Aqueous dispersion of fluorine-containing copolymer

Patent metadata

Field	Value
Publication number	US-10023733-B2
Application number	US-201414900897-A
Country	US
Kind code	B2
Filing date	Jun 11, 2014
Priority date	Jun 25, 2013
Publication date	Jul 17, 2018
Grant date	Jul 17, 2018

Abstract

An aqueous dispersion of a fluorine-containing copolymer comprising, as copolymerization units, (A) a (meth)acrylate represented by [CH2═CHRCOO(NH)rR1NR2R3R4]+Y−, (B) a perfluoroalkylalkyl(meth)acrylate represented by CmF2m+1CpH2p(NR′SO2)qOCOCR═CH2 or a polyfluoroalkylalkyl(meth)acrylate thereof, or a polyfluoroalkyl(meth)acrylate represented by CnF2n+1(CH2CF2)a(CF2CF2)b(CH2CH2)cOCOCR═CH2, (C) benzyl(meth)acrylate, (D) a fluorine-free polymerizable monomer other than components (A) and (C), and (E) a crosslinkable group-containing polymerizable monomer. The aqueous dispersion can improve the dispersion stability of an aqueous dispersion of a water- and oil-repellent when used as a water- and oil-repellent comprising the fluorine-containing copolymer as an active component.

First claim

The invention claimed is:

1. An aqueous dispersion of a fluorine-containing copolymer comprising, as copolymerization units,
(A) a (meth)acrylate represented by the general formula:
[CH 2 ═CHRCOO(NH) r R 1 NR 2 R 3 R 4 ] + Y −   [I]

wherein R is a hydrogen atom or a methyl group; R 1 is a linear, branched, or alicyclic alkylene group having 1 to 30 carbon atoms or a phenylene group; R 2 , R 3 , and R 4 are the same or different and each is a linear, branched, or alicyclic alkyl group having 1 to 30 carbon atoms or an aralkyl group; r is 0 or 1; and Y − is an anionic group;
(B)
a perfluoroalkylalkyl(meth)acrylate represented by the general formula:
C m F 2m+1 C p H 2p (NR′SO 2 ) q OCOCR═CH 2   [IIa]

wherein R is a hydrogen atom or a methyl group, R′ is an alkyl group having 1 to 5 carbon atoms, m is an integer of 4 to 14, p is an integer of 1 to 4, and q is 0 or 1;
a polyfluoroalkylalkyl(meth)acrylate which is prepared by replacing some of the fluorine atoms in the perfluoroalkyl group in the above perfluoroalkylalkyl(meth)acrylate with hydrogen atoms; or
a polyfluoroalkyl(meth)acrylate represented by the general formula:
C n F 2n+1 (CH 2 CF 2 ) a (CF 2 CF 2 ) b (CH 2 CH 2 ) c OCOCR═CH 2   [IIb]

wherein R is a hydrogen atom or a methyl group, n is an integer of 1 to 6, a is an integer of 1 to 4, b is an integer of 1 to 3, and c is an integer of 1 to 3;
(C) benzyl(meth)acrylate;
(D) a fluorine-free polymerizable monomer other than components (A) and (C); and
(E) a crosslinkable group-containing polymerizable monomer,
wherein 0.1 to 1.0 wt. % of component (A), 10 to 80 wt. % of component (B), 5 to 80 wt. % of component (C), 1 to 30 wt. % of component (D), and 0.3 to 30 wt. % of component (E), each in the fluorine-containing copolymer, are copolymerized using a water-soluble polymerization initiator.

2. The aqueous dispersion of the fluorine-containing copolymer according to claim 1 , wherein the fluorine-free polymerizable monomer as component (D) in the fluorine-containing copolymer is vinylidene chloride.

3. The aqueous dispersion of the fluorine-containing copolymer according to claim 1 , wherein the crosslinkable group-containing polymerizable monomer as component (E) in the fluorine-containing copolymer is polyalkylene glycol mono(meth)acrylate, hydroxyalkyl(meth)acrylate, or methylol group-containing (meth)acrylamide.

4. A water- and oil-repellent which is prepared by further diluting the aqueous dispersion of the fluorine-containing copolymer according to claim 1 , with a water-based medium to a solid matters content of 0.1 to 10 wt. %.

5. A fluorine-containing copolymer comprising, as copolymerization units,
(A) a (meth)acrylate represented by the general formula:
[CH 2 ═CHRCOO(NH) r R 1 NR 2 R 3 R 4 ] + Y −   [I]

wherein R is a hydrogen atom or a methyl group; R 1 is a linear, branched, or alicyclic alkylene group having 1 to 30 carbon atoms or a phenylene group; R 2 , R 3 , and R 4 are the same or different and each is a linear, branched, or alicyclic alkyl group having 1 to 30 carbon atoms or an aralkyl group; r is 0 or 1; and Y − is an anionic group;
(B)
a perfluoroalkylalkyl(meth)acrylate represented by the general formula:
C m F 2m+1 C p H 2p (NR′SO 2 ) q OCOCR═CH 2   [IIa]

wherein R is a hydrogen atom or a methyl group, R′ is an alkyl group having 1 to 5 carbon atoms, m is an integer of 4 to 14, p is an integer of 1 to 4, and q is 0 or 1;
a polyfluoroalkylalkyl(meth)acrylate which is prepared by replacing some of the fluorine atoms in the perfluoroalkyl group in the perfluoroalkylalkyl(meth)acrylate with hydrogen atoms; or
a polyfluoroalkyl(meth)acrylate represented by the general formula:
C n F 2n+1 (CH 2 CF 2 ) e (CF 2 CF 2 ) b (CH 2 CH 2 ) c OCOCR═CH 2   [IIb]

wherein R is a hydrogen atom or a methyl group, n is an integer of 1 to 6, a is an integer of 1 to 4, b is an integer of 1 to 3, and c is an integer of 1 to 3;
(C) benzyl(meth)acrylate;
(D) a fluorine-free polymerizable monomer other than components (A) and (C); and
(E) a crosslinkable group-containing polymerizable monomer, wherein 0.1 to 1.0 wt. % of component (A), 10 to 80 wt. % of component (B), 5 to 80 wt. % of component (C), 1 to 30 wt. % of component (D), and 0.3 to 30 wt. % of component (E) are copolymerized using a water-soluble polymerization initiator.

6. A water- and oil-repellent which is prepared by further diluting the aqueous dispersion of the fluorine-containing copolymer B according to claim 1 , with a water-based medium to a solid matters content of 0.1 to 10 wt. %.

7. A water- and oil-repellent which is prepared by further diluting the aqueous dispersion of the fluorine-containing copolymer according to claim 2 , with a water-based medium to a solid matters content of 0.1 to 10 wt. %.

8. A water- and oil-repellent which is prepared by further diluting the aqueous dispersion of the fluorine-containing copolymer according to claim 3 , with a water-based medium to a solid matters content of 0.1 to 10 wt. %.

Assignees

• Unimatec Co Ltd

Inventors

• Kaneumi Yoshiyama

Classifications

• D06M15/29

  containing a N-methylol group or an etherified N-methylol group; containing a N-aminomethylene group; containing a N-sulfidomethylene group · CPC title

• D06M2200/12

  Hydrophobic properties · CPC title

• D06M15/267

  of unsaturated carboxylic esters having amino or quaternary ammonium groups · CPC title

• D06M15/27

  of alkylpolyalkylene glycol esters of unsaturated carboxylic acids · CPC title

• D06M2200/11

  Oleophobic properties · CPC title