JP2008214767A - Protective sock - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a lightweight protective sock capable of effectively protecting the foot part of a worker from a gaseous or liquid organic chemical substance and harmful fine powder dust, germs, and viruses, excellent in attachability and detachability and moisture permeability, and suppressing stuffiness of the foot. <P>SOLUTION: This pair of protective socks has at least one layer each of a particle removing layer whose average monofilament diameter is 1-1,000 nm, and a gas adsorbing layer. The outside of the gas adsorbing layer, viewed from the inside of the socks, is arranged with at least one layer of the particle removing layer, and a layered body of the particle removing layer and the gas adsorbing layer has a thickness of ≤2.0 mm. The seam part of the socks is seal-processed with a permeation-suppressing resin to an organic chemical substance. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to socks used by workers handling hazardous chemical substances. More specifically, it can effectively protect the operator's feet from gaseous or liquid organic chemicals and harmful fine dust, bacteria, viruses, etc. that are absorbed from the skin and are harmful to the human body, such as organic phosphorus compounds. In addition, the present invention relates to protective socks that are lightweight, have good wearability, and are breathable, and can suppress the feeling of stuffiness of the wearer's feet.

  Conventionally, protective socks that protect the foot from harmful chemical substances have been proposed. For example, there is a material made of a material that does not allow permeation of harmful chemical substances, such as a rubber cloth, and has excellent protection performance. However, in this case, the feeling of wear is inferior due to the fabric's stiff feel, and there is no breathability and moisture permeability. Yes.

  On the other hand, a protective sock using a fabric that is breathable and includes an adsorbent material such as activated carbon is also exemplified. They can effectively release sweat and water vapor that emanates from the foot due to breathability and suppress stuffiness, but aerosols of liquid organic chemicals, harmful fine dust, bacteria, viruses, etc. There is a problem that complete protection cannot be obtained (for example, Patent Document 1).

  In addition, a protective sock with a little stuffiness that includes a film that is water-blocking while having a liquid barrier property is disclosed, but the protective property for gaseous organic chemicals is not specified, and general socks As for a film having a typical water vapor permeability, there is a high possibility that gaseous organic chemicals will invade and the wearer's feet cannot be protected (for example, Patent Document 2).

JP-A-8-218210 JP 2005-29938 A

  The present invention was made against the background of the problems of the prior art, and has protection against not only gaseous organic chemicals but also liquid organic chemicals, harmful aerosols and fine dusts, etc. An object of the present invention is to provide a protective sock having good breathability and low stuffiness.

In order to solve the above problems, the present invention has been completed as a result of intensive studies. That is, the present invention is as follows.
1. At least one particle removal layer and a gas adsorption layer each having an average single fiber diameter of 1-1000 nm, and at least one particle removal layer outside the gas adsorption layer as viewed from the inside of the sock A protective sock in which the thickness of the laminated body of the particle removal layer and the gas adsorbing layer is 2.0 mm or less, and the seam portion of the sock is sealed with a resin that inhibits permeation of organic chemicals.
2. ^2. The protective sock according to 1 above, wherein the particle removal layer has a moisture permeability of 83 g / m ² · h or more.
3. 3. The protective sock according to 1 or 2 above, wherein the particle removal layer is made of an organic fiber.
4). 4. The protective sock according to any one of the above 1 to 3, wherein the gas adsorption layer is in the form of fibrous activated carbon woven fabric, knitted fabric or nonwoven fabric.
5. 5. The protective sock according to any one of 1 to 4 above, wherein an outer layer additional layer and / or an inner layer additional layer are provided.

  The protective sock according to the present invention comprises a protective material characterized by having a particle removal layer and a gas adsorption layer, and has protection against gaseous and liquid organic chemicals and toxic aerosols and fine dusts. In addition, the breathability and moisture permeability can suppress the stuffiness on the inside of the sock, and is excellent in wear and detachability.

