Method of manufacturing a fluorocarbon-based coating film

Abstract

A method of contacting a substrate having a surface containing hydroxyl groups with a non-aqueous solution containing a material having a chrolosilyl group; washing if desired; coating the substrate with a non-aqueous solvent containing a compound having a fluorocarbon group and a chlorosilane group or a solvent containing a compound containing a fluorocarbon group and an alkoxysilane; and baking the substrate if necessary in order to form a fluorocarbon-based polymer coating film chemically bonded to the substrate surface. The hydroxyl groups on the substrate surface and chlorosilyl groups are reacted to form a thin film having a large number of silanol groups (-SiOH) capable of connecting the polymer coating film to the substrate to form a heat-, weather-, and wear-resistant film on various surfaces.

We claim:  
     
       1. A method of manufacturing a fluorocarbon-based polymer coating film comprising the steps of: 
       contacting a substrate having a surface containing hydroxyl groups with a non-aqueous solvent comprising a material comprising chlorosilyl groups;  
       coating the contacted substrate surface with either (1) a non-aqueous solvent comprising a compound comprising a fluorocarbon group, and a chlorosilyl group or (2) a solvent comprising (a) compound comprising a fluorocarbon group, and an alkoxysilane  alkoxysilyl group or (b) a compound of the following formula:  
       
         
           CF 3 —(CF 2 ) n —(R) m —SiY q (OA) 3-q    
         
       
       where n represents 0 or an integer; R represents an alkyl  alkylene group or a hydrocarbon substituted group containing C═C, or C≡C, a silicon atom or an oxygen atom; m represents 0 or 1; Y represents a hydrogen atom, an alkyl group, an alkoxy group, a fluorine-containing alkoxy group or a fluorine-containing alkyl group; A represents a hydrogen atom; and q represents 0, 1 or 2; and 
       baking the substrate after said contacting step and coating step.  
     
     
       2. The method of manufacturing the fluorocarbon-based polymer coating film according to  claim 1 , wherein the substrate is made of the member of a group consisting of glass, metals, plastics, and ceramics. 
     
     
       3. The method of manufacturing the fluorocarbon-based polymer coating film according to  claim 1 , wherein the substrate is mace  made of a plastic material treated in a plasma atmosphere containing oxygen. 
     
     
       4. The method of manufacturing the fluorocarbon-based polymer coating film according to  claim 1 , wherein said material comprising chlorosilyl groups comprises a member of the group consisting of SiCl 4 , SiHCl 3 , SiH 2 Cl 2  and Cl—(SiCl 2 O) n —SiCl 3 , wherein n is an integer. 
     
     
       5. A method of manufacturing the fluorocarbon-based polymer coating film according to  claim 1 , wherein said compound having a fluorocarbon group and a chlorosilyl group is represented by a formula: CF 3 —(CF 2 —(R) m —SiX p Cl 3-p  where n represents 0 or an integer; R represents an alkyl  alkylene group or a hydrocarbon substituted group containing C═C or C≡C, a silicon atom or an oxygen atom; m represents 0 or 1, X represents a hydrogen atom, an alkyl group, an alkoxy group, a fluorine-containing alkoxy group or a flourine-containing alkyl group; p represents 0, 1 or 2. 
     
     
       6. A method of manufacturing the fluorocarbon-based polymer coating film according to  claim 1 , wherein said compound (a) is represented by a formula: 
       
         
           CF 3 —(CF 2 ) n —(R) m SiY q′ (OA′) 3-q′   
         
       
       where n represents 0 or an integer; 
       R represents an alkyl  alkylene group or a hydrocarbon substituted group containing C═C or C≡C, a silicon atom or an oxygen atom; m represents 0 or 1;  
       Y represents a hydrogen atom, an alkyl group, an alkoxy group, a fluorine-containing alkoxy group or a fluorine-containing alkyl group;  
       OA′ represents an alkoxy group; and  
       q′ represents 0, 1 or 2.  
     
     
       7. A method of manufacturing the fluorocarbon-based polymer coating film according to  claim 1 , wherein a material represented by a formula: SiX s Cl 4-s  where X represents a hydrogen atom or an alkyl group, and s represents 0, 1 or 2; is added to the non-aqueous solvent containing the compound having a fluorocarbon group and a chlorosilyl group. 
     
     
       8. The method of manufacturing the fluorocarbon-based polymer coating film according to  claim 1 , wherein a material represented by a  the formula:  SiY t  (OA″) 4-t  where Y represents an alkyl group; , A″ represents a hydrogen atom or an alkyl group; , and t represents 0, 1, and 2, is added to the solvent of (2). 
     
     
       9. The method of manufacturing the fluorocarbon-based polymer coating film according to  claim 1 , wherein fine particles of a fluorocarbon-based polymer are dispersed in advance in either said non-aqueous solvent containing the compound having a fluorocarbon group and a chlorosilyl group or said solvent containing the compound having a fluorocarbon group and an alkoxysilane group. 
     
