CA1177600A - Method for making a plastic closure for liquid product containers - Google Patents

Method for making a plastic closure for liquid product containers

Info

Publication number
CA1177600A
CA1177600A CA000388118A CA388118A CA1177600A CA 1177600 A CA1177600 A CA 1177600A CA 000388118 A CA000388118 A CA 000388118A CA 388118 A CA388118 A CA 388118A CA 1177600 A CA1177600 A CA 1177600A
Authority
CA
Canada
Prior art keywords
closure
cavity
pigment
weight
blowing agent
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
Application number
CA000388118A
Other languages
French (fr)
Inventor
Gary V. Paisley
J. George Altschuler
Joseph Rommler
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Coca Cola Co
Original Assignee
Coca Cola Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Coca Cola Co filed Critical Coca Cola Co
Application granted granted Critical
Publication of CA1177600A publication Critical patent/CA1177600A/en
Expired legal-status Critical Current

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C67/00Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
    • B29C67/20Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 for porous or cellular articles, e.g. of foam plastics, coarse-pored
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/02Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
    • B29C44/04Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles consisting of at least two parts of chemically or physically different materials, e.g. having different densities
    • B29C44/0407Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles consisting of at least two parts of chemically or physically different materials, e.g. having different densities by regulating the temperature of the mould or parts thereof, e.g. cold mould walls inhibiting foaming of an outer layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65DCONTAINERS 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
    • B65D39/00Closures arranged within necks or pouring openings or in discharge apertures, e.g. stoppers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65DCONTAINERS 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
    • B65D39/00Closures arranged within necks or pouring openings or in discharge apertures, e.g. stoppers
    • B65D39/0005Closures arranged within necks or pouring openings or in discharge apertures, e.g. stoppers made in one piece
    • B65D39/0011Closures 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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/32Component parts, details or accessories; Auxiliary operations
    • B29C43/36Moulds for making articles of definite length, i.e. discrete articles
    • B29C43/361Moulds for making articles of definite length, i.e. discrete articles with pressing members independently movable of the parts for opening or closing the mould, e.g. movable pistons
    • B29C2043/3615Forming elements, e.g. mandrels or rams or stampers or pistons or plungers or punching devices
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/32Component parts, details or accessories; Auxiliary operations
    • B29C43/36Moulds for making articles of definite length, i.e. discrete articles
    • B29C43/361Moulds for making articles of definite length, i.e. discrete articles with pressing members independently movable of the parts for opening or closing the mould, e.g. movable pistons
    • B29C2043/3615Forming elements, e.g. mandrels or rams or stampers or pistons or plungers or punching devices
    • B29C2043/3621Forming elements, e.g. mandrels or rams or stampers or pistons or plungers or punching devices a plurality of individual elements acting on the material in the same or diferent directions, e.g. making tubular T-joints, profiles
    • B29C2043/3623Forming elements, e.g. mandrels or rams or stampers or pistons or plungers or punching devices a plurality of individual elements acting on the material in the same or diferent directions, e.g. making tubular T-joints, profiles coupled on a support, e.g. plate
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/04Condition, form or state of moulded material or of the material to be shaped cellular or porous
    • B29K2105/043Skinned foam
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2423/00Use of polyalkenes or derivatives thereof as filler
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037Other properties
    • B29K2995/0068Permeability to liquids; Adsorption
    • B29K2995/0069Permeability to liquids; Adsorption non-permeable
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29LINDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00Other particular articles
    • B29L2031/56Stoppers or lids for bottles, jars, or the like, e.g. closures
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29LINDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00Other particular articles
    • B29L2031/56Stoppers or lids for bottles, jars, or the like, e.g. closures
    • B29L2031/565Stoppers or lids for bottles, jars, or the like, e.g. closures for containers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04Homopolymers or copolymers of ethene
    • C08J2323/08Copolymers of ethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S264/00Plastic and nonmetallic article shaping or treating: processes
    • Y10S264/14Plastic and nonmetallic article shaping or treating: processes forming integral skin on a foamed product
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S264/00Plastic and nonmetallic article shaping or treating: processes
    • Y10S264/83Injection molding of polyolefin-type foam
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/24Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24355Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
    • Y10T428/24438Artificial wood or leather grain surface
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/249921Web or sheet containing structurally defined element or component
    • Y10T428/249953Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249987With nonvoid component of specified composition
    • Y10T428/249988Of about the same composition as, and adjacent to, the void-containing component
    • Y10T428/249989Integrally formed skin
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/3167Of cork

Abstract

ABSTRACT OF THE DISCLOSURE

A method for making closures resembling natural cork for sealing liquid product containers is described. A strand of expandable plastic material is injected into each mold cavity and is permitted to collect in that cavity in randomly oriented groups of coils which expand to fill the cavity and coalesce to create randomly oriented grain lines on the surface of the closure resembling the appearance of natural cork. Also described are methods of molding the closures which preclude the formation of leakage channels on the closure surface and preferred blends of plastic resins and pigment particles used to achieve the cork-like appearance.

