公开(公告)号：US5451459A

公开(公告)日：1995-09-19

申请号：US281681

申请日：1994-07-28

申请人： Kazufumi Ogawa ,  Norihisa Mino ,  Mamoru Soga

发明人： Kazufumi Ogawa ,  Norihisa Mino ,  Mamoru Soga

IPC分类号： B05D1/18 ,  C09D4/00 ,  B32B7/04 ,  B32B17/06

CPC分类号： B82Y30/00 ,  B05D1/185 ,  B82Y40/00 ,  C09D4/00 ,  Y10T428/261 ,  Y10T428/31612 ,  Y10T428/31663 ,  Y10T428/31667

摘要： According to the invention, a fluorine-based or siloxane -based chemical adsorbed film containing a fluorocarbon compound can be formed on a given substrate surface in a laminated state and through chemical bonds (i.e., covalent bonds) with the substrate, it is possible to obtain a laminated film which has satisfactory adhesion to the substrate, is substantially pin-hole free and is very thin. Further, since the outermost layer may be substituted by fluorocarbon groups or hydroxyl groups, it is possible to obtain a film which has excellent water- and oil-repelling properties or hydrophilic and oil-repelling properties and can replace fluorine-based coating films, thus improving the performance of products requiring a coating having a water- and oil-repelling resistant property, weather-resistant property, wear-resistant property and so forth which are desirable in electric products, vehicles, industrial devices and so forth.

摘要翻译： 根据本发明，可以在给定的基板表面上以层压状态和通过与基板的化学键（即共价键）形成含氟碳化合物的基于氟或硅氧烷的化学吸附膜， 获得对基材具有令人满意的粘合性的层压膜，其基本上无针孔，并且非常薄。 此外，由于最外层可以被碳氟基或羟基取代，所以可以获得具有优异的防水疏斥性或亲水性和拒油性能，并且可以代替氟基涂膜的膜 提高了在电气产品，车辆，工业装置等中需要具有耐斥油性，耐油污性，耐候性，耐磨性等的涂层的产品的性能。

公开(公告)号：US5380585A

公开(公告)日：1995-01-10

申请号：US37727

申请日：1993-03-26

申请人： Kazufumi Ogawa ,  Norihisa Mino ,  Mamoru Soga

发明人： Kazufumi Ogawa ,  Norihisa Mino ,  Mamoru Soga

IPC分类号： B05D1/18 ,  C08J7/04 ,  C09D4/00 ,  C09D183/08 ,  B32B7/00

CPC分类号： C04B41/52 ,  B05D1/185 ,  B82Y30/00 ,  B82Y40/00 ,  B82Y5/00 ,  C04B41/009 ,  C04B41/89 ,  C08J7/047 ,  C09D183/08 ,  C09D4/00 ,  C04B2111/00965 ,  C08J2483/00 ,  Y10T428/261 ,  Y10T428/31612 ,  Y10T428/31663 ,  Y10T428/31667

摘要： The invention to provide a chemically adsorbed monomolecular lamination film comprising a chemically adsorbed monomolecular film formed via a siloxane-based monomolecular or polymer film on a substrate surface. It also seeks to provide a method of forming a chemically adsorbed monomolecular film efficiently and with high density on a substrate surface with few hydroxyl groups, which method comprises a step of contacting a substrate containing hydroxyl groups present on the surface with a non-aqueous solution containing a material with plural chlorosilanol groups in molecule, a step of removing the material remaining on the substrate without reaction by washing the substrate with a non-aqueous organic solution (if this process is omitted, the siloxane-based polymer film is prepared on the substrate), a step of forming a monomolecular film constituted by a compound containing a silanol group in molecule on the substrate by exposing to the air containing moisture or washing with water, after the removal step, and a step of laminating a monomolecular adsorption film by abosorbing a chlorosilane-based surface active agent constituted by a straight hydrocarbon chain having a chlorosilane groups at one end onto the substrate after the monomolecular or polymer film formation step.

