WO2003068010A1 - Chemical-resistant protective clothes - Google Patents

Chemical-resistant protective clothes Download PDF

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Publication number
WO2003068010A1
WO2003068010A1 PCT/JP2003/001490 JP0301490W WO03068010A1 WO 2003068010 A1 WO2003068010 A1 WO 2003068010A1 JP 0301490 W JP0301490 W JP 0301490W WO 03068010 A1 WO03068010 A1 WO 03068010A1
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WO
WIPO (PCT)
Prior art keywords
chemical
film
layer
resistant protective
resin layer
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Application number
PCT/JP2003/001490
Other languages
French (fr)
Japanese (ja)
Inventor
Takeshi Konishi
Yasutoshi Kawasaki
Motochika Maki
Original Assignee
Kuraray Co., Ltd.
Meditec Japan Co., Ltd.
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Application filed by Kuraray Co., Ltd., Meditec Japan Co., Ltd. filed Critical Kuraray Co., Ltd.
Publication of WO2003068010A1 publication Critical patent/WO2003068010A1/en

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/12Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • AHUMAN NECESSITIES
    • A62LIFE-SAVING; FIRE-FIGHTING
    • A62DCHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D5/00Composition of materials for coverings or clothing affording protection against harmful chemical agents

Definitions

  • the present invention relates to a chemical-resistant protective garment, and more particularly to a protective garment having excellent resistance to acids, alkalis, organic chemicals, and other harmful chemical substances such as gas, liquid and particulate matter, particularly excellent in chemical resistance. is there. Background art
  • Chemical protective clothing includes hoods, gloves, and shoes in addition to work clothes.
  • these protective garments include, for example, a fabric in which a microporous film made of polypropylene resin is laminated on a fabric, a fabric made of a non-woven fabric obtained by flash-spinning a polyolefin resin, or a laminate of a fabric and an impermeable resin film. And others are known.
  • protective clothing using a microporous polypropylene membrane or protective clothing made of flash-spun nonwoven polypropylene are not sufficiently resistant to penetration of various harmful chemicals, and the harmful effects on the human body due to chemical permeation cannot be avoided. There was such a problem.
  • Japanese Patent Application Laid-Open No. 60-96627 proposes a protective suit in which a polyurethane film is formed on a fabric.
  • a strong protective suit has a resistance to transmission of gaseous harmful substances. Was insufficient, and there was a problem that it was easily stuffy when worn.
  • Japanese Patent Application Laid-Open No. H10-15989 proposes a disposable protective garment in which an impermeable resin film such as polyethylene, polypropylene, polyester, or nylon is laminated with a nonwoven fabric.
  • an impermeable resin film such as polyethylene, polypropylene, polyester, or nylon is laminated with a nonwoven fabric.
  • such protective clothing may penetrate these resin membranes depending on the type of harmful chemicals. Particularly, nylon is eroded by strong acids and polyester is eroded by strong alkalis. There was also the problem of poor performance.
  • An object of the present invention is to solve such problems in conventional protective clothing and provide a chemical-resistant protective clothing excellent in resistance to various harmful chemical substances.
  • the present inventors have intensively studied to develop protective clothing excellent in permeability to various harmful chemical substances, and as a result, a protective clothing made of a composite material having a specific configuration can meet the above-mentioned purpose.
  • the composite material is sino-welded with an ultrasonic sewing machine having a continuous pattern, preferably an ultrasonic sewing machine in which a continuous pattern and a discontinuous pattern are arranged in parallel, so that the seal portion is not hardened and the feeling of wearing is improved. It has been found that an excellent and chemically resistant protective garment free of pinholes can be obtained.
  • the present invention has been completed based on strength and knowledge.
  • a chemical-resistant protective garment made of a composite material in which a resin layer having at least one layer containing 50% by mass or more of an ethylene-vinyl alcohol copolymer and a fiber layer are laminated;
  • the resin layer is a laminated film comprising an ethylene-vinyl alcohol-based copolymer film and a polyolefin-based resin layer provided on at least one side thereof.
  • FIG. 1 is a schematic view showing an example of a pattern of an ultrasonic sewing machine used in the present invention.
  • FIG. 2 is a schematic view showing another example of the pattern of the ultrasonic sewing machine used in the present invention.
  • FIG. 3 is a schematic diagram showing another different example of the pattern of the ultrasonic sewing machine used in the present invention.
  • the protective clothing of the present invention includes various working clothes, hoods, gloves, shoe covers, and the like.
  • a resin layer constituting the protective clothing an ethylene-vinyl alcohol copolymer (hereinafter abbreviated as EVOH) is used.
  • EVOH ethylene-vinyl alcohol copolymer
  • the feature is that a layer containing a specific amount of is used.
  • EVOH for use in the protective clothing of the present invention is one obtained by saponifying ethylene one Bulle ester copolymer, the ethylene unit content is preferably 20 to 60 mole 0/0, more preferably 25 to 50 mol 0/0.
  • the degree of saponification of the vinyl ester component is preferably at least 90 mol%.
  • the resin layer constituting the protective garment of the present invention must have at least one layer containing 50% by mass or more of EVOH, and preferably has at least one layer containing 70% by mass or more of EVOH. It has layers. If the content of EVOH in the layer containing EVOH of the resin layer is less than 50% by mass, the gas permeation resistance to chemical substances is reduced, and the object of the present invention is not achieved.
  • a layer may be blended with other resins, such as, for example, polyethylene, but may be blended with other resins. More preferably, the ratio is less than 20 mass ° / o.
  • the resin layer used in the protective clothing of the present invention it is more preferable that the resin layer has at least one layer of a film composed of EVOH from the viewpoint of exhibiting resistance to various kinds of chemicals.
  • EVOH films are known to have excellent gas barrier properties against oxygen and the like, and are widely used in food packaging materials and the like.
  • the present inventors have found that by using at least one layer of a resin containing a specific amount of EVOH, a protective garment having improved chemical resistance to various harmful substances, whether gas, liquid or particulate, can be obtained.
  • an EVOH film may be used alone as the resin layer, but may have a multilayer structure having at least one layer containing 50% by mass or more of EVOH, and may include an EVOH film and at least one surface thereof.
  • a laminated film in which a resin layer having a resistance to permeation to methanol, particularly a layer made of polyolefin such as polyethylene or polypropylene, polyamide, polyester, or a highly functional resin is laminated is preferably used.
  • a resin layer having resistance to methanol a layer made of K-coat (polyvinylidene-coated) nylon, polyolefin, or polyester has excellent resistance to alcohols such as methanol and ethanol.
  • a composite material having chemical permeability is obtained.
  • a laminated film in which a polyolefin-based resin layer such as polyethylene or polypropylene is laminated on one or both sides of the EVOH film is used to improve strength and It is more preferable in terms of improving resistance and feeling to various kinds of chemical substances.
  • a laminate film with a polyamide resin layer such as nylon is useful for improving the feeling and preventing pinholes generated at the time of joining and the like.
  • a resin layer having resistance to permeation with methanol is defined as a resin layer constituting such a layer whose mass increase after immersion in methanol at 20 ° C. for one month is 0. Less than 1% by mass.
  • a non-stretched film or a monoaxially or biaxially stretched film can be used, but a non-stretched film is preferably used.
  • stretched EVOH film it is vulnerable to tearing In that sense, it is preferable to use a laminated film with another resin layer rather than the EV ⁇ H film alone.
  • the stretched EV ⁇ H film has better chemical resistance than unstretched film, but may have a harder hand. It is extremely effective to use a laminated film of the above.
  • the method of laminating the EVOH film with another resin layer is not particularly limited, and may be an extruded laminate or a lamination with an adhesive. It is advantageous.
  • One or more EVQH films may be laminated with another resin layer, or two or more resin layers other than EVOH may be laminated.
  • a laminated film with a total thickness of 30 / zm formed by combining a polyethylene layer with a thickness of 10 Aim on both sides of a stretched EVOH film with a thickness of 30 and an EVOH film with a thickness of 10 m having the same composition.
  • the tactile sensations are compared, the latter is clearly better and often has excellent resistance to many chemicals.
  • the total thickness of the EVOH film used in the present invention is preferably 5 to 200 ⁇ . (If the total thickness is less than 5 ⁇ m, it is difficult to obtain sufficient chemical resistance, and if it exceeds 200 ⁇ , it is uneconomical. In addition, the composite material may become hard and the wearing feeling may be reduced.
  • the total thickness of the other resin layer to be laminated on the EVOH film is preferably from 5 to 200 / m, more preferably from 10 to 100.
  • the total thickness is less than 5 m, the film strength is improved, and the chemical substance resistance is not sufficiently exhibited.
  • the total thickness is more than 200 ⁇ m, the composite material becomes hard and the wearing feeling may be reduced.
  • the total thickness mentioned here is the total thickness of each layer when two or more layers are used.
  • the resin layer having at least one EVOH-containing layer obtained in this way can be laminated with a fiber layer to improve the strength and a feeling of wearing, so that a composite material can be obtained.
  • a fiber layer used in the present invention various woven fabrics, knitted fabrics, and non-woven fabrics are used.
  • the film may be laminated on the fabric, which is rather preferable in order to ensure double chemical resistance.
  • Nonwoven fabrics include spunlace nonwoven fabric, thermal bonded nonwoven fabric, spun pound nonwoven fabric, laminate of spun pound nonwoven fabric and melt blown nonwoven fabric, laminate of spunbond nonwoven fabric and film, etc. Is used.