Description

~,.''~ 1.1'~ 0~

SPEClFlCATION

BACKGROUND OF THE INVENTION

Field of the Invention --The present invention relates to closures for liquid product containers and, methods and apparatus for making the same. More specifically, the present invention relates to molded synthetic plastic closures which resemble the appearance of natural cork and molding techniques for making tne same.
Description of Prior Art ~
It is known heretofore to manufacture articles from foamed thermoplastics by injection or extrusion of polyurethane, polystyrene or polyolefin. In these cases, the thermoplastic may be expanded from a granular form to assume a porous, solidified foam-like structure by the action of various propellants or agents for expanding or blowing the materials.
The blowing agents, in accordance with normal practice, are usually gases or gas generating substances that have been dissolved or otherwise intimately incorporated withln the thermoplastic resinous material while lt,is in an unexpanded granular form. The application of heat to such a mixture causes the blowing agent to be released or thermally expanded or both, while the thermoplastic l~aterial is attaining a foaming temperature at which it is sufficiently softened and yieldable to permit the pressure of the expanding blowing agent to expand it into the desired foam structure.
In a special case of extrusion forming of foamed thermoplastics, it is also known to decorate the surface of ~-~ ~ 7~0 '~
~rticlcs 50 pro(3uc~d to r~sc?lnble n~tural wood by im~rting to the sur~ace a parallel g~ain structu~e. Such ~ecoration is accomplished by extruding the material through a die having, in particular, a multiple number of apertures to form a corresponding number of strands of expanding resin, collecting these strands in parallel relationship, and then coalescing them into a body of any desired length. Contacting surfaces of the strands create parallel grain lines which remain clearly visible in the surface of the finished articles and resemble natural wood grain.
In a special case of injection molding of foam thermoplastics, it is known to mold articles by injecting into an enclosed cavity a measured amount of expandable thermoplastic resin so that the cavity is not comple~ely filled by the unexpanded material but becomes filled as the material expands. As expan$ion occurs, the softened resin is forced by a gaseous blowing agent into contact with the relatively cool walls of the mold cavity where the portion of the resin in-direct contact with the walls is solidified and forms a dense outer layer or skin conforming to the shape of the cavity and functioning as a barrier, thereby preventing the escape of the gaseous blowing agent from the article and causing gas bubbles to be entrapped in the article's interior region. Thus, articles molded in this manner are characterized by a porous, foam-like interior and a dense outer shell or skin having the same general size and shape as the mold cavity and which are essentially impermeable to most s~bstances.
_ By employing certain highly flexible thermoplastic materials such as the polyolefin copolymer, ethylene vinylacetate, in the previously described injection molding process, the resultiny foamed articles will exhibit elastic .
properties closely resembling similar products manufactured from other natural and synthetic elastomers. This flexibility and resiliency plus- the presence of an essentially impermeable skin allows these same articles if molded into the proper size `. f~ "7`~i~0 '-and shape, to function ~s closures or liquid pro~uct containers by being compre~sed ~nd itt~d into the container opening, then being allowed to expand, filling the opening and creating a continu~us seal about its perimeter.
Therefore, such articles would theoretically be useful as replacements for similar closure devices manufactured of more familiar mateeials, such as natural cork used in containers of medicine, wine and spirits. In reality, efforts at replacing natural cork closures in liquid product containers, especially containers for wine products, by manufacturing and utilizing closures from injection molded foamed thermoplastics have not been very successful. This has been due primarily, it is believed, to the lack of aesthet-ically created consumer appeal for such closures, and the relationship of-the dense~outer skin to the porous inner core which dense outer skin, while necessary to make the closure essentially impermeable, can be-a detriment to the sealing function of these articles, particularly when leakage channels are formed on the dense outer skin during the sealing of these articles.
Since such prior art closures must be compressed to be fitted into liquid product containers there is a tendency for the dense outer layer of the closures to wrinkle and form longitudinal channels in thé outer surface of the foamed articles. Such channels could form leakage paths for the container contents or allow the ingress of substances harmful to the product being contained, such as ambient air in the case of the medicine or food products. f Tests have shown that these channels are caused primarily by the presence of relatively large void spaces between the dense outer skins and the porous inner core of the foamed articles, their presence being the result of a previously unrecognized phenomena occuring duri~g the molding of the articles. Since the dense outer skin has a much higher resistance to compression than the porous inner core, it tends to deflect into any available void space, `~
v-~ ~ `7~
creating a ch~nnel on the outer s~rf~ce of the closu~c khat could result in a disrup~ion o the otherwise continuous perimeter seal.
In addition to the foregoing problems, prior art molded closures have not been unifoem and consistent in design and performance. Thus, such prior art closures have not been ound readily acceptable as a replacement for similar closure devices, such as natural cork used in containers of medicine!
wine and spirits. It is well known that natural cork contains various holes and crooks and many times will crumble and break when inserted or withdrawn from the product container.
.

SU~RY OF THE INVENTION -~.

Accordingly, it is a primary object of the present invention to provide a molded liquid product container closure having a foamed plastic interior and a liquid impervious plastic outer skin which is not subject to any appreciable wrinkling when compressed.
It is a further object of the present invention to incorporate into the molding technique a method of decorating the outer skin of the closure so that it resembles the appearance of natural cork.
It is another object of the present i,nvention to provide a synthetic cork article and a means of making same which approaches many of the physical properties of natural cork when employed as a closure for a liquid product container.
It is anotner object of the present invention to provide a synthetic cork article and a means of making same that may be employed as a wine bottle stopper and is removable using an ordinary corkscrew.

