阅读说明：本技术 容器用装饰性封闭件 (Decorative closure for container ) 是由 达雷尔·詹姆斯·米勒 奥拉夫·马库斯·奥高 克里斯蒂娜·披·普洛·董 于 2019-07-31 设计创作，主要内容包括：本发明涉及一种被构造为插入并牢固地保持在容器的形成入口的颈部中的封闭件(1),该封闭件(1)具有基本上圆柱形的形状并且包括形成封闭件(1)的相对端部的基本上平坦的终端表面,其中封闭件(1)还包括a.封闭件前体(2),其具有基本上圆柱形的形状并且包括侧表面和形成封闭件前体(2)的相对端部的基本上平坦的终端表面,其中封闭件前体(2)的侧表面和平坦的终端表面具有基本上均匀的颜色；以及b.至少部分地覆盖封闭件前体(2)的至少侧表面的装饰层(4)。(The present invention relates to a closure (1) configured to be inserted and securely held in an inlet-forming neck of a container, the closure (1) having a substantially cylindrical shape and comprising substantially flat terminal surfaces forming opposite ends of the closure (1), wherein the closure (1) further comprises a. a closure precursor (2) having a substantially cylindrical shape and comprising side surfaces and substantially flat terminal surfaces forming opposite ends of the closure precursor (2), wherein the side surfaces and the flat terminal surfaces of the closure precursor (2) have a substantially uniform color; a decorative layer (4) at least partially covering at least a side surface of the closure precursor (2).)

1. A closure (1) configured to be inserted and securely held in a neck of a container forming an inlet, the closure (1) having a substantially cylindrical shape and comprising substantially flat terminal surfaces forming opposite ends of the closure (1), wherein the closure (1) further comprises:

a. a closure precursor (2) having a substantially cylindrical shape and comprising a side surface and a substantially planar terminal surface forming opposite ends of said closure precursor (2), wherein said side surface and said planar terminal surface of said closure precursor (2) have a substantially uniform color; and

b. a decorative layer (4) at least partially covering at least the side surface of the closure precursor (2).

2. The closure (1) according to claim 1, wherein the uniform color is selected from the group consisting of white, yellow, orange, ochre and mixtures thereof, in particular from the group consisting of RAL 9001, RAL 9010, RAL 1000, RAL 1001, RAL 1002, RAL 1014, RAL 1015, RAL 8001 and mixtures thereof.

3. A closure (1) according to any one of claims 1 or 2, wherein the releasable trichloroanisole content of the closure and/or the closure precursor, measured according to the test method defined herein, is less than 2ng/L, preferably less than 1ng/L, preferably less than 0.5ng/L, preferably less than 0.3 ng/L.

4. The closure (1) according to any one of the preceding claims, wherein the total density of the closure (1) is at 100kg/m³To 500kg/m³Within the range of (1).

5. The closure (1) according to any one of the preceding claims, wherein the decorative layer (4) completely covers the side surface of the closure precursor (2).

6. The closure (1) according to any one of the preceding claims, wherein the decorative layer (4) also covers the flat terminal surface of the closure precursor (2) at least partially, in particular completely.

7. The closure (1) as set forth in any of the preceding claims wherein said decorative layer (4) is further defined as comprising a pigment or dye.

8. The closure (1) according to any one of the preceding claims, wherein the decor layer (4) is further defined as being applied by printing, in particular by offset printing, pad printing, screen printing, ink jet printing, hot foil transfer, fire branding or laser printing.

9. The closure (1) according to any one of the preceding claims, wherein the print resolution of the decor layer (4) is 25 dots per inch (dpi) or more, preferably 72dpi or more, preferably 150dpi or more, more preferably 300dpi or more, and more preferably 600dpi or more.

10. The closure (1) according to any one of the preceding claims, wherein the decorative layer (4) comprises one or more shades of at least a single color, in particular of two or more colors.

11. The closure (1) according to any one of the preceding claims, wherein the decorative layer (4) is monochromatic or multicoloured.

12. The closure (1) according to any one of the preceding claims, wherein the decorative layer (4) has photographic image quality, in particular in terms of sharpness, tone reproduction and/or contrast.

13. The closure (1) according to any one of the preceding claims, wherein the decorative layer (4) is further defined as comprising one or more materials that comply with or are approved by the U.S. Food and Drug Administration (FDA) or the European Union (EU) as Food Contact Substances (FCS).

14. The closure (1) according to any one of the preceding claims, wherein the decorative layer (4) depicts a first marking.

15. The closure (1) according to claim 14, wherein the first indicia comprises one or more selected from the group consisting of letters, symbols, colors, graphics, icons, logos, wood tones, natural cork appearance and photographs.

16. The closure (1) according to any one of the preceding claims, wherein the closure (1) further comprises a decor layer, in particular on top of the decor layer.

17. The closure (1) according to claim 16, wherein the decor layer is further defined as comprising a pigment or dye, and/or as being applied by printing, in particular by offset printing, pad printing, screen printing, inkjet printing, fire-branding, hot-foil transfer printing or laser printing, and/or depicting a second marking, in particular wherein the second marking comprises one or more selected from the group consisting of letters, symbols, colors, graphics, icons, logos, wood tones, natural cork appearance and photographs, and/or as comprising one or more materials meeting the standards of the united states Food and Drug Administration (FDA) or the European Union (EU) or being approved by the united states Food and Drug Administration (FDA) or the European Union (EU) as Food Contact Substance (FCS).

18. The closure (1) according to any one of the preceding claims, wherein the closure precursor (2) comprises from 1 to 99 wt. -%, in particular from 5 to 85 wt. -%, or from 20 to 75 wt. -%, or from 30 to 72 wt. -%, or from 33 to 65 wt. -%, or from 33 to 59 wt. -% cork, in each case based on the total weight of the closure precursor (2).

19. The closure (1) according to any one of the preceding claims, wherein the closure precursor (2) comprises, in each case, from 1% to 49% by weight, in particular from 5% to 32% by weight, or from 5% to 30% by weight, or from 5.5% to 26% by weight, of the first plastic material, based on the total weight of the closure precursor (2).

20. The closure (1) according to any one of the preceding claims, wherein the closure precursor (2) comprises in each case from 10% to 49% by weight, in particular from 12% to 49% by weight, or from 25% to 35% by weight, of the second plastic material, based on the total weight of the closure precursor (2).

21. The closure (1) according to any one of the preceding claims, wherein the closure precursor (2) comprises, in each case, from 0 to 10% by weight, in particular from 0.1 to 4% by weight, of one or more foaming agents, based on the total weight of the closure precursor (2); 0 to 15 wt% of one or more lubricants; and/or 0 to 10 wt% of one or more additives and/or fillers.

22. The closure (1) according to any one of claims 18 to 21, wherein the cork is in the form of cork granules.

23. Closure (1) according to claim 22, wherein the cork granules have a granulometric distribution D, determined by mechanical sieving according to ISO ICS19.120₅₀In the range of 0.25mm to 5mm, in particular in the range of 0.5mm to 2 mm.

24. The closure (2) according to claim 22 or 23, wherein the cork granules are substantially isotropic in shape, in particular substantially spherical in shape.

25. The closure (1) according to any one of claims 22 to 24, wherein, in each case, based on the total weight of the cork particles, the content of releasable trichloroanisole of the cork granules, measured according to the test method defined herein, is less than 6ng/L, preferably less than 5ng/L, preferably less than 4ng/L, preferably less than 3ng/L, preferably less than 2ng/L, preferably less than 1ng/L, and/or the density of the cork particles is in the range of 50g/L to 200g/L, and/or the moisture content of the cork particles is less than 8% by weight, in particular less than 7 wt.%, less than 6 wt.%, less than 5 wt.%, less than 4 wt.%, less than 3 wt.%, less than 2 wt.%, less than 1.5 wt.% or less than 1 wt.%.

26. The closure (1) according to any one of claims 18 to 25, wherein the cork, in particular the cork granulate, is bleached.

27. The closure (1) according to any one of claims 19 to 26, wherein the first plastic material comprises one or more thermoplastic polymers.

28. A closure according to any one of claims 19 to 27, wherein at least 90 wt%, preferably at least 95 wt%, in particular 100 wt% of the first plastic material is biodegradable according to ASTM D6400.

29. The closure (1) according to any one of claims 19 to 28, wherein said first plastic material comprises one or more thermoplastic polymers independently selected from the group consisting of: polyethylene; metallocene catalyst polyethylene; a polybutylene; polybutylene; a thermoplastic polyurethane; a silicone; a vinyl-based resin; a thermoplastic elastomer; a polyester; ethylene acrylic acid copolymers; ethylene-vinyl acetate copolymers; ethylene-methyl acrylate copolymers; a thermoplastic polyolefin; a thermoplastic vulcanizate; a flexible polyolefin; a fluororubber; a fluoropolymer; polytetrafluoroethylene; ethylene-butyl acrylate copolymers; ethylene-propylene rubbers; styrene butadiene rubber; styrene butadiene block copolymers; ethylene-ethyl-acrylic acid copolymers; an ionomer; polypropylene; copolymers of polypropylene and ethylenically unsaturated comonomers copolymerizable therewith; an olefin copolymer; an olefin block copolymer; a cycloolefin copolymer; styrene ethylene butadiene styrene block copolymers; styrene ethylene butylene styrene block copolymers; styrene ethylene butylene block copolymers; styrene butadiene styrene block copolymers; styrene butadiene block copolymers; styrene isoprene styrene block copolymers; styrene isobutylene block copolymers; styrene isoprene block copolymers; styrene ethylene propylene styrene block copolymers; styrene ethylene propylene block copolymers; polyvinyl alcohol; polyvinyl butyral; polyhydroxyalkanoates; copolymers of monomers of hydroxyalkanoates and biodegradable polymers; polylactic acid; copolymers of lactic acid and monomers of biodegradable polymers; an aliphatic copolyester; aromatic-aliphatic copolyesters; polycaprolactone; polyglycolide; poly (3-hydroxybutyrate); poly (3-hydroxybutyrate-co-3-hydroxyvalerate); poly (3-hydroxybutyrate-co-3-hydroxyhexanoate); poly (butylene succinate); poly (butylene succinate-co-adipate); poly (trimethylene terephthalate); poly (butylene adipate-co-terephthalate); poly (butylene succinate-co-terephthalate); poly (butylene sebacate-co-butylene terephthalate); caprolactone lactate copolymers; lactic acid ethylene oxide lactic acid copolymers; a polymer formed from monomer units selected from vinylidene chloride, acrylonitrile and methyl methacrylate; copolymers formed from two or more monomer units selected from vinylidene chloride, acrylonitrile and methyl methacrylate; PEF, PTF, bio-based polyester, and combinations of any two or more thereof.

30. The closure (1) according to any one of claims 19 to 29, wherein said first plastic material comprises one or more thermoplastic polymers independently selected from the group consisting of aliphatic (co) polyesters, aliphatic aromatic copolyesters, EVA, olefin polymers such as metallocene polyethylene, and styrene block copolymers.

31. The closure (1) according to any one of claims 19 to 30, wherein said first plastic material comprises one or more thermoplastic polymers independently selected from the group consisting of aliphatic (co) polyesters and aliphatic aromatic copolyesters.

32. The closure (1) according to any one of claims 19 to 31, wherein the first plastic material comprises one or more thermoplastic polymers having a Melt Flow Index (MFI) determined by ISO 1133-1(190 ℃, 2.14kg) of more than 1g/10min, in particular more than 3g/10min or more than 5g/10min or more than 10g/10min or more than 12g/10 min.

33. The closure (1) according to any one of claims 19 to 32, wherein the first plastic material is substantially free of a material selected from the group consisting of thermosetting polymers, cross-linkable polymers, curable polymers and non-thermoplastic polymers, and/or wherein the first plastic material is substantially free of polyurethane.

34. The closure (1) according to any one of claims 20 to 33, wherein the second plastic material is further independently defined by at least one feature of any one of claims 27 to 33, or wherein the second plastic material is a thermoplastic material comprising a polymeric elastomer gum comprising one or more thermoplastic polymers as defined in any one of claims 29 to 31, or wherein the second plastic material is a thermoplastic material comprising a polymeric elastomer dispersion comprising one or more thermoplastic polymers as defined in any one of claims 29 to 31.

35. The closure (1) according to any one of the preceding claims, wherein the closure (1) and/or the closure precursor (2) comprises a plurality of apertures, in particular wherein the first plastic material and/or the second plastic material comprises a polymer matrix comprising a plurality of apertures.

36. The closure (1) according to claim 35, wherein the plurality of apertures is a plurality of substantially closed apertures, in particular a plurality of closed apertures, and/or wherein the plurality of apertures comprised in the plastic material have an average aperture size in the range of about 0.025mm to about 0.5mm, in particular in the range of about 0.05mm to about 0.35 mm.

37. The closure (1) according to claim 35 or 36, wherein at least one of the size and distribution of the plurality of apertures in the closure (1) and/or the closure precursor (2) is substantially uniform throughout at least one of the length and distribution of the closure (1) and/or the closure precursor (2), preferably wherein at least one of the size and distribution of the plurality of apertures comprised in the first plastic material and/or the second plastic material is substantially uniform throughout at least one of the length and diameter of the closure (1) and/or closure precursor (2).

38. The closure (1) according to any one of claims 22 to 37, wherein the cork particles are evenly distributed throughout the closure precursor (2), and/or wherein the closure precursor (2) is formed by single extrusion or co-extrusion or injection molding.

39. The closure (1) according to any one of the preceding claims, wherein from 1 to 49 wt% of the closure precursor (2), based on the total weight of the closure precursor (2), is biodegradable according to ASTM D6400.

40. The closure (1) according to any one of the preceding claims, wherein the closure precursor (2) and/or the closure (1) is substantially free of thermosetting polymers comprising polyurethane and/or substantially free of adhesives comprising reactive and non-reactive adhesives.

41. The closure (1) according to any one of claims 1 to 17, wherein the closure precursor (2) comprises

a. A substantially cylindrical core member comprising at least one thermoplastic polymer, wherein the core member comprises terminal surfaces forming opposite ends of the cylindrical core member,

b. a peripheral layer at least partially surrounding and closely adhered to the cylindrical surface of the core member, the end surface of the core member being free of the peripheral layer, the peripheral layer comprising at least one thermoplastic polymer and including a side surface layer surface,

wherein the side surfaces of the closure precursor (2) are formed by the side surface layer surfaces and the substantially planar terminal surfaces forming the opposite ends of the closure precursor (2) are substantially formed by the terminal surfaces of the core member.

42. The closure (1) according to claim 41, wherein the at least one thermoplastic polymer comprised in the core member is selected from the group consisting of: polyethylene; metallocene catalyst polyethylene; a polybutylene; polybutylene; a thermoplastic polyurethane; a silicone; a vinyl-based resin; a thermoplastic elastomer; a polyester; ethylene acrylic acid copolymers; ethylene-vinyl acetate copolymers; ethylene-methyl acrylate copolymers; a thermoplastic polyolefin; a thermoplastic vulcanizate; a flexible polyolefin; a fluororubber; a fluoropolymer; polytetrafluoroethylene; ethylene-butyl acrylate copolymers; ethylene-propylene rubbers; styrene butadiene rubber; styrene butadiene block copolymers; ethylene-ethyl-acrylic acid copolymers; an ionomer; polypropylene; copolymers of polypropylene and ethylenically unsaturated comonomers copolymerizable therewith; an olefin copolymer; an olefin block copolymer; a cycloolefin copolymer; styrene ethylene butadiene styrene block copolymers; styrene ethylene butylene styrene block copolymers; styrene ethylene butylene block copolymers; styrene butadiene styrene block copolymers; styrene butadiene block copolymers; styrene isoprene styrene block copolymers; styrene isobutylene block copolymers; styrene isoprene block copolymers; styrene ethylene propylene styrene block copolymers; styrene ethylene propylene block copolymers; polyvinyl alcohol; polyvinyl butyral; polyhydroxyalkanoates; copolymers of monomers of hydroxyalkanoates and biodegradable polymers; polylactic acid; copolymers of lactic acid and monomers of biodegradable polymers; an aliphatic copolyester; aromatic-aliphatic copolyesters; polycaprolactone; polyglycolide; poly (3-hydroxybutyrate); poly (3-hydroxybutyrate-co-3-hydroxyvalerate); poly (3-hydroxybutyrate-co-3-hydroxyhexanoate); poly (butylene succinate); poly (butylene succinate-co-adipate); poly (trimethylene terephthalate); poly (butylene adipate-co-terephthalate); poly (butylene succinate-co-terephthalate); poly (butylene sebacate-co-butylene terephthalate); caprolactone lactate copolymers; lactic acid ethylene oxide lactic acid copolymers; a polymer formed from monomer units selected from vinylidene chloride, acrylonitrile and methyl methacrylate; copolymers formed from two or more monomer units selected from vinylidene chloride, acrylonitrile and methyl methacrylate; PEF, PTF, bio-based polyester, and combinations of any two or more thereof.

43. The closure (1) according to claim 41 or 42, wherein said at least one thermoplastic polymer comprised in the peripheral layer is selected from the group consisting of: polyethylene; metallocene catalyst polyethylene; a polybutylene; polybutylene; a thermoplastic polyurethane; a silicone; a vinyl-based resin; a thermoplastic elastomer; a polyester; ethylene acrylic acid copolymers; ethylene-vinyl acetate copolymers; ethylene-methyl acrylate copolymers; a thermoplastic polyolefin; a thermoplastic vulcanizate; a flexible polyolefin; a fluororubber; a fluoropolymer; polytetrafluoroethylene; ethylene-butyl acrylate copolymers; ethylene-propylene rubbers; styrene butadiene rubber; styrene butadiene block copolymers; ethylene-ethyl-acrylic acid copolymers; an ionomer; polypropylene; copolymers of polypropylene and ethylenically unsaturated comonomers copolymerizable therewith; an olefin copolymer; an olefin block copolymer; a cycloolefin copolymer; styrene ethylene butadiene styrene block copolymers; styrene ethylene butylene styrene block copolymers; styrene ethylene butylene block copolymers; styrene butadiene styrene block copolymers; styrene butadiene block copolymers; styrene isoprene styrene block copolymers; styrene isobutylene block copolymers; styrene isoprene block copolymers; styrene ethylene propylene styrene block copolymers; styrene ethylene propylene block copolymers; polyvinyl alcohol; polyvinyl butyral; polyhydroxyalkanoates; copolymers of monomers of hydroxyalkanoates and biodegradable polymers; polylactic acid; copolymers of lactic acid and monomers of biodegradable polymers; an aliphatic copolyester; aromatic-aliphatic copolyesters; polycaprolactone; polyglycolide; poly (3-hydroxybutyrate); poly (3-hydroxybutyrate-co-3-hydroxyvalerate); poly (3-hydroxybutyrate-co-3-hydroxyhexanoate); poly (butylene succinate); poly (butylene succinate-co-adipate); poly (trimethylene terephthalate); poly (butylene adipate-co-terephthalate); poly (butylene succinate-co-terephthalate); poly (butylene sebacate-co-butylene terephthalate); caprolactone lactate copolymers; lactic acid ethylene oxide lactic acid copolymers; a polymer formed from monomer units selected from vinylidene chloride, acrylonitrile and methyl methacrylate; copolymers formed from two or more monomer units selected from vinylidene chloride, acrylonitrile and methyl methacrylate; PEF, PTF, bio-based polyester, and combinations of any two or more thereof.

44. The closure (1) according to any one of claims 41 to 43, wherein the closure (1) and/or closure precursor (2), in particular a core member, comprises cork, in particular cork particles.

45. The closure (1) according to any one of claims 41 to 44, wherein the core member comprises a plurality of apertures, in particular a plurality of substantially closed apertures, and/or wherein the core member is foamed.

46. The closure (1) according to any one of claims 41 to 45, wherein the peripheral layer comprises a plurality of apertures, in particular a plurality of substantially closed apertures, and/or wherein the peripheral layer is foamed.

47. The closure (1) according to claim 45 or 46, wherein the plurality of apertures in the core member and the peripheral layer independently have an aperture size in the range of about 0.02mm to about 0.5mm, in particular in the range of about 0.05mm to about 0.35 mm.

48. The closure (1) according to any one of claims 45 to 47, wherein at least one of the size and distribution of the plurality of apertures in the core member is substantially uniform throughout at least one of the length and diameter of the core member.

49. The closure (1) according to any one of claims 45 to 48, wherein the core member comprises an average pore size ranging from about 0.02mm to about 0.50mm and a pore density ranging from about 8,000 pores/cm³To about 25,000,000 wells/cm³In particular wherein the core member comprises an average cell size in the range of about 0.05mm to about 0.1mm and a cell density in the range of about 1,000,000 cells/cm³To about 8,000,000 wells/cm³At least one closed hole.

50. A closure (1) as set forth in any one of claims 41-49, wherein the peripheral layer is further defined as having a thickness in the range of 0.05mm to 5mm, in particular 0.1mm to 2mm and/or 300kg/m³To 1500kg/m³In particular 750kg/m³To 1100kg/m³The density of the range.