摘要翻译： 本发明提供一种化学吸附的单分子层叠膜，其包含在基材表面上通过基于硅氧烷的单分子或聚合物膜形成的化学吸附的单分子膜。 它还寻求提供一种在几乎没有羟基的基材表面上有效且高密度地形成化学吸附的单分子膜的方法，该方法包括使含有表面上存在的羟基的基材与非水溶液接触的步骤 含有分子中具有多个氯硅烷醇基团的材料，通过用非水有机溶液洗涤基材而除去残留在基材上的材料而不反应的步骤（如果省略该方法，则将硅氧烷基聚合物膜制备在 底物），在除去步骤之后，通过暴露于含有水分的空气或用水洗涤的方式，在基板上分子形成由分子中含有硅烷醇基的化合物构成的单分子膜的步骤，以及将单分子吸附膜层叠 剥离由具有氯硅烷基的直链烃链构成的氯硅烷系表面活性剂 在单分子或聚合物膜形成步骤之后的一端到基底上。

公开(公告)号：US5284707A

公开(公告)日：1994-02-08

申请号：US812820

申请日：1991-12-24

申请人： Kazufumi Ogawa ,  Norihisa Mino ,  Mamoru Soga

发明人： Kazufumi Ogawa ,  Norihisa Mino ,  Mamoru Soga

IPC分类号： B05D1/18 ,  C03C17/42 ,  C08J7/04 ,  C09D4/00 ,  C09D183/02 ,  C09D183/08 ,  B32B17/06

CPC分类号： B82Y30/00 ,  B05D1/185 ,  B82Y40/00 ,  B82Y5/00 ,  C03C17/42 ,  C08J7/047 ,  C09D183/02 ,  C09D183/08 ,  C09D4/00 ,  C08J2483/00 ,  Y10T428/261 ,  Y10T428/31612 ,  Y10T428/31663

摘要： This invention provides for an anti-contaminating film which is adsorbed to a substrate surface. The film contains a --Si-- group and fluorocarbon group. The --Si-- group is covalently bonded to the substrate surface. It also provides a method of forming an anti-contaminating film on a hydrogen active substrate surface by contacting the substrate surface with a non-aqueous solution, containing a surface active material having fluorocarbon groups and chlorosilane groups, the substrate surface having active hydrogen groups, removing unreacted surface active material remaining on the substrate by washing the substrate with a non-aqueous organic solution for making a monomolecular precursor film, reacting chlorosilane groups unreacted in the adsorbed monomolecular precursor film with water after the removing step, and drying the adsorbed monomolecular film. The above washing step with the non-aqueous organic solution was omitted, and a fluorocarbon polymer film was formed to the substrate surface.

摘要翻译： 本发明提供一种吸附在基材表面上的防污膜。 该片含有-Si-基和氟碳基。 -Si-基团共价结合到基材表面。 它还提供了一种在氢活性基材表面上形成抗污染膜的方法，该方法是使基材表面与含有具有氟代烃基的表面活性材料和氯代硅烷基团的非水溶液接触，所述基材表面具有活性氢基团， 通过用用于制备单分子前体膜的非水有机溶液洗涤基底来除去残留在基底上的未反应的表面活性物质，在除去步骤后将吸附的单分子前体膜中未反应的氯硅烷与水反应，并将吸附的单分子膜 。 省略上述与非水有机溶液的洗涤步骤，并在基材表面上形成氟碳聚合物膜。

公开(公告)号：US5238746A

公开(公告)日：1993-08-24

申请号：US786824

申请日：1991-11-01

申请人： Mamoru Soga ,  Norihisa Mino ,  Kazufumi Ogawa ,  Yusuke Mochizuki ,  Tsuneo Shibata

发明人： Mamoru Soga ,  Norihisa Mino ,  Kazufumi Ogawa ,  Yusuke Mochizuki ,  Tsuneo Shibata

