Water repellent composition, fluorocarbon polymer coating composition and coating film therefrom

• US 6,124,388 A
• Filed: 07/17/1996
• Issued: 09/26/2000
• Est. Priority Date: 07/19/1995
• Status: Expired due to Fees

• Current Assignee: Nippon Telegraph and Telephone Corporation
• Original Assignee: Nippon Telegraph and Telephone Corporation
• Inventors: Saito, Hiroyuki, Takai, Kenichi, Yamauchi, Goro, Imori, Yasutaka, Takazawa, Hisayoshi
• Primary Examiner(s): Mulcahy, Peter D.
• Application Number:
  US08/682,353
• Time in Patent Office: 1,532 Days
• Field of Search: 524/366, 524/545, 524/546
• US Class Current: 524/366
• CPC Class Codes: C08L 23/02 not modified by chemical after-treatment
• CPC Class Codes: C08L 25/02 Homopolymers or copolymers of hydrocarbons
• CPC Class Codes: C08L 2666/04 Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
• CPC Class Codes: C08L 27/12 containing fluorine atoms
• CPC Class Codes: C08L 33/06 of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
• CPC Class Codes: C08L 43/04 Homopolymers or copolymers of monomers containing silicon
• CPC Class Codes: C08L 67/02 Polyesters derived from dicarboxylic acids and dihydroxy compounds C08L67/06 takes precedence
• CPC Class Codes: C09D 127/18 Homopolymers or copolymers of tetrafluoroethene
• 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

Abstract

Fluorocarbon polymer coating composition and coating film include a fluorocarbon polymer powder, a binder and an additive comprised by a substance having a surface free energy smaller than that of the binder. The coating composition and coating film have improved resistance to deterioration with time of the water repellent properties of the film.

Claims

1. A coating composition having a water contact angle of at least 150°

and having prolonged water repellent properties, consisting essentially of;

from 80 to 90% by volume of a fluorocarbon polymer powder comprised of a fluorocarbon polymer which has an average molecular weight ranging from 500 to 20,000, which has substantially completely fluorinated terminal groups and is prepared in an atmosphere having an oxygen concentration not higher than 0.1% so that groups in the polymer chain capable of forming hydrogen bonds with molecules of water are minimized, and which is selected from the group consisting of polytetrafluoroethylene, tetrafluoroethylene/hexafluoropropylene coploymer, polyvinylidene fluoride and mixtures thereof;

a binder comprised of a polymeric material which has a surface free energy which is different from that of the fluorocarbon polymer powder and which is at least one polymer selected from the group consisting of polyvinylidene fluoride, acrylic silicone resin, polyester resin, ethylene/carbon monoxide copolymer, ethylene/vinylketone copolymer, propylene/vinylketone copolymer, and styrene/vinylketone copolymer; and

an additive comprising a substance which is selected from the group consisting of a fluoro oil, a surfactant, and a mixture thereof, which has a surface free energy which is less than that of said binder and which exceeds that of said fluorocarbon polymer powder so that wetability of the fluorocarbon polymer powder with the binder is improved and gap formation there between reduced.

2. The coating composition as claimed in claim 1, wherein the fluoro oil is selected from the group consisting of perfluorinated polyether, perfluorinated alkyl polyether, and polytrifluoroethylene.

3. The coating composition as claimed in claim 1, wherein the surfactant is a fluorocarbon surfactant.

4. The coating composition as claimed in claim 1, wherein the fluorocarbon polymer powder has a particle size ranging from 1 to 100 μ

m.

14. The coating composition as claimed in claim 1, wherein the binder is selected from the group consisting of polyvinylidene fluoride, acrylic silicone resin, and polyester resin.