51. The closure (1) according to any one of the preceding claims, wherein the closure precursor (2) and/or the closure (1) has an oxygen ingress per container of less than about 5mg, in particular less than about 3mg, less than about 1mg, less than about 0.5mg, less than about 0.25mg, less than about 0.2mg or less than about 0.1mg of oxygen, determined according to ASTM F1307, in the first 100 days after closing the container, and/or wherein the closure precursor (2) and/or the closure (1) has an oxygen transmission of less than 0.05 cc/day, preferably in the range of 0.0002 cc/day to 0.02 cc/day, determined according to ASTM F1307 in 100% oxygen, and/or wherein the closure precursor (2) and/or the closure (1) has less than 8% by weight, determined according to ISO 9727-3, In particular a water content of less than 7 wt.%, less than 6 wt.%, less than 5 wt.%, less than 4 wt.%, less than 3%, less than 2.5%, 2%, 1.5% or 1%.

52. The closure (1) according to any one of the preceding claims, wherein the closure precursor (2) comprises a pigment or dye, in particular 0 to 2 wt% of at least one pigment or dye.

53. The closure (1) according to claim 52, wherein said pigment comprises antimony (III) oxide (Sb)₂O₃) Barium sulfate (BaSO)₄) Lithopone (BaSO)₄ZnS), calcium carbonate, titanium oxide (TiO)₂) And zinc oxide (ZnO).

54. The closure (1) according to any one of the preceding claims, wherein the closure precursor (2) comprises an inner coating (3) comprising an inner coating surface forming the side surface and/or the substantially flat terminal surface of the closure precursor (2).

55. The closure (1) according to claim 54, wherein said inner coating (3) has a uniform colour and/or is further defined as containing a pigment or dye and/or as being opaque.

56. The closure (1) according to claim 54 or 55, wherein the pigment or dye is added to the formulation of the inner coating (3).

57. The closure (1) according to any one of claims 54 to 56, wherein the inner coating (3) is further defined as being applied by molding, extrusion, coating, wrapping or printing.

58. A method for applying a decorative layer (4) on a closure precursor (2) for manufacturing a closure (1) for a product retaining container, the closure precursor (2) being configured to be inserted and securely retained in a neck of the container forming an inlet, and having a substantially cylindrical shape and a longitudinal axis, and comprising substantially flat terminal and side surfaces forming opposite ends of the closure precursor (2),

wherein the method comprises the step of passing the closure precursor (2) through a decoration layer application system, thereby applying a decoration layer (4) onto at least the side surfaces of the closure precursor (2), wherein the decoration layer (4) at least partially covers the side surfaces of the closure precursor (2), wherein at least immediately before applying the decoration layer (4) to the side surfaces and the substantially flat terminal surface of the closure precursor (2), the side surfaces and the substantially flat terminal surface of the closure precursor (2) have a uniform color.

59. Method according to claim 58, wherein the decorative layer (4) is also applied onto the substantially flat terminal surface of the closure precursor (2).

60. Method according to claim 58 or 59, wherein the decorative layer (4) completely covers the side surface and/or the substantially flat terminal surface of the closure precursor (2).

61. The method according to any one of claims 58 to 60, wherein the uniform color of the side surface and optionally the substantially flat terminal surface of the closure precursor (2) is selected from the group consisting of white, yellow, orange, ochre and mixtures thereof, in particular from the group consisting of RAL 9001, RAL 9010, RAL 1000, RAL 1001, RAL 1002, RAL 1014, RAL 1015, RAL 8001 and mixtures thereof.

62. The method according to any one of claims 58 to 61, wherein the decorative layer (4) is further defined by at least one feature of any one of claims 7 to 15.

63. A method according to any one of claims 58 to 62, wherein said method comprises the step of passing said closure precursor (2) through an inner coating application system prior to the step of passing said closure precursor (2) through a decorative layer application system, thereby applying an inner coating (3) having a substantially uniform color, to obtain a closure precursor (2) having a substantially uniform color on at least said side surface of said closure precursor (2).

64. The method of claim 63, wherein the inner coating (3) is further defined by at least one feature of any one of claims 55 to 57.

65. The method of any one of claims 58 to 64, wherein the decor layer application system and/or the inner coating application system is independently selected from an inkjet printing system, a pad printing system and a water transfer system, in particular a pad printing system.

66. A method as claimed in any one of claims 58 to 65, wherein the method comprises the step of passing the closure precursor (2) through a decor layer application system, thereby applying a decor layer onto the decor layer (4).

67. The method of claim 66, wherein the decorative layer is further defined by at least one feature of claim 17.

68. Method according to any one of claims 58 to 67, wherein the closure precursor (2) is rotated about a longitudinal axis during application of the decorative layer (4) in the decorative layer application system.

69. The method of any one of claims 63 to 68, wherein the closure precursor (2) is rotated about the longitudinal axis during application of the inner coating (3) in the inner coating application system.

70. The method according to any one of claims 67 to 69, wherein the closure precursor (2) is rotated about the longitudinal axis during application of the decor layer in the decor layer application system.

71. A method according to any one of claims 58 to 70, wherein the closure precursor (2) is further defined by at least one feature of any one of claims 1 to 40 or 51 to 53.

72. A method according to any one of claims 58 to 69, wherein the closure precursor (2) is further defined by at least one feature of any one of claims 41 to 53.

73. Use of a closure (1) according to any of claims 1 to 57 for sealing a container.

Technical Field

The present disclosure relates to a closure for a container, including but not limited to a wine bottle. The present disclosure also relates to a method for applying a decorative layer on a closure precursor that is configured to be inserted and securely retained in a container.

Background

With respect to the variety of products sold for dispensing from containers, particularly containers with a round neck defining a dispensing inlet, a wide variety of structures have been developed for container stoppers or closure devices for inlets, including, for example, screw caps, stoppers, corks, and crown caps, to name a few. In general, products such as vinegar, vegetable oils, laboratory liquids, detergents, honey, condiments, spices, alcoholic beverages, and the like, have similar requirements on the type and construction of closure means for containers for these products. However, wine sold in bottles represents the most demanding product in terms of bottle closure technology. In an attempt to best meet these needs, most wine bottle closures or stoppers have been produced from cork, a natural material.

While natural cork remains the primary material for wine closures, wine closures (also referred to as synthetic closures) made from alternative materials such as polymers have become increasingly popular, primarily due to the scarcity of high quality natural cork material and the realization that wine spoilage, a phenomenon associated with natural cork material, is a cause of "cork spoilage". The synthetic closure has the following advantages: through the closure technology, the material content and physical characteristics of the synthetic closure can be designed, controlled and fine-tuned to meet the different requirements imposed on the closure by the wide range of different wine types produced worldwide.

One of the major difficulties that any bottle closure suffers in the wine industry is the manner in which the closure is inserted into the bottle. Typically, the closure is placed in a jaw gripping member located above the bottle access opening. The clamping member comprises a plurality of separate and independent jaw members peripherally surrounding the closure member and movable relative to each other to compress the closure member to a diameter substantially less than its original diameter. Once the closure member has been fully compressed, the plunger moves the closure device from the jaws directly into the neck of the bottle where it can expand into engagement with the internal diameter and access opening of the bottle neck, thereby sealing the bottle and its contents.

Whereas the jaw members are generally independent of each other and are individually movable to enable the closure member to be compressed to a significantly reduced diameter, each jaw member includes a sharp edge which is brought into direct engagement with the closure member when the closure member is fully compressed. Score lines are often formed on the outer surface of the closure member that prevent a complete, leak-free seal from being created when the closure member is expanded into engagement with the bottle neck. This can occur, for example, if the jaw members of the bottling plant are not perfectly adjusted or are worn. Leakage of product, in particular liquid product, from the container may occur.

It is generally desirable that any bottle closure be able to withstand this conventional bottling and sealing method. In addition, many cork sealing members also experience breakage during the bottling process, resulting in wine leakage or wine spoilage.

Another problem in the wine industry is the ability of wine stoppers to withstand the pressure increase that can occur during the storage of wine products after they have been bottled and sealed. For example, during hotter months, the pressure increases due to the natural expansion of the wine, which may cause the stopper to become dislodged from the bottle. It is therefore generally desirable that bottle closures for wine products be capable of achieving a secure, tight, frictional engagement with the bottle neck to resist any such pressure increase.

Another problem in the wine industry is the general desire that such a firm sealing engagement of the stopper with the neck of the bottle should be achieved quickly if it cannot be achieved almost immediately after insertion of the stopper into the neck of the bottle. During conventional wine processing, the stopper is compressed and inserted into the neck of the bottle, as detailed above, so as to enable the stopper to expand in situ and seal the bottle. Since many processors tilt the bottle to one side or down the neck after the stopper is inserted into the neck of the bottle, it is desirable that this expansion occurs immediately upon insertion into the bottle, allowing the bottle to remain stored in this position for an extended period of time. Wine leakage occurs if the stopper does not expand rapidly into firm, tight, frictional contact with and engagement with the wall of the bottle neck.

It is further desirable that the closure be removable from the bottle using a reasonable extraction force. While the actual extraction force extends over a wide range, the commonly accepted conventional extraction forces are typically below 100 pounds (445 newtons).

In achieving a commercially viable stopper or closure, a careful balance must be struck between a secure seal and providing a reasonable extraction force (for removing the closure from the bottle). Since these two properties are believed to be in direct opposition to each other, a careful balance must be struck to enable the stopper or closure to securely seal the product (particularly bottled wine) to prevent or at least reduce both leakage and gas transmission, while also being removable from the bottle without excessive extraction forces.

Furthermore, it is generally desirable to effectively prevent or reduce the ingress of oxygen into the bottle. Too much oxygen can lead to premature spoilage of the wine. In fact, oxidation can occur over time, resulting in a beverage that is not potable. Therefore, it is generally desirable that the closure have low oxygen permeability in order to extend and maintain the freshness and shelf life of the product. Thus, any commercially viable wine stopper or closure should generally have a low Oxygen Transmission Rate (OTR). Additives that act as oxygen scavengers can also be incorporated into the closure. The combination of low closure permeability to oxygen and the incorporation of an oxygen scavenger can be effective in reducing oxygen-mediated wine spoilage.

In addition to the above aspects, it is also desirable to reduce the total amount of material, especially the amount of polymeric material, in closures made of materials such as polymers and the like for economic and environmental reasons. Since the size of the closure is determined by the size of the neck of the bottle, reducing the amount of material can be achieved mainly by reducing the density of the closure, in particular the core member, which is usually in the form of a foamed material comprising air or gas filled holes. However, reducing the density of the core members generally increases the deformability of the core members and, therefore, of the closure, which in turn leads to deteriorated sealing ability and increased leakage. To avoid this, thicker and/or denser outer layers or skins may be considered, as may the incorporation of stiffer and/or denser central elements within the core member. However, any of these methods increase the total amount of material, thereby diminishing or even eliminating any advantage realized by reducing the core density.

The amount of polymeric material may also be reduced by using a filler material. Closures incorporating fillers into a polymer matrix are known. For example, U.S. patent No.5,317,047 describes a stopper made of expandable microspheres, cork powder and a binder (such as a polyurethane or acrylic type glue). The method of making closures incorporating cork powder into a polyurethane or acrylic matrix generally involves combining cork powder with a polyurethane or acrylic monomer, oligomer, or prepolymer and performing in situ polymerization. However, residual monomers and low molecular weight compounds (such as dimers, trimers, and other oligomers) remain in the matrix and/or in the cork powder. These residual monomers and low molecular weight compounds may not be compatible with food safety considerations as they may migrate into the food product in contact with the closure. In addition, these methods typically require the application of heat for a period of several hours in order to cure and polish the glue.

It would be advantageous to be able to control the characteristics of a closure incorporating cork material in the same manner as a closure consisting essentially of a single material, such as a polymer or cork. It would be particularly advantageous to be able to achieve uniform characteristics within such a closure. It would also be advantageous to be able to ensure that the desired characteristics of such a closure (e.g. making it suitable as a closure for a wine bottle as described herein) are achievable in industrial scale production without significant variation of individual closures.

In addition to the above, it is generally desirable that closures not made of cork resemble natural cork closures as closely as possible in appearance. Both the longitudinal surface and the flat end of cylindrical cork closures typically have an irregular appearance, e.g., exhibiting naturally occurring irregularities in color, structure, and contour. The same is true of non-cylindrical cork or cork-type closures, such as those used for champagne bottles. Methods have been developed for providing synthetic closures with physical appearances similar to natural cork, for example, by blending pigments to create a striped effect on the exterior of the closure, along the cylindrical axis, or to provide a flat terminal end of the synthetic closure with physical appearances similar to natural cork. At the same time, it is desirable that the closure have an appearance similar to a cork closure, i.e., a cork closure made from a single piece of cork, such as premium cork. This applies not only to purely synthetic closures, but also to all types of closures, including but not limited to composite closures containing cork particles. Closures having a one-piece appearance made of natural cork have the greatest customer acceptance.

The cork industry generates a large amount of by-products, such as cork dust, cork powder and cork pieces, which are often considered waste products. It would be advantageous to convert these by-products into high value composite products. It is known to incorporate cork materials into composites with polymers. However, the incorporation of cork particles into a polymer matrix can be detrimental to its processing and performance characteristics. Composite materials containing significant amounts of cork particles (e.g., more than about 50% by weight of cork particles based on the total weight of the composite material) tend to have properties, such as hardness, density, and permeability, that make them unsuitable as closures for wine bottles. Crosslinking agents and/or compatibilizing agents are often recommended in order to improve properties. However, when used in products that come into contact with food, cross-linking and/or compatibilizing agents can create food safety issues. Furthermore, when used in large quantities or in composite materials as packaging materials, cork may contain and release substances that affect the sensory perception of the food product. Examples of such materials are organoleptic ingredients such as halogenated anisoles, particularly but not exclusively Trichloroanisole (TCA). In addition, closures containing cork should have good mechanical properties. It would be advantageous for the closure to overcome these problems as much as possible.

To date, the production methods for cork-containing composite closures have been largely limited to molding methods, in particular: reactive molding processes in which cork is blended with monomer or prepolymer units and then polymerized in situ in a mold; compression molding; or a combination of compression molding and reactive molding. These difficulties may include achieving a sufficient degree of foaming and/or a sufficient degree of uniformity of foaming, and thus a desired low and uniform polymer foam density, as well as achieving a uniform distribution of cork particles. It can also be difficult to obtain cylindrical extrudates with smooth polymer surfaces that do not suffer from surface melt fracture or undesirable surface roughness. If increased amounts of cork are incorporated, any difficulties and disadvantages in processing and performance are exacerbated. Composite materials containing a large amount of smaller particles (e.g., cork powder, such as more than about 50 weight percent cork powder based on the total weight of the composite material) tend to have properties, such as hardness, density, and permeability, that make them unsuitable as closures for wine bottles. Cross-linking agents are often required in order to improve properties. However, cross-linking agents can create food safety issues when used in products that come into contact with food. Composite materials containing larger particles (e.g., cork particles) can have the following disadvantages: the cork particles in the matrix contribute to or even dominate the mechanical and permeability properties of the composite, one result being that these properties are not uniform throughout the composite. In order to be useful as a closure for wine bottles, substantially uniform characteristics throughout the closure are desired.

Closures incorporating cork material in a synthetic matrix have been previously described. For example, FR 2799183 describes a synthetic closure consisting of a mixture of cork particles and cork powder in a polyurethane matrix. It is stated that a mixture of cork particles and cork powder is essential for the uniformity of the closure. However, the characteristics of such closures are typically not uniform throughout the closure due to the presence of different "regions" comprising cork or polyurethane. This can be difficult to avoid in the molding process due to the inherent lack of mixing of the components within the mold. This is exacerbated by the fact that: coating cork particles with glue is performed by mixing the components at low shear rate and low temperature. These conditions are necessary to not cure the glue prematurely. However, these conditions result in poor mixing and may produce clumping of cork or glue. Moreover, such closures can chip and even break apart due to the weakness of the matrix created by the incorporation of larger cork particles and/or the presence of clusters of cork particles that are somewhat adhesive-deficient. It would be advantageous to be able to mix at high shear and/or high temperature, something that could not be done with glue, as it would cure the glue prematurely. High shear mixing is preferred over low shear mixing in order to provide good uniform blending of the particles in the polymer.

Furthermore, halogenated anisoles, in particular Trichloroanisole (TCA) and other anisoles that may cause organoleptic problems, such as Tribromoanisole (TBA), tetrachloroanisole (TeCA) and pentachlorobenzymethyl ether (PCA), may be more difficult to remove from larger cork pieces, such as cork dust, than cork dust, such that closures containing such larger cork dust may have the problem of so-called cork taint to a greater extent than those containing cork dust. However, this can be overcome to a greater extent or completely by suitable cleaning methods. Because the ease of cleaning is expected to increase with smaller particle sizes, removal of the organoleptically active substance from the cork particles is still easier than removal from conventional closures made from a single block of natural cork.

For these reasons, it would be advantageous to be able to produce closures containing natural cork mass (particularly cork granules, wherein the cork granules are embedded in a polymer matrix) that do not have the problems of natural cork or known cork-polymer composite closures. It would be further advantageous for the appearance of these closures to resemble closures made from a single piece of cork.

In addition to the above aspects, for environmental reasons, it is also desirable that closures made of alternative materials (such as polymers) be biodegradable, recyclable, compostable or derived from renewable resources to the greatest extent possible. Biodegradability and compostability can be measured by standard test methods like e.g. DIN EN 13432 or ASTM D6400 and in compliance with relevant EU and USA laws and guidelines or e.g. the japanese GreenPla standard for compostable and biodegradable polymers. Biodegradable, recyclable and compostable materials can be, but need not be, made entirely from non-fossil resources. In fact, besides polymers derived from natural or renewable resources (which may be synthetic or natural polymers), there are available polymers, due to their chemical structure, made of fossil resources that can be metabolized, for example, by microorganisms. Some polyesters such as poly (caprolactone) or poly (butylene adipate-co-terephthalate) are made from fossil resources and are also biodegradable.

Furthermore, it is often desirable to provide decorative indicia such as letters and decorations, such as a logo or emblem of a brewery, on the surface of the wine stopper. Natural cork is often marked by a process commonly referred to as "fire branding," i.e., by applying a hot branding tool. Alternatively, natural cork can also be branded or printed by applying pigments or dyes.

Branding synthetic closures is also known. These closures are typically branded by ink-jet or offset printing using specific dyes or pigments approved for direct or indirect food contact. When pigments and dyes are used which are not approved for direct food contact, labeling of the closure with these pigments or dyes is usually only performed on curved cylindrical surfaces (peripheral or side surfaces) of the closure which are not in direct contact with the wine. Such indicia may be on the outermost surface or on the inner surface which is subsequently covered by an outer layer, preferably at least partially transparent. Closures for injection molding are generally better known for marking on a flat terminal surface of a closure made of an alternative material, such as a polymer, wherein the marking is performed by providing raised portions on the flat terminal surface during the closure molding process.

Methods for marking the planar terminal surface of a closure made of alternative materials, such as polymers, are available. Since laser marking allows avoiding direct food contact, it may in theory be a viable approach. This method may allow for in-line printing of closures manufactured, for example, by extrusion. Another method involves applying a decorative layer, particularly a decorative polymer layer, to a flat terminal surface by means of heat transfer and/or pressure transfer. This method allows for permanent branding of synthetic closures without creating food safety related concerns and without negatively affecting the gas permeation and/or mechanical properties of synthetic closures, particularly coextruded synthetic closures.

The main object of research to date has been to provide barrier layers for closures. Thus, WO96/28378a1 describes a closure for a container having an opening, the closure comprising a cork piece wholly or partially enclosed in at least one coating of a durable, liquid-impermeable coating material to isolate any contaminating agents present in the cork piece from the contents of the container. Similarly, US 7993743B 2 describes a stopper, in particular for wine bottles, comprising a barrier layer comprising a hot-melt polymer adhesive and optionally at least one sublayer having a lower oxygen permeability than the hot-melt adhesive. WO 0064649 a1 describes a method of preparing a coating or diffusion layer on a substrate for use in contact with food or beverage, which coating or diffusion layer prevents or inhibits passage of flavour or odour active compounds therethrough, and which method comprises applying to the surface of the substrate an effective amount of a copolymer comprising a flexible component and a retentive component.

It is possible that closures with a high proportion of synthetic material do not allow for certain types of wine to be used with the natural cork described as the choice of closure material. For example, according to European Union Council Resolution part No. 2, European Union Council of European Resolution resp (2004)2, on cork stoppers and other cork materials and products expected to come into contact with food, a closure may be defined as a cork closure if it contains a minimum of 51% w/w cork. Thus, the inclusion of 51% w/w cork in a closure may be advantageous in a broader market for the use of opening the closure. Synthetic closures, once removed, often cannot be reinserted into a bottle or present some difficulty in reinserting into a bottle, as compared to natural cork closures. It would therefore be advantageous to provide a closure with a synthetic component that, once removed, can be reinserted into a bottle.

There is therefore a need for a closure or stopper, in particular comprising at least one of the features described above, preferably having a physical appearance and/or tactile features similar in at least one aspect to natural cork closures, the appearance of which is similar to closures made of monolithic cork, which are preferably biodegradable, in particular wherein other properties of the closure, such as, in particular, OTR, leakage, ease of insertion and removal, compressibility and recovery from compression, and/or compatibility with food products, are only minimally impaired, in particular not impaired or even improved.

