WO1990008218A1 - Waterproof water vapor permeable deodorizing membrane and clothing - Google Patents

Waterproof water vapor permeable deodorizing membrane and clothing Download PDF

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Publication number
WO1990008218A1
WO1990008218A1 PCT/US1990/000179 US9000179W WO9008218A1 WO 1990008218 A1 WO1990008218 A1 WO 1990008218A1 US 9000179 W US9000179 W US 9000179W WO 9008218 A1 WO9008218 A1 WO 9008218A1
Authority
WO
WIPO (PCT)
Prior art keywords
membrane
water vapor
clothing
vapor permeable
deodorant
Prior art date
Application number
PCT/US1990/000179
Other languages
French (fr)
Inventor
Takashi Imai
Original Assignee
W.L. Gore & Associates, Inc.
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 W.L. Gore & Associates, Inc. filed Critical W.L. Gore & Associates, Inc.
Publication of WO1990008218A1 publication Critical patent/WO1990008218A1/en

Links

Classifications

    • 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
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0059Organic ingredients with special effects, e.g. oil- or water-repellent, antimicrobial, flame-resistant, magnetic, bactericidal, odour-influencing agents; perfumes
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0063Inorganic compounding ingredients, e.g. metals, carbon fibres, Na2CO3, metal layers; Post-treatment with inorganic compounds
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/04Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06N3/047Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds with fluoropolymers
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/18Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with two layers of different macromolecular materials
    • D06N3/183Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with two layers of different macromolecular materials the layers are one next to the other
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers

Definitions

  • the invention relates to membranes useful for clothing or garments which are waterproof, water vapor permeable, and will not become malodorous in continuous heavy service.
  • Cloth produced according to the methods cited above can be supplied for use in clothing adapted for comfortable wear without causing the wearer any feeling of stuffiness when the wearer perspires. This is based on the fact that the clothing is waterproof and water vapor permeable allowing water vapor
  • malodorus components end up adhering to the skin of the worker. Even after the worker's job has ended, said odors emanate from the body and underwear of said worker, and naturally cause discomfort to those in the worker's immediate surroundings.
  • the present invention comprises a membrane manufactured by coating a microporous organic polymer membrane selected from microporous polytetrafluoroethylene membrane or a polyolefin membrane with a hydrophilic resin which contains a deodorant admixed therein, to produce a liquid-waterproof water vapor permeable deodorizing membrane, useful for garments or clothing. DESCRIPTION OF THE PREFERRED EMBODIMENTS
  • hydrophilic resins uniformly admixed with a deodorant can be coated onto a microporous PTFE membrane or a microporous polyolefin membrane.
  • the deodorant which is mixed uniformly in the hydrophilic resin, acts to remove odors.
  • a membrane is obtained having a superior deodorizing function.
  • PTFE When PTFE is the microporous membrane it can be obtained as a material in which countless fine fibers are formed in a spider web-like pattern between micronodes by fibrillating a PTFE sheet by rolling or drawing (or by using both together). Membranes having the following specifications can be employed: pore percentage 50 to 95%; maximum pore size 0.1 to 3 um; thickness 10 to 200 um.
  • Polyether polyurethane resin or polymeric perfluorosulfonic acid or the like are useful as the hydrophilic resin.
  • a deodorant such as a metallic oxide salt (such as copper oxide or iron oxide), a metallic salt (such as phthalocyanine salt), and an organic acid (such as an aliphatic or aromatic carboxylic acid) in the amount of 5-100 g/m 2 of a mixture of 1-200 parts by weight per 100 parts by weight of the hydrophilic resin is then coated onto the microporous PTFE membrane.
  • the mixture can be applied by spraying, brushing, or roll-coating.
  • a membrane was prepared by coating a mixture of 30 parts by weight of a copper oxide-type deodorant blended with 100 parts by 'weight of a polyether polyurethane resin (a hydrophilic resin) onto a microporous PTFE membrane which was obtained by a drawing process such that the maximum pore size was approximately 0.2 m, the pore percentage was as much as 80%, and the thickness was approximately 35 um.
  • a polyether polyurethane resin a hydrophilic resin
  • the water pressure resistance and permeation capacity of the membrane obtained above are shown in Table 1.
  • the membrane had desirable water-proof moisture permeability.
  • the membrane obtained as above was measured in terms of its deodorizing property vis-a-vis the following malodorous
  • ammonia trimethylamine
  • hydrogen sulfide hydrogen sulfide
  • Hydrogen sulfide was formed by placing 1 ml of an 800 ppm hydrogen sulfide aqueous solution and 0.1 ml of 1 N sulfuric acid in a 300 ml Erlenmeyer flask, after which approximately 2 g. of sample was added thereto. The mixture was maintained at 25oC.
  • the residual concentration of the hydrogen sulfide in the flask was measured by a Kitagawa-type gas detector.
  • a fabric was prepared by laminating the above membrane produced eiccordirtg to the present invention with a 40 denier knitted fabric. The properties of this laminated cloth were tested and measured, with the results shown in Table 3. These results confirmed that the sample was water-proof, had moisture permeability desirable for use in all types of work clothes, and had superior deodorizing capabilities. Table 3

