Fluorine-containing composition and fluorine-containing polymer

• US 10,640,594 B2
• Filed: 12/12/2012
• Issued: 05/05/2020
• Est. Priority Date: 12/28/2011
• Status: Active Grant

• Current Assignee: Daikin Industries Ltd
• Original Assignee: Daikin Industries Ltd
• Inventors: Minami, Shinichi, Fukumori, Masaki, Uehara, Tetsuya, Nakamura, Hisako, Yamamoto, Ikuo
• Primary Examiner(s): Tatesure, Vincent
• Application Number:
  US14/369,425
• Publication Number:
  US 20140364028A1
• Time in Patent Office: 2,701 Days
• Field of Search: 442 80
• CPC Class Codes: C08F 220/1806 C6-(meth)acrylate, e.g. (cyclo)hexyl (meth)acrylate or phenyl (meth)acrylate
• CPC Class Codes: C08F 220/1811 C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
• CPC Class Codes: C08F 220/1818 C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
• CPC Class Codes: C08F 220/24 containing perhaloalkyl radicals
• CPC Class Codes: C08K 3/20 Oxides; Hydroxides graphene oxides C08K3/042
• CPC Class Codes: C08L 33/16 Homopolymers or copolymers of esters containing halogen atoms
• CPC Class Codes: D06M 15/263 of unsaturated carboxylic acids; Salts or esters thereof
• CPC Class Codes: D06M 15/277 containing fluorine
• CPC Class Codes: D06M 2200/12 Hydrophobic properties
• CPC Class Codes: Y10T 442/2172 Also specified as oil repellent

Abstract

Disclosed is a fluorine-containing composition which contains a fluorine-containing polymer that has repeating units respectively derived from (A) a fluorine-containing monomer that is an alpha-chloroacrylate having a fluoroalkyl group, (B) a monomer that has a linear or branched hydrocarbon group but does not have a fluoroalkyl group, and (C) a monomer that has a cyclic hydrocarbon group but does not have a fluoroalkyl group. This fluorine-containing composition is capable of providing a base such as a fiber product with excellent water repellency, especially strong water repellency.

Claims

1. A fluorine-containing composition comprising a fluorine-containing polymer which consists essentially of:

(A) repeating units formed from a fluorine-containing monomer which is alpha-chloroacrylate having a fluoroalkyl group,

(B) repeating units formed from a (meth)acrylate monomer which is free from a fluoroalkyl group and which has a linear or branched hydrocarbon group, and

(C) repeating units formed from a (meth)acrylate monomer which is free from a fluoroalkyl group and which has a cyclic hydrocarbon group,

wherein the monomer (B) having a linear or branched hydrocarbon group is an acrylate of the formula;

CH₂═

CA₁COOA₂

wherein A¹ is a hydrogen atom or a methyl group, and A² is an alkyl group represented by C_nH_2n+1 where n is 1-30,

wherein the fluorine-containing polymer is free from repeating units formed from a halogenated olefin, and

wherein the monomer (A) is a fluorine-containing monomer represented by the formula;

CH₂═

C(—

Cl)—

C(═

O)—

Y—

Z—

Rf

wherein

Y is —

O;

Z is a direct bond or divalent organic group; and

Rf is a fluoroalkyl group having 1 to 20 carbon atoms.

2. The fluorine-containing composition according to claim 1, wherein the cyclic hydrocarbon group is saturated, in the cyclic hydrocarbon group-containing (meth)acrylate monomer (C).

3. The fluorine-containing composition according to claim 1, wherein the cyclic hydrocarbon group has 4-20 carbon atoms, in the cyclic hydrocarbon group-containing (meth)acrylate monomer (C).

4. The fluorine-containing composition according to claim 1, wherein a carbon atom in a ring of the cyclic hydrocarbon group is directly bonded to an ester group in a (meth)acrylate group, in the cyclic hydrocarbon group-containing (meth)acrylate monomer (C).

5. The fluorine-containing composition according to claim 1, wherein the cyclic hydrocarbon group is at least one selected from the group consisting of a cyclohexyl group, a t-butyl cyclohexyl group, an isobornyl group, a dicyclopentanyl group and a dicyclopentenyl group, in the cyclic hydrocarbon group-containing (meth)acrylate monomer (C).

6. The fluorine-containing composition according to claim 1, wherein the cyclic hydrocarbon group-containing (meth)acrylate monomer (C) is at least one selected from the group consisting of cyclohexyl methacrylate, t-butyl cyclohexyl methacrylate, benzyl methacrylate, isobornyl methacrylate, isobornyl acrylate, dicyclopentanyl methacrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, adamantyl acrylate and adamantyl methacrylate.

