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WO1999012820A1 - Recipients d'emballage en plastique avec proprietes d'etancheite aux gaz ameliorees - Google Patents

Recipients d'emballage en plastique avec proprietes d'etancheite aux gaz ameliorees Download PDF

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Publication number
WO1999012820A1
WO1999012820A1 PCT/US1998/016839 US9816839W WO9912820A1 WO 1999012820 A1 WO1999012820 A1 WO 1999012820A1 US 9816839 W US9816839 W US 9816839W WO 9912820 A1 WO9912820 A1 WO 9912820A1
Authority
WO
WIPO (PCT)
Prior art keywords
gas barrier
label
polyamine
plastic packaging
packaging container
Prior art date
Application number
PCT/US1998/016839
Other languages
English (en)
Inventor
Ken W. Niederst
Original Assignee
Ppg Industries Ohio, Inc.
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 Ppg Industries Ohio, Inc. filed Critical Ppg Industries Ohio, Inc.
Priority to AU89059/98A priority Critical patent/AU8905998A/en
Publication of WO1999012820A1 publication Critical patent/WO1999012820A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D23/00—Details of bottles or jars not otherwise provided for
    • B65D23/08—Coverings or external coatings
    • B65D23/0842—Sheets or tubes applied around the bottle with or without subsequent folding operations
    • B65D23/085—Sheets or tubes applied around the bottle with or without subsequent folding operations and glued or otherwise sealed to the bottle
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins

Definitions

  • the technical field of the present invention relates to plastic containers designed to hold items which are oxygen-sensitive and/or carbonated, particularly to plastic food and beverage containers, and more particularly to plastic food and beverage containers having labels and/or plastic closures which are coated with a gas barrier coating composition.
  • Plastic containers have found increasing use as replacements for glass and metal containers in today ' s packaging industry. Some advantages of plastic packaging over its glass counterpart include lighter weight, decreased breakage and potentially lower costs. On the other hand, one particular advantage of plastic packaging over its metal counterpart (e.g., aluminum beverage cans) is that the former can more easily be designed as re-closable.
  • CPC CPC of such plastic materials quantifies for the packaging industry the amount of carbon dioxide which can pass through a film or coating under a specific set of circumstances and is also generally expressed in units of cubic centimeters-mil/100 square inches /atmosphere/day. This is a standard unit of permeation measured as cubic centimeters of carbon dioxide permeating through 1 mil thickness of a sample, 100 square inches in area, over a 24-hour period, under a partial pressure differential of one atmosphere at specific temperature and relative humidity conditions. As used herein, OPC and CPC values are reported at 30° C. and 50% R.H. unless otherwise stated.
  • oxygen sensitive items whose shelf-life would be greatly reduced if stored in conventional plastic containers are perishable foods and beverages such as tomato-based products (e g , ketchup, tomato sauces and tomato pastes), juices (e g , fruit and vegetable juices) and carbonated alcoholic beverages (e g , beer, ale, malt beverages, sparkling wines, champagnes, and the like)
  • tomato-based products e g , ketchup, tomato sauces and tomato pastes
  • juices e g , fruit and vegetable juices
  • carbonated alcoholic beverages e g , beer, ale, malt beverages, sparkling wines, champagnes, and the like
  • carbonated beverages whose shelf-life would be greath reduced if stored in conventional plastic containers aie soft drinks, malt beverages sparkling water sparkling wines champagnes, and the like
  • PET poly(ethylene teraphthalate)
  • OPC poly(ethylene teraphthalate)
  • PET has a CPC of about 20
  • Another method disclosed in the literature as a means of improving a plastic packaging material ' s GPC pertains to coating the plastic material with a gas barrier material (e g a gas barrier coating composition or a gas-barrier film)
  • a gas barrier material e g a gas barrier coating composition or a gas-barrier film
  • One example of a method w hich improves the OPC of a conv entional plastic packaging material the use of a gas barrier coating composition is disclosed in co- pending, U S Patent Application Serial No 221 , 161 which was filed on Maich 31 1994
  • the invention disclosed in that Application is an improvement m poKepoxide- polyamine resin based liquid barrier coatings which are suitable for use on polymeric containers and other packaging materials According to U S S N 221 , 161.
  • the coatings disclosed therein not only have exceptionally low oxygen and/or carbon dioxide permeabilities, but also have the ability to maintain these excellent barrier properties under high humiditx conditions considerably better than other polyepoxide-poKamine based bar ⁇ ei coatings
  • the polyamine employed in U S S N 221 , 161 is an adduct of a polyamine having high aromatic content reacted with epichlorohyd ⁇ n, certain polyepoxides. novolac resin, bisphenol F epoxy resin, or with phenol and formaldehyde to form Mannich base That polyamine adduct is then cured with polyepoxide which also may have aromatic content, with the exclusion of bisphenol A epoxy resins
  • U S S N 221,161 also pertains to a packaging material which includes at least one layer of a relatively gas-permeable polymeric material and at least one layer of a polyamine-polvepoxide barrier coating as defined above According to that Application, the composite packaging material exhibits gas permeabilities as set forth above in connection with the description of the barrier coating itself
  • the barrier coating included in the packaging material may be applied to one or more surfaces of the polv me ⁇ c material or it may be laminated between two layers of the polymeric material
  • U S S N 221 ,161 contemplates the use of stock sheets that mav be used as wrappings or formed into containers or other articles
  • U S S N 221.161 also contemplates that alternatively a container or other article mav be formed from the me ⁇ c material and the barrier coating of that invention applied onto the surface of the formed article such as by spraying, roll coating, or other conventional method of coating
  • U S Patent Application one example of a method which improves the OPC of a conventional plastic packaging material by the use of a gas
  • That patent discloses adhering a gas barrier label made from an aluminum foil to a plastic bottle with a heat-activated thermoplastic co-polyester resin adhesive that also has gas barrier properties. While the method disclosed in that patent reportedly improves the resulting plastic packaging container ' s GPC. it ill likely result in many recycling problems since the gas barrier adhesive is designed to tenaciously adhere to the plastic bottle. Accordingly, the implementation of the gas barrier adhesive disclosed in that patent would ultimately hinder the removal of the barrier label prior to or during conventional recycling procedures.
