Novel copolymer and water- and oil-repellent comprising the same

• US 5,055,538 A
• Filed: 06/11/1990
• Issued: 10/08/1991
• Est. Priority Date: 05/25/1987
• Status: Expired due to Term

• Current Assignee: Daikin Industries Ltd
• Original Assignee: Daikin Industries Ltd
• Inventors: Shinjo, Masayoshi, Enomoto, Takashi, Hayashi, Kazunori, Amimoto, Yoshio
• Primary Examiner(s): Schofer, Joseph L.
• Assistant Examiner(s): SAROFIM, NABIL F
• Application Number:
  US07/536,073
• Time in Patent Office: 484 Days
• Field of Search: 526/245, 526/242, 526/243
• US Class Current: 526/245
• CPC Class Codes: C08F 220/24 containing perhaloalkyl radicals
• CPC Class Codes: D06M 15/277 containing fluorine

Abstract

A fluorine-containing copolymer comprising

(a) 40 to 90% by weight of repeating units derived from a polymerizable compound having a C₄ -C₂₀ perfluoroalkyl group,

(b) 5 to 50% by weight of repeating units derived from at least one unsaturated ester selected from the group consisting of stearyl acrylate and stearyl methacrylate,

(c) 5 to 50% by weight of repeating units derived from at least one monomer selected from the group consisting of alkyl acrylate or methacrylate having 2 to 8 carbon atoms in the alkyl group, cyclohexylacrylate and cyclohexylmethacrylate, which is useful as an active component of a water- and oil-repellent.

Claims

1. A fluorine-containing copolymer comprising

(a) 40 to 90 % by weight of repeating units of a polymerizable compound having a C₄ -C₂₀ perfluoroalkyl group,

(b) 5 to 50 % by weight of repeating units of at least one unsaturated ester selected from the group consisting of stearyl acrylate and stearyl methacrylate,

(c) 5 to 50 % by weight of repeating units of at least one monomer selected from the group consisting of alkyl acrylate or methyacrylate having 2 to 8 carbon atoms in the alkyl group, cyclohexyl acrylate and cyclohexyl methacrylate.

2. The fluorine-containing copolymer according to claim 1, which further comprises 0.1 to 5 % by weight of (d) repeating units of an acrylate or methacrylate having at least one nitrogen atom or (e) repeating units of an acrylate and methacrylate having at least one hydroxyl group or (f) repeating units of glycidyl acrylate or methacrylate.

3. The fluorine-containing copolymer according to claim 1, which further comprises 0.1 to 5 % by weight of (d) repeating units of an acrylate or methacrylate having at least one nitrogen atom, and 0.1 to 5 % by weight of (e) repeating units of an acrylate and methacrylate having at least one hydroxyl group or (f) repeating units of glycidyl acrylate or methacrylate.

4. The fluorine-containing copolymer according to claim 1, which further comprises 0.1 to 5 % by weight of (e) repeating units of an acrylate and methacrylate having at least one hydroxyl group and 0.1 to 5 % by weight of (f) repeating units of glycidyl acrylate or methacrylate.

5. The fluorine-containing copolymer according to claim 1, which further comprises 0.1 to 5 % by weight of (d) repeating units of an acrylate or methacrylate having at least one nitrogen atom, 0.1 to 5 % by weight of (e) repeating units of an acrylate and methacrylate having at least one hydroxyl group and 0.1 to 5 % by weight of (f) repeating units of glycidyl acrylate or methacrylate.

11. The fluorine-containing copolymer according to claim 1, wherein the polymerizable compound of repeating units (a) is selected from the group consisting of ##STR8## (6) R_f (CH₂)_m COOCH═

CH₂ and (7) R_f CH═

CH(CH₂)_n OCOCR³ ═

CH₂

wherein R_f is a C₄ -C₂₀ perfluoroalkyl group, R¹ is a hydrogen atom or a C₁ -C₁₀ alkyl group, R² is a C₁ -C₁₀ alkylene group, R³ is a hydrogen atom or a methyl group, R⁴ is a C₁ -C₁₇ alkyl group, n is a number of 1 to 10, and m is a number of 0 to 10.

12. The fluorine-containing copolymer according to claim 1, wherein the weight of the repeating units of (a) is 50 to 90%.

13. The fluorine-containing copolymer according to claim 1, wherein the weight of the repeating units of (b) is 15 to 35%.

14. The fluorine-containing copolymer according to claim 1, wherein the weight of the repeating units of (c) is 5 to 25%.

6. A water- and oil-repellent comprising a fluorine-containing copolymer which comprises

(a) 40 to 90% by weight of repeating units of a polymerizable compound having a C₄ -C₂₀ perfluoro-alkyl group,

(b) 5 to 50% by weight of repeating units of at least one unsaturated ester selected from the group consisting of stearyl acrylate and stearyl methacrylate,

(c) 5 to 50 % by weight of repeating units of at least one monomer selected from the group consisting of alkyl acrylate or methacrylate having 2 to 8 carbon atoms in the alkyl group, cyclohexyl acrylate and cyclohexyl methacrylate.

7. The water- and oil-repellent according to claim 6, wherein the copolymer further comprises 0.1 to 5 % by weight of (d) repeating units of an acrylate or methacrylate having at least one nitrogen atom or (e) repeating units of an acrylate and methacrylate having at least one hydroxyl group of (f) repeating units of glycidyl acrylate or methacrylate.

8. The water- and oil-repellent according to claim 6, wherein the copolymer further comprises 0.1 to 5 % by weight of (d) repeating units of an acrylate or methacrylate having at least one nitrogen atom, and 0.1 to 5 % by weight of (e) repeating units of an acrylate and methacrylate having at least one hydroxyl group or (f) repeating units of glycidyl acrylate or methacrylate.

9. The water- and oil-repellent according to claim 6, wherein the copolymer further comprises 0.1 to 5 % by weight of (e) repeating units of an acrylate and methacrylate having at least one hydroxyl group and 0.1 to 5 % by weight of (f) repeating units of glycidyl acrylate or methacrylate.

10. The water- and oil-repellent according to claim 6, wherein the copolymer further comprises 0.1 to 5 % by weight of (d) repeating units of an acrylate or methacrylate having at least one nitrogen atom, 0.1 to 5 % by weight of (e) repeating units of an acrylate and methacrylate having at least one hydroxyl group and 0.1 to 5 % by weight of (f) repeating units of glycidyl acrylate or methacrylate.

15. The water- and oil-repellent according to claim 6, wherein the polymerizable compound of repeating units (a) is selected from the group consisting of ##STR9## (6) R_f (CH₂)_m COOCH═

CH₂ and (7) R_f CH═

CH(CH₂)_n OCOCR³ ═

CH₂

wherein R_f is a C₄ -C₂₀ perfluoroalkyl group, R¹ is a hydrogen atom or a A₁ -C₁₀ alkyl group, R² is a C₁ -C₁₀ alkylene group, R³ is a hydrogen atom or a methyl group, R⁴ is a C₁ -C₁₇ alkyl group, n is a number of 1 to 10, and m is a number of 0 to 10.

16. The water- and oil-repellent according to claim 6, wherein the weight of the repeating units of (a) is 50 to 90%.

17. The water- and oil-repellent according to claim 6, wherein the weight of the repeating units of (b) is 15 to 35%.

18. The water- and oil-repellent according to claim 6, wherein the weight of the repeating units of (c) is 5 to 25%.