JP2820167B2 - Waterproof and antifouling apparel components - Google Patents
Waterproof and antifouling apparel componentsInfo
- Publication number
- JP2820167B2 JP2820167B2 JP3049842A JP4984291A JP2820167B2 JP 2820167 B2 JP2820167 B2 JP 2820167B2 JP 3049842 A JP3049842 A JP 3049842A JP 4984291 A JP4984291 A JP 4984291A JP 2820167 B2 JP2820167 B2 JP 2820167B2
- Authority
- JP
- Japan
- Prior art keywords
- sicl
- film
- group
- apparel
- waterproof
- 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.)
- Expired - Fee Related
Links
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)
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 antifouling apparel member. More specifically, textiles,
The present invention relates to a high-performance apparel member having a high water-repellent, oil-repellent and antifouling effect for fabrics such as woven and knitted fabrics and nonwoven fabrics, sheets, 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。2. Description of the Related Art Conventionally, in order to prevent dirt and impart water repellency to apparel members such as textiles while maintaining a certain degree of air permeability, a fluorocarbon emulsion (fluororesin) is sprayed. To provide a porous coating film having fine holes. As another means, a method has been proposed in which a resin such as a urethane resin is thinly coated to provide a porous coating film having fine holes. As another means, it is also known that fine fibers having a relatively high shrinkage ratio are woven at a high density, and the fibers are shrunk by high-temperature treatment in a woven state.
【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。Further, natural fur such as mink is polished 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。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。However, in the above-mentioned prior art, it is extremely difficult to prevent dirt and impart water and oil repellency while maintaining a certain degree of air permeability. That is, the method of providing a porous coating film such as a urethane resin of a fluororesin has a problem that the air permeability is significantly impaired and humid, and also has an essential problem that the durability is not so high. In addition, since the material itself does not have a water-repellent effect in the high shrinkage treatment, there is a problem that the material is only temporarily water-repellent and is useless when rain or the like is severe. Furthermore, it is performed by natural fur processing such as mink,
Polishing using a coating solution containing a silicone compound or a fluorine compound also has a problem in durability.
【０００５】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] In order to solve the above-mentioned problems of the prior art, the present invention makes use of the properties of the material such as air permeability as it is,
It is an object of the present invention to provide a high-performance apparel member having excellent water-repellent, oil-repellent, and antifouling effects having excellent durability.
【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、本発明の第１番目の防水防汚性アパレル用部材は、
表層にＣＦ3−（ＣＦ2）n−（ＣＨ2）2− （ただし、
ｎは３〜２５の整数）で表される直鎖状のフルオロアル
キル基を基部にシロキサン結合をそれぞれ含むナノメー
タレベルの膜厚の化学吸着膜が、アパレル用部材の表面
に前記シロキサン結合を介して結合形成されてなるとい
う構成を備えたものである。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。In order to achieve the above object, a first waterproof / soil-resistant apparel member of the present invention comprises:
CF 3- (CF 2 ) n- (CH 2 ) 2- (however,
n is chemically adsorbed film with a thickness of nanometer level, each containing a siloxane bond based part a linear fluoroalkyl group represented by an integer) of 3 to 25 is, through the siloxane bond to the surface of the apparel member It is provided with a configuration that is formed by coupling. In the above configuration, the chemical adsorption film is preferably a monomolecular film.
【０００７】次に本発明の第２番目の防水防汚性アパレ
ル用部材は、表層にＣＦ 3 −（ＣＦ 2 ） n −（ＣＨ 2 ） 2 −
（ただし、ｎは３〜２５の整数）で表される直鎖状の
フル オロアルキル基を含み、基部にシロキサン結合を含
むナノメータレベルの膜厚の化学吸着膜が、アパレル用
部材の表面に形成されたシロキサン系単分子膜を介して
累積形成されてなるという構成を備えたものである。 Next, the second waterproof and stainproof apparel of the present invention.