5. A coating composition having prolonged water repellent properties, comprising:

from 80 to 90% by volume of a fluorocarbon polymer powder comprised of a fluorocarbon polymer which has an average molecular weight ranging from 500 to 20,000, which has substantially completely fluorinated terminal groups and is prepared in an atmosphere having an oxygen concentration not higher than 0.1% so that groups in the polymer chain capable of forming hydrogen bonds with molecules of water are minimized, and which is selected from the group consisting of polytetrafluoroethylene, tetrafluoroethylene/hexafluoropropylene coploymer, polyvinylidene fluoride and mixtures thereof;

a binder comprised of a polymeric material which has a surface free energy which is different from that of the fluorocarbon polymer powder and which is at least one polymer selected from the group consisting of polyvinylidene fluoride, acrylic silicone resin, polyester resin, ethylene/carbon monoxide copolymer, ethylene/vinylketone copolymer, propylene/vinylketone copolymer, and styrene/vinylketone copolymer; and

an additive comprising a substance which is selected from the group consisting of a fluoro oil, a surfactant, and a mixture thereof, which has a surface free energy which is less than that of said binder and which exceeds that of said fluorocarbon polymer powder so that wetability of the fluorocarbon polymer powder with the binder is improved and gap formation there between reduced,

wherein the coating composition has an agglomerated form comprised of agglomerates of the fluorocarbon polymer powder, the binder, and the additive, wherein gaps are defined between particles of the agglomerates, and wherein one of the binder or the additive fills the gaps between particles of the agglomerates.

6. A composition which is water repellent, which has a water contact angle of at least 150°

, and which has prolonged water repellant properties, consisting essentially of;

from 80 to 90% by volume of a fluorocarbon polymer powder comprised of a fluorocarbon polymer which has an average molecular weight ranging from 500 to 20,000,which has substantially completely fluorinated terminal groups and is prepared in an atmosphere having an oxygen concentration not higher than 0.1% so that groups in the polymer chain capable of forming hydrogen bonds with molecules of water are minimized, and which is selected from the group consisting of polytetrafluoroethylene, tetrafluoroethylene/hexafluoropropylene coploymer, polyvinylidene fluoride and mixtures thereof;

a matrix resin which is comprised of a polymeric material having a surface free energy which is different from that of the fluorocarbon polymer powder, and which is at least one polymer selected from the group consisting of polyvinylidene fluoride, acrylic silicone resin, polyester resin, ethylene/carbon monoxide copolymer, ethylene/vinylketone copolymer, propylene/vinylketone copolymer, and styrene/vinylketone copolymer; and

an additive comprised of a substance which is selected from the group consisting of a fluoro oil, a surfactant, and a mixture thereof, which has a surface free energy which is less than that of the matrix resin and which exceeds that of said fluorocarbon polymer powder so that wetability of the fluorocarbon polymer powder with the binder is improved and gap formation there between reduced.

7. The composition as claimed in claim 6, wherein the fluoro oil is selected from the group consisting of perfluorinated polyether, perfluorinated alkyl polyether, and polytrifluoroethylene.

8. The composition as claimed in claim 6, wherein the surfactant is a fluorocarbon surfactant.

15. The coating composition as claimed in claim 6, wherein the fluorocarbon polymer powder has a particle size ranging from 1 to 100 μ

m.

9. A composition which is water repellent and which has prolonged water repellant properties, comprising:

from 80 to 90% by volume of a fluorocarbon polymer powder comprised of a fluorocarbon polymer which has an average molecular weight ranging from 500 to 20,000, which has substantially completely fluorinated terminal groups and is prepared in an atmosphere having an oxygen concentration not higher than 0.1% so that groups in the polymer chain capable of forming hydrogen bonds with molecules of water are minimized, and which is selected from the group consisting of polytetrafluoroethylene, tetrafluoroethylene/hexafluoropropylene coploymer, polyvinylidene fluoride and mixtures thereof;

a matrix resin which is comprised of a polymeric material having a surface free energy which is different from that of the fluorocarbon polymer powder, and which is at least one polymer selected from the group consisting of polyvinylidene fluoride, acrylic silicone resin, polyester resin, ethylene/carbon monoxide copolymer, ethylene/vinylketone copolymer, propylene/vinylketone copolymer, and styrene/vinylketone copolymer; and

an additive comprised of a substance which is selected from the group consisting of a fluoro oil, a surfactant, and a mixture thereof, which has a surface free energy which is less than that of the matrix resin and which exceeds that of said fluorocarbon polymer powder so that wetability of the fluorocarbon polymer powder with the binder is improved and gap formation there between reduced,

wherein the composition has an agglomerated form comprised of agglomerates of the fluorocarbon polymer powder, the matrix resin, and the additive, wherein gaps are defined between particles of the agglomerates, and wherein one of the matrix resin or the additive fill the gaps between particles of the agglomerates.