  • One object of this invention is to provide a plastic packaging container which, while having significantly improved gas barrier properties, can easily be recycled by conventional practices.
  • the novel plastic packaging container comprises: (a) a plastic package body having an opening through which an oxygen-sensitive and/or carbonated item can be introduced into the container's hollow cavity, (b) a closure designed to seal the container after its contents have been placed therein, and (c) a label designed to cover at least 30% of the plastic package body ' s exterior surface
  • the particular label and/or closure employed provide enhanced gas barrier properties to the resulting plastic packaging container
  • the label providing enhanced gas barrier properties to the plastic packaging container is referred to as a "gas barrier label.
  • gas barrier closure Gas barrier labels and gas barrier closures are to be differentiated from their conventional counterparts While, for optimum gas barrier performance, it is preferred for the resulting plastic packaging material to include both, a gas barrier label and a gas barrier closure, when less than optimum performance is desired, the gas barrier label and a gas barrier closure can be used independently from one another
  • the gas barrier label used when practicing this inv ention is comprised of (a) a laver of a thermoplastic, gas-permeable label material, and (b) a lav er of a thermosetting gas barrier material
  • the thermosetting gas barrier material lav er is positioned such that w hen the gas barrier label is covering a portion of the plastic package body ' s exterior surface, the label s thermosetting gas barrier material layer is in intimate contact with the plastic package body 's exterior surface
  • the gas barrier closure used when practicing this invention is comprised of (a) a layer of a thermoplastic, gas-permeable closure material, and (b) a laver of a thermosetting gas barrier material
  • the thermosetting gas barrier material lav er is positioned such that w hen the gas barrier closure is sealing the plastic package body s opening, the ciosui e s thermosetting gas barrier material layer is at least on that portion of the closure s exterior surface which is directly aligned ith the plastic package body s opening
  • the gas barrier material of the present invention comprises the reaction product of a polyamine (A) and polyepoxide (B), wherein polyam ⁇ ne(A) comprises at least one of the following
  • R5-OH where R ⁇ is an aromatic group or fused aromatic group which may contain alkyl substitutions of 1 -4 carbon atoms
  • plastic packaging containers encompassed bv the present invention, they have significantly improved gas barrier properties and can easily be recycled by conventional practices
  • FIG. 1 is an elevational view of a plastic bottle hav mg a gas barrier label affixed to the side wall of the bottle and a gas barrier closure lor sealing its opening
  • FIG. 2 is a cross sectional view of the plastic bottle of FIG. 1 taken through line 2-2 so as to show the physical relationship between the layers of the gas barrier label and the exterior surface of the bottle
  • FIG. 3 is a cross-sectional view of the gas barrier closure for the plastic bottle of FIG. 1 taken through line 3-3 so as to show the physical relationship between layers of the gas bai ⁇ er closure
  • the plastic packaging container of this invention is especially useful for holding items which are oxygen-sensitiv e and/or carbonated
  • These packaging containers include (a) a plastic package body having an opening through which the ox gen-sensitive and/or carbonated item can be introduced into the container, (b) a gas barrier closure designed to seal the container after its contents have been placed therein, and/or (c) a gas barrier label designed to cover at least a portion of the plastic package bodv s exterior surface
  • the particular gas barrier label and/or gas barrier closure emplo ed provide enhanced gas barrier properties to the resulting plastic packaging container due to their improved gas barrier properties While for optimum gas barrier performance it is preferred for the resulting plastic packaging material to include both, a gas barrier label and a gas barrier closure, when less than optimum performance is desired, the gas barrier label and a gas barrier closure can be used independently from one another.
  • the gas barrier label is typically designed to cover at least 30% of the plastic package body ' s exterior surface, more typically at least 40% of a plastic package body ' s exterior surface, and even more typically at least 50 % of a plastic package body ' s exterior surface. If less than 30% of the plastic package body is covered by the gas barrier label, there will not be a sufficient improvement in gas barrier properties of the resulting plastic packaging container.
  • the gas barrier label is ty pically designed to cover not more than 90% of the plastic package body, more ty pically not more than 80%. and even more typically not more than 70%.
  • the preferred size and shape of the gas barrier label depends, in part, on parameters such as: the desired end use of the resulting plastic packaging container, the GPC of the plastic package body, the GPC of the gas barrier label, the GPC of the gas barrier closure (if employed), and the like. Notwithstanding the above, those skilled in the art can readily determine the preferred size and shape of the gas barrier label after reading this specification.
