Fluorocarbon-based polymer lamination coating film and method of manufacturing the same

Abstract: The invention seeks to provide 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. 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 adsoprtion film. The invention also seeks to provide a method of manufacturing a substrate material having a fluorine coating, which is simple and does not involve any electrolytic etching step. The 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.

Description: This invention relates to materials such as e.g. metals, ceramics, plastics or glass, which are laminated with a fluorine resin coating. The laminated materials (laminates) may be used as frying pans, pans and other cooking tools, copying rolls, stainless steel rolls, vessels or plates. Generally, a material with a fluorine resin coating is obtained by making the surface coarse by means of electrolytic etching or surface roughening for increased adhesion with a fluorine-based polymer. The surface is coated with a suspension of a fluorine-based polymer, followed by baking. Obtained in this way, however, the surface and fluorine-based polymer coating are coupled together weakly for there are no chemical bonds between the two. Therefore, when the material is used for a long time, the adhesion deteriorates resulting in a separation of the fluorine-based coating from the surface of the material. In addition, since the surface is electrolytically etched or roughened as a treatment for making it coarse, the manufacturing process is complicated, increasing the cost of manufacture. Therefore, it has been requested that a material with a fluorine-based coating having excellent adhesion to the surface be developed. Furthermore, it has been requested that a method of manufacturing a material with a fluorine-based coating, which is simple and free from any electrolytic etching or surface roughening step be developed. US-A-4539061 discloses a process for the production of built-up films by the stepwise adsorption of individual monolayers. EP-A-0363924 discloses a lubricant for recording media and a method for preparing lubricating layers for recording media. US-A-4863794 discloses a glass fiber reinforced fluorocarbon polymer coating composition. EP-A-0482613 discloses a laminate comprising a substrate, an inorganic siloxane-based film formed as an inner layer and a fluorocarbon-based polymer film formed as an outer layer. The inorganic inner layer is formed from inorganic molecules such as SiCl 4 . The primary object of this invention is to provide a laminate comprising a substrate having provided thereon a fluorocarbon-based polymer lamination coating film comprising at least an adsorbed layer formed as an inner layer and a fluorocarbon-based polymer layer formed as an outer layer, the substrate surface and the inner layer being bonded with covalent bonds, and the inner layer and the outer layer being bonded with cross-linking bonds. Another object of this invention is to provide a method of manufacturing such a laminate. The present invention provides a laminate comprising a substrate, a siloxane-based monomolecular or polymer inner layer covalently bonded to the surface of the substrate, and an outer layer of a fluorine-based polymer bonded to said inner layer with cross-linking bonds, with the proviso that said siloxane-based monomolecular or polymer inner layer is no inorganic layer. It is preferable that the inner layer is a siloxane-based monomolecular layer bonded to said substrate through covalent siloxane bonds. It is preferable that the inner layer is a siloxane-based polymer layer bonded to said substrate surface through covalent siloxane bonds. It is preferable that the inner layer is formed by covalently bonding to the substrate surface a silane-based surface active material selected from the group consisting of alkyl silane halides, alkenyl silane halides, alkynyl silane halides, alkoxyl-based silanes and fluorine derivatives thereof. It is preferable that the substrate is selected from metals, ceramics, glass and plastics. Further, the present invention provides a method of manufacturing a laminate, comprising the steps of contacting a substrate surface having active hydrogen groups with a silane-based surface active material, washing said substrate with a non-aqueous solution to remove surface