It is another object of the present invention to provide a synthetic cork article and a means of making same which may be used as a cork substitute in existing bottling equipment without malfunction of said equipment.

': .. , - 117~ 0 It is ~nother o~ject o the prcsant inv~ntion to pcovide a 5ynthetic coLk ar~icle tlla~ can bc manuf~ctueed with uniformity and will not break or crumble when inserted or withdrawn from the product container.
Thus, the combined objectives of the present invention are to provide a synthetic cork article and a means of making same which will perform satisfactorily as a substitute for natural cork in a closure, or portion of a closure, for a-liquid product container without fear of leakage into or out of said container and will satisfy the aestheti-c requirement for a natural cork closure in such containers as those for wine and liquor products.
The objects of the present invention are fulfilled by injecting the thermoplastic resin into each mold cav~ty through a single orifice in each mold cavity which forms the material into a single and continuous elongated strand within each mold cavity. As the strand length builds in each mold cavity, it is contained by the cavity walls which force the single and continuous elongated strand to collect in a random fashion when the strand meets resistance within the mold cavity and contact itself at various points along its length. The expansion of the blowing agent causes the randomly positioned loops of the strand to expand and coalesce leaving grain lines in the surface of the molded article similar to_those found in the surface of extruded articles manufactured in accordance with previously known teachings but which, in distinction, are not straight or parallel but of varyin,g direction, occasionally Intersecting, and which are formed from a single and continuous elongated strand of resin. Also, these articles contain the randomly oriented grain lines on the entire o~ter surface, including the ends thereof, and thus constitu~es an improvement over articles manufactured by extrusion that normally do not contain randomly oriented grain lines on the ends of the articles. These randomly oriented grain lines, when embodied _ ~ _ 1.1 ~ ; L;() O
in the ~ntir~'surace of an ~rticl~ having the s.llne gcn~ral size and shape as the natural cork portion of a closure for a liquid product container, cause the article to resemble natural co~k in appearance ~ esistance to wrinkling during subsequent compression of the article is improved to a satisfactory level by incorporating into the molding method of the present invention a specific technique and series of embodiments to the molding equipment which, together, eliminate the tendency of the foaming material to form large void spaces between the dense outer skin and the foamed interior of the article. This is ;
accomplished by insuring that all the resin material to be utilized in each article enters the mold'cavity, and that each cavity entrance is positively sealed prior to the expansion of the resin, to form a solidified outer skin adjacent to the cavity wall. ' ' It was found in prior molding techniques that further ingress of material after the relatively rigid and dense outer skin has formed, sets up a shear boundary layer within the material being molded and results in the still soft inner core of the article shifting relative to the dense outer skin, thus breaking the material bond between the dense outer skin and the inner core. Gas pressure subsequently forces the porous inner core of the article away from the dense outer skin thereby creating-large void spaces immediately beneath the rigid and dense outer skin. The lack of a complete bond between the dense outer skin and the porous inner core results in, during compression of the molded article, relative movement between the two components (i.e. dense outer skin and porous inner core) of the molded closure device, which results in wrinkles~
and leàkage paths on the outer surface of the molded closur~
device. -' Chronological separation of injection and expansion steps is achieved by several embodiments to the improved molding`-' technique and equiplnent of the present invention including:

- 1177~ )0 1. The Inaximization o the ~vailable injection pressure and speed with a corresponding Ininimization of venting within each mold cavity of a plurality of mold cavities with the result, during injection, of a temporary pressurization of each cavity caused by rapid ingress of expandable resin and the opposing slow escape of displaced gas which restricts the expansion of the thermoplastic resin to form a solidified exterior until the injection of each cavity is completed.
2. The creation of a runnerless molding technique by the incorporation within the single small orifice of each mold cavity through which all material must flow to reach each mold cavity of a positive means of shutting off the flow of material to or from each cavity such that no continuèd channel for-resin flow exists between each shutoff in its associated cavity and the heated runner channel following completion of the injection portion of the molding cycle of that particular cavity.
3. The utilization of each shutoff in its associated cavity as a means of initiating and terminating the~
injection of material. into each cavity such that the period for transfer of material.to or from each mold cavity through its respective injection orifice can be positively controlled.

BRIEF DESCRIPTION OF 'rHE DRAWINGS
. .' The objects of the present invention and the attendant -?

advantages thereof will become more readily apparent by ,.
reference to the following drawings wherein like reference characters are employed to designate like parts: ::

'`'"'"J

~ '7~
Fi~3ure 1 is a crns~.-s~ctional vi~w of a ty~ic~l mold which could be used in an attempt to manufacture closures for liquid product containers which resemble natural cork.
Figure 2 rs a cross-sectional view of the mold of the preferred embodilnent of the peesent invention for the manufacture of closures for liquid product containers which resemble natural cork, but do not have undesirable channels on the exterior surface of the molded article and not subject to appreciable wrinkling.
Figure 3 is a perspective view of one embodiment of a closure for a liquid product container in accordance with the present invention.
Figure 4 is a perspective view of another embodiment of the closure of the present invention. ~
Figure 5 is a perspective view of still another embodiment of a closure for a liquid product container in accordance with the present invention.
Figure 6 is a perspective view of a closure for a liquid product container which incorporates the present invention as only a portion of the closure.
Figure 7 is a cross-sectional view of a closure for a liquid product container formed from the mold of Figure 1.
Figure ~ is a cross-sectional view of a closure for a liquid product container of the improved type in accordance with the present invention made from the mold of Fiqure 2.