Hereinafter, the present invention will be described in detail.
The average single fiber diameter of the particle removal layer used in the protective socks of the present invention is preferably 1000 nm or less. By making the average single fiber diameter 1000 nm or less, a particle removal layer with high collection efficiency can be obtained even if it is thin, and it has both a high level of comfort, safety and protection, with good loading and unloading and resistance to stuffiness. Because it can be done. More preferably, it is 500 nm or less.
Moreover, it is preferable that the average single fiber diameter of the particle removal layer used for the protective socks of this invention is 1 nm or more. When the thickness is less than 1 nm, not only fiberization becomes difficult, but physical properties close to those of a film are obtained, and it becomes difficult to obtain a particle removal layer having practical strength, air permeability and moisture permeability. More preferably, it is 10 nm or more.

  The material of the particle removal layer is not particularly limited, but rayon, polynosic, cupra, lyocell, acetate, triacetate, nylon, aramid, vinylon, vinylidene, polyvinyl chloride, polyester, acrylic, acrylic, polyethylene, polyurethane, Polyclar, polyarylate, polyimide, polyphenylene sulfide, polyacrylonitrile, polysulfone, polycarbonate, polyparaphenylene benzoxazole (PBO), polybenzimidazole, polyvinyl alcohol, cellulose, polyethylene oxide, polypropylene oxide, polyvinyl acetate, polyethylene terephthalate, polybutylene Examples include terephthalate, polylactic acid, and polypropylene. It is a preferred form. Further, these materials may be used alone, mixed, or sequentially laminated with another reinforcing base material to form a film.

  Nylon, polyurethane and polycarbonate are preferred as the particle removal layer in view of the balance between air permeability and collection efficiency. Among these, when applied to socks, polyurethane is most preferable in terms of wearing feeling.

  The particle removal layer used in the protective socks of the present invention is preferably in the form of a nonwoven fabric. This is because the non-woven fabric shape can provide excellent particle removal performance, is excellent in the balance between flexibility and extensibility, has good attachment / detachment properties, and can improve wearing feeling. In addition, it is one of preferable modes to form a film by individually or mixing these materials or sequentially laminating with another reinforcing base material.

The method for producing the nonwoven fabric-like particle removal layer described above 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. However, the electrospinning method is preferable from the viewpoint that a non-woven fabric having a low pressure loss and a fine fiber diameter and a high particle removal rate can be produced.
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 basis weight of the particle removal layer used in the protective socks of the present invention is preferably 100 g / m ² or less. This is because if it is 100 g / m ² or less, the light weight and the load / unload property are not impaired even when laminated with a gas adsorption layer described later.

  The thickness of the particle removal layer used in the protective socks of the present invention is preferably 0.1 μm or more and 1 mm or less. This is because, by setting it in such a range, a protective sock having an excellent balance of strength, breathability and flexibility can be obtained. More preferably, it is 0.5 μm or more and 0.5 mm or less.

Breathable particle removal layer used to protect the sock of the present invention is preferably 0.1cm ³ / ^cm 2 · sec or more breathable test by the method described in ^{JIS L-1018 8.33, 1cm 3} / cm 2 · More preferably, it is sec or more. When it is 0.1 cm 3 / cm ² · sec or less, the air permeability is small, and when used in protective socks, sweat and vapor cannot be effectively released to the outside, and the feeling of wearing becomes worse.

The moisture permeability of the particle removal layer used in the protective socks of the present invention is preferably 83 g / m ² · h or more, and more preferably 167 g / m ² · h or more. If it is 83 g / m ² · h or less, sweat and vapor emitted from the wearer cannot be effectively released to the outside, and the feeling of wear becomes worse.

The particle removal layer may be used alone, but it is also one of preferred modes that it is combined with a breathable base material for reinforcement or protection. The air permeability of the substrate is preferably 10 cm ³ / cm ² · sec or more, and more preferably 20 cm ³ / cm ² · sec or more so as not to impair the air permeability of the particle removal layer. In order to make a lightweight and flexible protective sock while maintaining strength, the thickness of the substrate is preferably 0.05 mm or more and 1.00 mm or less. A sheet-like fiber aggregate or a breathable microporous film or membrane can be used for the substrate.
Sheet fiber aggregates include natural fibers such as cotton, hemp, hair, and silk, regenerated fibers such as rayon, polynosic, cupra, and lyocell, semi-synthetic fibers such as acetate and triacetate, nylon, aramid, vinylon, vinylidene, and polychlorinated Examples include woven fabrics, knitted fabrics, and nonwoven fabrics made of synthetic fibers such as vinyl, polyester, acrylic, acrylic, polyethylene, polypropylene, polyurethane, polyclar, polyarylate, polybenzazole, polyimide, polyphenylene sulfide, and the like. These fibers may be used alone or in combination by blending, union, union, etc. to form a sheet-like fiber assembly. Examples of the air-permeable microporous film or membrane include sheet-like materials such as polyethylene, polypropylene, polytetrafluoroethylene, copolymer polyester, polyurethane, polyether polyurethane, and acrylate. These materials may be used alone, mixed, or sequentially coated and laminated to form a film.

