Aqueous dispersion

• US 6,872,324 B2
• Filed: 01/30/2003
• Issued: 03/29/2005
• Est. Priority Date: 01/31/2002
• Status: Expired due to Term

• Current Assignee: Asahi Glass Company, Limited (AGC, Inc.)
• Original Assignee: Asahi Glass Company, Limited (AGC, Inc.)
• Inventors: Shimada, Minako, Maekawa, Takashige, Seki, Ryuji, Hoshino, Taiki
• Primary Examiner(s): Thexton, Matthew A.
• Application Number:
  US10/354,034
• Publication Number:
  US 20030176572A1
• Time in Patent Office: 789 Days
• Field of Search: 252/8.57, 252/8.62, 523/169, 524/805, 526/243, 526/245, 526/246, 526/247, 526/248, 526/249, 526/250, 526/252
• US Class Current: 252/8.57
• CPC Class Codes: C08K 5/0008 Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
• CPC Class Codes: C08L 33/16 Homopolymers or copolymers of esters containing halogen atoms
• CPC Class Codes: C09D 133/06 of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
• CPC Class Codes: C09D 133/16 Homopolymers or copolymers of esters containing halogen atoms
• CPC Class Codes: C09K 3/18 for application to surfaces to minimize adherence of ice, mist or water thereto rendering particulate materials free flowing, in general, e.g. making them hydrophobic B01J2/30; Thawing or antifreeze materials for application to surfaces used in liquids for heat-transfer, heat-exchange or heat-storage or for the production of heat or cold other than by combustion, e.g. radiator liquids, C09K5/00
• CPC Class Codes: D06M 15/21 Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: D06M 15/256 containing fluorine
• 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 2200/11 Oleophobic properties
• CPC Class Codes: D06M 2200/12 Hydrophobic properties

Abstract

An aqueous dispersion comprising a polymer (a) having a repeating unit (A) which comprises four carbon atoms connected in a linear chain and which has one double bond at the second position and a polyfluoroalkyl group bonded to an arbitrary carbon atom, and a surfactant (B) having a hydrophile-lipophile balance of at least 10, wherein the polymer (a) is dispersed in an aqueous medium by the surfactant (B).

Claims

1. An aqueous dispersion comprising a polymer (a) having a repeating unit (A) which comprises four carbon atoms connected in a linear chain and which has one double bond at the second position and a polyfluoroalkyl group bonded to an arbitrary carbon atom, and a surfactant (B) having a hydrophile-lipophile balance of at least 10, wherein surfactant (B) is a nonionic surfactant and/or a cationic surfactant, and wherein the polymer (a) is dispersed in an aqueous medium by the surfactant (B).

2. The aqueous dispersion according to claim 1, wherein in the polymer (a), the repeating unit (A) is at least 10 mass %.

3. The aqueous dispersion according to claim 1, wherein the polymer (a) has an average particle size of at most 10 μ

m.

4. The aqueous dispersion according to claim 1, wherein the polymer (a) has a repeating unit (A) formed from a compound of the following formula 1:

R^f—

X 

 

Formula 1

wherein R^f is a C_1-20 polyfluoroalkyl group which may have at least one carbon-carbon unsaturated double bond or which may have carbon atom(s) substituted by an etheric oxygen atom and X is a monovalent organic group having at least two double bonds.

5. The aqueous dispersion according to claim 4, wherein in the compound of the formula 1, R^f is a group represented by C_kF_2k+1—

, wherein k is an integer of from 1 to 12 or C_jF_2j+1—

(CY¹Y²CY³Y⁴)_i—

, wherein each of Y¹, Y², Y^and Y⁴ which are independent of one another, is a hydrogen atom, a fluorine atom or a chlorine atom, provided that at least one of them is a fluorine atom, and j and i are each an integer of at least 1 and satisfy 12≧

(j+2×

i)≧

1.

6. The aqueous dispersion according to claim 4, wherein in the compound of the formula 1, X is a group represented by —

CD¹═

CD²CH═

CH₂, wherein each of D¹ and D² which are independent of each other, is a hydrogen atom or a halogen atom.

