Patent Application
20080197103
The invention relates to closures for containers, especially bottles, comprising a sealing element or closure liner having improved barrier properties. The invention especially relates to sealing elements or closure liners for beverage containers comprising thermoplastic polymer compounds.
Closures made of metal or plastics are used to seal e.g. bottles containing mineral water, juices, carbonated soft drinks and water, beer and other liquid products. The sealing closures, such as a twist crown, a crown cork or a screw cap, for bottles, jars and the like, commonly have an elastic sealing element on their inside facing the container mouth, which sealing element is pressed or clamped between the closure and the container when the closure is fitted and ensures tightness.
While formerly the liners of crown corks or bottle screw closures were predominantly made of press cork which was, if appropriate, also coated with a thin plastics film or thin aluminum foil, today sealing elements are commonly produced completely from synthetic polymer compounds. The sealing element of closures such as crown corks, screw caps and screw lids, which are usually made of metal (such as aluminum) or plastics (such as polyolefin material), often takes the form of a liner adhered to, or placed loose in, the closure.
Such sealing elements or closure liners must meet several requirements, as e.g. good sealing properties, low closing and opening torques in the case of screw-on closures and good adhesion to the cap material to ensure good retention of gases such as carbon dioxide and closure integrity. Moreover, the closures should have a valve or venting effect in case of any excess pressures arising in the container, in particular in beer, lemonade or mineral water bottles, and said venting effect should reliably occur at certain internal pressures. It is also important that the sealing elements or liners are capable of withstanding headloads as encountered in packaging, storage and handling of, e.g., filled bottles, without damage to the liner.
With respect to the requirement of low closing and opening torques it is known, that if a container closure provided with a thermoplastic liner is fitted to the mouth of a container, such as a glass bottle containing a carbonated drink, and the container is stored for a long time, the opening torque of the container closure is increased and it is often difficult for a purchaser to open the closure by hand. As means for reducing the opening torque of container or bottle closures, it has been the practice to use a lubricant or a combination of lubricants.
Typical lubricants used in connection with container closures or liners comprise lubricants having a specific functional group selected from carboxyl, hydroxyl, amide and amino groups or non-polar lubricants. Especially the use of amide type lubricants is widespread. Fatty acid amides have been used for a long time as a lubricant/slip additive for thermoplastic polymers or olefin polymers used in a variety of applications to reduce coefficient of friction (COF). One of the most effective fatty acid amides is erucamide a monounsaturated C22 fatty acid (13-cis-docosenamide). Other saturated amides like behenamide (docosanamide) have been used with less impressive COF results due to the absence of the cis-double bond at the center of erucamide. Generally, the amide lubricant package is a mixture of unsaturated and saturated amides ranging from 14 to 22 carbons. Many of these lubricant packages are proprietary. Unsaturated amides contained in these additive packages are accessible for oxidation reactions, e.g. with ozone. However, ozone technology has proven very useful in the beverage market since the earliest 20th century. Recent changes in legislature and industry guidelines have increased the need for ozone in the beverage industry in general. In bottled water plants, ozone can be used to disinfect product water to comply with International Bottled Water Association (IBWA) guidelines while leaving no residual taste or odor.
One of the most important demands on sealing elements or liners is in the barrier properties of the sealing elements or liners. Ideally, the sealing elements or liners should prevent any substances which would affect aroma or taste from entering the container or bottle. Moreover, it is clear that the liner material should have no flavor of its own which it can impart to the contents of the container. Changes of the taste of the container's contents are mainly due to oxidative aroma changes after the entry of oxygen, and changes of taste caused by the entry of organic flavor-affecting compounds. The general class of compounds contributing to undesirable off-taste comprise in particular aromatic substances such as benzenes or also phenyl ethers, for instance chloroanisoles. The latter are e.g. contained in wood pallets and cardboard boxes used for the transport or storage of beverage containers. Moreover, it is assumed that oxidative aroma changes are also caused by aldehydes or ketone products resulting e.g. from the oxidation of unsaturated additives or polymer monomers during the manufacture of the sealing element, the ozone sterilization of the beverage or during storage of the filled container or bottle. More precisely, the formation of oxygen containing decomposition compounds can be caused by thermodegradation of the closure composition during the compounding phase at elevated processing temperatures and later when the closure compound is converted into the closure shell or liner as well as by chemically active materials like lubricant compounds which engage in surface reactions with ozone, oxygen and peroxide on the closure surface.
In this context, it was found that in a closure system, certain chemically unsaturated additives and polymer monomers are problematic, particularly where ozone sterilization of the beverage is used. Ozone reacts with unsaturated compounds forming unstable organic ozonides, which decompose rapidly into oxygen compounds, such as aldehydes, ketones, and peroxides, or react rapidly with oxidizing or reducing agents. Additives like lubricants, which function at the surface of the polymer, are traditionally migratory and migration occurs over time. The surface of polymeric shells and liners become sources of chemical precursors susceptible to ozonolysis from residual ozone or autoxidation from oxygen.
As described above, for example amides like erucamide, which are used as lubricants or for providing the desired opening torque, are unsaturated additives, which are susceptible to oxidizing agents. Ozone or other oxidizing agents react with the double bond of unsaturated amides like erucamide, to form two different aldehydes. The ozonolysis products resulting from erucamide are nonanal and as a second product the other 13 carbon amide with an aldehyde group on the opposite end. However, the formation of such oxidation products and the decomposition of lubricants is undesirable, since the decomposition products could contribute to undesirable off-taste.
Furthermore, the closures or the barrier properties of the sealing elements or liners should also prevent the migration of flavors or volatile flavoring substances from the inside of the container or the bottle. The escape of the volatile flavoring substances e.g. during storage of the filled containers causes a flat taste of the beverage, which is of course very undesirable.