  In the present invention, the above-mentioned base material may be subjected to post-processing such as water / oil repellent processing, flame retardant processing and the like. The water repellent is not particularly limited, such as fluorine, polysiloxane, and paraffin.

When the particle removal layer is combined with the base material, it can be laminated by a laminating method while preventing a decrease in air permeability and maintaining flexibility. When adhering between the particle removal layer and the substrate with polyurethane or acrylate emulsion, or when welding or fusing part of the particle removal layer or substrate, do not adhere to the entire surface, but instead adhere to dots. It is preferable to do. It is also possible to perform heat bonding through a low-weight nonwoven fabric, a net-like body, or a powder made of low-melting copolymer polyester, polyamide, or polyolefin. The adhesive used in the present invention is preferably non-woven. Since uniform application is difficult if it is in the form of particles, if it is adhered in a small amount, it cannot be adhered to the substrate, and if it is used in a large amount, it becomes hard.
In addition, the method of coating the substrate by the direct electrospinning method or the like does not require an adhesive, so that a decrease in air permeability can be minimized and is a very effective means.

In addition, in order to prevent the particle removal layer from getting wet due to liquid organic chemicals entering from the outside or sweat released from the body and reducing the collection efficiency, it is not possible to impart water repellency or oil repellency to the particle removal layer. It is an effective means. As a method for imparting water repellency and oil repellency to the particle removal layer, spraying by spraying or impregnation processing can be considered, but impregnation processing is preferable in consideration of uniformity. The water and oil repellents are not particularly limited, such as fluorine resin, silicon resin, wax, and cellulose reaction system.
The water repellency of the sheet is 2 or more, more preferably 4 or more in the 6.2 spray test described in JIS L-1092. Further, the oil repellency of the sheet is AATCC Test Method 118 of 2 or higher, more preferably 4 or higher.

  The protective sock material of the present invention preferably has a trapping efficiency of 90% or more, more preferably 95% or more, and still more preferably 99% of a particulate matter of 0.3 μm or more at an air line velocity of 10 cm / sec. That's it. This is because by providing such a particle removal layer, the human body can be effectively protected from harmful mist and fine dust.

  The protective sock material of the present invention preferably has at least one gas adsorption layer capable of adsorbing gaseous organic chemical substances. This is because toxic gas that cannot be prevented by the particle removal layer can be prevented from entering.

  The gaseous organic chemical substance here is a gaseous compound having one or more carbon elements. It is a gaseous chemical substance having a relatively large molecular weight of 50 or more and capable of adsorbing a gas adsorbing substance such as activated carbon. For example, 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 can be mentioned.

  The gas adsorbing layer used in the present invention may be a target adsorbed material such as a carbon-based adsorbent such as activated carbon or carbon black, or an inorganic adsorbent such as silica gel, zeolite-based adsorbent, silicon carbide, or activated alumina. It can be selected as appropriate. Among them, activated carbon capable of dealing with a wide range of gases is preferable, and fibrous activated carbon is more preferable because it has a large adsorption rate and adsorption capacity and can effectively prevent permeation when used in a small amount.

  The average pore diameter of the activated carbon is preferably 200 nm or less. This is because when the average pore diameter is larger than 200 nm, the adsorbed gaseous organic chemical substance is easily desorbed.

  The pore volume of the activated carbon is preferably 0.25 cc / g or more, more preferably 0.3 cc / g or more. This is because if the pore volume is less than 0.25 cc / g, a large amount of activated carbon is required to obtain sufficient protective performance, and the protective socks become heavy.