Le member is, CF 3 in the surface layer - (CF 2) n - ( CH 2) 2 -
(Where n is an integer of 3 to 25)
It includes full Oroarukiru group, containing a siloxane bond to the base
Nanometer-level chemisorption film for apparel
Through the siloxane-based monolayer formed on the surface of the member
This is provided with a configuration of being formed cumulatively.
【０００８】[0008]
【作用】前記した本発明の第１番目の構成によれば、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。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。According to the first aspect of the present invention, a chemical adsorption film having a surface layer containing a fluorocarbon group and having a base chemically bonded to a substrate by a siloxane bond is formed on the surface of the apparel member. Since it is formed, it is possible to provide a high-performance apparel member having excellent water-repellent, oil-repellent, and antifouling effects that is excellent in durability while utilizing the properties of the material such as air permeability and aesthetic appearance. That is, since the surface layer is formed of an extremely thin layer containing a fluorocarbon group, it is excellent in water / oil repellency and antifouling effect, and since the base is chemically bonded to the base material through a siloxane bond, peeling or the like occurs. And excellent in durability. Further, since it is a chemical adsorption film, it is extremely thin, and does not impair the properties of the material such as air permeability, color rendering, and aesthetic appearance. Further, according to the configuration of the present invention in which the chemical adsorption film is a monomolecular film, a high-performance apparel member that is thin, has excellent transparency, and has excellent water-repellent, oil-repellent, and antifouling effects can be obtained.
【０００９】次に、本発明の第２番目の構成によれば、
表層にＣＦ 3 −（ＣＦ 2 ） n −（ＣＨ 2 ） 2 − （ただし、
ｎは３〜２５の整数）で表される直鎖状のフルオロアル
キル基を含み、基部にシロキサン結合を含むナノメータ
レベルの膜厚の化学吸着膜が、アパレル用部材の表面に
形成されたシロキサン系単分子膜を介して累積形成され
ているので、表層のフッ化炭素基を含む分子を高密度に
固定できる。 Next, according to a second configuration of the present invention,
CF 3- (CF 2 ) n- (CH 2 ) 2- (however,
n is an integer of 3 to 25)
Nanometer with a kill group and a siloxane bond at the base
Level chemical adsorption film on the surface of apparel parts
Cumulatively formed through the formed siloxane-based monomolecular film
High density of molecules containing fluorocarbon groups on the surface
Can be fixed.
【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、一端にクロシリル基（ＳｉＣｌn Ｘ3-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リル基
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界面活
性剤のクロロシリル基を反応させて前記界面活性剤分子
よりなる単分子膜を前記繊維表面に析出させる。あるい
はクロル基を複数個含むシリル化合物を混合した非水系
溶媒に繊維製品などを接触させて前記繊維部表面の水酸
基やアミノ基と前記シリル化合物のクロル基を反応させ
て前記シリル化合物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未反応
前記シリル化合物を洗浄除去し、前記繊維製品等の表面
にシラノール基を複数個含むシロキサン系単分子膜を形
成する工程と、一端にクロルシリル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。DESCRIPTION OF THE PREFERRED EMBODIMENTS General apparel products and the like are made of natural fibers, leather and fur, and have hydroxyl groups and amino groups on the surface. Therefore, one end Kuroshio lil group (SiCl n X 3-n
Group, n = 1, 2, 3, X is contacted molecule, the non-aqueous solvent obtained by mixing a chlorosilane-based surface active agent containing, for example, fluorocarbon group and Kuroroshi Lil groups containing straight chain having a functional group) The hydroxyl group or amino group on the fiber surface and the surface activity
Reacting the chlorosilyl groups of sex agent the surfactant molecules <br/> consisting monomolecular film is deposited on the fiber surface. Non-aqueous solvent wherein the contacting the like textiles reacting a chloro group for a hydroxyl group or an amino group and the silyl compound of the fiber portion surface the silyl compound fibers or a mixture of silyl compounds containing a plurality of chloro groups Depositing on the surface of the fiber, and the unreacted residue remaining on the fiber surface using a non-aqueous organic solvent
Washing and removing the silyl compound, the surface of the textile product etc.