Beverage manufacturers have long searched for improved barrier materials. The sealing elements or liner materials known in the art, having at least some barrier properties, typically comprise polyvinylchloride, polyethylene or mixtures of these substances with vinylacetate or vinylacetate-ethylene copolymers. Although the use of PVC or other halogen-containing plastics leads to difficulties in the disposal and neutralization of the used container, PVC is still used in practice. It is also known in the art to use oxygen-bonding substances (oxygen scavengers) for improving the barrier properties of closures. These substances are reducing agents, intended to react with oxygen in the sealing element so that the oxygen does not reach the container contents. However, oxygen scavengers often do not have perfect sensory properties and they lose their effect with time.
An important improvement in the barrier properties of container closures is disclosed in U.S. Pat. No. 5,731,053. According to U.S. Pat. No. 5,731,053 the barrier properties of container closures can be improved by using a sealing element or liner, which is formed by placing and in-shell or out-shell molding, a molten piece of a polymer liner compound in the closure, wherein the molded sealing element or liner comprises a heterogeneous blend of butyl rubber and thermoplastic polymer. In the blend, the thermoplastic polymer, which preferably is HDPE, forms a continuous phase in the solid molded state, wherein the butyl rubber is contained in discrete separate phases or areas. In other words, the polymer liner compound according to U.S. Pat. No. 5,731,053 provides a pseudolaminate structure, with areas or layers enriched in butyl rubber adjoining or even alternating with areas or layers enriched in thermoplastic polymer, said layers being discrete enough to form an overall heterogeneous structure, and generally a structure with two separate solid phases.
In WO 97/33044 the use of cyclodextrin in rigid or semi-rigid cellulosic sheets is disclosed. The cyclodextrin acts as a barrier or a trap for contaminants. The barrier properties of the material disclosed in WO 97/33044 are based on entrapment of the respective permeants in the internal hydrophobic space of the cyclodextrin molecule. The cyclodextrin material is generally used in the form of a compatible, derivatized cyclodextrin. According to WO 97/33044 the preferred cyclodextrin is a derivatized cyclodextrin having at least one substituent group bonded to the cyclodextrin molecule.
According to the present invention the incorporation of cyclodextrin materials, preferably compatible derivatized cyclodextrin materials into polymer liner compounds or sealing elements leads to closure elements or sealing gaskets having improved barrier properties.
According to the present invention a closure element comprising a sealing element or polymer liner compound having improved barrier properties is provided, the sealing element or compound comprising
(a) a thermoplastic polymer; and
(b) an effective absorbing amount of a cyclodextrin material; wherein the cyclodextrin material is selected from the group comprising α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, derivatives of α-cyclodextrin, β-cyclodextrin and γ-cyclodextrin and mixtures thereof.
According to the present invention it is preferred, that the cyclodextrin material is dispersed in the thermoplastic polymer. It is especially preferred that the cyclodextrin material has pendant moieties or substituents that render the cyclodextrin more compatible with the thermoplastic polymer.
Preferably, the amount of cyclodextrin material in the sealing element is in the range from 0.01 to 5 wt-%, preferably from 0.1 to 1 wt-%, based on the thermoplastic polymer in the sealing element.
According to one preferred embodiment of the present invention the thermoplastic polymer comprises a polyolefin, preferably a polyethylene and more preferably high density polyethylene (HDPE). The cyclodextrin material having pendant moieties or substituents that render the cyclodextrin more compatible with the thermoplastic polymer preferably contains substituents having a silyl ether group, an alkyl ether group and/or an alkyl ester group. Suitable alkyl ester substituents comprise acetyl moieties, propyl moieties and/or butyl moieties. Preferred alkyl ether or silyl ether substituents comprise methyl moieties, ethyl moieties, propyl moieties and/or butyl moieties. It has been found that it is especially advantageous to incorporate a γ-cyclodextrin having acetyl moieties and preferably a γ-cyclodextrin having three acetyl-groups per cyclodextrin unit into the sealing element. However, also the corresponding β-cyclodextrins having acetyl moieties show excellent barrier or retention properties.
Furthermore, it has been found that the incorporation of cyclodextrin into polymer liner compounds or sealing elements comprising a heterogeneous blend of a rubber component, preferably butyl rubber and a thermoplastic polymer, especially HDPE, leads to closure elements or sealing gaskets having improved barrier properties. Preferred sealing elements comprising a heterogeneous blend of butyl rubber and HDPE as well as methods for manufacturing the corresponding closure elements are disclosed in U.S. Pat. No. 5,731,053.
In this context, it has been found, that it is generally advantageous if the cyclodextrin is dispersed in the continuous thermoplastic polymer phase, which preferably is a HDPE phase, which in the solid molded state further embeds or otherwise encloses the butyl rubber enriched areas or layers. Alternatively, the cyclodextrin material is contained in the aforementioned butyl rubber phase. While a polymer liner compound comprising a heterogeneous blend of thermoplastic polymer and butyl rubber having the cyclodextrin dispersed in the thermoplastic polymer often shows excellent barrier properties, the incorporation of the cyclodextrin material into the butyl rubber phase sometimes shows much less effect with respect to the barrier properties of the liner or closure element. Incorporation of the cyclodextrin in the butyl rubber is therefore generally less preferred.
It is also preferred, according to one embodiment of the present invention, to provide the cyclodextrin-containing polymer liner compound with one or more additional layers comprising a thermoplastic polymer and an effective absorbing amount of a cyclodextrin material, preferably of a compatible derivatized cyclodextrin material, dispersed in the thermoplastic polymer.
Said additional layer is preferably arranged on the inner side of the closure element being in contact with the contents of the container closed with said closure element.