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

The basis weight of the activated carbon is preferably 20 g / m ² or more and 200 g / m ² or less, more preferably 50 g / m ² or more and 150 g / m ² or less. When it is less than 20 g / m ² , the capacity that can be adsorbed is reduced, and the use time is limited. On the other hand, when it becomes larger than 200 g / m ^2, there is a problem that the material is heavy and thick, and the feeling of wearing becomes worse.

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

  As a method for forming fibrous activated carbon into a sheet, a method of adhering a gas adsorbing substance to a sheet substrate with a binder, or a method of making an adsorbent into a slurry including an appropriate pulp and binder, and making a paper with a wet paper machine, or The adsorbent sheet can be obtained by a known method in which the activated carbon fiber raw material fibers are woven, knitted, or nonwoven fabric in advance and subjected to a flame resistance treatment as necessary, followed by carbonization and activation.

  Therefore, the form of the fibrous activated carbon sheet includes woven, knitted, non-woven, felt, paper, film, and the like, but is woven from the wearability when wearing socks, flexibility, and ease of lamination. A knitted fabric is preferred.

It is also effective to give water and oil repellency to the activated carbon layer in order to prevent the activated carbon layer from getting wet due to liquid organic chemicals entering from the outside or perspiration released from the body and lowering the adsorption performance. It is. As a method for imparting water repellency and oil repellency to activated carbon, spraying by spraying or impregnation is generally considered, but impregnation is preferable in consideration of uniformity. The water and oil repellents are not particularly limited, such as fluororesin, silicon resin, wax, and cellulose reaction system, and the amount of addition is 0.1 to 15% by mass, preferably 0.5. -5 mass% is preferable. This is because the water repellency and oil repellency are low when the amount of adhesion is 0.1% by mass or less, and the adsorption performance of the gas adsorption layer is lowered when the amount is 15% by mass or more.
The water repellency of the sheet is 2 or more, more preferably 4 or more in the 6.2 spray test described in JIS L-1092. Further, the oil repellency of the sheet is AATCC Test Method 118 of 2 or higher, more preferably 4 or higher.

  The following method can be used as a means for laminating the particle removal layer and the gas adsorption layer. As a first method, a sheet-like, granular or powdery gas-adsorbing substance is bonded to the particle removal layer with an adhesive. In the second method, it is possible to sew without bonding and make a shape of a flash. As a third method, there is a method in which a particle removal layer is formed by directly applying a gas adsorption layer prepared in advance by an electrospinning method or the like. With the second and third lamination methods, lamination is possible without using an adhesive or the like, and the adsorption capacity of the gas adsorption layer is not lowered, and it becomes a lightweight protective sock material, so that the shape of the flash is made A laminating method in which coating is performed directly is more preferable.

  Examples of the adhesive used in the first method include urethane-based, vinyl alcohol-based, ester-based, epoxy-based, vinyl chloride-based, and olefin-based adhesives. A wet adhesive such as urethane, vinyl alcohol and ester are preferred.

  The melt index of the adhesive used is preferably 200 g / 10 min or less, and more preferably 150 g / 10 min or less. By setting the amount to 200 g / 10 min or less, the area where the adhesive covers the surface of the gas-adsorbing substance can be reduced at the time of bonding, and the deterioration of the gas-adsorbing performance due to the lamination can be suppressed. In addition, a decrease in moisture permeability can be suppressed.

  The adhesive used in the present invention is preferably non-woven. Since uniform application is difficult if particles are used, adsorbents cannot be fixed when adhered in small amounts, become hard when used in large amounts, and further reduce adsorption performance. Moreover, if it is a film, air permeability will fall.

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

  The order of stacking the particle removal layer and the gas adsorption layer is not particularly limited, but considering the life of the gas adsorption layer, at least one particle removal layer outside the gas adsorption layer as viewed from the inside of the garment. It is preferable that there is. Moreover, when using two or more particle removal layers, in order to protect a gas adsorption layer, it is good also as a structure which pinches | interposes a gas adsorption layer by a particle removal layer.

The basis weight of the laminate comprising a particle removal layer and gas adsorption layer is preferably 300 g / ^{m 2} or less, 250 g / ^{m 2} or less is more preferable. If it exceeds 300 g / m ² , it is difficult for the sweat and vapor emitted from the wearer's foot to be emitted, and the feeling of wear becomes worse.