Other and more specific needs will be in part apparent and in part pointed out hereinafter.

Disclosure of Invention

According to one aspect of the present disclosure, there is provided a closure as claimed in claim 1 for insertion and secure retention in a neck of a container forming an inlet. Claims 2 to 57 describe different preferred embodiments of the closure of the present disclosure.

According to another aspect of the present disclosure, there is provided a method for applying a decorative layer on a closure precursor to produce a closure for a container as claimed in claim 58. Preferred embodiments of the method are described in claims 58 to 72.

According to another aspect of the present invention, there is provided the use of a closure according to the present disclosure as claimed in claim 73 for sealing a container.

For completeness, a preferred closure precursor manufacturing method is also described herein. Furthermore, described herein is the use of a thermoplastic material in the manufacture of a coated particle comprising (1) a core comprising a cork material and (2) at least one shell comprising a thermoplastic material. The coated particles thus produced can be used, for example, to produce closure precursors for closures according to the present invention.

According to yet another aspect of the present disclosure, use of a thermoplastic material in a method of manufacturing a closure for a product retaining container configured to be inserted and securely retained in a neck of the container forming an inlet is described.

According to yet another aspect of the present disclosure, use of a thermoplastic material in a method of manufacturing a closure for a product retaining container configured to be inserted and securely retained in a neck of the container forming an inlet is described.

The contents of the appended claims are a part of this disclosure and the specification. The contents of the appended claims may exist in whole or in part independently, or may be read and/or combined with further description provided below.

The closure of the present disclosure may be used as a bottle closure or stopper for any desired product. However, for the reasons detailed above, wine products impose the most onerous criteria for bottle closures. Thus, to demonstrate the versatility of the closure of the present invention, the following disclosure focuses on the suitability and usability of the closure of the present invention as a closure or stopper for receiving wine bottles. This discussion is for illustrative purposes only and is not intended to be a limitation of the present disclosure.

As discussed above, wine bottle closures or stoppers must be capable of performing many separate and distinct functions. An important function is the ability to withstand pressure increases during storage due to temperature changes, and to prevent any leakage or weeping of wine from the bottle. Furthermore, a tight seal must also be established in order to prevent unwanted gas exchange between ambient conditions and the interior of the bottle, in order to prevent any unwanted oxidation or permeation of gases from the wine to the atmosphere. In addition, the unique corking procedure employed in the wine industry imposes substantial limitations on bottle closures, requiring a bottle closure that is highly compressible, has a high immediate compression recovery capability and can resist any deleterious effects caused by the clamping jaws of the bottle closure device. In view of environmental considerations, it would be an advantage to be able to provide an at least partially biodegradable, compostable or recyclable closure. The tactile properties and/or physical appearance should preferably resemble natural cork closures. Preferably, the closure should have an appearance similar to closures made from a single piece of cork. The contained product should not deteriorate due to the closure. In addition, it is advantageous for the closure to be easily extractable and re-insertable. Another advantage would be to print or brand on the closure as if it were a cork closure.

While prior art products have been produced in an attempt to meet the need for alternative bottle closures that may be employed in the wine industry, such prior art systems have often been found to be deficient in one or more of the generally desirable aspects of bottle closures for wine products. However, by employing the present disclosure, many of the prior art disadvantages have been reduced or even eliminated and an effective, easy to employ, mass produced closure has been achieved.

In the present disclosure, many of the drawbacks of the prior art can be reduced or even overcome by obtaining a closure for a product retaining container configured to be inserted and securely retained in a neck of the container forming an inlet, wherein the closure comprises a closure precursor and a decorative layer, wherein a side surface and a flat terminal surface of the closure precursor have a substantially uniform color, and a method for applying the decorative layer on the closure precursor. Due to the decorative layer, the closure preferably has the appearance of a closure made from a single piece of cork.

According to the present disclosure, there is provided a closure for a product retaining container, the closure having a substantially cylindrical shape and comprising substantially planar terminal surfaces forming opposite ends of the closure, wherein the closure further comprises (a) a closure precursor having a substantially cylindrical shape and comprising side surfaces and substantially planar terminal surfaces forming opposite ends of the closure precursor, wherein the side surfaces and the planar terminal surfaces of the closure precursor have a substantially uniform color; and (b) a decorative layer at least partially covering at least a side surface of the closure precursor.

The closure according to the invention therefore comprises a closure precursor comprising a side surface and a decorative layer applied at least on the side surface of the closure precursor. Non-limiting examples of closure precursors include synthetic closures, composite closures, cork particle agglomerate closures, or closures made from a single piece of cork. Closure precursors and/or closures according to the present invention can comprise thermosetting polymers (including polyurethanes) and/or adhesives (including reactive adhesives and non-reactive adhesives), such as is the case with certain cork particle agglomerate closures. However, it is preferred that the closure precursor and/or closure according to the present invention is free of thermosetting polymers (including polyurethanes) and/or substantially free of adhesives (including reactive and non-reactive adhesives). The closure may comprise one or more further layers, for example a decor layer, which may in particular comprise indicia, such as a logo or a medallion of a brewery. If the closure precursor is free of synthetic polymers or comprises at least one biodegradable polymer, the closure of the present invention may be biodegradable, or at least a portion of the closure contents may be biodegradable. The desired closure properties such as oxygen permeability, compressibility, and recovery capacity can be largely unchanged or even improved as compared to conventional cork closures. The closure also has good sealing properties. At the same time, the extraction force required to remove the closure from the bottle does not substantially change. The closure can be more easily reinserted into the bottle after opening. In addition, the closure has an appearance similar to a natural cork closure made from a single piece of cork. Furthermore, the tactile properties of the closure can be very similar to closures made of natural cork.

A closure manufactured according to any of the methods described herein will be referred to by terms such as "inventive closure", "closure of the present disclosure" or "closure". The phrases "according to this disclosure" and "according to the invention" are synonymous herein. Furthermore, anything herein with respect to the first plastic material is equally applicable to the second plastic material, and vice versa.

The closure of the present invention has a substantially cylindrical shape. The cylindrical closure member includes a substantially cylindrical outer peripheral surface and two substantially flat terminal end surfaces at opposite ends of the cylindrical shape. Herein, a shape may also be referred to as a form. This form is well known to the skilled person. The ends of the closure of the present invention may be beveled or chamfered as is known in the art. While any desired beveled or chamfered configuration may be employed, such as a fillet, curved or flat surface, it has been found that cutting the terminal end at an angle in the range of about 30 ° to about 75 °, for example in the range of about 35 ° to about 70 °, particularly in the range of about 40 ° to about 65 °, only at the intersection with the longitudinal cylindrical surface of the elongate length of material allows for the formation of a closure that is more easily inserted into the neck of the container. It has been found that angles of about 45 °, 46 °,47 °, 48 °, 49 °, 50 °, 51 °, 52 °, 53 °, 54 °, 55 °, 56 °, 57 °, 58 °, 59 °, or 60 ° are particularly helpful for the present disclosure. The bevel or chamfer angle is measured relative to the longitudinal axis of the cylindrical closure. The chamfer angle of the closure for a static wine bottle is in particular in the above range, in particular wherein the chamfer length is in the range of about 0.4mm to about 2.5mm, in particular in the range of about 0.5mm to about 2.0 mm. Closures for sparkling wine bottles advantageously have a chamfer in the above range, but typically have a deeper and/or longer chamfer than closures for static wine bottles, for example a chamfer angle in the range of about 35 ° to about 55 °, in particular in the range of about 40 ° to about 50 °, more in particular a chamfer angle of about 40 °,41 °, 42 °, 43 °, 44 °, 45 °, 46 °,47 °, 48 °, 49 ° or 50 °, and/or a chamfer length in the range of about 3mm to about 8mm, in particular in the range of about 4mm to about 7mm, in particular a chamfer length of about 3mm, 4mm, 5mm, 6mm, 7mm or 8 mm. In addition, end caps may be attached to one or both of the planar terminal surfaces of the closure. The end cap may be made of any material, preferably a plastic material. Preferably, the end cap has a circular cross-section with a diameter greater than the diameter of the closure.

The closure of the present invention comprises a closure precursor. The details mentioned herein with respect to the shape and/or structure of the closure are equally applicable to the closure precursor and vice versa. In particular, the closure precursor has a substantially cylindrical shape. The cylindrical closure precursor comprises a side surface preferably constituted by a substantially cylindrical outer peripheral surface of the closure precursor and two substantially flat terminal surfaces at opposite ends of the cylindrical shape.

The side surfaces and the planar terminal surface of the closure precursor are of substantially uniform color. Different colors can be used as uniform colors (uniform colors) for the side surfaces and the flat terminal surface of the closure precursor. Preferably, the uniform color is a color on which printing can be applied with great flexibility (flexibility), in particular a light color. In this way, the closed precursor is a transparent canvas on which the decorative layer can be applied with great flexibility. Preferably, the uniform colour of the surface of the closure precursor is selected from the group consisting of white, yellow, orange, ochre and mixtures thereof, in particular from the group consisting of RAL 9001, RAL 9010, RAL 1000, RAL 1001, RAL 1002, RAL 1014, RAL 1015, RAL 8001 and mixtures thereof. More preferably, the uniform colour of the surface of the closure precursor is selected from the group consisting of RAL 9001, RAL 9010, RAL 1000, RAL 1015 and mixtures thereof. The closure precursor provides a transparent canvas in which the side surfaces and the flat terminal surface have the above-mentioned uniform color, and the decorative layer can be applied, in particular printed, on the transparent canvas with great flexibility.

The decorative layer on the closure precursor may cover different portions of the surface of the closure precursor. The decorative layer may cover at least partially or completely, preferably completely, the side surface of the closure precursor. The decorative layer may also cover a flat terminal surface of the closure precursor. Thus, the flat terminal surface of the closure precursor may be at least partially or fully, preferably fully, covered. Advantageously, the decorative layer completely covers the side surfaces and the flat terminal surface of the closure precursor. In this way, a closure can be obtained that has an appearance similar to a cork closure made from a single piece of cork from every point of view.

The decorative layer of the closure precursor preferably comprises a pigment or a dye.

Different methods can be used to apply the decorative layer to the closure precursor. For example, the decorative layer can be applied by printing, in particular by offset printing, pad printing, screen printing, inkjet printing, fire-soldering or laser printing. Preferably, the decorative layer is applied by pad printing. Printing has the advantage that the desired content can be applied to the surface with good resolution and/or with great versatility. The printed decor layer is also very thin. In particular, the thickness of the decorative layer can be less than 0.1mm, in particular less than 0.01 mm.

The decorative layer preferably provides the closure with a look very similar to the appearance of: the appearance is similar to a cork closure made from a single piece of cork. For this purpose, the decorative layer preferably has a high printing resolution. Advantageously, the print resolution of the decor layer is 25 dots per inch (dpi) or greater, preferably 72dpi or greater, even preferably 150dpi or greater, more preferably 300dpi or greater, and more preferably 600dpi or greater. Decorative layers having print resolutions within these ranges may include very sharp prints.

Furthermore, the decorative layer may be monochromatic or polychromatic. The single-color decorative layer contains one color and the multi-color decorative layer contains two or more colors. Preferably, the decorative layer is multicolored. Each color may include several shades of color. Chroma is obtained in particular by adding different amounts of black to a certain hue. Preferably, the decorative layer comprises one or more shades of at least a single color. Even more preferably, the decorative layer comprises one or more shades of two or more colors. A multi-colored decorative layer comprising one or more, in particular two or more, shades of two or more colors can have a realistic appearance that is particularly similar to closures made from a single piece of cork.

Preferably, the decorative layer has photographic image quality. Such a decorative layer has in particular a realistic appearance which can be particularly similar to closures made from a single piece of cork. In particular, the sharpness, tone reproduction and/or contrast of the decorative layer has a photographic image quality.

The material for the decorative layer is preferably composed of one or more materials that meet the standards of the U.S. Food and Drug Administration (FDA) or the European Union (EU) or are approved by the U.S. Food and Drug Administration (FDA) or the European Union (EU) as Food Contact Substances (FCS). If the product is a food product, such as wine, the use of these materials ensures that the closure can safely access the product in the product retaining container. There is also no problem when the decorative layer covers a flat terminal surface of the closure precursor.

The decorative layer may depict the first indicia. The first indicia preferably comprises one or more selected from the group consisting of letters, symbols, colors, graphics, icons, logos, wood tones, natural cork appearance, and photographs. Most preferably, the first indicia comprises a natural cork appearance or photograph. The photos may show different themes. Advantageously, the photograph is of the surface of a cork closure made from a single piece of cork. However, the decorative layer may also comprise letters and symbols or figures, such as the name and logo of the brewery.

Preferably, the decorative layer is not a barrier layer. Instead, it is preferred that the decorative layer is a thin printed layer on top of the closure precursor. Thus, the decorative layer preferably does not substantially affect the oxygen permeability of the closure precursor and/or the closure.

As previously mentioned, the closure may comprise one or more further layers, in particular a decor layer. Preferably, the decorative layer is on top of the decorative layer. In the manufacture of the closure according to the invention, a decor layer is preferably applied on top of the decor layer. The decorative layer may be applied after the decorative layer is dried. The decorative layer may also be applied when the decorative layer is not completely dry. Preferably, the decor layer is applied after drying of the decor layer. Details concerning pigments or dyes, the method of application, the material constituting the decorative layer, the content of the decorative layer, etc. also apply to the decorative layer. Preferably, the decor layer depicts letters, symbols, graphics, icons and/or logos, such as the name and logo or medallion of the brewery.

As previously mentioned, different closure precursors can be used in the present invention. For example, the closure precursor may be a synthetic closure precursor and/or comprise a thermoplastic polymer. In the following, by way of non-limiting example, several preferred embodiments of closure precursors that can be used in the present invention are described.

The closure precursor may have a construction comprising a single component. This assembly may be referred to as a closure precursor or as a core member. If the closure precursor comprises more than one component, it may be referred to as a multi-component closure precursor or a multi-layer closure precursor. The multi-component closure precursor preferably has a configuration comprising: a core member corresponding to a closure precursor or a single component closure precursor; and another one or more peripheral layers at least partially surrounding and closely adhered to the outer peripheral surface of the core member. According to this embodiment of the present disclosure, the closure precursor comprises:

a) a substantially cylindrical core member comprising at least one thermoplastic polymer, wherein the core member comprises terminal surfaces forming opposite ends of the cylindrical core member, and

b) at least one peripheral layer at least partially surrounding and closely adhered to the cylindrical surface of the core member, the end surface of the core member being free of the peripheral layer, the peripheral layer comprising at least one thermoplastic polymer and including the side surface layer surface. In this embodiment, the side surfaces of the closure precursor are formed by side surface layer surfaces, and the substantially planar terminal surfaces forming the opposite ends of the closure precursor are substantially formed by terminal surfaces of the core member. An alternative type of closure precursor comprising components may comprise a construction such that a core member as described herein is provided with discs at one or both planar terminal ends, for example discs made of natural cork. The one or more discs (if present) completely cover one or both of the terminal ends of the closure precursor.

In the present disclosure, references to "core members" are intended to mean core members of single component closure precursors and/or multi-component closure precursors. Reference herein to "closure precursors" encompasses single component closure precursors and multi-component closure precursors, as well as core members of multi-component closure precursors, as the core members of the multi-component closure precursors and the single component closure precursors are generally the same in the closure precursors of the present disclosure, have the same composition and the same properties and features, and are generally formed in the same manner. Thus, any details herein regarding the core member apply to a single component closure precursor, and any details herein regarding the closure precursor or the single component closure precursor apply equally to the core member. In particular, any reference herein to a core member applies to the entire contents of a single component closure precursor. If the single component closure precursor comprises a plastics material, reference to "plastics material" is generally intended to mean the plastics material of the core member or single component closure precursor, although the disclosure relating to plastics material may also apply to the material of the peripheral layer. Details regarding the plastic material may also apply to the peripheral layer (if present) where indicated herein.

The closure and/or closure precursor or core member for use in the present invention preferably comprises a plurality of apertures. In particular, the plastic material preferably comprises a plurality of holes. In particular, the plastic material preferably comprises a polymer matrix with a plurality of pores. Preferably, the plastic material forms a polymer matrix comprising a plurality of pores. Natural cork includes a plurality of holes. Thus, a plurality of pores has been included in the cork or cork granules. A plurality of holes according to the invention is preferably also included in the plastic material. The plurality of apertures may be included in, for example, a foamed plastic material, also referred to as a foam, foamed polymer, foamed plastic material, plastic foam, polymer foam, foamed polymer material, or foamed plastic. The plastic material is preferably in the form of a foam. The closure precursor according to the present disclosure comprises in particular at least one foamed plastic material. Preferably, the core member is foamed. The foamed plastic material preferably forms a polymer matrix comprising a plurality of pores. If the closure precursor comprises cork or cork particles, the polymer matrix preferably forms a continuous phase in which a plurality of cork particles (or a plurality of coated particles as defined herein) are embedded. The peripheral layer (if present) may also comprise a plurality of apertures, for example in the form of an at least partially foamed material. The peripheral layer (if present) may be formed with a density significantly greater than the core material in order to impart the desired physical characteristics to the bottle closure of the present disclosure. According to an exemplary aspect of the disclosure, the core member is foamed and at least one peripheral layer (if present) is substantially unfoamed, in particular unfoamed. It is also contemplated that the peripheral layer, if present, is foamed. The peripheral layer may be foamed in the same way as the core member or to a lesser extent, for example by a smaller amount of foaming agent or expandable microspheres in the peripheral layer, for example in a way that makes it more flexible. However, the peripheral layer (if present) advantageously has a higher density than the core member.

Preferably, the plurality of apertures included in the closure precursor or core member are a plurality of substantially closed apertures, in particular a plurality of closed apertures. The holes included in natural cork are closed or substantially closed holes. It is particularly preferred that the plurality of holes comprised in the plastic material is a plurality of substantially closed holes, in particular a plurality of closed holes. In particular, it is preferred that the plastic material comprises a polymer matrix having a plurality of pores, and that the plurality of pores in the polymer matrix is a plurality of substantially closed pores, in particular a plurality of closed pores. By "substantially closed pores" is meant that although a majority, e.g. more than 90%, preferably more than 95%, preferably more than 99% of the pores in the plurality of pores are closed pores, some, e.g. at most 10%, preferably less than 5%, preferably less than 1%, of the plurality of pores may be open pores. The plurality of apertures of the disclosed closure are further advantageously defined as a plurality of substantially closed apertures, or the foam is a substantially closed-cell foam. Closed cell foams are generally defined as comprising cells (also referred to as air cells) that are not substantially interconnected with one another. Closed cell foams have higher dimensional stability, lower coefficient of moisture absorption, and higher strength than open cell structure foams. The foamed peripheral layer (if present) preferably comprises substantially closed cells.

The plurality of holes, in particular the plurality of holes comprised in the plastic material, preferably have an average hole size in the range of about 0.025mm to about 0.5mm, in particular about 0.05mm to about 0.35 mm. The average pore size in the plastic material may also be from about 0.05mm to about 0.3mm, from about 0.075mm to about 0.25mm, preferably from about 0.1mm to about 0.2 mm. The average pore size is measured according to standard test methods known to the skilled person, preferably by microscopy.

To ensure that the core member or closure precursor possesses inherent consistency, stability, functionality and the ability to provide long term performance, the pore size and/or pore distribution of the plurality of pores is preferably substantially uniform throughout the length and diameter of the core member or closure precursor, particularly throughout the plastics material. In this way, closure precursors and core members having substantially uniform properties, such as, for example, OTR, compressibility and compression recovery, may be provided. Preferably, at least one of the size or distribution of the plurality of apertures in the closure precursor or in the core member is substantially uniform throughout at least one of the length and diameter of the closure precursor. It is particularly preferred that at least one of the size and distribution of the plurality of apertures included in the foamed plastic material is substantially uniform throughout at least one of the length and diameter of the closure or core member, preferably throughout the plastic material included in the closure or core member. This uniformity contributes to the uniformity of the closure precursor or core member in both structural stability and performance characteristics. Uniform distribution of the cork particles (or coated particles) throughout the closure precursor or core member is also facilitated by providing a uniformly supported polymer and avoiding the cork particles (or coated particles) from clustering or clumping together, which may be caused, for example, by local weakness in the polymer matrix.

In another exemplary aspect of the present disclosure, a core member or closure precursor, particularly a plastic material, includes closed pores having an average pore size in a range of about 0.02 millimeters to about 0.50 millimeters and at about 8,000 pores/cm³To about 25,000,000 wells/cm³At least one of a pore density within the range of (a). While this pore configuration has been found to produce a highly effective product, an even more advantageous product has been found to be one in which the core member comprises closed pores having an average pore size in the range of about 0.05mm to about 0.1mm and in the range of about 1,000,000 pores/cm³To about 8,000,000 wells/cm³At least one of a pore density within the range of (a). According to one embodiment, the cork particles constituting the core of the coating particles as described herein have an average pore size in the range of 0.02mm to 0.05mm and a pore size of 4 x 10⁷Hole/cm³To 20X 10⁷Hole/cm³A pore density in the range of (a). Preferably, the plastic material has a thickness in the range of about 0.025mm to about 0.5mm, in particular in the range of about 0.05mm to about 0.35mm, preferably in the range of about 0.05mm to about 0.3mm, preferably about 0.075mm to about 0.25mm, preferably about 0.1mm to about 0.2mm and an average pore size of 1.8 x 10 mm⁶Hole/cm³To 5X 10⁶Hole/cm³A pore density in the range of (a).