  • gas barrier label refers to a label which has a GPC of at least 10% less than that of the plastic package body over which it is applied.
  • the gas barrier label's GPC is typically at least 20% less than that of the package body, and more typically at least 30% less than that of the package body.
  • the preferred GPC of the gas barrier label depends, in part, on parameters such as: its size and shape, the desired end use of the resulting plastic packaging container, the GPC of the plastic package body, the GPC of the gas barrier closure (if employed) and the like. Notwithstanding the above, those skilled in the art can determine the preferred GPC of the gas barrier label after reading this specification. On the other hand, if a gas barrier closure is used when practicing this invention either by itself or in conjunction with a gas barrier label, in order to observe a noticeable improvement in the gas barrier properties of the resulting plastic packaging container, the gas barrier closure is typically designed to completely seal the containers opening so as to minimize the amount of gas leakage between the closure ' s and package ' s interfacing surfaces.
  • the preferred size and shape of the gas barrier closure depends, in part, on parameters such as: the desired end use of the resulting plastic packaging container, the GPC of the plastic package body, the GPC of the gas barrier closure, the GPC of the gas barrier label (if employed), and the like. Notwithstanding the above, those skilled in the art can readily determine the preferred size and shape of the gas barrier closure after reading this specification.
  • gas barrier closure refers to a closure which has a GPC of at least 10% less than that of the closure ' s body over which it is applied.
  • the gas barrier closure ' s GPC is typically at least 20% less than that of the closure ' s body, and more typically at least 30% less than that of the closure ' s body.
  • the preferred GPC of the gas barrier closure depends, in part, on parameters such as: its size and shape, the desired end use of the resulting plastic packaging container, the GPC of the plastic package body, the GPC of the gas barrier label (if employed), and the like. Notwithstanding the above, those skilled in the art can determine the preferred GPC of the gas barrier closure after reading this specification.
  • plastic pa. aging container 5 has gas barrier label 10 positioned over the side wall 12 of plastic package body 14.
  • Plastic package bodv 14 has an opening 15 defined therein through which oxygen-sensitive and/or carbonated items can be introduced into the body ' s hollow cavity.
  • Plastic packaging container 5 also has a closure 17 designed to seal the container after its contents have been placed therein.
  • the plastic package body can be made of any suitable polymeric material.
  • the preferred material from which the plastic package body is made depends, in part, on parameters such as the desired contents of the plastic packaging container and the processing conditions, if any, of these contents after being placed into the plastic packaging container, the conditions under which the plastic packaging container will be manufactured, processed, filled shipped stored and/or recycled, the GPC of the gas barrier label, and the like
  • the plastic package bodv tvpically comprises at least one of the following lmeth-acry late) polycarbonate polyvinyl chloride polyvinyl acetate, poly(ethylene terephthalate), polystyrene, polyethylene, polypropylene, poly(ethylene naphthalate) and polytetrafiuoroethylene
  • the preferred mate ⁇ al(s) from which the plastic package body is made depends in part on parameters such as the desired end use of the resulting plastic packaging container the GPC of the particular material from which the plastic package bodv is to be made the GPC of the gas barrier label, and the like Notwithstanding the abov e those skilled in the art can readilv determine the prefeired materials ' ) from w hich to make the plastic package bodv after reading this specification Howev er, due to cost and availability , the plastic packaging industry presently prefers to use at least one of the following materials when making the plastic package body polyvinyl
  • the gas barrier label of this invention comprises (a) a thermoplastic gas- permeable label material lav er and (b) a thermosetting gas barrier material lav er
  • the thermoplastic gas-permeable material laver is typically treated to facilitate adhesion of the gas barrier material lav er thereto
  • the types of treatment procedures which can be used hen practicing this invention will be described later in this specification
  • the thermoplastic, gas-permeable label material layer can be made from anv suitable material
  • the preferred material from which the thermoplastic, gas-permeable label material layer is made depends in part on parameters such as the desired end use of the resulting plastic packaging container the GPC of the plastic package bodv , the GPC of the thermosetting gas barrier label lav er, the GPC of the thermoplastic, gas-permeable label material layer and the like
  • the thermoplastic, gas-permeable label material layer will typically comprise a polyolefin (e g polypropylene and/or polyethylene), a polyamide. a polyester, paper and mixtures thereof
  • a polyolefin e g polypropylene and/or polyethylene
  • a polyamide e.g. polypropylene and/or polyethylene
  • the most widely used thermoplastic, gas-peimeable label material for plastic carbonated beverage containers are comprised of poly olefins, and particularly, of a two-layer lamination of poly propylene films, with the outside lay er being a tiansparent poly propy lene layer of about 0 5 mils ( 13 microns) thick Ty pically this transparent layer is reverse printed with label graphics on the inside surface, and the inside layer is an opaque polypropylene layer of about 1 mil (25 microns) thick which is used to accentuate the printed label graphics
  • a label material made from a two layer lamination of polyolefin films is considered one layer of
  • the theimoplastic gas-permeable label material is typically pretieated to oxidize the label material surface befoie application of the thei osetting gas barrier matenal This is done in order to facilitate adhesion of the thermosetting gas bar ⁇ ei material thereon
  • the oxidative pretreatment increases the surface tension of the thermoplastic gas-permeable label material surface, thereby enhancing the adhesion of the gas barrier material and/or printing inks thereto
  • Several treatment methods can be employed to oxidize the surface of the thermoplastic gas-permeable label material These include flame treatment, plasma treatment and corona treatment
  • the presently preferred method of oxidizing the surface of the thermoplastic gas-permeable label material is bv a corona treatment
  • a corona treatment typically requires an equipment arrangement which consists of a high frequency generator high voltage transformer and a treater station assembly that includes
  • thermosetting gas barrier coating materials used when piacticmg this inv ention will be described later in this specification Howev er, w ith tegard to their physical orientation, the thermosetting gas barrier material layei is positioned on the gas barrier label such that, when the label covers a portion of the plastic package body's exterior surface, the label's thermosetting gas barrier material layer is in intimate contact with a portion of the plastic package body s exterior surface
  • FIG. 2 w hich is the cioss-sectional iew of the plastic packaging container of FIG. 1 taken through line 2-2 As shown in FIG.