     
       10. A method of manufacturing a fluorocarbon-based polymer coating film comprising the steps of: 
       contacting a substrate having a surface containing hydroxyl groups with a non-aqueous solvent comprising a material comprising chlorosilyl groups;  
       washing the contacted substrate with a non-aqueous solvent to remove unreacted material;  
       coating the washed substrate surface with either (1) a non-aqueous solvent comprising a compound comprising a fluorocarbon group and a chlorosilyl group or (2) a solvent comprising (a) a compound comprising a fluorocarbon group, and an alkoxysilane  alkoxysilyl group or (b) a compound of the following formula:  
       
         
           CF 3 —(CF 2 ) n —(R) m —SiY q (OA) 3-q    
         
       
       where n represents 0 or an integer; R represents an alkyl  alkylene group or a hydrocarbon substituted group containing C═C or C≡C, a silicon atom or an oxygen atom; m represents 0 or 1; Y represents a hydrogen atom, an alkyl group, an alkoxy group, a fluorine-containing alkoxy group or a fluorine-containing alkyl group; A represents a hydrogen atom; and q represents 0, 1 or 2; and 
       baking the substrate after said contacting step, washing step and coating step.  
     
     
       11. A method of manufacturing the fluorocarbon-based polymer coating film of  claim 1 , further comprising: 
       irradiating with an electron beam of about 5M-rads when the fluorocarbon group of the coating step comprises C═C or C≡C bonds, which irradiation is performed subsequent to the coating step and prior to the baking step.  
     
     
       12. A method of manufacturing a fluorocarbon- based polymer coating film comprising:    
         a. contacting a substrate having a surface containing hydroxyl groups with a non - aqueous solvent comprising a material comprising chlorosilyl groups to form a siloxane - based film on the substrate surface, wherein the substrate is made of a plastic material treated in a plasma atmosphere containing oxygen; and    
         b. coating the siloxane - based film with a non - aqueous solvent comprising a compound comprising a fluorocarbon group and a chlorosilyl group represented by the formula: CF   3 —( CF   2 ) n ( R ) m   —SiX   p   Cl   3-p    where n represents  0  or an integer; R represents an alkylene group or a hydrocarbon substituted group containing C═C or C≡C, a silicon atom or an oxygen atom; m represents  0  or  1 , X represents a hydrogen atom or an alkyl group; p represents  0 ,  1  or  2 .   
     
     
       13. A method of manufacturing a fluorocarbon- based polymer coating film comprising:    
         a. contacting a substrate having a surface containing hydroxyl groups with a non - aqueous solvent comprising a material comprising chlorosilyl groups to form a siloxane - based film on the substrate surface;    
         b. washing the contacted substrate with a non - aqueous solvent to remove unreacted material; and    
         c. coating the siloxane - based film with a non - aqueous solvent comprising a compound comprising a fluorocarbon group and a chlorosilyl group, represented by the formula: CF   3 —( CF   2 ) n —( R ) m   —SiX   p   Cl   3-p    where n represents  0  or an integer; R represents an alkylene group or a hydrocarbon substituted group containing C═C or C≡C, a silicon atom or an oxygen atom, m represents  0  or  1 , X represents a hydrogen atom or an alkyl group; p represents  0 ,  1  or  2 .   
     
     
       14. The method of manufacturing a fluorocarbon- based polymer coating film according to    claim 13   , wherein the substrate is selected from the group consisting of glass, metals plastics, and ceramics.   
     
     
       15. The method of manufacturing a fluorocarbon- based polymer coating film according to    claim 13   , wherein the substrate is a plastic material treated in a plasma atmosphere containing oxygen.   
     
     
       16. The method of manufacturing a fluorocarbon- based polymer coating film according to    claim 13   , wherein said material comprising chlorosilyl groups is selected from the group consisting of SiCl   4   , SiHCl   3   , SiH   2   Cl   2 , and Cl—( SiCl   2   O ) n   —SiCl   3   , wherein n is an integer.   
     
     
       17. A vehicle part comprising a substrate selected from the group consisting of ABS resin, cellulose plastic, fiber reinforced plastic, phenolic resin, polyacetal, polyamide, polyacrylate, polybutylene terephthalate, poly( amino - bismaleimide ),  methacrylate resin, polypropylene, polyphenylene oxide, polyurethane, and unsaturated polyester resin, and a fluorocarbon - based polymer coating film adhered thereto, wherein the fluorocarbon - based polymer coating is adhered to the substrate by a process comprising:    
         a. contacting hydroxyl groups at a surface of the substrate with a non - aqueous solvent comprising a material containing chlorosilyl groups to form a siloxane - based film on the substrate; and    
         b. coating the siloxane - based film with a non - aqueous solvent comprising a compound comprising a fluorocarbon group and a chlorosilyl group, represented by the formula: CF   3 —( CF   2 ) n —( R ) m   SiX   p   Cl   3-p    where n represents  0  or an integer; R represents an alkylene group or a hydrocarbon substituted group containing C═C or C≡C, a silicon atom or an oxygen atom; m represents  0  or  1 , X represents a hydrogen atom or an alkyl group; p represents  0 ,  1  or  2 .   
     
     
       18. The vehicle part of  claim 17 , wherein the material comprising chlorosilyl groups is selected from the group consisting of SiCl 4   , SiHCl   3   , SiH   2   Cl   2   , and Cl— ( SiCl   2   O ) n   —SiCl   3   , wherein n is an integer.   
     
     
       19. The vehicle part of  claim 17 , wherein the vehicle part is selected from the group consisting of a lamp cover, an installment panel, a trim part, a protector for a motorcycle, a car mark, a steering wheel, a bumper, an engine cover, a brake, a wiper gear, a gas valve, a radiator fan, a direction indicator lamp, a cowl board lens, a relay case, a rear end, a front fender, an engine part, a gear box, a wheel, a suspension drive system, a lamp cover lens, a meter panel, a center mark, a bumper, a radiator grille, a wheel cap, a bumper, a fender, a fan, a body, a fuel tank, a heater housing, and a meter panel.