Method of manufacturing a fluorocarbon-based coating film

Abstract

A method of contacting s 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; 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-a  where n represents  0  or an integer; R represents an alkyl group or a hydrocarbon substituted group containing C=C, 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, or 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 5 Cl 4—5 , 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 r (OA″) 5—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, 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 fluorocarbon-based polymer coating film comprising the steps of:
 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; 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 manufacturing the fluorocarbon-based polymer coating film according to  claim 12 , wherein the substrate is made of the member of a group consisting of glass, metals, plastics, and ceramics. 
     
     
       14. The method of manufacturing the fluorocarbon-based polymer coating film according to  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.   
     
     
       15. The method of manufacturing the fluorocarbon-based polymer coating film according to  claim 12 , wherein p represents  0 . 
     
     
       16. The method of manufacturing the fluorocarbon-based polymer coating film according to  claim 15 , 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 comprising the compound comprising a fluorocarbon group and a chlorosilyl group.   
     
     
       17. The method of manufacturing the fluorocarbon-based polymer coating film according to  claim 12 , wherein fine particles of a fluorocarbon-based polymer are dispersed in advance in said non-aqueous solvent containing the compound comprising a fluorocarbon group and a chlorosilyl group. 
     
     
       18. A product made by the process of  claim 15 . 
     
     
       19. A product made by the process of  claim 16 . 
     
     
       20. A product made by the process of  claim 17 .