JP5920644B1 - Protective clothing material - Google Patents
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- JP5920644B1 JP5920644B1 JP2015160868A JP2015160868A JP5920644B1 JP 5920644 B1 JP5920644 B1 JP 5920644B1 JP 2015160868 A JP2015160868 A JP 2015160868A JP 2015160868 A JP2015160868 A JP 2015160868A JP 5920644 B1 JP5920644 B1 JP 5920644B1
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- protective clothing
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- 239000000463 material Substances 0.000 title claims abstract description 58
- 230000001681 protective effect Effects 0.000 title claims abstract description 54
- 239000007788 liquid Substances 0.000 claims abstract description 86
- 230000000903 blocking effect Effects 0.000 claims abstract description 45
- 239000003921 oil Substances 0.000 claims abstract description 43
- 239000005871 repellent Substances 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000126 substance Substances 0.000 claims abstract description 27
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 24
- 239000010703 silicon Substances 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 238000012545 processing Methods 0.000 claims abstract description 16
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 13
- 239000011737 fluorine Substances 0.000 claims abstract description 13
- 230000002940 repellent Effects 0.000 claims abstract description 11
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims abstract description 10
- 238000001514 detection method Methods 0.000 claims abstract description 7
- 238000005259 measurement Methods 0.000 claims abstract description 6
- 238000004458 analytical method Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 50
- 230000004888 barrier function Effects 0.000 claims description 16
- 125000004429 atom Chemical group 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 28
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 95
- 239000007789 gas Substances 0.000 description 48
- 239000004744 fabric Substances 0.000 description 36
- 238000001179 sorption measurement Methods 0.000 description 28
- 239000000853 adhesive Substances 0.000 description 20
- 230000001070 adhesive effect Effects 0.000 description 19
- 239000000835 fiber Substances 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 230000035699 permeability Effects 0.000 description 15
- 239000004745 nonwoven fabric Substances 0.000 description 13
- 239000002759 woven fabric Substances 0.000 description 10
- -1 perfluoro groups Chemical group 0.000 description 9
- 239000004677 Nylon Substances 0.000 description 8
- 229920001778 nylon Polymers 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 229920000728 polyester Polymers 0.000 description 7
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- 239000003463 adsorbent Substances 0.000 description 5
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- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 239000011241 protective layer Substances 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- 239000004416 thermosoftening plastic Substances 0.000 description 4
- 229920003043 Cellulose fiber Polymers 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
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- 238000009987 spinning Methods 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
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- 229920002972 Acrylic fiber Polymers 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229920001407 Modal (textile) Polymers 0.000 description 2
- 229920006282 Phenolic fiber Polymers 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 231100000693 bioaccumulation Toxicity 0.000 description 2
- 238000010000 carbonizing Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 150000002903 organophosphorus compounds Chemical class 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000002964 rayon Substances 0.000 description 2
- 239000004627 regenerated cellulose Substances 0.000 description 2
- 238000009958 sewing Methods 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 229920000433 Lyocell Polymers 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004693 Polybenzimidazole Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000002519 antifouling agent Substances 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 235000013351 cheese Nutrition 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 230000008642 heat stress Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000004750 melt-blown nonwoven Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920002480 polybenzimidazole Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
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Abstract
【課題】液状有機化学物質の防護性能に優れ、さらには、ＰＦＯＡフリーの加工剤を使用した場合に特に顕著である、はっ水、はつ油性能の低下を抑制し、優れた液浸透抑制能をもつ防護衣材料を提供することにある。【解決手段】ＥＳＣＡ（Ｅｌｅｃｔｒｏｎ Ｓｐｅｃｔｒｏｓｃｏｐｅ ｆｏｒ Ｃｈｅｍｉｃａｌ Ａｎａｌｙｓｉｓ）測定での珪素検出量が１０ａｔｏｍ％以下である液遮断層を含み、前記液遮断層は炭素数が６以下のパーフルオロアルキル基を有するフッ素系はっ水はつ油加工剤が塗布されていることを特徴とする防護衣材料。【選択図】なしAn object of the present invention is to provide a liquid organic chemical having excellent protection performance and, moreover, particularly when a PFOA-free processing agent is used. The purpose is to provide protective clothing materials with performance. A fluorine-containing layer having a perfluoroalkyl group having a carbon number of 6 or less includes a liquid blocking layer having a silicon detection amount of 10 atom% or less in ESCA (Electron Spectroscope for Chemical Analysis) measurement. Water repellent is a protective clothing material that is coated with an oil repellent. [Selection figure] None
Description
本発明は、有機リン系化合物のような皮膚から吸収されて人体に悪影響を及ぼす液状およびガス状有機化学物質、さらには粒子状物質から作業者を有効に防護できるとともに、軽量で通気性を有することで、快適性にも優れる防護衣材料に関する。本発明の防護衣材料は、特にシェルター、衣服、手袋、靴、カバー等に好適に使用されるものである。 The present invention can effectively protect a worker from liquid and gaseous organic chemicals that are absorbed from the skin such as organophosphorus compounds and adversely affect the human body, and particulate matter, and is lightweight and breathable. That is, the present invention relates to a protective clothing material having excellent comfort. The protective clothing material of the present invention is particularly suitable for shelters, clothes, gloves, shoes, covers and the like.
化学防護衣服は、一般に有毒な液状有機化学物質、ガス状有機化学物質、および粒子状物質から人体を保護する目的で着用される特殊衣服である。化学防護衣服では、有毒な液状有機化学物質、ガス状有機化学物質、および粒子状物質が防護衣服内部に侵入しないよう、通常、生地にはっ水はつ油剤による処理が予め施されている。 Chemical protective clothing is special clothing worn for the purpose of protecting the human body from generally toxic liquid organic chemicals, gaseous organic chemicals, and particulate matter. In chemical protective clothing, the fabric is usually pre-treated with a water-repellent and oil-repellent agent so that toxic liquid organic chemicals, gaseous organic chemicals, and particulate matter do not enter the protective clothing.
有毒な有機化学物質などから人体を保護する防護衣材料としては、従来から様々なものが提案されている。例えば、活性炭の脱落、飛散抑制のために、織物や不織布等により活性炭を挟みこんだ、または包み込んだ吸着シートが提案されている。しかし、液状の有機化学物質に対する浸透抑制能を向上させるため、従来よりフッ素系のはっ水はつ油剤が使用されてきた。フッ素系の処理剤の中でも、特に、炭素数は８以上のパーフルオロアルキル基を有する含フッ素重合体が一般的に使用されている。 Various protective clothing materials that protect the human body from toxic organic chemicals have been proposed. For example, an adsorbing sheet in which activated carbon is sandwiched or wrapped with a woven fabric or a nonwoven fabric has been proposed in order to prevent the activated carbon from falling off or scattering. However, in order to improve the permeation suppression ability with respect to liquid organic chemicals, a fluorinated water-repellent oil repellant has been used conventionally. Among fluorine-based treatment agents, in particular, a fluorine-containing polymer having a perfluoroalkyl group having 8 or more carbon atoms is generally used.
