JPH04289273A - Member for waterproof-and-antifouling apparel - Google Patents
Member for waterproof-and-antifouling apparelInfo
- Publication number
- JPH04289273A JPH04289273A JP3049842A JP4984291A JPH04289273A JP H04289273 A JPH04289273 A JP H04289273A JP 3049842 A JP3049842 A JP 3049842A JP 4984291 A JP4984291 A JP 4984291A JP H04289273 A JPH04289273 A JP H04289273A
- Authority
- JP
- Japan
- Prior art keywords
- film
- groups
- apparel
- fabric
- fluorocarbon
- Prior art date
- Legal status (The legal status 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 status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 claims abstract description 15
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002344 surface layer Substances 0.000 claims abstract description 5
- 239000004744 fabric Substances 0.000 abstract description 28
- 239000000126 substance Substances 0.000 abstract description 26
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 15
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical group Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 abstract description 13
- 239000005871 repellent Substances 0.000 abstract description 12
- -1 sheet Substances 0.000 abstract description 12
- 239000004094 surface-active agent Substances 0.000 abstract description 10
- 238000001179 sorption measurement Methods 0.000 abstract description 6
- 239000003125 aqueous solvent Substances 0.000 abstract description 5
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 abstract description 5
- 239000010985 leather Substances 0.000 abstract description 5
- 230000002940 repellent Effects 0.000 abstract description 4
- 239000004753 textile Substances 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 230000003373 anti-fouling effect Effects 0.000 abstract description 2
- 238000007033 dehydrochlorination reaction Methods 0.000 abstract description 2
- 230000035699 permeability Effects 0.000 abstract description 2
- 239000011550 stock solution Substances 0.000 abstract 1
- 239000000835 fiber Substances 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 10
- 125000000217 alkyl group Chemical group 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- PPDADIYYMSXQJK-UHFFFAOYSA-N trichlorosilicon Chemical compound Cl[Si](Cl)Cl PPDADIYYMSXQJK-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 239000005046 Chlorosilane Substances 0.000 description 6
- 229920000742 Cotton Polymers 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 229910003910 SiCl4 Inorganic materials 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 5
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 229920002994 synthetic fiber Polymers 0.000 description 3
- 239000012209 synthetic fiber Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 241000772415 Neovison vison Species 0.000 description 2
- 229910003822 SiHCl3 Inorganic materials 0.000 description 2
- 229910020175 SiOH Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 210000003746 feather Anatomy 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 2
- 239000005052 trichlorosilane Substances 0.000 description 2
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229910003818 SiH2Cl2 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- SLLGVCUQYRMELA-UHFFFAOYSA-N chlorosilicon Chemical compound Cl[Si] SLLGVCUQYRMELA-UHFFFAOYSA-N 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical class Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 1
- BUMGIEFFCMBQDG-UHFFFAOYSA-N dichlorosilicon Chemical compound Cl[Si]Cl BUMGIEFFCMBQDG-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Laminated Bodies (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、防水防汚性アパレル用
部材に関するものである。さらに詳しくは、繊維製品、
織編物、不織布などの布帛、シート状物、詰め物体、皮
革製品、毛皮製品用の撥水撥油防汚効果の高い高性能ア
パレル用部材に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a waterproof and stain-resistant member for apparel. For more details, please refer to textile products,
The present invention relates to high-performance apparel members with high water-repellent, oil-repellent and stain-proofing effects for fabrics such as woven and knitted fabrics and non-woven fabrics, sheet-like objects, stuffed objects, leather products, and fur products.
【０００２】0002
【従来の技術】従来、繊維製品などのアパレル用部材に
ついては、通気性をある程度保有したまま、汚れを防止
したり、撥水性を付与するには、フロロカーボン系のエ
マルジョン（フッ素樹脂）をスプレー法でコートし、微
細な穴を有する多孔質性コーティング膜を設ける方法が
提案されている。別の手段としては、ウレタン樹脂等の
樹脂を薄くコーティングし、微細な穴を有する多孔質性
コーティング膜を設ける方法も提案されている。また別
の手段としては、収縮率の比較的高い細い繊維を高密度
に織り、織物の状態で高温処理して収縮させることも知
られている。[Prior Art] Conventionally, in order to prevent stains and impart water repellency to apparel materials such as textile products while retaining a certain degree of breathability, fluorocarbon emulsions (fluororesins) have been sprayed. A method has been proposed in which a porous coating film having fine pores is provided. As another method, a method has been proposed in which a porous coating film having fine holes is provided by coating the film thinly with a resin such as urethane resin. Another known method is to weave thin fibers with a relatively high shrinkage rate at a high density, and to shrink the woven fabric by subjecting it to high temperature treatment.
【０００３】さらにミンク等の天然毛皮については、シ
リコーン化合物やフッ素化合物を含む塗布液を用いてポ
リッシャー加工などが行われている。Furthermore, natural fur such as mink fur is subjected to polishing using a coating solution containing a silicone compound or a fluorine compound.