Forming a plurality including shea Rokisan based monomolecular film silanol groups, the silane-based surfactant comprising linear carbon chains having Kurorushi drill group at one end chemically adsorbed to the fibers, monomolecular adsorption film By the step of accumulating, a fluorocarbon-based chemically adsorbed monomolecular accumulation film can be formed on the fiber surface.
【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。In the above, when the material is a synthetic fiber having no hydroxyl group on the surface (for example, polyester fiber), the surface is previously subjected to an oxygen plasma treatment at 100 W for about 30 minutes to impart a hydroxyl group to make the surface hydrophilic. After that, it is treated with a non-aqueous solvent mixed with a chlorosilane-based 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 chemical adsorption film formed in the present invention is preferably formed using a chlorosilane-based surfactant having a fluoroalkyl 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 （ＣＨ
2 ）2 ＳｉＣｌ3 ，ＣＦ3 ＣＨ2 Ｏ（ＣＨ2 ）15ＳｉＣ
ｌ3，ＣＦ3 （ＣＨ2 ）2 Ｓｉ（ＣＨ3 ）2 （ＣＨ2 ）
15ＳｉＣｌ3 ，Ｆ（ＣＦ2 ）4 （ＣＨ2 ）2 Ｓｉ（ＣＨ
3 ）2 （ＣＨ2 ）9 ＳｉＣｌ3 ，Ｆ（ＣＦ2 ）8 （ＣＨ
2 ）2 Ｓｉ（ＣＨ3 ）2 （ＣＨ2 ）9 ＳｉＣｌ3 ，ＣＦ
3 ＣＯＯ（ＣＨ2 ）15ＳｉＣｌ3 ，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 （Ｃ2 Ｈ5 ）3-n ，ＣＦ3 Ｃ
Ｈ2 Ｏ（ＣＨ2 ）15ＳｉＣｌn （ＣＨ3 ）3-n ，ＣＦ3
ＣＨ2 Ｏ（ＣＨ2 ）15ＳｉＣｌn （Ｃ2 Ｈ5 ）3-n ，Ｃ
Ｆ3 （ＣＨ2 ）2 Ｓｉ（ＣＨ3 ）2 （ＣＨ2 ）15ＳｉＣ
ｌn （ＣＨ3 ）3-n ，Ｆ（ＣＦ2 ）4 （ＣＨ2 ）2 Ｓｉ
（ＣＨ3 ）2 （ＣＨ2 ）9 ＳｉＣｌn （Ｃ
2 Ｈ5 ）3-n ，Ｆ（ＣＦ2 ）8 （ＣＨ2）2 Ｓｉ（ＣＨ
3 ）2 （ＣＨ2 ）9 ＳｉＣｌn （ＣＨ3 ）3-n ，ＣＦ3
ＣＯＯ（ＣＨ2 ）15ＳｉＣｌn （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、ＣＦ3 （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-based surfactant having a fluorinated alkyl group include CF 3 (CF 2 ) 7 (CH
2 ) 2 SiCl 3 , CF 3 CH 2 O (CH 2 ) 15 SiC
l 3 , CF 3 (CH 2 ) 2 Si (CH 3 ) 2 (CH 2 )
15 SiCl 3 , F (CF 2 ) 4 (CH 2 ) 2 Si (CH
3 ) 2 (CH 2 ) 9 SiCl 3 , F (CF 2 ) 8 (CH
2 ) 2 Si (CH 3 ) 2 (CH 2 ) 9 SiCl 3 , CF
3 COO (CH 2 ) 15 SiCl 3 , CF 3 (CF 2 ) 5
Examples include trichlorosilane-based surfactants such as (CH 2 ) 2 SiCl 3 and CF 3 (CF 2 ) 7 (C
H 2 ) 2 SiCl n (CH 3 ) 3-n , CF 3 (CF 2 )
7 (CH 2 ) 2 SiCl n (C 2 H 5 ) 3-n , CF 3 C
H 2 O (CH 2 ) 15 SiCl n (CH 3 ) 3-n , CF 3
CH 2 O (CH 2) 15 SiCl n (C 2 H 5) 3-n, C
F 3 (CH 2 ) 2 Si (CH 3 ) 2 (CH 2 ) 15 SiC
l n (CH 3) 3- n, F (CF 2) 4 (CH 2) 2 Si
(CH 3 ) 2 (CH 2 ) 9 SiCl n (C
2 H 5) 3-n, F (CF 2) 8 (CH 2) 2 Si (CH
3 ) 2 (CH 2 ) 9 SiCl n (CH 3 ) 3-n , CF 3