しかしながら、最近になりテロメリゼーションによって得られる炭素数８のフルオロアルキル基を含有する化合物が、分解または代謝によりｐｅｒｆｌｕｏｒｏ−ｏｃｔａｎｏｉｃ ａｃｉｄ（以下、ＰＦＯＡと略す）を生成する可能性があると公表されている（ＥＰＡ ＯＰＰＴ ＦＡＣＴ ＳＨＥＥＴ Ａｐｒｉｌ １４，２００３）。また、このＰＦＯＡの生体蓄積性を問題視する報告も種々なされている。 However, recently, it has been announced that a compound containing a fluoroalkyl group having 8 carbon atoms obtained by telomerization may generate perfluoro-octanoic acid (hereinafter abbreviated as PFOA) by decomposition or metabolism. (EPA OPPT FACT SHEEET April 14, 2003). There have also been various reports regarding the bioaccumulation of PFOA as a problem.
一方で、炭素数が８より短い短鎖のパーフルオロアルキル、特に炭素数７以下のものについては、生体蓄積性が低いと言われている。そこで、環境負荷を下げるために、短鎖のパーフルオロアルキル基を側鎖に有する含フッ素アクリレート重合体が求められている。しかしながら、短鎖のパーフルオロ基で構成された含フッ素アクリレート重合体は、パーフルオロ基のフッ素数の減少に伴って、そのパーフルオロアルキル基の結晶化度が低下し、結晶融点（Ｔｍ）を示さず、十分なはっ水はつ油性が得られないという問題があった。 On the other hand, short-chain perfluoroalkyl having a carbon number shorter than 8 and particularly those having 7 or less carbon atoms are said to have low bioaccumulation. Therefore, in order to reduce the environmental burden, a fluorine-containing acrylate polymer having a short-chain perfluoroalkyl group in the side chain is required. However, in the fluorine-containing acrylate polymer composed of short-chain perfluoro groups, as the number of fluorine atoms in the perfluoro group decreases, the crystallinity of the perfluoroalkyl group decreases, and the crystal melting point (Tm) decreases. Not shown, there was a problem that sufficient water repellency could not provide oil repellency.
従来から提案されている文献等においては、高いはっ水はつ油性能が必要とされる分野では、炭素数８以上のパーフルオロアルキル基を含有する化合物から構成されるはっ水はつ油加工剤を併用しているものがほとんどである。特許文献１には、防汚性ポリエステルフィラメントカーペットの製法において、はっ水はつ油性に優れて、汚染されにくく、長期間美しさを保持し、裏打ち層の強度も十分なポリエステルフィラメントからなるカーペットが提案されている。この文献では、残留油分を０．０５〜０．３％まで除去し、油剤除去後の脱水、防汚加工処理において、脱水における含水率を１５〜２５％に制御することが記載されているが、防汚加工剤処理においての残留珪素率についての詳細は記載されていない。 In the literatures proposed so far, in the field where high water repellency is required, the water repellency composed of a compound containing a perfluoroalkyl group having 8 or more carbon atoms. Most of them use processing agents together. In Patent Document 1, in a method for producing an antifouling polyester filament carpet, water repellency is excellent in oil repellency, hardly contaminated, maintains beauty for a long period of time, and has a backing layer with sufficient strength. Has been proposed. In this document, it is described that the residual oil content is removed to 0.05 to 0.3%, and the water content in the dehydration is controlled to 15 to 25% in the dehydration and antifouling processing after the oil agent is removed. Details of the residual silicon ratio in the antifouling agent treatment are not described.
特許文献２には、防汚原着糸およびその製造方法が例示されている。原着顔料および／または原着染料を含有する熱可塑性合成繊維からなる原着糸において、その繊維表面に常温で固状の疎水性平滑剤を主成分とする油剤が、対繊維重量で０．３重量％以下付着されている防汚原着糸が提案されている。しかし、この文献についても、加工剤の種類、付着量等における記載はなく、はつ油性能等の要求される性能が不明瞭である。 Patent Document 2 exemplifies an antifouling original yarn and a production method thereof. In an original yarn composed of a thermoplastic synthetic fiber containing an original pigment and / or an original dye, an oil whose main component is a hydrophobic smoothing agent that is solid at room temperature on the fiber surface is 0.000 by weight of the fiber. An antifouling original yarn having 3% by weight or less attached has been proposed. However, this document also does not describe the type of processing agent, the amount of adhesion, etc., and the required performance such as oil repellency is unclear.
特許文献３には、紡績工程で繊維に付着した紡績油剤をカーペットのバツキング後のキュアリング工程において繊維表面より少なくとも一部除去することを特徴とするはっ水はつ油性カーペットの製造方法が記載されている。しかしながら、キュアリング処理で処理できない油剤成分等についての対応処方等の記載はない。 Patent Document 3 describes a method for producing a water-repellent oil-repellent carpet, characterized in that at least part of the spinning oil adhering to the fiber in the spinning process is removed from the fiber surface in the curing process after backing the carpet. Has been. However, there is no description of the corresponding prescription for oil agent components that cannot be processed by the curing process.
本発明は、かかる従来技術の問題に鑑み創案されたものであり、その目的は、特に液状有機化学物質の防護性能に優れ、ＰＦＯＡフリーの加工剤を使用した場合に顕著であるはっ水はつ油性能の低下を抑制し、優れた液浸透抑制能をもつ防護衣材料を提供することにある。 The present invention was devised in view of the problems of the prior art, and its purpose is particularly excellent in the protection performance of liquid organic chemicals, and the water repellent that is remarkable when a PFOA-free processing agent is used is It is an object of the present invention to provide a protective clothing material that suppresses a decrease in oil repellent performance and has an excellent ability to inhibit liquid penetration.
本発明者は、かかる目的を達成するために防護衣材料について鋭意検討した結果、少なくとも液遮断層を有する防護衣材料において、前記液遮断層は、炭素数が６以下のパーフルオロアルキル基を有するフッ素系はっ水はつ油加工剤が塗布され、ＥＳＣＡ（Ｅｌｅｃｔｒｏｎ Ｓｐｅｃｔｒｏｓｃｏｐｅ ｆｏｒ Ｃｈｅｍｉｃａｌ Ａｎａｌｙｓｉｓ）測定での珪素検出量が１０ａｔｏｍ％以下であることにより、特にはっ水はつ油性に優れ、さらには、はつ油性能の低下を抑制可能で、液状有機化学物質からの有効な保護性能を有することを見出し、本発明の完成に至った。 As a result of earnestly examining the protective clothing material in order to achieve such an object, the present inventor has at least a protective clothing material having a liquid blocking layer, and the liquid blocking layer has a perfluoroalkyl group having 6 or less carbon atoms. Fluorine-based water-repellent oil-repellent processing agent is applied, and when the amount of silicon detected by ESCA (Electron Spectroscope for Chemical Analysis) is 10 atom% or less, water-repellent water is particularly excellent in oil-repellent property. It has been found that it is possible to suppress a drop in the oil repellency performance and has an effective protection performance from liquid organic chemicals, and the present invention has been completed.