  • the basis weight of the fabric is about 20 to 300 g / m 2 . If the basis weight is less than 200 g / m 2 , sufficient strength is not obtained, and if the basis weight exceeds 300 g // m 2 , the feeling of wearing tends to be reduced.
  • the material of the fabric is a fiber such as polyolefin, polyamide, polyester, rayon, cotton, wool, or a mixture thereof.
  • a joining method of a resin layer having at least one layer containing EVOH and a fiber layer joining by heat or an adhesive may be mentioned.
  • ultrasonic bonding or hot emboss bonding having a bonding area ratio of about 5 to 30% can be used.
  • the composite thus obtained is sewn to protective clothing such as protective clothing so that the resin layer side is preferably the front side, that is, the side farther from the body.
  • a laminated film composed of an EVOH film and a polyolefin-based resin layer is used as the resin layer
  • sewing using a sewing machine or the like is not preferable because a chemical substance permeates between stitches or through a needle hole of the sewing machine.
  • sewing by joining using heat, ultrasonic waves, an adhesive, or the like, and in particular, continuous joining using an ultrasonic sewing machine is preferable because efficient work is possible.
  • FIGS. 1, 2 and 3 are schematic diagrams showing different examples of the pattern of the ultrasonic sewing machine used in the present invention.
  • reference numeral 1 denotes a continuous pattern
  • 2 denotes a discontinuous pattern. These 1 and 2 are running in parallel along the flow direction.
  • this pattern is applied, that is, the inclined portion in the figure is fused by ultrasonic waves.
  • the continuous pattern and the discontinuous pattern may be arranged in two rows as shown in FIG. 1, or may be arranged in three rows or more rows as shown in FIGS.
  • the width of the fused portion of the continuous pattern is preferably in the range of 0.01 to 3 mm, particularly preferably in the range of 0.05 to 0.5 mm. If the width is less than 0.0 lmm, it is not enough to prevent the permeation of chemical substances, while if it exceeds 3 mm, the joints may become hard and the wearing feeling may be impaired.
  • the width of the discontinuous pattern is about 0.1 to 5 mm, the length is about 0.5 to 1.5 mm, and the length of the discontinuous portion, that is, the unfused portion is 0.5. ⁇ 1 ⁇ O mm. If the values are out of the range, it is difficult to obtain the necessary joining strength, and the feeling of the joint may be reduced. It is effective that the width of the discontinuous pattern is larger than the width of the continuous pattern.
  • test piece was mounted in the middle of the test cell, and two compartments were created for the test piece: an upper cell compartment and a lower senor compartment.
  • a specified amount of test solution is introduced into the upper cell compartment, and gas or liquid permeating the test piece is collected from the upper and lower cell compartments. From the time when the test solution was placed in the upper cell compartment, the collected concentration was graphed with time to determine the breakthrough time and the permeation mass, and the permeation resistance was evaluated according to the following grade.
  • Ethylene one Bulle alcohol copolymer manufactured by Kuraray Co., "Ebaru” (brand F 1 0 1, ethylene copolymer ratio of 3 2 mole 0/0, and the melting point 1 8 3 ° C) the central layer, on both site de
  • a layer of modified polyethylene (“ADMER” manufactured by Mitsui Chemicals, Inc.) is placed between the low-density polyethylene layer and the EVOH layer and the low-density polyethylene layer, and co-extrusion is performed to obtain a five-layer film with a thickness of 69 ⁇ .
  • the extrusion conditions were adjusted so that the thickness of the EVOH layer was 15 ⁇ m, the thickness of the low-density polyethylene layers on both sides was 20 Atm, and the thickness of the intermediate modified polyethylene layer was 7 ⁇ . Further, one side of the laminated film was subjected to a corona treatment.
  • a hydrophilic oil agent was applied to both sides of a polyethylene film having a microporosity and a thickness of (18 g / m 2 ), respectively.
  • a 0.2 mm thick polypropylene spun pond nonwoven fabric was laminated by hot embossing to obtain a nonwoven fabric composite.
  • the obtained nonwoven fabric composite was bonded to the above-mentioned laminated film by spraying an EVA-based hot melt resin (manufactured by Tokyo Ink) at a ratio of 7 gZm 2 by a melt blown method to obtain a composite material.
  • a one-piece (coverall) chemical protective suit was manufactured with the film on the outside. Bonding of each part was performed by an ultrasonic sewing machine having the pattern shown in FIG.
  • the width of the continuous pattern was 0.4 mm
  • the width of the fused part of the discontinuous pattern was lmm
  • the length was 2 mm
  • the length of the discontinuous part was 1.5 mm.
  • the distance between the continuous pattern and the discontinuous pattern was 0.5 mm.
  • the fastener portion of the chemical protective suit was designed to be covered with the composite material of the present invention, one side of which was fastened with double-sided adhesive tape and installed so as not to infiltrate the chemical.
  • the obtained chemical protective clothing has a tensile strength (compared to JISL 1093, measured by the grab method) of 39.5N in the composite part, which is sufficient, and has a good feel.
  • Chloroform is used in the permeability test including the joint part.
  • Example 1 a low-density polyethylene film was used in place of EVOH, and a three-layer laminated film having a thickness of 55 ⁇ was manufactured without using modified polyethylene and styrene, and a chemical protective suit was manufactured in the same manner as in Example 1. .
  • the resulting chemical protective suit showed a supple feel, but exhibited breakthrough times of less than or equal to 3 grades for dichloromethane and toluene, respectively, typically selected from the chemicals shown in Example 1. .
  • K-coat (polychlorinated bilidene coat) Nylon, ethylene-vinyl alcohol-based copolymer (Kuraray Co., Ltd., “EVAL” brand HI 01, ethylene copolymerization ratio 38 mol%, melting point 175 ° C), modified polyethylene ( and arranged in the order of Mitsui Chemicals, Inc. "Admer”) and polyethylene (LLDPE), respectively conditions set to be 25 ⁇ m, 1 5 / im s 10 ⁇ and 20 ⁇ , manufacturing a laminated film comprising four layers did.
  • Example 1 The K-coated nylon side of the laminated film and the nonwoven fabric were bonded to the laminated film and the nonwoven fabric obtained in the same manner as in Example 1 to obtain a composite material.
  • the polyethylene side was joined by an ultrasonic sewing machine, and a chemical protective suit was manufactured in the same manner as in Example 1.
  • the obtained chemical protective suit showed excellent feeling and chemical resistance.
  • the obtained chemical protective clothing exhibited a chemical permeation resistance of 6 grades to methanol and ethanol in addition to the chemicals shown in Example 1.
  • Chemical protective clothing was manufactured in the same manner as in Example 2 except that a nylon 6 film was used instead of EVOH in Example 2. As in Comparative Example 1, the obtained chemical protective suit showed only breakthrough time of 3 grades for dichloromethane and toluene, respectively.
  • the core layer is an ethylene-butyl alcohol-based copolymer (Kuraray clay, “EVAL” (brand F101, ethylene copolymerization ratio 32 monoles, melting point 183 ° C)), and low-density polyethylene layers are arranged on both sides. Three layers were co-extruded to obtain a laminated film with a thickness of 5 ⁇ The extrusion conditions were adjusted so that the thickness of the EVOH layer was 16 Atm and the thickness of the low-density polyethylene layers on both sides was 17 ⁇ each. did.
  • EVAL brand F101, ethylene copolymerization ratio 32 monoles, melting point 183 ° C
  • microporous, 2 (basis weight 18 g /; m 2) laminated polypropylene spunbond having on both sides of Poryechi Ren film having a thickness of basis weight 20 GZm 2, thickness 0. 2 mm did.
  • the bonding was performed by spraying an EVA hot melt resin (manufactured by Tokyo Ink) at a rate of 7 g / m 2 by a melt blown method.
  • the total basis weight is 72 gZm 2 .
  • the thus obtained film having a thickness of 50 im and a nonwoven fabric laminate having a basis weight of 7 g / m 2 were adhered under substantially the same conditions by the same melt blown method as above to obtain a composite material.
  • the obtained chemical protective clothing has sufficient strength of the composite part, good feeling, including the joint Permeability black port Holm in the test, Asetonitoriru, acetone, acetic Echiru, Jefferies Chinoreamin, dichloromethane, N, N-dimethyl formamidine de, sodium 50 weight 0/0 aqueous hydroxide, tetrachlorethylene, as tetrahydrofuran, toluene, xylene, It exhibited permeation resistance of the above-mentioned grades 5 or more to a wide range of chemicals such as nitrobenzene, carbon disulfide, normal hexane, methanol, and 93% by weight sulfuric acid solution.
  • Ethylene monobutyl alcohol copolymer (Kuraray Co., Ltd., “EVAL” brand HI 01, ethylene copolymerization ratio 38 mol%, melting point 175 ° C), 6 nylon, modified polyethylene (Mitsui Chemicals “Admer”) and Polyethylene (LLDPE) was placed in this order, and the conditions were set to be 30 / im, 15 / im, 15 ⁇ m, and 20 ⁇ m, respectively, to produce a four-layer laminated film.
  • Example 3 The film thus obtained and the nonwoven fabric were bonded while continuously extruding low density polyethylene having a thickness of 22 / zm between the EVOH side of the film and the nonwoven fabric to produce a composite material. .
  • a chemical protective suit was produced in the same manner as in Example 1.
  • the obtained chemical protective suit exhibited excellent feeling and chemical resistance.
  • Chemical protective clothing was manufactured in the same manner as in Example 4, except that a nylon 6 film was used instead of EVOH in Example 4. As in Comparative Example 1, the obtained chemically protective suit showed only three grades of breakthrough time for dichloromethane and toluene, respectively.
  • Example 1 K-coated nylon film polychlorinated Biyuridenkoto thickness 10 ⁇ ⁇ , total thickness 25 ⁇
  • the laminated film having a six-layer structure was obtained.
  • the obtained chemical protective suit exhibited excellent permeation resistance of not less than 5 grades to alcohols such as methanol and ethanol in addition to the chemicals shown in Example 1.
  • the protective clothing of the present invention has a feature of excellent resistance to permeation of various harmful chemicals, and is extremely useful as protective clothing and the like.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Toxicology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Business, Economics & Management (AREA)
  • Emergency Management (AREA)
  • Laminated Bodies (AREA)
  • Professional, Industrial, Or Sporting Protective Garments (AREA)