【０００４】0004
【発明が解決しようとする課題】しかしながら前記従来
技術においては、通気性をある程度保有したまま、汚れ
を防止したり、撥水撥油性を付与することはきわめて困
難なことであった。すなわち、前記フッ素樹脂のウレタ
ン樹脂等の多孔質性コーティング膜を設ける方法は、通
気性が大幅に損なわれ、蒸れるという問題があり、その
うえ耐久性がそれ程高くないという本質的な課題がある
。また、前記高収縮処理は、素材そのものが撥水効果を
有しているわけではないので、一時的な撥水に止まり、
雨などが激しいときには役にたたないという課題がある
。[Problems to be Solved by the Invention] However, in the above-mentioned prior art, it is extremely difficult to prevent stains or impart water and oil repellency while retaining a certain degree of breathability. That is, the method of providing a porous coating film such as a fluororesin urethane resin has the problem that air permeability is significantly impaired and stuffiness occurs, and furthermore, there is an essential problem that the durability is not very high. In addition, the high shrinkage treatment is only a temporary water repellent because the material itself does not have a water repellent effect.
The problem is that it is useless when it rains heavily.
【０００５】さらにミンク等の天然毛皮加工で行われて
いる、シリコーン化合物やフッ素化合物を含む塗布液を
用いるポリッシャー加工などでも、耐久性に問題があっ
た。本発明は、前記従来技術の課題を解決するため、素
材が有する通気性等の特性をそのまま生かし、耐久性に
優れた撥水撥油防汚効果の高い高性能アパレル用部材を
提供することを目的とする。[0005] Furthermore, polisher processing using a coating liquid containing a silicone compound or a fluorine compound, which is used to process natural fur such as mink, has problems with durability. In order to solve the problems of the prior art, the present invention aims to provide a high-performance apparel member that is highly durable, water-repellent, oil-repellent, and highly stain-resistant, by making use of the breathability and other characteristics of the material. purpose.
【０００６】[0006]
【課題を解決するための手段】前記目的を達成するため
、本発明の防水防汚性アパレル用部材は、表層にフッ化
炭素基を含み、基部がシロキサン結合によって基材に化
学結合されてなる化学吸着膜が、アパレル用部材の表面
に形成されてなるという構成を備えたものである。[Means for Solving the Problems] In order to achieve the above object, the waterproof and stain-resistant apparel member of the present invention includes a fluorocarbon group in the surface layer, and the base is chemically bonded to the base material by a siloxane bond. It has a structure in which a chemical adsorption film is formed on the surface of an apparel member.
【０００７】前記構成においては、化学吸着膜が単分子
膜であることが好ましい。[0007] In the above structure, it is preferable that the chemisorption film is a monomolecular film.
【０００８】[0008]
【作用】前記した本発明の構成によれば、表層にフッ化
炭素基を含み、基部がシロキサン結合によって基材に化
学結合されてなる化学吸着膜が、アパレル用部材の表面
に形成されているので、素材が有する通気性や美観等の
特性をそのまま生かし、かつ耐久性に優れた撥水撥油防
汚効果の高い高性能アパレル用部材を提供することがで
きる。すなわち、表層にフッ化炭素基を含むきわめて薄
い層で形成されているので、撥水撥油防汚効果に優れ、
また基部がシロキサン結合によって基材に化学結合され
ているので、剥離などが起こらず耐久性に優れたものと
なる。さらに化学吸着膜であるから、きわめて薄く、素
材が有する通気性、演色性や美観等の特性を損ねること
がない。[Operation] According to the configuration of the present invention described above, a chemical adsorption film containing a fluorocarbon group in the surface layer and having a base chemically bonded to the base material through a siloxane bond is formed on the surface of the apparel member. Therefore, it is possible to provide a high-performance apparel member that is highly durable, water- and oil-repellent, and highly stain-resistant, while making full use of the characteristics of the material such as breathability and aesthetic appearance. In other words, since it is formed of an extremely thin layer containing fluorocarbon groups on the surface, it has excellent water and oil repellent and stain resistant effects.
Furthermore, since the base is chemically bonded to the base material through a siloxane bond, peeling does not occur and the product has excellent durability. Furthermore, since it is a chemically adsorbed film, it is extremely thin and does not impair the properties of the material, such as breathability, color rendering, and aesthetics.
【０００９】また、化学吸着膜が単分子膜であるという
本発明の構成によれば、薄くて透明性に優れ、さらに優
れた撥水撥油防汚効果の高い高性能アパレル用部材とす
ることができる。Furthermore, according to the structure of the present invention in which the chemically adsorbed film is a monomolecular film, it is possible to obtain a high-performance apparel member that is thin and has excellent transparency, and also has excellent water-, oil-, and stain-repellent effects. Can be done.