The closure precursors used in the present invention may be formed, for example, by extrusion or molding. In known closures or closure precursors formed from thermoplastic polymers by means of extrusion or molding, the synthetic component or polymer may be foamed by means of a foaming agent (also referred to as a blowing agent). It is well known in the industry that the use of foaming agents such as for closure precursors is advantageous in forming plastic materials, for example extruded or shaped foam plastic materials. In the present disclosure, various foaming agents may optionally be employed during the manufacturing process to produce the closure precursor. Typically, physical or chemical blowing agents, or a combination of physical and chemical blowing agents, are employed. Expandable microspheres may also be used. The foaming agent useful in forming the closure precursor may, for example, be selected from the group consisting of: expandable microspheres, chemical blowing agents, physical blowing agents, and combinations of two or more thereof. Particularly preferably, the foaming agent comprises or is expandable microspheres.

Chemical blowing agents include azodicarbonamide (azodicarbonamide), azobisisobutyronitrile, benzenesulfonylhydrazide (benzylsulfonhydrazide), 4-phenolsulfonylsemicarbazide, p-toluenesulfonylsemicarbazide, barium azodicarboxylate, N '-dimethyl-N, N' -dinitrosoterephthalamide, and trihydrazinotriazine. Examples of suitable chemical blowing agents are available under the trade name Clariant International Ltd, BU Masterbatches (Rothausstr.61,4132Muttenz, Switzerland), from Clariant International LtdAnd (7) selling.

Alternatively or in addition to chemical foaming agents, inorganic or physical foaming agents may be used to make closure precursors according to the present disclosure. Examples of physical blowing agents include carbon dioxide, water, air, helium, nitrogen, argon, and mixtures thereof. Carbon dioxide and nitrogen are particularly useful blowing agents.

Suitable physical blowing agents that have been found to be effective in producing the closure precursors of the present disclosure may include one or more selected from the group consisting of: aliphatic hydrocarbons having 1 to 9 carbon atoms, halogenated aliphatic hydrocarbons having 1 to 9 carbon atoms, and aliphatic alcohols having 1 to 3 carbon atoms. Aliphatic hydrocarbons include: methane, ethane, propane, n-butane, isobutane, n-pentane, isopentane, neopentane, and the like. Among the halogenated and fluorinated hydrocarbons, they include, for example, fluoromethane, perfluoromethane, fluoroethane, 1, 1-difluoroethane (HFC-152a), 1,1, 1-trifluoroethane (HFC-430a), 1,1,1, 2-tetrafluoroethane (HFC-134a), pentafluoroethane, perfluoroethane, 2-difluoropropane, 1,1, 1-trifluoropropane, perfluoropropane, perfluorobutane, perfluorocyclobutane. Partially hydrogenated chlorocarbons and chlorofluorocarbons for use in the present disclosure include: methyl chloride, methylene chloride, ethyl chloride, 1,1, 1-trichloroethane, 1, 1-dichloro-1-fluoroethane (HCFC-141b), 1-chloro-1, 1-difluoroethane (HCFC-142b), 1, 1-dichloro-2, 2, 2-trifluoroethane (HCFC-123), and 1-chloro-1, 2,2, 2-tetrafluoroethane (HCFC-124). Perhalogenated chlorofluorocarbons include: trichloromonofluoromethane (CFC11), dichlorodifluoromethane (CFC-12), trichlorotrifluoroethane (CFC-113), dichlorotetrafluoroethane (CFC-114), chloroheptafluoropropane, and dichlorohexafluoropropane. Perhalofluorocarbons are not preferred because of their ozone depletion potential. Aliphatic alcohols include: methanol, ethanol, n-propanol and isopropanol.

If chemical and/or physical blowing agents are used, nucleating agents are often employed during the foaming of the plastic material in order to control the cell size in the closure, particularly in the plastic material, and to obtain the desired cell size as detailed herein. Preferred nucleating agents are selected from the group consisting of: calcium silicate, talc, clay, titanium oxide, silica, barium sulfate, diatomaceous earth, and a mixture of citric acid and sodium bicarbonate, which enable the desired pore density and pore size to be achieved. In particular embodiments of the present invention, it has been found that a nucleating agent, such as one of the nucleating agents listed herein, may be employed. Cork particles may also act as nucleating agents.

If a chemical or physical blowing agent, or a combination of one or more chemical blowing agents and one or more physical blowing agents, is used, the one or more blowing agents may be incorporated into the plastic material in an amount in the range of from about 0 wt% to about 10 wt%, preferably from about 0.005 wt% to about 10 wt%, more preferably from about 0.1 wt% to about 4 wt%, more preferably from 0.1 wt% to about 2 wt%, based on the total weight of the closure precursor.

For the purpose of the present invention, a plurality of pores is preferably obtained by using expandable microspheres as a foaming agent. Expandable microspheres are composed of a thin thermoplastic shell, usually made from a copolymer of monomers such as vinylidene chloride, acrylonitrile and/or methyl methacrylate, which encapsulates a low boiling point liquid hydrocarbon blowing agent, typically isobutylene or isopentane. Upon heating, the polymer shell gradually softens and the hydrocarbons expand, increasing the internal pressure within the microspheres and causing the polymer shell to expand. When the heat is removed, the shell hardens and the microspheres remain in their expanded form. When fully expanded, the volume of the microspheres can increase by more than 40 times, potentially up to 60 to 80 times. It is believed that in the closure precursor used in the present invention, the one or more thermoplastic polymers of the microsphere shell fuse into the polymer matrix while maintaining the integrity of the microspheres or expanded microspheres and thus form at least a portion of the pore walls of the plurality of pores in the polymer matrix. It is believed that the walls of the pores defining the pores of the plurality of pores and facing the interior of the corresponding pores comprise predominantly the one or more thermoplastic polymers of the expandable microsphere shell. In this way, at least one of the plurality of pores comprised in the plastic material is defined by at least one pore wall facing the interior of the pore, the plastic material of at least a part of the pore wall comprising a different thermoplastic polymer composition than the plastic material forming the remaining part of the polymer matrix. Preferably, the pores of the plurality of pores comprised in the plastic material are defined by pore walls, the plastic material of the pore walls facing the interior of the pores comprising a different thermoplastic polymer composition than the plastic material forming the remainder of the polymer matrix. If thermoplastic expandable microspheres are used, the use of a nucleating agent as described herein is not required, preferably not employed. It is particularly preferred that no nucleating agent is added to the composition forming the closure.

The amount of expandable microspheres that may be used in the manufacture of the closure precursor used in the present invention is in the range of about 0.005 wt.% to about 10 wt.%, preferably in the range of about 0.05 wt.% to about 10 wt.%, preferably in the range of about 0.5 wt.% to about 10 wt.%, preferably in the range of about 0.1 wt.% to about 5 wt.%, preferably in the range of about 0.1 wt.% to about 4 wt.%, preferably in the range of about 1.0 wt.% to about 4 wt.%, preferably in the range of about 1.5 wt.% to about 3 wt.%, preferably in the range of about 2 wt.% to about 2.5 wt.%, based on the total weight of the composition. The expandable microspheres may be used in combination with one or more foaming agents selected from chemical foaming agents and physical foaming agents, or the expandable microspheres may be used as the sole foaming agent in the absence of one or more foaming agents selected from chemical foaming agents and physical foaming agents. In the absence of a blowing agent, such as a chemical blowing agent and/or a physical blowing agent, the cells in the foam are substantially formed by the expandable microspheres. In this case, the amount of expandable microspheres is preferably sufficient to achieve the desired foam density of the plastic material. According to one embodiment of the invention, if expandable microspheres are used as blowing agent in the absence of a chemical or physical blowing agent, no nucleating agent is used and the composition for forming the closure precursor does not comprise a nucleating agent. According to another embodiment of the present invention, if expandable microspheres are used in combination with one or more chemical and/or physical blowing agents, the composition may comprise a nucleating agent.

The overall density of the closure and/or closure precursor according to the invention is preferably in the range of 100kg/m³To 500kg/m³In the range of about 125kg/m, preferably³To 500kg/m³In the range of about 150kg/m, preferably³To 500kg/m³Example (A) ofIn the enclosure, preferably at about 150kg/m³To 480kg/m³In the range of about 150kg/m, preferably³To 450kg/m³Preferably in the range of about 175kg/m³To 450kg/m³In the range of about 200kg/m, or³To 420kg/m³In the range of about 200kg/m, or³To 400kg/m³Within the range of (1). The bulk density takes into account the density of the cork particles, which are generally in the range of about 150kg/m³To 280kg/m³In the range of (1), typically about 180kg/m³To 280kg/m³In the range of (1), often about 180kg/m³. The density of the plastics material is preferably about 25kg/m³To 800kg/m³In the range of about 50kg/m, preferably³To 800kg/m³In the range of about 75kg/m, preferably in the range of about 75kg/m³To 800kg/m³In the range of about 100kg/m, preferably³To 800kg/m³In the range of about 150kg/m, preferably³To 700kg/m³In the range of about 150kg/m, preferably³To 600kg/m³In the range of about 150kg/m, preferably³To 500kg/m³In the range of about 180kg/m, preferably³To 500kg/m³In the range of about 200kg/m, or³To 450kg/m³In the range of about 200kg/m, preferably³To 420kg/m³Within the range of (1). These density ranges allow the closure to achieve the desired closure characteristics as disclosed herein.

The closure precursor may comprise cork. According to one embodiment, the closure precursor comprises in each case from 1 to 99% by weight, in particular from 5 to 85% by weight or from 20 to 75% by weight or from 30 to 72% by weight or from 33 to 65% by weight or from 33 to 59% by weight of cork, based on the total weight of the closure precursor. According to this embodiment, it is preferred that the closure precursor comprises more than 50% by weight of cork, based on the total weight of the closure precursor. Advantageously, the cork is in the form of cork granules.

It has been found that in known closures and methods for producing closures (particularly extrusion methods), the use of selected chemical and/or physical foaming agents to achieve a desired uniform foam density can be adversely affected by the presence of a significant amount, such as greater than about 40 weight percent, of cork particles (or coated particles as defined herein), based on the total closure weight. It is believed that when conventional chemical or physical blowing agents of choice are used, the cork particles (or coated particles as defined herein) may in some way adversely affect the formation of a uniform foam with a density within the desired range. While chemical and/or physical foaming agents may be used in accordance with the present invention, it has been found that the use of expandable microspheres generally produces a foam having desirable characteristics. In one aspect of the invention, expandable microspheres are used as the blowing agent. In this respect, according to a preferred embodiment of the present invention, no further chemical or physical blowing agent and no added nucleating agent are employed, in particular no further chemical or physical blowing agent and no added nucleating agent are added to the composition for forming the closure precursor.

One difficulty associated with incorporating cork particles (or coated particles as defined herein) into extruded or molded polymeric matrices of the kind described herein, particularly in relatively large quantities (e.g., comprising greater than about 40 weight percent cork particles), is embedding these particles in the polymeric matrix such that a smooth, continuous peripheral surface is achieved without bulging of the cork pieces and without discontinuous or rough areas on the peripheral surface. This is a particular problem in the case of extruded parts, as the peripheral surface of the polymer matrix may get stuck and dragged where it contacts the extrusion equipment, creating an uneven surface. While some degree of surface roughness can be smoothed by sanding, such as is done with natural cork closures, this adds an additional processing step and generates additional waste that cannot always be recycled but must be disposed of. In addition, if the surface roughness is increased, any sanding step must remove more material, which may also require that the extrudate contain more material, such as a wider diameter, in order to accommodate the greater amount of sanding. According to one embodiment, the closure and/or closure precursor comprises more than 50 wt% cork particles (or coated particles as defined herein). The cork particles (or coated particles as defined herein) may form a portion of the outer peripheral surface. This may be advantageous, inter alia, in terms of the appearance of the closure. In this case, the plurality of particles (or coated particles as defined herein), and in particular individual particles or groups of particles, preferably do not protrude from the peripheral surface. Thus, it is preferred that the closure precursor for use in the present invention is cylindrical or in the form of a sparkling wine closure and comprises an outer peripheral surface, wherein the outer peripheral surface preferably comprises a smooth surface comprising a plastics material and particles comprising cork (or coated particles as defined herein), or a smooth continuous surface comprising a plastics material.

Preferably, the closure precursor does not have surface melt fracture, sometimes referred to as sharkskin. While the exact cause of surface melt fracture is a controversial topic in the scientific literature, it appears that surface melt fracture may occur in extruded polymer melts based on extrusion rate, with higher extrusion rates producing greater degrees of surface melt fracture. At lower levels of surface melt fracture, surface irregularities are less pronounced and may appear as surface roughness. A higher degree of surface melt fracture results in significant surface deformation and cracking, crazing or breaking of the extrudate surface, which is not always limited to the surface, but may extend to a significant depth within the extrudate. This high degree of deformation will render the extrudate useless as a closure precursor. Polymer matrices with high loadings of cork particles (e.g., greater than 40 weight percent cork particles or greater than 50 weight percent cork particles based on the total weight of the formulation) are susceptible to melt stress cracking. This significantly affects the available window of process parameters for producing an extruded cylindrical closure precursor containing a significant amount of cork particles. The present invention allows for the reduction or substantial elimination of surface melt fracture while maintaining commercially and technically advantageous production methods and processing parameters.

If a closure precursor comprising cork, particularly cork particles, is used, the distribution of cork particles (or coated particles as defined herein) in the closure precursor is preferably substantially uniform throughout at least one of the length and diameter of the closure precursor. This prevents weak areas within the closure precursor, such as areas that substantially contain cork particles (or coated particles as defined herein) without sufficient plastic material to form a supporting matrix, which could lead to chipping and fracture of the closure precursor. This can be achieved by selecting the composition components, in particular the combination of plastic material and pre-coated cork particles ("coated particles") as described herein. The optional use of expandable microspheres as a blowing agent according to preferred embodiments of the present invention may also help to achieve this advantage, for example, by helping to form a uniform stable porous polymer matrix that is capable of supporting a uniform distribution of cork particles (or coated particles as defined herein) throughout the matrix. The exact composition used may vary within the parameters and ranges disclosed herein.

The closure precursors for use in the present invention may be formed by moulding, for example injection moulding or compression moulding, particularly compression moulding, or by extrusion. Preferably, the closure precursor is formed by means of extrusion. Extrusion allows for convenient, reliable, continuous mass production of closure precursors comprising polymeric components.

According to one embodiment, the closure precursor does not include a separately formed peripheral layer that surrounds and is intimately bonded to the cylindrical surface of the core member. If such a separate peripheral layer is not included, the closure precursor according to the invention is preferably formed by means of moulding or by means of a single extrusion, preferably by means of a single extrusion. This means that an extrudate with a single component, i.e. an elongated cylindrical rod, is formed.

It is possible that the closure precursor comprises one or more peripheral layers peripherally surrounding and intimately bonded to the cylindrical surface of the core member. The optional peripheral layer is preferably tightly bonded to substantially the entire cylindrical surface of the core member, particularly the entire cylindrical surface of the substantially cylindrical core member. The end faces of the core member are preferably free of peripheral layers. If there are any large unbonded areas, flow paths for gases and liquids may result. Thus, a strong, tight, adhesive mutual engagement of the at least one peripheral layer with the core member is advantageous for obtaining a bottle closure for the wine industry. To achieve integral adhesive interconnection between the at least one peripheral ply and the core member, the at least one peripheral ply is formed around the core member in a manner that ensures intimate adhesive engagement.

The closure precursors used in the present disclosure are preferably formed by extrusion. If the closure precursor comprises one or more peripheral layers, these layers are preferably formed as a single layer or as a plurality of separate layers by means of co-extrusion. In particular, the required firm, tight, adhesive mutual engagement is obtained by: the method may further include the step of co-extruding the at least one peripheral layer and the core member simultaneously or applying the at least one peripheral layer to the continuous elongated length of material after the continuous elongated length of material has been formed. By employing either process, a close adhesive interengagement of the at least one peripheral layer with the continuous elongate length of material is achieved.

Thus, in a particular aspect of the present disclosure, a closure precursor may be produced by a method comprising at least one co-extrusion process step. According to this aspect of the disclosure, the synthetic closure includes a core member and a peripheral layer that are formed by co-extrusion. Suitable coextrusion processes are known to the skilled worker.

In one aspect of the present disclosure that includes a core member and a peripheral layer, the core member and the at least one peripheral layer are extruded substantially simultaneously. In another aspect, the core member is extruded separately and, after that, the at least one peripheral layer peripherally surrounding and encapsulating the preformed core member is formed in an extrusion apparatus.

In further aspects, the closure precursor can include two or more peripheral layers. As described herein, it is possible that the first peripheral layer which is in firm, intimate, adhesive interengagement with the outer surface of the core member, particularly with the outer cylindrical surface of the cylindrical core member, is formed by extrusion substantially simultaneously with the core member, or by subsequent extrusion, or by molding. Then, as described herein for the first peripheral layer, the second peripheral layer and subsequent peripheral layers may be formed, again by extrusion substantially simultaneously with the core member and the first or further peripheral layers, or by subsequent extrusion. In the case of multiple peripheral layers, it is also possible to subsequently extrude two or more peripheral layers, but substantially simultaneously with each other, as described herein.

In one embodiment, the closure precursor does not include a peripheral layer. This may be preferred, for example, in the case of closures for sparkling wine bottles, but may also be preferred, for example, in the case of cylindrical closures for static wine bottles. One advantage of the present disclosure is that the closure precursors used in the present invention have a sufficiently smooth surface to obtain a closure even when containing greater than 50 wt%, for example 51 wt% or more cork particles (or coated particles as defined herein) of the total closure precursor weight, even in the absence of a peripheral layer.

The closure precursor may comprise a first plastic material. The closure precursor may also comprise a second plastic material. The first and second plastic materials may each independently comprise at least one thermoplastic polymer. The first and second plastic materials may be the same or different. The first and second plastic materials may be independently selected. In other words: the plastic material used to coat the particles (the first plastic material) may be the same as or different from the second material. Any of the descriptions herein with respect to "plastic material" may apply to the first plastic material and/or the second plastic material. The plastic material may comprise one thermoplastic polymer, or more than one thermoplastic polymer, for example two, three or more thermoplastic polymers. If expandable microspheres are used as blowing agent, the plastic material typically comprises more than one thermoplastic polymer. This is because the thermoplastic polymer or polymers of the microsphere shell remain in the closure precursor. The term "polymer" is intended to include all materials having a polymer chain made up of a number of subunits, which may be the same or different, such as, for example, all types of homopolymers and copolymers, including statistical, random, graft, periodic, block copolymers, each of which may be linear or branched. The term "thermoplastic" has its usual meaning in the art.

In each case, the closure precursor may comprise from 1 to 49 wt%, in particular from 5 to 32 wt% or from 5 to 30 wt% or from 5 to 26 wt%, of the first plastic material, based on the total weight of the closure precursor.

In each case, the closure precursor may comprise from 10 to 49 wt%, in particular from 12 to 49 wt% or from 25 to 35 wt%, of the second plastic material, based on the total weight of the closure precursor.

According to one embodiment, the second plastic material is a thermoplastic material comprising a polymeric elastomer gum comprising one or more thermoplastic polymers as defined herein. According to another embodiment, the second plastic material is a thermoplastic material comprising a polymer elastomer dispersion comprising one or more thermoplastic polymers as defined herein.

According to a preferred aspect of the closure precursor for use in the present invention, the plastics material is thermoplastically processable. This means that the plastics material of the closure precursor, once formed into the closure precursor, can be reformed or reprocessed thermally (i.e. by the application of heat). This is preferably achieved if the plastic material comprises a thermoplastic polymer without the addition of a crosslinking agent. However, it is possible to add small amounts of crosslinking agents or some types of glues (such as epoxy glues), for example in order to change the rheological properties or to make the polymers compatible, and still maintain thermoplasticity processability. Thermoplasticity can be advantageous if it is desired to separate portions of a closure, such as cork pellets, for example, in order to recycle or reuse any portion of the closure, such as cork pellets or plastic material or both. While closure precursors comprising thermosetting polymers and/or adhesives (including reactive and non-reactive adhesives) can be used in the present invention, these known non-thermoplastic closures cannot be thermally processed, making it difficult, if not impossible, to separate different components such as cork and polymer and thereby recycle or reuse any portion of the closure separately. Thus, the formulation of the closure precursor used in the present invention (which allows the closure precursor to be formed by a thermoplastic extrusion or moulding process) helps to make this possible.

According to one embodiment of the present disclosure, at least one, preferably each, thermoplastic polymer comprised in the plastic material optionally has a molecular weight of at 0.7g/cm³To 1.4g/cm³A low density polymer of unfoamed density within the range of (a). This aspect may be particularly advantageous in the following cases: if the core member comprises a relatively large amount of cork particles (or coated particles as defined herein) within the ranges disclosed herein, for example, more than 40 wt%, more than 45 wt%, more than 50 wt%, and particularly more than 51 wt% of the particles. The lower polymer density helps to offset the possible increased density of the closure precursor due to the inclusion of particles.