すなわち、本発明は、以下の通りである。
（１）ＥＳＣＡ（Ｅｌｅｃｔｒｏｎ Ｓｐｅｃｔｒｏｓｃｏｐｅ ｆｏｒ Ｃｈｅｍｉｃａｌ Ａｎａｌｙｓｉｓ）測定での珪素検出量が１０ａｔｏｍ％以下である液遮断層を含み、前記液遮断層は炭素数が６以下のパーフルオロアルキル基を有するフッ素系はっ水はつ油加工剤が塗布されていることを特徴とする防護衣材料。
（２）液遮断層のはつ油度がＡＡＴＣＣ１１８法で３級以上である（１）に記載の防護衣材料。
（３）（１）または（２）に記載の防護衣材料を用いた防護衣服。
That is, the present invention is as follows.
(1) A liquid blocking layer having a silicon detection amount of 10 atom% or less in ESCA (Electron Spectroscope for Chemical Analysis) measurement, wherein the liquid blocking layer has a fluorocarbon group having a perfluoroalkyl group having 6 or less carbon atoms. A protective clothing material characterized in that a water repellant finish is applied.
(2) The protective clothing material according to (1), wherein the liquid barrier layer has a degree of oiliness of 3 or more according to the AATCC118 method.
(3) Protective clothing using the protective clothing material according to (1) or (2).
本発明の防護衣材料は、はっ水はつ油性に優れる材料であり、特に液状有機化学物質からの優れた防護が可能であり、防護衣服に使用するのに極めて好適である。 The protective clothing material of the present invention is a material having excellent water repellency and water repellency. Particularly, the protective clothing material can be excellently protected from liquid organic chemicals, and is very suitable for use in protective clothing.
本発明の防護衣材料は、ＥＳＣＡ（Ｅｌｅｃｔｒｏｎ Ｓｐｅｃｔｒｏｓｃｏｐｅ ｆｏｒ Ｃｈｅｍｉｃａｌ Ａｎａｌｙｓｉｓ）測定での珪素検出量が１０ａｔｏｍ％以下である液遮断層を含み、前記液遮断層は炭素数が６以下のパーフルオロアルキル基を有するフッ素系はっ水はつ油加工剤が塗布されている防護衣材料である。 The protective clothing material of the present invention includes a liquid barrier layer having a silicon detection amount of 10 atom% or less in ESCA (Electron Spectroscope for Chemical Analysis) measurement, and the liquid barrier layer contains a perfluoroalkyl group having 6 or less carbon atoms. The fluorine-based water repellent possessed is a protective clothing material coated with an oil processing agent.
液遮断層とは、はっ水はつ油材による加工を施すことにより、有害な液状有機化学物質に対する耐液浸透性を付与した、比較的緻密な構造の層であり、繊維を含むシート状物からなる層である。 A liquid barrier layer is a layer with a relatively dense structure that has been treated with a water-repellent oil-repellent material to provide liquid penetration resistance to harmful liquid organic chemicals. It is a layer consisting of things.
本発明の繊維を含むシート状物からなる液遮断層を構成する繊維は、特に限定されるものではなく、レーヨン、ポリノジック、キュプラ、リヨセル、アセテート、トリアセテート、ナイロン、アラミド、ビニロン、ビニリデン、ポリ塩化ビニル、ポリエステル、アクリル、アクリル系、ポリエチレン、ポリウレタン、ポリクラール、ポリアリレート、ポリイミド、ポリアミドイミド、ポリフェニレンスルフィド、ポリアクリロニトリル、ポリスルホン、ポリカーボネート、ポリパラフェニレンベンズオキサゾール、ポリベンゾイミダゾール、ポリビニルアルコール、セルロース、ポリエチレンオキサイド、ポリプロピレンオキサイド、ポリ酢酸ビニル、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリ乳酸、ポリプロピレン、ＰＶＤＦ、ＰＰＳ等を素材とする繊維が挙げられ、これらの繊維を複数混紡・混綿して使用してもよい。 The fiber constituting the liquid blocking layer comprising the sheet-like material of the present invention is not particularly limited, and rayon, polynosic, cupra, lyocell, acetate, triacetate, nylon, aramid, vinylon, vinylidene, polychlorinated Vinyl, polyester, acrylic, acrylic, polyethylene, polyurethane, polyclarate, 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 PVDF, include fibers from a material of PPS or the like, may be used these fibers plurality blended-cotton mixing.
液遮断層の形態は、織物、編物、組物、レース、網、不織布等のシート状物や、これらの積層体が好ましく使用できる。中でも、織物、編物、不織布等が好適に使用できる。 As the form of the liquid blocking layer, woven fabrics, knitted fabrics, braids, laces, nets, non-woven fabrics and the like, and laminates thereof can be preferably used. Among these, woven fabrics, knitted fabrics, nonwoven fabrics, and the like can be suitably used.
前記織物や編物には、加圧下での液滴の浸透を効果的に防止できる「カットパイル織編物」も含まれる。「カットパイル織編物」とは、片面または両面にパイルを形成した織編物について、形成されたパイルの一部または全部をカットした織編物である。例えば、特開平８−３０８９４５号公報に示されているカットパイル編物も本発明には好ましく使用できる。 The woven fabric and the knitted fabric also include a “cut pile knitted fabric” that can effectively prevent the penetration of droplets under pressure. The “cut pile knitted fabric” is a woven or knitted fabric obtained by cutting a part or all of the formed pile with respect to the woven or knitted fabric in which the pile is formed on one side or both sides. For example, a cut pile knitted fabric disclosed in JP-A-8-308945 can be preferably used in the present invention.
本発明の液遮断層の厚さは、０．１〜２．０ｍｍであることが好ましい。かかる範囲とすることにより、粒子除去性能、加圧時における耐液性能、さらには、通気性、使用感のバランスに優れた、液遮断層が得られる。 The thickness of the liquid blocking layer of the present invention is preferably 0.1 to 2.0 mm. By setting it as such a range, a liquid blocking layer having an excellent balance of particle removal performance, liquid resistance performance during pressurization, air permeability and usability can be obtained.
本発明の液遮断層の通気性は、ＪＩＳ Ｌ １０９６（２０１０） ８．２６．１に記載のフラジール法による通気性試験で、５〜１００ｃｍ３/ｃｍ２・ｓｅｃであることが好ましく、７〜８０ｃｍ３/ｃｍ２・ｓｅｃであることがより好ましい。通気性が５ｃｍ３/ｃｍ２・ｓｅｃ未満であると、防護衣着用時の蒸れ感につながり、使用感を満足出来ない原因となる。一方、１００ｃｍ３/ｃｍ２・ｓｅｃを超える場合には、粒子除去性能、さらには加圧時における耐液性能が悪くなる。 The air permeability of the liquid blocking layer of the present invention is preferably 5 to 100 cm 3 / cm 2 · sec in the air permeability test by the Frazier method described in JIS L 1096 (2010) 8.26.1. More preferably, it is 80 cm 3 / cm 2 · sec. 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, when it exceeds 100 cm 3 / cm 2 · sec, the particle removal performance and further the liquid resistance performance during pressurization are deteriorated.