Abstract

Waterproof water vapor permeable deodorizing membranes and fabrics made therefrom which comprise microporous organic polymeric membrane coated with a hydrophilic resin layer, such as a polyether urethane or perfluorosulfonic acid group-containing polymer, containing a deodorant.

Description

WATERPROOF WATER VAPOR PERMEABLE DEODORIZING MEMBRANE AND CLOTHING
FIELD OF THE INVENTION
The invention relates to membranes useful for clothing or garments which are waterproof, water vapor permeable, and will not become malodorous in continuous heavy service. BACKGROUND OF THE INVENTION
Owing to the fact that waterproof, water vapor permeable cloth not only prevents the penetration and adhesion of rainwater, but also allows the vapor content produced from perspiration to permeate, such cloth is highly adapted for manufacture of clothing which is comfortable to wear in continuous heavy service. Various examples of such clothing that have been wet-coated with polyurethane or laminated with microporous polytetrafluoroethylene (PTFE) film have been illustrated in Japanese Patent Publication Nos. 58-38456, 60-47955 and 60-39014. Such clothing is being used on a commerical scale.
Cloth produced according to the methods cited above can be supplied for use in clothing adapted for comfortable wear without causing the wearer any feeling of stuffiness when the wearer perspires. This is based on the fact that the clothing is waterproof and water vapor permeable allowing water vapor
permeation therethrough. However, when the clothing is worn in surroundings where unpleasant odors are present, such as the farming and dairy industries, malodorus components end up adhering to the skin of the worker. Even after the worker's job has ended, said odors emanate from the body and underwear of said worker, and naturally cause discomfort to those in the worker's immediate surroundings. The penetration and adhesion of malodorous
components cannot be prevented in the case of clothing utilizing water vapor permeable sheets of the above type. BRIEF DESCRIPTION OF THE INVENTION
The present invention comprises a membrane manufactured by coating a microporous organic polymer membrane selected from microporous polytetrafluoroethylene membrane or a polyolefin membrane with a hydrophilic resin which contains a deodorant admixed therein, to produce a liquid-waterproof water vapor permeable deodorizing membrane, useful for garments or clothing. DESCRIPTION OF THE PREFERRED EMBODIMENTS
It has been found that hydrophilic resins uniformly admixed with a deodorant can be coated onto a microporous PTFE membrane or a microporous polyolefin membrane. The deodorant, which is mixed uniformly in the hydrophilic resin, acts to remove odors. In other words, a membrane is obtained having a superior deodorizing function.
When PTFE is the microporous membrane it can be obtained as a material in which countless fine fibers are formed in a spider web-like pattern between micronodes by fibrillating a PTFE sheet by rolling or drawing (or by using both together). Membranes having the following specifications can be employed: pore percentage 50 to 95%; maximum pore size 0.1 to 3 um; thickness 10 to 200 um.
Polyether polyurethane resin or polymeric perfluorosulfonic acid or the like are useful as the hydrophilic resin.
