 3: Lower layer 4: Protective material 5: Weight (1 kg / cm ² )
6: test solution 7: outer layer additional layer 8: protective material + inner layer additional layer 9: filter paper 10: glass slide 11: duct 12: outer layer additional layer + protective material + inner layer additional layer 13: flow meter 14: valve 15: blower 16 : Particle measuring instrument 17: 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 lower layer of at least three layers of sheet materials are laminated, and the upper layer of the protective material is a non-fluorine resin-based water repellent finish A protective material in which the intermediate layer and the lower layer of the protective material are coated with a fluororesin-based water repellent, and the oil repellency of AATCC Test Method 118-2002 is grade 3 or higher.   The protective material according to claim 1, wherein the non-fluororesin water-repellent agent is at least one water-repellent agent selected from silicon-based, wax-based, and natural water-repellent agents.   Protective clothing using the protective material according to claim 1.