  • FIG. 2 is merely to show the physical relationship of the plastic packaging container s various layers
  • FIG. 2 also shows an optional embodiment of the present invention wherein a second gas barrier layer 24 is positioned over on the exterior surface 26 of thermoplastic, gas-permeable layer 20 If present, this second gas barrier layer can be comprised of a thermoplastic or thermosetting gas barrier material Specific examples of thermoplastic and thermosetting gas barrier materials which can be used when practicing this invention will be discussed later in this specification.
  • the gas barrier material used to form the gas barrier material layer of the present invention has unique adhesion properties. Specifically, the gas barrier material used when practicing this invention adheres well to the polymeric gas permeable layer of the label and/or closure, even to the extent that the two layers typically do not separate from one another during conventional plastic recycling processes (e.g., those conventionally used to recycle plastic beverage bottles). Accordingly, the use of adhesives, tie layers or the like between the polymeric gas permeable layer and the thermosetting gas barrier material are typically not necessary. On the other hand, the gas barrier material used when practicing this invention does not adhere well to the plastic package body of the plastic packaging container.
  • the gas barrier layer is easily separated from the plastic package body with little, if any, trace of the thermosetting gas barrier material layer being present on the plastic package body ' s exterior surface. As explained above, this is a highly desirable feature to those in the plastic packaging and recycling industries.
  • the gas barrier labels of this invention can be applied onto the plastic package body by any suitable means.
  • One technique which minimizes the amount of adhesive emplo ed is the standard industry practice of placing labels on plastic carbonated beverage bottles. This particular technique comprises the steps of: (a) spot or strip tacking one end of the label to the plastic package body with an adhesive, (b) wrapping the label completely around the container, and (c) glue sealing the label overlap onto the exterior surface of the label.
  • the gas barrier label When practicing this invention, it is not necessary for the gas barrier label to completely encircle the plastic package body. For those embodiments wherein the gas barrier label does not completely encircle the plastic package body, r is preferred to minimize the amount of adhesive used to affix the label onto the body.
  • One example of such a technique comprises the utilization of a bead of adhesive around the entire inner periphery of the gas barrier label. Using adhesive on essentially the entire inner surface of the gas barrier label to attach the label to the plastic package body is outside the scope of this invention since it would significantly impair the recycleability of the resulting plastic packaging container when conventional recycling practices are employed..
  • the plastic packaging containers of this invention further comprise a closure which is designed to seal the opening defined in the plastic package body.
  • closures can be designed to be unusable after the container is opened for the first time (e.g., pull-top or pop-top closures), or reusable (e.g., screw-top closures).
  • Any suitable type of closure can be used when practicing this invention.
  • the closures used when practicing this invention can be made of any suitable material. Examples of such suitable materials include: plastics (e.g., polyolefins), metal and/or metal alloys (e.g., aluminum and steel), and the like.
  • the preferred closure will depend, in part, on parameters such as: the desired contents of the plastic packaging container and the processing conditions, if any, of these contents after being placed into the plastic packaging container, the conditions under which the plastic packaging container will be manufactured, processed, filled, shipped, stored and/or recycled, the GPC of the closure, and the like. Notwithstanding the above, those skilled in the art can readily determine the preferred closure after reading this specification.
  • a gas barrier closure which comprises: (a) a thermoplastic, gas-permeable closure body, and (b) at least one gas barrier material layer.
  • FIG. 3 is the cross-sectional view of the closure 17 of FIG. 1 taken through line 3-3.
  • closure 17 includes plastic closure body 30 and gas barrier material layer 32.
  • Gas barrier layer 32 is positioned on the outer top surface 34 of closure body 30. It is within the scope of this invention for the entire outer surface of closure body 30 to be covered with a gas barrier layer However, since in order for the gases to escape from the container through the side walls 36 of closure 17, they must first pass through the side walls of plastic package body which is sealed thereby, it is ty pically not economically feasible and/or necessary to apply a gas barrier layer to closure side walls 36
  • gas barrier material layer can have any suitable dry film thickness
  • thicker coatings typically provide greater gas barrier protection
  • the packaging mdustiy ty pically prefers thinner coating for appearance and/or economic reasons
  • the gas barrier material layers of the present invention generally have a dry film thickness of not more than about 1 0 mil (25 4 microns) If even thinner films are desired, the gas barrier material layers can often provide acceptable gas barrier properties at a dry film thickness of not more than about 0 5
  • the gas barrier coating may be applied onto the thermoplastic, gas- permeable label layer or. optionally, on the closure as a single layer or as multiple layers
  • a sheet or film stock of the a thermoplastic, gas-permeable label material is coated w ith the gas bar ⁇ ei material to form a continuous sheet of a gas barrier label This continuous sheet can then be cut to size to form indi idual gas barrier labels for use on individual plastic package bodies
  • thermosetting gas bai ⁇ er coating material used w hen practicing this invention to form the gas barrier material layer for the gas barrier label or, optionally, for a gas barrier closure comprises the reaction product of a polyamine (A) and a polyepoxide (B).