DETAILED DESCRI PTIO~l OF THE DRAWINGS

To provide a synthetic cork closure device which can function satisfactorily as a replacement for the natural cork, portion of closures for containers of medicine and food products such as wine and spirits, it has been found necessary to control the size, shape, surface smoothness, elasticity, density distribution and aesthetic appearance of such ~ lr~
1~7'7~V
articles. Fac~ors ound to be of particular importance inachieviny the desired results in these areas include thermoplastic resin types and blends, blowing agent type and level, processing temperatures, injection pressure and speed, mold design and mold temperature.
The basic resin material utilized in the invention is preferably a polyolefin having good flexibility and resiliency such as ethylene-vinylacetate copolymer (EVA). To achieve the exact combination of properties desired in the finished articles, it is necessary to choose an EVA material based on the percentage of vinylacetate (~VA) incorporated into the copolymer and the melt index of the resin, typically usable resin grades vary between 9 and 25% VA and between 2.0 and 8.0 in melt index and are available from a number of sou~ces. The properties of the finished closures may be enhanced by the addition to the basic resin of small quantities of a hardness modifying additive, such as polyethylene homopolymer or ionically cross-linked ethylene-methacrylic acid copolymers.
The addition of such a hardness modifying additives, such as polyethylene homopolymer or ionically cross-linked ethylene methacrylic acid copolymers,-tends to vary the hardness and strength of the finished article.
To the basic resin or mixture of resins is added a suitable chemical blowing agent to expand the resin to proper density.
The preerred blowing agent is azodicarbonamide (ABFA) because of its decomposition temperature which is in the normal processing range of EVA resin and ,because of its relatively high rate of gas evolution. Of course, other known blowing agents, such as o~odecarbonoxide may be utilized without departing from the spirit and scope of the present invention ~
The amount of blowing agent to be added is dependent on the density distribution desired in the finished article and the`

processing temperature of the raw material. For example, it has been found that by minimi~ing the proportion of blowing agent level and/or the processing temperature, atticles are _ 9 _ ~ l t'~'7~
~roduce~ that exhibit a l~ss dt!n~c outer ~kin 1nd ~ l~ss porous innee core, thereby makiny the density distribution through the article more uniform, which of course, is more desirable to prevent leakage paths on the exterior surface of the molded articles.
In addition to the resins and chemical blowing agent, pigments are added to the raw material blend to give a cork-like color to the molded article. Optionally, a number of other materials also may be added including surface lubricants, chemical blowing agent activators and ultra-violet radiation stabilizers, all of which may add slight improvements to the producibility and/or performance of the articles.
In producing synthetic cork closures, appropriate amounts of each of the materialSare mixed thoroughly prior t~ molding.
A typlcally preferred blend is as follows:

EVA, 9-25% VA and melt index 2.0-8.0 80% by wt.
Polyethylene homopolymer 19%
ABFA 0-5%
Pigment blend 0.5%
100.0% by wt.
With this blend, 24mm diameter by 1.75 inch long closures 12 of the type often utilized is standard 750 mL wine bottles, and as shown in Figure 3 and 4, were manufactured at processing tem-peratures in the range of 370-400F. This particular closure size and resultant density distribution showed superior mechanical performance characteristics-~o similar natural cork closures or to other synthetic cork closures of a different density distribution. Other closure styles can be manufactured using this blend of materials and have shoi~n comparable results. These include a closure 12 having an enlarged end 12A
for gripping as shown in Figure 5! and the shank portion 12S of a 2-piece closure as shown in Figure 6, which is subsequently attached or glued to a metal, plastic or wooden cap 13 with , adhesive.

'7'~
To miniln~e the cooliny time of the molded ar~icle, the optimulnlnold tcmpcrature was ~ound to be 70-gOF. ~fter molding, the closures are ejected from each mald cavity into water or refrigerared environment for cooling purposes.
In order to achieve an authentic cork-like color and appearance, it is a discovery of the present invention that the use of coarse ground powdered pigments as a portion of the pigment blend enhances the cork-like appearance of the finished articles by leaving specks in or near the surface of the closure. These specks improve the likeness to cork which also contains such "blemishes". In a preferred embodiment, a pigment blend was utilized, wherein at least 5~ of the pigment blend contained a FD&C certified alumina-lake powder having a particle size in the range of 40-60 microns. Such affpigment blend produced a closure having a cork-like color and appear-ance.
To produce articles which would perform adequately as closures and which incorporate the decorative surface resembling natural cork, it is necessary to design a special mold which causes the melted resin material to be injected into each mold cavity in the form oE a single long continuous strand. This is done by fitting each mold of a plurality of mold cavities with a single aperture or gate of extremely small size through which all rêsin entering the cavity must pass.
The surface decoration was found to be alterable by changing the size of the orifice. However, articles molded using an orifice diameter between 0.030 and 0.055 inch was most preferred from an aesthetic standpoint. Pressure on the melted resin material from the injection unit forces the melted resin material to be injected into each cavity through its respectiye orifice, thereby depositing a single strand of softened resi;n in the cavity. The cavity walls of each enclosure, in turn, produce resistance to the strand and force the strand to collect in a randomly oriented group of coils which expand to fill the cavity. The coalesence of the loops during expansion . .

