CA1126211A - Closures for containers for wine or wine-based products - Google Patents
Closures for containers for wine or wine-based productsInfo
- Publication number
- CA1126211A CA1126211A CA344,278A CA344278A CA1126211A CA 1126211 A CA1126211 A CA 1126211A CA 344278 A CA344278 A CA 344278A CA 1126211 A CA1126211 A CA 1126211A
- Authority
- CA
- Canada
- Prior art keywords
- wine
- stopper
- vinyl acetate
- closure
- oxygen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D39/00—Closures arranged within necks or pouring openings or in discharge apertures, e.g. stoppers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D39/00—Closures arranged within necks or pouring openings or in discharge apertures, e.g. stoppers
- B65D39/0005—Closures arranged within necks or pouring openings or in discharge apertures, e.g. stoppers made in one piece
- B65D39/0011—Closures arranged within necks or pouring openings or in discharge apertures, e.g. stoppers made in one piece from natural or synthetic cork, e.g. for wine bottles or the like
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Closures For Containers (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
ABSTRACT
CLOSURES FOR CONTAINERS FOR
WINE OR WINE-BASED PRODUCTS
A closure for a container of wine or a wine-based product which can replace a conventional cork and provide a good barrier against ingress of oxygen, is in the form of a stopper moulded from an ethylene/vinyl acetate copolymer with a vinyl acetate content of from 10% to 25%, the stopper having a closed-cell foamed core (which may contain water and sulphur dioxide to act as an oxygen scavenger) and a liquid-impervious skin, the degree of foaming being from 45% to 70%. The preferred VA content is from 10% to 20%.
The stopper is preferably coated with a silicone lubricant.
CLOSURES FOR CONTAINERS FOR
WINE OR WINE-BASED PRODUCTS
A closure for a container of wine or a wine-based product which can replace a conventional cork and provide a good barrier against ingress of oxygen, is in the form of a stopper moulded from an ethylene/vinyl acetate copolymer with a vinyl acetate content of from 10% to 25%, the stopper having a closed-cell foamed core (which may contain water and sulphur dioxide to act as an oxygen scavenger) and a liquid-impervious skin, the degree of foaming being from 45% to 70%. The preferred VA content is from 10% to 20%.
The stopper is preferably coated with a silicone lubricant.
Description
i2~L~
CLOSUR:E:S FOR C CNTAIME~RS FOR
WINE .OR WINE-BASi3D PRODUCTS
This invention relates to closures for containers for wine or wine-based products. Traditionally such clo-sures have been of cork, in the form of bungs or stoppersinserted into the necks of glass bottles. Cork has the - advantages of high elasticity, resilience and softne~s, which enable cork stoppers to be compressed to a di~meter - less than that of the bottle neck for insertion into the neck and then to recover elastically to such an extent as to seal the neck effectively. The frictional charactçristics - of cork are such that the stopper grips the neck tightly and is not liable ~o accidental displacement but can be drawn out when required, and the gas barrier characteristics are such that a cork stopper of conventional size, having a length of ~8 mm. or 44 mmO and a diameter when uncompressed of 22 mm. (19 mm~ when compressed in a bottle necX), will restrict ingress of oxygen into the bottle to a low figure.
Against these advantages, one must set the disadvantages that cork, being a natural produc~, is variable in quality, and good quality cork suitable for stoppers is relatively expensive. Any defects in the cork may lead to deterioration in the effectiveness of the stopper and deleterious e~fects on the taste of the contents.
For the preservation of wine and wine-based ~ro-ducts, it is essential that access of oxygen to the product "
'~
21~l should be restricted, to prevent oxidation of the flavour constituents and of the alcohol content. To stabilise the product against oxidation, it is normal practice for the producer to incorporate a small proportion of free sulphur dioxide (S02) in the product, though the amount which may be incorporated is restricted by law. Thus a light table wine may, for example, contain 50 parts per million of free S02.
To achieve an adequate shelf life for the wine, say one year for a mass-produced light table wi~e, the bottle and stopper must co-operate to restrict access of oxygen to the wine to a total amount during that year which is less than the total amount which can be dealt with by the S0~ in the wine. For a wine contained in a standard 75 centilitre bottle and incorporating 50 p.p.m. S02, it can be calculated that the amount of oxygen which can be dealt with by the S02 in the wine is 6.5 ml. at normal temperature and pressure.