Abstract

Chemical-resistant protective clothes which comprise a composite material comprising a fibrous layer and superposed thereon a resinous layer comprising at least one layer comprising at least 50 wt.% ethylene/vinyl alcohol copolymer. The chemical-resistant protective clothes have excellent impermeability to various harmful chemical substances.

Description

明 細 書 耐薬品性防護衣料 技術分野  Description Chemical resistant protective clothing Technical field
本発明は耐薬品性防護衣料、 さらに詳しくは、 酸、 アルカリ、 有機薬品、 その 他の気体、 液体又は粒子状物の有害化学物質に対する耐性、 とりわけ耐薬品透過 性に優れた防護衣料に関するものである。 背景技術  TECHNICAL FIELD The present invention relates to a chemical-resistant protective garment, and more particularly to a protective garment having excellent resistance to acids, alkalis, organic chemicals, and other harmful chemical substances such as gas, liquid and particulate matter, particularly excellent in chemical resistance. is there. Background art
酸、 アル力リ、 有機薬品、 その他の気体、 液体又は粒子状の有害化学物質を取 り扱う作業において、 人体の保護のために着用し、 これら有害化学物質等の浸透 の防止を目的として使用される化学防護衣料には、 作業服の他にフード、 手袋、 靴等がある。 従来、 これらの防護衣料としては、 例えば布帛にポリプロピレン樹 脂からなる微多孔膜を積層したもの、 ポリオレフイン樹脂をフラッシュ紡糸した 不,織布からなるもの、 あるいは布帛と不通気性樹脂膜とをラミネートしたものな どが知られている。 このうち、 ポリプロピレン微多孔膜を用いた防護衣料やポリ ォレフィンのフラッシュ紡糸不織布からなる防護衣料は、 いずれも各種有害薬品 に対する耐浸透性が充分でなく、 薬品透過による人体への悪影響が避けられない といった問題があった。  Wear it to protect the human body when working with acids, alkaline chemicals, organic chemicals, other gaseous, liquid, or particulate hazardous chemicals, and use it to prevent the penetration of these hazardous chemicals. Chemical protective clothing includes hoods, gloves, and shoes in addition to work clothes. Conventionally, these protective garments include, for example, a fabric in which a microporous film made of polypropylene resin is laminated on a fabric, a fabric made of a non-woven fabric obtained by flash-spinning a polyolefin resin, or a laminate of a fabric and an impermeable resin film. And others are known. Of these, protective clothing using a microporous polypropylene membrane or protective clothing made of flash-spun nonwoven polypropylene are not sufficiently resistant to penetration of various harmful chemicals, and the harmful effects on the human body due to chemical permeation cannot be avoided. There was such a problem.
また、 特開昭 6 0 - 9 6 2 6 7号公報には、 布帛にポリウレタン皮膜を形成さ せた防護服が提案されている力 力かる防護服は気体の有害性物質に対する耐透 過性が不十分であり、 着用時に蒸れやすいという問題があった。 一方、 特開平 1 0— 1 5 8 9 0 9号公報には、 ポリエチレン、 ポリプロピレン、 ポリエステル、 ナイ口ン等の不通気性樹脂膜と不織布を積層した使い捨て保護衣料が提案されて いる。 しかしながら、 かかる防護衣料は、 有害薬品の種類によってはこれらの樹 脂膜を透過してしまうものもあり、 特にナイロンが強酸に、 ポリエステルが強ァ ルカリによつて浸蝕されるなど特定の薬品に対する耐性が劣るといった問題もあ つた。 また、 防護衣料を製造時、 縫製部分より有害薬品が透過しないよう、 縫製に代 つて熱シールするケースが多いが、 この熱シーノレの場合、 熱シール部分が固くな り、 着用感を低下させるばかりでなく、 シール部分にピンホールが生じ、 耐薬品 性透過性や耐水度が著しく低下するという欠点があつた。 発明の開示 Japanese Patent Application Laid-Open No. 60-96627 proposes a protective suit in which a polyurethane film is formed on a fabric. A strong protective suit has a resistance to transmission of gaseous harmful substances. Was insufficient, and there was a problem that it was easily stuffy when worn. On the other hand, Japanese Patent Application Laid-Open No. H10-15989 proposes a disposable protective garment in which an impermeable resin film such as polyethylene, polypropylene, polyester, or nylon is laminated with a nonwoven fabric. However, such protective clothing may penetrate these resin membranes depending on the type of harmful chemicals. Particularly, nylon is eroded by strong acids and polyester is eroded by strong alkalis. There was also the problem of poor performance. Also, when manufacturing protective clothing, there are many cases where heat sealing is performed instead of sewing so that harmful chemicals do not permeate through the sewn part.In this case, however, the heat seal part becomes hard and only reduces the feeling of wearing. In addition, a pinhole was formed in the sealing part, and the chemical resistance, permeability and water resistance were significantly reduced. Disclosure of the invention
本発明は、 このような従来の防護衣料における問題点を解決し、 各種有害化学 物質に対する耐透過性に優れた耐薬品性防護衣料を提供することを目的とするも のである。  An object of the present invention is to solve such problems in conventional protective clothing and provide a chemical-resistant protective clothing excellent in resistance to various harmful chemical substances.
本発明者らは、 各種有害化学物質に対する透過性に優れた防護衣料を開発すベ く鋭意研究を重ねた結果、 特定の構成の複合材料からなる防護衣料が、 前記目的 に適合し得ること、 そして、 該複合材料を、 連続するパターンを有する超音波ミ シン、 好ましくは連続パターンと不連続パターンを並列に配置した超音波ミシン によってシーノレすることにより、 シール部が固くなることなく、 着用感に優れ、 しかもピンホールの発生しない耐薬品性防護衣料が得られることを見出した。 本 発明は、 力、かる知見に基づいて完成したものである。  The present inventors have intensively studied to develop protective clothing excellent in permeability to various harmful chemical substances, and as a result, a protective clothing made of a composite material having a specific configuration can meet the above-mentioned purpose. Then, the composite material is sino-welded with an ultrasonic sewing machine having a continuous pattern, preferably an ultrasonic sewing machine in which a continuous pattern and a discontinuous pattern are arranged in parallel, so that the seal portion is not hardened and the feeling of wearing is improved. It has been found that an excellent and chemically resistant protective garment free of pinholes can be obtained. The present invention has been completed based on strength and knowledge.
すなわち、 本発明は、  That is, the present invention
( 1 ) エチレン一ビニルアルコール系共重合体 5 0質量%以上を含む層を少なく とも 1層有する樹脂層と繊維層とが積層された複合材料からなる耐薬品性防護衣 料、  (1) a chemical-resistant protective garment made of a composite material in which a resin layer having at least one layer containing 50% by mass or more of an ethylene-vinyl alcohol copolymer and a fiber layer are laminated;
( 2 ) 樹脂層が、 エチレン一ビュルアルコール系共重合体フィルムと、 その少な くとも片面に設けられたメタノールに対する耐透過性樹脂層とからなる積層フィ ルムである上記 ( 1 ) 記載の耐薬品性防護衣料、  (2) The chemical resistance according to the above (1), wherein the resin layer is a laminated film comprising an ethylene-vinyl alcohol copolymer film and a resin layer provided on at least one side thereof and having resistance to methanol. Sex protective clothing,
( 3 ) 樹脂層が、 エチレン一ビニルアルコール系共重合体フィルムと、 その少な くとも片面に設けられたポリオレフイン系樹脂層とからなる積層フィルムである 上記 (1 ) 記載の耐薬品性防護衣料、  (3) The chemical-resistant protective garment according to (1), wherein the resin layer is a laminated film comprising an ethylene-vinyl alcohol-based copolymer film and a polyolefin-based resin layer provided on at least one side thereof.
( 4 ) 繊維層が、 不織布である上記 ( 1 ) 記載の耐薬品性防護衣料、  (4) The chemical-resistant protective garment according to (1), wherein the fiber layer is a non-woven fabric.
( 5 ) 複合材料が、 超音波接合により接合されたものである上記 (1 ) 記載の耐 薬品性防護衣料、 (6) 超音波接合が、 連続パターンと不連続パターンを並列に配置した超音波ミ シンによって施されたものである上記 (5) 記載の耐薬品性防護衣料、 および(5) The chemical-resistant protective garment according to (1), wherein the composite material is bonded by ultrasonic bonding. (6) The chemical-resistant protective clothing according to (5), wherein the ultrasonic bonding is performed by an ultrasonic sewing machine in which a continuous pattern and a discontinuous pattern are arranged in parallel, and
(7)複合材料が、樹脂層面同士を重ね合わせて接合されたものである上記(1) 記載の耐薬品性防護衣料、 (7) The chemical-resistant protective garment according to the above (1), wherein the composite material is formed by joining resin layer surfaces together.
を提供するものである。 図面の簡単な説明 Is provided. BRIEF DESCRIPTION OF THE FIGURES
図 1は、 本発明に使用される超音波ミシンのパターンの一例を示す模式図であ る。  FIG. 1 is a schematic view showing an example of a pattern of an ultrasonic sewing machine used in the present invention.
図 2は、 本発明に使用される超音波ミシンのパターンの他の一例を示す模式図 である。  FIG. 2 is a schematic view showing another example of the pattern of the ultrasonic sewing machine used in the present invention.