COO (CH 2 ) 15 SiCl n (CH 3 ) 3-n , CF 3
(CF 2 ) 5 (CH 2 ) 2 SiCl n (CH 3 )
Examples thereof include lower alkyl group-substituted monochlorosilane-based or dichlorosilane-based surfactants such as 3-n (where n is 1 or 2). Among these, chlorosilyl bonds other than the chlorosilyl bond bonded to the hydrophilic group of the trichlorosilane-based surfactant form intermolecular bonds between adjacent chlorosilane groups and siloxane bonds, resulting in a stronger chemical adsorption film. Is preferred. In addition, CF 3 (CF 2 ) n CH 2 CH 2 SiCl 3 (where n is an integer, and 3 to 25 is the easiest to handle) has a solvent solubility, a chemical adsorption property, a water repellency and an antifouling property. It is preferable because it is balanced with the functionality such as properties. Furthermore,
If an ethylene group or an acetylene group is incorporated into the fluorinated alkyl chain portion, it can be crosslinked by electron beam irradiation of about 5 megarads after the formation of the chemisorption film, so that the hardness of the chemisorption film itself can be further improved.
【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 ＳｉＣｌ2 、Ｒ
3 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、Ｓｉ
Ｃｌ4 、ＳｉＨＣｌ3 、ＳｉＨ2 Ｃｌ2 、Ｃｌ−（Ｓｉ
Ｃｌ2 Ｏ）n −ＳｉＣｌ3 （但し式中ｎは自然数）、Ｓ
ｉＣｌm （ＣＨ3 ）4-m 、ＳｉＣｌm （Ｃ2 Ｈ5 ）4-m
（但し式中ｍは１〜３の整数）、ＨＳｉＣｌl （Ｃ
Ｈ3 ）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-based surfactant that can be used in the present invention is not limited to a linear one as exemplified above, but may also be a branched alkyl fluoride group or a hydrocarbon group, or an alkyl fluoride at the terminal silicon. Group or a group substituted by a hydrocarbon group (that is, R, R 1 , R 2 , R 3 are represented by a general formula R 2 SiCl 2 , R 3
3 SiCl, R 1 R 2 SiCl 2 or R 1 R 2 R 3
SiCl or the like may be used, but in order to increase the adsorption density, a linear shape is generally preferred. Further, for example, Si
Cl 4, SiHCl 3, SiH 2 Cl 2, Cl- (Si
Cl 2 O) n -SiCl 3 (where n is a natural number), S
iCl m (CH 3 ) 4-m , SiCl m (C 2 H 5 ) 4-m
(Where m is an integer of 1 to 3), HSiCl 1 (C
After chemically adsorbing a substance containing a plurality of chlorosilyl bonds, such as H 3 ) 3-l , HSiCl 1 (C 2 H 5 ) 3-l (where 1 is 1 or 2), and reacting with water The chlorosilyl bond on the surface changes to a hydrophilic silanol bond, and the surface becomes hydrophilic when the substrate is a synthetic fiber or the like.