10. A film which is a fluorocarbon polymer coating having a water contact angle of at least 150°

and having prolonged water repellant properties, consisting essentially of;

from 80 to 89% by volume of a fluorocarbon polymer powder comprised of a fluorocarbon polymer which has an average molecular weight ranging from 500 to 20,000, which has substantially completely fluorinated terminal groups and is prepared in an atmosphere having an oxygen concentration not higher than 0.1% so that groups in the polymer chain capable of forming hydrogen bonds with molecules of water are minimized, and which is selected from the group consisting of polytetrafluoroethylene, tetrafluoroethylene/hexafluoropropylene coploymer, polyvinylidene fluoride and mixtures thereof;

a binder comprised of a polymeric material which has a surface free energy which is different from that of the fluorocarbon polymer powder and which is at least one polymer selected from the group consisting of polyvinylidene fluoride, acrylic silicone resin, polyester resin, ethylene/carbon monoxide copolymer, ethylene/vinylketone copolymer, propylene/vinylketone copolymer, and styrene/vinylketone copolymer; and

an additive comprising a substance which is selected from the group consisting of a fluoro oil, a surfactant, and a mixture thereof, which has a surface free energy which is less than that of the binder and which exceeds that of said fluorocarbon polymer powder so that wetability of the fluorocarbon polymer powder with the binder is improved and gap formation there between reduced.

11. The film as claimed in claim 10, wherein the fluoro oil is selected from the group consisting of perfluorinated polyether, perfluorinated alkyl polyether, and polytrifluoroethylene.

12. The film as claimed in claim 10, wherein the surfactant is a fluorocarbon surfactant.

16. The film as claimed in claim 10, wherein the binder is selected from the group consisting of polyvinylidene fluoride, acrylic silicone resin, and polyester resin.

17. The film as claimed in claim 10, wherein the fluorocarbon polymer powder has a particle size ranging from 1 to 100 μ

m.

13. A film which is a fluorocarbon polymer coating having prolonged water repellant properties, comprising:

from 80 to 89% by volume of a fluorocarbon polymer powder comprised of a fluorocarbon polymer which has an average molecular weight ranging from 500 to 20,000, which has substantially completely fluorinated terminal groups and is prepared in an atmosphere having an oxygen concentration not higher than 0.1% so that groups in the polymer chain capable of forming hydrogen bonds with molecules of water are minimized, and which is selected from the group consisting of polytetrafluoroethylene, tetrafluoroethylene/hexafluoropropylene coploymer, polyvinylidene fluoride and mixtures thereof;

a binder comprised of a polymeric material which has a surface free energy which is different from that of the fluorocarbon polymer powder and which is at least one polymer selected from the group consisting of polyvinylidene fluoride, acrylic silicone resin, polyester resin, ethylene/carbon monoxide copolymer, ethylene/vinylketone copolymer, propylene/vinylketone copolymer, and styrene/vinylketone copolymer; and

an additive comprising a substance which is selected from the group consisting of a fluoro oil, a surfactant, and a mixture thereof, which has a surface free energy which is less than that of the binder and which exceeds that of said fluorocarbon polymer powder so that wetability of the fluorocarbon polymer powder with the binder is improved and gap formation there between reduced,

wherein the film comprises agglomerates comprising the fluorocarbon polymer powder, the binder, and the additive, wherein gaps are defined between particles of the agglomerates, and wherein one of the binder or the additive fills the gaps between particles of the agglomerates.