図 3は、 本発明に使用される超音波ミシンのパターンの別の異なる一例を示す 模式図である。 発明を実施するための最良の形態  FIG. 3 is a schematic diagram showing another different example of the pattern of the ultrasonic sewing machine used in the present invention. BEST MODE FOR CARRYING OUT THE INVENTION
本発明の防護衣料は、 各種作業服、 フード、 手袋あるいは靴カバーなどを含む ものであり、 当該防護衣料を構成する樹脂層として、 エチレン一ビエルアル ー ル系共重合体 (以下、 EVOHと略記する場合がある。 ) を特定量含む層を用い る点に特徴を有する。  The protective clothing of the present invention includes various working clothes, hoods, gloves, shoe covers, and the like. As a resin layer constituting the protective clothing, an ethylene-vinyl alcohol copolymer (hereinafter abbreviated as EVOH) is used. The feature is that a layer containing a specific amount of is used.
本発明の防護衣料に用いる EVOHは、 エチレン一ビュルエステル共重合体を ケン化して得られるものであり、 そのエチレン単位含有率は 20〜60モル0 /0が 好ましく、 より好ましくは 25〜50モル0 /0である。 また、 ビニルエステル成分 のケン化度は 90モル%以上が好ましい。 EVOH for use in the protective clothing of the present invention is one obtained by saponifying ethylene one Bulle ester copolymer, the ethylene unit content is preferably 20 to 60 mole 0/0, more preferably 25 to 50 mol 0/0. The degree of saponification of the vinyl ester component is preferably at least 90 mol%.
本発明の防護衣料を構成する樹脂層は、 EVOHを 50質量%以上含む層を少 なくとも 1層有するものであることが必要であり、 好ましくは EVOHを 70質 量%以上含む層を少なくとも 1層有するものである。 該樹脂層の EVOHを含む 層における EVOHの含有量が 50質量%未満の場合であると、 化学物質に対す る耐ガス透過性が低下し本発明の目的が達成されない。 かかる層には、 例えばポ リエチレンなどの他の樹脂がブレンドされていてもよいが、 他の樹脂のブレンド 比率は 2 0質量 °/o未満であることがより好ましい。 The resin layer constituting the protective garment of the present invention must have at least one layer containing 50% by mass or more of EVOH, and preferably has at least one layer containing 70% by mass or more of EVOH. It has layers. If the content of EVOH in the layer containing EVOH of the resin layer is less than 50% by mass, the gas permeation resistance to chemical substances is reduced, and the object of the present invention is not achieved. Such a layer may be blended with other resins, such as, for example, polyethylene, but may be blended with other resins. More preferably, the ratio is less than 20 mass ° / o.
本発明の防護衣料に用いる樹脂層としては、 E V O Hからなるフィルムを少な くとも 1層有するものであることが、 より多種の化学薬品に対して耐性を発揮で きる点からさらに好ましい。  As the resin layer used in the protective clothing of the present invention, it is more preferable that the resin layer has at least one layer of a film composed of EVOH from the viewpoint of exhibiting resistance to various kinds of chemicals.
E V O Hフィルムは、 酸素などのガスバリア性に優れていることが知られてお り、 食品包材などに多用されている。 本発明者らは、 E V O Hを特定量含む樹脂 少なくとも 1層を用いることで、 気体、 液体又は粒子状を問わず各種の有害物質 に対する耐薬品性の向上した防護衣料が得られることを見出した。  EVOH films are known to have excellent gas barrier properties against oxygen and the like, and are widely used in food packaging materials and the like. The present inventors have found that by using at least one layer of a resin containing a specific amount of EVOH, a protective garment having improved chemical resistance to various harmful substances, whether gas, liquid or particulate, can be obtained.
本発明の防護衣料においては、 前記樹脂層として E V O Hフィルムを単独で用 いてもよいが、 E V O Hを 5 0質量%以上含む層を少なくとも 1層有する多層構 造としてもよく、 E V O Hフィルムとその少なくとも片面にメタノールに対して 耐透過性を有する樹脂層、 特にポリエチレンやポリプロピレンなどのポリオレフ イン、 ポリアミド、 ポリエステルさらには高機能樹脂等からなる層とがラミネ一 トされた積層フィルムが好ましく用いられる。 メタノールに対して耐透過性を有 する樹脂層としては、 K一コート (ポリ塩化ビ-リデンコート) ナイロン、 ポリ ォレフィン、 またはポリエステルからなる層がメタノール、 エタノール等のアル コール類に対して優れた耐薬品透過性を有する複合材料が得られる点で好ましい 中でも、 E V O Hフィ^/ムの片面または両面にポリエチレンやポリプロピレン などのポリオレフイン系樹脂層がラミネートされた積層フィルムを用いることが、 強度が向上すると共に、 より多種の化学物質に対する耐性や風合が向上するなど の点でより好ましい。 また、 ナイロン等のポリアミド系樹脂層とのラミネートフ イルムは風合の向上や接合時等に発生するピンホールの防止に役立つ。 なお、 こ こでメタノ一ルに対して耐透過性を有する樹脂層とは、 かかる層を構成する樹脂 を 2 0 °Cのメタノ一ノレ中に 1ケ月間浸漬した後の質量増加が 0 . 1質量%未満の ものをいう。  In the protective garment of the present invention, an EVOH film may be used alone as the resin layer, but may have a multilayer structure having at least one layer containing 50% by mass or more of EVOH, and may include an EVOH film and at least one surface thereof. A laminated film in which a resin layer having a resistance to permeation to methanol, particularly a layer made of polyolefin such as polyethylene or polypropylene, polyamide, polyester, or a highly functional resin is laminated is preferably used. As a resin layer having resistance to methanol, a layer made of K-coat (polyvinylidene-coated) nylon, polyolefin, or polyester has excellent resistance to alcohols such as methanol and ethanol. Among them, it is preferable in that a composite material having chemical permeability is obtained.A laminated film in which a polyolefin-based resin layer such as polyethylene or polypropylene is laminated on one or both sides of the EVOH film is used to improve strength and It is more preferable in terms of improving resistance and feeling to various kinds of chemical substances. In addition, a laminate film with a polyamide resin layer such as nylon is useful for improving the feeling and preventing pinholes generated at the time of joining and the like. Here, a resin layer having resistance to permeation with methanol is defined as a resin layer constituting such a layer whose mass increase after immersion in methanol at 20 ° C. for one month is 0. Less than 1% by mass.
また本発明の防護衣料にお V、て E V O Hフィルムを用いる場合、 無延伸フィル ムあるいは一軸または二軸に延伸された延伸フィルムを用いることができるが、 好ましくは無延伸フィルムを用いる。  When the protective clothing of the present invention uses an EVOH film, a non-stretched film or a monoaxially or biaxially stretched film can be used, but a non-stretched film is preferably used.
特に延伸された E V O Hフィルムを用いる場合は、 引き裂きなどに対して弱い 場合があるので、 その意味でも EV〇Hフィルム単体よりも、 他の樹脂層との積 層フィルムを用いることが好ましい。 また、 延伸された EV〇Hフィルムは未延 伸フィルムよりも耐薬品性は優れているものの、風合が硬くなる場合があるため、 触感の改良という意味でも、 ポリエチレンなどのポリオレフィン系樹脂層との積 層フィルムを用いるのは極めて有効である。 Especially when using stretched EVOH film, it is vulnerable to tearing In that sense, it is preferable to use a laminated film with another resin layer rather than the EV〇H film alone. The stretched EV〇H film has better chemical resistance than unstretched film, but may have a harder hand. It is extremely effective to use a laminated film of the above.
E V O Hフィルムと他の樹脂層との積層方法は特に限定されず、 押出しラミネ ートでもよいし、 接着剤によるラミネートでもよいが、 共押出しラミネートが風 合の良い積層フィルムが得られ、 経済面で有利である。 EVQHフィルムは 1層 または 2層以上、 他の樹脂層とラミネートされてもよく、 また EVOH以外に 2 種以上の樹脂層がラミネートされてもよい。 例えば、 厚み 30 の延伸された EVOHフィルムと、 同じ組成を有する厚み 10 mの EVOHフィルムの両サ ィドにそれぞれ 10 Aimの厚みを有するポリエチレン層を複合化してなる総厚み 30 /zmのラミネートフィルムとの触感を比較した場合、 後者の方が明らかに触 感が良く、 しかも多くの化学薬品に対して優れた耐性を有している場合が多い。 本発明に用いられる EVOHフィルムの総厚みは 5〜 200 μπιが好適である ( 総厚みが 5 μ m未満では充分な耐化学物質性が得られにくく、 逆に 200 μιηを 超えると不経済である上、 複合材料が固くなり着用感が低下することがある。 The method of laminating the EVOH film with another resin layer is not particularly limited, and may be an extruded laminate or a lamination with an adhesive. It is advantageous. One or more EVQH films may be laminated with another resin layer, or two or more resin layers other than EVOH may be laminated. For example, a laminated film with a total thickness of 30 / zm formed by combining a polyethylene layer with a thickness of 10 Aim on both sides of a stretched EVOH film with a thickness of 30 and an EVOH film with a thickness of 10 m having the same composition. When the tactile sensations are compared, the latter is clearly better and often has excellent resistance to many chemicals. The total thickness of the EVOH film used in the present invention is preferably 5 to 200 μπι. (If the total thickness is less than 5 μm, it is difficult to obtain sufficient chemical resistance, and if it exceeds 200 μιη, it is uneconomical. In addition, the composite material may become hard and the wearing feeling may be reduced.