~ -. ~'17 î'~
cr~atcs ran~olnly ori~ntcd grain lin~s w~ich r~main cle~lrly visible in the article's sur~ace following solidification. Tl-e presence of the randomly oriented grain lines, results in a molded article tha~ closely resembles natural cork. These randomly oriented grain lines may be accentuated by using a pigment blend that contains at least 5% of a FDhC certiied alumina-lake powder having a particle size in the range of 40-60 microns.
One type of mold which can be utilized is depicted in Figure 1. Because the molded article's ability to seal the container is improved by its smoothness on the surface which contacts the container, it is desirable that this surface contain no parting lines or gating blemishes. Therefore, the mold should be designed so that the parting line is ~long the edge of the contact surface and gating is accomplished on a surface which will not contact the container, when the closure is used in sealing the container, namely, an end of the closure being formed. In the mold of Figure 1, utilizing a permanent channel for plastic flow to the mold cavity, referred to as a sprue S and runner EA, a mold having at least four plates which separate during the ejection sequence was required. Plate A
contains the sprue bushing SBU which has a means of pulling the solidified material 10 remaining in the sprue S and runner EA
away from the molded art~cle during ejection. Plate X-l is designed to strip the solidified material from the sprue bushing SBU. Plate X-2 forms the top surface of the cavities and contains the runner EA and the!orifice gates OG required for injection of material into the cavities C. Plate B
contains the cavities C, themselves.
Although four plates including Plate A are illustrated in~
Figure 1, the three plates X-l, X-2, and B constitute a con-ventional type of 3-plate injection mold. In use, the Plate A
is bolted to the fixed platen (not shown) of the molding machine using the locating ring LR for alignment with a corresponding hole on the platen. The ejector housing EH is ~ iO (1 ¦ then ~oltc~ to the movin~ pJ~cn ~not shcwn). Th~ mold is then ¦ operated silnply by trav 1 of the moving platen which opens and closes the mold as follows: From the full shut position, which ¦ is shown, the movi~g platen starts pulling the Inold apart, the ¦ plates sliding on four guide pins GP. The mold may part ¦ originally at either parting line Pl or P2. Assuming parting ¦ line Pl, the ejector housing EH and Plate B which are bolted ¦ together plus the plate X-2, will travel away with the moving ¦ platen until the stripper bolts SB2 take up. This action ¦ breaks the connection between the molded part 12 and the ¦ solidified material in the sprue S and runner 10 at the gate ¦ opening OG. At take up, the distance between the X-l and X-2 ¦ plates is held and, as the platen continues to travel, the mold ¦ parts at parting line P2. Plate B will continue to separate ¦ from plate X-2 until stripper bolts SBl take up. During this ¦ travel, the ejector plate EP makes contact with a fixed stop, ¦ forcing the ejector pin EJ to remain still while the Plate B
¦ continues to travel. This forces the molded parts 12 to be ¦ automatically ejected from their respective cavity.
¦ After stripper bolts SBl and SB2 have taken up, plate X-l ¦ is pulled away from Plate A. The Plate X-l was o~iginally held ¦ in position by the solidified material in the sprue and runner ¦ channel which forms the shape of the sprue channel 5 having a ¦ bulge BU and a runner EA. The bulge holds the solidified ¦ material l0 in the sprue bushing SBU when the plate X-2 starts away, allowing the sprue and runner to break at the gate OG.
~7hen the plate X-l starts to travel it acts on the solidified : material to pull it from the sprue channel. The plate X-l is slotted (not shown) so that after the solidified material is pulled from the channel it drops through the slot and out of;~
the mold. The mold is reclosed by reversing the moving ~.
platen.