A deodorant such as a metallic oxide salt (such as copper oxide or iron oxide), a metallic salt (such as phthalocyanine salt), and an organic acid (such as an aliphatic or aromatic carboxylic acid) in the amount of 5-100 g/m2 of a mixture of 1-200 parts by weight per 100 parts by weight of the hydrophilic resin is then coated onto the microporous PTFE membrane. The mixture can be applied by spraying, brushing, or roll-coating.
EXAMPLE
A membrane was prepared by coating a mixture of 30 parts by weight of a copper oxide-type deodorant blended with 100 parts by 'weight of a polyether polyurethane resin (a hydrophilic resin) onto a microporous PTFE membrane which was obtained by a drawing process such that the maximum pore size was approximately 0.2 m, the pore percentage was as much as 80%, and the thickness was approximately 35 um.
The water pressure resistance and permeation capacity of the membrane obtained above are shown in Table 1. The membrane had desirable water-proof moisture permeability.
Tabl e 1
Capaci ty Method of Measurement
Water Pressure Resi stance (kg/cm2 ) 30 JIS L-1092
Moi sture Permeabili ty (g/M2● 24 hr) 60,000 JIS L-1099 B Method
The membrane obtained as above was measured in terms of its deodorizing property vis-a-vis the following malodorous
components: ammonia, trimethylamine, and hydrogen sulfide. The methods for measuring this property are as described below.
A) Ammonia
10 ml of 28% aqueous ammonia was placed in a 300 ml Erlenmeyer flask. After the ammonia had completely vaporized, approximately 1 g. of sample was added thereto and the temperature maintained at 25°C. After 2 hours had elapsed, the residual ammonia
concentration in the flask was measured by a Kitagawa-type gas detector.
B) Trimethylamine
10 ml of an 0.8% trimethylamine aqueous solution was, placed in a 300 ml Erlenmeyer flask. Following the same procedure as for ammonia, the residual concentration of trimethylami ne in the flask was measured by a Kitagawa-type gas detector. C) Hydrogen Sulfide
Hydrogen sulfide was formed by placing 1 ml of an 800 ppm hydrogen sulfide aqueous solution and 0.1 ml of 1 N sulfuric acid in a 300 ml Erlenmeyer flask, after which approximately 2 g. of sample was added thereto. The mixture was maintained at 25ºC.
After two hours had elapsed, the residual concentration of the hydrogen sulfide in the flask was measured by a Kitagawa-type gas detector.
The results from each of the above measurements are shown in Table 2.
Table 2
Ammonia Trimethvlamine Hydrogen Sulfide
Blank (ppm) 900 32 140
Sample Film (ppm) ND 2.0 ND
(ND = not detected)
A fabric was prepared by laminating the above membrane produced eiccordirtg to the present invention with a 40 denier knitted fabric. The properties of this laminated cloth were tested and measured, with the results shown in Table 3. These results confirmed that the sample was water-proof, had moisture permeability desirable for use in all types of work clothes, and had superior deodorizing capabilities. Table 3
Water Pressure Resistance >3.0 kg/cm2
Moisture Permeability 30.000 g/m2 ● 24 hours
Deodorizing Capability
Ammonia Blank 6,000
Sample 120
Trimethyl ami ne Blank 32
Saniple ND
Hydrogen Sulfide Blank 140
Sample ND
(ND = not detected)
Work clothes and the like which are used in malodorous surroundings can be furnished with desirable waterproof and moisture permeability properties so as to provide comfort during work while wearing such clothes. Furthermore, it is possible to obtain a product which has odor-preventing properties and in which no unpleasant odors are left on the body of the wearer or on the wearer's undergarments. Such garments are highly useful in an industrial environment.