According to one preferred embodiment, the diameter of the additional liner layer is smaller than the diameter of the polymer liner compound comprising e.g. the heterogeneous blend, so that the additional layer material fits into the aperture of the mouth of a bottle and does not extend to the area clamped between the vessel mouth and the closure, so that it is not exposed to headloads.
According to a further embodiment the sealing element or liner according to the present invention can have a laminated structure e.g. comprising at least one layer containing a thermoplastic polymer and an effective absorbing amount of a cyclodextrin material and/or can be coated with a thermoplastic polymer and an effective absorbing amount of a cyclodextrin material, preferably of a compatible derivatized cyclodextrin material, dispersed in the thermoplastic polymer.
The sealing element or polymer liner compound of the present invention meets the requirements to sealing elements or closures as mentioned above and additionally provides improved barrier resistance to permeants, such as aromatic substances, especially trichloroanisole, aldehydes or ketones and/or impurities from the polymer.
Also decomposition compounds formed e.g. during compounding or processing of the sealing element or liner are trapped or complexed by the cyclodextrin, which is added during the compounding of the liner composition. In other words, the cyclodextrin also functions during conversion processes, or when the liner composition is in a solid state by trapping impurities, which diffuse through the polymer matrix.
Moreover, it was found that the addition of cyclodextrin to the liner composition also results in the reduction of contamination with oxidative decomposition products resulting from the lubricant. Without wishing to be bound to any theory, it is assumed that an inclusion complex of the susceptible unsaturated amide is formed by adding cyclodextrin during the compounding step thereby protecting the unsaturated amides from ozonolysis or other autoxidation reaction mechanisms and producing a reduced amount of undesirable aldehyde and amide migrants in the contact beverage.
Analysis of ozonated water which has contacted closure materials containing lubricants or slip additives as erucamide has shown a significant reduction of nonanal (and other aldehydes which may arise for the various unsaturated amides) and the corresponding amides. It is assumed that the addition of cyclodextrin to the liner composition leads to the formation of an inclusion complex resulting in an important modification of the properties of the unsaturated compound. This modification probably influences the reactivity of the double bond of the unsaturated compound or amide resulting in a reduction of oxidized compounds. In any case a significant reduction of undesirable decomposition compounds resulting from the unsaturated lubricant is observed.
Moreover, the ingress of oxygen is reduced or prevented by adding cyclodextrin, especially compatible derivatized cyclodextrin, to the thermoplastic polymer e.g. of the heterogeneous blend of the liner. The sealing element or liner compound according to the present invention also prevents or dramatically reduces the loss of flavors or volatile flavoring substances from the inside of the container or the bottle through the cap.
The preferred cyclodextrin derivative is selected, based on the functional group compatibility with the polymer, the thermal stability of the cyclodextrin material and the cyclodextrin's ability to form an inclusion complex with volatile substances. The cyclodextrin derivative can contain one substituent on the single primary carbon hydroxyl and/or one substituent on one or both of the secondary carbon hydroxyls.
Cyclodextrin is commonly produced by a highly selective enzymatic synthesis. It generally consists of six, seven, or eight glucose monomers arranged in a donut shaped ring, which are denoted alpha-, beta-, or gamma-cyclodextrin, respectively. The specific coupling of the glucose monomers gives the cyclodextrin a rigid, truncated conical molecular structure with a hollow interior of a specific volume. This internal cavity is a key structural feature of the cyclodextrin, providing the ability to complex molecules (e.g., aromatics, alcohols, halides and hydrogen halides, carboxylic acids and their esters, etc.). The complexed molecule must satisfy the size criterion of fitting at least partially into the cyclodextrin internal cavity, resulting in an inclusion complex.
According to the present invention the cyclodextrin material is selected from α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, derivatives of α-cyclodextrin, β-cyclodextrin and γ-cyclodextrin and mixtures thereof. Also, according to the present invention a preferred cyclodextrin derivative inter alia is selected based on the functional group compatibility with the polymer on one hand and the cyclodextrin's ability to form an inclusion complex with targeted substances on the other hand.
According to the present invention it is preferred that the cyclodextrin material is compatible with the liner material. According to the present invention, “compatible” means that preferably the cyclodextrin material can be uniformly dispersed into the melt polymer, can retain the ability to trap or complex permeant materials or polymer impurity, and can reside in the polymer without substantial reductions in barrier properties.
Moreover, the cyclodextrin's internal cavity size (i.e., α, β, γ) must be considered and the derivative functional group modification must be suitable for forming an inclusion complex with targeted volatiles or impurities. To achieve a specific result, more than one cavity size and functional group may be necessary. For example, blends of a and/or P that contain γ-cyclodextrin have greater complexation efficiencies for some volatile substances than without γ-cyclodextrin. Computational modelling has shown that the type and number of functional groups on the ring provide different complexation energies for specific ligands (i.e., complexed substances). These complexation energies (ΔEsteric and ΔEelectrostatic) can be calculated for a specific derivative, cavity size and ligand. Hence, inclusion complexation is predictable to some extent. For example, the inventors found out that acetylated α-cyclodextrin, β-cyclodextrin and acetylated γ-cyclodextrin are very effective cyclodextrin derivatives for improving the barrier properties of the inventive closure element or polymer liner compound.
The compatible cyclodextrin derivative according to the present invention is a compound substantially free of an inclusion complex. For this invention, the term “substantially free of an inclusion complex” means that the quantity of the dispersed cyclodextrin material in the bulk polymer contains a large fraction having cyclodextrin free of a polymer contaminant, a permeant or other inclusion compound in the interior of the cyclodextrin molecule. A cyclodextrin compound is typically added and blended in the bulk polymer without any inclusion compound but some complexing can occur during manufacture. Such complexing can occur as polymer impurities and degradation materials become the inclusion compound in a cyclodextrin inclusion complex.