【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。The apparel members according to the present invention include: clothing such as hats, mufflers, outerwear, pants, socks, and gloves;
Umbrellas, tents, rucksacks, ropes, nets, shoes, coats, rainwear such as kappa, winter clothes such as jumpers, anoraks, feathers, cushions, duvet covers, carpets, cushions, wadding, feathers, furniture, etc. Textile products or leather products represented by interior products such as curtains and cloth for walls,
There is an apparel member for a fur product, and a raincoat fabric will be described as a representative example 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
シリル基を含む物質を混合した非水系の溶媒、例えば、
ＣＦ3 （ＣＦ2）7 （ＣＨ2 ）2 ＳｉＣｌ3 を用い、１
重量％程度の濃度で溶かした８０重量％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重量％四塩化炭素、８重量％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
基及びクロロシリル基を含む物質の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、ＣＦ3 （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約１５オングストローム（１．５
ｎｍ）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 (a hydrophilic fabric such as vinylon can be used in the same manner) was prepared, washed well, dried, and treated with a fluorocarbon group. the non-aqueous solvent obtained by mixing a substance containing a chloro <br/> silyl group, for example,
Using CF 3 (CF 2 ) 7 (CH 2 ) 2 SiCl 3 ,
Wt% of 80 wt% was dissolved at a concentration n- hexadecane (toluene, xylene, or dicyclohexyl etc.), 12 wt% carbon tetrachloride, and adjust the 8 wt% chloroform solution, when the fabric is immersed about 2 hours, since the surface of the cotton fabric has a great many hydroxyl groups, and the hydroxyl group react with SiCl groups of substances containing a fluorocarbon group and Kuroroshi Lil groups dehydrochlorination reaction is over the fabric fiber surface entirely occurs, CF 3 ( A bond of CF 2 ) 7 (CH 2 ) 2 Si (O—) 3 is generated, and the monomolecular film 2 containing fluorine is formed on the member surface 1.
About 15 angstroms (1.5
nm) (FIG. 1). In addition, since the monomolecular film was very strongly chemically bonded, 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。The water- and oil-repellent treated fabric was used for actual use. However, compared to the non-treated fabric, the adhesion of dirt could be greatly reduced. Could be removed. In addition, water resistance was tested, but the wetting angle was about 150 degrees, and no water droplets remained on the surface. In addition, the characteristics of the material, such as air permeability, wearing feeling, and appearance (aesthetic appearance), could be used as they were.
【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。In the above embodiment, a cotton product is shown as an example. However, when the material of the fabric is synthetic fiber such as water-repellent acryl, polyester, polyamide, etc., it is about 100 W for 30 minutes in a plasma atmosphere containing oxygen. It may be treated to make the surface hydrophilic. (In addition to this, as a method of making hydrophilic,
80% in a solution of 10% potassium dichromate in concentrated sulfuric acid
C. for 3 minutes, or a method of adding 10% potassium perchlorate to concentrated sulfuric acid at 80.degree. C. for 1 hour can be used.) The same method can be used for leather products and fur products. Was available.
【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、クロル基を複数個含むシリル化合物（例えば、Ｓ
ｉＣｌ4 、またはＳｉＨＣｌ3 、ＳｉＨ2 Ｃｌ2 、Ｃｌ
−（ＳｉＣｌ2Ｏ）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）を混合した非水系溶媒、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前記シリル化合物の単分子膜が形
成される。Example 2 In the case of a fabric which is hydrophilic but has a small proportion of hydroxyl groups (for example, an acrylic fiber fabric which is plasma-treated), a silyl compound containing a plurality of chloro groups (for example, S
iCl 4 , or SiHCl 3 , SiH 2 Cl 2 , Cl
- (SiCl 2 O) n -SiCl 3 (n is an integer). In particular, the use of SiCl 4, since the molecule is active also large for small hydroxyl group, a non-aqueous solvent obtained by mixing a large effect) be uniformly hydrophilic member surface, the solution was 1% by weight soluble in e.g. chloroform solvent for 30 minutes When immersed to a certain degree, the surface of the member 11 has OH groups 12 that are hydrophilic to some extent due to the plasma treatment (FIG. 2), so that a dehydrochlorination reaction occurs on the surface, and a monomolecular film of the silyl compound is formed.