IPC分类号： B05D1/18 ,  C09D4/00

CPC分类号： B82Y30/00 ,  B05D1/185 ,  B82Y40/00 ,  C09D4/00 ,  Y10T428/31536 ,  Y10T428/3154 ,  Y10T428/31663

摘要： A substrate such as metal, ceramic, plastic, and glass material having a fluorine-based coating film having strong adhesion to a surface of the substrate wherein the substrate material comprises a monomolecular or polymer adsorption film formed on a base substrate surface and having siloxane bonds and a fluorine-based coating film provided on the adsorption film and a method of manufacturing a substrate material having a fluorine coating, which is simple and does not involve any electrolytic etching step which method comprises a step of forming a monomolecular or polymer adsorbed film having --Si-- bonds from dehydrochlorination or dealchoholation the bonded on the substrate surface and causing a silane-based surface active material, capable of reaction with an active hydrogen, to be brought in contact with the substrate surface, and laminating a fluorine-based polymer bonded by a cross-linking reaction process on the adsorbed film.

公开(公告)号：US06503567B2

公开(公告)日：2003-01-07

申请号：US09804854

申请日：2001-03-13

申请人： Kazufumi Ogawa ,  Norihisa Mino ,  Mamoru Soga

发明人： Kazufumi Ogawa ,  Norihisa Mino ,  Mamoru Soga

IPC分类号： B05D138

CPC分类号： B82Y30/00 ,  B05D1/185 ,  B82Y40/00 ,  C03C17/30 ,  Y10T428/261 ,  Y10T428/3154 ,  Y10T428/31612 ,  Y10T428/31663

摘要： At least one monomolecule film is formed on a transparent substrate surface directly or via a protective film. The monomolecule film is formed with chemical coupling of chlorosilane surface active compound, for example, of the formula: F(CF2)m(CH2)nSiRqX3—q where m is an integer of from 1 to 15, n is an integer of from 0 to 15 provided that the total of m and n is an integer of from 10 to 30 and R is an alkyl or an alkoxyl group, or F(CF2)m′(CH2)n′A(CH2)pSiRqX3−q where m represents an integer ranging from 1 to 8, n′ represents an integer ranging from 0 to 2, p represents an integer ranging from 5 to 25, q represents an integer ranging from 0 to 2, X represents a halogen atom or an alkoxyl group, R represents an alkyl or an alkoxyl group, and A represents —O—, a —COO— or —Si(CH3)2—. The transparent substrate such as glass is made hydrophobic and free of contamination.

摘要翻译： 至少一个单分子膜直接或通过保护膜形成在透明基板表面上。 单分子膜由氯硅烷表面活性化合物的化学偶合形成，例如下式：其中m为1至15的整数，n为0至15的整数，条件是m和n的总和为 10〜30的整数，R为烷基或烷氧基，m表示1〜8的整数，n'表示0〜2的整数，p表示5〜25的整数，q表示 表示0〜2的整数，X表示卤素原子或烷氧基，R表示烷基或烷氧基，A表示-O-，-COO-或-Si（CH 3）2 - 。 透明基板如玻璃被制成疏水性并且没有污染。

公开(公告)号：US5629088A

公开(公告)日：1997-05-13

申请号：US426477

申请日：1995-04-20

申请人： Kazufumi Ogawa ,  Mamoru Soga ,  Norihisa Mino

发明人： Kazufumi Ogawa ,  Mamoru Soga ,  Norihisa Mino

IPC分类号： B05D1/18 ,  C08J7/04 ,  C09D4/00 ,  D06M10/00 ,  D06M15/643 ,  D06M23/00 ,  B32B9/00

CPC分类号： B82Y30/00 ,  B05D1/185 ,  B82Y40/00 ,  C08J7/047 ,  C09D4/00 ,  D06M10/00 ,  D06M15/643 ,  D06M23/005 ,  C08J2483/00 ,  Y10T428/252 ,  Y10T428/2918 ,  Y10T428/2933 ,  Y10T428/2962 ,  Y10T428/2964 ,  Y10T428/31623 ,  Y10T428/31663 ,  Y10T428/31678