In one exemplary aspect according to the present disclosure, a closure precursor for use in the present disclosure includes as its main component a core member formed of an extruded foamed plastics material comprising one or more thermoplastic polymers selected from copolymers, homopolymers, or combinations of any two or more thereof. While any known thermoplastic polymeric material, and particularly any foamable thermoplastic polymeric material, may be used in the closure precursors used in the present disclosure, the plastic material is preferably selected to produce physical characteristics similar to natural cork so as to be able to provide a synthetic closure for use in place of natural cork as a closure for wine bottles. By way of example, the plastics material for the core member may be a closed cell foamed plastics material.

If the closure precursor includes one or more peripheral layers, the material of the peripheral layer or layers comprises aOne or more thermoplastic polymers. In one exemplary aspect, the at least one peripheral layer (if included) comprises a thermoplastic polymer that is the same as or similar to the thermoplastic polymer contained in the core member. In another aspect, the peripheral layer may comprise a thermoplastic polymer that is different from the one or more thermoplastic polymers contained in the core member. However, as detailed herein, in either case, regardless of the one or more polymers, the physical characteristics imparted to the peripheral layer are preferably substantially different from the physical characteristics of the core member, particularly the peripheral layer density is substantially greater than the core member density. The preferred density of the peripheral layer is 50kg/m³To 1500kg/m³In the range of 100kg/m, preferably in the range of 100kg/m³To 1500kg/m³In the range of 200kg/m, preferably³To 1500kg/m³In the range of 300kg/m, preferably in the range of 300kg/m³To 1500kg/m³In the range of 400kg/m, preferably in the range of 400kg/m³To 1500kg/m³In the range of 500kg/m, preferably in the range of 500kg/m³To 1500kg/m³In the range of 600kg/m, preferably in the range of 600kg/m³To 1500kg/m³In the range of 700kg/m, preferably in the range of 700kg/m³To 1500kg/m³In the range of 750kg/m, preferably in the range of 750kg/m³To 1500kg/m³In the range of 700kg/m, or in the range of 700kg/m³To 1350kg/m³In the range of 700kg/m, or in the range of 700kg/m³To 1100kg/m³In the range of 750kg/m, or in the range of 750kg/m³To 1350kg/m³In the range of 750kg/m, or in the range of 750kg/m³To 1100kg/m³Within the range of (1).

According to a preferred aspect of the closure precursor for use in the present invention, the plastics material comprises one or more polymers which are biodegradable according to ASTM D6400. Preferably, at least 90 wt.%, more preferably at least 95 wt.%, in particular 100 wt.% of the plastic material, in particular the first plastic material, is biodegradable according to ASTM D6400. Because cork particles are biodegradable, most or all of the closure precursor and/or closure can be made biodegradable if the plastic material comprises one or more biodegradable polymers. If it is desired that the multi-component closure precursor is biodegradable, compostable or recyclable, it is preferred that the plastic material of the core member and the plastic material of the peripheral layer or layers are both biodegradable, compostable or recyclable.

In each case, preferably from 50 to 100 wt% of the closure precursor, preferably from 60 to 100 wt% of the closure precursor, preferably from 70 to 100 wt% of the closure precursor, preferably from 80 to 100 wt% of the closure precursor, preferably from 85 to 99.9 wt% of the closure precursor, preferably from 90 to 99 wt% of the closure precursor, preferably from 90 to 98 wt% of the closure precursor (for example) is biodegradable as determined according to ASTM D6400, based on the total weight of the closure precursor (including any peripheral layer or layers, if present). If a chemical or physical foaming agent is used to form the foamed plastics material, biodegradability up to and including about 100% of the closure precursor, for example, from 90 to 100% by weight of the closure precursor, preferably from 95 to 100% by weight of the closure precursor, preferably from 98 to 100% by weight of the closure precursor, based on the total weight of the closure precursor, can be achieved by selecting one or more biodegradable thermoplastic polymers as the plastics material. Currently available polymer formulations of available expandable microsphere shells are not biodegradable. If the closure precursor used in the present invention is made using currently available expandable microspheres as a blowing agent, the closure precursor will contain about the same weight percent amount of non-biodegradable polymer as the weight percent amount of expandable microspheres in the closure precursor, and the biodegradable portion of the closure precursor will be correspondingly reduced by the same amount. Thus, if expandable microspheres are employed as the foaming agent, the plastic material may comprise non-biodegradable thermoplastic polymer in an amount of up to 10 wt. -%, preferably in an amount of about 0.005 wt. -% to about 10 wt. -%, preferably in an amount in the range of about 0.05 wt. -% to about 10 wt. -%, preferably in an amount in the range of about 0.5 wt. -% to about 10 wt. -%, preferably in an amount in the range of about 1.0 wt. -% to about 8 wt. -%, preferably in an amount in the range of about 1.0 wt. -% to about 5 wt. -%, preferably in an amount in the range of about 1.0 wt. -% to about 4 wt. -%, or in an amount in the range of about 1.5 wt. -% to about 4.0 wt. -%, based on the total weight of the plastic material. If suitable biodegradable expandable microspheres become available, the amount of biodegradable material in the closure can be increased accordingly.

The plastic material of the closure according to the invention preferably comprises one or more thermoplastic polymers selected from the group consisting of: polyethylene; metallocene catalyst polyethylene; a polybutylene; polybutylene; a thermoplastic polyurethane; a silicone; a vinyl-based resin; a thermoplastic elastomer; a polyester; ethylene acrylic acid copolymers; ethylene-vinyl acetate copolymers; ethylene-methyl acrylate copolymers; a thermoplastic polyolefin; a thermoplastic vulcanizate; a flexible polyolefin; a fluororubber; a fluoropolymer; polytetrafluoroethylene; ethylene-butyl acrylate copolymers; ethylene-propylene rubbers; styrene butadiene rubber; styrene butadiene block copolymers; ethylene-ethyl-acrylic acid copolymers; an ionomer; polypropylene; copolymers of polypropylene and ethylenically unsaturated comonomers copolymerizable therewith; an olefin copolymer; an olefin block copolymer; a cycloolefin copolymer; styrene ethylene butadiene styrene block copolymers; styrene ethylene butylene styrene block copolymers; styrene ethylene butylene block copolymers; styrene butadiene styrene block copolymers; styrene butadiene block copolymers; styrene isoprene styrene block copolymers; styrene isobutylene block copolymers; styrene isoprene block copolymers; styrene ethylene propylene styrene block copolymers; styrene ethylene propylene block copolymers; polyvinyl alcohol; polyvinyl butyral; polyhydroxyalkanoates; copolymers of monomers of hydroxyalkanoates and biodegradable polymers; polylactic acid; copolymers of lactic acid and monomers of biodegradable polymers; an aliphatic copolyester; aromatic-aliphatic copolyesters; polycaprolactone; polyglycolide; poly (3-hydroxybutyrate); poly (3-hydroxybutyrate-co-3-hydroxyvalerate); poly (3-hydroxybutyrate-co-3-hydroxyhexanoate); poly (butylene succinate); poly (butylene succinate-co-adipate); poly (trimethylene terephthalate); poly (butylene adipate-co-terephthalate); poly (butylene succinate-co-terephthalate); poly (butylene sebacate-co-butylene terephthalate); caprolactone lactate copolymers; lactic acid ethylene oxide lactic acid copolymers; a polymer formed from monomer units selected from the group consisting of: vinylidene chloride, acrylonitrile, methacrylonitrile, and methyl methacrylate; a copolymer formed from two or more monomer units selected from the group consisting of: vinylidene chloride, acrylonitrile, and methyl methacrylate; PEF, PTF, bio-based polyesters, and combinations of any two or more thereof.

The first plastic material preferably comprises one or more thermoplastic polymers selected from the group consisting of: aliphatic (co) polyesters, aliphatic aromatic copolyesters, EVA, olefin polymers such as metallocene polyethylene, and styrene block copolymers.

The thermoplastic polymer for the plastic material may be selected from the group consisting of polyolefins, in particular polyethylene and/or polypropylene. In one exemplary aspect of the closure precursor disclosed herein, if polyethylene is employed, the polyethylene may comprise one or more polyethylenes selected from the group consisting of: high density polyethylene, medium density polyethylene, low density polyethylene, linear low density polyethylene, ultra high density polyethylene, and medium and low density polyethylene. Suitable plastic materials for the closure precursor or the core element thereof may be polyethylene (in particular LDPE) and/or ethylene vinyl acetate copolymer (EVA). These materials may be used alone or in combination with one or more other thermoplastic polymers disclosed herein, in particular in combination with metallocene PE or metallocene PP, in particular in combination with metallocene PE.

The closure precursor may comprise a cyclic olefin copolymer. Suitable cyclic olefin copolymers are, for example,and their synthesis and characterization methods are described in U.S. patent No.8,063,163B2, the contents of which are incorporated herein by reference and form a part of this disclosure. A suitable cycloolefin copolymer is the nameElastomer E-140 is commercially available from Topas Advanced Polymers, Germany (Topas Advanced Polymers, Germany). One preferred cycloolefin copolymer is a copolymer of ethylene and norbornene.

Particularly preferred plastic materials are thermoplastic elastomers based on one or more polyesters. Thermoplastic elastomers have both thermoplastic and elastomeric properties and are sometimes also referred to as thermoplastic rubbers. Elastomeric properties may be useful for closure precursors as they may contribute to, for example, elasticity, compression recovery, compressibility, and the like. Elastomers generally have a thermoset and are therefore not thermoplastically processable. For this reason, elastomers are generally not recyclable. They cannot be thermoplastically processed, for example by extrusion. The thermoplastic elastomer is thermoplastically processable. The thermoplastic elastomer can also be recycled. Polyester-based thermoplastic elastomers may additionally be biodegradable to a significant extent due to ester linkages, which are more susceptible to cleavage than other polymer linkage types. Thermoplastic elastomers based on one or more polyamides are also contemplated. However, thermoplastic elastomers based on one or more polyesters are preferred. The entire plastic material may be formed from one or more thermoplastic elastomers, or the plastic material may comprise one or more thermoplastic elastomers, in particular one or more thermoplastic elastomers based on one or more polyesters, in an amount of up to 80 wt. -%, in particular in an amount in the range of 2 to 80 wt. -%, in particular in an amount in the range of 5 to 80 wt. -%, in particular in an amount in the range of 10 to 80 wt. -%, in particular in an amount in the range of 15 to 80 wt. -%, in particular in an amount in the range of 20 to 80 wt. -%, in particular in an amount in the range of 25 to 80 wt. -%, based on the total weight of the plastic material.

Advantageously, the closure precursor is at least partially biodegradable, compostable, recyclable, or made using at least a portion of renewable and/or sustainable materials. If it is desired that the closure precursor should be biodegradable, or more than 85% by weight, preferably more than 90% by weight biodegradable, the plastics material preferably comprises one or more biodegradable thermoplastic polymers. Preferably, the first plastic material independently comprises one or more thermoplastic polymers selected from the group consisting of aliphatic (co) polyesters and aliphatic aromatic copolyesters. In particular, the plastic material preferably comprises one or more biodegradable thermoplastic polymers selected from the group consisting of: polyhydroxyalkanoates; copolymers of monomers of hydroxyalkanoates and biodegradable polymers; polylactic acid; copolymers of lactic acid and monomers of biodegradable polymers; an aliphatic copolyester; aliphatic-aromatic copolyesters; polycaprolactone; polyglycolide; poly (3-hydroxybutyrate); poly (3-hydroxybutyrate-co-3-hydroxyvalerate); poly (3-hydroxybutyrate-co-3-hydroxyhexanoate); poly (butylene succinate) (poly (butylenesuccinate)); poly (butylene succinate-co-adipate); poly (trimethylene terephthalate); poly (butylene adipate-co-terephthalate); poly (butylene succinate-co-terephthalate); poly (butylene sebacate-co-terephthalate); caprolactone lactate copolymers; lactic acid ethylene oxide lactic acid copolymers; and combinations of any two or more thereof. If Polyhydroxyalkanoate (PHA) is included, the polyhydroxyalkanoate monomer preferably contains at least four carbon atoms, preferably four or five carbon atoms. Advantageously, the repeating units of polyhydroxyalkanoates according to the present disclosure include [ -O-CHR-CH₂-CO-]Wherein R is of the formula C_nH_2n+1 linear or branched alkyl group, wherein n is an integer from 1 to 15, in particular from 1 to 6. In an exemplary aspect of the present disclosure, if a PHA is employed, the PHA preferably comprises one or more PHAs selected from the group consisting of: poly (3-hydroxybutyrate), poly (3-hydroxybutyl) and their useAcid ester-co-3-hydroxyvalerate), and poly (3-hydroxybutyrate-co-3-hydroxyhexanoate). Advantageously, these polymers have a molecular weight of from 100,000 to 1,000,000g/mol and/or a melting point of from 100 to 200 ℃. Mixtures of one or more PHAs with poly (lactic acid) are also particularly useful. In an exemplary aspect of the present disclosure, if a polyester is employed, the polyester preferably comprises one or more polyesters selected from the group consisting of: polycaprolactone, polyglycolide, poly (butylene succinate), poly (lactic acid), polybutylene succinate adipate, polytrimethylene terephthalate, polybutylene adipate terephthalate, polybutylene succinate terephthalate, polybutylene sebacate terephthalate. In an exemplary aspect of the present disclosure, if a block copolymer of lactic acid is used, the block copolymer of lactic acid includes a lactic acid-caprolactone-lactic acid copolymer, a lactic acid-ethylene oxide-lactic acid copolymer.

If expandable microspheres are used as blowing agent, the plastic material may further comprise one or more thermoplastic polymers selected from the group consisting of: a polymer formed from monomer units selected from vinylidene chloride, acrylonitrile and methyl methacrylate; a copolymer formed from two or more monomer units selected from vinylidene chloride, acrylonitrile, and methyl methacrylate; and combinations of any two or more thereof.

A particularly preferred biodegradable thermoplastic polymer is one or more aliphatic-aromatic copolyesters. According to a preferred aspect of the closure precursor, the closure precursor comprises an aliphatic-aromatic copolyester. The aliphatic-aromatic copolyester is preferably selected from aliphatic-aromatic copolyesters having a glass transition temperature of less than 0 ℃, preferably less than-4 ℃, more preferably less than-10 ℃, more preferably less than-20 ℃, more preferably less than-30 ℃ as measured by Differential Scanning Calorimetry (DSC) according to ASTM D3418-15. The aliphatic-aromatic copolyester is preferably a statistical copolyester based on at least adipic acid and/or sebacic acid. In statistical copolyesters, the constituent monomer units are irregularly distributed along the polymer chain. Statistical copolyesters are also sometimes referred to as random copolyesters. Generally, aliphatic-aromatic copolyesters comprising terephthalate units derived from terephthalic acid or substituted terephthalic acid as aromatic units are preferred. It has been found that aliphatic-aromatic copolyesters comprising terephthalate units derived from terephthalic acid or substituted terephthalic acid as aromatic units and aliphatic units derived from difunctional aliphatic organic acids and/or difunctional aliphatic alcohols (such as aliphatic diacids, aliphatic diols) or aliphatic units comprising at least one alcohol functional group and at least one acid functional group can meet the requirements imposed on the plastic materials of closures as described herein, particularly closures for wine bottles. Preferably, the aliphatic-aromatic copolyester according to the present disclosure is a copolyester or statistical copolyester based on 1, 4-butanediol, adipic or sebacic acid, and terephthalic acid or ester-forming derivatives of terephthalic acid. Preferably, the aliphatic-aromatic copolyester according to the present disclosure exhibits a glass transition temperature, measured according to ASTM D3418-15, of from-25 ℃ to-40 ℃, more preferably from-30 ℃ to-35 ℃, and/or a melting temperature region of from 100 ℃ to 120 ℃, more preferably from 105 ℃ to 115 ℃. This ensures suitable handling and use characteristics in a typical temperature range.

Particularly preferred biodegradable thermoplastic polymers are one or more selected from the group consisting of: polybutylene adipate terephthalate; polybutylene succinate terephthalate; polybutylene sebacate terephthalate; and combinations of two or more thereof. Suitable commercially available biodegradable thermoplastic aliphatic-aromatic copolyesters are available from BASF Corporation (BASF SE, Ludwigshafen, Germany) of Ludwigshafen, Germany or BASF Corporation of Wyandotte, michigan, usaC1200。C1200 is polybutylene adipate terephthalate (PBAT) copolymerA copolymer which is a statistical, aliphatic-aromatic copolyester in the polymer chain based on the monomers 1, 4-butanediol, adipic acid and terephthalic acid.

If the closure precursor includes one or more peripheral layers, the one or more peripheral layers may comprise a thermoplastic polymer that is the same as or similar to the thermoplastic polymer contained in the core member. In another aspect, the peripheral layer may comprise a thermoplastic polymer that is different from the one or more thermoplastic polymers contained in the core member.

According to one exemplary aspect of the closure precursor for use in the present disclosure comprising a core member and at least one peripheral layer, wherein the peripheral layer comprises at least one thermoplastic polymer selected from the group consisting of: polyethylene, metallocene-catalyzed polyethylene, polypropylene, metallocene-catalyzed polypropylene, polyisobutylene, polybutylene, other polyolefins, fluorinated polyolefins, particularly partially or perfluorinated polyethylene, polyurethane, EPDM rubber, silicone, vinyl-based resins, thermoplastic elastomers, polyesters, ethylene acrylic acid copolymers, ethylene vinyl acetate copolymers, ethylene methyl acrylate copolymers, thermoplastic polyurethanes, polyether urethanes, thermoplastic olefins, thermoplastic vulcanizates, flexible polyolefins, fluoroelastomers, fluoropolymers, polyethylene, polytetrafluoroethylene, and blends thereof, ethylene butyl acrylate copolymers, ethylene propylene rubbers, styrene butadiene block copolymers, ethylene ethyl acrylic acid copolymers, ionomers, Polypropylene, and copolymers of polypropylene and copolymerizable ethylenically unsaturated comonomers, olefin copolymers, olefin block copolymers, cycloolefin copolymers, styrene ethylene butadiene styrene block copolymers, styrene ethylene butylene block copolymers, styrene butadiene styrene block copolymers, styrene butadiene block copolymers, styrene isoprene styrene block copolymers, styrene isobutylene block copolymers, styrene isoprene block copolymers, styrene ethylene propylene styrene block copolymers, styrene ethylene propylene block copolymers, polyvinyl alcohol, polyvinyl butyral, polyhydroxyalkanoates, copolymers of hydroxyalkanoates and monomers of biodegradable polymers, aliphatic copolyesters, aromatic-aliphatic copolyesters, poly (lactic acid), poly (lactic, Copolymers of lactic acid and monomers of biodegradable polymers, polycaprolactone, polyglycolide, poly (3-hydroxybutyrate), poly (3-hydroxybutyrate-co-3-hydroxyvalerate), poly (3-hydroxybutyrate-co-3-hydroxyhexanoate), poly (butylene succinate-co-adipate), poly (trimethylene terephthalate), poly (butylene adipate-co-butylene terephthalate), poly (butylene succinate-co-butylene terephthalate), poly (butylene sebacate-co-butylene terephthalate), caprolactone lactate copolymers, ethylene oxide lactate copolymers, and combinations of two or more thereof. According to an exemplary aspect of the present disclosure, the at least one peripheral layer is further defined as comprising one selected from the group consisting of foamed plastic and non-foamed plastic, advantageously having a density significantly greater than the core member, in order to impart the desired physical characteristics to the bottle closure of the present disclosure. In particular, the composition for the at least one peripheral layer is particularly chosen so as to withstand the compressive forces exerted on it by the jaws of the corking machine. However, as detailed herein, many different polymers are capable of withstanding these forces and may therefore be used for the at least one peripheral layer.

Specific examples of plastic materials for the at least one peripheral layer are polyethylene, thermoplastic vulcanizates, styrene ethylene butylene styrene block copolymers, poly (butylene adipate terephthalate) (PBAT), lactic acid-caprolactone-lactic acid copolymers, and combinations thereof. If desired, the at least one peripheral layer may be formed of a transparent material. Further, the material selected for the at least one peripheral layer may be different from the material of the core member.

In order to form a bottle closure comprising a core member and at least one peripheral layer having some or all of the desired inherent physical and chemical characteristics detailed above, it may be advantageous to include a metallocene catalyst polyethylene in the at least one peripheral layer. As detailed herein, at least one peripheral layer may, for example, substantially comprise a metallocene catalyst polyethylene as a single component, or the metallocene catalyst polyethylene may be combined with one or more thermoplastic elastomers, for example with one or more thermoplastic elastomers as detailed above. If the closure precursor comprises a peripheral layer, at least one peripheral layer may, for example, comprise one or more polyethylenes selected from the group consisting of medium density polyethylene, medium low density polyethylene and low density polyethylene in an amount in the range of from about 5% to about 100% by weight, in particular in the range of from about 5% to about 80% by weight, in particular in the range of from about 10% to about 60% by weight, in particular in the range of from about 15% to about 40% by weight, based on the weight of the total composition.