In principle, the preferred cyclodextrin derivative can contain one substituent on the single primary carbon hydroxyl and one substituent on one or both of the secondary carbon hydroxyls. Because of the geometry of the cyclodextrin molecule, and the chemistry of the ring substituents, the hydroxyl groups are not equal in reactivity. However, with care and effective reaction conditions, the cyclodextrin molecule can be reacted to obtain a derivatized molecule having a certain number of hydroxyl groups derivatized with a single substituent type. Further directed synthesis of a derivatized molecule with two different substituents or three different substituents is also possible. These substituents can be placed at random or directed to a specific hydroxyl. For the purposes of this invention, a broad range of pendant substituent moieties can be used on the molecule. These derivatized cyclodextrin molecules can include alkyl ether, silyl ether, alkyl ester, including cyclodextrin esters such as tosylates, mesylate and other related sulfo derivatives, hydrocarbyl-amino cyclodextrin, alkyl phosphono and alkyl phosphato cyclodextrin, imidazoyl substituted cyclodextrin, pyridine substituted cyclodextrin, hydrocarbyl sulphur containing functional group cyclodextrin, silicon-containing functional group substituted cyclodextrin, carbonate and carbonate substituted cyclodextrin, carboxylic acid and related substituted cyclodextrin and others.
Acyl groups that can be used as compatibilizing functional groups include acetyl, propionyl, butyryl, trifluoroacetyl, benzoyl and acryloyl groups. The formation of such groups on the hydroxyls of the cyclodextrin molecule involve well known reactions. The acylation reaction can be conducted using the appropriate acid anhydride, acid chloride, and well known synthetic protocols.
According to the present invention suitable cyclodextrin derivatives also can be obtained by reacting a cyclodextrin molecule with a functionalized polyolefin in which the cyclodextrin is grafted onto the functionalized polyolefin. The hydroxyl functionality of the cyclodextrin reacts with the anhydride or epoxide component of the functionalized polyolefin to form a reaction product. Useful functionalized polyolefins are maleated polyethylene and polypropylene (Orevac™ and Lotryl™ from ATOFINA, Plexar® resins from EQUISTAR, Fusabond® resins from DuPont, OP™ resins from MÂNAS, and EXXELOR™ from Exxon/Mobil), functionalized EP, EVA and EPDM, ethylene-octene copolymers, ethylene-n butyl acrylate-maleic anhydride, ethylene-ethylacrylate-maleic anhydride terpolymers and copolymers of ethylene-glycidyl methacrylate and the like.
Cyclodextrin materials can also be reacted with alkylating agents to produce an alkylated cyclodextrin. Typical examples of alkyl groups useful in forming the alkylated cyclodextrin include methyl, propyl, benzyl, isopropyl, tertiary butyl, allyl, trityl, alkyl-benzyl and other common alkyl groups. Such alkyl groups can be made using conventional preparatory methods, such as reacting the hydroxyl group under appropriate conditions with an alkyl halide, or with an alkylating alkyl sulfate reactant.
Tosyl (4-methylbenzene sulfonyl), mesyl (methane sulfonyl) or other related alkyl or aryl sulfonyl forming reagents can also be used in manufacturing compatibilized cyclodextrin molecules.
Sulfonyl containing functional groups can be used to derivatize either of the secondary hydroxyl groups or the primary hydroxyl group of any of the glucose moieties in the cyclodextrin molecule. The reactions can be conducted using a sulfonyl chloride reactant that can effectively react with either primary and secondary hydroxyl. The sulfonyl chloride is used at appropriate mole ratios depending on the number of target hydroxyl groups in the molecule requiring substitution. Sulfonyl groups can be combined with acyl or alkyl groups.
The sulfonyl derivatized cyclodextrin molecule can be used to generate the amino derivative from the sulfonyl group substituted cyclodextrin molecule via nucleophilic displacement of the sulfonate group by an azide-ion. The azido derivatives are subsequently converted into substituted amino compounds by reduction. Large numbers of these azido or amino cyclodextrin derivatives have been manufactured. Examples of nitrogen containing groups that can be useful in the invention include acetylamino groups (—NHAc), alkylamino including methylamino, ethylamino, butylamino, isobutylamino, isopropylamino, hexylamino, and other alkylamino substituents. The amino or alkylamino substituents can further be reactive with other compounds that react with the nitrogen atom to further derivatize the amine group.
The cyclodextrin molecule also can be substituted with heterocyclic nuclei including pendent imidazole groups, histidine, imidazole groups, pyridino and substituted pyridino groups.
Cyclodextrin derivatives can be modified with sulfur containing functional groups to introduce compatibilizing substituents onto the cyclodextrin. Apart from the sulfonyl acylating groups mentioned above, sulfur containing groups manufactured based on sulfhydryl chemistry can be used to derivatize cyclodextrin. Such sulfur containing groups include methylthio (—SMe), propylthio (—SPr), t-butylthio (—S—C(CH3)3), hydroxyethylthio (—S—CH2CH2OH), imidazolylmethylthio, phenylthio, substituted phenylthio, aminoalkylthio and others. Based on the ether or thioether chemistry set forth above, cyclodextrin having substituents ending with a hydroxyl aldehyde ketone or carboxylic acid functionality can be prepared. Cyclodextrin with derivatives formed using silicone chemistry can contain compatibilizing functional groups.
Cyclodextrin derivatives with functional groups containing silicone herein called silicon ether can be prepared. Silicone groups generally refer to groups with a single substituted silicon atom or a repeating silicone-oxygen backbone with substituent groups. Typically, a significant proportion of silicone atoms in the silicone substituent bear hydrocarbyl (alkyl or aryl) substituents. Silicone substituted materials generally have increased thermal and oxidative stability and chemical inertness. Further, the silicone groups increase resistance to weathering, add dielectric strength and improve surface tension. The molecular structure of the silicone group can be varied because the silicone group can have a single silicon atom or two to twenty silicon atoms in the silicone moiety, can be linear or branched, have a large number of repeating silicone-oxygen groups and can be further substituted with a variety of functional groups. For the purposes of this invention the simple silicone containing substituent moieties are preferred including trimethylsilyl, mixed methyl-phenyl silyl groups, etc.