  For liquid organic chemicals entering from the outside, it is effective to sandwich liquid-resistant non-woven fabric and oil-absorbing paper etc. outside the particle removal layer or between the particle removal layer and the gas adsorption layer. It becomes a means. The material used for the nonwoven fabric, paper or the like is not particularly limited, such as polyolefin, polyester, polylactic acid, polycarbonate, polyvinyl chloride, and polyvinylidene chloride.

  As shown in FIG. 1, it is preferable to provide an outer layer additional layer on the outermost side of the laminated material composed of the particle removal layer and the gas adsorption layer. The purpose of the outer layer addition layer is to protect the particle removal layer and the gas adsorbing layer from the mechanical force given from the outside, to supplement the mechanical strength, and to provide the fabric with water repellency and oil repellency, A knitted fabric or a nonwoven fabric is preferred. As the material for the outer layer additional layer, those that can take the form of woven fabric, knitted fabric and nonwoven fabric can be used without limitation, and cotton, nylon, aromatic polyamide, wholly aromatic polyester, polybenzazole fiber, fluorine fiber, etc. It can be used.

As an outer layer additional layer, a woven fabric, a knitted fabric, or a non-woven fabric having a water repellency of 4 or more when subjected to the 6.2 spray test described in JIS L-1092 and an oil repellency of AATCC Test Method 118 of 4 or more. Can be used preferably, but it is recommended to use one that is flexible.
The laminated material consisting of the particle removal layer and the gas adsorbing layer and the outer layer additional layer may be pre-adhered with an adhesive, or may be sewn in a state of being superposed without bonding, considering flexibility, Socks may be made.

As shown in FIG. 1, it is preferable to provide the inner layer additional layer on the innermost side of the laminated material composed of the particle removal layer and the gas adsorption layer. 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 in terms of air permeability and flexibility.
The purpose of the inner layer additional layer is to protect the gas adsorbing substance and the particle removal layer from mechanical force applied from the outside, and to suppress the sticky feeling caused by the sweat that radiates from the wearer's foot.

  Laminating the inner layer additional layer and the gas adsorbing layer in advance by quilting is an effective means for suppressing the deterioration of the performance of the gas adsorbing layer due to the lamination and obtaining a more flexible laminated material.

The basis weight of the laminate provided with the outer layer additional layer and / or the inner layer additional layer is preferably 500 g / m ² or less, more preferably 450 g / m ² or less. This is because if it exceeds 500 g / m ² , the material becomes thick and the feeling of wear decreases.

  The thickness of the sock material of the present invention is 3.0 mm or less, preferably 2.5 mm or less. This is because if it exceeds 3.0 mm, the feeling of wear will be reduced, and it will be hard and unsuitable for the intended sock material.

  The method of producing socks with the above materials is, for example, cutting a laminate of a particle removal layer, a gas adsorption layer and an inner layer additional layer into a foot shape, and sewing two outer peripheral portions with a heat fusion method or a sewing thread, After the inner socks are prepared in advance by applying a seal process to the sewing part with protective sealing tape, the outer layer additional layer is similarly sewn and sealed into two socks that are cut into the foot shape. There is a method to make the laminated gloves. Alternatively, the outer layer additional layer, the laminate of the moisture permeable membrane layer and the gas adsorbing layer, and the inner layer additional layer may each be a sock, and these may be stacked without bonding to form a sock having a three-layer structure. Alternatively, after all the materials are bonded, socks may be used. Moreover, the sock which consists of an outer layer addition layer, a moisture-permeable film layer, and a gas adsorption layer which does not comprise the inner layer addition layer may be sufficient.

  Protective socks need to prevent the penetration of gaseous and liquid chemicals from seams and the entry of harmful fine dust, bacteria, viruses and other aerosols, and do not impair moisture permeability and flexibility. is required. For this purpose, it is preferable that the sewing is performed by flash sewing. In the present invention, the seam is further sealed to prevent penetration from the seam.

