Multilayer material, process of preparation and applications

• US 6,365,278 B1
• Filed: 12/07/1999
• Issued: 04/02/2002
• Est. Priority Date: 12/20/1995
• Status: Expired due to Term

• Current Assignee: Hutchinson (Welltower, Inc.)
• Original Assignee: Hutchinson (Welltower, Inc.)
• Inventors: Hoerner, Pierre, Busnel, René Guy, Cheymol, André, Riess, Gérard
• Primary Examiner(s): TARAZANO, DONALD LAWRENCE
• Application Number:
  US09/455,917
• Time in Patent Office: 847 Days
• Field of Search: 428/423.1, 428/423.9, 428/424.2, 428/424.8, 428/409, 428/500, 428/515, 428/516, 428/517, 428/520, 428/522, 216/17, 216/8, 128/844, 128/918, 604/57, 604/168, 604/349
• US Class Current: 428/423.1
• CPC Class Codes: A61B 42/00 Surgical gloves; Finger-stalls specially adapted for surgery; Devices for handling or treatment thereof
• CPC Class Codes: A61B 42/10 Surgical gloves
• CPC Class Codes: B32B 25/04 comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material next to a layer of a particular substance B32B9/043; next to a bituminous or tarry layer B32B11/044; next to a water setting substance layer B32B13/042; next to a metal layer B32B15/06; next to a glass layer B32B17/063; next to a layer formed of natural mineral fibres or particles B32B19/043; next to a wood layer B32B21/045; next to a cellulosic plastic layer B32B23/046
• CPC Class Codes: Y10S 128/918 Condoms and shields
• CPC Class Codes: Y10T 428/31 Surface property or characteristic of web, sheet or block
• CPC Class Codes: Y10T 428/31551 Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
• CPC Class Codes: Y10T 428/31569 Next to natural rubber
• CPC Class Codes: Y10T 428/31573 Next to addition polymer of ethylenically unsaturated monomer
• CPC Class Codes: Y10T 428/31587 Hydrocarbon polymer [polyethylene, polybutadiene, etc.]
• CPC Class Codes: Y10T 428/31855 Of addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31909 Next to second addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31913 Monoolefin polymer
• CPC Class Codes: Y10T 428/31917 Next to polyene polymer
• CPC Class Codes: Y10T 428/31928 Ester, halide or nitrile of addition polymer
• CPC Class Codes: Y10T 428/31935 Ester, halide or nitrile of addition polymer

Abstract

Multilayer elastomer films (multilayer material) comprising at least one continuous layer, carrying an active chemical substance (such as corrosion inhibitors, lubricants or alternatively biocides for medical use), inserted between inert elastomer barrier layers, processes for the preparation and various applications of these films. The multilayer polymeric material comprises at least one layer A composed of a gel which is reversible or non-reversible, as a function of the temperature, and which carries at least one active chemical substance x, and at least two barrier layers E comprising a synthetic elastomer e, the said layers being held together by a polymeric bonding agent y incorporated in at least one of the said layers A or E and/or by an independent bonding layer Z comprising a polymer z and/or by a chemical or physical treatment of at least one of the said layers A or E.

Claims

1. A multilayer polymer material, which comprises:

at least one continuous layer A composed of a gel which is irreversible as a function of the temperature, which comprises at least one active chemical substance x, a structuring polymer c, a crosslinking agent ic selected from the group consisting of aldehydes, dialdehydes, and prepolymers containing isocyanate functional groups, and a solvent s_a; and

at least two barrier layers E which comprise a synthetic elastomer e,

said layers A and E being held together by;

a polymeric bonding agent y incorporated in at least one of said layers A or E.

2. The multilayer material according to claim 1, wherein the structuring polymer c of the layer A is a polymer which is immiscible with the synthetic elastomer e, and which is compatible with the active chemical substance x and/or the solvent s_a.

3. The multilayer material according to claim 1, wherein the said polymeric bonding agent y is incorporated into said layer A.

4. The multilayer material according to claim 1, wherein the structuring polymer c is a synthetic polymer selected from the group consisting of (a) polyethyleneimine, (b) poly(acrylic acid), (c) polyvinyl alcohol, (d) polyacrylamide, (e) polyvinylpyrrolidone, (f) poly(vinyl ether);

and (g) a derivative of any of (a)-(f).

5. The multilayer material according to claim 1, wherein the active chemical substance x is a compound capable of causing an essentially instantaneous denaturation of proteins on simple contact by a chemical reaction or by a physicochemical effect.

6. The multilayer material according to claim 5, wherein said physicochemical effect is a modification of surface tension.