本発明の液遮断層の防水性は、ＪＩＳ Ｌ １０９２（２００９） ７．１に記載の方法による耐水圧試験（静水圧法）で、２０〜１５００ｍｍであることが好ましく、５０〜１３００ｍｍであることがより好ましい。防水性が２０ｍｍ未満であると、加圧時の耐液性能、粒子除去性能を満足出来ない原因となる。一方、１５００ｍｍを越えると、防護性能は高くなるが、通気性が低く、防護衣とした場合の着用間、使用感の優れたものとはならない。 The waterproof property of the liquid blocking layer of the present invention is preferably 20 to 1500 mm, and preferably 50 to 1300 mm in a water pressure resistance test (hydrostatic pressure method) according to the method described in JIS L 1092 (2009) 7.1. Is more preferable. If the waterproofness is less than 20 mm, the liquid resistance performance during pressurization and the particle removal performance cannot be satisfied. On the other hand, when the thickness exceeds 1500 mm, the protective performance is improved, but the air permeability is low, and the feeling of use is not excellent during wearing when the protective clothing is used.
本発明に用いる液遮断層へは、液状有機化学物質に対する防護性を発現させるために、はっ水はつ油加工を施すことが必要である。はっ水はつ油加工は従来公知のいかなる方法でもよく、特に限定されるものでない。液遮断層のＪＩＳ Ｌ １０９２（２００９） ７．２に記載の方法によるはっ水度試験（スプレー試験）ではっ水度が２級以上、ＡＡＴＣＣ Ｔｅｓｔ Ｍｅｔｈｏｄ １１８法によるはつ油度が３級以上であることが好ましい。 The liquid barrier layer used in the present invention needs to be water-repellent and oil-repellent in order to develop protection against liquid organic chemicals. The water-repellent and oil-repellent processing may be any conventionally known method and is not particularly limited. In the water repellency test (spray test) according to the method described in JIS L 1092 (2009) 7.2 of the liquid blocking layer, the water repellency is 2nd grade or higher, and the oil repellency by the AATCC Test Method 118 method is 3rd grade or higher. It is preferable that
本発明で使用するはっ水はつ油加工剤は、はっ水性、はつ油性および経時的なはつ油性能の安定性を考慮するとフッ素樹脂系のはっ水はつ油加工剤が好ましい。 The water-repellent oil-repellent finishing agent used in the present invention is preferably a fluororesin-based water-repellent oil-repellent finishing agent in consideration of water repellency, oil repellency, and stability of oil repellency over time. .
本発明の液遮断層はＥＳＣＡ（Ｅｌｅｃｔｒｏｎ Ｓｐｅｃｔｒｏｓｃｏｐｙ ｆｏｒＣｈｅｍｉｃａｌ Ａｎａｌｙｓｉｓ）測定で、珪素検出量が１０ａｔｏｍ％以下である。珪素検出量が１０ａｔｏｍ％を超える液遮断層では、はつ油度が３級以上のはつ油性能が発現せず、はつ油性能の経時的な安定性も欠ける結果となる。 The liquid blocking layer of the present invention has a silicon detection amount of 10 atom% or less as measured by ESCA (Electron Spectroscopy for Chemical Analysis). In the liquid blocking layer in which the silicon detection amount exceeds 10 atom%, the oil repellency of the oil repellency is not less than the third grade, resulting in the lack of stability of the oil repellency over time.
本発明の液遮断層のＥＳＣＡ測定による珪素検出量を上記範囲とする方法としては、液遮断層をシート状物やその積層体とした後にバッチ法や連続法により精練する方法やシート状やその積層体とする前のカセやチーズなどの糸状の状態でバッチ法により精練する方法がある。精練には、通常使用される精練剤を使用する方法や熱水による方法などが使用可能である。いずれの方法によっても、ＥＳＣＡ測定による珪素検出量が１０ａｔｏｍ％となるように精練を実施することが必要である。 As a method of setting the silicon detection amount by ESCA measurement of the liquid blocking layer of the present invention in the above range, a method in which the liquid blocking layer is made into a sheet-like material or a laminate thereof and then scoured by a batch method or a continuous method, a sheet shape or the like There is a method of scouring by a batch method in a thread-like state such as casserole or cheese before making a laminate. For scouring, a method using a commonly used scouring agent or a method using hot water can be used. In any method, it is necessary to carry out scouring so that the amount of silicon detected by ESCA measurement is 10 atom%.
本発明の防護衣材料には、液遮断層の上および下の一方側、または、両側にガス吸着層を積層することで、ガスに対する防護性も付与できるものとなる。ガス吸着層の使用するガス吸着材としては、活性炭やカーボンブラックなどの炭素系吸着材、シリカゲル、ゼオライト系吸着材、炭化ケイ素、または活性アルミナなどの無機系吸着材等からなるガス吸着材が挙げられるが、対象とする被吸着物質に応じて適宜選択されることができる。その中でも広範囲なガスに対応できる活性炭が好ましく、特に吸着速度や吸着容量が大きく少量の使用で効果的なガス透過抑制能が得られる繊維状活性炭がより好ましい。 The protective clothing material of the present invention can be provided with a protective property against gas by laminating a gas adsorbing layer on one side or both sides above and below the liquid blocking layer. Examples of the gas adsorbent used in the gas adsorbing layer include carbon adsorbents such as activated carbon and carbon black, and gas adsorbents made of inorganic adsorbents such as silica gel, zeolite adsorbent, silicon carbide, or activated alumina. However, it can be appropriately selected depending on the 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.
ガス吸着層の被吸着物質としてのガスには、炭素元素を１つ以上持つガス状化合物が含まれる。例えば、ガス状化合物には、５０以上の比較的大きな分子量を持ち、活性炭等のガス吸着層が吸着可能なガス状化学物質が含まれる。具体的には、農薬、殺虫剤、除草剤に使用される有機リン系化合物や、塗装作業などに使用されるトルエン、塩化メチレン、クロロホルムなどの一般的な有機溶剤が挙げられる。 The gas as the substance to be adsorbed in the gas adsorption layer 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.
ガス吸着層に繊維状活性炭を用いる場合、そのＢＥＴ比表面積は、７００〜３０００ｍ２／ｇが好ましく、１０００〜２５００ｍ２／ｇがより好ましい。ＢＥＴ比表面積が上記範囲未満であると、十分な防護性を得るために多くの活性炭が必要となり材料が重くなり、柔軟性が劣ることが懸念される。一方、上記範囲より大きくなると、吸着したガス状有機化学物質を脱離する問題が起こりうる。 When using fibrous activated carbon for a gas adsorption layer, 700-3000 m < 2 > / g is preferable and the BET specific surface area has more preferable 1000-2500 m < 2 > / g. 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 poor. On the other hand, when it becomes larger than the above range, a problem of desorbing the adsorbed gaseous organic chemical substance may occur.
ガス吸着層に含有する繊維状活性炭の質量としては、５０〜３００ｇ／ｍ２が好ましく、７０〜２５０ｇ／ｍ２がより好ましい。質量が上記範囲未満であると、吸着できる容量が小さくなり使用時間が制限される。一方、上記範囲より大きくなると、材料の柔軟性が劣ることが懸念される。 As mass of the fibrous activated carbon contained in a gas adsorption layer, 50-300 g / m < 2 > is preferable and 70-250 g / m < 2 > is more preferable. 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.