Efforts have been made previously to produce stoppers for wine bottles from synthetic plastics materials, in particular polyolefins such as polyethylene. Difficulties have been encountered, however, because these materials are too hard and incompressible for a solid stopper to be easily inserted into a bottle neck or to conform with irregularities in the interior surface of the neck to pro-duce a good seal, when inserted. It has been proposed that such sto~pers should be made with hollow interiors or in the form oi a closed-cell elastic foam w.th a densified .
periphery offering a smooth external surface, in order to make the more compressible, but the relative lack of resilience in the material still makes it difficult to achieve suffi-cient conformity with irregularities in the neck to produce a good seal. Further, the material has a relatively low creep resistance so that such stoppers tend to take a perma-nent set after insertion into a bottle neck and thereby lose their grip in the neck after a time. The frictional character-istics of the material are such that the stopper can then slide out of the neck.
In our French patent application 7711990 filed April 21st, 1977 and published November 25th, 1977 with Serial Number 2349508 we have described and claimed a closure for a container of a wine or a wine-based product, at least a part of said closure intended to contact the product being in the form of a moulded stopper of a thermoplastics material, such as an ethylene/vinyl acetate copolymer, having a foamed core within a liquid-impervious skin, wherein the foamed core has been produced by blowing the thermoplastics material with a blowing agent including a thermally decompos-able sulphite and a water-producing compound, whereby said foamed core contains sulphur dioxide and water enabling the sulphur dioxide to act as an oxygen scavenger.
It is an object of the present invention to provide closures for containers for wine or wine-based products which will avoid the above-mentioned disadvantages, and , ~, ., iZ~
. . specifically to provide closures for synthetic plastics E
' materials which can be made at relatively low cost and which will have the advantages.of natural cork closures as regards insertion and retention of the closures, with-5 out the disadvantages described above.
. .' . According to the invention, there is provided a closure'for a co'ntainer for a wine or wine-based ' product, at least the part of said closure which:is intended to be exposed to the product being in the form 10 of a moulded stopper of.a thermoplastic material having .'~
a closed-cell foamed core'within a liquid-impervious skin, wherein the thermoplastic material is an ethylene!vinyl acetate copolymer with a vinyl acetate content of from . 10/o to 25% and the deg.ree of foaming of the'moulded stopper, .15 measured in terms of the reduction of density as'compared ' with the unfoamed material, is from 45% to 70%. ' -. Preferably the ethylene~vinyl acetate copolymer :. .
- . .
has.a vinyl.acetate content of from 10% to 20~o.
It has been found that by selecting the material 20 and the degree of foaming in this manner the stopper can be made to reproduce the de.sirable properties of natulal cork as regards compressibility and resilience, so that it is readily inserted into the neck of a.container, such as a bottle, and conforms with any irregularities therein so 25 as to produce a good seal. The material has.a good creep resistance so that the stopper retains its grip in the neck and is not liable to be accidentally dislodged, Stoppers .. . . .
.... .
.. .
.
,: .
i21~
in accordance with the invention, when made of appropriate conventional size, can thus be employed with existing cork inserting machinery in bottling plants.
sy selecting the material to have a vinyl acetate content within the specified range, it has also been found possible to achieve satisfactory gas barrier characteristics for restriction of ingress of oxygen into the container. In particular, where the moulded stopper is of conventional dimensions for a wine bottle cork, having a length between 30 mm and 50 mm and an uncompressed diameter of substantially 22 mm., it has proved possible to provide an oxygen barrier sufficient to restrict passage of oxygen into a container in which the closure is fitted to less than 4 ml. per annum.
The oxygen barrier can be further improved by arranging that the cells of the foamed core contain sulphur dioxide and water enabling the sulphur dioxide to act as an oxygen scavenger. This can be done as described and claimed in our above published French Patent Application 2349508, by producing the foamed core by blowing with a blowing agent including a thermally decomposable sulphite and a water-producing compound.
To achieve desirable frictional characteristics and thereby facilitate handling of the closures in exist-ing cork-inserting machinery, it is preferable to coat the moulded stoppers with a lubricant.
CLOSUR:E:S FOR C CNTAIME~RS FOR
WINE .OR WINE-BASi3D PRODUCTS
This invention relates to closures for containers for wine or wine-based products. Traditionally such clo-sures have been of cork, in the form of bungs or stoppersinserted into the necks of glass bottles. Cork has the - advantages of high elasticity, resilience and softne~s, which enable cork stoppers to be compressed to a di~meter - less than that of the bottle neck for insertion into the neck and then to recover elastically to such an extent as to seal the neck effectively. The frictional charactçristics - of cork are such that the stopper grips the neck tightly and is not liable ~o accidental displacement but can be drawn out when required, and the gas barrier characteristics are such that a cork stopper of conventional size, having a length of ~8 mm. or 44 mmO and a diameter when uncompressed of 22 mm. (19 mm~ when compressed in a bottle necX), will restrict ingress of oxygen into the bottle to a low figure.