7. The aqueous dispersion according to claim 4, wherein R^f is

CF₃—

, F(CF₂)₂—

, F(CF₂)₃—

, F(CF₂)₄—

, F(CF₂)₅—

, F(CF₂)₆—

, F(CF₂)₄CH₂CF₂—

, F(CF₂)₄(CH₂CF₂)₂—

, F(CF₂)₄(CH₂CF₂)₃—

, F(CF₂)₅CH₂CF₂—

, F(CF₂)₆(CH₂CF₂)₂—

, F(CF₂)₆(CH₂CF₂)₃—

, (CF₃)CF(CF₂)₂—

, H(CF₂)₆—

, H(CF₂)₂—

, Cl(CF₂)₄—

, F(CF₂)₄(CH₂CF₂)₃—

, F(CF₂)₆(CH₂CF₂)₃—

, F(CF₂)₄(CFClCF₂)₂—

, CF₃CF═

CFCF₂CF═

CF—

, CF₃CF₂C(CF₃)CH(CF₃)(CF₂)₂—

, C_eF_2e+1O[CF(CF₃)CF₂O]_gCF(CF₃)—

or C₃F₇O[CF(CF₃)CF₂O]_g(CF₂)_h, wherein e is an integer of from 3 to 10, g is an integer of from 0 to 8, and h is an integer of from 0 to 10.

8. The aqueous dispersion according to claim 4, wherein X is —

CF═

CHCH═

CH₂, —

CH═

CFCH═

CH₂ or —

CH═

CHCH═

CH₂.

9. The aqueous dispersion according to claim 1, wherein the proportion of the surfactant (B) is from 0.5 to 20 parts by mass per 100 parts by mass of the polymer (a).

10. A method for producing an aqueous dispersion of claim 1, which comprises subjecting a 1,3-diene having a polyfluoroalkyl group to an emulsion polymerization reaction in an aqueous medium in the presence of a surfactant (B) having a hydrophile-lipophile balance of at least 10, to form an aqueous dispersion having a polymer (a) having the repeating unit (A) of claim 1 dispersed.

11. The method for producing an aqueous dispersion according to claim 10, wherein the surfactant (B) is a nonionic surfactant and/or a cationic surfactant.

12. The aqueous dispersion according to claim 1, wherein the proportion of the surfactant (B) is from 1 to 10 parts by mass per 100 parts by mass of the polymer (a).

13. The aqueous dispersion according to claim 1, wherein the polymer (a) further has a polymerized unit derived from a monomer (b) having no fluorine atom.

14. The aqueous dispersion according to claim 13, wherein the proportion of the polymerized unit derived from the monomer (b) in the polymer (a) is represented by a mass ratio of monomers such that the compound having repeating unit (A)/the monomer (b)=10/90 to 95/5.

15. The aqueous dispersion according to claim 13, wherein monomer (b) is a (meth)acrylate containing a saturated hydrocarbon group having at least 14 carbon atoms.

16. The aqueous dispersion according to claim 13, wherein the proportion of the polymerized unit derived from the monomer (b) in the polymer (a) is represented by a mass ratio of monomers such that the compound having repeating unit (A)/the monomer (b)=15/85 to 85/15.

17. The aqueous dispersion according to claim 1, wherein the polymer (a) further has a polymerized unit derived from a monomer (d) of the following formula 3:

(Z-Y)_n-G 

 

Formula 3

wherein n is 1 or 2, Z is a polyfluoroalkyl group, Y is a bivalent connecting group, and G is a monovalent or bivalent polymerizable group.

18. The aqueous dispersion according to claim 17, wherein the proportion of the polymerized unit derived from the monomer (d) in the polymer (a) is at most 40 mass %.

19. The aqueous dispersion according to claim 17, wherein Y is an alkylene group, a polyoxyalkylene group, an imino group, a group having an ester bond, an amide bond, an urethane bond or an ether linkage or a group represented by —

R^M-Q-R^N—

, wherein each of R^M and R^N, which are independent of each other, is a single bond, or a saturated or unsaturated C_1-22 hydrocarbon group which may contain at least one hydrogen atom, and Q is a single bond, —

OCONH—

, —

CONH—

, —

SO₂NH—

or —

NHCONH—

.

20. The aqueous dispersion according to claim 17, wherein G is a residual group of a (meth)acrylate, a residual group of a maleic acid ester or a fumaric acid ester.

21. A method for producing an aqueous dispersion comprising a polymer (a) having a repeating unit (A) which comprises four carbon atoms connected in a linear chain and which has one double bond at the second position and a polyfluoroalkyl group bonded to an arbitrary carbon atom, which comprises subjecting a 1,3-diene having a polyfluoroalkyl group to an emulsion polymerization reaction in an aqueous medium in the presence of a surfactant (B) having a hydrophile-lipophile balance of at least 10, to form an aqueous dispersion.

22. The method for producing an aqueous dispersion according to claim 21, wherein the surfactant (B) is a nonionic surfactant and/or a cationic surfactant.