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

The protective socks produced by the method described above preferably have a gas permeability from the outside to the inside of the socks with the socks attached to less than 1%, and more preferably less than 0.1%. . This is because if it exceeds 1%, the human body may be adversely affected.
The protective socks preferably have a particle collection efficiency of 90% or more, more preferably 99% or more, from the outside to the inside of the glove with the socks attached. This is because if it is less than 90%, viruses and bacteria may adversely affect the human body.

  The present invention will be specifically described using Examples and Comparative Examples, but the present invention is not limited to these Examples. The various evaluations and test values obtained in the present invention are based on the methods described below.

(Gas permeability test method):
Test apparatus: The gas permeability test apparatus shown in FIG. 2 was used, and the following procedures (1) to (3) were performed.
(1) 1m ³ (Width 1 x Depth 1 x Height 1 (m)) A foot type mannequin fitted with protective socks is installed in the chamber, and a sampling tube is installed so that the gas permeation concentration inside and outside the socks can be measured. Connect it (completely seal it with vinyl tape so that there is no gap between the foot mannequin and the hem of the sock).
(2) A toluene special grade reagent (Nacalai Tesque) was placed in a gas cleaning bottle (manufactured by AS ONE), and toluene-containing nitrogen bubbled with dry nitrogen was fed into the chamber for a certain period of time. At this time, the initial concentration of toluene gas is adjusted to about 1000 ppm.
(3) The gas inside and outside the protective socks is sampled with a syringe at regular intervals, measured with a gas chromatography (Japan Hewlett-Packard Company HP6890), gas permeability is calculated by the following formula, and an average value of 24 hr is obtained. .
Gas permeability (%) = (sock inner gas concentration / sock outer gas concentration) × 100

(Particle collection efficiency measurement method):
Test apparatus: Measurement was performed according to the following procedures (1) to (4) using the particle collection efficiency measuring apparatus shown in FIG.
(1) 1m ³ (Width 1 x Depth 1 x Height 1 (m)) A foot type mannequin with protective socks is installed in the chamber, and the sampling tube is particled so that the number of particles inside and outside the sock can be measured. Connect to a measuring instrument (KC-14 manufactured by RION Co., Ltd.) (Completely seal with vinyl tape so that there is no gap between the foot mannequin and the bottom of the sock.)
(2) The atmospheric dust in the BOX is completely removed with a HEPA filter.
(3) NaCl particles were generated in the chamber using a Ruskin nozzle type particle generator and a diffusion dryer (Model 306200, manufactured by TSI). At this time, the NaCl particles are adjusted to have an average particle diameter of 0.1 μm and a particle concentration of about 50,000 (pieces / 10 ⁻² CF).
(4) The number of NaCl particles of 0.3 μm or more on the inner side and outer side of the protective socks is measured with the above measuring device, and the particle collection efficiency is calculated by the following equation.
Particle collection efficiency (%) = (1−number of socks inside particles / number of socks outside particles) × 100

(Moisture permeability):
According to JIS L-1099 calcium chloride method.

(BET specific surface area):
The BET specific surface area was measured by measuring several points of nitrogen adsorption on the sample when the relative pressure was raised in the range of 0.0 to 0.15 in the atmosphere of the boiling point of liquid nitrogen (-195.8 ° C), and a BET plot. Was used to determine the surface area (m ² / g) per unit mass of the sample.

(Pore volume):
The pore volume was measured by a nitrogen gas adsorption method at a relative pressure of 0.95.

(Average pore diameter):
The average pore diameter was determined by the following formula.
dp = 4000 Vp / S (where dp: average pore diameter (nm))
Vp: pore volume (cc / g)
S: BET specific surface area (m ² / g)

(Average single fiber diameter):
The average single fiber diameter is photographed with a scanning electron microscope (SEM), and 20 fibers are randomly selected from a large number of fibers projected on a 5000 times or 10,000 times SEM image, and the single fiber diameter is measured. The average value of the measured 20 single fiber diameters was calculated and used as the average single fiber diameter.

(Mass (weight)):
According to JIS L-1018 8.4 and JIS L-1096 8.4.

(thickness):
According to JIS L-1018 8.5 and JIS L-1096 8.5.

(Melt index):
According to JIS K-7210.

(Removability):
A questionnaire survey was conducted to determine the ease of wearing, the ease of taking off, and the feeling of wearing when wearing / removing socks.