Against these advantages, one must set the disadvantages that cork, being a natural produc~, is variable in quality, and good quality cork suitable for stoppers is relatively expensive. Any defects in the cork may lead to deterioration in the effectiveness of the stopper and deleterious e~fects on the taste of the contents.
For the preservation of wine and wine-based ~ro-ducts, it is essential that access of oxygen to the product "
'~
21~l should be restricted, to prevent oxidation of the flavour constituents and of the alcohol content. To stabilise the product against oxidation, it is normal practice for the producer to incorporate a small proportion of free sulphur dioxide (S02) in the product, though the amount which may be incorporated is restricted by law. Thus a light table wine may, for example, contain 50 parts per million of free S02.
To achieve an adequate shelf life for the wine, say one year for a mass-produced light table wi~e, the bottle and stopper must co-operate to restrict access of oxygen to the wine to a total amount during that year which is less than the total amount which can be dealt with by the S0~ in the wine. For a wine contained in a standard 75 centilitre bottle and incorporating 50 p.p.m. S02, it can be calculated that the amount of oxygen which can be dealt with by the S02 in the wine is 6.5 ml. at normal temperature and pressure.
Efforts have been made previously to produce stoppers for wine bottles from synthetic plastics materials, in particular polyolefins such as polyethylene. Difficulties have been encountered, however, because these materials are too hard and incompressible for a solid stopper to be easily inserted into a bottle neck or to conform with irregularities in the interior surface of the neck to pro-duce a good seal, when inserted. It has been proposed that such sto~pers should be made with hollow interiors or in the form oi a closed-cell elastic foam w.th a densified .
periphery offering a smooth external surface, in order to make the more compressible, but the relative lack of resilience in the material still makes it difficult to achieve suffi-cient conformity with irregularities in the neck to produce a good seal. Further, the material has a relatively low creep resistance so that such stoppers tend to take a perma-nent set after insertion into a bottle neck and thereby lose their grip in the neck after a time. The frictional character-istics of the material are such that the stopper can then slide out of the neck.
In our French patent application 7711990 filed April 21st, 1977 and published November 25th, 1977 with Serial Number 2349508 we have described and claimed a closure for a container of a wine or a wine-based product, at least a part of said closure intended to contact the product being in the form of a moulded stopper of a thermoplastics material, such as an ethylene/vinyl acetate copolymer, having a foamed core within a liquid-impervious skin, wherein the foamed core has been produced by blowing the thermoplastics material with a blowing agent including a thermally decompos-able sulphite and a water-producing compound, whereby said foamed core contains sulphur dioxide and water enabling the sulphur dioxide to act as an oxygen scavenger.
It is an object of the present invention to provide closures for containers for wine or wine-based products which will avoid the above-mentioned disadvantages, and , ~, ., iZ~
. . specifically to provide closures for synthetic plastics E
' materials which can be made at relatively low cost and which will have the advantages.of natural cork closures as regards insertion and retention of the closures, with-5 out the disadvantages described above.
. .' . According to the invention, there is provided a closure'for a co'ntainer for a wine or wine-based ' product, at least the part of said closure which:is intended to be exposed to the product being in the form 10 of a moulded stopper of.a thermoplastic material having .'~
a closed-cell foamed core'within a liquid-impervious skin, wherein the thermoplastic material is an ethylene!vinyl acetate copolymer with a vinyl acetate content of from . 10/o to 25% and the deg.ree of foaming of the'moulded stopper, .15 measured in terms of the reduction of density as'compared ' with the unfoamed material, is from 45% to 70%. ' -. Preferably the ethylene~vinyl acetate copolymer :. .
- . .
has.a vinyl.acetate content of from 10% to 20~o.
It has been found that by selecting the material 20 and the degree of foaming in this manner the stopper can be made to reproduce the de.sirable properties of natulal cork as regards compressibility and resilience, so that it is readily inserted into the neck of a.container, such as a bottle, and conforms with any irregularities therein so 25 as to produce a good seal. The material has.a good creep resistance so that the stopper retains its grip in the neck and is not liable to be accidentally dislodged, Stoppers .. . . .
.... .
.. .
.
,: .
i21~
in accordance with the invention, when made of appropriate conventional size, can thus be employed with existing cork inserting machinery in bottling plants.
sy selecting the material to have a vinyl acetate content within the specified range, it has also been found possible to achieve satisfactory gas barrier characteristics for restriction of ingress of oxygen into the container. In particular, where the moulded stopper is of conventional dimensions for a wine bottle cork, having a length between 30 mm and 50 mm and an uncompressed diameter of substantially 22 mm., it has proved possible to provide an oxygen barrier sufficient to restrict passage of oxygen into a container in which the closure is fitted to less than 4 ml. per annum.
