Water repellent coating film having low refractive index

Abstract

To provide a highly hard coating film formed on a substrate, as adhered to the surface of the substrate and having a refractive index of from 1.28 to 1.41 and a contact angle with water of from 90° to 115°. A coating film having a refractive index of from 1.28 to 1.41 and a contact angle with water of from 90° to 115°, which is formed as adhered to a substrate surface by forming a reaction mixture comprising a silicon compound (A) of the formula Si(OR) 4 , a silicon compound (B) of the formula CF 3 (CF 2 ) n CH 2 CH 2 Si(OR 1 ) 3 , a silicon compound (C) of the formula H 2 NCOH(CH 2 ) m Si(OR 2 ) 3 , an alcohol (D) of the formula R 3 CH 2 OH and oxalic acid (E), in a specific ratio, heating this reaction mixture at a temperature of from 40 to 180° C. in the absence of water to form a solution of a polysiloxane, then applying a coating fluid comprising the polysiloxane solution on a substrate surface to form a coating, and heat-curing the coating at a temperature of from 40 to 450° C.; a process for forming such a coating film, and a process for producing such a coating fluid.

1 . A process for preparing a coating fluid containing a polysiloxane, which comprises forming a reaction mixture comprising a silicon compound (A) of the formula (1):  
       Si(OR) 4   (1)  
     wherein R is a C 1-5  alkyl group, a silicon compound (B) of the formula (2):  
       CF 3 (CF 2 ) n CH 2 CH 2 Si(OR 1 ) 3   (2)  
     wherein R 1  is a C 1-5  alkyl group, and n is an integer of from 0 to 12, a silicon compound (C) of the formula (3):  
       H 2 NCONH(CH 2 ) m Si(OR 2 ) 3   (3)  
     wherein R 2  is a C 1-5  alkyl group, and m is an integer of from 1 to 5, an alcohol (D) of the formula (4):  
       R 3 CH 2 OH  (4)  
     wherein R 3  is a hydrogen atom or a C 1-12  alkyl group wherein the alkyl group is optionally substituted by one or more substituents of the same or different types selected from the group consisting of a C 1-3  alkyl group, a C 1-3  hydroxyalkyl group, a C 2-6  alkoxyalkyl group, a C 2-6  hydroxyalkoxyalkyl group and a C 3-6  alkoxyalkoxyalkyl group, and oxalic acid (E), in a ratio of from 0.05 to 0.43 mol of the silicon compound (B) per mol of the silicon compound (A), in a ratio of from 0.01 to 0.20 mol of the silicon compound (C) per mol of the silicon compound (A), in a ratio of from 0.5 to 100 mol of the alcohol (D) per mol of the total alkoxy groups contained in the silicon compounds (A), (B) and (C) and in a ratio of 0.2 to 2 mol of the oxalic acid (E) per mol of the total alkoxy groups contained in the silicon compounds (A), (B) and (C), and heating the reaction mixture at a temperature of from 40 to 180° C. until the total amount of the silicon compounds (A), (B) and (C) remaining in the reaction mixture becomes at most 5 mol %, while maintaining at a SiO 2  concentration of from 0.5 to 10 wt % as calculated from silicon atoms in the reaction mixture and in the absence of water.  
   
   
       2 . The process for preparing a coating fluid according to  claim 1 , wherein in the formation of the reaction mixture, in addition to the silicon compounds (A), (B) and (C), the alcohol (D) and the oxalic acid (E), at least one alkylalkoxysilane selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, dimethyldimethoxysilane and dimethyldiethoxysilane, is incorporated as a modifier (F) in a ratio of from 0.02 to 0.2 mol per mol of the silicon compound (A).  
   
   
       3 . The process for preparing a coating fluid according to  claim 1 , wherein at least one sol selected from the group consisting of silica sol, alumina sol, titania sol, zirconia sol, magnesium fluoride sol and ceria sol is incorporated as an additive (G) to the coating fluid.  
   