active material remaining on the surface without reaction, washing said substrate with water or exposing said substrate to the air to react with moisture, thereby forming a covalently bonded siloxane-based monomolecular inner layer on the substrate surface, and laminating a fluorine-based polymer on the inner layer by a cross-linking reaction process. Moreover, the present invention provides a method of manufacturing a laminate, comprising the steps of contacting a substrate surface having active hydrogen groups with a silane-based surface active material, washing said substrate with water or exposing said substrate to the air to react with moisture, thereby forming a covalently bonded siloxane-based polymer inner layer on the substrate surface, and laminating a fluorine-based polymer on the inner layer by a cross-linking reaction process. It is preferable that the silane-based surface active material is selected from the group consisting of alkyl silane halides, alkenyl silane halides, alkynyl silane halides, alkoxyl-based silanes and fluorine derivatives thereof. It is preferable that the covalently bonded inner layer is formed by bringing the substrate in contact with a non-aqueous organic solvent containing the silane-based surface active material, thereby causing chemical bonding of the silane-based surface active material to the substrate surface, and the fluorine-based polymer film is formed on said covalently bonded inner layer by coating the fluorine-based polymer thereon. It is preferable that the fluorine-based polymer is irradiated. It is preferable that at least the silane-based surface active material or the fluorine-based polymer contains C=C and/or C≡C bonds. It is preferable that the fluorine-based polymer is a solvent soluble type polymer. It is preferable that the substrate is selected from metals, ceramics, glass and plastics. It is preferable that the substrate is a plastic material treated in a plasma or corona atmosphere containing oxygen. Figure 1 is a fragmentary schematic side sectional view, enlarged in scale to the molecular level, showing a metal material used in this invention, before irradiation; and Figure 2 is a fragmentary schematic side sectional view, enlarged in scale to the molecular level, showing a metal material used in this invention, after irradiation. The product of Figure 2 is a laminate according to the present invention. Now, the invention will be described with reference to the drawings. As shown in Figure 1, for instance, on the entire surface of a metal plate 1, an inner layer 2 having siloxane bonds is formed by causing an adsorption reaction of a silane-based surface active material having an ethylene group at a distal end of the molecule by a chemical adsorption process. The metal substrate 1 used according to the invention may be of any metal material, e.g., aluminium, copper, iron, stainless steel, nickel, silver, platinum, gold and various alloys of these metals. In particular, a base metal material such as aluminum, copper or iron permits ready formation of a metal oxide layer on the surface and the oxygen in the metal oxide film reacts with silicon in the silane-based surface active material to form siloxane bonds. Examples of the silane-based surface active material used according to the invention are chlorosilane-based compounds or alkoxylsilane-based compounds represented by the following formulae: (CH 3 (CH 2 ) n ) a SiCl 4-a ((CH 3 ) 3 SiC≡C(CH 2 ) n ) a SiCl 4-a (CH 2 =CH(CH 2 ) n ) a SiCl 4-a ((CF 3 ) 3 SiC≡C(CF 2 )) a SiCl 4-a (CF 2 =CF(CF 2 ) n ) a SiCl 4-a (CH 2 =CH(CF 2 ) n -CH 2 CH 2 ) a SiCl 4-a (CH 3 (CH 2 ) n ) a Si(OR) 4-a ((CH 3 ) 3 SiC≡C(CH 2 ) n ) a Si(OR) 4-a (CH 2 =CH(CH 2 ) n ) a Si(OR) 4-a ((CF 3 ) 3 SiC≡C(CF 2 ) n ) a Si(OR) 4-a (CF 2 =CF(CF 2 ) n ) a Si(OR) 4-a (CH 2 =CH(CF 2 ) n -C 2 H 4 ) a Si(OR) 4-a (where n represents an integer, preferably 5 to 25, a represents an integer of 1 to 3, and R is a lower alkyl group, preferably CH 3 or C 2 H 5 .) Particularly preferable compounds are those based on trichlorosilane (where a in the above formulae (1) to (6) is 1 ). This is because their molecules have a single hydrocarbon chain coupled to silicon and firmly bonded transversally by siloxane bonds, thus providing excellent mechanical strength. As a method of adsorption of the silane-based surface active material, the