The oxygen barrier can be further improved by arranging that the cells of the foamed core contain sulphur dioxide and water enabling the sulphur dioxide to act as an oxygen scavenger. This can be done as described and claimed in our above published French Patent Application 2349508, by producing the foamed core by blowing with a blowing agent including a thermally decomposable sulphite and a water-producing compound.
To achieve desirable frictional characteristics and thereby facilitate handling of the closures in exist-ing cork-inserting machinery, it is preferable to coat the moulded stoppers with a lubricant.
2~ ~ ~
The lubricant must be insoluble in water, because water-soluble lubricants could mix with the product in the container and allow the stopper to slide in the neck.
It is also important that the lubricant should not migrate -5 into the body of the stopper and thus be lost from the surface. The preferred lubricant which is coated on to the moulded stopper is a silicone, specifically a polymethyi - !
siloxane, which is insoluble in water and remains on the surface of the stopper.
Specific examples of the invention will n~w be described by way of example.
Cylindrical stoppers similar to conventional - wine corks, having a length of 38 mm and a diameter of 22 mm, were formed from three different ethylene/vinyl 15 acetate (EVA) copolymers having vinyl acetate (VA) contents -of 12~%, 15% and 18yoJ respectively. An injection moulding technique was used in which the EVA copolymer was mixed -with a blowing agent, heated, and injected into a cool mould so as to produce in known manner a stopper having a closed-cell foamed core within a smooth liquid-impervious skin.
The melt flow index values for the EVA copolymers were 4, 8 and 10, respectively. It is believed that the melt flow index is not particularly relevant in this context, though excessively fluid copolymers should be avoided because o~
difficulty of ensuring formation of the desired multiplicity of small clo~ed cells and avoiding cell collapse in the foaming process. The feedstock was formulated and the blp-n--ing controlled to achieve a degree of foaming of from 50% to . ~ , . . . .
- it . ' . . .
~2~1 '`. . . i . 70% measured in terms of the reduction in density as com-pared with the unf.oamed material. The degree of foaming has been found to be critical. Below 45% foaming the stop-~ per is insufficiently soft and compressible, and a minimum of 50% is usually to be preferred, whereas above 70% the skin of.the stopper is too thin to~retain adequate strength and oxygen barrier properties.
The blowing agent used in this series of experi-ments was a mixture of sodium bicarbonate and sodium metabi-sulphite, the composition of the feedstock being:
Ethylene/Vinyl acetate copolymer 96%
. . Sodium bicarbonate 1%
Sodium metabisulphite 2%
. . Pigment 1%
- 15 The sodium bicarbonate and the sodium metabi-sulphite decompose at the temperature to which the feedstock is heated prior to injection into the mould, to produce carbon dioxide, water vapour and sulphur dioxide, and some of the sulphur dioxide reacts with the sodium carbonate formed by decomposition of the sodium bicarbonate to liberate more carbon dioxide:-Na2S2o5, _ Na2S03 + SO2 2NaHC03 - _ Na2C03 ~ H20 + C0 N C0 S0 _ N 0 C0 m e sodium metabisulphite ~eing present in stoichiometric excess, the blowing gas contains sulphur dioxide, carbon di-oxide and water vapour which expand to cause foaming of the mixture as the feedstock enters the mould, the effect of ihe . ' " ' " .
.
" : ~
, .
. , - . ~ , ~ , :, ;,. .
: , - . , ;:
~ fiZ~
i ~` 8 cool mould walls being to restrict the ~ormation of cells at or near the sur~ace of the moulded stopper, so that it has a closed-cell foamed core within a smooth liquid-impervious skin. The sulphur dioxide, carbon dioxide and water produced in the blowing process are retained in the cells.
There would be a tendency for the sulphur dioxide to diffuse slowly out of the cells if the s~oppers were stored in air. m ey are therefore preferably stored in a sealed container in an atmosphere of sulphur dioxide until they are required for use.
Stoppers made as described above were coated with a polymethyl siloxane lubricant and'inserted into the necks (of 19 mm.' internal diameter) of wine bottles using conventional cork-inserting machinery, in which the stoppers are compressed - 15 to a diameter of 15 mm. bèfore being irserted into the necks.
- The compressibility, resilience, creep resistance and frictional characteristics'of the stoppers proued to be well suited to the .
machinery so as to enable the stoppers to be readily inserted, and to cause them to grip the necks tightly and form effective and lasting seals with no tendenc'y for the stoppers to slip out.
