Fluorine-containing water-repellent composition

• US 10,597,816 B2
• Filed: 07/03/2015
• Issued: 03/24/2020
• Est. Priority Date: 07/04/2014
• Status: Active Grant

• Current Assignee: Archroma IP GmbH
• Original Assignee: Archroma IP GmbH
• Inventors: Knaup, Wolfgang, Gasafi-Martin, Waltraud
• Primary Examiner(s): Egwim, Kelechi C
• Application Number:
  US15/323,332
• Publication Number:
  US 20170130394A1
• Time in Patent Office: 1,726 Days
• Field of Search: 524763
• CPC Class Codes: C08F 2/44 Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• CPC Class Codes: C08F 214/06 Vinyl chloride
• CPC Class Codes: C08F 220/1804 C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
• CPC Class Codes: C08F 220/1818 C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
• CPC Class Codes: C08F 220/20 of polyhydric alcohols or phenols , e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
• CPC Class Codes: C08F 220/24 containing perhaloalkyl radicals
• CPC Class Codes: C08F 220/325 containing glycidyl radical, e.g. glycidyl (meth)acrylate
• CPC Class Codes: C08K 5/01 Hydrocarbons C08K5/0091 takes precedence
• CPC Class Codes: C08L 2203/12 used for fibers
• CPC Class Codes: C08L 2205/025 containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
• CPC Class Codes: C08L 33/066 containing -OH groups
• CPC Class Codes: C08L 33/068 containing glycidyl groups
• CPC Class Codes: C08L 33/10 Homopolymers or copolymers of methacrylic acid esters
• CPC Class Codes: C08L 33/16 Homopolymers or copolymers of esters containing halogen atoms
• CPC Class Codes: C08L 91/06 Waxes
• CPC Class Codes: C09D 133/066 containing -OH groups
• CPC Class Codes: C09D 133/068 containing glycidyl groups
• CPC Class Codes: C09D 133/08 Homopolymers or copolymers of acrylic acid esters
• CPC Class Codes: C09D 133/12 Homopolymers or copolymers of methyl methacrylate
• CPC Class Codes: C09D 133/16 Homopolymers or copolymers of esters containing halogen atoms
• CPC Class Codes: C09D 191/06 : Waxes
• CPC Class Codes: C09D 4/00 : Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
• CPC Class Codes: C09D 5/00 : Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced electrically insulating plastics, resins or waxes H01B3/30; Filling pastes
• CPC Class Codes: C09D 7/63 : organic
• CPC Class Codes: D06M 13/02 : with hydrocarbons
• CPC Class Codes: D06M 13/224 : Esters of carboxylic acids; Esters of carbonic acid
• CPC Class Codes: D06M 15/248 : containing chlorine
• CPC Class Codes: D06M 15/263 : of unsaturated carboxylic acids; Salts or esters thereof
• CPC Class Codes: D06M 15/273 : of unsaturated carboxylic esters having epoxy groups
• CPC Class Codes: D06M 15/277 : containing fluorine
• CPC Class Codes: D06M 15/29 : containing a N-methylol group or an etherified N-methylol group; containing a N-aminomethylene group; containing a N-sulfidomethylene group
• CPC Class Codes: D06M 2101/06 : cellulosic
• CPC Class Codes: D06M 2101/32 : Polyesters
• CPC Class Codes: D06M 2200/01 : Stain or soil resistance
• CPC Class Codes: D06M 2200/11 : Oleophobic properties
• CPC Class Codes: D06M 2200/12 : Hydrophobic properties

Abstract

Composition, comprising at least components (A) and (B) and optionally at least one of components (C) to (E):

• • (A) a polyacrylate obtained in the polymerisation of monomers
    • (M1) CH₂═CR³COO—R¹ with
    • (M2) CH₂═CR³COO—R² and optionally
    • (M3) CH₂═CR⁶COO—Y—R_F
    • (M4) CH₂═CR³—X—R⁴;
  • (B) a wax;
  • (C) a blocked isocyanate;
  • (D) an organic polysiloxane;
  • (E) a melamine resin.

Claims

1. A composition, comprising components (A) and (B) and optionally at least one of components (C) to (E):

(A) a polyacrylate obtained in the polymerisation of monomers consisting of

(M1) CH₂═

CR³COO—

R¹

(M2) CH₂═

CR³COO—

R²

(M3) CH₂═

CR⁶COO—

Y—

R_F and optionally

(M4) CH₂═

CR³—

X—

R⁴;

(B) a wax;

(C) a blocked isocyanate;

(D) an organic polysiloxane;

(E) a melamine resin;

wherein

R¹ is an alcohol moiety in (meth)acrylate monomer (M1) containing from 1 to 8 carbon atoms;

R² is an alcohol moiety in (meth)acrylate monomer (M2) containing from 9 to 40 carbon atoms;

R_F—

Y is an alcohol moiety in (meth)acrylate monomer (M3), wherein

Y is —

(CH₂)_m—

, wherein m is an integer in a range of from 1 to 10; and

R_F is C_xF_2x+1, wherein x is an integer in a range of from 1 to 12;

R⁶ is selected from the group consisting of H, CH₃, Cl, and F;

R³ in monomer (M1), (M2) and (M4) is independently selected from the group consisting of H, CH₃, and C₂H₅;

X in monomer (M4) is COO or CONH;

R⁴ is glycidyl or CH₂(CH₂)_n—

OR⁵, wherein n is an integer in a range of from 1 to 10 and R⁵ is H or a residue containing from 1 to 6 carbon atoms;

and wherein the composition comprises water and/or an organic solvent.

2. The composition according to claim 1, wherein R¹ contains from 1 to 6 carbon atoms and R² contains from 12 to 40 carbon atoms.

