WO2003068010A1 - Vetements de protection resistant aux agents chimiques - Google Patents

Vetements de protection resistant aux agents chimiques 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
Prior art date
Application number
PCT/JP2003/001490
Other languages
English (en)
Japanese (ja)
Inventor
Takeshi Konishi
Yasutoshi Kawasaki
Motochika Maki
Original Assignee
Kuraray Co., Ltd.
Meditec Japan Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kuraray Co., Ltd., Meditec Japan Co., Ltd. filed Critical Kuraray Co., Ltd.
Publication of WO2003068010A1 publication Critical patent/WO2003068010A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D5/00—Composition 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

La présente invention concerne des vêtements de protection résistant aux agents chimiques qui comprend une matière composite constituée d'une couche fibreuse recouverte d'une couche de résine comprenant au moins une couche, laquelle comprend au moins 50% en poids de copolymère d'alcool éthylène/vinyle. Ces vêtements de protection résistant aux agents chimiques possèdent une excellente imperméabilité à diverses substances chimiques nocives.
PCT/JP2003/001490 2002-02-15 2003-02-13 Vetements de protection resistant aux agents chimiques WO2003068010A1 (fr)

Applications Claiming Priority (2)

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

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WO2003068010A1 true WO2003068010A1 (fr) 2003-08-21

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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 (fr) * 1972-11-14 1974-07-31
JPS59133624U (ja) * 1983-02-26 1984-09-07 旭化成株式会社 通気性を有する防塵・防水作業用衣料素材
JPS62136319U (fr) * 1986-02-20 1987-08-27
JPH01501160A (ja) * 1986-10-20 1989-04-20 バータシス　ジェイムズ　イー 防護服の材料及びその構造
JPH05132803A (ja) * 1991-09-19 1993-05-28 Mitsubishi Kasei Corp 防水着

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4988063U (fr) * 1972-11-14 1974-07-31
JPS59133624U (ja) * 1983-02-26 1984-09-07 旭化成株式会社 通気性を有する防塵・防水作業用衣料素材
JPS62136319U (fr) * 1986-02-20 1987-08-27
JPH01501160A (ja) * 1986-10-20 1989-04-20 バータシス　ジェイムズ　イー 防護服の材料及びその構造
JPH05132803A (ja) * 1991-09-19 1993-05-28 Mitsubishi Kasei Corp 防水着

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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