Measuremen~ were made of the rate of oxygen diffusion through the stoppers described above, under normal atmospheric pressure conditions. Stoppers made with the 12~% and 15y VA
copolymers showed figures of approximately 3 ml. per annum in the firs~ year. Stoppers of the 18% VA copolymer gave an average figure of 3.3~ ml in the first ~ear with a maximum of 3.5 ml in that year. After the first year, there was a ..
.
z:~
9 ~ ~
. drop to a rate of 2.5 ml per annum. These figures are well below the.figure of 6.5 ml of oxygen which can be dealt with by the normal content'of 50 p.p.m. free S02 in a mass-produced light table wine, indicating that a good shelf life could be expected. It will be understood that most other wines and wine-based products have a better resis-tance to oxidation so that even.bëtter.shelf lives could be expected for such other products'from use of stoppers in ' accordance with the invention.
. 10 By contrast, stoppers made in the same manner from ' various samples of ethyléne/vinyl acetate copolymer having - a vinyl acetate content of 28% were found to show. oxygen diffusion rates of 6.5 ml per annum.and higher and thus to 'have an unacceptably low~oxygen barrier.
. ~hile.the blowing agent described ab.ove is designed to produce sulphur dioxide and water in the cells to act as an oxygen s~avenger and thus improve the oxygen barrier, it would naturally be possible to use other conventional blowing agents such as nitrogen, pentane, low boiling compounds such as methylene chloride or fluorinated hydrocarbons. Alternatively sulphur dioxide and water. can be produced in the cells by other bl~wing agents apart from the sodlum metabisulphite and sodium bicarbonate mentioned above'. For example, metabisulphites and bicarbonates of other metals, particularly other alkali metals such as potassium, may be used. The water vapour or part thereof may be'provided by. incorporation of hydrated sodium citrate in the blowing agen~.
, .
2fi2~1 The stoppers may be moulded with a small chamfer at each end. Alternatively they may be provided with a flanged end or head, e.g. of spherical or part-spherical shape, which may be moulded of the same EVA copolymer or of a different polymer.
. ' ~.
.. ~. . ...
The lubricant must be insoluble in water, because water-soluble lubricants could mix with the product in the container and allow the stopper to slide in the neck.
It is also important that the lubricant should not migrate -5 into the body of the stopper and thus be lost from the surface. The preferred lubricant which is coated on to the moulded stopper is a silicone, specifically a polymethyi - !
siloxane, which is insoluble in water and remains on the surface of the stopper.
Specific examples of the invention will n~w be described by way of example.
Cylindrical stoppers similar to conventional - wine corks, having a length of 38 mm and a diameter of 22 mm, were formed from three different ethylene/vinyl 15 acetate (EVA) copolymers having vinyl acetate (VA) contents -of 12~%, 15% and 18yoJ respectively. An injection moulding technique was used in which the EVA copolymer was mixed -with a blowing agent, heated, and injected into a cool mould so as to produce in known manner a stopper having a closed-cell foamed core within a smooth liquid-impervious skin.
The melt flow index values for the EVA copolymers were 4, 8 and 10, respectively. It is believed that the melt flow index is not particularly relevant in this context, though excessively fluid copolymers should be avoided because o~
difficulty of ensuring formation of the desired multiplicity of small clo~ed cells and avoiding cell collapse in the foaming process. The feedstock was formulated and the blp-n--ing controlled to achieve a degree of foaming of from 50% to . ~ , . . . .
- it . ' . . .
~2~1 '`. . . i . 70% measured in terms of the reduction in density as com-pared with the unf.oamed material. The degree of foaming has been found to be critical. Below 45% foaming the stop-~ per is insufficiently soft and compressible, and a minimum of 50% is usually to be preferred, whereas above 70% the skin of.the stopper is too thin to~retain adequate strength and oxygen barrier properties.
The blowing agent used in this series of experi-ments was a mixture of sodium bicarbonate and sodium metabi-sulphite, the composition of the feedstock being:
Ethylene/Vinyl acetate copolymer 96%
. . Sodium bicarbonate 1%
Sodium metabisulphite 2%
. . Pigment 1%
- 15 The sodium bicarbonate and the sodium metabi-sulphite decompose at the temperature to which the feedstock is heated prior to injection into the mould, to produce carbon dioxide, water vapour and sulphur dioxide, and some of the sulphur dioxide reacts with the sodium carbonate formed by decomposition of the sodium bicarbonate to liberate more carbon dioxide:-Na2S2o5, _ Na2S03 + SO2 2NaHC03 - _ Na2C03 ~ H20 + C0 N C0 S0 _ N 0 C0 m e sodium metabisulphite ~eing present in stoichiometric excess, the blowing gas contains sulphur dioxide, carbon di-oxide and water vapour which expand to cause foaming of the mixture as the feedstock enters the mould, the effect of ihe . ' " ' " .