EVOHフィルムにラミネートされる他の樹脂層の総厚みは 5〜200 / mが 好ましく、 より好ましくは 10〜100 である。 この総厚みが 5 m未満で はフィルム強度の向上ゃ耐化学物質性が充分に発揮されにくく、 一方、 200 μ mを超えると複合材料が固くなり着用感が低下することがある。 なお、 ここで言 う総厚みとは 2層以上用いられた場合、 各層の厚みの合計である。  The total thickness of the other resin layer to be laminated on the EVOH film is preferably from 5 to 200 / m, more preferably from 10 to 100. When the total thickness is less than 5 m, the film strength is improved, and the chemical substance resistance is not sufficiently exhibited. On the other hand, when the total thickness is more than 200 μm, the composite material becomes hard and the wearing feeling may be reduced. In addition, the total thickness mentioned here is the total thickness of each layer when two or more layers are used.
このようにして得られた EVOHを含む層を少なくとも 1層有する樹脂層は、 強度や着用感などの向上のため、 繊維層と積層することで複合材料を得ることが できる。 本発明に用いる繊維層としては、 各種織物、 編物等の布帛、 不織布が用 いられる。 布帛にフィルムが積層されていても差し支えないし、 耐化学物質性を 二重に確保する上ではむしろ好ましいことである。 不織布としてはスパンレース 不織布、 サーマルボンド不織布、 スパンポンド不織布、 スパンポンド不織布とメ ルトブローン不織布との積層体、 スパンボンド不織布とフィルムとの積層体など が用いられる。 The resin layer having at least one EVOH-containing layer obtained in this way can be laminated with a fiber layer to improve the strength and a feeling of wearing, so that a composite material can be obtained. As the fiber layer used in the present invention, various woven fabrics, knitted fabrics, and non-woven fabrics are used. The film may be laminated on the fabric, which is rather preferable in order to ensure double chemical resistance. Nonwoven fabrics include spunlace nonwoven fabric, thermal bonded nonwoven fabric, spun pound nonwoven fabric, laminate of spun pound nonwoven fabric and melt blown nonwoven fabric, laminate of spunbond nonwoven fabric and film, etc. Is used.
布帛の目付は、 2 0〜3 0 0 g /m 2程度のものが採用される。 この目付が 2 0 gノ m 2未満では充分な強力がなく、 3 0 0 g //m 2を超えると着用感を低減さ せる傾向がある。 布帛の材質はポリオレフイン、 ポリアミド、 ポリエステル、 レ 一ヨン、 綿、 羊毛などの繊維、 あるいはこれらの混合物が用いられる。 The basis weight of the fabric is about 20 to 300 g / m 2 . If the basis weight is less than 200 g / m 2 , sufficient strength is not obtained, and if the basis weight exceeds 300 g // m 2 , the feeling of wearing tends to be reduced. The material of the fabric is a fiber such as polyolefin, polyamide, polyester, rayon, cotton, wool, or a mixture thereof.
E V O Hを含む層を少なくとも 1層有する樹脂層と繊維層の接合方法としては、 熱あるいは接着剤などによる接合が挙げられる。 この際、 得られる複合材料の風 合を低下させないために 3〜 5 0 g /m 2程度の範囲内で、 スプレー状あるいは 粉末状に塗布されたホットメルト樹脂などで接着するのが有利である。 また、 接 着面積率が 5〜 3 0 %程度である超音波接合や熱エンボス接合も使用可能である。 このようにして得られた複合体は、 好ましくは樹脂層側が表側、 すなわち身体 より遠い側となるように、 防護服などの防護衣料に縫製加工される。 特に樹脂層 として E V O Hフィルムとポリオレフイン系樹脂層とからなる積層フィルムを用 いる場合は、 ポリオレフイン系樹脂を表側とすることにより接合をスムーズに行 えるのでより好ましい。 ただしミシン等を用いる縫製は縫目の間やミシンの針穴 を通して化学物質が透過するので好ましくない。 本発明では、 熱や超音波あるい は接着剤などを用いた接合による縫製、 中でも超音波ミシンによる連続的な接合 は効率的な作業が可能な点から好ましい。 特に、 樹脂層側同士を重ね合わせて接 合することが化学薬品の透過を防ぐ上で好ましい。 すなわち化学薬品の透過を防 ぐためには接合部分からの化学薬品の透過を防ぐことは極めて重要であり、 力か る観点からも樹脂層面同士を重ねて接合することは極めて有効である。 樹脂層面 と繊維層面と重ね合わせた接合や繊維層面同士の接合は接合面に微細なすき間が できやすく、 そのすき間を通して化学薬品が透過する場合がある。 As a joining method of a resin layer having at least one layer containing EVOH and a fiber layer, joining by heat or an adhesive may be mentioned. At this time, in the range of about 3~ 5 0 g / m 2 in order not to lower the wind if the composite material obtained, it is advantageous to adhere such a spray-like or powdered coated hot-melt resin . Also, ultrasonic bonding or hot emboss bonding having a bonding area ratio of about 5 to 30% can be used. The composite thus obtained is sewn to protective clothing such as protective clothing so that the resin layer side is preferably the front side, that is, the side farther from the body. In particular, when a laminated film composed of an EVOH film and a polyolefin-based resin layer is used as the resin layer, it is more preferable to use a polyolefin-based resin on the front side so that bonding can be performed smoothly. However, sewing using a sewing machine or the like is not preferable because a chemical substance permeates between stitches or through a needle hole of the sewing machine. In the present invention, sewing by joining using heat, ultrasonic waves, an adhesive, or the like, and in particular, continuous joining using an ultrasonic sewing machine is preferable because efficient work is possible. In particular, it is preferable to overlap and join the resin layer sides from each other in order to prevent the permeation of chemicals. That is, in order to prevent the transmission of chemicals, it is extremely important to prevent the permeation of chemicals from the joints, and it is extremely effective to join the resin layer surfaces with each other from a powerful viewpoint. When the resin layer surface and the fiber layer surface are overlapped or the fiber layer surfaces are joined, a fine gap is easily formed in the joint surface, and a chemical agent may permeate through the gap.
ただし、 従来のように連続パターンで充分な接合強度が得られる程度に接合す ると接合部分が固くなり着用感を損なうおそれがある。 そこで、 本発明において は、 連続パターンと不連続パターンとが並列になっている超音波ミシンによりシ ールすることによって、シール部が固くなることがなく充分な接合強力が得られ、 その上化学物質の透過を防ぐことのできる化学防護衣料を得ることができる。  However, if joining is performed to the extent that sufficient joining strength can be obtained with a continuous pattern as in the conventional case, the joining portion becomes hard and the feeling of wearing may be impaired. Therefore, in the present invention, by using an ultrasonic sewing machine in which a continuous pattern and a discontinuous pattern are arranged in parallel, a sufficient bonding strength can be obtained without the seal portion becoming hard, A chemical protective garment that can prevent the permeation of a substance can be obtained.
次に、 本発明の防護衣料の接合部分を添付図面に従って説明する。 図 1、 図 2及び図 3は、 それぞれ本発明において使用される超音波ミシンのパ ターンの異なる例を示す模式図であって、各図において、符号 1は連続パターン、. 2は不連続パターンを示し、 この 1と 2は流れ方向に沿って並列に走っている。 接合部分においてはこのパターンのとおり、 すなわち図の斜歸部分が超音波によ つて融着されている。 Next, the joint portion of the protective garment of the present invention will be described with reference to the accompanying drawings. FIGS. 1, 2 and 3 are schematic diagrams showing different examples of the pattern of the ultrasonic sewing machine used in the present invention. In each figure, reference numeral 1 denotes a continuous pattern, and 2 denotes a discontinuous pattern. These 1 and 2 are running in parallel along the flow direction. At the joint portion, this pattern is applied, that is, the inclined portion in the figure is fused by ultrasonic waves.
連続パターンと不連続パターンは図 1のように 2列に配列されてもよく、 また 図 2や図 3のように 3列さらに多列に配列されてもよい。  The continuous pattern and the discontinuous pattern may be arranged in two rows as shown in FIG. 1, or may be arranged in three rows or more rows as shown in FIGS.
連続パターンの融着部分、 すなわち図における斜線部分の巾は 0 . 0 1〜3 m mの範囲が好ましく、特に 0 . 0 5〜0 . 5 mmの範囲が好ましい。この巾が 0 . 0 l mm未満では化学物質の透過を防ぐのに充分ではなく、 反対に 3 mmを超え ると接合部分が固くなり着用感を阻害することがある。  The width of the fused portion of the continuous pattern, that is, the width of the hatched portion in the figure is preferably in the range of 0.01 to 3 mm, particularly preferably in the range of 0.05 to 0.5 mm. If the width is less than 0.0 lmm, it is not enough to prevent the permeation of chemical substances, while if it exceeds 3 mm, the joints may become hard and the wearing feeling may be impaired.
一方、 不連続パターンの巾は 0 . l〜5 mm程度、 長さは 0 . 5〜1 . 5 mm 程度であり、また、不連続部分すなわち融着していない部分の長さは 0 . 5〜 1 · O mm程度である。 これらの数値の範囲外である場合は必要な接合強度が得られ にくく、 また接合部分の風合の低下をきたすおそれがある。 不連続パターンの巾 は連続パターンの巾よりも大きい方が効果的である。 実施例  On the other hand, the width of the discontinuous pattern is about 0.1 to 5 mm, the length is about 0.5 to 1.5 mm, and the length of the discontinuous portion, that is, the unfused portion is 0.5. ~ 1 · O mm. If the values are out of the range, it is difficult to obtain the necessary joining strength, and the feeling of the joint may be reduced. It is effective that the width of the discontinuous pattern is larger than the width of the continuous pattern. Example
次に、 本発明を実施例により、 さらに詳細に説明するが、 本発明は、 これらの 例によって何ら限定されるものではない。  Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
なお、 各例における耐薬品透過性は、 以下に示す方法に従って評価した。  The chemical permeation resistance in each example was evaluated according to the method described below.