摘要： According to the invention, a durable hydrophilic absorbed film is formed on the surface of a substrate including metals, glass, plastics and the like in which the substrate has a surface layer containing hydroxyl groups or imino groups. The film is formed by covalently bonding chemical absorbents of silane groups containing a pluralilty of chloro groups to the substrate surfaces. The substrate 1 such as glass or nylon is dipped and held in a non-aqueous solution containing fluorocarbon groups and hydrocarbon groups containing chemical absorbents of silane groups containing a plurality of chloro groups including SiCl.sub.4, Cl.sub.3 SiOSiCl.sub.3, HSiCl.sub.3 or Cl.sub.3 SiOSiCl.sub.2 OSiCl.sub.3. After taking out the substrate 1 from the solution, drying it in a low moisture or substantially moistureless atmosphere to remove said non-aqueous solvents, the substrate is exposed to the air. A hydrophilic adsorbed ultra-thin film is thus formed by a dehydrochlorination reaction.

摘要翻译： 根据本发明，在包括金属，玻璃，塑料等的基板的表面上形成耐久的亲水性吸收膜，其中基板具有含有羟基或亚氨基的表面层。 该膜通过将含有多个氯基团的硅烷基团的化学吸收剂共价键合到基底表面而形成。 将基板1如玻璃或尼龙浸渍并保持在含氟碳基团的非水溶液中，并且含有含有多个氯基团的硅烷基团的化学吸收剂的烃基包括SiCl 4，Cl 3 SiOSiCl 3，HSiCl 3或Cl 3 SiOSiCl 2 OSiCl 3。 从溶液中取出基材1后，将其在低水分或基本无水的气氛中干燥以除去所述非水溶剂，将基材暴露于空气中。 因此，通过脱氯化氢反应形成亲水吸附的超薄膜。

公开(公告)号：US5466523A

公开(公告)日：1995-11-14

申请号：US250943

申请日：1994-05-31

申请人： Kazufumi Ogawa ,  Norihisa Mino ,  Mamoru Soga

发明人： Kazufumi Ogawa ,  Norihisa Mino ,  Mamoru Soga

IPC分类号： B05D1/18 ,  B29D11/00 ,  G02B1/10 ,  B32B7/04

CPC分类号： B82Y30/00 ,  B05D1/185 ,  B29D11/00865 ,  B82Y40/00 ,  G02B1/10 ,  Y10T428/261 ,  Y10T428/31663 ,  Y10T428/31667

摘要： A chemically adsorbed film containing hydrophilic groups is formed on a substrate such that it is chemically bonded by Si covalent bonds to the substrate. The adsorbed film has an improved hydrophilic property. In addition, the film provides an excellently durable and transparent fog-proof substrate. According to the method of the invention, a substrate containing hydrophilic groups is contacted with a non-aqueous solution containing a surface active material having straight chain molecules each having at one end a chlorosilyl group and at the other end at least one functional group selected from the group consisting of a bromo group, iodo group, cyano group, thiocyano group, chlorosilyl group etc. to cause a dehydrochlorination reaction between hydrophilic groups on the substrate surface and chlorosilyl groups of the surface active material, thereby forming a chemically adsorbed film on the substrate surface. The functional group at the other end of the surface active material is converted into at least one hydrophilic group selected from the group consisting of --OH, --COOH, --NH.sub.2, .dbd.NH, --N.sup.+ R.sub.3 X.sup.- (X representing a halogen atom, R represents a lower alkyl group), --NO.sub.2, --SH, and --S).sub.3 H groups.