.
" : ~
, .
. , - . ~ , ~ , :, ;,. .
: , - . , ;:
~ fiZ~
i ~` 8 cool mould walls being to restrict the ~ormation of cells at or near the sur~ace of the moulded stopper, so that it has a closed-cell foamed core within a smooth liquid-impervious skin. The sulphur dioxide, carbon dioxide and water produced in the blowing process are retained in the cells.
There would be a tendency for the sulphur dioxide to diffuse slowly out of the cells if the s~oppers were stored in air. m ey are therefore preferably stored in a sealed container in an atmosphere of sulphur dioxide until they are required for use.
Stoppers made as described above were coated with a polymethyl siloxane lubricant and'inserted into the necks (of 19 mm.' internal diameter) of wine bottles using conventional cork-inserting machinery, in which the stoppers are compressed - 15 to a diameter of 15 mm. bèfore being irserted into the necks.
- The compressibility, resilience, creep resistance and frictional characteristics'of the stoppers proued to be well suited to the .
machinery so as to enable the stoppers to be readily inserted, and to cause them to grip the necks tightly and form effective and lasting seals with no tendenc'y for the stoppers to slip out.
Measuremen~ were made of the rate of oxygen diffusion through the stoppers described above, under normal atmospheric pressure conditions. Stoppers made with the 12~% and 15y VA
copolymers showed figures of approximately 3 ml. per annum in the firs~ year. Stoppers of the 18% VA copolymer gave an average figure of 3.3~ ml in the first ~ear with a maximum of 3.5 ml in that year. After the first year, there was a ..
.
z:~
9 ~ ~
. drop to a rate of 2.5 ml per annum. These figures are well below the.figure of 6.5 ml of oxygen which can be dealt with by the normal content'of 50 p.p.m. free S02 in a mass-produced light table wine, indicating that a good shelf life could be expected. It will be understood that most other wines and wine-based products have a better resis-tance to oxidation so that even.bëtter.shelf lives could be expected for such other products'from use of stoppers in ' accordance with the invention.
. 10 By contrast, stoppers made in the same manner from ' various samples of ethyléne/vinyl acetate copolymer having - a vinyl acetate content of 28% were found to show. oxygen diffusion rates of 6.5 ml per annum.and higher and thus to 'have an unacceptably low~oxygen barrier.
. ~hile.the blowing agent described ab.ove is designed to produce sulphur dioxide and water in the cells to act as an oxygen s~avenger and thus improve the oxygen barrier, it would naturally be possible to use other conventional blowing agents such as nitrogen, pentane, low boiling compounds such as methylene chloride or fluorinated hydrocarbons. Alternatively sulphur dioxide and water. can be produced in the cells by other bl~wing agents apart from the sodlum metabisulphite and sodium bicarbonate mentioned above'. For example, metabisulphites and bicarbonates of other metals, particularly other alkali metals such as potassium, may be used. The water vapour or part thereof may be'provided by. incorporation of hydrated sodium citrate in the blowing agen~.
, .
2fi2~1 The stoppers may be moulded with a small chamfer at each end. Alternatively they may be provided with a flanged end or head, e.g. of spherical or part-spherical shape, which may be moulded of the same EVA copolymer or of a different polymer.
. ' ~.
.. ~. . ...
Claims (5)
1. A closure for a container for a wine or wine-based product, at least the part of said closure which is intended to be exposed to the product being in the form of a moulded stopper of a thermoplastic material having a closed-cell foamed core within a liquid-impervious skin, wherein the thermoplastic material is an ethylene/vinyl acetate copolymer with a vinyl acetate content of from 10% to 25% and the degree of foaming of the moulded stopper, measured in terms of the reduction of density as compared with the unfoamed material, is from 45% to 70%.
2. A closure according to claim 1, wherein the ethylene/
vinyl acetate copolymer has a vinyl acetate content of from 10% to 20%.
vinyl acetate copolymer has a vinyl acetate content of from 10% to 20%.
3. A closure according to claim 1 wherein the moulded stopper has a length of between 30 and 50 mm and an uncompressed diameter of substantially 22 mm and provide an oxygen barrier sufficient to restrict passage of oxygen into a container in which the closure is fitted to less than 4 ml per annum.
4. A closure according to claim 1, wherein the cells of the foamed core contain sulphur dioxide and water enabling the sulphur dioxide to act as an oxygen scavenger.