   
       4 . A process for forming a coating film, which comprises forming a reaction mixture comprising a silicon compound (A) of the formula (1):  
       Si(OR) 4   (1)  
     wherein R is a C 1-5  alkyl group, a silicon compound (B) of the formula (2):  
       CF 3 (CF 2 ) n CH 2 CH 2 Si(OR 1 ) 3   (2)  
     wherein R 1  is a C 1-5  alkyl group, and n is an integer of from 0 to 12, a silicon compound (C) of the formula (3):  
       H 2 NCONH(CH 2 ) m Si(OR 2 ) 3   (3)  
     wherein R 2  is a C 1-5  alkyl group, and m is an integer of from 1 to 5, an alcohol (D) of the formula (4): 
 R 3 CH 2 OH  (4)  
   
 wherein R 3  is a hydrogen atom or a C 1-12  alkyl group wherein the alkyl group is optionally substituted by one or more substituents of the same or different types selected from the group consisting of a C 1-3  alkyl group, a C 1-3  hydroxyalkyl group, a C 2-6  alkoxyalkyl group, a C 2-6  hydroxyalkoxyalkyl group and a C 3-6  alkoxyalkoxyalkyl group, and oxalic acid (E), in a ratio of from 0.05 to 0.43 mol of the silicon compound (B) per mol of the silicon compound (A), in a ratio of from 0.01 to 0.20 mol of the silicon compound (C) per mol of the silicon compound (A), in a ratio of from 0.5 to 100 mol of the alcohol (D) per mol of the total alkoxy groups contained in the silicon compounds (A), (B) and (C) and in a ratio of 0.2 to 2 mol of the oxalic acid (E) per mol of the total alkoxy groups contained in the silicon compounds (A), (B) and (C); heating the reaction mixture at a temperature of from 40 to 180° C. until the total amount of the silicon compounds (A), (B) and (C) remaining in the reaction mixture becomes at most 5 mol %, while maintaining a SiO 2  concentration of from 0.5 to 10 wt % as calculated from silicon atoms in the reaction mixture and in the absence of water, and forming a solution of a polysiloxane; then applying a coating fluid comprising the polysiloxane solution on a substrate surface to form a coating; and heat-curing the coating at a temperature of from 40 to 450° C., to form a coating film having a refractive index of from 1.28 to 1.41 and a contact angle with water of from 90° to 115°, as adhered to the substrate surface.  
 
   
   
       5 . The process for forming a coating film according to  claim 4 , wherein in the formation of the reaction mixture, in addition to the silicon compounds (A), (B) and (C), the alcohol (D) and the oxalic acid (E), at least one alkylalkoxysilane selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, dimethyldimethoxysilane and dimethyldiethoxysilane, is incorporated as a modifier (F) in a ratio of from 0.02 to 0.2 mol per mol of the silicon compound (A).  
   
   
       6 . The process for forming a coating film according to  claim 4 , wherein at least one sol selected from the group consisting of silica sol, alumina sol, titania sol, zirconia sol, magnesium fluoride sol and ceria sol is further incorporated as an additive (G) to the coating fluid.  
   
   
       7 . A coating film having a refractive index of from 1.28 to 1.41 and a contact angle with water of from 90° to 115°, which is formed as adhered to a substrate surface by forming a reaction mixture comprising a silicon compound (A) of the formula (1):  
       Si(OR) 4   (1)  
     wherein R is a C 1-5  alkyl group, a silicon compound (B) of the formula (2):  
       CF 3 (CF 2 ) n CH 2 CH 2 Si(OR 1 ) 3   (2)  
     wherein R 1  is a C 1-5  alkyl group, and n is an integer of from 0 to 12, a silicon compound (C) of the formula (3):  
       H 2 NCONH(CH 2 ) m Si(OR 2 ) 3   (3)  
     wherein R 2  is a C 1-5  alkyl group, and m is an integer of from 1 to 5, an alcohol (D) of the formula (4):  
       R 3 CH 2 OH  (4)  
     wherein R 3  is a hydrogen atom or a C 1-12  alkyl group wherein the alkyl group may is optionally substituted by one or more substituents of the same or different types selected from the group consisting of a C 1-3  alkyl group, a C 1-3  hydroxyalkyl group, a C 2-6  alkoxyalkyl group, a C 2-6  hydroxyalkoxyalkyl group and a C 3-6  alkoxyalkoxyalkyl group, and oxalic acid (E), in a ratio of from 0.05 to 0.43 mol of the silicon compound (B) per mol of the silicon compound (A), in a ratio of from 0.01 to 0.20 mol of the silicon compound (C) per mol of the silicon compound (A), in a ratio of from 0.5 to 100 mol of the alcohol (D) per mol of the total alkoxy groups contained in the silicon compounds (A), (B) and (C) and in a ratio of 0.2 to 2 mol of the oxalic acid (E) per mol of the total alkoxy groups contained in the silicon compounds (A), (B) and (C); heating the reaction mixture at a temperature of from 40 to 180° C. until the total amount of the silicon compounds (A), (B) and (C) remaining in the reaction mixture becomes at most 5 mol %, while maintaining a SiO 2  concentration of from 0.5 to 10 wt % as calculated from silicon atoms in the reaction mixture and in the absence of water, and forming a solution of a polysiloxane; and applying a coating fluid comprising the polysiloxane solution on a substrate surface to form a coating; and heat-curing the coating at a temperature of from 40 to 450° C.  
   
   
       8 . The coating film according to  claim 7 , wherein in the formation of the reaction mixture, in addition to the silicon compounds (A), (B) and (C), the alcohol (D) and the oxalic acid (E), at least one alkylalkoxysilane selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, dimethyldimethoxysilane and dimethyldiethoxysilane, is incorporated as a modifier (F) in a ratio of from 0.02 to 0.2 mol per mol of the silicon compound (A).  
   
   
       9 . The coating film according to  claim 7 , wherein at least one sol selected from the group consisting of silica sol, alumina sol, titania sol, zirconia sol, magnesium fluoride sol and ceria sol is incorporated as an additive (G) to the coating fluid.  
   
   
       10 . A process for forming a coating film, which comprises forming a reaction mixture comprising a silicon compound (A) of the formula (1):  
       Si(OR) 4   (1)  
     wherein R is a C 1-5  alkyl group, a silicon compound (B) of the formula (2):  
       CF 3 (CF 2 ) n CH 2 CH 2 Si(OR 1 ) 3   (2)  
     wherein R 1  is a C 1-5  alkyl group, and n is an integer of from 0 to 12, a silicon compound (C) of the formula (3):  
       H 2 NCONH(CH 2 ) m Si(OR 2 ) 3   (3)  
     wherein R 2  is a C 1-5  alkyl group, and m is an integer of from 1 to 5, an alcohol (D) of the formula (4):  
       R 3 CH 2 OH  (4)  
     wherein R 3  is a hydrogen atom or a C 1-12  alkyl group wherein the alkyl group optionally substituted by one or more substituents of the same or different types selected from the group consisting of a C 1-3  alkyl group, a C 1-3  hydroxyalkyl group, a C 2-6  alkoxyalkyl group, a C 2-6  hydroxyalkoxyalkyl group and a C 3-6  alkoxyalkoxyalkyl group, and oxalic acid (E), in a ratio of from 0.05 to 0.43 mol of the silicon compound (B) per mol of the silicon compound (A), in a ratio of from 0.01 to 0.20 mol of the silicon compound (C) per mol of the silicon compound (A), in a ratio of from 0.5 to 100 mol of the alcohol (D) per mol of the total alkoxy groups contained in the silicon compounds (A), (B) and (C) and in a ratio of 0.2 to 2 mol of the oxalic acid (E) per mol of the total alkoxy groups contained in the silicon compounds (A), (B) and (C); heating the reaction mixture at a temperature of from 40 to 180° C. until the total amount of the silicon compounds (A), (B) and (C) remaining in the reaction mixture becomes at most 5 mol %, while maintaining a SiO 2  concentration of from 0.5 to 10 wt % as calculated from silicon atoms in the reaction mixture and in the absence of water, forming a solution of a polysiloxane; and applying a coating fluid comprising the polysiloxane solution on a substrate surface to form a coating; drying the coating at a temperature of from 40 to 150° C. and aging the coating at a temperature of from 20 to 100° C. for curing, to form a coating film having a refractive index of from 1.28 to 1.41 and a contact angle with water of from 90° to 115°, as adhered to the substrate surface.  
   