【００１０】0010
【実施例】一般のアパレル製品などは、天然繊維、皮革
や毛皮でできているため表面に水酸基、アミノ基などを
含む。そこで、一端にクロルシラン基（ＳｉＣｌｎ Ｘ
３−ｎ 基、ｎ＝１、２、３、Ｘは官能基）を有する直
鎖状炭素鎖を含む分子、例えばフッ化炭素基及びクロロ
シラン基を含むクロロシラン系界面活性剤混ぜた非水系
溶媒に接触させて前記繊維表面の水酸基やアミノ基と前
記クロロシリル基を複数個含む物質のクロロシリル基を
反応させて前記物質よりなる単分子膜を前記繊維表面に
析出させる、あるいはクロロシリル基を複数個含む物質
を混ぜた非水系溶媒に接触させて前記繊維部表面の水酸
基やアミノ基と前記クロロシリル基を複数個含む物質の
クロロシリル基を反応させて前記物質を前記繊維部表面
に析出させる工程と、非水系有機溶媒を用い前記繊維表
面に残った余分なクロロシリル基を複数個含む物質を洗
浄除去し、前記繊維にクロロシリル基を複数個含む物質
よりなるシロキサン系単分子膜を形成する工程と、一端
にクロルシラン基を有する直鎖状炭素鎖を含むシラン系
界面活性剤を繊維に化学吸着し単分子吸着膜を累積する
工程とにより繊維表面にフッ化炭素系化学吸着単分子累
積膜を形成できる。[Example] Since general apparel products are made of natural fibers, leather, and fur, they contain hydroxyl groups, amino groups, etc. on the surface. Therefore, a chlorosilane group (SiCln
3-n group, n = 1, 2, 3, A monomolecular film made of the substance is deposited on the fiber surface by causing the hydroxyl group or amino group on the surface of the fiber to react with the chlorosilyl group of the substance containing a plurality of chlorosilyl groups, or a substance containing a plurality of chlorosilyl groups. a step of causing the hydroxyl group or amino group on the surface of the fiber portion to react with the chlorosilyl group of the substance containing a plurality of chlorosilyl groups to precipitate the substance on the surface of the fiber portion; A step of washing and removing an excess substance containing a plurality of chlorosilyl groups remaining on the fiber surface using an organic solvent to form a siloxane-based monomolecular film made of a substance containing a plurality of chlorosilyl groups on the fiber, and adding chlorosilane to one end. A fluorocarbon-based chemically adsorbed monomolecular cumulative film can be formed on the fiber surface by chemically adsorbing a silane surfactant containing a linear carbon chain having a group onto the fiber and accumulating a monomolecularly adsorbed film.
【００１１】前記において、素材が水酸基を表面にもた
ない合成繊維（例えばポリエステル繊維など）の場合は
、予め表面を１００Ｗ、３０分程度の酸素プラズマ処理
を行ない水酸基を付与して親水性化した後に、クロロシ
ラン系界面活性剤混ぜた非水系溶媒で処理する。[0011] In the above, when the material is a synthetic fiber (such as polyester fiber) that does not have hydroxyl groups on its surface, the surface is previously subjected to oxygen plasma treatment at 100 W for about 30 minutes to add hydroxyl groups and make it hydrophilic. Afterwards, it is treated with a non-aqueous solvent mixed with a chlorosilane surfactant.
【００１２】本発明で形成する化学吸着膜は、フッ化ア
ルキル基を有するクロロシラン系界面活性剤を用いて形
成することが好ましい。The chemisorption film formed in the present invention is preferably formed using a chlorosilane surfactant having a fluorinated alkyl group.
【００１３】フッ化アルキル基を有するクロロシラン系
界面活性剤としては、例えばＣＦ３ （ＣＦ２ ）７