Claims

I claim:
1. A liquid waterproof, water vapor permeable deodorizing membrane comprising a microporous organic polymeric membrane selected from the class consisting of polyolefin or
polytetrafluoroethylene, coated with a hydrophilic resin layer containing a deodorant.
2. A membrane of Claim 1 wherein said hydrophilic resin layer comprises a polyether polyurethane resin.
3. A membrane of Claim 1 wherein said hydrophilic resin layer comprises a polymeric perfluorosulfonic acid resin.
4. A membrane of Claim 1, 2, or 3 wherein said deodorant comprises a metallic oxide salt, a metal salt, or an organic acid.
5. A laminate of the membrane of Claim 1 and a fabric.
PCT/US1990/000179 1989-01-17 1990-01-16 Waterproof water vapor permeable deodorizing membrane and clothing WO1990008218A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP1/5898 1989-01-17
JP1005898A JP2933938B2 (en) 1989-01-17 1989-01-17 Sheet material with waterproof moisture permeability and deodorant

Publications (1)

Publication Number Publication Date
WO1990008218A1 true WO1990008218A1 (en) 1990-07-26

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WO (1) WO1990008218A1 (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5928792A (en) * 1997-05-01 1999-07-27 Millipore Corporation Process for making surface modified porous membrane with perfluorocarbon copolymer
US5976380A (en) * 1997-05-01 1999-11-02 Millipore Corporation Article of manufacture including a surface modified membrane and process
US6273271B1 (en) 1997-05-01 2001-08-14 Millipore Corporation Surface modified porous membrane and process
CN109504006A (en) * 2018-11-21 2019-03-22 湖北彩砼新材料有限公司 Modified super-hydrophobic composite film of a kind of self-cleaning nona and preparation method thereof
CN112543786A (en) * 2018-07-31 2021-03-23 W.L.戈尔及同仁股份有限公司 Polyethylene film
US11561495B2 (en) 2020-12-25 2023-01-24 Canon Kabushiki Kaisha Pressing rotating member and production method thereof, fixing apparatus, and electrophotographic image forming apparatus

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2712011B2 (en) * 1995-06-27 1998-02-10 株式会社東京電▲気▼工務所 Valve protection cover
WO2022138491A1 (en) * 2020-12-25 2022-06-30 キヤノン株式会社 Resin membrane and water-resistant and moisture-permeable membrane

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3111450A (en) * 1961-02-01 1963-11-19 Armstrong Cork Co Polyvinyl fluoride film capable of being adhesively secured and method
GB2024100A (en) * 1978-06-29 1980-01-09 Gore & Ass Flexible layered article
JPS6357669A (en) * 1986-08-29 1988-03-12 Panatsuku Kogyo Kk Deodorizing film
DE3734297A1 (en) * 1986-10-09 1988-06-23 Daicel Chem DESODORING LAYER
JPS63153130A (en) * 1986-08-29 1988-06-25 パナック株式会社 Deodoring film and manufacture thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4613544A (en) * 1984-12-04 1986-09-23 Minnesota Mining And Manufacturing Co. Waterproof, moisture-vapor permeable sheet material and method of making the same
JPS6354453A (en) * 1986-08-25 1988-03-08 Nok Corp Deodorizing polyurethane foam
JPS6357054A (en) * 1986-08-29 1988-03-11 エヌオーケー株式会社 Deodorizing material

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3111450A (en) * 1961-02-01 1963-11-19 Armstrong Cork Co Polyvinyl fluoride film capable of being adhesively secured and method
GB2024100A (en) * 1978-06-29 1980-01-09 Gore & Ass Flexible layered article
JPS6357669A (en) * 1986-08-29 1988-03-12 Panatsuku Kogyo Kk Deodorizing film
JPS63153130A (en) * 1986-08-29 1988-06-25 パナック株式会社 Deodoring film and manufacture thereof
DE3734297A1 (en) * 1986-10-09 1988-06-23 Daicel Chem DESODORING LAYER

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 109, no. 24, 12 December 1988 Columbus, Ohio, USA page 47; column 1; ref. no. 212125 & JP-A-63153130 (PANAC KOGYO) 25 JUNE 1988 see abstract *
PATENT ABSTRACTS OF JAPAN vol. 12, no. 279 (C-517)(3126) 01 August 1988, & JP-A-63 57669 (PANATSUKU KOGYO) 12 March 1988, see the whole document *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5928792A (en) * 1997-05-01 1999-07-27 Millipore Corporation Process for making surface modified porous membrane with perfluorocarbon copolymer
US5976380A (en) * 1997-05-01 1999-11-02 Millipore Corporation Article of manufacture including a surface modified membrane and process
US6273271B1 (en) 1997-05-01 2001-08-14 Millipore Corporation Surface modified porous membrane and process
US6354443B1 (en) 1997-05-01 2002-03-12 Millipore Corporation Surface modified porous membrane and process
CN112543786A (en) * 2018-07-31 2021-03-23 W.L.戈尔及同仁股份有限公司 Polyethylene film
CN109504006A (en) * 2018-11-21 2019-03-22 湖北彩砼新材料有限公司 Modified super-hydrophobic composite film of a kind of self-cleaning nona and preparation method thereof
US11561495B2 (en) 2020-12-25 2023-01-24 Canon Kabushiki Kaisha Pressing rotating member and production method thereof, fixing apparatus, and electrophotographic image forming apparatus

Also Published As

Publication number Publication date
JP2933938B2 (en) 1999-08-16
JPH02187436A (en) 1990-07-23

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