silane-based surface active material is used by e.g. dissolving it in a non-aqueous solvent, e.g., hexadecane, cyclohexane and carbon tetrachloride. For example, it is necessary only to prepare a solution containing 80 % wt of hexadecane, 12 % wt of carbon tetrachloride and 8 % wt of chloroform by dissolving the silane-based surface active material to a concentration of 2 x 10 -3 to 5 x 10 -2 Mol/l and dipping a metal plate in the solution for one hour. The metal plate 1 has natural oxide formed on its surface, and the surface contains hydroxyl groups. Thus, chlorosilyl groups of the silane-based surface active material and hydroxyl groups react to form bonds of -SiO- on the surface, thus forming one monomolecular layer in a chemically bonded (covalent bond) form via oxygen atoms as shown in equation [1]. And then, the substrate was washed with a non-aqueous solution, e.g., fleon 113 or chloroform, to remove the material remaining on the surface without reaction, followed by washing with water or exposing to the air to react with moisture in the air, and the -SiCl group was converted into a -SiOH group as shown in equation [2]. It was formed a monomolecular adsorbed film on the substrate. And then, the silanol groups (-SiOH) were subjected to a dehydration reaction to crosslink by siloxan bonds (-SiO-) as shown in equation [3]. If the substrate was not washed with the non-aqueous solution, a polymer inner layer was formed on the substrate. By the consecutive reaction, a single adsorbed monomolecular layer or polymer layer (inner layer) was never separated in a checkerboard test. It is preferable in this invention that the inner layer is a siloxane based monomolecular adsorbed layer. The single adsorbed monomoleclar layer was formed to a thickness of nanometer level such that it was chemically bonded (covalent bond) to a protective layer via oxygen atoms. Alkoxysilane groups of the silane-based surface active material and hydroxyl groups react to form bonds as shown in equation [4]. The reaction proceeds substantially in the same way as shown in equations [1] to [3]. (wherein R is a lower alkyl group, preferably CH 3 or C 2 H 5 .) Further, the concentration of hydroxyl groups contained on the surface may be increased to raise the adsorption efficiency by forming an oxide protective film by treating the metal surface with an aqueous alkali solution. As the substrate having a surface containing hydroxyl groups used according to the invention, metal and non-metal elements and ceramics may be used. According to the invention, since hydrophilic groups formed on the substrate and chlorosilyl groups are reacted, where metals are used, base metals such as aluminum, copper and iron are suitable. Further, a material without any oxide film such as plastic substrates are used after a surface treatment to render them hydrophilic. The surface treatment may be carried out by usual means such as a treatment in a plasma atmosphere containing oxygen at 100 W, for 20 minutes or a corona treatment. However, a surface oxygen treatment is not necessary for plastics containing -NH groups or -NH 2 groups, such as polyamide or polyurethane substrates. Because -NH or -NH 2 groups have active hydrogen, it is easy to cause the dehydrochlorination reaction with chlorosilyl groups of the surface active material. Thus, chlorosilyl groups of the silane-based surface active material and imino groups (-NH) react to form bonds as shown in equation [5]. The reaction proceeds substantially in the same way as shown in equations [1] to [3]. Subsequently, a solution or suspension of a fluorine-based polymer is coated on the inner layer 2, followed by drying and baking to form a fluorine-based coating layer 3 such as shown in Figure 1. Since the fluorine-based coating layer 3 is formed on the inner layer 2 having siloxane bonds, the main chains are entangled at the interface with the hydrocarbon group component of the inner layer 2. Examples of the fluorine-based polymer molecule constituting the fluorine-based coating layer 3 are copolymers of denatured fluorine polystyrene, ethylene polyfluoride, vinylidene polyfluoride, polytetrafluoroethylene and tetrafluoroethylene with perfluoroalkylvinylether. Among these compounds, the greater the fluorine substitution becomes, the more superior the hydrophilic and oil-repelling properties are. An example