In preferred embodiments of the present invention the cyclodextrin material comprises substituents having a silyl ether group, an alkyl ether group and/or an alkyl ester group. According to the present invention the alkyl ester substituents preferably comprise acetyl moieties, propyl moieties and/or butyl moieties, the alkyl ether substituents preferably comprise methyl moieties, ethyl moieties and/or propyl moieties and the silyl ether substituents preferably comprise methyl moieties, ethyl moieties, propyl moieties and/or butyl moieties.
It has been found by the inventors of the present invention that residual contaminants contained in sealing element and closure liner materials, referred to as migrants, can be complexed by cyclodextrins during the compounding phase of manufacturing. The importance of complexing mobile substances that originate within the closure structure is to prevent their migration from the closure structure to the content of the container, e.g. the beverage. Sealing element and closure liner migrant reduction can be achieved by dispersing active cyclodextrin compounds and preferably cyclodextrin compounds with a moisture content less than 2,000 ppm in the sealing and liner materials during the compounding phase of manufacturing. After compounding, the composition retains a residue comprising cyclodextrin complexes and active cyclodextrins without complexes. Residual volatile reduction occurs during compounding when cyclodextrins complex migrants that are inherent in polymer materials or are produced by thermooxidation, photodegradation and photooxidation of the polymer materials, processing aids, etc. and subsequently reside in the closure structure. A new non-volatile, complex with the migrants is formed via the cyclodextrin thereby preventing their release and sensory detection.
The moisture content in the cyclodextrin should be less than 5,000 ppm by weight. Cyclodextrin containing very high moisture levels will not readily form complexes with plastic oxidation products or other resin impurities during the extrusion-processing phase. However, moisture does not affect the complex formation in the sealing element.
Polymers used in this invention can also contain other additives, which do not adversely affect the performance of the cyclodextrin, such as catalysts, stabilizers, processing aids, fillers, pigments, dyes and antioxidants.
Commercially available equipment, used in the manufacture of sealing elements, especially polymer liner compound may be used to make sealing elements or polymer liner compounds according to the present invention.
The inventive composition comprising at least one thermoplastic polymer and a cyclodextrin material is created by physically mixing and dispersing the minor constituent, preferably a modified cyclodextrin, into the major constituent, the polymer, e.g. by extrusion. Suitable extrusion techniques include the so-called “direct incorporation” and “masterbatch addition.” In either method it is preferred to use twin-screw co-rotating segmented barrel extruders. Of course it is also possible to use counter rotating or single screw extruders for mixing or dispersing the cyclodextrin material into the polymeric material. It is clear that the modified cyclodextrin can be added individually or in combination with other suitable additives or adjuvants. After mixing or dispersing the cyclodextrin material into the polymeric material the resulting molten plastic is e.g. pumped out of the extruder and pelletized.
There are several methods for incorporating modified cyclodextrin into polymer liner compounds comprising a heterogeneous blend of butyl rubber and a thermoplastic polymer, especially HDPE. For example, it has been found, that a cyclodextrin-containing heterogeneous blend can be obtained by feeding a masterbatch of modified cyclodextrin and e.g. the HDPE resin into the feed section of an extruder containing the other liner material, which preferably is butyl rubber. The masterbatch can e.g. be prepared by using the direct incorporation method mentioned above. The ratio of the HDPE resin to butyl rubber in the resulting liner is easily adjustable by using the aforementioned process.
The production of the closure element with liner or sealant usually uses the so-called “in-shell” molding technique. According to said known process the granules of the compound are fed into an extruder which melts and pumps the molten product to an orifice. External of this orifice is a rotating blade which cuts the extrudate into a pellet. In in-shell molding each of these pellets, which each weigh approximately 180 to 200 mg, is individually flipped or placed onto the inner surface of a crown cork, an aluminum or a plastic closure which forms the body of a screw cap. The still plastic polymer compound is spread over this inner surface or centre panel by a die punch and stamped to form a thin, approximately disc-like molding. At the same time, it is possible to form any annular projections of the molding which may be desired, which embrace the bottle rim in the mouth region when the cap is fitted.
In out-shell molding, the pellet is formed outside of the closure, on a “puck,” and is then placed in the closure and molded into its final shape.
For some specific applications as for example the sealing of beer bottles, it is preferred to provide the cyclodextrin-containing polymer liner compound with one or more additional layers comprising a thermoplastic polymer and a compatible derivatized cyclodextrin dispersed in the thermoplastic polymer. As mentioned above, the additional layer preferably is arranged on the inner side of the liner, preferably having a diameter which is smaller than the diameter of the polymer liner compound comprising the heterogeneous blend, so that the additional layer material contacts the inner side of the neck of the bottle.
A laminated container sealing element or polymer liner compound can be made by any conventional method. An additional liner layer e.g. can be supplied by injection molding on the heterogeneous blend-liner (additional barrier polymer inside of the cap). Such a multi-step formation can also be done on a single machine having the appropriate internal working components for such injection molding operations.
According to the present invention it is also contemplated to apply coating compositions containing a thermoplastic polymer and an inventive cyclodextrin derivative in order to improve the barrier properties of the coated liner. Coating machines commonly apply a liquid composition containing a film forming material, additives that can help form and maintain the coating composition along with the effective amount of the cyclodextrin material.
The foregoing discussion illustrates various exemplary embodiments of the application and barrier properties of sealing compounds and closure elements of the present invention. The following examples and data further exemplify the present invention.