前記繊維状活性炭の原料としては、綿、麻といった天然セルロース繊維の他、レーヨン、ポリノジック、溶剤紡糸法によるといった再生セルロース繊維、さらにはポリビニルアルコール繊維、アクリル系繊維、芳香族ポリアミド繊維、リグニン繊維、フェノール系繊維、石油ピッチ繊維等の合成繊維が挙げられるが、得られる繊維状活性炭の物性（強度等）や吸着性能から再生セルロース繊維、フェノール系繊維、アクリル系繊維が好ましい。繊維状活性炭は、従来公知の方法によって製造されることができるが、例えばこれらの原料繊維の短繊維あるいは長繊維を用いて製織、製編、不織布化した布帛に必要に応じて適当な耐炎化剤を含有させた後、４５０℃以下の温度で耐炎化処理を施し、次いで５００℃以上１０００℃以下の温度で炭化賦活することによって製造されることができる。 As the raw material of the fibrous activated carbon, in addition to natural cellulose fibers such as cotton and hemp, regenerated cellulose fibers such as rayon, polynosic, solvent spinning method, and further, polyvinyl alcohol fibers, acrylic fibers, aromatic polyamide fibers, lignin fibers, Synthetic fibers such as phenolic fibers and petroleum pitch fibers can be mentioned. Regenerated cellulose fibers, phenolic fibers, and acrylic fibers are preferred from the physical properties (such as strength) 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.
ガス吸着層の作成方法としては、従来公知の方法を採用することができ、例えばシート基材にガス吸着材をバインダーにより接着する方法、ガス吸着材を適当なパルプおよびバインダーを含めスラリー状とし、湿式抄紙機により抄造する方法、またはガス吸着材の原料繊維をあらかじめ製織、製編、不織布化し、必要に応じて耐炎化処理したのち炭化・賦活する方法を採用することができる。 As a method for creating the gas adsorbing layer, a conventionally known method can be adopted, for example, a method of adhering the gas adsorbing material to the sheet base material with a binder, the gas adsorbing material in a slurry form 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 adsorbing material in advance after weaving, knitting, or non-woven fabric, and flame-proofing as necessary can be employed.
ガス吸着層は、織物、編物、不織布、またはフェルトのいずれかの形態を有することが好ましい。これらのうち織物または編物の形態が通気性、積層の容易性、柔軟性などの面からより好ましい。 The gas adsorption layer preferably has any form of woven fabric, knitted fabric, non-woven fabric, or felt. Among these, the form of woven fabric or knitted fabric is more preferable from the viewpoints of air permeability, ease of lamination, flexibility, and the like.
液遮断層とガス吸着層の積層手段としては、通気性を考慮すると、部分的に接着されていることが好ましい。部分接着に使用する接着剤としては、特に限定されないが、合成ゴム、酢酸ビニル樹脂、ウレタン樹脂、エポキシ樹脂、アクリル樹脂系、ポリエステル系、塩化ビニル等の溶剤型または無溶剤接着剤が好ましい。なお、溶剤系接着剤を使用する場合には、接着剤に含有する有機溶剤がガス吸着層により吸着され、ガス吸着性能が低下する恐れがあるため、脱着工程により十分に接着剤中の溶剤を気化させる必要がある。ガス吸着層に吸着された溶剤の脱着方法については、接着剤に使用されている溶剤の種類に応じて設定する必要がある。ガス吸着層に対する残存溶剤率は２０％以下であることが好ましく、１５％以下であることがより好ましい。 As a means for laminating the liquid blocking layer and the gas adsorption layer, it is preferable that the liquid blocking layer and the gas adsorbing layer 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, and more preferably 15% or less.
部分接着の方法としては、特に限定されないが、柔軟性、通気性等を考慮すると、グラビア方式やスクリーン方式、スプレー塗工等により非全面のドット状、格子状、スパイラル状、棒状に接着剤を均一に塗布して接着する方法が好ましい。なお、接着剤は、液遮断層面またはガス吸着層面のいずれでも塗布することが可能であるが、ガス吸着性能を考慮すると、液遮断層面へ塗布することが好ましい。 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 liquid blocking layer surface or the gas adsorbing layer surface, but it is preferable to apply the adhesive to the liquid blocking layer surface in consideration of gas adsorption performance.
接着剤の塗布量としては、５〜５０ｇ／ｍ２であることが好ましく、１０〜４０ｇ／ｍ２であることがより好ましい。塗布量が上記範囲未満であると、接着強度の低下の問題が生じ、一方、上記範囲を越えると、柔軟性と通気性が低下する原因となる。 The coating amount of the adhesive is preferably 5 to 50 g / m 2, and more preferably 10 to 40 g / m 2. If the coating amount is less than the above range, there will be a problem of a decrease in adhesive strength. On the other hand, if it exceeds the above range, flexibility and air permeability will be reduced.
部分接着時の接着面積の割合（ガス吸着層の面積に対する接着剤塗布面積の割合）は５〜８０％であることが好ましく、１０〜７０％であることがより好ましい。割合が上記範囲未満であると、接着強度が低下する問題が発生し、一方、上記範囲を越えると、接着剤の塗布量が大きくなり、部分接着にはなりにくく、柔軟性、通気性が低下する問題が発生する。 The ratio of the adhesion area at the time of partial adhesion (ratio of the adhesive application area to the area of the gas adsorption layer) is preferably 5 to 80%, more preferably 10 to 70%. 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 over the above range, the amount of adhesive applied is increased, and partial adhesion is difficult to occur, and flexibility and air permeability are lowered. Problems occur.
グラビア方式、スクリーン方式、またはスプレー方式により部分接着させる場合、使用するグラビアロール、スクリーンまたはスプレーノズル条件等は、接着面積および接着剤塗布重量に応じて適宜選択することができる。グラビア方式の場合には、グラビアの線数、深度により、スクリーン方式の場合には、メッシュ厚みと開口率、スプレー方式の場合には、ノズル形状、ノズル圧等によりこれらを任意に設定することが可能である。 In the case of partial adhesion by a gravure method, a screen method, or a spray method, the gravure roll, screen, or spray nozzle condition 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.
液遮断層とガス吸着層との接着剤を介した接着界面での剥離強度は、材料の長さ方向と幅方向の両方において３０ｇｆ/ｃｍ以上であることが好ましく、４０ｇｆ/ｃｍ以上であることがより好ましい。剥離強度が低いと、液遮断層とガス吸着層の剥離が生じ、ガス吸着層の強度または衣服としたときの取り扱い性等の問題が発生する。剥離強度の上限は、現実的には１５０ｇｆ/ｃｍである。 The peel strength at the adhesion interface between the liquid blocking layer and the gas adsorption layer via the adhesive is preferably 30 gf / cm or more in both the length direction and the width direction of the material, and is 40 gf / cm or more. Is more preferable. When the peel strength is low, the liquid blocking layer 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.
液遮断層とガス吸着層の積層体からなる防護材料の質量としては、５００ｇ／ｍ２以下が好ましく、４００ｇ／ｍ２以下がより好ましい。積層体の質量が上記範囲を越えると、重量が重く柔軟性に乏しい材料にとなり、防護衣服とした場合には、着用性、運動追従性、使用感を満足出来ないといった問題となる。質量の下限は、現実的には１００ｇ／ｍ２である。 The mass of the protective material comprising a laminate of a liquid blocking layer and gas adsorption layer is preferably 500 g / m 2 or less, 400 g / m 2 or less is more preferable. 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, motion following ability, and feeling of use cannot be satisfied. The lower limit of mass is practically 100 g / m 2 .
