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.

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 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 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 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 metals, plastics, and ceramics. 
     
     
       3. The method of manufacturing the fluorocarbon-based polymer coating film according to  claim 1 , wherein the substrate is mace 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 ) n —(R) m —SiX p Cl 3-p  where n represents  0  or an integer; R represents an alkyl 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 fluorine-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 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 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 substrate with a non-aqueous solvent to remove unreacted material;    coating the 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 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 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.  
 
     
     
       11. A method of manufacturing the fluorocarbon-based polymer coating film of  claim 1 , further comprising:
 irradiating with an electron beam of about  5 M-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 vehicle part comprising:
 a. contacting a vehicle part 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 vehicle part surface; 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. The method of  claim 12 , 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.  
     
     
       14. The method of  claim 12 , wherein p represents  0 .  
     
     
       15. A vehicle part made by the method of  claim 12 .  
     
     
       16. A method of applying a fluorocarbon-based polymer coating film to an apparatus comprising:
 a. contacting an apparatus having a surface containing hydroxyl group with a non-aqueous solvent comprising a material comprising chlorosilyl groups to form a siloxane-based film on the apparatus surface; 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 .    
     
     
       17. The method of manufacturing the fluorocarbon-based polymer coating film according to  claim 12 , wherein the compound comprising a fluorocarbon group and a alkoxysilyl group is represented by:
   CF 3 —(CF 2 ) n —(R) m —SiY q (OA′) 3 -q    
       wherein 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 ;  
 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 ;  
 and the method further comprises a step of baking the substrate after coating. 
 
     
     
       18. The method of  claim 16 , wherein p represents  0 . 
     
     
       19. The method of  claim 16 , wherein the apparatus is an electric apparatus, a vehicle or an industrial apparatus. 
     
     
       20. An apparatus made by the method of  claim 16 . 
     
     
       21. A method of producing a fluorocaron-based coating film on a glass substrate comprising:
   depositing a siloxane-based inner layer on a surface of the glass; and      coating the siloxane-based inner layer with a compound comprising ( 1 ) a fluorocarbon group and a chlorosilyl group or ( 2 ) a fluorocarbon group and an alkoxysilyl group.   
     
     
       22. A product made by the process of  claim 16 . 
     
     
       23. A product made by the process of  claim 17 .  
     
     
       24. A product made by the process of  claim 18 .  
     
     
       25. A product made by the process of  claim 20 . 
     
     
       26. A product made by the process of  claim 21 .  
     
     
       27. 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 .   
     
     
       28. The method of manufacturing a fluorocarbon-based polymer coating film according to  claim 27 , wherein the substrate is selected from the group consisting of glass, metals, plastics, and ceramics.  
     
     
       29. The method of manufacturing a fluorocarbon-based polymer coating film according to  claim 27 , wherein the substrate is a plastic material treated in a plasma atmosphere containing oxygen.  
     
     
       30. The method of manufacturing a fluorocarbon-based polymer coating film according to  claim 27 , 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.  
     
     
       31. A production method of an apparatus comprising a part comprising a fluorocarbon-based polymer coating film comprising:
 a. contacting the part 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 apparatus surface; 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 alkoxy group; p represents  0 ,  1  or  2 .   
     
     
       32. A production method of  claim 31 , 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. 
     
     
       33. A production method of  claim 31 , wherein p represents  0 . 
     
     
       34. A production method of  claim 31 , wherein the apparatus is an electric apparatus, a vehicle or an industrial apparatus. 
     
     
       35. A apparatus made by the method of  claim 34 . 
     
     
       36. The method of  claim 27 , wherein the vehicle part is made of the member of a group consisting of glass, metals, plastics and ceramics. 
     
     
       37. The method of  claim 31 , wherein the part is selected from the group consisting of glass, metals, plastics and ceramics. 
     
     
       38. A method of manufacturing a vehicle part comprising:
 forming a siloxane-based film on the vehicle part surface; and    coating the siloxane-based film with a non-aqueous solvent comprising a compound comprising a fluorocarbon group and a chlorosilyl group.    
     
     
       39. The method of  claim 38 , wherein the siloxane-based film is made with a material comprising chlorosilyl groups selected from the group consisting of SiCl 4 , SiHCl 3 , SiH 2 Cl 2  and Cl—(SiC 2 O) n —SiCl 3 , wherein n is an integer.  
     
     
       40. The method of  claim 38 , wherein the vehicle part is a window glass of a vehicle.  
     
     
       41. A production method of an apparatus having a part applied with a fluorocarbon-based polymer coating film comprising:
 forming a siloxane-based film on the part surface; and    coating the siloxane-based film with a non-aqueous solvent comprising a compound comprising a fluorocarbon group and a chlorosilyl group.    
     
     
       42. The method of  claim 41 , wherein the siloxane-based film is made with a material comprising chlorosilyl groups selected from the group consisting of SiCl 4 , SiHCl 3   , SiH   2 Cl 2  and Cl—(SiC 2 O) n —SiCl 3 , wherein n is an integer.  
     
     
       43. The production method of  claim 41 , wherein the apparatus is an electric apparatus, a vehicle or an industrial apparatus.  
     
     
       44. An apparatus made by the method of  claim 43 .  
     
     
       45. The apparatus of  claim 44 , wherein the apparatus is a vehicle.