The permeant concentration gradient shown above can be simulated experimentally in the laboratory making it possible to measure barrier improvement of cyclodextrin-containing sealing compounds and closure elements.
The following procedures were used to measure improved closure material barrier to organoleptic permeants, such as, aliphatic aldehydes, unsaturated aldehydes and ketones and trichloroanisole.
Permeation across a barrier can be explained where the membrane at time zero (t0) is initially free from permeant vapor. The penetrant pressure p2 at the upstream face of the membrane is increased giving a concentration in the surface layer c2 (see
The permeation test method used to evaluate organic barrier involves experimental techniques to measure organic molecule transport through a closure material test disc, using a static concentration gradient. The schematic assembly of the permeation cell is shown in
A monolayer disc of the liner material and various organic test permeants were used to evaluate barrier performance. High-resolution gas chromatography was used to qualitatively and quantitatively measure the cumulative downstream penetrant concentration p1 at a specified time. The invention shows cyclodextrin dispersed into a liner material then formed into a disc reduces organic vapor transport, compared to the same material without cyclodextrin, both measured in static test cells (
Monolayer discs and test permeants (i.e., aldehydes and ketones) were initially evaluated to create a permeation profile. The time when p2=p1 is determined for each liner material. The midpoint of the steady state profile or time t1/2 is established for each liner material without cyclodextrin. An example closed-volume static permeation profile illustrating p2=p1 and t1/2 is provided in
Liner materials were compounded with triacetyl gamma cyclodextrin (TA-γ-CD) using a laboratory scale batch mixer. Triacetyl gamma cyclodextrin was dry blend mixed with the resin prior to compounding on a weight to weight basis of 0.30% and 0.4% triacetyl gamma cyclodextrin. The triacetyl gamma cyclodextrin was manufactured by Wacker Biochem Corporation, Adrian, Mich.
A Brabender fusion bowl or batch mixer was used to compound the liner materials. The fusion bowl consists of two counter rotating roller blades in a number eight-shaped bowl. Control liner material (no CD) and liner material+CD material was run using the procedure described below.
The fusion bowl temperature was set at 125° C. With the rpm of the blades set at 60, 40 grams of resin was dropped into the bowl. All the material is fed into the bowl over a 30-second period. After another 6.5 minutes of processing, the screw speed was reduced to zero and the molten resin is removed and collected on aluminum foil. The bowl and the roller blades were thoroughly cleaned before starting the next run.
Liner Material Disc Preparation. Several grams of compounded liner material were placed into an Atlas lab-mixing molder. The mold was heated to 175° C., the resin mixed to a molten state, and then the resin was injected into the heated (85° C.) mold. The dimensions of the mold cavity are 1.75-cm×4.45-cm×0.10-cm thick. A 1.27-cm diameter punch is used to cut two discs from the molded part for static permeation testing.
Organic Vapor Permeation. The permeation method involves experimental techniques to measure organic molecule transport through a polymer packaging structure, using a static concentration gradient. High-resolution gas chromatography (HRGC) operated with a flame ionization detector (FID) or with electron capture detection (ECD) is used to measure the cumulative downstream penetrant concentration at time t1/2.
Apparatus. Disc samples (˜1,000 μm thick×1.27 cm diameter and weighing approximately 125 mg) were tested in a closed-volume vapor permeation device (refer to
The test disc is placed into the upper cell; the cell is assembled using an o-ring to firmly seal the test disc and screws to pull upper and lower cells together. Next, the upper cell is capped with a Teflon® faced butyl rubber septa and aluminum crimp-top. Two permeation standards are prepared. The first permeant standard contains octanal, nonanal, trans-2-nonenal and 1-octen-3-one, and the second permeation standard contains 2,4,6-trichloroanisole. All of the permeants are dispersed in a deionized water/surfactant mixture. The permeant water/surfactant mixture is injected into the lower cell providing a concentration p2 at to shown in Tables 2 to 6. Individual permeant concentrations p2 in the lower cell are expressed in parts per million μL/L (vol./vol.) using gas law conversion. Then the lower cell is immediately capped with Teflon® faced butyl rubber septa and aluminum crimp-top.
Aldehydes and Ketone. This method involves experimental techniques designed to simultaneously measure the flux of co-permeants across the liner material test disc. The test methodology simulates accelerated shelf-life testing conditions by using an elevated cell storage temperature of 50° C.
HRGC operated with a FID was used to measure the change in the cumulative penetrant concentration at time t1/2, in the upstream cell. At time t1/2, a sample was collected by solid phase microextraction (SPME) from the upper cell and analyzed by HRGC/FID. Individual permeant concentrations were determined from calibration standards and measured in nL/L or parts per billion (vol./vol.) using gas laws.
Test cells were prepared and analyzed in triplicate. Tables 2 and 3 contain four permeants, the concentration p2 of each of the permeants in the lower cell at t=0, and the concentration p1 of each of the permeants in the upper cell at time t1/2 or 6-hours in the control and the triacetyl gamma cyclodextrin (TA-γ-CD) samples.
Trichloroanisole. HRGC operated with an ECD was used to measure the change in the cumulative trichloroanisole concentration at time t1/2 in the upstream cell. At time t1/2, a sample was collected by solid phase microextraction (SPME) from the upper cell and analyzed by HRGC/ECD. The trichloroanisole concentration is determined from calibration standards and measured in pL/L or parts per trillion (vol./vol.) using gas laws. Test cells are prepared and analyzed in triplicate. Tables 4 to 6 contain the concentration p2 of TCA in the lower cell at t=0, and the concentration p1 of TCA in the upper cell at time t1/2 in the control and the triacetyl gamma cyclodextrin (TA-γ-CD) samples.