   
       11 . The process for forming a coating film according to  claim 10 , wherein in the formation of the reaction mixture, in addition to the silicon compounds (A), (B) and (C), the alcohol (D) and the oxalic acid (E), at least one alkylalkoxysilane selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, dimethyldimethoxysilane and dimethyldiethoxysilane, is incorporated as a modifier (F) in a ratio of from 0.02 to 0.2 mol per mol of the silicon compound (A).  
   
   
       12 . The process for forming a coating film according to  claim 10 , wherein at least one sol selected from the group consisting of silica sol, alumina sol, titania sol, zirconia sol, magnesium fluoride sol and ceria sol is incorporated as an additive (G) to the coating fluid.  
   
   
       13 . A coating film having a refractive index of from 1.28 to 1.41 and a contact angle with water of from 90° to 115°, which is formed as adhered to a substrate surface by forming a reaction mixture comprising a silicon compound (A) of the formula (1):  
       Si(OR) 4   (1)  
     wherein R is a C 1-5  alkyl group, a silicon compound (B) of the formula (2):  
       CF 3 (CF 2 ) n CH 2 CH 2 Si(OR 1 ) 3   (2)  
     wherein R 1  is a C 1-5  alkyl group, and n is an integer of from 0 to 12, a silicon compound (C) of the formula (3):  
       H 2 NCONH(CH 2 ) m Si(OR 2 ) 3   (3)  
     wherein R 2  is a C 1-5  alkyl group, and m is an integer of from 1 to 5, an alcohol (D) of the formula (4):  
       R 3 CH 2 OH  (4)  
     wherein R 3  is a hydrogen atom or a C 1-12  alkyl group, wherein the alkyl group is optionally substituted by one or more substituents of the same or different types selected from the group consisting of a C 1-3  alkyl group, a C 1-3  hydroxyalkyl group, a C 2-6  alkoxyalkyl group, a C 2-6  hydroxyalkoxyalkyl group and a C 3-6  alkoxyalkoxyalkyl group, and oxalic acid (E), in a ratio of from 0.05 to 0.43 mol of the silicon compound (B) per mol of the silicon compound (A), in a ratio of from 0.01 to 0.20 mol of the silicon compound (C) per mol of the silicon compound (A), in a ratio of from 0.5 to 100 mol of the alcohol (D) per mol of the total alkoxy groups contained in the silicon compounds (A), (B) and (C) and in a ratio of 0.2 to 2 mol of the oxalic acid (E) per mol of the total alkoxy groups contained in the silicon compounds (A), (B) and (C); heating this reaction mixture at a temperature of from 40 to 180° C. until the total amount of the silicon compounds (A), (B) and (C) remaining in the reaction mixture becomes at most 5 mol %, while it is maintained at a SiO 2  concentration of from 0.5 to 10 wt % as calculated from silicon atoms in the reaction mixture and in the absence of water, forming a solution of a polysiloxane; applying a coating fluid comprising the polysiloxane solution on a substrate surface to form a coating; drying the coating at a temperature of from 40 to 150° C. and aging the coating at a temperature of from 20 to 100° C. for curing.  
   
   
       14 . The coating film according to  claim 13 , wherein in the formation of the reaction mixture, in addition to the silicon compounds (A), (B) and (C), the alcohol (D) and the oxalic acid (E), at least one alkylalkoxysilane selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-aminopropyltrimethoxysilane, aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, dimethyldimethoxysilane and dimethyldiethoxysilane, is incorporated as a modifier (F) in a ratio of from 0.02 to 0.2 mol per mol of the silicon compound (A).  
   
   
       15 . The coating film according to  claim 13 , wherein at least one sol selected from the group consisting of silica sol, alumina sol, titania sol, zirconia sol, magnesium fluoride sol and ceria sol is incorporated as an additive (G) to the coating fluid.