【００２０】例えば、クロル基を複数個含むシリル化合
物として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, a silyl compound containing a plurality of chloro groups
If SiCl 4 is used as a material, a small amount of hydrophilic OH group is exposed on the surface of the member 11, so a dehydrochlorination reaction occurs on the surface, and as shown in the following (Chemical Formula 1) and (Chemical Formula 2) Molecules are fixed to the surface via -SiO- bonds.
【００２１】[0021]
【化１】 Embedded image
【００２２】[0022]
【化２】 Embedded image
【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）。Thereafter, washing with a non-aqueous solvent such as chloroform and further washing with water removes SiCl 4 molecules which have not reacted with the surface of the fabric fiber, and as shown in the following (Chemical Formula 3) and (Chemical Formula 4) A siloxane monomolecular film 13 such as on the fiber surface is obtained (FIG. 3).
【００２４】[0024]
【化３】 Embedded image
【００２５】[0025]
【化４】 Embedded image
【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。当初の水酸基の約３倍程度の数が生成される。Since the monomolecular film 13 formed at this time is completely bonded to the fabric fiber through a chemical bond of -SiO-, it does not peel off at all. The obtained monomolecular film has many silanol groups (SiOH groups) on the surface. About three times the number of 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
リル基を含む物質を混合した非水系の溶媒、例えば、Ｃ
Ｆ3 （ＣＦ2 ）7 （ＣＨ2 ）2 ＳｉＣｌ3 を用い、３重
量％程度の濃度で溶かした８０重量％ｎ−ヘキサデカ
ン、１２重量％四塩化炭素、８重量％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
（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
に約１５オングストローム（１．５ｎｍ）の膜厚で形成
できた（図４）。Therefore, further, a fluorocarbon group and a chlorosilane
The non-aqueous solvent obtained by mixing a substance containing an Lil group, for example, C
The reference F 3 (CF 2) 7 ( CH 2) 2 SiCl 3, 3 -fold
The amount% about 80 wt% dissolved at a concentration of n- hexadecane, 12 wt% carbon tetrachloride, and adjust the 8 wt% chloroform solution, the fabric formed of the monomolecular film having numerous SiOH bonds on the surface for about 1 hour When immersed, CF 3
A bond of (CF 2 ) 7 (CH 2 ) 2 Si (O—) 3 is generated, and the fluorine-containing monomolecular film 14 is chemically bonded to the underlying siloxane monomolecular film in a high density over the entire fabric surface. A film having a thickness of about 15 angstroms (1.5 nm) was formed (FIG. 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。The monomolecular film did not peel at all even when a peeling test was performed.
【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 ＳｉＣ
ｌ3 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（エチニレン基と同一）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。Further, in the above embodiment, CF 3 (CF 2 ) 7 (CH 2 ) 2 SiC was used as the fluorocarbon surfactant.
It was used l 3, further monomolecular because if incorporated or adding ethylene group or an acetylene group (same as ethynylene group) in the alkyl chain moiety, can be crosslinked by electron beam irradiation of about 5 Mrads after monolayer formation It is also possible to improve the hardness of the film.