  • Polyamine (A) can be an initial polyamine, an ungelled polyamine adduct. or a mixture thereof
  • ' ungelled polyamine adduct ' refers to an amine-functional polymeric resin which is a soluble and/or dispersible in a liquid medium
  • the initial polyamine used as. or in the making of, polyamine (A) is typically characterized as having a substantial aromatic content Specifically , at least about 50 percent of the carbon atoms in the initial polyamine are in aromatic rings (e g pheny lene groups and/or naphthy lene groups) Preferably the number of the initial poh amine carbon atoms in aromatic rings is at least about 60 percent, more preferably at least about 70 percent, and even more preferably at least about 80 percent.
  • This initial polyamine can be represented bv the structure
  • A- is 1 5 or greater
  • ⁇ is an aromatic-containing organic compound
  • R1 IS an alkyl group having between 1 and 4 carbon atoms
  • A is 1 7 or greater, more preferably 1 9 or greater, and ev en more preferably, 2 0 or greater
  • Pieferablv ⁇ comprises an arv l group and more preferably a benzy 1 or a naphthyl group
  • gas barrier coating compositions of the present inv ention can be produced without having to form an ungelled polyamine adduct
  • all of the epoxide required for curing the gas barrier coating composition (/ e polyepoxide (B)) is blended with the initial polyamine (1 e polyamine (A))
  • a polyamine adduct is formed by reacting the initial poly amine with epichlorohyd ⁇ n
  • a primary reaction product is polyamine groups joined by 2-hydroxypropylene linkages
  • MXDA m-xylylenediamine
  • X is the intermediate linking group and is N, N ⁇ CH 2 N. CH NR3, O, and/or C(0)-0 where R ⁇ IS an alky 1 group containing 1 to 4 carbon atoms a cy anoethyl group or cyanopropy 1 group.
  • m is 2 to 4
  • polyepoxides examples include N,N,N',N'-tetrak ⁇ s (ox ⁇ ranylmethyl)-l ,3-benzene dimethanamine (e g that which is commercially av ailable under the tradename TETRAD X epoxy resin from Mitsubishi Gas Chemical Co ), resorcinol diglycidyl ether (e g that which is commei cially available under the tradename HELOXY® 69 epoxy resin from Shell
  • a polyamine adduct is formed by the reaction of the initial polyamine w ith a novolac epoxy resin or a bisphenol F epoxy resin Notably excluded are bisphenol A type epoxy resins Preferred in this group are diglycidy 1 novolacs such as that which is commercially available under the tradename DEN-43 1 from Dow Chemical Co
  • bisphenol A type epoxy resins Preferred in this group are diglycidy 1 novolacs such as that which is commercially available under the tradename DEN-43 1 from Dow Chemical Co
  • Alternatives include novolacs with higher glycidyl functionality such as those which are commercially available under the tradenames DEN-438 and DEN-439. also from Dow Chemical Co
  • forming the polyamine adduct involves formation of Mannich bases from reaction of the initial polyamine
  • R 3 is an aromatic group or fused aromatic group which may contain 1 to 4 carbon alkyl substitutions
  • a commercially available example in which the polyamine is metaxylylenediamine is commercially available under the tradename ANCAMINE 1856 from Pacific Anchor
  • Notablv excluded from the ty pes of epoxides that can be reacted w ith the initial polyamine to form a polyamine adduct are bisphenol A type epoxy resins
  • reaction of the epoxide and the initial polyamine to produce the ungelled adduct is carried out at temperatures and concentrations of reactants sufficient to produce the desired ungelled product These temperatures and concentrations will v ary depending upon the selection of starting materials Ty picallv howev er, reaction temperatures w ill range fi om about 40° C to about 140° C , with lower temperatures (e g from about 40° C to about 1 10°
  • concentrations of reactants will typically range from about 5 to about 100 percent by weight of reactant in an appropriate solvent depending upon the particular molar ratio and type of reactants Lower concentrations of reactants are generally preferred for those systems that are more susceptible to gellation
  • Polyepoxide (B) used when practicing this invention may be any epoxide known to those of skill in the art which can react with polyamine (A) to form gas barrier coating compositions.
  • polyepoxide (B) includes those polyepoxides in which a plurality of glycidyl groups are linked to an aromatic member.
  • General examples of such polyepoxides include those represented by Formula (I) described earlier.
  • Specific and preferred examples of such a group of polyepoxides also include those described earlier which can be reacted with the initial polyamine to form the ungelled polyamine adduct.