(Steaminess):
The feeling of stuffiness after wearing socks for 1 hr was determined from a questionnaire survey.

[Production example]
(Example of gas adsorption layer production)
A fibrous activated carbon knitted fabric was produced as a gas adsorption layer by the following method. A milled knitted fabric with a basis weight of 200 g / m ² made of spun yarn of 2.2 decitex 20 novolak phenol resin fiber was heated in an inert atmosphere at 400 ° C. for 30 minutes, and then inactive to 870 ° C. for 30 minutes. Heating was performed in the atmosphere to cause carbonization, and then activation was performed at a temperature of 870 ° C. for 2 hours in an atmosphere containing 12% by volume of water vapor. The obtained knitted fibrous activated carbon had an absolute dry weight of 105 g / m ² , a specific surface area of 1400 m ² / g, and a thickness of 1.15 mm.

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

(Inner layer additional layer production example)
The inner layer additional layer was produced by the following method. Using a 28 gauge two-sheet tricot machine, set polyester filaments (82.5 dtex, 36 filaments) on the front cage and polyester filaments (22 dtex, monofilament) on the back cage, respectively. After knitting a warp knitted fabric with a back 1-0 / 2-3 structure, it was refined by a conventional method and further dyed with a disperse dye. The knitted fabric thus obtained has a thickness of 0.32 mm, a basis weight of 60 g / m ² , a breathability of 700 cm ³ / cm ² · s with a water level gauge of 1.27 cm, water repellency of 5, oil repellency It was 6th grade.

[Example 1]
As a particle removal layer, the average single fiber diameter made of polyacrylonitrile resin is 2 g / m ² , the thickness is 0.01 mm, the air permeability is 3 cm ³ / cm ² · sec, the pressure difference is 1.27 cm, and the permeability is 3 cm ³ / cm ² · sec. A nonwoven fabric with a wetness of 456 g / m ² · h was used. The particle removal layer, the gas adsorption layer, and the inner layer addition layer are bonded with a breathable non-woven hot melt adhesive (Dynac, Kureha Tech Co., Ltd.) having a basis weight of 10 g / m ² and a melt index of 60 g / 10 min. did. The laminate was cut and sewn into a sock shape, and the seam portion was sealed by the following sealing method to form an inner sock.
Seal processing method:
Eval EF-XL manufactured by Kuraray Co., Ltd. was used as the selectively permeable membrane for the seal tape. Eval EF-XL had a thickness of 12 μm and a mass of 15 g / m ² .
A curable moisture-permeable polyurethane resin having a solid content of 30% by mass (Samprene LQ120 manufactured by Sanyo Chemical Industries, Ltd.) is cast on the permselective membrane, and is applied while adjusting the film thickness with a coater and dried at 100 ° C. It was. The seal tape was cut to a width of 20 mm, and the seal tape was placed on the seam of a sock so that the adhesive surface would be down and pressure-bonded, and then moisture-cured under conditions of 60 ° C. and RH 95% for 24 hours.
Further, the outer layer additional layer was cut into a sock shape, sewed by flash stitching, and further subjected to seal processing in the same manner as described above to obtain an outer sock. A protective sock was produced by superimposing these inner and outer socks. The material of the protective socks had a basis weight of 355 g / m ² , a thickness of 1.88 mm, and a moisture permeability of 437 g / m ² · h. Table 1 shows the gas permeability test results, the particle collection efficiency measurement results, the moisture permeability, and the feeling of stuffiness when this protective sock is used.

[Example 2]
The particle removal layer has an average single fiber diameter of 350 nm made of polyurethane resin, a basis weight of 10 g / m ² , a thickness of 0.01 mm, and air permeability of 1 cm ³ / cm ² · sec with a water level difference of 1.27 cm, moisture permeability A sock was produced in the same manner as in Example 1 except that a non-woven fabric of 388 g / m ² · h was used. The material of the protective socks had a basis weight of 364 g / m ² , a thickness of 1.88 mm, and a moisture permeability of 366 g / m ² · h. Table 1 shows the gas permeability test results, the particle collection efficiency measurement results, the moisture permeability, and the feeling of stuffiness when this protective sock is used.