<耐薬品透過性 >  <Chemical resistance>
J I S T 8 1 1 5 : 1 9 9 8に準拠して耐薬品透過性を評価した。  Chemical permeation resistance was evaluated in accordance with JIS T 811: 19: 98.
まずテストセルの中間に試験片を装着し、 試験片に対して上方セル隔室と下方 セノレ隔室の二つの隔室を作った。 次に上方セル隔室に試験液を規定量流入させ、 試験片を透過した気体又は液体を上下セル隔室から採取する。 試験液を上方セル 隔室に入れた時点から経時的に採取濃度をグラフ化し破過時間と透過質量を求め、 下記の等級に従って耐透過性を評価した。  First, a test piece was mounted in the middle of the test cell, and two compartments were created for the test piece: an upper cell compartment and a lower senor compartment. Next, a specified amount of test solution is introduced into the upper cell compartment, and gas or liquid permeating the test piece is collected from the upper and lower cell compartments. From the time when the test solution was placed in the upper cell compartment, the collected concentration was graphed with time to determine the breakthrough time and the permeation mass, and the permeation resistance was evaluated according to the following grade.
耐透過性 等級 石 咼時、間 (分)ノ Permeability Grade Stone hour
6 48 OP上  6 48 On OP
5 240以上  5 240 or more
4 1 20以上  4 1 20 or more
3 60以上  3 60 or more
2 3 0以上  2 3 0 or more
1 1 0以上 ぐ実施例 1〉  Example 1 1 or more
エチレン一ビュルアルコール系共重合体 (クラレ社製、 「ェバール」 (銘柄 F 1 0 1、 エチレン共重合比率 3 2モル0 /0、 融点 1 8 3°C) を中心層とし、 両サイ ドに低密度ポリエチレン層、 EVOH層と低密度ポリエチレン層の間にそれぞれ 変性ポリエチレン(三井化学社製「ァドマー」)の層を配置して共押出しを行い、 厚み 6 9 μπιの 5層の積層フィルムを得た。なお、 EVOH層の厚みは 1 5 μ m、 両サイドの低密度ポリエチレン層の厚みはそれぞれ 20 At m、 中間の変性ポリェ チレン層の厚みはそれぞれ 7 μΐηとなるように押出し条件を調整した。 また、 該 積層フィルムの片面にはコロナ処理を施した。 Ethylene one Bulle alcohol copolymer (manufactured by Kuraray Co., "Ebaru" (brand F 1 0 1, ethylene copolymer ratio of 3 2 mole 0/0, and the melting point 1 8 3 ° C) the central layer, on both site de A layer of modified polyethylene (“ADMER” manufactured by Mitsui Chemicals, Inc.) is placed between the low-density polyethylene layer and the EVOH layer and the low-density polyethylene layer, and co-extrusion is performed to obtain a five-layer film with a thickness of 69 μπι. The extrusion conditions were adjusted so that the thickness of the EVOH layer was 15 μm, the thickness of the low-density polyethylene layers on both sides was 20 Atm, and the thickness of the intermediate modified polyethylene layer was 7 μΐη. Further, one side of the laminated film was subjected to a corona treatment.
他方、 微多孔を有し、 (目付 1 8 g/m2 ) の厚みを有するポリェチ レンフィルムの両サイドにそれぞれ親水性油剤を塗布した目付 20
Figure imgf000010_0001
厚さ 0. 2 mmのポリプロピレンスパンポンド不織布を熱エンボスにより積層し、 不 織布複合体を得た。 得られた不織布複合体と上記積層フィルムとの接着は、 E V A系ホットメルトレジン (東京インキ製) をメルトブローン方式により、 7gZ m2 の割合で吹きつけて行い、 複合材料を得た。
On the other hand, a hydrophilic oil agent was applied to both sides of a polyethylene film having a microporosity and a thickness of (18 g / m 2 ), respectively.
Figure imgf000010_0001
A 0.2 mm thick polypropylene spun pond nonwoven fabric was laminated by hot embossing to obtain a nonwoven fabric composite. The obtained nonwoven fabric composite was bonded to the above-mentioned laminated film by spraying an EVA-based hot melt resin (manufactured by Tokyo Ink) at a ratio of 7 gZm 2 by a melt blown method to obtain a composite material.
この複合材料を用いてフィルムが外側となるようにしてワンピース形 (カバー オール形) 化学防護服を製造した。 各部の接合はフィルム側同士を図 3に示され たパターンを有する超音波ミシンによって行った。 連続パターンの巾は 0. 4m mであり、 不連続パターンの融着部分の巾は lmm、 長さは 2 mmであり、 不連 続部分の長さは 1. 5 mmであった。 また連続パターンと不連続パターンとの間 は 0. 5 mmであった。 化学防護服のファスナー部分は、本発明の複合材料で覆われるように設計され、 その片側は両面接着テープでとめられ、 化学物質の滲入がないように設置した。 得られた化学防護服は複合部における引張強さ ( J I S L 1093準拠、 グ ラブ法にて測定) は 39. 5Nと充分であり、 風合も良く、 接合部も含めた透過 性試験ではクロロホルム、 ァセトニトリル、 アセトン、 酢酸ェチル、 ジェチルァ ミン、' ジクロロメタン、 N, N—ジメチルホルムアミド、 水酸化ナトリウム 50 質量0 /0水溶液、 テトラクロ口エチレン、 テトラヒ ドロフラン、 トルエン、 キシレ ン、 ニトロベンゼン、 二硫化炭素、 ノルマルへキサンなど広範な薬品に対して前 述の 5等級以上の耐透過性を示した。 Using this composite material, a one-piece (coverall) chemical protective suit was manufactured with the film on the outside. Bonding of each part was performed by an ultrasonic sewing machine having the pattern shown in FIG. The width of the continuous pattern was 0.4 mm, the width of the fused part of the discontinuous pattern was lmm, the length was 2 mm, and the length of the discontinuous part was 1.5 mm. The distance between the continuous pattern and the discontinuous pattern was 0.5 mm. The fastener portion of the chemical protective suit was designed to be covered with the composite material of the present invention, one side of which was fastened with double-sided adhesive tape and installed so as not to infiltrate the chemical. The obtained chemical protective clothing has a tensile strength (compared to JISL 1093, measured by the grab method) of 39.5N in the composite part, which is sufficient, and has a good feel. Chloroform is used in the permeability test including the joint part. Asetonitoriru, acetone, acetic Echiru, Jechirua Min, 'dichloromethane, N, N- dimethylformamide, sodium 50 weight 0/0 aqueous hydroxide, tetrachloroethene port ethylene, as tetrahydrofuran, toluene, xylene, nitrobenzene, carbon disulfide, to normal It exhibited permeation resistance of the above-mentioned grades of 5 or more to a wide range of chemicals such as xane.
また、 J I S T81 15附属書 2に示されている方法に準拠して耐浸透性を 測定したところ、 50質量%水酸化ナトリゥム水溶液、 30質量%塩化力リゥム 水溶液および 93. 1質量 °/0硫酸溶液に対して浸透が全く認められなかった。 <比較例 1 > The measured penetration resistance in accordance with the method indicated in JIS T81 15 Annex 2, 50 wt% aqueous Natoriumu solution, 30 wt% chloride force Riumu solution and 93.1 wt ° / 0 sulfate No penetration was observed for the solution. <Comparative Example 1>
実施例 1において、 EVOHの代わりに低密度ポリエチレンフィルムを用い、 かつ変性ポリェ、チレンを用いずに厚み 55 μπιを有する 3層積層フィルムを製造 し、 実施例 1と同様に化学防護服を製造した。 得られた化学防護服は、 しなやか な風合を示したが、 実施例 1に示した薬品から代表的に選んだジクロロメタン及 びトルエンに対して、 それぞれ 3等級以下の破過時間しか示さなかった。  In Example 1, a low-density polyethylene film was used in place of EVOH, and a three-layer laminated film having a thickness of 55 μπι was manufactured without using modified polyethylene and styrene, and a chemical protective suit was manufactured in the same manner as in Example 1. . The resulting chemical protective suit showed a supple feel, but exhibited breakthrough times of less than or equal to 3 grades for dichloromethane and toluene, respectively, typically selected from the chemicals shown in Example 1. .
ぐ実施例 2 > Example 2>
K—コート (ポリ塩化ビエリデンコート) ナイロン、 エチレン一ビュルアルコ 一ル系共重合体 (クラレ社製、 「ェバール」 銘柄 HI 01、 エチレン共重合比率 38モル%、 融点 175°C) 、 変性ポリエチレン (三井化学社製 「アドマー」 ) 及びポリエチレン (LLDPE) の順に配置し、 それぞれ 25 μ m、 1 5 /i ms 10 μπι及び 20 μπιとなるように条件設定し、 4層からなる積層フィルムを製 造した。 K-coat (polychlorinated bilidene coat) Nylon, ethylene-vinyl alcohol-based copolymer (Kuraray Co., Ltd., “EVAL” brand HI 01, ethylene copolymerization ratio 38 mol%, melting point 175 ° C), modified polyethylene ( and arranged in the order of Mitsui Chemicals, Inc. "Admer") and polyethylene (LLDPE), respectively conditions set to be 25 μ m, 1 5 / im s 10 μπι and 20 μπι, manufacturing a laminated film comprising four layers did.
また、 1. 7 dT e Xのレーヨン繊維 60質量%と芯がポリプロピレン、 鞘が ポリエチレンからなる 2. 2 d T e xの複合繊維 40質量0 /0からなるクロスレイ ドウエブを製造し、高圧水流(最高圧力 6. 9 MP a)によって絡合させたのち、 乾燥熱処理し、 目付 70 gZm2、 タテ、 ョコ強力がそれぞれ 68. 6N/5 c m、 58. 8NZ5 cm、 厚み0. 50 mmの不織布を得た。 Moreover, 1. 7 dT e X of rayon fibers 60% by weight and the core is polypropylene, sheath manufactured Crossley Douebu of composite fiber 40 mass 0/0 2. 2 d T ex consisting of polyethylene, high-pressure water jet (up After being entangled by a pressure of 6.9 MPa a), dried and heat-treated, the basis weight is 70 gZm 2 , the length and the strength are each 68.6 N / 5 c m, 58.8 NZ5 cm, and 0.50 mm thick nonwoven fabric were obtained.