液遮断層とガス吸着層の積層体からなる防護衣材料の厚みとしては、５．０ｍｍ以下が好ましく、４．０ｍｍ以下がより好ましい。厚みが上記範囲を越えると、積層体のごわつきが大きくなり、防護衣への加工性が悪くなる。厚みの下限は、現実的には１．０ｍｍである。 The thickness of the protective clothing material composed of the laminate of the liquid blocking layer and the gas adsorption 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.
液遮断層とガス吸着層の積層体からなる防護衣材料の柔軟性の指標となる剛軟度は、材料の長さ方向と幅方向の両方において０．０８Ｎ・ｃｍ以下であることが好ましく、０．０５Ｎ・ｃｍ以下であることがより好ましい。剛軟度が上記範囲を越えると、材料が堅くなり、吸着シートとしての加工が困難になる。剛軟度の下限は、現実的には０．００２Ｎ・ｃｍである。 The bending resistance, which is an indicator of the flexibility of the protective clothing material composed of the laminate of the liquid blocking 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, it is 0.05 N · cm or less. If the bending resistance exceeds the above range, the material becomes stiff and it becomes difficult to process as an adsorbing sheet. The lower limit of the bending resistance is actually 0.002 N · cm.
液遮断層とガス吸着層の積層体からなる防護衣材料の通気性は、５〜１００ｃｍ３／ｃｍ２・ｓであることが好ましく、１０〜８０ｃｍ３／ｃｍ２・ｓであることがより好ましい。通気性が上記範囲未満では、通気性が劣り、上記範囲を越えると接着が不充分な材料となり、剥離の問題が生じ、さらには、耐粒子性に劣ることがある。 Breathable protective clothing material comprising a laminate of a liquid blocking layer and gas adsorption layer is preferably 5~100cm 3 / cm 2 · s, and more preferably 10~80cm 3 / cm 2 · s . When the air permeability is less than the above range, the air permeability is inferior. When the air permeability exceeds the above range, the material becomes insufficiently bonded, causing a problem of peeling, and further, the particle resistance may be inferior.
液遮断層とガス吸着層の積層体からなる防護衣材料のトルエン吸着性能（トルエンガス平衡吸着量）としては、２０ｇ／ｍ２以上であることが好ましく、２５ｇ／ｍ２以上であることがより好ましい。トルエン吸着性能が上記範囲未満では、吸着性が劣りガスに対する防護性が劣る結果となる。トルエン吸着性能の上限は、現実的には２００ｇ／ｍ２である。 The toluene adsorption performance (toluene gas equilibrium adsorption amount) of the protective clothing material composed of the laminate of the liquid blocking layer and the gas adsorption layer is preferably 20 g / m 2 or more, more preferably 25 g / m 2 or more. preferable. 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 .
防護衣材料の液状有機化学物質に対する防護性をより向上させるために、ガス吸着層にあらかじめはっ水はつ油加工を施した材料を使用してもよい。はっ水はつ油加工は従来公知のいかなる方法でもよく、特に限定されるものでない。防護衣材料を構成するガス吸着層のＪＩＳ Ｌ １０９２（２００９） ７．２に記載の方法によるはっ水度試験（スプレー試験）を実施した場合のはっ水度が２級以上、ＡＡＴＣＣ Ｔｅｓｔ Ｍｅｔｈｏｄ １１８法による撥油度が３級以上であることが好ましい。 In order to further improve the protective property of the protective clothing material against the liquid organic chemical, 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 water repellency when the water repellency test (spray test) according to the method described in JIS L 1092 (2009) 7.2 of the gas adsorbing layer constituting the protective clothing material is A grade or higher, AATCC Test Method. The oil repellency according to the 118 method is preferably 3 or more.
液遮断層とガス吸着層の積層体からなる防護衣材料に、機械的強度の大幅な向上を目的としたり、対象ガスが複数にわたる時などは、液防護層およびガス吸着層をそれぞれ必要枚数重ね合わせて使用することは有効である。 The protective clothing material consisting of a laminate of a liquid barrier layer and a gas adsorption layer is used for the purpose of significantly improving the mechanical strength or when there are multiple target gases, the liquid protection layer and the gas adsorption layer are overlapped as many as necessary. It is effective to use them together.
液遮断層とガス吸着層の積層体からなる防護衣材料の最も外側に外布を、最も内側に内布を、少なくともそれぞれ１層以上必要に応じて設けても良い。 If necessary, at least one outer cloth may be provided on the outermost side of the protective clothing material composed of the laminate of the liquid blocking layer and the gas adsorbing layer, and one or more inner cloths may be provided on the innermost side, if necessary.
外布の目的としては、外部から与えられる機械的な力から液防護層およびガス吸着層を保護することと、はっ水性とはつ油性が付与されている織物、編物、または不織布を外布に適用することで、耐液浸透性をさらに向上させることが可能となる。外布としては、本発明の液遮断層と同様の手法により得られるＪＩＳ Ｌ１０９２（２００９） ７．２に記載のはっ水度試験（スプレー試験）を実施した場合のはっ水度が２級以上、ＡＡＴＣＣ Ｔｅｓｔ Ｍｅｔｈｏｄ １１８法によるはつ油度が３級以上である織物、編物、または不織布などが好適に用いることができるが、柔軟性を考慮したものの使用が推奨される。液遮断層とガス吸着層の積層体からなる防護衣材料と外布とは、あらかじめ接着剤により接着されている形態でもよいし、柔軟性を考慮し、接着せずに重ね合わせた状態で縫製加工し、防護衣服を作製してもよい。 The purpose of the outer fabric is to protect the liquid protective layer and gas adsorbing layer from mechanical force applied from the outside, and to fabricate woven fabric, knitted fabric or non-woven fabric with water repellency and oil repellency. By applying to, it becomes possible to further improve the liquid penetration resistance. As the outer fabric, the water repellency when the water repellency test (spray test) described in JIS L1092 (2009) 7.2 obtained by the same method as the liquid barrier layer of the present invention is second grade. As described above, a woven fabric, a knitted fabric, a non-woven fabric or the like having a degree of oil repellency of 3 or more according to the AATCC Test Method 118 method can be preferably used, but the use of a fabric considering flexibility is recommended. The protective clothing material and outer fabric made of a laminate of a liquid barrier layer and a gas adsorbing layer may be pre-adhered with an adhesive, or sewed in a superposed state without bonding in consideration of flexibility. It may be processed to make protective clothing.
内布の目的としては、外部から与えられる機械的な力から液防護層およびガス吸着層を保護する役割と防護衣着用者の汗によるべたつき感を抑制する役割である。内布としては、織物、編物、不織布、または開孔フィルム等の材料があげられるが、通気性、柔軟性等の観点から粗い密度で製織または製編された織物もしくは編物が好ましい。液防護層とガス吸着層の積層体からなる材料と内布とは、あらかじめ接着剤により接着されている形態でもよいし、柔軟性を考慮し、接着せずに重ね合わせた状態で縫製加工し、または、あらかじめガス吸着層とキルティング加工した後、液遮断層と積層を行っても良い。キルティング加工は、従来公知の方法を採用することができ、ポリエステル、ナイロン、綿等のミシン糸が好ましく使用される。液状物質に対する防護性を考慮すると、撥油性ミシン糸を使用することが特に好ましい。 The purpose of the inner cloth is to protect the liquid protective layer 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. Examples of the inner fabric include materials such as woven fabrics, knitted fabrics, non-woven 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 material consisting of the laminate of the liquid protective layer and the gas adsorbing layer and the inner cloth may be pre-adhered with an adhesive, or may be sewn in a superposed state without bonding, considering flexibility. Alternatively, after the quilting process with the gas adsorption layer in advance, the liquid blocking layer 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.