7. The multilayer material according to claim 5, wherein said chemical substance x is a biocide.

8. The multilayer material according to claim 7, wherein said biocide is selected from the group consisting of (a) a quaternary ammonium, (b) a biguanide, (c) a phthalaldehyde, (d) a phenol derivative, (e) formaldehyde, (f) a non-ionic surfactant containing at least one polyoxyethylene sequence, (g) hexamidine, (h) an iodinated compound, (i) a virucidally active non-ionic surfactant, (j) sodium or potassium dichromate or hypochlorite, and (k) a mixture of any of (a)-(j).

9. The multilayer material according to claim 8, wherein said quaternary ammonium is dimethyldidecylammonium chloride, or said iodinated compound is a polyvinylpyrrolidone-iodine complex.

10. The multilayer material according to claim 1, wherein the solvent s_a for the layer A is selected from the group consisting of (i) a polyol or a polyethylene glycol which is liquid at room temperature and has a molecular weight of between about 62 Da and 750 Da;

and (ii) a volatile solvent, the solvents (i) and (ii) being used alone or as mixtures.

11. The multilayer material according to claim 10, wherein said polyol or polyethylene glycol is ethylene glycol, propylene glycol or glycerol, and wherein said volatile solvent is an alcohol, a ketone, an ether, a dimethylformamide, dimethyl sulphoxide or water.

12. The multilayer material according to claim 1 wherein the bonding agent y is selected from the group consisting of:

(i) polymers containing both at least one poly A sequence compatible with the layer A and at least one poly E sequence compatible with the layer E which are selected from the group consisting of;

di-block copolymers of formula poly A-block-poly E,

tri-block copolymers of formulas poly E-block-poly A-block-poly E (EAE), poly A-block-poly E-block-poly A (AEA), poly A-block-poly E-block-poly F (AEF) or poly A-block-poly F-block-poly E (AFE), and

grafted copolymers of formulas poly A-grafted-poly E, poly E-grafted-poly A, or poly A-grafted-poly E and -poly F, it being possible for the poly F sequence to be compatible with the layer A or with the layer E.

13. The multilayer material according to claim 1, wherein the gel layer A comprises:

between 0 and 98% of solvent s_a with respect to the gel,

between 0.1 and 74% of structuring polymer c with respect to the gel,

between 1 and 80% of the active chemical substance x with respect to the gel, and

between 0.0001 and 0.1% by weight of crosslinking agent ic per combined other constituents.

14. The multilayer material according to claim 13, wherein said gel layer A comprises between 25% and 98% of the solvent s_a with respect to the gel.

15. The multilayer material according to claim 13, wherein said gel layer A comprises between 1% and 74% of the structuring polymer c with respect to the gel.

16. The multilayer material according to claim 13, wherein said gel layer A comprises between 1% and 74% of the active chemical substance x with respect to the gel.

17. The multilayer material according to claim 13, wherein, when the gel layer A additionally comprises a bonding agent y, the proportions by weight of the latter are between 0.01 and 25% with respect to the gel, the proportions of solvent s_a being consequently adjusted.

18. The multilayer material according to claim 1, wherein the elastomer layers E comprise a synthetic elastomer e selected from the group consisting of polybutadiene, polyisoprene, an acrylic polymer, polychloroprene, polyurethane, a chlorobutadiene-methacrylic acid copolymer, an ethylene vinyl acetate copolymer, a styrene butadiene rubber (SBR) copolymer, a styrene-butadiene-styrene (SBS) copolymer, a styrene-isoprene-styrene (SIS) copolymer and a styrene-ethylene-butylene-styrene (SEBS) copolymer, and said polymeric bonding agent y is incorporated into said layers E.

19. A glove coated with a multilayer material according to claim 1.

20. A fingerstall coated with a multilayer material according to claim 1.

21. A condom coated with a multilayer material according to claim 1.

22. A multilayer polymer material, which comprises:

(a) at least one continuous layer A composed of a gel which is irreversible as a function of the temperature, which comprises at least one active chemical substance x, a structuring polymer c, a crosslinking agent ic and a solvent s_a; and

(b) at least two barrier layers E which comprise a synthetic elastomer e, said layers A and E being held together by a polymeric bonding agent y incorporated in at least one of said layers A or E;

wherein the bonding agent y is selected from the group consisting of;

(i) polymers containing both at least one poly A sequence compatible with the layer A and at least one poly E sequence compatible with the layer E which are selected from the group consisting of;

(a) di-block copolymers of formula poly A-block-poly E;

(b) tri-block copolymers of formulas poly E-block-poly A-block-poly E (EAE), polyA-block-poly E-block-polyA (AEA), poly A-block E-block poly F (AEF) or poly A-block-poly F-block-poly E (AFE); and

(c) grafted copolymers of formulas poly A-grafted-poly E, poly E-grafted-poly A, or poly A-grafted-poly E and -poly F, it being possible for the poly F sequence to be compatible with the layer A or with E;

wherein the poly A sequences are selected from the group consisting of polyoxyethylene, polyvinylpyridine, poly(acrylic acid)s, polyvinyl alcohol and quaternized polyvinylpyridine and the poly E sequences are selected from the group consisting of polydienes, polyolefins, polyoxypropylene and polydimethylsiloxane.