  • polyepoxides When polyepoxides are employed in the formation of a polyamine adduct, they may be the same or different as those used as polyepoxide (B). Ty pically, if a polyamine adduct is used in the formation of the gas barrier coatings of this invention, the epoxides used in forming the polyamine adduct and those used as polyepoxide (B) have epoxy functionality of at least about 1 .4. and preferably at least about 2.0 The presence of small amounts of monoepoxides may not. however, be objectionable.
  • Polyepoxide (B) may include polyepoxides that are saturated or unsaturated. aliphatic, cycloaliphatic. aromatic, or heterocyclic, and may be substituted with non- interfering substituents such as hydroxyl groups or the like.
  • such polyepoxides may include polyglycidvl ethers of aromatic polyols. which may be formed by etherification of aromatic polyols with epichlorohydrin or dichlorohydrin in the presence of an alkali. Specific examples of such include: bis(2-hydroxynaphthyl)methane. 4,4'-dihydroxylbenzo- phenone, 1 ,5-dihydroxy-naphthalene and the like.
  • polyepoxide (B) also included in the category of a suitable polyepoxide (B) are polyglycidvl ethers of polyhydric aliphatic alcohols including cyclic and poiycyclic alcohols.
  • the epoxy group equivalent weight of polyepoxide (B) is preferably minimized so as to avoid unnecessarily introducing molecular groups into the cured polymeric network that are not the preferred groups of this invention
  • polyepoxide (B) has a molecular weight above about 80
  • the molecular weight of polyepoxide (B) is in the range from about 100 to about 1 ,000, and more preferably from about 200 to about 800
  • polyepoxide (B) generally has an epoxy equivalent weight above about 40
  • the equivalent weight of poly epoxide (B) is in the range from about 60 to about 400, and more preferably from about 80 to about 300
  • the diglycidyl ethers of an aromatic polyol such as bisphenol A or an aliphatic alcohol such as 1 ,4-butaned ⁇ ol are not preferred when practicing the present invention Howev er they may be toleiated when used to cure preferred embodiments of the polvamme adduct
  • Diglycidyl ethers of bisphenol F are preferred ov er bisphenol A based epoxides for the sake of low oxygen permeability It is theorized that the presence of methy l groups in bisphenol A has a detrimental effect on gas barrier properties
  • isopropy lidene groups are preferably avoided
  • Other unsubstituted alkyl groups are believed to have a similar effect, and constituents containing such groups are preferably avoided in the present invention
  • the polymers that comprise the chief film-forming resin of the gas barrier coating of the present invention are cured in situ when polyamine (A) and polyepoxide (B) are mixed together
  • Each amine hydrogen of polyamine (A) is theoretically able to react w ith one epoxv gioup and is considered as one amine equivalent Fl JS a pi unary amine nitrogen is considered as difunctional in the reaction with epoxides to form the gas barrier coating
  • these two components are typically reacted in a iatio of the equivalents of active amine hydrogens in polyamine (A) to equivalent of epoxy group in polyepoxide (B) of at least about 1 : 1 5
  • the ratio of the equivalents of active amine hydrogens in polyamine (A) to equivalent of epoxy group in polyepoxide (B) is preferably in the range from about 1 : 1 5 to about 1 :3 0, more preferably from about 1 : 1 7 to about 1 :2 8, and even more preferably from about 1 :2 0 to about 1 :2 5
  • the cured reaction product of polyamine (A) and polyepoxide (B) contains a substantial number of unreacted amine hydrogens
  • maximizing the amount of polyamine reactant is generally desirable for the sake of maximizing gas barrier properties, insufficient numbers of epoxy groups may not provide enough crosslinking to y ield a film which is strong, moisture resistant and solv ent resistant
  • the use of more epoxy than the preferred amounts may prov ide excessive crosslinking to ield a film that is very brittle
  • the coating ' s GPC values typically decrease
  • the amine nitrogen content in the cured gas barrier coating is typically at least about 6 0 weight percent
  • the cured gas barrier coatings of this invention have an amine nitrogen content of at least about 6 5 weight percent, and more preferably of at least about 7 0 weight percent
  • the maximum amount of amine nitrogen content in the cured gas barrier coating of this invention is generally less than about 20 weight peicent more typically less than about 17 weight percent, and even more preferably less than about 15 weight percent
  • Cured films of the gas barrier coating compositions prepared in accordance with the present inv ention have a molecular network that consists predominantly of two molecular groups
  • R 4 is an alkyl group containing not more than 4 carbons, pieferably not more than 3. more preferably not more than 2, and even more preferably not more than 1 carbon atom), and ⁇ is an aromatic-containing organic compound, and
  • the amount of the aminoalkyl substituted aromatic groups present in the cured gas barrier coating is at least about 50 weight percent, more preferably at least about 55 weight percent, and even more preferably at least about 60 weight percent
  • the amount of the 2-hydroxy-propylene groups present in the cured gas barrier coating is typically at least about 20 weight percent, more preferably at least about 30 w eight percent, and even more preferably at least about 40 weight percent These weight percentages are based upon the total weight of resin solids of the gas barrier coating Examples of these embodiments include m-xylylenediamine adducted with epichlorohyd ⁇ n or ith N,N,N',N' tetrakis (ox ⁇ rany lmethyl)- l ,3-benzene dimethanamine (TETRAD X epoxy resin) and cured with TETRAD X epoxy resin
  • the cured film network of the gas barrier coating contains at least about 70 weight percent of aminoalky l substituted aromatic groups and/or 2-hydroxypropane groups