Test cells were prepared and analyzed in triplicate. Tables 4 and 6 contain 2,4,6-trichloroanisole permeant, the concentration p2 of each of the permeants in the lower cell at t=0, and the concentration p1 of each of the permeants in the upper cell at time t1/2 (6-hours for Svelon and Polyliner, and 16-hours for Oxylon) in the controls and the triacetyl gamma cyclodextrin (TA-γ-CD) samples.
The data in Tables 2 to 6 show a low loading of cyclodextrin material having compatible pendant groups can provide excellent mass flux reduction in sealing compounds and liner materials. These data show that the sealing elements or liners according to the present invention provide excellent barrier properties and organic permeants reductions.
The following procedures were used to measure the reduction or complexation of residual volatiles in liner materials.
Svelon® 855 was compounded with triacetyl beta cyclodextrin using a laboratory scale batch mixer. Triacetyl beta cyclodextrin (moisture content <2,000 ppm by weight) was dry blend mixed with the resin prior to compounding on a weight to weight basis of 0.40% triacetyl beta cyclodextrin. The cyclodextrin is dried at 105° C. for a minimum of 6 hours at 1″ Hg vacuum.
A Brabender fusion bowl or batch mixer was used to compound the Svelon® 855+CD. The fusion bowl consists of two counter rotating roller blades in a number eight-shaped bowl. A control Svelon®855 (no CD) and the Svelon® 855+CD material was run using the procedure described below.
The fusion bowl temperature was set at 125° C. With the rpm of the blades set at 60, 40 grams of resin is dropped into the bowl. All the material is fed into the bowl over a 30-second period. After another 6.5 minutes of processing, the screw speed is reduced to zero and the molten resin is removed and collected on aluminum foil. The bowl and the roller blades are thoroughly cleaned before starting the next run.
Compounded Svelon®855 material is milled into shavings having ˜20 um thickness for residual resin volatiles testing.
Residual Resin Volatiles. Volatile compounds in the Svelon® 855 samples out-gas into the vial's headspace during confinement. These volatiles are then purged from the vial's headspace and the individual components subsequently identified and quantitated by dynamic headspace high-resolution gas chromatography/mass spectrometry (DH HRGC/MS). Seventy-six (76) specific compounds quantitated in the DH HRGC/MS method are combined into ten broad chemical families (i.e., aliphatic alcohols, aliphatic aldehydes, aromatic aldehydes, unsaturated aldehydes, saturated ketones, alpha unsaturated ketones, aromatics, alkanes, alkenes and acetates) typically associated with off-odor/flavor compounds.
A 2.00+/−0.02 g sample is placed into a 22-ml glass headspace vial. The vial is capped using a Teflon faced septa and aluminum crimp-top. Residual resin volatiles are desorbed from the sample into the headspace by heating the vial at 85° C. for 24-hours. At the end of the time interval, the sample is removed from the controlled environment to a purge and trap sampler interfaced via a jet separator to the mass spectrometer. Mass spectra from the sample total ion chromatograms are searched against an in-house reference spectra file of the seventy-six compounds. Quantitation is carried out with two internal standards and two surrogate standards, all added prior to sample purge. The analytical results (compounds are expressed in nanograms per gram of resin or parts per billion) are provided in Table 7.
When a commercial closure liner material (Svelon® 855) is analyzed by gas chromatography for mobile migrant contaminants, it is shown to contain a very complex mixture of volatiles. Over fifty individual compounds are detected chromatographically. These residual volatile materials are principally branched alkanes, alkenes and cycloalkanes to a smaller number of organoleptic compounds such as saturated and unsaturated aldehydes and substituted aromatic compounds.
The largest chemical families represented by Svelon® 855 residual volatiles are aromatic (ten individual compounds) and alkanes (three individual compounds). Saturated and unsaturated aldehydes and the saturated ketone families contained only a single compound each. In all, sixteen of the seventy-six compounds were identified above the estimated quantitation level of the method—generally low parts per billion for most of the listed compounds.
The organoleptic compounds of most interest in Table 7 are the aldehydes (acetaldehyde and acrolein) and to a lesser extent styrene and alpha methylstyrene. Acetaldehyde is the one of the larger analytes in the Svelon® 855 and generally associated with off-flavor in bland beverages such as mineral water. Further acetaldehyde is a very mobile contaminant in the resin. The aromatic and alkane family compounds have significantly less odor and taste impact. The compound(s) and their off-odor/flavor impact is dependent on the specific beverage or container content.
Triacetyl beta cyclodextrin (TA-β-CD) shows the best reduction of Svelon® 855 residual resin volatiles. Using DH HRGC/MS (Dynamic Headspace High-Resolution Gas Chromatography/Mass Spectrometry) to measure residual volatiles, the total volatile compounds (all sixteen compounds detected in the 76 compound list) reduction is 38% for an admix of 0.4% TA-β-CD.
Specific organoleptic compounds (e.g., acetaldehyde and acrolein) present in large amounts were greatly reduced by TA-β-CD. Acetaldehyde and acrolein were reduced by 45% and 69% respectively. Styrene and alpha methylstyrene were reduced 31% and 30% respectively. Acetone, not considered an organoleptic compound, was reduced by 46%. The more difficult resin volatiles to reduce are in the aromatic and alkane families; smaller reductions of 29% and 21% were achieved for the combined compounds in the aromatic and alkane families, respectively.
The following procedures were used to measure the reduction of the contamination with oxidative decomposition products of unsaturated lubricants:
A liner composition was tested comprising low density polyethylene (LDPE). Molded liner compositions were compounded with and without cyclodextrin materials [maleic anhydride grafted alpha cyclodextrin copolymer (MA Graft α-CD), triacetyl alpha cyclodextrin (TA α-CD) and alpha cyclodextrin (α-CD)] and immersed in deionized water containing ozone inside glass bottles, which were sealed with aluminum faced metal screw cap closures. The bottles containing the liner compositions were stored at 40° C. for 7 days. At the end of the accelerated storage period, the aqueous contents were solvent extracted, concentrated and then analyzed.