23. The multilayer material according to claim 22, wherein the structuring polymer c of the layer A is a polymer which is immiscible with the synthetic elastomer e and which is compatible with the active chemical substance x and/or solvent s_a.

24. The multilayer material according to claim 22, wherein the said irreversible gel additionally contains a bonding agent y.

25. The multilayer material according to claim 22, wherein the structuring polymer c is a synthetic polymer selected from the group consisting of (a) polyethyleneimine, (b) poly(acrylic acid), (c) polyvinyl alcohol, (d) polyacrylamide, (e) polyvinylpyrrolidone, (f) poly(vinyl ether);

and (g) a derivative of any of (a)-(f).

26. The multilayer material according to claim 22, wherein the crosslinking agent ic is selected from the group consisting of aldehydes, dialdehydes, and prepolymers containing isocyanate functional groups.

27. The multilayer material according to claim 22, wherein the active chemical substance x is a compound capable of causing an essentially instantaneous denaturation of proteins upon simple contact by a chemical reaction or by a physicochemical effect.

28. The multilayer material according to claim 27, wherein said physicochemical effect is a modification of surface tension.

29. The multilayer material according to claim 27, wherein said chemical substance x is a biocide.

30. The multilayer material according to claim 29, wherein said biocide is selected from the group consisting of (a) a quaternary ammonium, (b) a biguanide, (c) a phthalaldehyde, (d) a phenol derivative, (e) formaldehyde, (f) a non-ionic surfactant containing at least one polyoxyethylene sequence, (g) hexamidine, (h) an iodinated compound, (i) a virucidally active non-ionic surfactant, (j) sodium or potassium dichromate or hypochlorite, and (k) a mixture of any of (a)-(j).

31. The multilayer material according to claim 30, wherein said quaternary ammonium is dimethyldidecylammonium chloride, and said iodinated compound is a polyvinylpyrrolidone-iodine complex.

32. The multilayer material according to claim 22, wherein the solvent s_a, for the layer A is selected from the group consisting of (i) a polyol or a polyethylene glycol which is liquid at room temperature and has a molecular weight of between about 62 Da and 750 Da;

and (ii) a volatile solvent, the solvents (i) and (ii) being used alone or as mixtures.

33. The multilayer material according to claim 32, wherein said polyol or polyethylene glycol is ethylene glycol, propylene glycol or glycerol, and wherein said volatile solvent is an alcohol, a ketone, an ether, a dimethylformamide, dimethyl sulfoxide or water.

34. The multilayer material according to claim 22, wherein said gel layer A comprises:

between 0% and 98% of the solvent s_a with respect to the gel,

between 0.1% and 74% of the structuring polymer c with respect to the gel.

between 1% and 80% of the active chemical substance x with respect to the gel, and

between 0.0001% and 0.1% by weight of crosslinking agent ic per combined other constituents.

35. The multilayer material according to claim 34, wherein said gel layer A comprises between 25% and 98% of the solvent s_a with respect to the gel.

36. The multilayer material according to claim 34, wherein said gel layer A comprises between 1% and 74% of the structuring polymer c with respect to the gel.

37. The multilayer material according to claim 34, wherein said gel layer A comprises between 1% and 74% of the active chemical substance x with respect to the gel.

38. The multilayer material according to claim 34, wherein, when the bonding agent y is incorporated in the gel layer A the proportions by weight of said bonding agent y are between 0.01 and 25% with respect to the gel, the proportions of solvent s_a being consequently adjusted.

39. The multilayer material according to claim 22, wherein the elastomer layers E comprise a synthetic elastomer e selected from the group consisting of polybutadiene, polyisoprene, acrylic polymers, polychloroprene, polyurethane, chlorobutadiene-methacrylic acid copolymers, ethylene-vinyl acetate copolymers, styrene butadiene rubber (SBR) copolymers, styrene-butadiene-styrene (SBS) copolymers, styrene-isoprene-styrene (SIS) copolymers, styrene-ethylene-butylene-styrene (SEBS) copolymers, and said polymeric bonding agent y is incorporated into said layers E.

40. A glove coated with a multilayer material according to claim 22.

41. A fingerstall coated with a multilayer material according to claim 22.

42. A condom coated with a multilayer material according to claim 22.