このようにして得られた積層フィルムと不織布とを、 実施例 1と同様にして積 層フィルムの K—コートナイロン側と不織布とを接着して複合材料を得た。 この 複合材料を用いて、 ポリエチレン側を超音波ミシンによって接合し、 実施例 1と 同様の方法で化学防護服を製造した。 得られた化学防護服は実施例 1と同様、 優 れた風合と耐化学薬品透過性を示した。 また、 得られた化学防護服は、 実施例 1 で示された薬品の他にメタノールやエタノールに対しても 6等級の耐薬品透過性 を示した。  The K-coated nylon side of the laminated film and the nonwoven fabric were bonded to the laminated film and the nonwoven fabric obtained in the same manner as in Example 1 to obtain a composite material. Using this composite material, the polyethylene side was joined by an ultrasonic sewing machine, and a chemical protective suit was manufactured in the same manner as in Example 1. As in Example 1, the obtained chemical protective suit showed excellent feeling and chemical resistance. In addition, the obtained chemical protective clothing exhibited a chemical permeation resistance of 6 grades to methanol and ethanol in addition to the chemicals shown in Example 1.
<比較例 2〉 <Comparative Example 2>
実施例 2において EVOHの代わりにナイロン 6フィルムを用いた以外は、 実 . 施例 2と同様に化学防護服を製造した。 得られた化学防護服は比較例 1と同様ジ クロ口メタン及びトルエンに対して、 それぞれ 3等級の破過時間しか示さなかつ た。  Chemical protective clothing was manufactured in the same manner as in Example 2 except that a nylon 6 film was used instead of EVOH in Example 2. As in Comparative Example 1, the obtained chemical protective suit showed only breakthrough time of 3 grades for dichloromethane and toluene, respectively.
ぐ実施例 3 > Example 3>
エチレン一ビュルアルコール系共重合体 (クラレネ土製、 「ェバール」 (銘柄 F 101、 エチレン共重合比率 32モノレ%、 融点 183°C) を中心層とし、 両サイ ドに低密度ポリエチレン層を配置して三層の共押出しを行い、 厚み 5 Ομπιの積 層フィルムを得た。 EVOH層の厚みは 16 Atm、 両サイ ドの低密度ポリエチレ ン層の厚みはそれぞれ 17 μηιとなるように押出し条件を調整した。  The core layer is an ethylene-butyl alcohol-based copolymer (Kuraray clay, “EVAL” (brand F101, ethylene copolymerization ratio 32 monoles, melting point 183 ° C)), and low-density polyethylene layers are arranged on both sides. Three layers were co-extruded to obtain a laminated film with a thickness of 5 μμπι The extrusion conditions were adjusted so that the thickness of the EVOH layer was 16 Atm and the thickness of the low-density polyethylene layers on both sides was 17 μηι each. did.
他方、 微多孔を有し、 2 (目付 18 g/;m2 ) の厚みを有するポリェチ レンフィルムの両サイドにそれぞれ目付 20 gZm2、厚さ 0. 2 mmを有するポ リプロピレンスパンボンドを積層した。 なお接着は、 EVA系ホットメルトレジ ン (東京インキ製) をメルトブローン方式により、 7 g/m2 の割合で吹きつけ て行った。 合計目付は 72 gZm2となる。 On the other hand, has a microporous, 2 (basis weight 18 g /; m 2) laminated polypropylene spunbond having on both sides of Poryechi Ren film having a thickness of basis weight 20 GZm 2, thickness 0. 2 mm did. The bonding was performed by spraying an EVA hot melt resin (manufactured by Tokyo Ink) at a rate of 7 g / m 2 by a melt blown method. The total basis weight is 72 gZm 2 .
このようにして得られた厚み 50 imのフィルムと目付 7 g/m2の不織布積 層物を上記と同じメルトブローン方式によりほぼ同じ条件で接着し、 複合材料を 得た。 The thus obtained film having a thickness of 50 im and a nonwoven fabric laminate having a basis weight of 7 g / m 2 were adhered under substantially the same conditions by the same melt blown method as above to obtain a composite material.
この複合材料を用いて、 実施例 1と同様な方法で化学防護服を製造した。  Using this composite material, a chemical protective suit was manufactured in the same manner as in Example 1.
得られた化学防護服は複合部の強力も充分であり、 風合も良く、 接合部も含め た透過性試験ではクロ口ホルム、 ァセトニトリル、 アセトン、 酢酸ェチル、 ジェ チノレアミン、 ジクロロメタン、 N, N—ジメチルホルムアミ ド、 水酸化ナトリウ ム 50質量0 /0水溶液、 テトラクロロエチレン、 テトラヒ ドロフラン、 トルエン、 キシレン、 ニトロベンゼン、 二硫化炭素、 ノルマルへキサン、 メタノール、 硫酸 93質量%溶液など広範な薬品に対して前述の 5等級以上の耐透過性を示した。 く実施例 4〉 . The obtained chemical protective clothing has sufficient strength of the composite part, good feeling, including the joint Permeability black port Holm in the test, Asetonitoriru, acetone, acetic Echiru, Jefferies Chinoreamin, dichloromethane, N, N-dimethyl formamidine de, sodium 50 weight 0/0 aqueous hydroxide, tetrachlorethylene, as tetrahydrofuran, toluene, xylene, It exhibited permeation resistance of the above-mentioned grades 5 or more to a wide range of chemicals such as nitrobenzene, carbon disulfide, normal hexane, methanol, and 93% by weight sulfuric acid solution. Example 4>.
エチレン一ビュルアルコール系共重合体 (クラレ社製、 「ェバール」 銘柄 HI 01、 エチレン共重合比率 38モル%、 融点 175°C) 、 6ナイロン、 変性ポリ エチレン (三井化学社製 「アドマー」 ) 及びポリエチレン (LLDPE) の順に 配置し、 それぞれ 30 /im、 1 5 /im、 1 5 μ m及び 20 ^ mとなるように条件 設定し、 4層からなる積層フィルムを製造した。  Ethylene monobutyl alcohol copolymer (Kuraray Co., Ltd., “EVAL” brand HI 01, ethylene copolymerization ratio 38 mol%, melting point 175 ° C), 6 nylon, modified polyethylene (Mitsui Chemicals “Admer”) and Polyethylene (LLDPE) was placed in this order, and the conditions were set to be 30 / im, 15 / im, 15 μm, and 20 ^ m, respectively, to produce a four-layer laminated film.
また、 1. 7 dT e Xのレーヨン繊維 60質量%と芯がポリプロピレン、 鞘が ポリエチレンからなる 2. 2 d T e xの複合繊維 40質量0 /0からなるクロスレイ ドウエブを製造し、高圧水流(最高圧力 6. 9MP a)によって絡合させたのち、 乾燥熱処理し、 目付 70 g/m2 、 タテ、 ョコ強力がそれぞれ 68. 6N/5 c m、 58. 8 N/ 5 cm、 厚み 0. 5 Ommの不織布を得た。 Moreover, 1. 7 dT e X of rayon fibers 60% by weight and the core is polypropylene, sheath manufactured Crossley Douebu of composite fiber 40 mass 0/0 2. 2 d T ex consisting of polyethylene, high-pressure water jet (up After being entangled with a pressure of 6.9 MPa a), dried and heat-treated, the basis weight is 70 g / m 2 , the vertical and horizontal strengths are 68.6 N / 5 cm, 58.8 N / 5 cm, thickness 0.5, respectively. An Omm nonwoven fabric was obtained.
このようにして得られたフィルムと不織布とを、 厚み 22 /zmの低密度ポリエ - チレンをフィルムの E V O H側と不織布との間に連続的に溶融押出ししながら接 着し、 複合材料を作製した。 この複合材料を用いて、 実施例 1と同様の方法で化 学防護服を製造した。 得られた化学防護服は実施例 3と同様、 優れた風合と耐化 学薬品透過性を示した。  The film thus obtained and the nonwoven fabric were bonded while continuously extruding low density polyethylene having a thickness of 22 / zm between the EVOH side of the film and the nonwoven fabric to produce a composite material. . Using this composite material, a chemical protective suit was produced in the same manner as in Example 1. As in Example 3, the obtained chemical protective suit exhibited excellent feeling and chemical resistance.
<比較例 3 >  <Comparative Example 3>
実施例 4において EVOHの代わりにナイロン 6フィルムを用いた以外は、 実 施例 4と同様に化学防護服を製造した。 得られた化学防護服は比較例 1と同様ジ クロロメタン及びトルエンに対して、 それぞれ 3等級の破過時間しか示さなかつ た。  Chemical protective clothing was manufactured in the same manner as in Example 4, except that a nylon 6 film was used instead of EVOH in Example 4. As in Comparative Example 1, the obtained chemically protective suit showed only three grades of breakthrough time for dichloromethane and toluene, respectively.
く実施例 5 >  Example 5>
実施例 1で得られた合計 5層の積層フィルムに K—コートナイロンフィルム (ポリ塩化ビユリデンコート厚み 10 μιη、 総厚み 25 μιη) をドライラミネ一 ト法にてラミネートし、 6層構造を有する積層フィルムを得た。 A laminated film of a total of five layers obtained in Example 1 K-coated nylon film (polychlorinated Biyuridenkoto thickness 10 μ ιη, total thickness 25 μιη) the Dorairamine one The laminated film having a six-layer structure was obtained.
得られた積層フィルムと目付 4 0 g /m2のポリプロピレンスパンボンド不織 布 (旭化成社製エルタスアクア P A 3 0 4 0 ) の間に 5 gノ m2の湿気硬化型ポリ ウレタン系樹脂を配し、 ノードソン社製ポーラスコートシステム機を用いてラミ ネートし複合材料を得た。 得られた複合材料を用いて実施例 1と同様に化学防護 服を製造した。 The resulting distribution of 5 g Roh m 2 of moisture-curable poly urethane resin between laminated film and basis weight 4 0 g / m 2 polypropylene spunbond nonwoven fabric (manufactured by Asahi Kasei Corporation Eltas Aqua PA 3 0 4 0) Then, lamination was performed using a porous coat system machine manufactured by Nordson to obtain a composite material. Using the obtained composite material, a chemical protective suit was produced in the same manner as in Example 1.
得られた化学防護服は、 実施例 1で示された薬品に加え、 メタノール、 ェタノ ール等のアルコール類に対しても 5等級以上の優れた耐透過性を示した。 産業上の利用可能性  The obtained chemical protective suit exhibited excellent permeation resistance of not less than 5 grades to alcohols such as methanol and ethanol in addition to the chemicals shown in Example 1. Industrial applicability
本発明の防護衣料は、各種有害化学薬品に対する耐透過性に優れた特徴を有し、 防護服などとして極めて有用なものである。  INDUSTRIAL APPLICABILITY The protective clothing of the present invention has a feature of excellent resistance to permeation of various harmful chemicals, and is extremely useful as protective clothing and the like.