（ＣＦ２ ）２ ＳｉＣｌ３ ，ＣＦ３ ＣＨ２ Ｏ（
ＣＨ２ ）１５ＳｉＣｌ３ ，ＣＦ３ （ＣＨ２ ）２
Ｓｉ（ＣＨ３ ）２ （ＣＨ２ ）１５ＳｉＣｌ３
，Ｆ（ＣＦ２ ）４ （ＣＨ２ ）２ Ｓｉ（ＣＨ３
）２ （ＣＨ２ ）９ ＳｉＣｌ３ ，Ｆ（ＣＦ２ ）
８ （ＣＨ２ ）２ Ｓｉ（ＣＨ３ ）２ （ＣＨ２
）９ ＳｉＣｌ３ ，ＣＦ３ ＣＯＯ（ＣＨ２ ）１５
ＳｉＣｌ３ ，ＣＦ３ （ＣＦ２ ）５ （ＣＨ２ ）
２ ＳｉＣｌ３ などのようなトリクロロシラン系界面
活性剤をはじめ、例えばＣＦ３ （ＣＦ２ ）７ （Ｃ
Ｈ２）２ ＳｉＣｌｎ （ＣＨ３ ）３−ｎ ，ＣＦ３
（ＣＦ２ ）７ （ＣＨ２ ）２ ＳｉＣｌｎ （Ｃ
２ Ｈ５ ）３−ｎ ，ＣＦ３ ＣＨ２Ｏ（ＣＨ２ ）
１５ＳｉＣｌｎ （ＣＨ３ ）３−ｎ ，ＣＦ３ ＣＨ
２Ｏ（ＣＨ２ ）１５ＳｉＣｌｎ （Ｃ２ Ｈ５ ）３
−ｎ ，ＣＦ３ （ＣＨ２ ）２ Ｓｉ（ＣＨ３ ）２
（ＣＨ２ ）１５ＳｉＣｌｎ （ＣＨ３ ）３−ｎ
，Ｆ（ＣＦ２ ）４ （ＣＨ２ ）２ Ｓｉ（ＣＨ３
）２ （ＣＨ２ ）９ ＳｉＣｌｎ （Ｃ２ Ｈ５ ）
３−ｎ ，Ｆ（ＣＦ２ ）８ （ＣＨ２ ）２ Ｓｉ（
ＣＨ３ ）２ （ＣＨ２ ）９ ＳｉＣｌｎ （ＣＨ３
）３−ｎ ，ＣＦ３ ＣＯＯ（ＣＨ２ ）１５ＳｉＣ
ｌｎ （ＣＨ３ ）３−ｎ ，ＣＦ３ （ＣＦ２ ）５
（ＣＨ２）２ ＳｉＣｌｎ （ＣＨ３ ）３−ｎ （
但し式中のｎは何れも１又は２）等のような低級アルキ
ル基置換のモノクロロシラン系あるいはジクロロシラン
系界面活性剤が挙げられる。これらの中でも特にトリク
ロロシラン系界面活性剤の親水性基と結合したクロロシ
リル結合以外のクロロシリル結合が、隣合うクロロシラ
ン基とシロキサン結合で分子間結合を形成するため、よ
り強固な化学吸着膜となることから好ましい。また、Ｃ
Ｆ３ （ＣＦ２ ）ｎ ＣＨ２ ＣＨ２ ＳｉＣｌ３
（但し式中のｎは整数であり、３〜２５程度が最も扱い
やすい）が、溶剤溶解性、化学吸着性と撥水・防汚性等
の機能性との釣合が取れているため好ましい。さらにま
た、フッ化アルキル鎖部分にエチレン基やアセチレン基
を組み込んでおけば、化学吸着膜形成後５メガラド程度
の電子線照射で架橋できるのでさらに化学吸着膜自体の
硬度を向上させることも可能である。Examples of the chlorosilane surfactant having a fluorinated alkyl group include CF3 (CF2)7
(CF2)2SiCl3,CF3CH2O(
CH2)15SiCl3,CF3(CH2)2
Si(CH3)2(CH2)15SiCl3
,F(CF2)4(CH2)2Si(CH3
)2 (CH2)9 SiCl3,F(CF2)
8 (CH2)2 Si(CH3)2 (CH2
)9 SiCl3, CF3 COO(CH2)15
SiCl3, CF3 (CF2)5 (CH2)
2 SiCl3, etc., as well as trichlorosilane surfactants such as CF3 (CF2)7 (C
H2)2SiCln(CH3)3-n,CF3
(CF2)7 (CH2)2 SiCln (C
2H5)3-n, CF3CH2O(CH2)
15SiCln (CH3)3-n, CF3CH
2O(CH2)15SiCln(C2H5)3
-n, CF3 (CH2)2 Si(CH3)2
(CH2)15SiCln (CH3)3-n
,F(CF2)4(CH2)2Si(CH3
)2 (CH2)9 SiCln (C2 H5)
3-n,F(CF2)8(CH2)2Si(
CH3 )2 (CH2 )9 SiCln (CH3
)3-n,CF3COO(CH2)15SiC
ln (CH3)3-n, CF3 (CF2)5
(CH2)2 SiCln (CH3)3-n (
However, n in the formula may be a lower alkyl group-substituted monochlorosilane or dichlorosilane surfactant such as 1 or 2). Among these, in particular, chlorosilyl bonds other than the chlorosilyl bonds bonded to the hydrophilic group of the trichlorosilane surfactant form intermolecular bonds with adjacent chlorosilane groups and siloxane bonds, resulting in a stronger chemisorption film. preferred. Also, C
F3 (CF2)n CH2 CH2 SiCl3
(However, n in the formula is an integer, and 3 to 25 is easiest to handle) is preferable because it has a good balance between solvent solubility, chemical adsorption, and functionality such as water repellency and stain resistance. . Furthermore, if an ethylene group or acetylene group is incorporated into the fluorinated alkyl chain portion, the hardness of the chemisorption film itself can be further improved since it can be crosslinked by electron beam irradiation of about 5 megarads after formation of the chemisorption film. be.