摘要翻译： 在基板上形成含有亲水基团的化学吸附膜，使其通过Si共价键与基材进行化学键合。 吸附的膜具有改善的亲水性。 此外，该膜还提供了耐用和透明的防雾基材。 根据本发明的方法，将含有亲水基团的基材与含有直链分子的表面活性物质的非水溶液接触，所述表面活性物质的一端各自具有氯甲硅烷基，另一端与至少一个选自 由溴基，碘基，氰基，硫氰基，氯代甲硅烷基等组成的基团，从而在基材表面的亲水基团与表面活性物质的氯甲硅烷基之间产生脱氯化氢反应，从而在 基材表面。 将表面活性物质的另一端的官能团转化为至少一种选自-OH，-COOH，-NH 2，= NH，-N + R 3 X - （X表示卤素原子， R表示低级烷基），-NO 2，-SH和-S）3 H基。

公开(公告)号：US5443511A

公开(公告)日：1995-08-22

申请号：US89629

申请日：1993-07-12

申请人： Kazufumi Ogawa ,  Norihisa Mino ,  Mamoru Soga

发明人： Kazufumi Ogawa ,  Norihisa Mino ,  Mamoru Soga

IPC分类号： A61L33/00 ,  B05D1/18 ,  C09D4/00 ,  A61F2/28 ,  A61K6/08

CPC分类号： B82Y30/00 ,  A61L33/0088 ,  B05D1/185 ,  B82Y40/00 ,  B82Y5/00 ,  C09D4/00 ,  Y10S623/923

摘要： A medical member having active hydrogen groups such as hydroxyl, amino or imino groups at its surface, is dipped, either directly or after formation of an inner layer on its surface, into a solution. The solution is prepared by dissolving a surface active material, e.g., CF.sub.b 3 (CF.sub.2).sub.7 (CH.sub.2).sub.2 SiCl.sub.3 in a non-aqueous solvent. A dehydrochlorination reaction is brought about between active hydrogen groups at the surface of the member and SiCl groups of the surface active material, thus producing bonds ofCF.sub.3 (CF.sub.2).sub.7 (CH.sub.2).sub.2 Si(O--).sub.3over the entire surface. A fluorine-containing monomolecular film is formed, which is chemically (or covalently) bonded to the member surface and has a thickness at the nanometer level. Since the chemically adsorbed film is covalently bonded to the member or inner layer, it is chemically stable and difficult to separate. Excellent medical members can be obtained when the invention is applied to an artificial tooth, a joint, a bone, a blood bag, a catheter, a blood transportation tool, a dialysis equipment part, an operation thread, a medical implant and an operation tool.

摘要翻译： 在其表面具有羟基，氨基或亚氨基的活性氢基团的医学成分在其表面上直接或内层形成后溶解成溶液。 通过将表面活性物质例如CFb 3（CF 2）7（CH 2）2 ClCl 3溶解在非水溶剂中来制备溶液。 在构件表面的活性氢基团和表面活性物质的SiCl基团之间产生脱氯化氢反应，从而在整个表面上产生CF 3（CF 2）7（CH 2）2 Si（O - ）3的键。 形成化学（或共价）结合到构件表面并具有纳米级厚度的含氟单分子膜。 由于化学吸附的膜共价结合到构件或内层，因此化学稳定且难以分离。 将本发明应用于人造牙，关节，骨，血袋，导管，血液输送工具，透析设备部件，手术线，医疗植入物和操作工具时，可以获得优异的医疗部件 。

公开(公告)号：US5425989A

公开(公告)日：1995-06-20

申请号：US145669

申请日：1993-11-04

申请人： Kazufumi Ogawa ,  Norihisa Mino ,  Mamoru Soga

发明人： Kazufumi Ogawa ,  Norihisa Mino ,  Mamoru Soga

IPC分类号： B05D1/18 ,  B05D5/08 ,  C09D4/00 ,  B32B7/04

CPC分类号： B82Y30/00 ,  B05D1/185 ,  B82Y40/00 ,  C09D4/00 ,  B05D5/08 ,  Y10T428/261 ,  Y10T428/266 ,  Y10T428/268 ,  Y10T428/31536 ,  Y10T428/31663