Claims

請 求 の 範 囲 The scope of the claims
1 . エチレン一ビニルアルコール系共重合体 5 0質量。 /。以上を含む層を少なく とも 1層有する樹脂層と繊維層とが積層された複合材料からなる耐薬品性防護衣 料。 1. 50 mass of ethylene-vinyl alcohol copolymer. /. A chemical-resistant protective garment comprising a composite material in which a resin layer having at least one layer containing the above and a fiber layer are laminated.
2 . 樹脂層が、 エチレン一ビニルアルコール系共重合体フィルムと、 その少な くとも片面に設けられたメタノールに対する耐透過性樹脂層とからなる積層フィ ルムである請求項 1記載の耐薬品性防護衣料。  2. The chemical-resistant protective film according to claim 1, wherein the resin layer is a laminated film comprising an ethylene-vinyl alcohol-based copolymer film and a resin-resistant resin layer provided on at least one surface thereof. Clothing.
3 . 樹脂層が、 エチレン一ビュルアルコール系共重合体フィルムと、 その少な くとも片面に設けられたポリオレフィン系樹脂層と力 らなる積層フィルムである 請求項 1記載の耐薬品性防護衣料。  3. The chemical-resistant protective clothing according to claim 1, wherein the resin layer is a laminated film composed of an ethylene-vinyl alcohol-based copolymer film and a polyolefin-based resin layer provided on at least one side thereof.
4 . 繊維層が、 不織布である請求項 Ί記載の耐薬品性防護衣料。  4. The chemical-resistant protective clothing according to claim 4, wherein the fiber layer is a non-woven fabric.
5 . 複合材料が、 超音波接合により接合されたものである請求項 1記載の耐薬 品性防護衣料。  5. The chemical-resistant protective clothing according to claim 1, wherein the composite material is bonded by ultrasonic bonding.
6 . 超音波接合が、 連続パターンと不連続パターンを並列に配置した超音波ミ シンによって施されたものである請求項 5記載の耐薬品性防護衣料。  6. The chemical-resistant protective clothing according to claim 5, wherein the ultrasonic bonding is performed by an ultrasonic sewing machine in which a continuous pattern and a discontinuous pattern are arranged in parallel.
7 . 複合材料が、 樹脂層面同士を重ね合わせて接合されたものである請求項 1 記載の耐薬品性防護衣料。  7. The chemical-resistant protective garment according to claim 1, wherein the composite material is formed by joining the resin layers so that the resin layers face each other.
PCT/JP2003/001490 2002-02-15 2003-02-13 Chemical-resistant protective clothes WO2003068010A1 (en)

Applications Claiming Priority (2)

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JP2002038660 2002-02-15
JP2002-38660 2002-02-15

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8037550B2 (en) 2008-02-01 2011-10-18 Gore Enterprise Holdings, Inc. Stretchable chemical protective material

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4988063U (en) * 1972-11-14 1974-07-31
JPS59133624U (en) * 1983-02-26 1984-09-07 旭化成株式会社 Breathable dustproof and waterproof work clothing material
JPS62136319U (en) * 1986-02-20 1987-08-27
JPH01501160A (en) * 1986-10-20 1989-04-20 バータシス ジェイムズ イー Materials of protective clothing and their structure
JPH05132803A (en) * 1991-09-19 1993-05-28 Mitsubishi Kasei Corp Waterproof wear

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4988063U (en) * 1972-11-14 1974-07-31
JPS59133624U (en) * 1983-02-26 1984-09-07 旭化成株式会社 Breathable dustproof and waterproof work clothing material
JPS62136319U (en) * 1986-02-20 1987-08-27
JPH01501160A (en) * 1986-10-20 1989-04-20 バータシス ジェイムズ イー Materials of protective clothing and their structure
JPH05132803A (en) * 1991-09-19 1993-05-28 Mitsubishi Kasei Corp Waterproof wear

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8037550B2 (en) 2008-02-01 2011-10-18 Gore Enterprise Holdings, Inc. Stretchable chemical protective material

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