[Comparative Example 1]
Protection was performed in the same manner as in Example 1 except that a melt blown nonwoven fabric having an average single fiber diameter of 4 μm, a basis weight of 30 g / m ² , a thickness of 0.20 mm, and a moisture permeability of 458 g / m ² · h was used as the particle removal layer. Socks were made. The material of the protective socks had a basis weight of 383 g / m ² , a thickness of 2.07 mm, and a moisture permeability of 441 g / m ² · h. Table 1 shows the gas permeability test results, the particle collection efficiency measurement results, the moisture permeability, and the feeling of stuffiness when this protective sock is used.

[Comparative Example 2]
In Example 1, protective socks were made of a laminate excluding the gas adsorption layer. The material of the protective socks had a basis weight of 198 g / m ² , a thickness of 0.71 mm, and a moisture permeability of 452 g / m ² · h. Table 1 shows the gas permeability test results, the particle collection efficiency measurement results, the moisture permeability, and the feeling of stuffiness when this protective sock is used.

[Comparative Example 3]
In Example 1, protective socks were made of a laminate excluding the particle removal layer. The material of the protective socks had a basis weight of 351 g / m ² , a thickness of 1.87 mm, and a moisture permeability of 485 g / m ² · h. Table 1 shows the gas permeability test results, the particle collection efficiency measurement results, the moisture permeability, and the feeling of stuffiness when this protective sock is used.

[Comparative Example 4]
Basis weight 59 g / ^{m 2,} thickness 38 [mu] m, except that the moisture permeability was used polyvinyl fluoride film of 0.46g / ^{m 2} · h as particle removal layer was prepared sock in the same manner as in Example 1. The material of the protective socks had a basis weight of 402 g / m ² , a thickness of 1.89 mm, and a moisture permeability of 0.3 g / m ² · h. Table 1 shows the gas permeability test results, the particle collection efficiency measurement results, the moisture permeability, and the feeling of stuffiness when this protective sock is used.

  Examples 1 and 2 are suitable protective socks with excellent gas permeation suppression, particle collection efficiency, and wear / removability, and less stuffiness, while Comparative Examples 1 and 3 have low particle collection efficiency. Example 2 is a result of inferior gas permeation suppression, and Comparative Example 4 is a result of lack of breathability and low moisture permeability, resulting in a feeling of stuffiness, which is not sufficient for the purpose of the present invention. It was.

  The protective socks of the present invention are protective socks that can protect workers from gaseous and liquid organic chemicals, and are less sticky due to sweat, etc. due to breathability, and have good wearability, contributing to the industry. Is big.

It is a schematic cross section which shows an example of the laminated body which comprises the protective socks of this invention. It is the schematic which shows a gas-permeability test method. It is the schematic which shows the particle collection efficiency measuring method.

Explanation of symbols

1: outer layer additional layer 2: particle removal layer 3: gas adsorption layer 4: inner layer additional layer 5: chamber 6: protective socks 7: foot type mannequin 8: sampling tube (inside socks)
9: Sampling tube (outside of socks)
10: Gas cleaning bottle 11: Chamber 12: Protective socks 13: Foot mannequin 14: Sampling tube (inside socks)
15: Sampling tube (outside of socks)
16: Particle measuring device 17: Particle measuring device 18: Ruskin nozzle type particle generator 19: Diffusion dryer

Claims (5)

  At least one particle removal layer and a gas adsorption layer each having an average single fiber diameter of 1-1000 nm, and at least one particle removal layer outside the gas adsorption layer as viewed from the inside of the sock A protective sock in which the thickness of the laminated body of the particle removal layer and the gas adsorbing layer is 2.0 mm or less, and the seam portion of the sock is sealed with a resin that inhibits permeation of organic chemicals. The protective sock according to claim 1, wherein the particle removal layer has a moisture permeability of 83 g / m ² · h or more.   The protective sock according to claim 1 or 2, wherein the particle removal layer comprises an organic fiber.   The protective sock according to any one of claims 1 to 3, wherein the gas adsorption layer is a fibrous activated carbon woven fabric, a knitted fabric, or a nonwoven fabric. The protective sock according to any one of claims 1 to 4, wherein an outer layer additional layer and / or an inner layer additional layer are provided.

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