【００１４】本発明に使用できるクロロシラン系界面活
性剤は、上述に例示したように直鎖状だけではなく、フ
ッ化アルキル基又は炭化水素基が分岐した形状でも、又
は末端の珪素にフッ化アルキル基もしくは炭化水素基が
置換した形状（即ちＲ、Ｒ１ 、Ｒ２ 、Ｒ３ をフッ
化アルキル基又は炭化水素基として一般式Ｒ２ ＳｉＣ
ｌ２ 、Ｒ３ ＳｉＣｌ、Ｒ１ Ｒ２ ＳｉＣｌ２ も
しくはＲ１ Ｒ２ Ｒ３ ＳｉＣｌ等）であってもよい
が、吸着密度を高めるためには一般には直鎖状が好まし
い。さらに、例えば、ＳｉＣｌ４ 、ＳｉＨＣｌ３ 、
ＳｉＨ２ Ｃｌ２ 、Ｃｌ−（ＳｉＣｌ２ Ｏ）ｎ −
ＳｉＣｌ３ （但し式中ｎは自然数）、ＳｉＣｌｍ （
ＣＨ３ ）４−ｍ 、ＳｉＣｌｍ （Ｃ２ Ｈ５ ）４
−ｍ （但し式中ｍは１〜３の整数）、ＨＳｉＣｌｌ
（ＣＨ３ ）３−ｌ 、ＨＳｉＣｌｌ （Ｃ２ Ｈ５
）３−ｌ （但し式中ｌは１又は２）等のようなクロロ
シリル結合を複数個含む物質を化学吸着させた後、水と
反応すると、表面のクロロシリル結合が親水性のシラノ
ール結合に変わり、基材が合成繊維などの場合、表面が
親水性となる。The chlorosilane surfactant that can be used in the present invention is not only linear as exemplified above, but also has a branched form with a fluorinated alkyl group or a hydrocarbon group, or has a fluorinated alkyl group on the terminal silicon. or a hydrocarbon group (i.e., R, R1, R2, R3 are fluorinated alkyl groups or hydrocarbon groups, and the general formula R2 SiC
12 , R3 SiCl, R1 R2 SiCl2 or R1 R2 R3 SiCl, etc.), but in order to increase the adsorption density, a linear shape is generally preferred. Furthermore, for example, SiCl4, SiHCl3,
SiH2Cl2, Cl-(SiCl2O)n-
SiCl3 (where n is a natural number in the formula), SiClm (
CH3)4-m, SiClm(C2H5)4
-m (where m is an integer from 1 to 3), HSiCll
(CH3)3-l, HSiCl(C2H5
) 3-l (where l is 1 or 2 in the formula), etc. When a substance containing multiple chlorosilyl bonds is chemically adsorbed and then reacted with water, the chlorosilyl bonds on the surface change to hydrophilic silanol bonds, When the base material is synthetic fiber or the like, the surface becomes hydrophilic.
【００１５】以下に本発明に関するアパレル用部材とし
て、帽子、マフラー、上着、ズボン、靴下、手袋等の衣
類や羽織、着物、足袋、帯、草履、下駄等の和装品、傘
、テント、リュックサック、ロープ、網、靴、コート、
合羽等の雨具、ジャンパー、アノラック、羽毛服などの
防寒着、座布団、布団カバー、カーペット、クッション
、布団などの詰綿、羽毛、家具、カーテン、壁用クロス
等の内装品で代表される繊維製品または皮革製品、毛皮
製品用のアパレル用部材があるが、代表例としてレイン
コート用布地を取り上げ順に説明する。Apparel members related to the present invention include clothing and haori such as hats, mufflers, jackets, pants, socks, and gloves, Japanese clothing such as kimonos, tabi, obi, sandals, and geta, umbrellas, tents, and backpacks. Sacks, ropes, nets, shoes, coats,
Textile products such as rain gear such as coats, winter clothing such as jumpers, anoraks, and feather clothes, cushions, futon covers, carpets, cushions, cotton padding such as futons, feathers, furniture, curtains, interior goods such as wall cloths, etc. There are also apparel members for leather products and fur products, but a raincoat fabric will be taken as a representative example and explained in order.
【００１６】実施例１
まず、加工の終了した綿製レインコート用布地（ビニロ
ンなど、親水性の布地であれば同様に使用できる）を用
意し、よく洗浄した後乾燥し、フッ化炭素基及びクロロ
シラン基を含む物質を混ぜた非水系の溶媒、例えば、Ｃ
Ｆ３ （ＣＦ２ ）７ （ＣＨ２ ）２ ＳｉＣｌ３
を用い、１％程度の濃度で溶かした８０％ｎ−ヘキサデ
カン（トルエン、キシレン、ジシクロヘキシルなどでも
よい）、１２％四塩化炭素、８％クロロホルム溶液を調
整し、前記布地を２時間程度浸漬すると、綿製布地の表
面は水酸基が多数含まれているので、フッ化炭素基及び
クロロシラン基を含む物質のＳｉＣｌ基と前記水酸基が
反応し脱塩酸反応が生じ布地繊維表面全面に亘り、ＣＦ
３ （ＣＦ２ ）７ （ＣＨ２ ）２ Ｓｉ（Ｏ−）３
の結合が生成され、フッ素を含む単分子膜２が部材表
面１と化学結合した状態でおよそ１５オングストローム
の膜厚で形成できた（図１）。なお、単分子膜はきわめ
て強固に化学結合しているので全く剥離することがなか
った。Example 1 First, a processed cotton raincoat fabric (any hydrophilic fabric such as vinylon can be used in the same way) is prepared, thoroughly washed and dried, and fluorocarbon groups and A non-aqueous solvent mixed with a substance containing a chlorosilane group, such as C
F3 (CF2)7 (CH2)2 SiCl3
Using a solution of 80% n-hexadecane (toluene, xylene, dicyclohexyl, etc. may also be used) dissolved at a concentration of about 1%, 12% carbon tetrachloride, and 8% chloroform, and soaking the fabric for about 2 hours, Since the surface of cotton fabric contains a large number of hydroxyl groups, the hydroxyl groups react with the SiCl groups of substances containing fluorocarbon groups and chlorosilane groups, resulting in a dehydrochloric acid reaction, which spreads over the entire surface of the fabric fibers.