In operation, the injection nozzle valve Nl is brought into contact with the sprue bushing SBU. It is then opened by retracting pin Pl and softened resin i5 injected into the sprue _ l3-~ ~ ~.~'7'~.~;iOO
channel dcfined by sprue bushin~ S~U ~here it initially starts to expand. Contlnucd injection, however, fills and pressurizes the sprue chânnel, compressing the resin back towards its ori-ginal state. At a certain pressure, the resin will begin to be injected through the small orifice gates OG leading to the mold cavities C where it again starts to expand. At the appropriate time, before each cavity C becolnes completely filled, the nozzle valve Nl is shut off, stopping the flow of material to the sprue channel. Material will continue to flow, however, from the sprue chamber to the mold cavity at a decreasing rate as the two different pressures attempt to equalize. At some point, depending on the initial temperature and viscosity characteristics of the resin, the mold temperature and the size of the orifice OG, the material within the orifice i~self will stop moving and solidify, preventing further transfer to or from the cavities C. Simultaneously with this injection sequence, the material entering the cavities C will undergo expansion, the rate of expansion being a function of the material blend, the material temperature, the design of the mold with regard to venting in the cavities C and the total amount of material injected. It has been found that subtle changes in resin blend or telnperature will cause significant differences in the amount of resin which actually enters the cavity. Therefore, a well-balanced runner system is a necessity in the mold machine.
The rapid injection of material into the mold is of impor-tance to the subsequent performance of the molded article as a closure for a liquid product container. If injection occurs too slowly, the initial portion of the resin entering the cavity will have time to expand, contact the relatively cool walls of the mold cavity and solidify into a rigid and dense.
outer skin before the remainder of the resin can enter the cavity. Continued injection after this dense outer skin has formed will set up a shear boundary layer within the article being molded between the still soft inner core and the rigid ': ~ l a 7 ,~
outer skin whi~h re3ults in a shit bctwcen the ~wo portions.
~i~i5 shi~t breaks the material bond between the two distinct portions of the molded closure. Expanding gas will ultimately collect in the boundary layer sucface and force the two segments of the closure apart, thereby creating large voids V
immediately beneath the dense outer skin of the closure as illustrated in Figure 7.
During subsequent compression of the molded closures 12 for use in liquid product containers, these voids would serve as spaces into which the dense outer skin of the article could deflect to avoid comprèssion, thereby creating a longitudinal channel on the molded closure surface. These longitudinal channels often become leakage paths between the molded closure-and the container wall allowing substances into or out of the container. To avoid these leaks, it is necessary to eliminate the presence of the void spaces by completing the injection of resin material into the mold cavity prior to its expansion to form a rigid and dense outer skin.
It should be understood that the mold of Figure 1 can be successfully utilized to achieve one object of the present invention, namely, a synthetic cork having an external appear-ance resembling natural cork. However, the mold of Figure 2 and the method of utilizing the same described hereinafter, eliminates the creation of the aforeme~nti-oned void spaces.
The mold of Figure 2 works similarly to that of Figure 1, except that there are far fewer parts since no solidified -~-material must be ejected from the sprue and runner chamber. A
hot runner system is utilized instead. The hot runner manifold HR and the hot tip bushings HTB, contain heaters (not shown) which prevent the plastic resin in the runner system EA from solidifying. A lone parting line Pl exists between plates A
and B since the X-l and X-2 plates no longer exist.

To accomplish this task of eliminating void spaces, it is desirable to increase the injection pressure to the maximum available on the molding machine (at the time of the test,;~-- ~5 ~

~ ~7~n~(~
~pproxilnarely 16,000 p5ig), ~nd ~bec~ 5e injeation pressure is created in this case by a hy~raulic ~luid cylindcr/), to enlarge the flow channel of pressurized hydra~lic fluid to the cylinder so that a very high pressure can be maintained on the resin at all times during injection. Next~ mold cavity venting should be decreased to minimum by reducing the clearances between the mold parts such as plates A and B which form the cavities C. This results in the cavities being temporarily pressùrized by the entrance of the resin and subsequent dis-placement of the air so that the pressure, which served to restrict the expansion of the resin, is retained longer.
However, when a mold is utilized such as the mold of Figure 1, even with extremely rapid injection times and minimum venting, some shear boundary layer damage may still o~ccur to the interior of the molded articles 12 due to the continued -slow ingress of pressurized material from the sprue chamber to the cavity C long after actual injection has ceased. It is a discovery of the present invention that to control the transfer of material more directly, it is necessary to incorporate a valve within the orifice gate OG itself. This led to the invention of the preferred mold and valve configuration depicted in Figure 2.
The valve pins SP of Figure 2 are specially designed to fit -into orifice gates OG of the mold and to perform the intended function of allowing sprueless molding.
The pins SP slide back and forth in the runner system EA, opening and closing the orifice ga~es. The pins SP can be powered hydraulically or pneumatically, using a piston arrangement PN as shown in Figure 2. Of additional importance is the fact that tne sealing is accomplished at the very tip ~f the orifice gate OG to prevent any premature expansion of resin.

With this Figure 2 mold, a cycle is also initiated as in Figure 1 by bringing the nozzle into contact with the hot runner manifold HR, opening the valves Pl and SP and injecting ,. ~ 1~7t7600 a mea~ured lmount o resin into each c~vity. ~gain, before each cavity is completely ~illed, the valves are shutoff, allowing the material already in each cavity C to expand.
.~
However, because tne shutoff pins in Figure 2 are directly adjacent to the mold cavities at openings OG, no volume of softened, pressurized material remains in direct contact with the material being molded during the cooling and solidification period of the molded articles 12 which could cause the con-tinued slow ingress of material into the cavities C. By the continued utilization of high injection pressure and minimum mold venting, it is possible, in this Figure 2 design to complete and terminate the injection of material into each mold cavity proper prior to its expansion to form a skin. Thus, the creation of the undesirable void spaces is eliminate~
The remainder of the molding cycle is similar to other conventional injection molding operations, as described in-the operation of the mold of Figure 1. After a sufficient cooling period, the mold is opened and the solidified closure 12 is automatically ejected into water or similar refrigerated envi-ronment. Reclosing the mold initiates a repeat of the cycle.
Closures molded by this method of Figure 2, as shown in Figure 8, have been found to exhibit none of the boundary layer-created voids of previous methods. Subsequent usage in liquid product containers has shown that leakage, due to channels in the closure surface has ceased to be a problem. Furthermore, in the present molding method, no material is wasted by solidification in the sprue and runner chamber, thereby reducing molding costs.
The invention being thus described, it will be obvious that the same may be varied in many ways. Such variations are not~
to be regarded as a departure from the spirit and scope of ~he present invention and all such modifications as would be obvious to one skilled in the art are intended to be included within the scope of the following claims.