【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 ＳｉＣｌ3 とＦ
（ＣＦ2）8 （ＣＨ2 ）2 Ｓｉ（ＣＨ3 ）2 （ＣＨ2 ）
6 ＳｉＣｌ3 、またはＣＦ3 （ＣＦ2 ）7 （ＣＨ2 ）2
ＳｉＣｌ3 とＣＦ3 （ＣＦ2 ）5 （ＣＨ2 ）2 ＳｉＣｌ
3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。Further, two kinds of adsorption reagents having different molecular lengths are mixed (for example, F (CF 2 ) 8 (C
H 2 ) 2 Si (CH 3 ) 2 (CH 2 ) 9 SiCl 3 and F
(CF 2 ) 8 (CH 2 ) 2 Si (CH 3 ) 2 (CH 2 )
6 SiCl 3 or CF 3 (CF 2 ) 7 (CH 2 ) 2
SiCl 3 and CF 3 (CF 2 ) 5 (CH 2 ) 2 SiCl
By adsorbing, the composition can be made uneven at the molecular level, the water and oil repellency is further improved, and the antifouling action is further improved. 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。As described above, since a fluorocarbon-based monomolecular film having a very small thickness on the order of nanometers is formed on the surface of the member, the original color tone and gloss of the member are not impaired. Further, this fluorocarbon-based monomolecular film is also excellent in water and oil repellency, and can enhance the waterproof and antifouling effect on the surface. Moreover, it has excellent durability. Therefore, it is possible to provide a high-performance apparel member having a very high waterproof and antifouling effect.
【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 in which a fiber surface of a cotton fabric of the present invention is enlarged to a 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 before treatment in which the surface of an acrylic fabric fiber is enlarged to a molecular level in order 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 during processing in which the surface of an acrylic fabric fiber is enlarged to a molecular level in order 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 after a process of expanding the surface of an acrylic fabric fiber to a molecular level in order 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 DESCRIPTION OF SYMBOLS 1 Cotton fabric 2,14 Monomolecular film 11 Acrylic fabric fiber 12 Hydroxyl group 13 Siloxane monomolecular film
───────────────────────────────────────────────────── フロントページの続き (72)発明者 曽我 眞守 大阪府門真市大字門真1006番地松下電器 産業株式会社内 (56)参考文献 特開 昭52−94884（ＪＰ，Ａ) 特開 平２−234977（ＪＰ，Ａ) 特公 昭44−3566（ＪＰ，Ｂ１) ────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Mamoru Soga 1006 Kazuma Kadoma, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. (56) References JP-A-52-94884 (JP, A) JP-A-2- 234977 (JP, A) JP44-3566 (JP, B1)
Claims (3)
− （ただし、ｎは３〜２５の整数）で表される直鎖状
のフルオロアルキル基を基部にシロキサン結合をそれぞ
れ含むナノメータレベルの膜厚の化学吸着膜が、アパレ
ル用部材の表面に前記シロキサン結合を介して結合形成
されてなる防水防汚性アパレル用部材。[Claim 1] A surface layer CF 3 - (CF 2) n - (CH 2) 2
- (where, n is an integer of 3 to 25) which siloxane bonds based part a linear fluoroalkyl group represented by
A waterproof / fouling-resistant apparel member comprising a chemically adsorbed film having a thickness of nanometer level including the siloxane bond formed on the surface of the apparel member.
記載の防水防汚性アパレル用部材。2. The waterproof and antifouling apparel member according to claim 1, wherein the chemical adsorption film is a monomolecular film.
− （ただし、ｎは３〜２５の整数）で表される直鎖状
のフルオロアルキル基を含み、基部にシロキサン結合を
含むナノメータレベルの膜厚の化学吸着膜が、アパレル
用部材の表面に形成されたシロキサン系単分子膜を介し
て累積形成されてなる防水防汚性アパレル用部材。3. The method according to claim 1, wherein the surface layer comprises CF 3 — (CF 2 ) n — (CH 2 ) 2.
-(Where n is an integer of 3 to 25), a chemisorption film having a thickness of nanometer level containing a linear fluoroalkyl group and containing a siloxane bond at the base is formed on the surface of the apparel member. Waterproof and antifouling apparel member formed cumulatively via the siloxane-based monomolecular film thus formed.
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 JPH04289273A (en) | 1992-10-14 |
| JP2820167B2 true 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) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2601758C (en) * | 2005-03-16 | 2014-05-27 | Stuart Press | Hydrophobic insulation material |
Family Cites Families (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
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04289273A (en) | 1992-10-14 |
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