polymer has the following repetition unit: (a) -(CF 2 ) m - (b) (c) -(CF 2 ) m -CH=CH- (d) -(CF 2 ) m -C≡C- (e) (f) where m, and x represent integers, m is most preferably 5 to 500, x is preferably 1 to 10. A polymer with less fluorine content (e.g., denatured fluorine polystyrene, ethylene polyfluoride and vinylidene polyfluoride) can be dissolved in a selected solvent, chosen so that the entangling of molecule chains can be increased. With a structure such as shown in Figure 1, where the inner layer 2 contains unsaturated bonds such as C=C bonds and also the fluorine-based coating layer 3 contains unsaturated bonds such as C=C bonds, irradiation causes breakage of C=C bonds in the inner layer 2 having siloxane bonds and those in the fluorine-based coating layer 3, such as shown in Figure 2, thus forming chemical bonds between the inner layer 2' and the fluorine-based coatings layer 3'. In Figures 1 and 2, unsaturated C=C bonds are contained in the inner layer 2 and the fluorine-based coating layer 3. According to the invention, however, only the inner layer 2 or the fluorine-based coating layer 3 may contain C=C bonds. The unsaturated bond may be a triple bond such as a C≡C bond as well as a double bond such as a C=C bond. For efficient cross-linking with the inner layer 2' with irradiation, however, a fluorine-based polymer containing C=C or C≡C bonds in the main or side chain as shown in Figure 2 is preferred so that an increased mechanical strength can be obtained. The following may be used as the radiation for irradiation of the fluorine-based coating layer 3; an electron beam, a corona treatment, a neutron beam, alpha rays, beta rays and gamma rays. With this structure, it is most preferably that the monomolecular layer, coupled via the siloxane bonds to the metal plate and the fluorine-based polymer coating layer, can attain a status of chemical bonding. For this reason, it is possible to obtain a metal material with a fluorine-based polymer coating, which is never separated even after long use of the material and has excellent adhesion compared to the prior art fluorine-based coating layer, for which only the anchor effect has been expected. With this method of treating the material (eg. metal), e.g. a monomolecular layer of a silane-based surface active material is formed on a metal plate by a chemical adsorption process, and a fluorine-based polymer is coated by a coating process on the monomolecular layer. Thus, an electrolytic etching or a surface roughening step is unnecessary, and the method of manufacturing a laminate is simplified. The invention can widely be applied to the following uses. Materials made of e.g. metal, cermic, plastic, glass, wood or stone may be used as the substrate. The surface of the substrate can also be coated with paint or the like. Examples of cutlery: a kitchen knife, scissors, a knife, a cutter, a graner, a razor, hair clippers, a saw, a plane, a chisel, a gimlet, a badkin, bite (cutting tools), the edge of a drill, the edge of a mixer and a juicer blade, a blade of a mill, a blade of a lawnmower, a punch, a straw cutter, a staple of a stapler, a can opener or a surgical knife. Examples of needles: an acupuncture, a needle, a sewing needle, a matting needle, an injection needle, a surgical needle, a safety pin. Examples of products in pottery (ceramics) industry: products made of pottery, glass, ceramics or enameled products. For example, sanitary potteries (a chamber pot, a wash-bowl, a bathtub), tableware (a rice-bowl teacup, a dish (plate), a bowl, a teacup, a glass, a bottle, a coffee-pot (siphon), a pan, an earthenware mortar, a cup), vases (a flower bowl, a flowerpot, a bud vase), water tanks (a breeding cistern, an aquarium water tank), chemical experiment appliances (a beaker, a reactor vessel, a test tube, a flask, a laboratory dish, condenser, a mixing rod, a stirrer, a mortar, a bat, a syringe) a roof tile, and enameled ware, an enameled washbowl, and an enameled pan. Examples of molding parts: dies for press molding, dies for cast molding, dies for injection molding, dies for transfer molding, dies for compression molding, dies for transfer molding, dies for inflation molding, dies for vaccum molding, dies for blow forming, dies for extrusion molding, dies for fiber spinning, and a calendar processing roll. Examples of forming molds for food: cake, cookies, bread-baking, chocolate, jelly, ice cream, an oven ware, and an ice tray. Examples of cookware: kitchen utensils (a pan and a pot), a kettle, a pot, a frying-pan, a hot plate, a toasting net, and a takoyaki plate. Examples of resin(s): a polyolefin such as a polypropylene and polyethylene, a polyvinylchloride plastic, a polyamide, a polyimide, a polyamideimide, a polyester, a aromatic polyester, a polycarbonate, a polystyrene, a polysulfide, a polysulfone, a polyethersulfone, a polyphenylenesulfide, a phenolic resin, a furan resin, a urea resin, a epoxy resin, a polyurethane, a silicon resin, an ABS resin, a methacrylic resin, an acrylate resin, a polyacetal, a polyphenylene oxide, a poly methylepentene, a melamine resin, a alkyd resin, and a unsaturated polyester cured resin. Examples of rubber(s): a styrene-butadien rubber, a butyl rubber, a nitrile rubber, a chloroprene rubber, a polyurethane rubber, and a silicone rubber. Examples of household electrical appliances: a refrigerator of freezing machines, a freezer, an air conditioner, a juicer, a mixer, a blade of an electric fan, a lighting apparatus, a dial plate, and a dryer(or drier) for perm. Examples of sports articles: skis, a pole vaulting pole, a boat, a yacht, a surfboard, a fishing rod, and a float. Examples applying to vehicle parts: (1) ABS resin: a lamp cover, an installment pannel, trimming parts, a protector for a motorcycle. (2) Cellulose plastic: a car mark, a steering wheel (3) FRP (fiber reinforced plastics): a bumper, an engine cover (jacket) (4) Phenolic resin: a brake (5) Polyacetal: wiper gear, a gas valve (6) Polyamide: a radiator fan (7) Polyarylate (polycondensation polymerization by bisphenol A and pseudo phtalic acid): a direction indicator lamp (or lense), a cowl board lense, a relay case (8) Polybutylene terephthalate (PBT): a rear end, a front fender (9) Poly(amino-bismaleimide) : engine parts, a gear box, a wheel, a suspension drive system (10) Methacrylate resin: a lamp cover lens, a meter pannel and its cover, center mark (11) Polypropylene: a bumper (12) Polyphenylene oxide : a radiator grille, a wheel cap (13) polyurethane: a bumper, a fender, an installment pannel, a fan (14) Unsaturated polyester resin: a body, a fuel tank, a heater housing, a meter pannel. Examples of office supplies: a desk, a chair, a bookshelf, a rack, a telephone stand table, a rule (measure), and a drawing instrument. Examples of building materials: materials for a roof, and outer wall and interiors. Roof materials such as brick, slate and tin (a galvanized iron sheet). Outer wall materials such as wood (including processed manufactured wood), mortar, concrete, ceramic sizing, metalic sizing, brick, stone, plastic and metal like aluminium. Interior materials such as wood (including processed wood), metal like aluminium, plastic, paper, and fiber. Examples of building stones: granite, marble and others for use as a building,a building material, an architecture, an ornament, a bath, a grave stone, a monument, a gatepost, a stone wall, and a paving stone. Examples of a thermos bottle, a vacuum bottle, and a vacuum vessel. Examples of a highly resisiting voltage insulator such as a power supplying insulator or a spark plug, which have high hydrophobic, oilphobic and prevention of contamination properties. Examples of the invention will now be given where aluminum is used as a metal material. Example 1 An aluminum plate (2 x 5 x 0.1 cm) was dipped in 10 -2 mol/l ω-nonadecenyltrichlorosilane solution (containing 80 % wt hexadecane, 12 % wt carbon tetrachloride and 8 % wt chloroform) at room temperature in an nitrogen atmosphere for 60 minutes, followed by washing with chloroform and then with water to obtain a monomolecular layer formed on the aluminum surface. On the surface of this aluminum plate was spray coated a suspension of a polymer having the following repetition unit [-(CF 2 -CF 2 ) 8 -CH=CH-] n (where n is a natural number, preferably 5 to 500), followed by drying at 150 °C for 10 minutes and then baking at 380 °C for 20 minutes, thus forming a fluorine-based coating layer with a thickness of 500 µm. A sample produced in the above way was irradiated with an electron beam of 300 keV and 0.02 Mrads/1 for one minute. Example 2 The same experiment as in Example 1 was conducted except that ω-nonadecenyltrichlorosilane