While the peripheral layer comprising polyethylene provides preferred closure performance characteristics for forming bottle closures comprising a core member and at least one peripheral layer having some or all of the desired inherent physical and chemical characteristics according to the present invention, particularly increased environmental friendliness, particularly increased biodegradability of the closure, it is preferred that if one or more peripheral layers are present, the at least one peripheral layer comprises poly (butylene adipate terephthalate) (PBAT). As detailed herein, at least one peripheral layer (if present) may comprise PBAT as substantially the only polymer component, or PBAT may be combined, if desired, with one or more thermoplastic elastomers, in particular with one or more thermoplastic elastomers as detailed above, in particular with one or more biodegradable thermoplastic elastomers as detailed above. In this respect, it has been found to be advantageous that the at least one peripheral layer comprises in particular one or more polyesters selected from the group consisting of biodegradable polyesters in an amount in the range from about 5% to about 100% by weight, in particular in the range from about 15% to about 95% by weight, in particular in the range from about 25% to about 90% by weight, based on the weight of the entire composition.

One of the embodiments hereinIn an exemplary configuration, the preferred PBAT for forming the at least one peripheral layer is or includes that sold by BASF corporation of Wynoddt, MichIt has been found that this compound results in an outer layer combined with the core member which achieves at least one, in particular more than one, in particular almost all or even all of the physical and chemical characteristics suitable for obtaining a highly efficient closure for the wine industry.

Formulations that are highly effective in providing a peripheral layer have been found to comprise at least one lactic acid and/or at least one styrene block copolymer. Suitable styrenic block copolymers that may be considered may be selected from the group consisting of: styrene ethylene butadiene styrene block copolymers, styrene ethylene butylene block copolymers, styrene butadiene styrene block copolymers, styrene butadiene block copolymers, styrene isobutylene block copolymers, styrene isoprene styrene block copolymers, styrene isoprene block copolymers, styrene ethylene propylene styrene block copolymers, styrene ethylene propylene block copolymers, and combinations of two or more thereof. In particular aspects of the present disclosure, the at least one styrenic block copolymer is selected from the group consisting of: styrene ethylene butadiene styrene block copolymers, styrene ethylene butylene styrene block copolymers, styrene ethylene propylene block copolymers, and combinations of two or more thereof. Examples of commercially available styrenic block copolymers according to the present disclosure are SBS, SIS, SEBS, SIBS, SEPS, SEEPS, MBS, which are available for example under the following trade names:and(Won, Michigan, USA)Dutbbasf Corporation (BASF Corporation of Wyandotte, Mich., USA)),Q、v, and herbicidal agents (Kuraray America, Inc., Houston, Tex., USA)), (herbicide, N.E., herbicide,TPE (Nantong Polymax Elastomer Technology Co., Ltd)), GLOB (GlOB)Polymers (Liangrong Chemical Corporation),And(Teknor Apex Company) of Penes corporation,Series (Elastocon TPE Technologies Inc.), TPR (Washington Penn Penn), Evoprene^TM(Alpha Gary, Alphagairy) Inc.), (GLS Thermoplastic Elastomers, Sevrene)^TM(Vichem Corporation), Vector^TM(Dexco Polymers LP) Dexco Polymers (Dexco Polymers Co.) and (Co.) Co., Ltd. (Co., Ltd.)),And(Dynasol, Inc.)),TEA andTPE (Multi base, Inc.)) (TPE),Sol T (Polimeri Europe), Sunprene^TM(PolyOne corporation),(Riken technologies Corporation), RTP 2700 and 6000 series (RTP Corporation (RTP)), (Riken technologies Corporation), and,(schulman corporation (a. schulman)),(VTC Elastotechnik) Inc.),(Ray-Weak company (Zeon)),and(API spa, Inc.), Asaprene^TMAnd Tufprene^TM(Asahi Kasei) company, Lifoflex (Mullerunthttoffe, Germany)) and,(Wall, Germany)Dekriburg-Iceland GmbH ((Kraiburg TPE GmbH)&Kg, Waldkraiberg, Germany)) orFor exampleD、G orFG (Kraton Polymers, Houston, Tex., USA, Houston, USA)). Suitable lactic acid copolymers that may be considered may be selected from the group consisting of: caprolactone lactate lactic acid block copolymers, ethylene oxide lactate lactic acid block copolymers, and mixtures thereof. Additional sources of biodegradable polymers can be found in "Bio-Based Plastics: Materials and Applications [" Bio-Based Plastics: materials and applications "]", Stephan Kabasci, John Wiley (John Wiley)&Sons)，2014，ISBN 978-1119994008。

Another formulation that has been found to be highly effective in providing a peripheral layer comprises at least one thermoplastic vulcanizate.

Another formulation which has been found to be highly effective in providing a peripheral layer which provides at least one, particularly more than one, particularly almost all or even all, of the physical and chemical properties to obtain a commercially viable closure, comprises at least one of at least one polyether thermoplastic polyurethane and at least one olefin block copolymer, or a blend of at least two of them.

The materials disclosed as being suitable for the peripheral layer may each be used alone or in combination with one or more of these materials. By employing the material or materials and forming the material or materials in circumferential, surrounding, adhesive engagement with any desired foamed core member, a highly effective multi-layer closure precursor can be obtained which can be used to provide at least one, particularly more than one, particularly almost all or even all of the properties suitable for wine bottle closures.

In one exemplary construction of this embodiment, the particular polyether-type thermoplastic polyurethane used to form the at least one peripheral layer comprises that manufactured by BASF Corporation of Wyandotte, michigan (US), usaLP 9162. It has been found that this compound results in an outer layer combined with the core member which provides at least one, in particular more than one, in particular almost all or even all, of the physical and chemical characteristics suitable for obtaining a highly efficient closure for the wine industry.

In another exemplary aspect of the closure precursor including a core member and at least one peripheral layer, the peripheral layer comprises thermoplastic vulcanizate (TPV). Such thermoplastic vulcanizates are well known in the art and are commercially available, for example, under the trade nameAvailable from ExxonMobil Chemical Company of Houston, Tex (USA) under the trade name of Texas (U.S.)Obtained from Tenor Apex B.V. of Tenoer, Glan (Netherlands) (Geleen (NL)), or under the trade nameObtained from pleckian corporation of anglin Lake, ohio (usa) (PolyOne inc. of Avon Lake, ohio (us)).

In addition to employing the polyether thermoplastic polyurethanes detailed above, another composition that has been found to be highly effective in providing at least one of the desired attributes to at least one peripheral layer, particularly more than one, particularly substantially all or even all of the attributes, is a blend of at least one polyolefin (particularly at least one thermoplastic polyolefin) and at least one thermoplastic vulcanizate. The construction of a closure precursor using a peripheral layer formed from this blend provides a closure precursor that is highly suitable for use as a wine bottle closure.

Another composition that can provide at least one, particularly more than one, particularly almost all or even all, of the desired attributes to at least one peripheral layer is a blend of at least one polyolefin, particularly at least one thermoplastic polyolefin, and at least one styrenic block copolymer, or a blend of at least one thermoplastic vulcanizate and at least one styrenic block copolymer. The construction of a closure precursor using a peripheral layer formed from this blend provides a closure that is highly suitable for use as a wine bottle closure.

In another alternative embodiment, a closure precursor may be obtained by employing at least one of at least one metallocene catalyst polyethylene and at least one olefin block copolymer independently or in combination with at least one selected from the group consisting of low density polyethylene, medium density polyethylene, and medium low density polyethylene.

It has been found that it is highly efficient to provide at least one of the desired properties, in particular more than one, in particular almost all or even all of the properties to at least one peripheral layer and another composition preferred according to the present invention is a blend of at least one polyester, in particular at least one statistical aromatic-aliphatic copolyester, and at least one lactic acid block copolymer. Suitable blends of at least one polyester (preferably at least one statistical aromatic-aliphatic copolyester, preferably PBAT) and at least one lactic acid polymer or lactic acid derivative (in particular at least one lactic acid block copolymer) comprise a polyester (preferably a statistical aromatic-aliphatic copolyester) in an amount in the range of from about 5 to about 95 wt. -%, or in an amount in the range of from about 20 to about 80 wt. -%, or in an amount in the range of from about 30 to about 70 wt. -%, or in an amount in the range of from about 40 to about 60 wt. -%, based on the weight of the entire composition, and a lactic acid polymer or lactic acid derivative (preferably a lactic acid block copolymer) in an amount in the range of from about 95 to about 5 wt. -%, in particular in an amount in the range of from about 80 to about 20 wt. -%, in particular in an amount in the range of from about 70 to about 30 wt. -%, in particular in an amount in the range of from about 60 to about 40 wt. -%, based on the weight of the entire composition ). Exemplary weight ratios of the lactic acid block copolymer to the statistical aliphatic-aromatic copolyester are about 95:5, about 90:10, about 85:15, about 80:20, about 75:25, about 70:30, about 65:35, about 60:40, about 55:45, about 50:50, based on the total weight of the lactic acid block copolymer and the statistical aliphatic-aromatic copolyester. The construction of a closure precursor using a peripheral layer formed from this blend provides a closure precursor that is highly suitable for use in providing wine bottle closures, particularly biodegradable wine bottle closures.

It has been found that still further additional compounds which provide a highly effective peripheral layer for forming a closure according to the present disclosure includeFluoroelastomer compounds and fluoropolymers. It has been found that these compounds, whether used alone or in combination with each other or with other compounds as detailed above, are highly effective in creating a peripheral layer that is capable of providing at least one, in particular more than one, in particular almost all or even all of the characteristics that make it suitable for use in a bottle closure.

Any of the compounds detailed herein for providing the at least one peripheral layer may be used alone or in combination with one another to produce a peripheral layer that is securely and integrally bonded to the core member and/or a different peripheral layer, as a foamed or non-foamed outer layer, or as an intermediate layer, using suitable manufacturing methods detailed herein.

According to a particular aspect of the present disclosure, at least one, preferably each, thermoplastic polymer contained in the peripheral layer is biodegradable according to ASTM D6400.

The at least one peripheral layer, if present, and in particular the outer peripheral layer, is in particular formed with a thickness and/or density capable of imparting the desired physical characteristics (such as resistance to bottling conditions) to the closure precursors and/or closures of the present disclosure. In particular, the at least one peripheral layer, in particular the outer peripheral layer, is formed with a density significantly greater than the inner core and/or is formed with a selected thickness.

Accordingly, the at least one peripheral layer (if present) is specifically further defined as comprising a thickness in the range of about 0.05mm to about 5 mm. While this range has been found to be effective for producing a closure precursor that functions fully and achieves most or all of the desired objectives, exemplary aspects for wine bottles specifically include thicknesses in the range of about 0.05mm to about 2mm, with exemplary lower limits of the thickness being about 0.05mm, about 0.06mm, about 0.07mm, about 0.08mm, about 0.09mm, about 0.1mm, about 0.2mm, about 0.3mm, about 0.4mm, or about 0.5mm and exemplary upper limits of the thickness being about 1mm, about 2mm, about 3mm, about 4mm, or about 5 mm. Exemplary thicknesses of the at least one peripheral layer (if present) can be selected based on criteria such as, for example, the composition, physical properties, and/or density of the material of the at least one peripheral layer, and the desired properties of the at least one peripheral layer.

As discussed herein, a close adhesive interengagement of the at least one peripheral layer (if present) with the core member is advantageous for providing a closure precursor for a bottle closure that can be used in the wine industry. In this regard, while it has been found that the methods detailed herein provide a secure, intimate adhesive engagement of the at least one peripheral layer with the core member, alternative layers or adhesive chemistries may be employed, depending on the particular materials used to form the core member and the at least one peripheral layer.

If desired, for closure precursors comprising a core member and at least one peripheral layer, an adhesive or tie layer known to the skilled artisan may be employed on the outer surface of the core member to provide a secure, intimate adhesive engagement of the at least one peripheral layer therewith. If an adhesive layer is used, the adhesive layer will effectively be interposed between the core member and the at least one peripheral layer to provide a tight adhesive interengagement by effectively adhering the peripheral layer and the core member to the intermediately positioned adhesive layer. However, regardless of the process or bonding step employed, all such alternative embodiments are within the scope of the present disclosure. If more than one peripheral layer is present, such adhesive or tie layers may be similarly employed between corresponding peripheral layers.

The closure precursor may comprise cork. The cork may particularly be in the form of cork granules. The cork particles (or coated cork particles as defined herein) may have a particle size distribution as measured by mechanical sieving according to ISO standard test method ICS19.120 such that D₅₀The value is in the range of 0.25mm to 5 mm. The plurality of granules preferably has a D, measured by mechanical sieving according to ISO standard test method ICS19.120, in the range of 0.3mm to 3mm, or in the range of 0.5mm to 2.0mm, in particular in the range of more than 1.0mm to 2.0mm₅₀The value is obtained.

Alternatively or additionally, the cork particles (or coated particles as defined herein) may be defined by their average or mean particle size as measured by mechanical sieving according to ISO standard test method ICS 19.120. Preferably, the particles have an average or mean particle size in the range of 0.25mm to 5mm, preferably in the range of 0.5mm to 4mm, preferably in the range of 0.5mm to 6mm, preferably in the range of 0.5mm to 5.0mm, preferably in the range of 0.5mm to 4.0mm, preferably in the range of 0.8mm to 3.8mm, preferably in the range of 0.8mm to 3.5mm, preferably in the range of 1.0mm to 3.3mm, most preferably in the range of 1.0mm to 3.0 mm. The plurality of particles may alternatively or alternatively have an average or mean particle size or D in the range of greater than 2.0mm to 10.0mm, in particular in the range of greater than 2.0mm to 8.0mm, preferably in the range of greater than 2.0mm to 5.0mm, or in the range of greater than 2.0mm to 4.0mm, preferably in the range of greater than 2.0mm to 3.5mm, in particular in the range of greater than 2.0mm to 3.0mm₅₀The value is obtained. Average or mean particle size or D₅₀Preferred ranges of (d) are selected from the range from 0.9mm to 1.0mm, from 1.0mm to 2.0mm, from 1.5mm to 2.5mm, from 2.0mm to 3.0mm, from 2.5mm to 3.5mm, and from 3.0mm to 4.0 mm. Average particle size or D₅₀Particularly preferred ranges of (a) are selected from the range from 1.0mm to 2.0mm, and from 2.0mm to 3.0mm, or from greater than 1.0mm to less than 2.0mm, or from greater than 2.0mm to 3.0 mm.

As used herein, the term "particle" may refer to a core comprising a cork material (e.g., a cork particle as defined herein that forms a core of a coated particle) or a coated particle as defined herein, or both. The same applies to the term "plurality of particles".

The cork particles may have a substantially isotropic shape, in particular a substantially spherical shape.

The cork material is preferably suitable for food contact. The cork material is preferably a plurality of "clean" cork particles. This means that the particles are cleaned or washed using a suitable cleaning or washing method prior to incorporation into or use in the closure of the present invention. The plurality of clean particles is preferably free or substantially free of any contaminants, such as contaminants that may be present due to previous use or processing steps, and agents that may affect the taste, odor, and/or other characteristics of the product to be held in the container. The plurality of clean particles is particularly preferably free or substantially free of sensory feel agents, in particular free of all or substantially all halogenated anisoles, in particular TCA, but optionally also TBA, TeCA and/or PCA. If the plurality of particles are cork particles, the particles have preferably been washed to remove all or substantially all of the organoleptic agents, particularly all or substantially all of the halogenated anisoles, particularly TCA, but optionally also TBA, TeCA and/or PCA that may be present in the cork. Such a washing step can be accomplished, for example, by any suitable solvent including, but not limited to, organic solvents such as hydrocarbons, aqueous fluids such as washing solutions or dispersions capable of removing TCA from cork, or supercritical fluids such as supercritical carbon dioxide. Environmentally friendly solvents that are also food safe are preferred, such as aqueous fluids or supercritical fluids. During the washing step, the cork particles may be suspended in a solvent, optionally with stirring, and then the solvent is removed by filtration or the like. The washing step may be repeated as many times as necessary to achieve acceptable levels of halogenated anisoles, particularly chloroanisoles, particularly TCAs, but also optionally TBA, TeCA and/or PCA in these particles, particularly in cork particles. The amount of halogenated anisole released from cork into wine can be measured as so-called "releasable halogenated anisole" by the following method: cork or a sample of cork is soaked in wine, untreated cork is soaked for 24 hours, or treated cork is soaked for 48 hours, and the amount of each of the haloanisole compounds in the wine is measured, for example, by chromatography or spectroscopy such as gas chromatography or nuclear magnetic resonance. Acceptable levels are generally considered to be levels that produce amounts of chloroanisole or chloroanisoles in wine corresponding to an average sensory threshold of less than about 6ng/L for TCA or TBA, whereby TeCA and PCA have been reported to be about one-third and one-thousand times effective in their sensory thresholds, respectively. The releasable trichloroanisole content of the cork granules, measured by the above test method, is preferably less than 6ng/L, preferably less than 5ng/L, more preferably less than 4ng/L, more preferably less than 3ng/L, even more preferably less than 2ng/L, most preferably less than 1 ng/L. The closures and/or closure precursors disclosed herein have a releasable halogenated anisole content of less than 2ng/L, preferably less than 1ng/L, preferably less than 0.5ng/L, preferably less than 0.3 ng/L.

The cork material preferably has a moisture content in the range of about 0% to about 10%, particularly in the range of about 0% to about 8%, particularly in the range of about 0% to about 7%, particularly in the range of about 0% to about 6%, more particularly in the range of about 0% to about 5%, more particularly in the range of about 0% to about 4%, more particularly in the range of about 0% to about 3%, more particularly in the range of about 0% to about 2%, more particularly in the range of about 0% to about 1%. Preferably, the moisture content of the cork particles is in each case less than 8% by weight, in particular less than 7% by weight, less than 6% by weight, less than 5% by weight, less than 4% by weight, less than 3% by weight, in particular less than 2% by weight, less than 1.5% by weight or less than 1% by weight, based on the total weight of the cork particles.

Advantageously, the density of the cork particles is in the range of 50g/L to 200 g/L.

According to one embodiment, cork, in particular cork granules, are bleached. Closure precursors containing bleached cork or bleached cork particles can provide a surface with a uniform light color on which a highly flexible decorative layer can be applied.

In particular, if the closure precursor comprises cork particles, the cork particles (or coated particles as defined herein) are preferably uniformly distributed within the polymer matrix, preferably substantially each individual particle is surrounded by and embedded within the polymer matrix. Thus, in one embodiment, the cork particles are preferably uniformly distributed throughout the closure precursor. This is possible because the formulation is processable to allow the formation of a polymeric matrix by way of extrusion, the polymeric matrix having physical properties, such as pore structure and pore density, that support uniform distribution of the cork particles (or coated particles as defined herein) throughout the polymeric matrix. A uniform distribution of cork particles (or coated particles as defined herein) is advantageous as it allows individual particles to be coated and/or embedded within the polymer matrix, which avoids the formation of local clusters of particles without sufficient polymer, which in turn may lead to weak points and chipping of the closure and/or closure precursor.

According to one aspect of a closure precursor for use in the present disclosure, the closure includes a core member and does not include a peripheral layer. In this aspect, the core member forms the entire closure precursor, and the plurality of particles are contained in the core member. This aspect may be particularly advantageous in reducing the cost of each closure and simplifying production.

If a peripheral layer is included, and if the closure precursor comprises cork particles, the cork particles (or coating particles as defined herein) are contained in at least one of the core member and the peripheral layer, preferably in the core member or the peripheral layer, or in both the core member and the peripheral layer.

In a particular aspect of the present disclosure, if a peripheral layer is present, the cork particles (or coated particles as defined herein) are contained in the core member and in the peripheral layer.

In another aspect of the disclosure, the plurality of particles are contained in the core member, if the peripheral layer is present, and are substantially absent from the peripheral layer.

In a particular aspect of the present disclosure, the closure precursor includes a peripheral layer, and the cork particles (or coated particles as defined herein) are contained in the peripheral layer. According to this aspect, the cork particles (or the coating particles as defined herein) may be substantially absent from the core member.

In another embodiment, the closure precursor does not include a peripheral layer, or does not include a separately extruded peripheral layer.

In each case, the plurality of coated particles may be included in an amount within the following ranges, based on the total weight of the closure precursor: an amount in the range of 51 to 80 wt.%, more specifically an amount in the range of 52 to 75 wt.%, more specifically an amount in the range of 53 to 70 wt.%, more specifically an amount in the range of greater than 55 to 65 wt.%, or an amount in the range of 51 to 60 wt.%, more specifically an amount in the range of 51 to 55 wt.%.

According to one aspect of the invention, a closure precursor including a peripheral layer can include a plurality of coated particles in the peripheral layer. However, the plurality of coated particles is preferably contained in the core member, or in both the core member and the peripheral layer.

The inclusion of a plurality of coating particles can adversely affect the processability of the compositions used to prepare the closure precursors used in the present invention, and potentially negatively affect closure performance and characteristics. In order to reduce or eliminate any reduction in processability or performance, particularly due to the plurality of coated particles, the closure precursors used in the present invention may optionally comprise one or more processing aids.