7. The fluorine-containing composition according to claim 1, which also contains an aqueous medium.

8. The fluorine-containing composition according to claim 1, which is an aqueous dispersion.

9. A water- and oil-repellent agent which is the fluorine-containing composition according to claim 1.

11. A method of treating a substrate, which comprises treating the substrate with the fluorine-containing composition according to claim 1.

12. A textile treated with the fluorine-containing composition according to claim 1.

15. The fluorine-containing composition according to claim 1, wherein the cyclic hydrocarbon group in the (meth)acrylate monomer (C) is a saturated or unsaturated, bridged ring group.

16. The fluorine-containing composition according to claim 1, wherein the amount of the monomer having a linear or branched hydrocarbon group (B) is 1-1000 parts by weight, and

the amount of the monomer having a cyclic hydrocarbon group (C) is 1-1000 parts by weight,

based on 100 parts by weight of the fluorine-containing monomer (A).

10. A fluorine-containing polymer which consists essentially of repeating units formed from:

(A) a fluorine-containing monomer which is alpha-chloroacrylate having a fluoroalkyl group,

(B) a (meth)acrylate monomer which is free from a fluoroalkyl group and which has a linear or branched hydrocarbon group, and

(C) a (meth)acrylate monomer which is free from a fluoroalkyl group and which has a cyclic hydrocarbon group,

wherein the monomer (B) having a linear or branched hydrocarbon group is an acrylate of the formula;

CH₂═

CA₁COOA₂

wherein A¹ is a hydrogen atom or a methyl group, and A² is an alkyl group represented by C_nH_2n+1 where n is 1-30,

wherein the fluorine-containing polymer is free from repeating units formed from a halogenated olefin, and

wherein the monomer (A) is a fluorine-containing monomer represented by the formula;

CH₂═

C(—

Cl)—

C(═

O)—

Y—

Z—

Rf

wherein

Y is —

O;

Z is a direct bond or divalent organic group; and

Rf is a fluoroalkyl group having 1 to 20 carbon atoms.

17. The fluorine-containing polymer according to claim 10, wherein the amount of the monomer having a linear or branched hydrocarbon group (B) is 1-1000 parts by weight, and

the amount of the monomer having a cyclic hydrocarbon group (C) is 1-1000 parts by weight,

based on 100 parts by weight of the fluorine-containing monomer (A).

13. A fluorine-containing composition comprising a fluorine-containing polymer which consists essentially of:

(A) repeating units formed from a fluorine-containing monomer which is alpha-chloroacrylate having a fluoroalkyl group,

(B) repeating units formed from a (meth)acrylate monomer which is free from a fluoroalkyl group and which has a linear or branched hydrocarbon group,

(C) repeating units formed from a (meth)acrylate monomer which is free from a fluoroalkyl group and which has a cyclic hydrocarbon group, and

(D) repeating units formed from a fluorine-free crosslinkable monomer which is a compound having at least two reactive groups and/or carbon-carbon double bonds,

wherein the monomer (B) having a linear or branched hydrocarbon group is an acrylate of the formula;

CH₂═

CA₁COOA₂

wherein A¹ is a hydrogen atom or a methyl group, and A² is an alkyl group represented by C_nH_2n+1 where n is 1-30,

wherein the fluorine-containing polymer is free from repeating units formed from a halogenated olefin, and

wherein the monomer (A) is a fluorine-containing monomer represented by the formula;

CH₂═

C(—

Cl)—

C(═

O)—

Y—

Z—

Rf

wherein

Y is —

O;

Z is a direct bond or divalent organic group; and

Rf is a fluoroalkyl group having 1 to 20 carbon atoms.

14. The fluorine-containing composition according to claim 13, wherein the monomer (D) is at least one selected from the group consisting a mono(meth)acrylate having at least one reactive group, a mono-(meth)acrylamide having at least one reactive group and a di(meth)acrylate.

18. The fluorine-containing composition according to claim 13, wherein the amount of the monomer having a linear or branched hydrocarbon group (B) is 1-1000 parts by weight,

the amount of the monomer having a cyclic hydrocarbon group (C) is 1-1000 parts by weight, and

the amount of the fluorine-free crosslinkable monomer (D) is 1-200 parts by weight,

based on 100 parts by weight of the fluorine-containing monomer (A).