was replaced with 19-trimethylsilyl-18-nonadecenyltrichlorosilane. Example 3 The same experiment as in Example 1 was conducted except that the fluorine-based polymer was replaced with a polymer having the repetition unit (where n is a natural number, preferably 5 to 500) Example 4 The same experiment as in Example 1 was conducted except that the fluorine-based polymer was replaced with a polymer having the repetition unit (where n is a natural number, preferably 5 to 500) Example 5 The same experiment as in Example 1 was conducted except that the fluorine-based polymer was replaced with a copolymer of tetrafluoroethylene and perfluoroalkylvinylether. Example 6 The same experiment as in Example 1 was conducted except that ω-nonadecenyltrichlorosilane and the fluorine-based polymer were respectively replaced with nonadecenyl-trichlorosilane and a copolymer of tetrafluoroethylene and perfluoroalkylvinylether. Example 7 The same experiment as in Example 1 was conducted except that ω-nonadecenyltrichlorosilane and the fluorine-based polymer were respectively replaced with nonadecenyl-trichlorosilane and a copolymer of tetrafluoroethylene and perfluoroalkylvinylether and the electron beam irradiation was dispensed with. Example 8 An aluminum plate (2 x 5 x 0.1 cm) was dipped in 10 -2 mol/l ω-nonadecenyltrichlorosilane solution (containing 80 % wt hexadecane, 12 % wt carbon tetrachloride and 8 % wt chloroform) at room temperature in an nitrogen atmosphere for 60 minutes, followed by a reaction with water to obtain a polymer layer (inner layer) formed on the aluminum surface. On the surface of this aluminum plate was spray coated a suspension of a polymer having the following repetition unit [-(CF 2 -CF 2 ) 8 -CH=CH-] n (where n is a natural number, preferably 5 to 500), followed by drying at 150 °C for 10 minutes and then baking at 380 °C for 20 minutes, thus forming a fluorine-based coating layer with a thickness of 500 µm. A sample produced in the above way was irradiated with an electron beam of 300 keV and 0.02 Mrads/1 for one minute. Comparative example 1 An aluminum plate (2 x 5 x 0.1 cm) was electrolytically etched and then spray coated with a suspension of polytetrafluoroethylene, followed by drying and baking under the same conditions as in Example 1 to form a fluorine-based coating layer. Peel tests were conducted on the samples of Examples 1 to 8 and the Comparative example 1. Table 1 shows the results of peel(or adhesion) strength measurements conducted by setting the width of the fluorine-based coating layer under a test to 10 mm. Sample Peel(or adhesion) strength (kg/10mm) (N/10mm) Example 1 15.0 147.0 Example 2 17.0 166.6 Example 3 20.0 196.0 Example 4 21.0 205.8 Example 5 14.0 137.2 Example 6 12.0 117.6 Example 7 10.0 98.0 Example 8 14.0 137.2 Comparative example 1 6.0 58.8 The peel (or adhesion) strength of the fluorine-based coating layers produced in the examples and the comparative example was measured as follows. (1) A sample with a width of 30 mm and a length of 60 mm, and pre-adhesion of fluorine-based resin plate such as FEP (tetrafuoroethylene-hexafluoropropylene copolymer) resin plate at 300 °C ∼ 350 °C by heat press roller. (2) Main heat adhesion by electric furnance at 350 °C for 15 minutes. (3) Cut the test piece with a width of 10 mm, and peel (or adhesion) strength was measured by ordinary adhesion test apparatus. As is seen from Table 1, all of the laminates according to the invention had peel strengths of 10.0 kg/10mm (98 N/10mm) or above, indicating superiority in adhesion to that of the comparative example, in which the peel (or adhesion) strength was 6.0 kg/10mm (58.8 N/10mm). While the above examples used aluminum plates, the same effects could be obtained with such metals as steel, stainless steel, iron, copper, nickel, Alumite, and zinc and also alloys of these metals. As has been described in the foregoing, the laminate according to the invention has a fluorine-based coating layer bonded to a substrate via siloxane bonds and has excellent adhesion compared to the prior art metal plates. Further, there is no need of electrolytic etching as a treatment prior to the fluorine-based coating layer formation. Thus, it is possible to simplify the manufacturing process and to reduce manufacturing costs. As has been shown, the invention is greatly beneficial to the industry.