5. A closure according to claim 1, wherein the moulded stopper is coated with a silicone lubricant.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB7903186A GB2040889B (en) | 1979-01-30 | 1979-01-30 | Closures for containers for wine or wine-based products |
| GB7903186 | 1979-01-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1126211A true CA1126211A (en) | 1982-06-22 |
Family
ID=10502815
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA344,278A Expired CA1126211A (en) | 1979-01-30 | 1980-01-23 | Closures for containers for wine or wine-based products |
Country Status (20)
| Country | Link |
|---|---|
| AR (1) | AR220811A1 (en) |
| AU (1) | AU534845B2 (en) |
| BE (1) | BE881443A (en) |
| BR (1) | BR8008727A (en) |
| CA (1) | CA1126211A (en) |
| CH (1) | CH643504A5 (en) |
| DK (1) | DK411480A (en) |
| ES (1) | ES488512A1 (en) |
| FR (1) | FR2447867A1 (en) |
| GB (1) | GB2040889B (en) |
| GR (1) | GR74430B (en) |
| IE (1) | IE49152B1 (en) |
| IL (1) | IL59249A (en) |
| IN (1) | IN153890B (en) |
| IT (1) | IT1130915B (en) |
| MA (1) | MA18718A1 (en) |
| NL (1) | NL8020011A (en) |
| PT (1) | PT70732A (en) |
| WO (1) | WO1980001559A1 (en) |
| ZA (1) | ZA80296B (en) |
Families Citing this family (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4363849A (en) * | 1980-10-30 | 1982-12-14 | The Coca-Cola Company | Foamed thermoplastic resin cork having a natural cork-like appearance and a method of injection molding the cork |
| US4499141A (en) * | 1980-10-30 | 1985-02-12 | The Coca-Cola Company | Composition for making a plastic closure for liquid product containers |
| FR2493853A1 (en) * | 1980-11-10 | 1982-05-14 | Pupi Matic Sa | CAPS OF CELLULAR PLASTIC MATERIAL |
| GB8509745D0 (en) * | 1985-04-16 | 1985-05-22 | Spadel Sa | Controlling & reducing opening torques of caps & lids |
| GB8803065D0 (en) * | 1988-02-10 | 1988-03-09 | Grace W R & Co | Container closure & materials for use in these |
| US5227411A (en) * | 1988-02-10 | 1993-07-13 | W. R. Grace & Co.-Conn. | Sealed containers and sealing compositions for them |
| US5204389A (en) * | 1988-02-10 | 1993-04-20 | W. R. Grace & Co.-Conn. | Sealed containers and sealing compositions for them |
| GB8803062D0 (en) * | 1988-02-10 | 1988-03-09 | Grace W R & Co | Sealed containers & sealing compositions for them |
| JPH021651U (en) * | 1988-06-16 | 1990-01-08 | ||
| US6709724B1 (en) | 1990-05-02 | 2004-03-23 | W. R. Grace & Co.-Conn. | Metal catalyzed ascorbate compounds as oxygen scavengers |
| US5202052A (en) * | 1990-09-12 | 1993-04-13 | Aquanautics Corporation | Amino polycarboxylic acid compounds as oxygen scavengers |
| FR2662142B1 (en) * | 1990-05-18 | 1993-05-07 | Cofarep Sa | EXPANDED POLYMER CAP. |
| US5364555A (en) * | 1991-04-30 | 1994-11-15 | Advanced Oxygen Technologies, Inc. | Polymer compositions containing salicylic acid chelates as oxygen scavengers |
| US5496862A (en) | 1993-05-05 | 1996-03-05 | Supreme Corq | Molded styrene block copolymer closure for a wine container |
| US5663223A (en) * | 1994-08-11 | 1997-09-02 | Zapata Technologies, Inc. | Flavor protectant closure liner compositions |
| US5904965A (en) * | 1997-04-24 | 1999-05-18 | Nomaco, Inc. | Synthetic closure |
| AUPP591998A0 (en) | 1998-09-15 | 1998-10-08 | Anthony Smith Australasia Pty Ltd | Closure |
| FR2799183B1 (en) * | 1999-10-05 | 2001-12-14 | Bouchages Delage | AGGLOMERATED CORK CAP AND PROCESS FOR OBTAINING SAME |
| DE10012394A1 (en) | 2000-03-15 | 2001-10-04 | Ulrich Stieler | Closure for bottle-like containers and method for the production thereof |