  • the gas barrier coating preferably contains at least about 80 weight percent of these tw o molecular groups more preferably at least about 90 weight percent, and even more preferably at least about 95 weight percent These weight percentages are based upon the total weight of resin solids of the gas barrier coating
  • At least 50 percent of the carbon atoms in the initial polyamine used as, or in the making of, polyamine (A) are in an aromatic ⁇ ng(s)
  • R ⁇ in the >N R 4 ⁇ R 4 N ⁇ group contains a single carbon atom Accordingly, when ⁇ is a benzyl group, at least seventy percent of the carbon atoms are in aromatic rings
  • the lequisite amount of gas bar ⁇ ei properties necessary for the purposes of this invention may still be attained w ithout the optimum levels of the aminoalkyl substituted aromatic groups and/or the 2-hy droxypropane groups molecular groups described above
  • some of the aminomethyl substitutions can be replaced w ith oxy substitutions, (z e -O- ⁇ -O- groups) These may be introduced into the network by adducting the initial polyamine with the polyglycidyl ethers of polyphenols (e g diglycidyl ether of resorcinol) or by curing one of the preferred adducts with su h a polyglycidyl ether of a polyphenol
  • some of the aminomethyl substitutions can also be replaced with mixed substitutions such as -0- ⁇ -N ⁇ groups
  • the groups that are preferably avoided include unsubstituted alkyl chains, particularly alkylene polyamine groups as well as isopropv lidene groups (/ e as in bisphenol A)
  • the desired molecular groups may be introduced into the cured polymeric network of the gas barrier coating by the initial polyamine, the polyamine adduct or the epoxide curing component (i e polyepoxide (B))
  • the various substitutions on the aromatic members described abo e may be provided in combination w ith each other on the same molecule in the reactants
  • the gas barrier coating can be applied on to the labels and/or the plastic closures as either a solv ent-based or an aqueous-based thermosetting coating composition
  • solvents aie used they should be chosen so as to be compatible w ith the thermoplastic, gas-permeable label material being coated, and also provide desirable flow properties to the liquid composition during application
  • Suitable solvents which can be used when practicing this invention include oxygenated solvents, such as glycol ethers (e g , 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol,
  • the use of l -methoxy-2-propanol is preferred for its rapid evaporation rate, which minimizes solvent retention in the cured film In order to obtain desired flow characteristics in some of the embodiments using a pre-reacted adduct.
  • the solvents listed here may be diluted with less costly solvents such as toluene or xylene
  • the solvent may also be a halogenated hydrocarbon
  • a chlorinated hydrocarbon such as methylene chloride, 1 , 1 ,1 -t ⁇ chloroethane and the like (usually considered fast evaporating solvents)
  • Mixtures of such solvents may also be employed
  • Non-halogenated solvents are pieferred where the resultant barrier coating is desired to be hahde-free
  • the resin may also be in an aqueous medium (i e the ungelled polyamine adduct may be an aqueous solution or dispersion)
  • the ungelled polyamine adduct when polyepoxide (B) is water-soluble (e g the polyglycidyl ether of an aliphatic diol), the ungelled polyamine adduct can be utilized as an aqueous solution
  • the ungelled poly amine adduct can have sufficient amine groups neutralized with an organic acid (e g , formic acid, lactic acid or acetic acid), or with an inorganic acid (e g hydrochloric acid or phosphoric acid), to allow solubihzation of the ungelled polyamine adduct in an aqueous medium
  • an organic acid is typically preferred
  • the solution of the polyamine adduct ready for application will have a
  • the gas barrier coatings of this invention further include a filler (C). It has been observed that the presence of a sufficient amount of a filler having the appropriate particle size distribution even further improves the CPC and OPC values of the gas barrier coatings of this invention while maintaining a 20° gloss of at least 60% reflected light
  • filler (C) is typically characterized as a platelet-type filler which has the following particle size distribution (a) a number mean particle diameter ranging from about 5 5 to about 15 microns, and (b) a volume mean particle diameter ranging from about 8 to about 25 microns
  • the platelet-type filler included in filler (C) has the following particle size distribution: (a) a number mean particle diameter ranging from about 7.5 to about 14 microns, and (b) a volume mean particle diameter ranging from about 10 to about 23 microns: and
  • the platelet-type filler included in filler (C) further has the following particle size distribution: (a) at least about 55 percent by number of its particles having a diameter greater than 7 microns, and (b) less than about 15 percent by number of its particles having a diameter greater than 30 microns: preferably: (a) at least about 75 percent by number of its particles having a diameter greater than 7 microns, and (b) less than about 10 percent by number of its particles having a diameter greater than '0 microns: and more preferably: (a) at least about 95 percent by number of its particles having a diameter greater than 7 microns, and (b) less than about 5 percent by number of its particles having a diameter greater than 30 microns.
  • number mean particle diameter refers to the sum of the equivalent circle diameter of all the particles in the sample that were analyzed divided by the total number of the particles that were analyzed.
  • equivalent circle diameter refers to the diameter of a circle having a projected area equal to the projected area of the particle in the sample being analyzed.
  • volume mean particle diameter refers to the cube root of the sum of the equivalent spherical diameter of all the particles in the sample that were analyzed divided by the total number of the particles that were analyzed.