液防護層およびガス吸着層に外布および／また内布をさらに積層した防護衣材料の質量としては、７００ｇ/ｍ２以下が好ましく、６００ｇ/ｍ２以下がより好ましい。質量が７００ｇ/ｍ２を超えると防護衣服の重量が大きくなり熱ストレスの原因となる。 The mass of the protective clothing material in which an outer cloth and / or an inner cloth is further laminated on the liquid protective layer and the gas adsorption layer is preferably 700 g / m 2 or less, and 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.
次に、実施例および比較例を用いて本発明の効果を具体的に説明するが、本発明はこれらによって限定されるものではない。なお、実施例に記載の評価方法は以下の通りである。 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）はつ油度
ＡＡＴＣＣ Ｔｅｓｔ Ｍｅｔｈｏｄ １１８法による。
(1) Oil repellency According to AATCC Test Method 118 method.
（２）はつ油度の経時変化
はつ油加工後１ヶ月経過品のＡＡＴＣＣ Ｔｅｓｔ Ｍｅｔｈｏｄ １１８法による。
(2) Change with time of oil repellency According to the AATCC Test Method 118 method after 1 month after oil repellency processing.
（３）珪素含有率
アルバック・ファイＥＳＣＡ５８０１ＭＣを用いて、全元素スキャンを行い、その後検出された元素と存在が予想される元素についてナロースキャンを行い、存在比を評価した。
(3) Silicon content rate Using ULVAC-Phi ESCA5801MC, all element scans were performed, then narrow scans were performed on the detected elements and elements expected to exist, and the abundance ratio was evaluated.
＜実施例１＞
液遮断層を以下の方法で作製した。２２ゲージ６枚筬ダブルラッセル機により、地糸としてナイロンフィラメント糸（８４ｄｔｅｘ、２４フィラメント）を、パイル糸としてナイロンフィラメント（１７６ｄｔｅｘ、モノフィラメント）を夫々供給し、図１の組織および糸配列で経編地を編成した後精錬し、パイル先端部を熱溶融し球状物を形成させた。
その先端溶融パイル布のＥＳＣＡによる珪素含有率は、０．５ａｔｏｍ％であった。また、液遮断層を３ｗｔ％のフッ素系撥水剤（日華化学株式会社製 ＮＫガードＳ−１１ ＰＦＯＡフリー）の加工浴に浸漬して乾燥し、１００℃で乾燥処理し、１５０℃まで上げてキュアを施した。得られた液遮断層のＥＳＣＡによる珪素含有率、はつ油度および１ヶ月経過後のはつ油度をそれぞれ表１に示す。
<Example 1>
A liquid blocking layer was produced by the following method. The 22 gauge six guide bars double raschel machine, nylon filament yarn as the ground yarn (84 dtex, 24 filament) and nylon filament (176Dtex, monofilaments) as the pile yarn and respectively supply, warp-knitted fabric in tissue and yarn arrangement in FIG. 1 After knitting, it was refined and the tip of the pile was melted by heat to form a sphere.
The silicon content by ESCA of the tip melt pile fabric was 0.5 atom%. Also, the liquid blocking layer is dipped in a processing bath of 3 wt% fluorine-based water repellent (NK Guard S-11 PFOA-free, manufactured by Nikka Chemical Co., Ltd.), dried, dried at 100 ° C., and raised to 150 ° C. And cured. Table 1 shows the silicon content by ESCA, oil repellency, and oil repellency after one month of the obtained liquid barrier layer.
＜実施例２＞
液遮断層を以下の方法で作製した。２２ゲージ６枚筬ダブルラッセル機により、地糸としてナイロンフィラメント糸（８４ｄｔｅｘ、２４フィラメント）を、パイル糸としてナイロンフィラメント（１７６ｄｔｅｘ、モノフィラメント）を夫々供給し、図１の組織および糸配列で経編地を編成した後精錬し、パイル先端部を熱溶融し球状物を形成させた。
その先端溶融パイル布のＥＳＣＡによる珪素含有率は、２．０ａｔｏｍ％であった。また、液遮断層を３ｗｔ％のフッ素系撥水剤（日華化学株式会社製 ＮＫガードＳ−１１ ＰＦＯＡフリー）の加工浴に浸漬して乾燥し、１００℃で乾燥処理し、１５０℃まで上げてキュアを施した。得られた液遮断層のＥＳＣＡによる珪素含有率、はつ油度および１ヶ月経過後のはつ油度をそれぞれ表１に示す。
<Example 2>
A liquid blocking layer was produced by the following method. The 22 gauge six guide bars double raschel machine, nylon filament yarn as the ground yarn (84 dtex, 24 filament) and nylon filament (176Dtex, monofilaments) as the pile yarn and respectively supply, warp-knitted fabric in tissue and yarn arrangement in FIG. 1 After knitting, it was refined and the tip of the pile was melted by heat to form a sphere.
The silicon content by ESCA of the tip melted pile fabric was 2.0 atom%. Also, the liquid blocking layer is dipped in a processing bath of 3 wt% fluorine-based water repellent (NK Guard S-11 PFOA-free, manufactured by Nikka Chemical Co., Ltd.), dried, dried at 100 ° C., and raised to 150 ° C. And cured. Table 1 shows the silicon content by ESCA, oil repellency, and oil repellency after one month of the obtained liquid barrier layer.
＜実施例３＞
液遮断層を以下の方法で作製した。２２ゲージ６枚筬ダブルラッセル機により、地糸としてナイロンフィラメント糸（８４ｄｔｅｘ、２４フィラメント）を、パイル糸としてナイロンフィラメント（１７６ｄｔｅｘ、モノフィラメント）を夫々供給し、図１の組織および糸配列で経編地を編成した後精錬し、パイル先端部を熱溶融し球状物を形成させた。
その先端溶融パイル布のＥＳＣＡによる珪素含有率は、７．０ａｔｏｍ％であった。また、液遮断層を３ｗｔ％のフッ素系撥水剤（日華化学株式会社製 ＮＫガードＳ−１１ ＰＦＯＡフリー）の加工浴に浸漬して乾燥し、１００℃で乾燥処理し、１５０℃まで上げてキュアを施した。得られた液遮断層のＥＳＣＡによる珪素含有率、はつ油度および１ヶ月経過後のはつ油度をそれぞれ表１に示す。
<Example 3>
A liquid blocking layer was produced by the following method. The 22 gauge six guide bars double raschel machine, nylon filament yarn as the ground yarn (84 dtex, 24 filament) and nylon filament (176Dtex, monofilaments) as the pile yarn and respectively supply, warp-knitted fabric in tissue and yarn arrangement in FIG. 1 After knitting, it was refined and the tip of the pile was melted by heat to form a sphere.