3. The composition according to claim 1, wherein R¹ is branched or unbranched or cyclic C₁ to C₆ alkyl and R² is branched or unbranched or cyclic C₁₂ to C₄₀ alkyl.

4. The composition according to claim 1, wherein R¹ is selected from one or more of the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl and isomers thereof, n-hexyl and isomers thereof, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl;

and R² is selected from one or more of the group consisting of n-dodecyl (lauryl) and isomers thereof, n-tridecyl and isomers thereof, n-tetradecyl (myristyl) and isomers thereof, n-pentadecyl and isomers thereof, n-hexadecyl (cetyl) and isomers thereof, n-heptadecyl and isomers thereof, n-octadecyl (stearyl) and isomers thereof, n-nonadecyl and isomers thereof, n-eicosyl and isomers thereof, n-heneicosyl and isomers thereof, n-docosyl (behenyl) and isomers thereof, n-tricosyl and isomers thereof, n-tetracosyl and isomers thereof, n-pentacosyl and isomers thereof, n-hexacosyl (ceryl) and isomers thereof, n-heptacosyl and isomers thereof, n-octacosyl and isomers thereof, n-nonacosyl and isomers thereof, and n-triacontyl (myricyl) and isomers thereof.

5. The composition according to claim 1, wherein (A) is obtained in the polymerization of

5 to 40% by weight of monomer (M1);

30 to 85% by weight of monomer (M2);

1 to 50% by weight of monomer (M3); and

optionally

0.1 to 20% by weight of monomer (M4);

based on a total amount of (A) (=100% by weight).

6. The composition according to claim 1, wherein (A) is obtained in the polymerization of

5 to 30% by weight of monomer (M1);

30 to 70% by weight of monomer (M2);

5 to 40% by weight of monomer (M3); and

optionally

0.1 to 10% by weight of (M4);

based on a total amount of (A) (=100% by weight).

7. The composition according to claim 1, wherein wax (B) has a melting point in a range of from 50 to 130°

C.

8. The composition according to claim 1, wherein wax (B) has a melting point in a range of from 60 to 90°

C.

9. The composition according to claim 1, wherein wax (B) is a paraffin wax.

10. The composition according to claim 1, wherein the composition comprises from

5 to 90% by weight of (A);

5 to 90% by weight of (B);

0 to 40% by weight of a blocked isocyanate (C);

0 to 40% by weight of an organic polysiloxane (D);

0 to 40% by weight of a melamine resin (E);

0.1-90% by weight of water and/or the organic solvent;

based on a total amount of the composition (=100% by weight).

11. A method of making the composition according to claim 1, comprising (C1) to (C2):

(C1) homogenizing a mixture comprising monomers consisting of (M1), (M2), (M3) and optionally (M4), and wax (B), and water and/or an organic solvent;

(C2) polymerizing the mixture obtained in (C1).

12. A method of treating a substrate, comprising (S1):

(S1) contacting the substrate with the composition according to claim 1.

13. A substrate, coated with a composition according to claim 1.

14. The substrate according to claim 13, wherein the substrate is in a form of a linear formation, in a form of a planar formation, or in a form of a spatial formation;

or wherein the substrate is a textile, fiber, fabric, paper, nonwoven, leather, or a combination of two or more thereof.

15. The method according to claim 12, wherein the substrate is in a form of a linear formation, in a form of a planar formation, or in a form of a spatial formation;

or wherein the substrate is a textile, fiber, fabric, paper, nonwoven, leather, or a combination of two or more thereof.

16. The composition according to claim 10, wherein (C) is present.

18. The composition according to claim 1, wherein (M4) is present, wherein R4 is CH₂(CH₂)_n—

OR⁵, and wherein n is an integer in a range from 1 to 4 and R⁵ is H or a residue containing from 1 to 4 carbon atoms.

19. The composition according to claim 1, wherein (E) is present.

20. The substrate according to claim 13, wherein the substrate is a textile.

17. A composition comprising components (A) and (B) and optionally at least one of components (C) and (E):

(A) a polyacrylate obtained in the polymerisation of monomers

(M1) CH₂═

CR³COO—

R¹

(M2) CH₂═

CR³COO—

R²

(M3) CH₂═

CR⁶COO—

Y—

R_F and optionally

(M4) CH₂═

CR³—

X—

R⁴;

(B) a wax;

(C) a blocked isocyanate;

(D) an organic polysiloxane;

(E) a melamine resin;

wherein

R¹ is an alcohol moiety in (meth)acrylate monomer (M1) containing from 1 to 8 carbon atoms;

R² is an alcohol moiety in (meth)acrylate monomer (M2) containing from 9 to 40 carbon atoms;

R_F—

Y is an alcohol moiety in (meth)acrylate monomer (M3), wherein

Y is —

(CH₂)_m—

, wherein m is an integer in a range of from 1 to 10; and

R_F is C_XF_2X+1, wherein x is an integer in a range of from 1 to 12;

R⁶ is selected from the group consisting of H, CH₃, Cl, and F;

R³ in monomer (M1), (M2) and (M4) is independently selected from the group consisting of H, CH₃, and C₂H₅;

X in monomer (M4) is COO or CONH;

R⁴ is glycidyl or CH₂(CH₂)_n—

OR⁵, wherein n is an integer in a range of from 1 to 10 and R⁵ is H or a residue containing from 1 to 6 carbon atoms;

and wherein the composition comprises water and/or an organic solvent,

wherein the composition comprises from

5 to 90% by weight of (A);

5 to 90% by weight of (B);

0 to 40% by weight of a blocked isocyanate (C);

0 to 40% by weight of an organic polysiloxane (D);

0 to 40% by weight of a melamine resin (E);

0.1-90% by weight of water and/or the organic solvent;

based on a total amount of the composition (=100% by weight),

wherein (D) is present.