- 17- ` - `' -

Claims (28)

  1. CLAIMS: 1. A method for making a plastic closure for liquid product containers, the external surface of said closure having an appearance resembling a natural cork closure comprising the steps of:
    providing a mold cavity having the shape of said clo-sure and predetermined internal dimensions; and injecting a strand of expandable plastic material containing a blowing agent into said mold cavity, the cross-sectional dimension of said strand relative to said internal dimensions of said cavity being so selected that said strand collects in said cavity in randomly oriented groups of coils which expand to fill said cavity and the coalesence of said groups of coils during expansion creates randomly oriented grain lines on the surface of said closure which resemble the appearance of natural cork.
  2. 2. The method for making a plastic closure for liquid product containers according to claim 1 wherein said mold cavity is disposed in a sprueless mold and has walls defining the shape of said closure and an entrance orifice in one of said walls and said strand contains a predetermined amount of expandable plastic material-injected directly into said mold cavity through said entrance orifice, and comprising the further step of:
    sealing said entrance orifice immediately when said predetermined amount of material has been injected into said cavity to stop any further flow of, material into said cavity and keeping said entrance orifice sealed until said material expands to form said closure;

    whereby the closure formed has a liquid impervious outer skin and a foamed core with no appreciable void spaces or separations between said outer skin and said foamed core into which said outer skin will collapse when compressed.
  3. 3. The method of claim 1 wherein said plastic material comprises a blend of:

    ethylene-vinyl acetate copolymer having a melt index of about 2.0 to 8.0 and containing vinyl acetate in an amount of about 9 to 25% by weight;
    a blowing agent; and pigment for imparting the color of natural cork to said article.
  4. 4. The method of claim 2 wherein said plastic material comprises a blend of:

    ethylene-vinyl acetate copolymer having a melt index of about 2.0 to 8.0 and containing vinyl acetate in an amount of about 9 to 25% by weight;
    a blowing agent; and pigment for imparting the color of natural cork to said article.
  5. 5. The method of claim 3, the plastic material further including polyethylene homopolymer.
  6. 6. The method of claim 5 wherein the ethylene-vinyl acetate copolymer is present in about 80% by weight and contains about 19% polyethylene by weight, the blowing agent present in about 0.5%
    by weight and the pigment present in about 0.5% by weight.
  7. 7. The method of claims 3 or 4 wherein said blowing agent is azodicarbonamide.
  8. 8. The method of claims 3 or 4 the plastic material further including an ionically cross-linked ethylene-methacrylic acid copolymer.
  9. 9. The method of claims 1 or 2 wherein said plastic material is mixed with a pigment blend, of which at least 5% of the pigment blend is a powdered pigment having a particle size in the range of 40-60 microns.
  10. 10. The method of claims 3 or 4 wherein said pigment blend includes at least 5% of a powdered pigment having a particle size in the range of 40-60 microns.
  11. 11. A method for making a plastic closure for liquid product containers comprising the steps of:
    providing a hot runner mold assembly having a plurality of mold cavities, wherein each cavity includes walls defining the shape of said closure and plurality of a cavity entrance orifice in one of said walls of each cavity;
    injecting a predetermined amount of expandable plastic material having a blowing agent therein directly into each of said mold cavities through said entrance orifice of each cavity; and sealing said entrance orifice immediately when said predetermined amount of material has been injected into said cavity to stop any further flow of material into said cavity and keeping said entrance orifice sealed until said material expands and solidifies to form said closure;
    whereby the closure formed has a liquid impervious outer skin and a foamed inner core with no appreciable void spaces or separations between said outer skin and said foamed inner core into which said outer skin will collapse when compressed.
  12. 12. The method of claim 11 wherein the entrance orifice of each said mold cavities is sealed by mechancial means.
  13. 13. The method of claim 12 wherein the mechanical sealing means comprises valve pins specially designed to fit into the entrance orifice of each mold cavity, said valve pins being actuated by hydraulic or pneumatic means.
  14. 14. A composition for forming a molded plastic article having an external appearance resembling natural cork comprising a blend of:
    ethylene-vinyl acetate copolymer having a melt index of about 2.0 to 8.0 and containg vinyl acetate in an amount of about 9 to 25% by weight;
    a blowing agent; and pigment for imparting the color of natural cork to said article.
  15. 15. The composition of claim 14, wherein the blend further includes polyethylene homopolymer.
  16. 16. The composition of claim 15 wherein the ethylene-vinyl acetate copolymer is present in about 80% by weight and contains about 19% polyethylene by weight, the blowing agent is present in about 0.5% by weight and the pigment is present in about 0.5 by weight.
  17. 17. The composition of claim 14, wherein said blowing agent is azodicarbonamide.
  18. 18. The composition of claims 14, 15 or 17, further including an ionically cross-linked ethylene methacrylic acid copolymer.
  19. 19. The composition of claim 14 wherein said pigment blend includes at least 5% of a powdered pigment having a particle size in the range of 40-60 microns.
  20. 20. A molded plastic closure for liquid product con-tainers having an external appearance resembling natural cork comprising a blend of:
    ethylene-vinyl acetate copolymer having a melt index of about 2.0 to 8.0 and containing vinyl acetate in an amount of about 9 to 25% by weight;
    a blowing agent; and pigment for imparting the color of natural cork to said article.
  21. 21. The closure of claim 20 wherein the closure further includes polyethylene homopolymer.
  22. 22. The closure of claim 21 wherein the ethylene-vinyl acetate copolymer is present in about 80% by weight and contains about 19% polyethylene by weight, the blowing agent is present in about 0.5% by weight and the pigment is present in about 0.5% weight.
  23. 23. The closure of claim 20 wherein said blowing agent is azodicarbonamide.
  24. 24. The closure of claims 20, 22 or 23 further including an ionically cross-linked ethylene methacrylic acid copolymer.
  25. 25. The closure of claim 20 wherein said pigment blend includes at least 5% of a powdered pigment having a particle size in the range of 40-60 microns.
  26. 26. A synthetic cork closure having an external appearance resembling natural cork comprising a blend of:
    expandable plastic material;
    a blowing agent; and pigment blend wherein at least 5% of the blend constitutes a powdered pigment having a particle size in the range of 40-60 microns.
  27. 27. The synthetic cork closure of claim 26, wherein the expandable plastic material is ethylene-vinyl acetate copolymer and the blowing agent is azodicarbonamide.
  28. 28. The product formed by the process of either claims 1,2 or 11.
CA000388118A 1980-10-30 1981-10-16 Method for making a plastic closure for liquid product containers Expired CA1177600A (en)