Claims: A laminate comprising a substrate, a siloxane-based monomolecular or polymer inner layer covalently bonded to the surface of the substrate, and an outer layer of a fluorine-based polymer bonded to said inner layer with cross-linking bonds, with the proviso that said siloxane-based monomolecular or polymer inner layer is no inorganic layer. The laminate according to claim 1, wherein said inner layer is a siloxane-based monomolecular layer bonded to said substrate through covalent siloxane bonds. The laminate according to claim 1, wherein said inner layer is a siloxane-based polymer layer bonded to said substrate surface through covalent siloxane bonds. The laminate according to claim 1, wherein said inner layer is formed by covalently bonding to the substrate surface a silane-based surface active material selected from the group consisting of alkyl silane halides, alkenyl silane halides, alkynyl silane halides, alkoxyl-based silanes and fluorine derivatives thereof. The laminate according to claim 1, wherein the substrate is selected from metals, ceramics, glass and plastics. A method of manufacturing a laminate according to claim 1, comprising the steps of contacting a substrate surface having active hydrogen groups with a silane-based surface active material, washing said substrate with a non-aqueous solution to remove surface active material remaining on the surface without reaction, washing said substrate with water or exposing said substrate to the air to react with moisture, thereby forming a covalently bonded siloxane-based monomolecular inner layer on the substrate surface, and laminating a fluorine-based polymer on the inner layer by a cross-linking reaction process. A method of manufacturing a laminate according to claim 1, comprising the steps of contacting a substrate surface having active hydrogen groups with a silane-based surface active material, washing said substrate with water or exposing said substrate to the air to react with moisture, thereby forming a covalently bonded siloxane-based polymer inner layer on the substrate surface, and laminating a fluorine-based polymer on the inner layer by a cross-linking reaction process. The method according to claim 6 or 7, wherein the silane-based surface active material is selected from the group consisting of alkyl silane halides, alkenyl silane halides, alkynyl silane halides, alkoxyl-based silanes and fluorine derivatives thereof. The method according to claim 6 or 7, wherein the covalently bonded inner layer is formed by bringing the substrate in contact with a non-aqueous organic solvent containing the silane-based surface active material, thereby causing chemical bonding of the silane-based surface active material to the substrate surface, and the fluorine-based polymer film is formed on said covalently bonded inner layer by coating the fluorine-based polymer thereon. The method according to claim 6 or 7, wherein said fluorine-based polymer is irradiated. The method according to claim 6 or 7, wherein at least the silane-based surface active material or the fluorine-based polymer contains C=C and/or C≡C bonds. The method according to claim 6 or 7, wherein said fluorine-based polymer is a solvent soluble type polymer. The method according to claim 6 or 7, wherein said substrate is selected from metals, ceramics, glass and plastics. The method according to claim 6 or 7, wherein said substrate is a plastic material treated in a plasma or corona atmosphere containing oxygen.

Inventors: MINO NORIHISA, MOCHIZUKI YUSUKE, OGAWA KAZUFUMI, SHIBATA TSUNEO, SOGA MAMORU, MINO, NORIHISA, MOCHIZUKI, YUSUKE, OGAWA, KAZUFUMI, SHIBATA, TSUNEO, SOGA, MAMORU
Applicants: MATSUSHITA ELECTRIC IND CO LTD, MATSUSHITA ELECTRIC INDUSTRIAL CO., LTD.
Application year: 1991
Main classification: B05D1
IPC codes: B05D1, C09D4