| DE102004008109B4 (en) * | 2004-02-18 | 2007-07-12 | Sebastian Heintges | Artificial cork |
| WO2006130923A1 (en) * | 2005-06-10 | 2006-12-14 | Advanced Beverage Closures Pty Ltd | A stopper with a foamed core and an outer skin |
| AU2007262671B2 (en) * | 2006-06-23 | 2014-04-17 | Amcor Limited | Closure with line having specified oxygen transmission rate |
| ITRA20090019A1 (en) * | 2009-06-22 | 2010-12-23 | Trere Chimica S A S Del Dott Tre Re Massimilia | PROCEDURE, COMPOUND AND USE OF THE COMPOUND FOR SULFURING AND SECONDARY ADSORBENT ACTION OF INSTABLE PROTEINS AND PHENOLIC COMPOUNDS OF MUSTS AND WINES, PROVIDED FOR THE SELF-MIXING OF ACTIVE SUBSTANCES OF THE TREATED VINEYARD MASS |
| US20230337703A1 (en) | 2020-03-06 | 2023-10-26 | Csp Technologies, Inc. | Tea-based compositions for oxygen modified packaging |
| EP4114750A2 (en) | 2020-03-06 | 2023-01-11 | CSP Technologies, Inc. | Daucus-based compositions for oxygen modified packaging |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2284534A1 (en) * | 1974-09-12 | 1976-04-09 | Bouchage Mecanique | IMPROVEMENTS FOR SHUTTERS FOR MOUTH CONTAINERS |
| GB1572902A (en) * | 1976-04-29 | 1980-08-06 | Metal Box Co Ltd | Closures for liquid product containers |
| DE2700259A1 (en) * | 1977-01-05 | 1978-07-13 | Mueller Karl Heinz | Synthetic foam bottle stopper treatment - with silicone oil-water emulsion for smooth surface finish |
-
1979
- 1979-01-30 GB GB7903186A patent/GB2040889B/en not_active Expired
-
1980
- 1980-01-17 ZA ZA00800296A patent/ZA80296B/en unknown
- 1980-01-23 CA CA344,278A patent/CA1126211A/en not_active Expired
- 1980-01-23 FR FR8001397A patent/FR2447867A1/en active Granted
- 1980-01-24 NL NL8020011A patent/NL8020011A/en not_active Application Discontinuation
- 1980-01-24 BR BR8008727A patent/BR8008727A/en unknown
- 1980-01-24 AU AU54928/80A patent/AU534845B2/en not_active Ceased
- 1980-01-24 WO PCT/GB1980/000014 patent/WO1980001559A1/en active Application Filing
- 1980-01-24 CH CH737780A patent/CH643504A5/en not_active IP Right Cessation
- 1980-01-25 PT PT70732A patent/PT70732A/en not_active IP Right Cessation
- 1980-01-29 GR GR61070A patent/GR74430B/el unknown
- 1980-01-29 IL IL59249A patent/IL59249A/en unknown
- 1980-01-29 AR AR279779A patent/AR220811A1/en active
- 1980-01-29 MA MA18915A patent/MA18718A1/en unknown
- 1980-01-29 IE IE175/80A patent/IE49152B1/en unknown
- 1980-01-30 BE BE0/199182A patent/BE881443A/en not_active IP Right Cessation
- 1980-01-30 IT IT19566/80A patent/IT1130915B/en active
- 1980-01-30 ES ES488512A patent/ES488512A1/en not_active Expired
- 1980-07-11 IN IN795/CAL/80A patent/IN153890B/en unknown
- 1980-09-29 DK DK411480A patent/DK411480A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| GR74430B (en) | 1984-06-28 |
| GB2040889B (en) | 1983-01-26 |
| BE881443A (en) | 1980-07-30 |
| ES488512A1 (en) | 1980-10-01 |
| IN153890B (en) | 1984-08-25 |
| MA18718A1 (en) | 1980-10-01 |
| FR2447867B1 (en) | 1984-01-06 |
| DK411480A (en) | 1980-09-29 |
| IT8019566A0 (en) | 1980-01-30 |
| NL8020011A (en) | 1981-06-16 |
| IL59249A (en) | 1982-01-31 |
| AU534845B2 (en) | 1984-02-16 |
| ZA80296B (en) | 1981-03-25 |
| IL59249A0 (en) | 1980-05-30 |
| GB2040889A (en) | 1980-09-03 |
| IE800175L (en) | 1980-07-30 |
| FR2447867A1 (en) | 1980-08-29 |
| IT1130915B (en) | 1986-06-18 |
| BR8008727A (en) | 1981-04-28 |
| WO1980001559A1 (en) | 1980-08-07 |
| PT70732A (en) | 1980-02-01 |
| AR220811A1 (en) | 1980-11-28 |
| CH643504A5 (en) | 1984-06-15 |
| IE49152B1 (en) | 1985-08-07 |
| AU5492880A (en) | 1980-08-07 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |