Silicon-containing organic fluoropolymers and use of the same

A mixture of silicon-containing organic fluoropolymers represented by the general formula (Ia) and having a number average molecular weight of from 5×102 to 1×105, wherein g is 0 or an integer of 1 or above and the mean value of the g is greater than 1 in said mixture provided said mixture of silicon-containing organic fluoropolymers contains a silicon-containing organic fluoropolymer wherein the g is an integer of 2 or above:

• wherein Rf represents perfluoroalkyl;
• Z represents fluoro or trifluoromethyl;
• a, b, c, d and e each independently represent 0 or an integer of 1 or above, provided that a+b+c+d+e is not less than 1 and the order of the repeating units parenthesized by subscripts a, b, c, d and e occurring in the formula is not limited to that shown;
• Y represents hydrogen or alkyl containing 1 to 4 carbon atoms;
• X represents hydrogen, bromo or iodo;
• R1 represents hydroxy or a hydrolyzable substituent group;
• R2 represents hydrogen or a monovalent hydrocarbon group;
• 1 represents 0, 1 or 2;
• and m represents 1, 2 or 3.

A mixture of silicon-containing organic fluoropolymers represented by the general formula (IIa) and having a number average molecular weight of from 5×102 to 1×105, wherein g is 0 or an integer of 1 or above and the mean value of the g is greater than 1 in said mixture, provided said mixture of silicon-containing organic fluoropolymers contains a silicon-containing organic fluoropolymer wherein the g is an integer of 2 or above:

• wherein p represents an integer of 1 or above;
• Y represents hydrogen or alkyl containing 1 to 4 carbon atoms;
• X represents hydrogen, bromo or iodo;
• R1 represents hydroxy or a hydrolyzable substituent group;
• R2 represents hydrogen or a monovalent hydrocarbon group;
• 1 represents 0, 1 or 2;
• and m represents 1, 2 or 3.

A surface-treating method for a substrate, which comprises coating the substrate surface with a treating solution comprising (1) a silicon-containing organic fluoropolymer represented by the general formula (Ix), (2) a fluorine-containing organic solvent and (3) a silane compound excepting said silicon-containing organic fluoropolymer (1):

• wherein Rf represents perfluoroalkyl;
• Z represents fluoro or trifluoromethyl;
• a, b, c, d and e each independently represent 0 or an integer of 1 or above, provided that a+b+c+d+e is not less than 1 and the order of the repeating units parenthesized by subscripts a, b, c, d and e occurring in the formula is not limited to that shown;
• Y represents hydrogen or alkyl containing 1 to 4 carbon atoms;
• X represents hydrogen, bromo or iodo;
• R1 represents hydroxy or a hydrolyzable substituent group;
• R2 represents hydrogen or a monovalent hydrocarbon group;
• 1 represents 0, 1 or 2;
• m represents 1, 2 or 3;
• and nx represents an integer of 1 or above.

A surface-treating method for a substrate, which comprises coating the substrate surface with a treating solution (N) comprising (3) a silane compound excepting a silicon-containing organic fluoropolymer (1) represented by the general formula (Ix) for forming an under-layer, and then coating the under-layer with a treating solution (M) comprising (1) the silicon-containing organic fluoropolymer and (2) a fluorine-containing organic solvent:

• wherein Rf represents perfluoroalkyl;
• Z represents fluoro or trifluoromethyl;
• a, b, c, d and e each independently represent 0 or an integer of 1 or above, provided that a+b+c+d+e is not less than 1 and the order of the repeating units parenthesized by subscripts a, b, c, d and e occurring in the formula is not limited to that shown;
• Y represents hydrogen or alkyl containing 1 to 4 carbon atoms;
• X represents hydrogen, bromo or iodo;
• R1 represents hydroxy or a hydrolyzable substituent group;
• R2 represents hydrogen or a monovalent hydrocarbon group;
• 1 represents 0, 1 or 2;
• m represents 1, 2 or 3;
• and nx represents an integer of 1 or above.

A surface-treating composition which comprises (1) a silicon-containing organic fluoropolymer represented by the general formula (Ix), (2) a fluorine-containing organic solvent and (4) an organic solvent excepting said fluorine-containing organic solvent (2):

• wherein Rf represents perfluoroalkyl;
• Z represents fluoro or trifluoromethyl;
• a, b, c, d and e each independently represent 0 or an integer of 1 or above, provided that a+b+c+d+e is not less than 1 and the order of the repeating units parenthesized by subscripts a, b, c, d and e occurring in the formula is not limited to that shown;
• Y represents hydrogen or alkyl containing 1 to 4 carbon atoms;
• X represents hydrogen, bromo or iodo;
• R1 represents hydroxy or a hydrolyzable substituent group;
• R2 represents hydrogen or a monovalent hydrocarbon group;
• 1 represents 0, 1 or 2;
• m represents 1, 2 or 3;
• and nx represents an integer of 1 or above.

An anti-icing agent which comprises a silicon-containing organic fluoropolymer represented by the general formula (Ix):

• wherein Rf represents perfluoroalkyl;
• Z represents fluoro or trifluoromethyl;
• a, b, c, d and e each independently represent 0 or an integer of 1 or above, provided that a+b+c+d+e is not less than 1 and the order of the repeating units parenthesized by subscripts a, b, c, d and e occurring in the formula is not limited to that shown;
• Y represents hydrogen or alkyl containing 1 to 4 carbon atoms;
• X represents hydrogen, bromo or iodo;
• R1 represents hydroxy or a hydrolyzable substituent group;
• R2 represents hydrogen or a monovalent hydrocarbon group;
• 1 represents 0, 1 or 2;
• m represents 1, 2 or 3;
• and nx represents an integer of 1 or above.