The silicon content by ESCA of the tip melt pile fabric was 7.0 atom%. Also, the liquid blocking layer is dipped in a processing bath of 3 wt% fluorine-based water repellent (NK Guard S-11 PFOA-free, manufactured by Nikka Chemical Co., Ltd.), dried, dried at 100 ° C., and raised to 150 ° C. And cured. Table 1 shows the silicon content by ESCA, oil repellency, and oil repellency after one month of the obtained liquid barrier layer.
＜実施例４＞
液遮断層を以下の方法で作製した。下層としてＰＥＴ製スパンレース不織布（ユウホウ株式会社製、質量４０ｇ/ｍ２）を使用し、該ＰＥＴ製スパンレース不織布の片面に、ポリエステル系不織布状熱可塑性接着剤（呉羽テック株式会社製「ダイナック（登録商標）ＬＮＳ００１５」、質量１５ｇ/ｍ２）を重ね合わせた。該ポリエステル系不織布状熱可塑性接着剤側の表面へ、Ｎｙ製メルトブローン不織布（平均単繊維直径０．５μｍ、質量１５ｇ／ｍ２）を重ね合わせた。その後、該ポリウレタン製ナノファイバー不織布側に、前記ポリエステル系不織布状熱可塑性接着剤を重ね、その上に前記ＰＥＴ製スパンレース不織布を積層し、加熱ローラで圧着することで液遮断層を作製した。その液遮断層のＥＳＣＡによる珪素含有率は、０ａｔｏｍ％であった。また、液遮断層を３ｗｔ％のフッ素系撥水剤（日華化学株式会社製 ＮＫガードＳ−１１ ＰＦＯＡフリー）の加工浴に浸漬して乾燥し、１００℃で乾燥処理し、１５０℃まで上げてキュアを施した。得られた液遮断層のＥＳＣＡによる珪素含有率、はつ油度および１ヶ月経過後のはつ油度をそれぞれ表１に示す。
<Example 4>
A liquid blocking layer was produced by the following method. A PET spunlace nonwoven fabric (manufactured by Yuho Co., Ltd., mass 40 g / m 2 ) is used as the lower layer, and a polyester nonwoven fabric thermoplastic adhesive (“DYNAC” manufactured by Kureha Tech Co., Ltd.) is applied to one side of the PET spunlace nonwoven fabric. (Registered trademark) LNS0015 ", mass 15 g / m 2 ). A melt blown nonwoven fabric made of Ny (average single fiber diameter 0.5 μm, mass 15 g / m 2 ) was superimposed on the surface of the polyester-based nonwoven fabric-like thermoplastic adhesive. Thereafter, the polyester-based nonwoven fabric-like thermoplastic adhesive was laminated on the polyurethane nanofiber nonwoven fabric side, the PET spunlace nonwoven fabric was laminated thereon, and pressure-bonded with a heating roller to prepare a liquid blocking layer. The silicon content by ESCA of the liquid blocking layer was 0 atom%. Also, the liquid blocking layer is dipped in a processing bath of 3 wt% fluorine-based water repellent (NK Guard S-11 PFOA-free, manufactured by Nikka Chemical Co., Ltd.), dried, dried at 100 ° C., and raised to 150 ° C. And cured. Table 1 shows the silicon content by ESCA, oil repellency, and oil repellency after one month of the obtained liquid barrier layer.
＜参考例＞
液遮断層を処理するフッ素系撥水剤として、旭硝子株式会社製「ＡＧ−７１０５（ＰＦＯＡ含有）」を使用した以外は実施例１と同様の方法で液遮断層を作製した。得られた液遮断層のＥＳＣＡによる珪素含有率、はつ油度および１ヶ月経過後のはつ油度をそれぞれ表１に示す。
<Reference example>
A liquid blocking layer was prepared in the same manner as in Example 1 except that “AG-7105 (PFOA-containing)” manufactured by Asahi Glass Co., Ltd. was used as the fluorine-based water repellent for treating the liquid blocking layer. Table 1 shows the silicon content by ESCA, oil repellency, and oil repellency after one month of the obtained liquid barrier layer.
＜比較例１＞
先端溶融パイル布を精練をせずに使用したため、そのＥＳＣＡによる珪素含有率が、１２．０ａｔｏｍ％となった以外は実施例１と同様の方法により防護衣材料を作製した。得られた液遮断層のＥＳＣＡによる珪素含有率、はつ油度および１ヶ月経過後のはつ油度をそれぞれ表１に示す。
<Comparative Example 1>
Since the tip melt pile fabric was used without scouring, a protective clothing material was produced in the same manner as in Example 1 except that the silicon content by ESCA was 12.0 atom%. Table 1 shows the silicon content by ESCA, oil repellency, and oil repellency after one month of the obtained liquid barrier layer.
＜比較例２＞
先端溶融パイル布へのはっ水剤をシリコン系はっ水剤（日華化学社製 ドライポン６００Ｅ）とした以外は実施例１と同様の方法により防護衣材料を作製した。得られた液遮断層のＥＳＣＡによる珪素含有率、はつ油度及び１ヶ月経過後のはつ油度をそれぞれ表１に示す。
<Comparative Example 2>
A protective clothing material was produced in the same manner as in Example 1 except that the water-repellent agent for the tip melt pile fabric was a silicon-based water-repellent agent (Drypon 600E manufactured by Nikka Chemical Co., Ltd.). Table 1 shows the silicon content rate, oil repellency, and oil repellency after one month of the obtained liquid barrier layer by ESCA.
表１の結果から明らかなように、実施例１〜４の防護衣材料は、はつ油性およびはつ油性の経時変化において良好であるのに対して、比較例１、２の防護衣材料は、はつ油性が低く、比較例の防護衣材料は、いずれかの評価項目で実施例よりも劣るものであった。 As is apparent from the results in Table 1, the protective clothing materials of Examples 1 to 4 are good in oil repellency and aging change over time, whereas the protective clothing materials of Comparative Examples 1 and 2 are The oil repellency was low, and the protective clothing material of the comparative example was inferior to the examples in any of the evaluation items.
本発明の防護衣材料は、はっ水はつ油性に優れ、さらには液状有機化学物質に優れた液浸透抑制能を有する材料であり、さらには、通気性を有し、軽量で快適性に優れた防護衣材料を提供することで、業界に寄与することが大である。 The protective clothing material of the present invention is a material that has excellent water repellency and oil repellency, and also has excellent liquid permeation suppression ability for liquid organic chemicals, and further has air permeability, light weight and comfort. It is important to contribute to the industry by providing excellent protective clothing materials.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP6069721B1 (en) * | 2016-04-26 | 2017-02-01 | 東洋紡株式会社 | Sewing thread, protective material, protective clothing and protective equipment using the sewing thread |
| IT202000006748A1 (en) * | 2020-03-31 | 2021-10-01 | Pointex S P A | BACTERIAL FILTRATION FABRIC, METHOD FOR MAKING THIS FABRIC AND USE OF SAID FABRIC FOR MAKING PERSONAL PROTECTIVE EQUIPMENT |
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| JP7279111B2 (en) | 2021-06-21 | 2023-05-22 | デサントジャパン株式会社 | Laminated fabric manufacturing method |
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