Applications Claiming Priority (2)

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US202,156 1980-10-30
US06/202,156 US4363849A (en) 1980-10-30 1980-10-30 Foamed thermoplastic resin cork having a natural cork-like appearance and a method of injection molding the cork

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CA1177600A true CA1177600A (en) 1984-11-06

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Cited By (7)

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Publication number Priority date Publication date Assignee Title
FR2799183A1 (en) 1999-10-05 2001-04-06 Bouchages Delage Stopper, especially for wine or spirit bottles, formed from cork particles and open cell foam polymeric binder, having similar structure and mechanical properties to natural cork stoppers
WO2001025103A1 (en) 1999-10-05 2001-04-12 Les Bouchages Delage Bonded cork stopper and method for making same
MD20010345A (en) * 2001-08-17 2003-06-30 Феликс ШЕПЕЛЬ Process for processing of the clary sage Salvia sclarea vegetal mass and application thereof in the treatment of the locomotor apparatus
US7703167B2 (en) 2001-12-06 2010-04-27 Jamak Fabrication-Tex, Llc Squeegee having reduced friction characteristics
MD2193C2 (en) * 2001-12-28 2003-12-31 Анатоль ЕФКАРПИДИС Composition for manufacture of corks
US7997439B2 (en) 2003-06-06 2011-08-16 Jamak Fabrication-Tex, Llc Flexible bakeware having a multi-piece carrier system
MD2404G2 (en) * 2003-10-17 2004-09-30 Уиспак, Сочиетате Ку Рэспундере Лимитатэ Composition for corks manufacturing

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PL141888B1 (en) 1987-09-30
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EP0051277A3 (en) 1983-01-26
ES276981Y (en) 1986-02-16
MA19318A1 (en) 1982-07-01
ES515420A0 (en) 1984-01-16
KR830007377A (en) 1983-10-19
CS241490B2 (en) 1986-03-13
PT73896A (en) 1981-11-01
DE3172058D1 (en) 1985-10-03
NZ198810A (en) 1985-05-31
GR76316B (en) 1984-08-04
IE56507B1 (en) 1991-08-28
BR8106897A (en) 1982-07-13
ATE57665T1 (en) 1990-11-15
EP0156957A3 (en) 1987-10-14
BG50383A3 (en) 1992-07-15
ATE15163T1 (en) 1985-09-15
IL64141A0 (en) 1982-01-31
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US4363849A (en) 1982-12-14
EP0156957A2 (en) 1985-10-09
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ZA817139B (en) 1982-09-29
HU201698B (en) 1990-12-28
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ES8306665A1 (en) 1983-06-01
PL233643A1 (en) 1982-09-27
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EP0051277A2 (en) 1982-05-12
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CS799881A2 (en) 1985-06-13
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ES8402201A1 (en) 1984-01-16
ES276981U (en) 1985-06-16

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