Masterbatch Materials. α-CD, triacetyl α-CD and α-CD grafted LDPE were individually compounded into masterbatches. The three masterbatches and closure liner composition (Polyliner 461, DS-Chemie, Bremen, Germany) were compounded to provide an α-CD loading of 0.50 wt.-%. The final let down liner compositions with CD polyolefin masterbatch compositions were further prepared prior to accelerated ozonated water storage.
The ethylene-maleic anhydride copolymer/LDPE was compounded with a stoichiometric weight loading of unmodified α-CD (2.78 wt-%) using a Brabender Plasticorder Mixing Bowl forming the masterbatch. Two masterbatch samples of LDPE resin were also compounded on a Brabender Plasticorder Mixing Bowl containing unmodified α-CD and TA α-CD (2.78 wt.-%). All resins were dried at 85° C. for 2 hours under vacuum (<0.1″ of Hg) before use, while α-CD and TA-α-CD were dried at 105° C. for 30 minutes. The following masterbatch compositions were compounded.
Alpha Cyclodextrin Compounding in ethylene-maleic anhydride copolymer/LDPE (EMA/LDPE) Masterbatch. 1.11 gms of alpha cyclodextrin (Wacker Biochem Corp) was compounded into 39.89 gms of EMA/LDPE (Plexar PX 175) and 1.11 gms of α-CD or TA α-CD (Wacker Biochem Corp) was compounded in LDPE (NA 204, Equistar Chemicals, L.P.) using a Brabender Plasticorder Mixing Bowl for 5 minutes at 130° C. and 80 rpm.
Closure liner test compositions. Final test compositions of CD masterbatches and closure liner composition were made compounding the materials in a Brabender Plasticorder Mixing Bowl for 5 minutes at 130° C. and 80 rpm. The wt.-% test compositions are provided in Table 8. This material was then molded into sample coupons 4.45 cm×1.59 cm×0.10 cm with an Atlas Laboratory Mixing Molder set at 140 rpm, 150° C. for 2 minutes, with a mold temperature of 90° C.
A laboratory system to generate ozone includes passing pure oxygen from a feed gas (5.5 liters/min) into a corona discharge ozone generator producing high purity ozone. A continuous ozone monitor records the ozone generator output. Ozone is absorbed into the water yielding a substantial level of dissolved ozone gas in a given volume of water (approximately 800 ppb ozone). The ozone containing water is suitable for use in testing sealing element materials.
The test involves liner material test coupons exposed to water sterilized with 800 ppb ozone and stored in 500 mL glass bottles with 475 ml of ozonated DI water, metal screw caps with aluminum-faced liners. A 4.45 cm×1.59 cm×0.10 cm in test coupon is wedged into the mouth of the bottle. Triplicate bottles are stored on their sides for seven days at 40° C.
Following the storage period, the aqueous contents are extracted 3 times with 30 mL methylene chloride, the methylene chloride extracts are dried through sodium sulfate drying columns, and the volume reduced to 0.5 mL using Kuderna-Danish evaporator. The internal standard acenaphthene d-10 was added to the reduced extracts.
Standards were prepared by spiking three levels of aldehyde (0.1 ppb, 0.25 ppb and 1.0 ppb) into the same water used to fill the test sample bottles and then liquid extracted with dichloromethane and volume reduced to 0.5 mL. Erucamide was spiked at 11.5 ppb and extracted in the same manner. The internal standard acenaphthene d-10 was added to the reduced extracts. All mass spectrometer response factors were taken relative to an internal standard of acenaphthene d-10 that was spiked into the final solvent extract. The solvent extracted and concentrated samples were analyzed by gas chromatography/mass spectrometry GC/MS using the conditions in Table 9.
When exposed to ozone treated water, closure liner compositions containing TA α-CD and α-CD produced ppb and sub-ppb levels of C6 to C9 aldehydes, while the MA grafted α-CD showed concentrations less than the GC/MS method detection limit of 0.10 ppb. In all cases, the cyclodextrin containing closure liner compositions produced lower aldehyde migrants. In the ozonated water, a number of saturated and unsaturated amides were detected as migrants. In the control water sample, as well as the cyclodextrin containing samples, the principal unsaturated and saturated fatty acid amide migrants were C18, C14 to C16 unsaturated and saturated fatty acid amides were approximately 4× less than C18, C12 to C14 unsaturated and saturated fatty acid amides were approximately 15× less than C18 and erucamide was a trace migrant at approximately 1 ppt. In all cases, the cyclodextrin containing closure liner compositions produced lower fatty acid amide migrants in the ozonated water. The obtained results are shown in Table 10.
Fatty acid amide lubricants provide internal and external lubrication to the liner composition. The rate of penetration of the lubricant into the polymer is governed by its solubility, which depends on the carbon length and unsaturation. The results clearly show the effectiveness of the three alpha cyclodextrin compositions for reducing oxidative decomposition products of the lubricant and transfer of amide lubricants from the liner surface into the ozone treated water. The cyclodextrin containing liner formulations did not adversely affect closure torque measurements.
This application is a continuation of pending U.S. application Ser. No. 10/347,649, filed Jan. 17, 2003; which is a continuation-in-part of pending U.S. application Ser. No. 10/139,140 filed on May 3, 2002 entitled “Sealing Element for Vessel or Container Closures Having Improved Barrier Properties,” the entire disclosures of which are both incorporated herein by reference.
| Number | Date | Country | |
|---|---|---|---|
| Parent | 10347649 | Jan 2003 | US |
| Child | 12057155 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 10139140 | May 2002 | US |
| Child | 10347649 | US |