3 (CF2)7 (CH2)2 Si(O-)3
A monomolecular film 2 containing fluorine was formed with a film thickness of approximately 15 angstroms in a state of chemical bonding with the member surface 1 (FIG. 1). It should be noted that the monomolecular film had extremely strong chemical bonds, so it did not peel off at all.
【００１７】この撥水撥油処理した布地を用い実使用を
試みたが、処理しないものに比べ汚物の付着を大幅に低
減できた、またたとえ付着した場合にもブラシでこする
程度で簡単に除去できた。また、防水性を試してみたが
、濡れ角度は約１５０度であり水滴が表面に残ることは
全く無かった。その他、通気性や着用感、外観（美観）
などは、素材の特性をそのまま生かすことができた。[0017] When we tried using this water- and oil-repellent fabric, we found that the adhesion of dirt was significantly reduced compared to fabrics that were not treated, and even if it did get stuck, it was easy to wipe it off with a brush. I was able to remove it. I also tested the waterproofness, but the wetting angle was about 150 degrees, and no water droplets remained on the surface. Other aspects such as breathability, wearability, and appearance (aesthetics)
etc., we were able to take advantage of the characteristics of the material as is.
【００１８】なお、上記実施例では綿製品を例に示した
が、布地の材質が撥水性のアクリル、ポリエステル、ポ
リアミド等の合成繊維の場合は、酸素を含むプラズマ雰
囲気中で１００Ｗ、３０分程度処理し表面を親水性化し
ておけばよい。（この他、親水性化する方法としては、
濃硫酸に１０％重クロム酸カリを添加した溶液に８０℃
、３分浸漬する方法、あるいは濃硫酸に１０％過塩素酸
カリを添加した溶液に８０℃、１時間浸漬する方法等が
利用可能である）また、皮革製品や毛皮製品でも同様の
方法が利用できた。[0018] Although cotton products were used as an example in the above embodiments, if the material of the fabric is water-repellent synthetic fiber such as acrylic, polyester, or polyamide, it may be heated at 100W for about 30 minutes in a plasma atmosphere containing oxygen. It is sufficient to treat the surface to make it hydrophilic. (In addition, as a method to make it hydrophilic,
Add 10% potassium dichromate to a solution of concentrated sulfuric acid at 80°C.
The same method can be used for leather products and fur products. did it.
【００１９】実施例２
親水性ではあるが水酸基を含む割合が少ない布地（例え
ば、アクリル繊維製の布地をプラズマ処理したもの）の
場合、トリクロロシリル基を複数個含む物質（例えば、
ＳｉＣｌ４ 、またはＳｉＨＣｌ３ 、ＳｉＨ２ Ｃｌ
２ 、Ｃｌ−（ＳｉＣｌ２ Ｏ）ｎ −ＳｉＣｌ３ （
ｎは整数）。特に、ＳｉＣｌ４ を用いれば、分子が小
さく水酸基に対する活性も大きいので、部材表面を均一
に親水化する効果が大きい）を混ぜた非水系溶媒、例え
ばクロロホルム溶媒に１重量パーセント溶解した溶液に
３０分間程度浸漬すると、部材１１の表面には、プラズ
マ処理によりある程度親水性のＯＨ基１２が存在するの
で（図２）、表面で脱塩酸反応が生じトリクロロシリル
基を複数個含む物質のクロロシラン単分子膜が形成され
る。Example 2 In the case of a fabric that is hydrophilic but contains a small proportion of hydroxyl groups (for example, a fabric made of acrylic fiber treated with plasma), a substance containing a plurality of trichlorosilyl groups (for example,
SiCl4, or SiHCl3, SiH2Cl
2, Cl-(SiCl2O)n-SiCl3 (
n is an integer). In particular, if SiCl4 is used, it has a small molecule and high activity toward hydroxyl groups, so it has a great effect of uniformly making the surface of the member hydrophilic. When immersed, a certain amount of hydrophilic OH groups 12 are present on the surface of the member 11 due to the plasma treatment (Fig. 2), so a dehydrochloric acid reaction occurs on the surface and a chlorosilane monomolecular film of a substance containing a plurality of trichlorosilyl groups is formed. It is formed.
【００２０】例えば、トリクロロシリル基を複数個含む
物質としてＳｉＣｌ４ を用いれば、部材１１表面には
少量の親水性のＯＨ基が露出されているので、表面で脱
塩酸反応が生じ、下記に示す（化１）、（化２）のよう
に分子が−ＳｉＯ−結合を介して表面に固定される。For example, if SiCl4 is used as a substance containing a plurality of trichlorosilyl groups, a small amount of hydrophilic OH groups are exposed on the surface of the member 11, so a dehydrochlorination reaction occurs on the surface, resulting in the following ( As shown in chemical formulas 1) and (chemical formula 2), molecules are immobilized on the surface via -SiO- bonds.