One or more processing aids may be included at least in the assembly of the closure precursor comprising a plurality of coated particles. The preferred processing aid or aids are preferably selected from processing aids capable of modifying the processability of the formulation during formation of the closure precursor, such as the melt processability of the formulation during formation of the closure precursor by extrusion or moulding, in particular by extrusion. The processing and processability modification can be, for example, a reduction in operating pressure and/or temperature, a reduction in friction between the composition and forming equipment, an improvement in the dispersibility of the cork in the polymer matrix, an improvement in the wettability of the cork in the polymer matrix, an improvement in the torque release for flow improvement during extrusion, a reduction or elimination of melt fracture during extrusion, a reduction in die packing, an increase in speed and output, melt viscosity, melt flow rate, melt index, thermal stability, and/or an increase in surface properties. The one or more processing aids preferably help to improve the mechanical and performance characteristics of the closure precursor and/or closure, such as the pore size and/or pore density of the plastic material, the pore stability, the uniform distribution of the plurality of particles throughout the polymer matrix, the viscosity under conditions of varying shear and/or temperature, in particular increased shear and/or temperature, and the like. A particular advantage observed with the one or more processing aids is that the density of the plastic material in the closure and/or closure precursor can be reduced compared to the density of the plastic material in a closure that does not contain the one or more processing aids according to the present invention. The lower density of the plastic material contributes to the achievement of the objects of the invention, such as, for example, a reduced content of plastic material of the closure and/or closure precursor, elasticity, compressibility, and even distribution of the plurality of particles throughout the plastic material. Because the one or more processing aids remain in the closure precursor after closure production, they are preferably suitable for use in food applications. Preferably, one or more of the one or more processing aids is one or more of biodegradable, compostable and thermoplastically processable. While it is possible that a single processing aid achieves all or most of the desired advantages, it is also possible that a processing aid comprises two or more processing aids. Suitable processing aids that may be used alone or in combination with one or more other processing aids may be, for example, lubricants, slip agents, release agents, antiblock agents, or any agent or combination of agents that achieves one or more of the desired advantages. The closure precursor may comprise from 0 wt% to 15 wt% of one or more lubricants, based on the total weight of the closure precursor. The closure precursor may comprise from 0 wt% to 10 wt% of one or more additives and/or fillers, based on the total weight of the closure precursor.

Suitable optional processing aids that may be included in the closure precursors used in the present invention are preferably selected from the group consisting of: a fatty acid; a fatty acid ester; a fatty acid amide; a wax; a wax ester; an ester wax; a plasticizer; alcohols; a glyceride; a polyol ester; partial esters of polyhydric alcohols; polyethylene glycol esters; fatty acid polyglycol esters; fatty acid polyglycol ethers; fatty alcohol polyglycol ether; a metal soap; a fluoropolymer; a polyol; a silicone; glycerol monostearate; fatty acid esters of polyhydric alcohols; a high molecular weight polyester; and combinations of any two or more thereof. Suitable processing aids may also be polymer blends that produce a large molecular weight dispersion. For example, the processing aid can comprise a combination of a higher molecular weight polymer and a lower molecular weight polymer to achieve a broad molecular weight distribution that provides a lower melt viscosity. The one or more polymers in the form of such a polymer blend may be the same as one or more of the one or more thermoplastic polymers contained in the plastics material forming the body of the closure precursor, in particular the core member of the closure precursor, or the entire closure precursor (if the peripheral layer is not included). In this case, the amount of plastic material increases with the amount of processing aid as disclosed herein. The one or more polymers in the form of such polymer blends may also be different from at least one or more of the one or more thermoplastic polymers comprised in the plastic material, such that different amounts of one or more processing aids are comprised for the one or more processing aids as disclosed herein. Such polymer blends may be used as one or more processing aids, or may be used in combination with one or more of the other processing aids disclosed herein.

If two or more processing aids are employed, these processing aids preferably complement or complement each other in achieving the properties and advantages mentioned herein. For example, the processing aid may comprise at least one processing aid that reduces the melt viscosity of the plastic material, and at least one processing aid that assists in the release of the plastic material from the forming apparatus, such as at least one processing aid that reduces friction of the plastic material against at least one extruder surface during extrusion, and/or at least one processing aid that assists in the release of the plastic material from the die. The processing aid that reduces friction of the plastic material against at least one extruder surface during extrusion may be the same processing aid that assists in stripping the plastic material from the die, or the processing aids may be different processing aids.

The one or more optional processing aids may be selected from the processing aids as described herein. Any processing aid may be combined with any other processing aid in order to achieve the objects and advantages of the present invention. According to a preferred aspect of the invention, the at least one processing aid that reduces the melt viscosity of the plastic material is selected from the group consisting of: a fatty acid; a fatty acid ester; a fatty acid amide; a wax; a wax ester; an ester wax; a plasticizer; alcohols; a glyceride; a polyol ester; partial esters of polyhydric alcohols; polyethylene glycol esters; fatty acid polyglycol esters; fatty acid polyglycol ethers; fatty alcohol polyglycol ether; glycerol monostearate; a metal soap; and combinations of any two or more thereof; and at least one processing aid that reduces friction of the plastic material against at least one extruder surface during extrusion is selected from the group consisting of: a fatty acid; a fatty acid ester; a fatty acid amide; a fluoropolymer; a polyol; a silicone; a glyceride; glycerol monostearate; a polyol ester; partial esters of polyhydric alcohols; polyethylene glycol esters; fatty acid polyglycol esters; fatty acid polyglycol ethers; fatty alcohol polyglycol ether; fatty acid esters of polyhydric alcohols; a wax ester; an ester wax; a metal soap; a high molecular weight polyester; and combinations of any two or more thereof.

In the closures and/or closure precursors according to the present invention it may be advantageous that at least one processing aid is solid or at least partially solid at atmospheric pressure at a temperature of up to 160 ℃, or at a temperature of up to 150 ℃, or at a temperature of up to 140 ℃, or at a temperature of up to 130 ℃, or at a temperature of up to 120 ℃. Optionally, at least one processing aid comprises one or more fatty acid derivatives which are solid or at least partially solid at atmospheric pressure at a temperature of up to 160 ℃, or at a temperature of up to 150 ℃, or at a temperature of up to 140 ℃, or at a temperature of up to 130 ℃, or at a temperature of up to 120 ℃. This may be advantageous in terms of transportation and storage of the processing aid, and blending of the processing aid with the plastic material and the plurality of particles, which may occur in a dry blending step, so as to form a uniform blend of the processing aid with the plastic material and the plurality of particles. It is also preferred that the processing aid which remains at least substantially in the closure precursor after formation of the closure may be solid at the use temperature of the closure, for example to avoid exudation of the processing aid or a greasy feel of the closure. It may be advantageous for processing and/or blending if the processing aid softens, melts, or partially melts at the processing temperature. Typical processing temperatures are indicated herein along with the method of forming the closure precursor.

In the closure precursor used in the present invention, it may be advantageous that at least one processing aid is at least partially in liquid form, for example at least partially in the form of a melt, at a temperature above 50 ℃ at atmospheric pressure. Optionally, at least one processing aid comprises one or more fatty acid derivatives, which are at least partially in liquid form at atmospheric pressure at a temperature above 50 ℃. This may allow for lower processing temperatures while not substantially causing the processing aid to bleed out of the finished closure or the closure to feel greasy.

Processing aids suitable for use in the closure precursors used in the present invention may, for example, comprise one or more processing aids selected from the group consisting of: fatty acid derivatives derived from saturated or unsaturated fatty acids having from 12 to 45 carbon atoms, preferably from 25 to 38 carbon atoms; modified fatty acid derivatives derived from modified saturated or unsaturated fatty acids having from 12 to 45 carbon atoms, preferably from 25 to 38 carbon atoms; a natural wax; synthesizing wax; a plasticizer; and combinations of two or more thereof. By way of example, the processing aid may comprise one or more fatty acid derivatives and/or modified fatty acid derivatives derived from a fatty acid selected from the group consisting of: lauric acid, palmitic acid (palmitic acid), arachidic acid, behenic acid, stearic acid, 12-hydroxystearic acid, oleic acid, erucic acid, ricinoleic acid (recinolic acid), adipic acid, sebacic acid, myristic acid, palmitoleic acid, palmitic acid (sapienic acid), elaidic acid, vaccenic acid, linoleic acid, elaidic acid, alpha-linoleic acid, gamma-linoleic acid, dihomo-gamma-linolenic acid, arachidonic acid, eicosapentaenoic acid, docosahexaenoic acid, caprylic acid, capric acid, myristic acid, lignoceric acid, cerotic acid, tridecanoic acid, pentadecanoic acid, heptadecanoic acid, nonadecanoic acid, heneicosanoic acid, tricosanoic acid, pentacosanoic acid, heptacosanoic acid, montanic acid, nonacosanoic acid, melissic acid, hendecanoic acid, tridecanoic acid, cerotic acid, heptacosanoic acid, and palmitic acid, Triacontanoic acid, stearidonic acid, docosatetraenoic acid, palmitoleic acid, vaccenic acid, eicosenoic acid, elaidic acid, macrocephalic cetaceanic acid, nervonic acid, eicosatrienoic acid, modified fatty acids derived from one or more of the fatty acids included in the group, and mixtures of any two or more of the fatty acids included in the group and the modified fatty acids.

It may be advantageous for the closure precursor used in the present invention if the processing aid comprises one or more processing aids selected from the group consisting of: erucamide; a fatty acid; a wax; stearamide; glycerol monostearate; high-monoglyceryl monostearate; a glyceride; ethylene-bis-stearamide; calcium stearate; erucamide; oleic acid amide; stearic acid amide; trimellitic acid ester; an adipate ester; sebacate esters; azelaic acid ester; a diester; a polymeric plasticizer; and any combination of two or more thereof.

The processing aid may, for example, have one or more of the following characteristics:

-a drop point in the range of 50 ℃ to 160 ℃, or in the range of 50 ℃ to 150 ℃, or in the range of 50 ℃ to 140 ℃, or in the range of 50 ℃ to 130 ℃, in the range of 50 ℃ to 120 ℃ measured according to ASTM D2265;

-a specific gravity at 4 ℃ relative to water in the range of 0.900 to 1.300 measured according to ASTM D1298-12 b.

The closure precursor used in the present invention preferably does not contain an adhesive; and/or the closure preferably does not contain a cross-linking agent; and/or the plastic material is preferably not cross-linked by means of a cross-linking agent. The closure preferably contains no adhesive and no crosslinking agent. Known closures containing relatively large amounts (e.g., greater than about 50 wt.%, based on the total weight of the closure) of cork powder or cork particles are generally composite closures, wherein the adhesive is typically a polyurethane or polyacrylate glue formed by in situ reactive polymerization of a corresponding monomer and/or prepolymer (such as an oligomer). These adhesives or glues are not thermoplastically processable nor are they thermoplastic polymers or plastic materials according to the definition of the invention. Known closures often contain one or more cross-linking agents (also known as cross-linkers) in order to improve certain properties. Crosslinking agents, not only adhesives or their monomers, may also raise concerns in food safety. In addition, adhesives or crosslinked polymers are typically neither biodegradable nor thermoplastically processable. Thus, it is generally not possible to recycle, biodegrade or compost closures containing adhesives or cross-linking agents or cross-linked polymers. However, although it is preferred that the closure precursor and/or closure according to the present invention does not comprise a cross-linking agent, it is possible that the closure precursor and/or closure according to the present invention comprises a small amount of a cross-linking agent, for example a cross-linking agent in an amount sufficient to: changing the rheology of the composition used to prepare the closure, in particular the rheology of the thermoplastic component of the composition, in a desired manner; and/or to alter one or more other characteristics of the closure precursors and/or the compositions used to prepare the closure precursors, in particular one or more other characteristics of their thermoplastic components, such as viscosity, elasticity, and/or hardness. The amount of cross-linking agent (if present) should be sufficiently small that the thermoplasticity processability of the closure precursor is not affected, or at least not substantially affected, in particular the recyclability of the closure and/or closure precursor is not affected, or at least not substantially affected.

In one embodiment of the present disclosure, the closure precursor is produced by a method comprising at least one extrusion process step. For closure precursors that include a core member and at least one peripheral ply, this allows for integral adhesive interconnection between the at least one peripheral ply and the core member, since the at least one peripheral ply is formed around the core member in a manner that ensures a tight adhesive bond.

According to a particular aspect of the closures and/or closure precursors, compositions and methods according to the present disclosure, the temperature of the composition, closure precursor, and/or any method step, particularly during formation of the closure precursor or composition, preferably does not exceed 200 ℃, preferably is maintained in the range of about 120 ℃ to about 170 ℃, or in the range of about 125 ℃ to about 170 ℃, or in the range of about 130 ℃ to about 165 ℃, or in the range of about 135 ℃ to about 165 ℃, or in the range of about 140 ℃ to about 160 ℃. During extrusion of the material comprising cork particles, an extrusion temperature within the disclosed ranges is maintained in particular. If the temperature exceeds this range, there is a risk of degradation of the cork particles and possibly of affecting the scorched taste of the food product in contact with the closure.

It has also been found that additional additives can be incorporated into the closures and/or closure precursors of the present disclosure. For closure precursors used in the present disclosure that include a core member and at least one peripheral layer, additives can be incorporated into the core member and/or at least one peripheral layer of the closure precursor in order to provide further enhancements and desired performance characteristics. These additional additives may include, for example, colorants such as pigments, antimicrobial agents, antimicrobial compounds, and/or oxygen scavenging materials. Suitable additives are known to those skilled in the art. Antimicrobial and antibacterial additives may be incorporated into the closure, giving additional confidence that there is little likelihood of microbial or bacterial growth in the presence of the liquid. These additives preferably have a long-term release capacity and further extend the shelf life without further treatment by those involved in the wine bottling process. Furthermore, it is possible for the closure precursor and/or the aperture of the closure to be substantially filled with a non-oxidising gas in order to further reduce the ingress of oxygen into the container. The manner in which this is achieved is known in the art. It is possible that for the filler or fillers, in particular the particulate filler, preferably the particulate filler having a particle size of less than 0.2mm, is incorporated into the closure precursor according to the invention, preferably by incorporation into the composition used for preparing the closure precursor used in the invention. Preferred fillers are inorganic fillers such as mineral fillers which may be selected from talc, chalk, silica, mica, alumina, clay, calcium carbonate, magnesium carbonate, calcium aluminate, titanium dioxide, vermiculite, perlite, and combinations of one or more thereof. It may be advantageous to include one or more fillers for example to modify the rheological or other properties of the closure precursor and/or the composition,

depending on the sealing method employed to insert the closure of the present disclosure in the desired bottle, if the closure precursor used in the present disclosure includes a core member and at least one peripheral layer, additives such as slip additives, softeners, and sealing compounds may be incorporated into the peripheral layer, for example, to provide lubrication of the closure during the insertion method. In addition, other additives typically employed in the bottling industry may be incorporated into the closure precursors used in the present disclosure for improving the sealing engagement of the closure with the bottle and reducing the extraction force required to remove the closure from the bottle to open the bottle.

Additionally, indicia containing ink visible under normal lighting and/or temperature conditions may be included in the closure. Normal lighting conditions in the context of the present disclosure mean light from a light source having a spectrum substantially comprising the visible spectral range. Normal temperature conditions in the context of the present disclosure mean temperatures from 10 ℃ to 35 ℃. These markers may be used, for example, as localization markers. These indicia may, for example, be part of the decorative layer described herein.

The closure according to the present disclosure may further comprise a lubricant layer on at least one of its surfaces, in particular on its peripheral surface. The lubricant layer may include, for example, silicone, wax, paraffin, andone or more of a layer, or any type of layer known for natural cork or synthetic closures. Such a layer may assist, for example, the insertion of the closure into the container and be formed by any means known and seemingly suitable. If a silicone, wax and/or paraffin layer is present, this layer may be formed, for example, by extrusion and/or by tumbling.

By employing the materials and methods disclosed herein, a highly effective closure can be obtained that is capable of providing at least one, particularly more than one, particularly almost all or even all, of the characteristics suitable for use with wine bottle closures.

The closure precursor and/or closure according to the present disclosure has advantageous properties that make it particularly suitable for packaging and in particular for use as a closure for wine bottles. If the product is packaged under inert conditions, the closure advantageously has an oxygen ingress per container of less than about 5mg of oxygen, as determined according to ASTM F1307, within the first 100 days after closure of the container. During the first 100 days after closing the container, the oxygen ingress is advantageously selected from the group consisting of: less than about 3mg oxygen, less than about 1mg oxygen, less than about 0.5mg oxygen, less than about 0.25mg oxygen, less than about 0.2mg oxygen, and less than about 0.1mg oxygen per container. With respect to closures for wine bottles, the closure precursors and/or closures according to the present disclosure or closures produced according to the methods of the present disclosure achieve at least one comparable performance to known closures made of alternative materials, such as polymers, as demonstrated by results determined, for example, by at least one, particularly more than one, particularly all, of the properties of oxygen transmission, extraction force and leakage. In addition, the closure precursor and/or closure according to the present disclosure or the closure produced according to the method of the present disclosure has an appearance similar to that of natural cork and may be marked, in some aspects, preferably in the same manner as a natural cork closure. Furthermore, the tactile properties of the closure according to the present disclosure are very similar to closures made of natural cork.

Closures according to the present invention preferably have less than 0.05 cc/day, preferably in the range of 0.0001 cc/day to 0.05 cc/day, preferably in the range of 0.0002 cc/day to 0.02 cc/day, or about 0.0001 cc/day/closure to about 0.1000 cc/day/closure, or about 0.0005 cc/day/closure to about 0.050 cc/day/closure, measured in 100% oxygen according to ASTM F1307.

The details and characteristics of all components of the closure and/or closure precursor are also applicable to the compositions and methods according to the present disclosure as described below.

Advantageously, closures according to the present disclosure have an extraction force of not more than about 445N (100lb), in particular not more than about 440N, in particular not more than about 430N, in particular not more than about 420N, in particular not more than about 410N, preferably not more than about 400N, in particular not more than about 390N, in particular not more than about 380N, in particular not more than about 370N, in particular not more than about 360N, in particular not more than about 350N, in particular not more than about 340N, in particular not more than about 330N, more in particular not more than about 320N, more in particular not more than about 310N, more in particular not more than about 300N, determined according to the test method described herein, thereby, an extraction force in the range of about 200N to about 400N, in particular in the range of about 210N to about 380N, in particular in the range of about 220N to about 350N, in particular in the range of about 230N to about 300N, is advantageously achieved. The extraction force describes the force required to remove the closure from the container, in particular from the bottle, under standardized conditions. A lower extraction force relates to easier extraction of the closure. An extraction force in the range of about 150N to about 445N is generally considered acceptable for wine bottle closures. The closure of the present disclosure achieves an extraction force within a range considered acceptable for wine bottle closures.

The plastic material, thermoplastic polymer, plurality of particles, processing aids, additives and blowing agents, and all details related thereto (including preferred embodiments and aspects) are as defined herein with respect to the closure and/or closure precursor, the composition for forming the closure precursor, the method for forming the composition, and the method for forming the closure precursor.

Closure precursors containing cork granules can be made by the exemplary method described below, which is not intended to be limiting. According to one embodiment, a closure precursor can be manufactured by a method of manufacturing a closure precursor for a closure for a product retaining container configured to be inserted and securely retained in a neck of the container forming an inlet, the method comprising at least the following method steps:

i. homogeneously blending the following components to form a composition:

(a)51 to 80 weight% (dry weight) of a plurality of particles comprising softwood and having a particle size distribution D in the range of 0.25 to 5 millimeters as determined by mechanical sieving according to ISO ICS19.120₅₀；

(b)12 to 49 wt% of a plastic material comprising one or more thermoplastic polymers;

(c) optionally, 0 to 10 wt% of one or more blowing agents;

(d) optionally, 0 to 15 wt% of one or more lubricants;

(e) optionally, 0 to 2 weight% of one or more pigments; and

(f) optionally, 0 to 10 wt% of one or more additives and/or fillers;

heating the composition obtained in step i to form a melt;

forming a raw closure precursor from the melt obtained in step ii by extrusion or molding, wherein a plurality of the cork-containing pellets in the raw closure precursor have a moisture content of less than 3 wt.%;

optionally cutting and/or finishing the raw closure precursor to form a closure precursor.

All of the features that have been described so far in relation to the closures and/or closure precursors used in the present disclosure are also optionally applicable to the closure and/or closure precursor forming method as well.

The plastic material, thermoplastic polymer, plurality of particles, processing aid, and optional blowing agent, and all details related thereto (including contents, preferred embodiments and aspects) and relating to the method steps are as defined herein with respect to the closure and/or closure precursor, the composition for forming the closure precursor, the method for forming the composition, and the method for forming the closure precursor. The closure and/or closure precursor may be a cylindrical closure comprising an outer peripheral surface and two substantially flat terminal surfaces, such as a closure for a static wine bottle. Alternatively, the closure and/or closure precursor may be in the form of a closure for a sparkling wine bottle.

The plurality of particles is preferably a plurality of clean particles, as defined herein. It is contemplated that at least one step of washing the plurality of particles may be performed in order to remove, inter alia, all or substantially all of the halogenated anisole, particularly TCA, but also optionally TBA, TeCA and/or PCA, as disclosed herein. The closure precursors produced by the process disclosed herein preferably have a releasable trichloroanisole content of less than 2ng/L, preferably less than 0.5ng/L, preferably less than 0.3 ng/L.