A water-repellent glass member which comprises a glass substrate and, as formed on the glass surface, a layer of a silicon-containing organic fluoropolymer represented by the general formula (Ix), and which is used in vehicles:

• wherein Rf represents perfluoroalkyl;
• Z represents fluoro or trifluoromethyl;
• a, b, c, d and e each independently represent 0 or an integer of 1 or above, provided that a+b+c+d+e is not less than 1 and the order of the repeating units parenthesized by subscripts a, b, c, d and e occurring in the formula is not limited to that shown;
• Y represents hydrogen or alkyl containing 1 to 4 carbon atoms;
• X represents hydrogen, bromo or iodo;
• R1 represents hydroxy or a hydrolyzable substituent group;
• R2 represents hydrogen or a monovalent hydrocarbon group;
• 1 represents 0, 1 or 2;
• m represents 1, 2 or 3;
• and nx represents an integer of 1 or above.

An antifouling substrate which comprises a substrate and, as formed on the surface thereof, a layer of a silicon-containing organic fluoropolymer represented by the general formula (Ix) and having a number average molecular weight of from 5×102 to 1×105:

• wherein Rf represents perfluoroalkyl;
• Z represents fluoro or trifluoromethyl;
• a, b, c, d and e each independently represent 0 or an integer of 1 or above, provided that a+b+c+d+e is not less than 1 and the order of the repeating units parenthesized by subscripts a, b, c, d and e occurring in the formula is not limited to that shown;
• Y represents hydrogen or alkyl containing 1 to 4 carbon atoms;
• X represents hydrogen, bromo or iodo;
• R1 represents hydroxy or a hydrolyzable substituent group;
• R2 represents hydrogen or a monovalent hydrocarbon group;
• 1 represents 0, 1 or 2;
• m represents 1, 2 or 3;
• and nx represents an integer of 2 or above.

A process for preparing an antifouling substrate, which comprises coating the substrate surface with a treating solution comprising a mixture of silicon-containing organic fluoropolymers represented by the general formula (Ia) and having a number average molecular weight of from 5×102 to 1×105, wherein g is 0 or an integer of 1 or above and the mean value of the g is greater than 1 in said mixture provided said mixture of silicon-containing organic fluoropolymers contains a silicon-containing organic fluoropolymer wherein the g is an integer of 2 or above:

• wherein Rf represents perfluoroalkyl;
• Z represents fluoro or trifluoromethyl;
• a, b, c, d and e each independently represent 0 or an integer of 1 or above, provided that a+b+c+d+e is not less than 1 and the order of the repeating units parenthesized by subscripts a, b, c, d and e occurring in the formula is not limited to that shown;
• Y represents hydrogen or alkyl containing 1 to 4 carbon atoms;
• X represents hydrogen, bromo or iodo;
• R1 represents hydroxy or a hydrolyzable substituent group;
• R2 represents hydrogen or a monovalent hydrocarbon group;
• 1 represents 0, 1 or 2;
• and m represents 1, 2 or 3.

A water-repellent glass member which comprises a glass substrate and, as formed on the glass surface, a layer of a silicon-containing organic fluoropolymer represented by the general formula (Ix):

• wherein Rf represents perfluoroalkyl;
• Z represents fluoro or trifluoromethyl;
• a, b, c, d and e each independently represent 0 or an integer of 1 or above, provided that a+b+c+d+e is not less than 1 and the order of the repeating units parenthesized by subscripts a, b, c, d and e occurring in the formula is not limited to that shown;
• Y represents hydrogen or alkyl containing 1 to 4 carbon atoms;
• X represents hydrogen, bromo or iodo;
• R1 represents hydroxy or a hydrolyzable substituent group;
• R2 represents hydrogen or a monovalent hydrocarbon group;
• 1 represents 0, 1 or 2;
• m represents 1, 2 or 3;
• and nx represents an integer of 2 or above.

A process for preparing a water-repellent glass member, which comprises coating the glass surface with a treating solution comprising a mixture of silicon-containing organic fluoropolymers represented by the general formula (Ia) and having a number average molecular weight of from 5×102 to 1×105, wherein g is 0 or an integer of 1 or above and the mean value of the g is greater than 1 in said mixture provided said mixture of silicon-containing organic fluoropolymers contains a silicon-containing organic fluoropolymer wherein the g is an integer of 2 or above:

• wherein Rf represents perfluoroalkyl;
• Z represents fluoro or trifluoromethyl;
• a, b, c, d and e each independently represent 0 or an integer of 1 or above, provided that a+b+c+d+e is not less than 1 and the order of the repeating units parenthesized by subscripts a, b, c, d and e occurring in the formula is not limited to that shown;
• Y represents hydrogen or alkyl containing 1 to 4 carbon atoms;
• X represents hydrogen, bromo or iodo;
• R1 represents hydroxy or a hydrolyzable substituent group;
• R2 represents hydrogen or a monovalent hydrocarbon group;
• 1 represents 0, 1 or 2;
• and m represents 1, 2 or 3.