【００２１】[0021]
【化１】[Chemical formula 1]
【００２２】[0022]
【化２】[Case 2]
【００２３】その後非水系の溶媒例えばクロロホルムで
洗浄して、さらに水で洗浄すると布地繊維表面と反応し
ていないＳｉＣｌ４ 分子は除去され、下記に示す（化
３）、（化４）のように繊維表面に等のシロキサン単分
子膜１３が得られる（図３）。[0023] After that, by washing with a non-aqueous solvent such as chloroform and further washing with water, the SiCl4 molecules that have not reacted with the surface of the fabric fibers are removed and the fibers are A siloxane monomolecular film 13 is obtained on the surface (FIG. 3).
【００２４】[0024]
【化３】[Chemical formula 3]
【００２５】[0025]
【化４】[C4]
【００２６】なお、このときできた単分子膜１３は布地
繊維とは−ＳｉＯ−の化学結合を介して完全に結合され
ているので剥がれることが全く無い。また、得られた単
分子膜は表面にシラノール基（ＳｉＯＨ基）を数多く持
つ。当初の水酸基のおよそ３倍程度の数が生成される。[0026] The monomolecular film 13 formed at this time is completely bonded to the fabric fibers through -SiO- chemical bonds, so that it will not peel off at all. Further, the obtained monomolecular film has many silanol groups (SiOH groups) on the surface. Approximately three times as many hydroxyl groups as the original hydroxyl groups are generated.
【００２７】そこでさらに、フッ化炭素基及びクロロシ
ラン基を含む物質を混ぜた非水系の溶媒、例えば、ＣＦ
３ （ＣＦ２ ）７ （ＣＨ２ ）２ ＳｉＣｌ３ を
用い、３％程度の濃度で溶かした８０％ｎ−ヘキサデカ
ン、１２％四塩化炭素、８％クロロホルム溶液を調整し
、表面にＳｉＯＨ結合を数多く持つ単分子膜の形成され
た布地を１時間程度浸漬すると、表面にＣＦ３ （ＣＦ
２ ）７ （ＣＨ２ ）２ Ｓｉ（Ｏ−）３ の結合が
生成され、フッ素を含む単分子膜１４が下層のシロキサ
ン単分子膜と化学結合した状態で布地表面全面に亘り高
密度におよそ１５オングストロームの膜厚で形成できた
（図４）。Therefore, a non-aqueous solvent containing a substance containing a fluorocarbon group and a chlorosilane group, such as CF
3 Using (CF2)7(CH2)2SiCl3, a solution of 80% n-hexadecane, 12% carbon tetrachloride, and 8% chloroform dissolved at a concentration of about 3% was prepared, and a single molecule with many SiOH bonds on the surface was prepared. When the fabric on which the film has been formed is soaked for about an hour, CF3 (CF
2)7 (CH2)2Si(O-)3 bonds are generated, and the fluorine-containing monomolecular film 14 is chemically bonded to the underlying siloxane monomolecular film, covering the entire surface of the fabric at a high density of approximately 15 angstroms. It was possible to form a film with a film thickness of (Figure 4).
【００２８】なお、単分子膜は剥離試験を行なっても全
く剥離することがなかった。[0028] The monomolecular film did not peel off at all even when a peel test was conducted.
【００２９】さらにまた上記実施例ではフッ化炭素系界
面活性剤としてＣＦ３ （ＣＦ２ ）７ （ＣＨ２ ）
２ ＳｉＣｌ３ を用いたが、アルキル鎖部分にエチレ
ン基やアセチレン基を付加したり組み込んでおけば、単
分子膜形成後５メガラド程度の電子線照射で架橋できる
のでさらに単分子膜の硬度を向上させることも可能であ
る。Furthermore, in the above examples, CF3 (CF2)7 (CH2) was used as the fluorocarbon surfactant.
2 SiCl3 was used, but if an ethylene group or acetylene group is added or incorporated into the alkyl chain part, it can be crosslinked by electron beam irradiation of about 5 megarads after monolayer formation, which further improves the hardness of the monolayer. It is also possible.
【００３０】また、吸着用試薬の分子の長さを変えたも
の２種を混合して（たとえば、Ｆ（ＣＦ２ ）８ （Ｃ
Ｈ２ ）２ Ｓｉ（ＣＨ３ ）２ （ＣＨ２ ）９ Ｓ
ｉＣｌ３ とＦ（ＣＦ２ ）８ （ＣＨ２ ）２ Ｓｉ
（ＣＨ３ ）２ （ＣＨ２ ）６ ＳｉＣｌ３ 、また
はＣＦ３ （ＣＦ２ ）７ （ＣＨ２ ）２ ＳｉＣｌ
３ とＣＦ３ （ＣＦ２ ）５ （ＣＨ２ ）２ Ｓｉ
Ｃｌ３ の組合せで、組成を３：１〜１：３とする）吸
着すれば、布地表面を分子レベルで凸凹にする事が可能
であり、撥水撥油性がさらに良くなり、防汚作用がさら
に大きくなる。In addition, two adsorption reagents with different molecular lengths may be mixed (for example, F(CF2)8(C
H2)2Si(CH3)2(CH2)9S
iCl3 and F(CF2)8 (CH2)2Si
(CH3)2 (CH2)6 SiCl3, or CF3 (CF2)7 (CH2)2 SiCl
3 and CF3 (CF2)5 (CH2)2 Si
By adsorbing Cl3 (with a composition of 3:1 to 1:3), it is possible to make the fabric surface uneven at the molecular level, further improving water and oil repellency and improving stain resistance. growing.