摘要： A chemically adsorbed film having a surface layer containing fluorine groups and a stem layer chemically bonded by siloxane bonds to a substrate is formed on the surface of a frictional portion of a machine part such as a gear or a bearing or on the surface of a game ball. An excellently self-lubricating low frictional resistance machine part or game ball thus can be obtained. A frictional portion of a gear or the like, made of SiO.sub.2 or like ceramic material, is dipped and held in a solution containing a surface active material, e.g., CF.sub.3 (CF.sub.2).sub.7 (CH.sub.2).sub.2 SiCl.sub.3 dissolved in a non-aqueous solvent. A hydrochloric acid removal reaction is brought about between SiCl groups of the material, which contains a fluorocarbon and a chlorosilane group, and hydroxyl groups numerously present on the SiO2 surface, thus forming bonds ofCF.sub.3 (CF.sub.2).sub.7 (CH.sub.2).sub.2 Si(O--).sub.3over the entire frictional portion surface. A fluorine-containing monomolecular film thus is formed, which is chemically bonded to the substrate and has a thickness of about 1.5 nm.

摘要翻译： 在机械部件例如齿轮或轴承的摩擦部分的表面上或游戏表面上形成具有含氟基团的表面层和通过硅氧烷键合到基材上的茎层的化学吸附膜 球。 因此可以获得优异的自润滑低摩擦阻力机器部件或游戏球。 将由SiO 2或类似陶瓷材料制成的齿轮等的摩擦部分浸渍并保持在含有溶解在非水溶剂中的表面活性物质例如CF 3（CF 2）7（CH 2）2 ClCl 3）的溶液中。 在含有碳氟化合物和氯硅烷的材料的SiCl基团和SiO 2表面上大量存在的羟基之间产生盐酸去除反应，从而形成CF 3（CF 2）7（CH 2）2 Si（O- ）3在整个摩擦部分表面上。 因此，形成与基板化学键合并且具有约1.5nm的厚度的含氟单分子膜。

公开(公告)号：US5407709A

公开(公告)日：1995-04-18

申请号：US148499

申请日：1993-11-08

申请人： Kazufumi Ogawa ,  Norihisa Mino ,  Mamoru Soga

发明人： Kazufumi Ogawa ,  Norihisa Mino ,  Mamoru Soga

IPC分类号： B05D1/18 ,  C03C17/42 ,  C08J7/04 ,  C09D4/00 ,  C09D183/02 ,  C09D183/08 ,  B05D3/06

CPC分类号： B82Y30/00 ,  B05D1/185 ,  B82Y40/00 ,  B82Y5/00 ,  C03C17/42 ,  C08J7/047 ,  C09D183/02 ,  C09D183/08 ,  C09D4/00 ,  C08J2483/00 ,  Y10T428/261 ,  Y10T428/31612 ,  Y10T428/31663

摘要： This invention provides for an anti-contaminating film which is adsorbed to a substrate surface. The film contains a --Si-- group and fluorocarbon group. The --Si-- group is covalently bonded to the substrate surface. It also provides a forming method of an anti-contaminating film on a hydrogen active substrate surface by contacting the substrate surface with a non-aqueous solution, containing a surface active material having fluorocarbon groups and chlorosilane groups, the substrate surface having active hydrogen groups, removing unreacted surface active material remaining on the substrate by washing the substrate with a non-aqueous organic solution for making a monomolecular precursor film, reacting chlorosilane groups unreacted in the adsorbed monomolecular a precursor film with water after the removing step, and drying the adsorbed monomolecular film.

摘要翻译： 本发明提供一种吸附在基材表面上的防污膜。 该片含有-Si-基和氟碳基。 -Si-基团共价结合到基材表面。 还通过使基板表面与含有具有氟代烃基的表面活性物质和氯代硅烷基的非水溶液接触，具有活性氢基团的基材表面，在氢活性基材表面上提供抗污染膜的形成方法， 通过用用于制备单分子前体膜的非水有机溶液洗涤基底来除去残留在基底上的未反应的表面活性物质，在除去步骤后将吸附的单分子前体膜中的未反应的氯硅烷与水反应，并将吸附的单分子 电影。