Fluorochemicals and fibrous substrates treated therewith: compositions of cationic and non-ionic fluorochemicals

• US 4,566,981 A
• Filed: 03/30/1984
• Issued: 01/28/1986
• Est. Priority Date: 03/30/1984
• Status: Expired due to Term

• Current Assignee: Minnesota Mining and Manufacturing Co (3M Company)
• Original Assignee: Minnesota Mining and Manufacturing Co (3M Company)
• Inventors: Howells, Richard D.
• Primary Examiner(s): Clingman, A. Lionel
• Application Number:
  US06/595,349
• Time in Patent Office: 669 Days
• Field of Search: 252/8.8, 252/8.6
• US Class Current: 428/96
• CPC Class Codes: C08F 12/20 Fluorine
• CPC Class Codes: C08G 18/0814 containing ammonium groups or groups forming them
• CPC Class Codes: C08G 18/095 oligomerisation to carbodiimide or uretone-imine groups
• CPC Class Codes: C08G 18/2885 containing halogen atoms
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C08L 33/16 Homopolymers or copolymers of esters containing halogen atoms
• CPC Class Codes: D06M 13/428 containing fluorine atoms
• CPC Class Codes: D06M 15/53 Polyethers polyacetals D06M15/39
• CPC Class Codes: D06M 15/576 containing fluorine
• CPC Class Codes: D21H 17/11 Halides
• CPC Class Codes: Y10T 428/23986 With coating, impregnation, or bond

Abstract

Cationic and non-ionic fluorochemicals, mixtures of cationic and non-ionic fluorochemicals, blends of the mixtures with fluorochemical poly(oxyalkylenes), and compositions of the fluorochemicals with hydrocarbon nonionic surfactants are provided. These fluorochemicals and compositions, in dispersions, emulsions and microemulsions, may be applied to porous fibrous substrates to give oil and water repellancy and soil resistance.

Claims

1. A fluorochemical composition comprising a mixture of

(a) a cationic fluorochemical having one or more monovalent fluoroaliphatic radicals having at least three fully fluorinated carbon atoms, one or more N-containing moieties selected from carbodiimido, urylene, and carbonylimino, said radicals and moieties being bonded together by hetero atom-containing or organic linking groups, said linking groups being free of active hydrogen atoms, and an organo amino nitrogen derived cationic moiety, said cationic moiety bonded to said N-containing moiety by hetero atom-containing or organic linking groups, and

(b) a non-ionic fluorochemical having one or more monovalent fluoroaliphatic radicals, having at least three fully fluorinated carbon atoms, and one or more N-containing moieties selected from carbodiimido, urylene, and carbonylimino, said radicals and moieties bonded together by hetero atom-containing or organic linking groups, said linking groups being free of active hydrogen atoms.

2. A fluorochemical composition according to claim 1 wherein said cationic fluorochemical (a) is represented by the general formula

3. A fluorochemical composition according to claim 2 wherein said terminal monovalent organic radicals are selected from alkyl, cycloalkyl, aryl radicals and combinations thereof, which are free of active hydrogen atoms that can readily react with isocyanate under urethane bond forming conditions.

4. A fluorochemical composition according to claim 2 wherein said terminal monovalent organic radicals contain hetero moieties selected from O, S, N, Si, and CO.

5. A fluorochemical composition according to claim 2 wherein R--Q is C₈ F₁₇ SO₂ N(C₂ H₅)C₂ H₄ CONH--, A is selected from --C₆ H₄ CH₂ C₆ H₄ --, --(CH₃)C₆ H₃ --, and --CH₂ C₆ H₄ CH₂ --, B is selected from --N═

C═

N--, --NHCONH--, --OCONH, and --SCONH--, Q--Z is selected from NHCOOC₂ H₄ N⁺ (CH₃)₂ C₂ H₅ and NHCOOC₂ H₄ N⁺ (CH₃)₃, Y is selected from CH₃ SO₄^-, C₂ H₅ SO₄^-, and I^-, n is 1 to 5 and p is 1.

6. A fluorochemical composition comprising a blend of the composition of claim 2 and a fluoroaliphatic radical-containing poly(oxyalkylene) having one or more monovalent fluoroaliphatic radicals having at least three fully fluorinated carbon atoms and one or more poly(oxyalkylene) moieties, said radicals and moieties bonded together by hetero atom-containing groups or organic linking groups.

7. A fluorochemical composition according to claim 6 wherein said polyoxyalkylene is a copolymer of C₈ H₁₇ SO₂ N(CH₃)CH₂ CH₂ OCOCH═

CH₂, CH₂ ═

C(CH₃)CO₂ (C₂ H₄ O)₉₀ H, and CH₂ ═

C(CH₃)CO₂ (C₂ H₄ O)₉₀ COC(CH₃)═

CH₂.

8. A fluorochemical composition comprising a blend of the fluorochemical composition of claim 2 and a hydrocarbon nonionic surfactant.

9. A fluorochemical composition according to claim 6 further comprising a hydrocarbon nonionic surfactant.

10. The fluorochemical composition according to claim 8, wherein said hydrocarbon nonionic surfactant has a hydrophile/lipophile balance of 13 to 16.

11. A fluorochemical composition according to claim 10 wherein said hydrocarbon nonionic surfactant is selected from alkarylpoly(oxyethylene) and poly(oxyethylene)sorbitan monoaleate.

12. A fiber finish comprising an organic solution or aqueous microemulsion of the fluorochemical composition of claim 6 or 7.

13. A method for imparting oil and water repellency to a fibrous substrate, which comprises treating the surface thereof with the composition of claim 1.

14. A fibrous substrate treated with the fluorochemical composition of claim 1.

15. A fluorochemical composition comprising a mixture of

(a) a cationic fluorochemical having one or more monovalent fluoroaliphatic radicals, said fluoroaliphatic radicals having at least three fully fluorinated carbon atoms and being stable, inert, non-polar, and both oleophobic and hydrophobic, one or more N-containing moieties selected from carbodiimido, urylene, and carbonylimino, said radicals and moieties being bonded together by linking groups selected from polyvalent aliphatic, polyvalent aromatic, oxy, thio, carbonyl, sulfone, sulfoxy, --N(CH₃)--, sulfonamido, carbonamido, sulfonamidoalkylene, carbonamidoalkylene, carbonyloxy, urethane, urea, and combinations thereof, said linking groups being free of isocyanate-reactive hydrogen atoms, and an organo amino nitrogen derived cation moiety, said cationic moiety bonded to said N-containing moiety by said linking groups, and

(b) a non-ionic fluorochemical having one or more monovalent fluoroaliphatic radicals, having at least three fully fluorinated carbon atoms, and one or more N-containing moieties selected from carbodiimido, urylene, and carbonylimino, said radicals and moieties bonded together by linking groups selected from polyvalent aliphatic, polyvalent aromatic, oxy, thio, carbonyl, sulfone, sulfoxy, --N(CH)₃ --, sulfonamido, carbonamido, sulfonamidoalkylene, carbonamidoalkylene, carbonyloxy, urethane, urea, and combinations thereof, said linking groups being free of isocyanate-reactive hydrogen atoms.