The process may be continuous or discontinuous. In a continuous process, the blending in process step i. may occur by way of any one or more of the following: blending, dry blending, mixing, melting, pultrusion, extrusion, compounding, or any other method known to the skilled person and which appears to be suitable. Preferably, method step i. of any of the methods defined herein involves applying shear to the components, preferably while heating. The composition, which may be obtained, for example, in the form of a dry blend or melt, from process step i. The heating in method step ii. During method step i; after method step i. and before method step iii; during method step iii; or any combination of two or more thereof. In a preferred aspect of process steps i.and ii. (which may be combined with any other aspect of the process or any process step), process step i.is carried out at atmospheric pressure or at a pressure below atmospheric pressure and process step ii. is carried out at a pressure above atmospheric pressure. Preferably, at least in method step iii. In a discontinuous process, any or all of the process steps may be discontinuous, or one or more of the process steps may be continuous or discontinuous. For example, a masterbatch of the composition may be prepared beforehand in process step i, or a masterbatch of the plastic material and the plurality of particles may be prepared beforehand and optionally stored before further process steps, as defined herein with respect to the composition. If a masterbatch of plastics material and a plurality of particles is prepared beforehand, it is admixed with all the other components in process step i. In a discontinuous process, if one or more blowing agents are incorporated in a discontinuous process step, care must be taken that the temperature to which the one or more blowing agents are exposed should be below the initiation temperature of the one or more blowing agents, unless the one or more blowing agents are incorporated in a process step intended to cause foaming. The respective initiation temperature depends on the blowing agent and is known or obtainable by the skilled person.

The heating in process step ii. is preferably carried out to a temperature at which the composition provided in process step i. can be foamed to a desired density and/or the composition can be extruded or shaped to form a closure precursor. If a foaming agent is used which requires heat to provide or initiate the foaming effect, the heating in step ii of the process preferably takes place to a temperature at which this foaming effect can take place. The foaming agent is preferably selected from the group consisting of: expandable microspheres, chemical blowing agents, physical blowing agents, and combinations of two or more thereof. If the blowing agent comprises or consists of expandable microspheres, a temperature is selected at which the expandable microspheres expand to form expanded microspheres. The expanded microspheres form individual pores of a plurality of pores. Preferably a temperature is selected at which the expanded microspheres have the desired pore size. Suitable temperatures depend primarily on the thermoplastic polymer and blowing agent selected and can be readily determined by the skilled person based on known characteristics of the thermoplastic polymer and blowing agent and/or based on simple experimentation. The heating temperature is preferably maintained in the range of about 120 ℃ to about 170 ℃. This temperature range is preferred for all process steps involving heating, particularly process steps involving heating a composition comprising cork particles (or coated particles as defined herein), including mixing, combining, extruding and molding. It is envisaged to maintain the extrusion or moulding temperature within this range, particularly during extrusion or moulding of any composition comprising cork powder. During the heating step ii, the plastic material is preferably foamed. Particularly preferably, the plastic material is foamed to a foam density of about 25kg/m³To 800kg/m³In the range of about 50kg/m, preferably³To 800kg/m³In the range of about 75kg/m, preferably in the range of about 75kg/m³To 800kg/m³In the range of about 100kg/m, preferably³To 800kg/m³In the range of about 150kg/m, preferably³To 700kg/m³In the range of about 150kg/m, preferably³To 600kg/m³In the range of about 150kg/m, preferably³To 500kg/m³In the range of about 180kg/m, preferably³To 500kg/m³In the range of about 200kg/m, or³To 450kg/m³In the range of about 200kg/m, preferably³To 420kg/m³Within the range of (1).

According to a preferred aspect of the exemplary method for forming the closure precursor described herein, the second plastic material used in the method according to the present invention has a particle size distribution D measured by mechanical sieving according to ISO ICS19.120₅₀The particle size distribution D₅₀Less than 1000 microns, in particular less than 800 microns, 600 microns, 500 microns, 400 microns, 300 microns, 200 or 50 microns. It has been found that by using such a small particle size for the second plastic material, the processing difficulties caused by the inclusion of a plurality of coated particles, as well as the potential negative impact on closure performance and characteristics, can be eliminated or reduced. Particles of plastics material of this size may be obtained, for example, by suitable milling techniques, such as cryogenic milling.

The process step iii can be carried out in any manner known to the skilled worker and which appears suitable, in particular using known extrusion equipment or known shaping equipment. The use of the composition according to the invention means that there is no need to change the extrusion equipment or the shaping equipment, or any of their surfaces, nor to significantly change the process parameters or equipment parameters, for example to provide additional heating, in order to prevent undesirable phenomena such as surface melt fracture or surface roughness. This is particularly advantageous in large scale production facilities, particularly in continuous production processes, where it may be impractical, time consuming and expensive to significantly change equipment parameters and/or process parameters when switching production from one type of closure to a different type of closure. This applies to all process steps, but in particular to heating step ii and to forming step iii.

If a peripheral layer is formed in the method of manufacturing the closure precursor, the details regarding the composition of the peripheral layer are the same as those described herein regarding suitable materials, compounds and compositions for the peripheral layer of the closure precursor of the present disclosure. Any peripheral layers, if present, are preferably formed by means of co-extrusion as described herein and known to the skilled person, which is preferably carried out substantially simultaneously with process step iii. According to another aspect of the method, the method steps of forming the peripheral layer may be repeated one or more times so as to obtain one or more further peripheral layers, whereby the one or more further peripheral layers are separately extruded in tight adhesive engagement with the cylindrical outer surface of the preceding peripheral layer so as to form a multi-layer elongated cylindrical structure.

After extrusion in method step iii, the raw closure precursor in the form of a continuous elongated cylindrical length of plastic material or a multi-layer elongated structure may be cooled by methods known to the skilled person, optionally with co-extrusion of one or more peripheral layers. These methods include, for example, passing through a cooling bath, spraying, blowing, and the like.

If a raw closure precursor is formed by means of extrusion in method step iii, it is cut to a length suitable for the closure precursor in step iv. If the raw closure precursor is formed by forming in method step iii, no cutting is required in method step iv. The closure precursor is preferably adjusted in method step iv. In particular, the peripheral surface and optionally the end surface of the closure are smoothed, for example by sanding, grinding or polishing, preferably polishing, as is known for natural cork closures. The optional finishing in method step iv, which may be applied to the cut length or the formed raw closure precursor, may be, for example, a coating or post-treatment, any or all of which may be carried out in any manner known to those skilled in the art and which appears suitable. Post-treatment may include, for example, surface treatment such as plasma treatment, corona treatment, or providing lubricant to the surface of the closure. If the outermost peripheral surface comprises cork particles, it may be desirable and/or possible to use branding to impart an image or to write on the peripheral surface or one or both terminal surfaces of the closure, for example using branding methods known for natural cork closures.

All of the details disclosed herein for closures and/or closure precursors in accordance with the present disclosure also relate to the methods as described in clauses 1 to 42 above and thus also form part of the disclosure of the methods disclosed herein.

In a preferred embodiment of the use, the closure has an oxygen ingress per container of less than about 1mg of oxygen, as determined according to ASTM F1307, within the first 100 days after closure of the container. In another preferred embodiment of the use, the oxygen ingress is selected from the group consisting of: less than about 0.5mg oxygen, less than about 0.25mg oxygen, less than about 0.2mg oxygen, and less than about 0.1mg oxygen per container.

The present disclosure also relates to a closure system comprising a product holding container and a closure according to the present invention.

According to the present disclosure, a closure is obtained which is capable of providing at least one, in particular more than one, in particular almost all or even all, of the requirements imposed thereon by the wine industry, as well as any other bottle closure/packaging industry. Thus, a bottle closure can be obtained which can be used to completely seal and close a desired bottle and reliably and safely store a product held therein, wherein the closure has an appearance similar to a closure made of a single piece of cork. The disclosure herein relating to closure precursors for use in the present disclosure is also applicable to closure precursors made by the manufacturing methods of the present disclosure. The disclosure herein relating to closure precursors prepared by the methods of the present disclosure also applies to closure precursors of the present disclosure.

According to one embodiment, the closure precursor comprises a pigment or dye, in particular 0 to 2 wt% of at least one pigment or dye. In this way, a surface having a flat side surface can be obtainedThe closure precursor, the side surfaces and the planar terminal surface of the planar terminal surface have a substantially uniform color, in particular a uniform light color. The decorative layer can be applied to such a closure with great flexibility. Many different pigments may be used in this embodiment. Advantageously, the pigments have a light color, in particular white. Preferably, the pigment comprises antimony (III) oxide (Sb)₂O₃) Barium sulfate (BaSO)₄) Lithopone (BaSO)₄ZnS), calcium carbonate, titanium oxide (TiO)₂) And zinc oxide (ZnO).

According to another embodiment, the closure precursor comprises an inner coating comprising an inner coating surface forming a side surface and/or a substantially flat terminal surface of the closure precursor. The inner coating preferably has a uniform color. Advantageously, the inner coating comprises a pigment or a dye. Pigments or dyes are preferably added to the formulation of the undercoating. Preferably, the inner coating is opaque. The inner coating can be applied in different ways to obtain a closure precursor. Preferably, the inner coating is applied by molding, extrusion, coating, wrapping or printing. For example, the inner coating may be applied as a peripheral layer to the core member. Preferably, the inner coating is applied by printing. The inner coating may be included in different types of closure precursors, such as synthetic closures, composite closures, cork particle agglomerate closures, closure precursors comprising thermosetting polymers including polyurethane and/or adhesives including reactive and non-reactive adhesives, or closures made from a single piece of cork. For example, if a closure made from a single piece of cork is aesthetically unpleasing, an internal coating may be applied to the closure.

The inner coating is preferably opaque and of uniform color. The homogeneous color of the inner coating is preferably selected from the group consisting of white, yellow, orange, ochre and mixtures thereof, in particular from the group consisting of RAL 9001, RAL 9010, RAL 1000, RAL 1001, RAL 1002, RAL 1014, RAL 1015, RAL 8001 and mixtures thereof. Advantageously, the inner coating is white, for example RAL 9001 or RAL 9010 or a mixture thereof. The inner coating preferably does not resemble natural cork. Instead, it is preferred that the inner coating be used as an empty canvas for applying the decorative layer.

The inner coating is particularly advantageous because it provides flexibility with respect to the closure precursor. As noted above, the inner coating can be included in a variety of closure precursors. In the case of an inner coating, an empty canvas is provided for applying the decor layer.

The present invention also provides a method for applying a decorative layer on a closure precursor for producing a closure for a product retaining container, the closure precursor being configured for insertion and secure retention in a neck of the container forming an inlet and having a substantially cylindrical shape and a longitudinal axis and comprising a substantially flat terminal surface and side surfaces forming opposite ends of the closure precursor, wherein the method comprises the step of passing the closure precursor through a decorative layer application system, thereby applying the decorative layer onto at least the side surfaces of the closure precursor, wherein the decorative layer at least partially covers the side surfaces of the closure precursor, wherein at least the side surfaces and the substantially flat terminal surface of the closure precursor have a uniform color immediately before the decorative layer is applied onto the side surfaces and the substantially flat terminal surface of the closure precursor. Advantageously, the decorative layer is also applied to the substantially flat terminal surface of the closure precursor. The decorative layer preferably completely covers the side surfaces. The decorative layer preferably completely covers the substantially flat terminal surface of the closure precursor. Most preferably, the decorative layer completely covers the side surfaces and the substantially flat terminal surface of the closure precursor. In this way, a closure can be obtained which has the appearance of a closure made of a single piece of cork all around.

The uniform colour of the side surfaces and optionally the substantially flat terminal surface of the closure precursor is preferably a colour, in particular a light colour, on which printing can be applied with great flexibility. In this way, the closure precursor is a transparent canvas on which the decorative layer can be applied with great flexibility. Preferably, the uniform colour of the surface of the closure precursor is selected from the group consisting of white, yellow, orange, ochre and mixtures thereof, in particular from the group consisting of RAL 9001, RAL 9010, RAL 1000, RAL 1001, RAL 1002, RAL 1014, RAL 1015, RAL 8001 and mixtures thereof. More preferably, the uniform colour of the surface of the closure precursor is selected from the group consisting of RAL 9001, RAL 9010, RAL 1000, RAL 1015 and mixtures thereof. The surface with the uniform color described above provides a transparent canvas on which the decorative layer can be applied, in particular printed, with great flexibility.

The details mentioned herein in relation to the decorative layer of the closure of the invention also apply to the decorative layer of the method of the invention and vice versa.

The method may comprise further steps. According to one embodiment, the method comprises the step of passing the closure precursor through an inner coating application system prior to the step of passing the closure precursor through the decorative layer application system, thereby applying an inner coating having a substantially uniform color to obtain a closure precursor having a substantially uniform color on at least a side surface of the closure precursor.

The details mentioned herein in relation to the inner coating of the closure of the invention are equally applicable to the inner coating of the method of the invention and vice versa.

Different application systems can be used for the decorative layer application system and/or the inner coating application system. The same type of system can be used for both the decor layer application system and the inner coating application system. However, different application systems may be employed for the decorative layer system and the undercoating application system. The two systems can be selected independently. Preferably, the decor layer application system and/or the inner coating application system are independently selected from the group consisting of an inkjet printing system, a pad printing system and a water transfer printing system, in particular a pad printing system.

According to one embodiment, the method for applying a decorative layer on a closure precursor further comprises the step of passing the closure precursor through a decorative layer application system, thereby applying a decorative layer on the decorative layer. The details mentioned herein in relation to the decor layer of the closure of the invention apply equally to the decor layer of the method of the invention and vice versa.

During the application of the decorative layer, it is advantageous if the closure precursor is rotated about the longitudinal axis.

Also during application of the inner coating layer, it is advantageous if the closure precursor is rotated about the longitudinal axis.

Furthermore, it is advantageous if the closure precursor is rotated about the longitudinal axis during the application of the decor layer.

For the method of applying the decorative layer on the closure precursor, different closure precursors as described herein may be employed.

The invention also relates to the use of a closure according to the invention for sealing a container.

Accordingly, the present disclosure includes articles of manufacture having the features, characteristics, and element relationships illustrated in the articles of manufacture described herein, and the scope of the present disclosure is set forth in the claims.

Drawings

For a fuller understanding of the nature and objects of the present disclosure described herein, reference should be made to the following detailed description taken in conjunction with the accompanying drawings in which:

FIG. 1 is a perspective view of a closure according to one aspect of the present disclosure, the closure including an inner coating (not shown in FIG. 1);

FIG. 2 is a cross-section of a closure including an inner coating according to one aspect of the present disclosure;

Detailed Description

The construction of the closure and method of production for use in the present disclosure can be best understood by reference to the drawings and the following detailed disclosure. In these figures, and in the detailed disclosure herein, the closure of the present disclosure is depicted and discussed as a bottle closure for a wine product. However, as detailed herein, the present disclosure is applicable as a closure for sealing and retaining any desired product in any desired closure system. However, due to the stringent and difficult requirements imposed on closures for wine products, the detailed disclosure herein focuses on the applicability of the bottle closure of the present disclosure as a closure for wine bottles. However, it should be understood that this detailed discussion is provided for exemplary purposes only, and is not intended to limit the disclosure to this particular application and embodiment.

In fig. 1 and 2, an exemplary configuration of the closure 1 is depicted, comprising a generally cylindrical shape formed by the closure precursor 2, and preferably an inner coating 3, the inner coating 3 comprising an inner coating surface forming a surface of the closure precursor 2. In this aspect, the closure precursor 2 comprises a substantially cylindrical shaped surface, terminating in a substantially flat end surface. On top of the inner coating 3, the closure 1 comprises a decorative layer 4. The following detailed description of the closure with an internal coating should also apply to a closure without an internal coating whenever applicable.

In one exemplary aspect, the inner coating 3 comprises a pigment, particularly in the range of 0 to 2 wt%. In this way, the inner coating 3 has a uniform color. The color of the inner coating 3 is preferably white, in particular RAL 9001. The inner coating 3 forms in particular the side surfaces and the flat terminal surfaces of the closure precursor 2. The inner coating 4 is preferably applied by printing.

In this exemplary aspect, the closure 1 further comprises a decorative layer 4 covering both the side surfaces and the planar terminal surface of the closure precursor 2. The decorative layer 4 thus completely covers the inner coating 3. The decorative layer 4 is preferably applied by pad printing. The decorative layer 4 preferably depicts a first indicia, particularly a photograph of the appearance of natural cork. Decorative layer 4 thus has, in particular, a printing resolution of 300dpi or more and is multicoloured, comprising one or more shades of two or more colours. Preferably, the decorative layer 4 is composed of one or more materials that meet FDA and EU standards or are approved by FDA and EU as food contact substances.

To help ensure that the bottle closure 1 enters the bottle inlet into which the closure 1 is inserted, the terminal edge may be beveled or chamfered. Similarly, the terminal edge may include a similar bevel or chamfer. Although any desired bevel or chamfer configuration may be employed, such as rounded, curved or flat, it has been found that by cutting the terminal edge at only about a 45 ° or about a 60 ° angle, the desired reduced diameter area may be provided to achieve the desired effect. The chamfer angle and chamfer length, i.e. the length of the chamfer surface, are exemplary within the ranges described herein for a static wine closure or champagne closure.

By introducing a chamfered or beveled end on the bottle closure 1, automatic self-centering is achieved. Thus, when the bottle closure 1 is compressed and ejected from the compression jaws into an open bottle for forming its closure, the bottle closure 1 is automatically guided into the bottle opening even if the clamping jaws are slightly misaligned with the mouth of the bottle. By adopting this configuration, the unwanted difficulty of inserting the bottle closure 1 into any desired bottle is avoided. However, in applications where alternative plug insertion techniques are employed, chamfering of the terminal ends may not be required. Furthermore, to facilitate insertion of the closure into the bottle neck, the outer surface may be fully or partially coated with a suitable lubricant, such as silicone. Coating with the lubricant may be performed by various techniques known in the art, including tumbling and/or extrusion coating. For closures for champagne or sparkling wine, cross-linkable silicones are preferred if silicone lubricants are used, as silicones can act as antifoaming agents.

In the exemplary aspect shown in fig. 1 and 2, in order to manufacture a closure that simulates a closure made from a single piece of cork, the closure precursor 2 contains cork particles in addition to the plastic material. As described herein, the plastic material is preferably foamed. The plastic material is preferably biodegradable, thereby enabling the production of a biodegradable closure. Thus, since the decorative layer 4 takes on the appearance of natural cork and the closure precursor 2 contains cork particles, a closure is obtained which has an appearance and smell similar to closures made from a single piece of cork. The cork granules preferably have a content of releasable trichloroanisole of less than 2ng/L, measured according to the test method defined herein.

Although these figures show a cylindrical closure, the present invention also covers closures for sparkling wine bottles.

Any embodiment or aspect described or defined herein, whether defining a closure, composition, or method, may be combined with any other aspect or embodiment, or any feature thereof, whether defining a closure, composition, or method, even when such a combination is not explicitly claimed. All combinations of embodiments, aspects and features are within the scope of the invention. In particular, any aspect of any claim may be combined with any aspect of any one or more claims. Where a range of values is defined, any numerical limitation of any range can be combined with any other numerical limitation of the same range. For example, the upper limit of a range can be combined with the upper limit of a range, or the lower limit of a range can be combined with the lower limit of a range, or the upper limit of a range can be combined with the lower limit of a range, while remaining within the scope of the present invention.

The test method comprises the following steps:

film health testing (Mocon test) of OTR oxygen ingress was performed according to ASTM F-1307 using 100% oxygen.

And (3) extraction force:

the test of the pull-out force was performed on random sample selection according to the method described in WO03/018304a1 (pull-out test, page 48, page 1.13-page 49, page 1.10), WO03/018304a1 being incorporated herein and forming part of the present disclosure. Three empty clean "boldo" style wine bottles were stoppered using a semi-automatic stoppering machine (model 4040, from GAI s.p.a. company (GAI s.p.a.), italy). The bottles were stored for one hour. The closures were then pulled out at ambient temperature using a Dillon AFG-1000N dynamometer (from Dillon Mass Plus, Inc., USA) to determine the force required for pull-out.

Surface hardness:

surface hardness was tested at room temperature (25 ℃) using a Shore 902 robotic arm from Instron to test surface hardness according to ASTM D2240-10.

Coefficient of friction:

the Coefficient of dynamic Friction was determined at room temperature (25 ℃) using an Instron Model 2810Coefficient of Friction test jig (Instron Model 2810Coefficient of Friction Testing texture) according to ASTM D1894-14. For the determination of the dynamic coefficient of friction, the closure was divided in half along its long axis and the flat side of the interior of the closure was mounted onto a steel plate. This sample was then loaded with a 200 gram weight and pulled across the stainless steel surface at 15.2 cm/min.

Releasable halogenated anisoles

The amount of halogenated anisole released from cork into wine can be determined as so-called "releasable halogenated anisole" by the following method: cork or a sample of cork is soaked in wine, untreated cork is soaked for 24 hours, or treated cork is soaked for 48 hours, and the amount of each of the haloanisole compounds in wine is determined by gas chromatography. An acceptable amount is generally considered to be a level that produces in the wine an amount of chloroanisole or chloroanisoles corresponding to an average sensory threshold of less than about 6ng/L, preferably less than about 2ng/L for TCA or TBA.