【００３１】[0031]
【発明の効果】以上説明した通り、きわめて薄いナノメ
ータレベルの膜厚のフッ化炭素系単分子膜を部材表面に
形成するため、部材本来の色調や光沢を損なうことがな
い。また、このフッ化炭素系単分子膜は撥水撥油性にも
優れており、表面の防水防汚効果を高めることが可能と
なる。そのうえ耐久性にも優れている。従って、きわめ
て防水防汚効果の高い高性能アパレル用部材を提供する
ことができる。[Effects of the Invention] As explained above, since an extremely thin fluorocarbon monomolecular film with a thickness on the nanometer level is formed on the surface of the member, the original color tone and gloss of the member are not impaired. Furthermore, this fluorocarbon monomolecular film has excellent water and oil repellency, making it possible to enhance the waterproof and antifouling effect of the surface. Moreover, it has excellent durability. Therefore, it is possible to provide a high-performance apparel member that is extremely waterproof and stain-proof.
【図１】 本発明の綿製布地の繊維表面を分子レベル
まで拡大した断面概念図である。FIG. 1 is a conceptual cross-sectional view of the fiber surface of the cotton fabric of the present invention, enlarged to the molecular level.
【図２】 本発明の布地の第２の実施例を説明するた
めにアクリル布地繊維の表面を分子レベルまで拡大した
処理前の断面概念図である。FIG. 2 is a conceptual cross-sectional view of the surface of acrylic fabric fibers before treatment, enlarged to the molecular level, to explain a second embodiment of the fabric of the present invention.
【図３】 本発明の布地の第２の実施例を説明するた
めにアクリル布地繊維の表面を分子レベルまで拡大した
処理中の断面概念図である。FIG. 3 is a conceptual cross-sectional view of the surface of acrylic fabric fibers during processing, enlarged to the molecular level, to explain a second embodiment of the fabric of the present invention.
【図４】 本発明の布地の第２の実施例を説明するた
めにアクリル布地繊維の表面を分子レベルまで拡大した
処理後の断面概念図である。FIG. 4 is a conceptual cross-sectional view of the surface of acrylic fabric fibers after processing, enlarged to the molecular level, to explain a second embodiment of the fabric of the present invention.
１ 綿製布地 ２，１４ 単分子膜 １１ アクリル製布地繊維 １２ 水酸基 １３ シロキサン単分子膜 1 Cotton fabric 2,14 Monolayer 11 Acrylic fabric fiber 12 Hydroxyl group 13 Siloxane monolayer
Claims (2)
ロキサン結合によって基材に化学結合されてなる化学吸
着膜が、アパレル用部材の表面に形成されてなる防水防
汚性アパレル用部材。1. A waterproof and stain-resistant apparel member, wherein a chemically adsorbed film containing a fluorocarbon group on the surface layer and having a base chemically bonded to a base material through a siloxane bond is formed on the surface of the apparel member.
記載の防水防汚性アパレル用部材。[Claim 2]Claim 1, wherein the chemisorption film is a monomolecular film.
The waterproof and stain-resistant apparel member described above.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3049842A JP2820167B2 (en) | 1991-03-14 | 1991-03-14 | Waterproof and antifouling apparel components |
| EP19920104188 EP0508136B1 (en) | 1991-03-14 | 1992-03-11 | Surface-treated apparel material |
| DE1992625743 DE69225743T2 (en) | 1991-03-14 | 1992-03-11 | Surface treated material for clothing |
| KR1019920004216A KR950004492B1 (en) | 1991-03-14 | 1992-03-14 | Surface treated apparel material |
| US08/165,569 US5474839A (en) | 1991-03-14 | 1993-12-13 | Surface-treated apparel material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3049842A JP2820167B2 (en) | 1991-03-14 | 1991-03-14 | Waterproof and antifouling apparel components |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04289273A true JPH04289273A (en) | 1992-10-14 |
| JP2820167B2 JP2820167B2 (en) | 1998-11-05 |
Family
ID=12842330
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3049842A Expired - Fee Related JP2820167B2 (en) | 1991-03-14 | 1991-03-14 | Waterproof and antifouling apparel components |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2820167B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008533323A (en) * | 2005-03-16 | 2008-08-21 | プレス、スチュアート | Hydrophobic insulation |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5294884A (en) * | 1976-02-06 | 1977-08-09 | Teijin Ltd | Water and oil repellent laminated product |
| JPH02234977A (en) * | 1989-03-03 | 1990-09-18 | Toray Ind Inc | Cloth having water-repellency |
-
1991
- 1991-03-14 JP JP3049842A patent/JP2820167B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5294884A (en) * | 1976-02-06 | 1977-08-09 | Teijin Ltd | Water and oil repellent laminated product |
| JPH02234977A (en) * | 1989-03-03 | 1990-09-18 | Toray Ind Inc | Cloth having water-repellency |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008533323A (en) * | 2005-03-16 | 2008-08-21 | プレス、スチュアート | Hydrophobic insulation |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2820167B2 (en) | 1998-11-05 |
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| LAPS | Cancellation because of no payment of annual fees |