  • equivalent spherical diameter refers to the diameter of a sphere having a volume equal to the volume of the particle being analyzed.
  • All particle size measurements pertaining to the filler used when practicing the embodiment of this invention which employs filler (C) are as determined by a HORIBA LA-900 laser scattering particle size distribution analyzer from Horiba Instruments, Inc. in Irving, California.
  • the HORIBA LA-900 works off the same principle as many conventional laser scattering particle size distribution analyzers.
  • the particles cause the light to scatter.
  • the amount of scattering in a particular direction depends upon the size, shape, and composition of the particle and the wavelength of the incident light.
  • light scattered from all of the particles contributes to the total intensity of light scattered in a particular direction relative to the incident light.
  • the pattern of scattered light is indicative of the sizes of the scattering particles.
  • Particle size analyzers using this technique typically sample the angular distribution of the intensity of the light scattered from the mixture, process the data, and produce numerical values and possibly a graph or a histogram as output.
  • the analyzer output represents the number or volume fraction of scattering particles in the mixture as a function of the size of the particles and is usually called a particle size distribution.
  • a source of unpola ⁇ zed light is projected in a beam to impinge upon a sample
  • the sample contains the particles whose sizes are under investigation
  • the particles are dispersed in the region of the sample that is illuminated by the incident light beam
  • the particles scatter light in patterns that are dependent on the ratio of the size of the particle to the wavelength of the light, and on the refractiv e index of the particle material
  • the refractive index, a complex function of wavelength is a measure of how much the light is refracted, reflected and absorbed by the material Tor a beam of unpola ⁇ zed light incident on a random mixture of small particles the scattering pattern is symmetric about the axis of the incident beam
  • the scattering is the iesult of the refraction, reflection and
  • the inner and outer cones of an angle class define a circular annular region on a plane perpendicular to the incident beam and a more complex shaped region (corresponding to a conic section) on a plane not perpendicular to the incident beam.
  • Scattered light rays intersecting the interior of such a region are rays which have scattered through an angle bet een the two generating angles of the cones.
  • any light ray intersecting such a region belongs to the angle class defined by that region.
  • Some conventional analyzers employ ring-shaped light detectors to measure the amount of light that scatters in an angle class determined by the radius and width of the ring and its distance from the scattering region. To correlate correctly the detected light with a scattering angle, these ring-shaped detectors are typically mounted and aligned precisely perpendicular to the incident beam.
  • the interaction region of the incident beam with the particles generally has a finite extent, multiple particles at different locations in the incident beam will each contribute multiple ov erlapping cones of scattered light, with the ap ves of the cones offset by the distance between the particles. Particles of the same size will have overlapping scattered-light cones of similar intensity variations, whereas particles of different sizes will have overlapping scattered- light cones of different intensity variations.
  • a converging lens may be used to direct parallel rays of light, each by definition scattered through the same scattering angle (by different particles), to a single point on a light detector in the focal plane of the lens.
  • a lens that functions in this manner performs a Fourier transform, so that all light arriving at a given point on the detector is known to have been scattered by the sample through a particular scattering angle, regardless of the location of the scattering particle in the sample volume.
  • the effect of the converging lens is to transform the spatial distribution of the scattered light it receives to that of an equivalent virtual system in which the light distribution in the focal plane of the lens is the same as if all the scattering particles were located at a point coincident with the optic center of the lens.
  • the light detectors are placed in the focal plane of the lens.
  • the line from the optic center of the lens to the focal point of the lens is usually called the optic axis.
  • a scattered ray passes through different refracting media, such as air and a sample suspension fluid, before detection, then an appropriate correction is typically applied to the ray's apparent angle of scatter to determine its true angle of scatter.
  • refracting media such as air and a sample suspension fluid
  • the intensity of light scattered as a function of scattering angle when experimentally determined as above for a sample composed of many particles of a range of different sizes, consists of the summation of the scattered light from all the particles. If it is assumed that each size particle in the sample scatters light according to a given mathematical theory and in proportion the relative number of such size particles present, then it is mathematically possible to determine from the experimental data the relative numbers of each size particle constituting the sample (i.e., to determine the size distribution of the sample.
  • the well-known mathematical process by which the size distribution may extracted from the composite data is called an inversion process, or sometimes a deconvolution process.
  • HORIBA LA-900 works by irradiating particles dispersed in a solution with a red light beam and a blue light beam which is obtained by filtering a tungsten lamp in parallel with an He- Ne laser. The particles cause the light to scatter at various angles.
  • a condenser lens is used with an array detector at the focal point of the lens. There are also detectors positioned in the front, side and rear of the sample. From the angular measurement of the scattered light by all the detectors, the particle size distribution of the sample is calculated. These computations are made by the particle size distribution analyzer by using the Mie scattering light theory.
  • the HORIBA LA-900 laser scattering particle size distribution analyzer can provide an accurate, reproducible assessment of particle sizes in the range from 0 04 microns to 1,000 microns
  • the HORIBA LA-900 uses three separate detectors — one for the front, side and rear scattering As the light source for detecting scattering on the side and rear, the HORIBA LA-900 uses a tungsten lamp In the HORIBA LA-900.
  • filler (C) has the following particle size distribution (a) a liumbei mean particle diameter ranging from about 9 5 to about 15 microns, and (b) a v olume mean particle diameter ranging from about 14 to about 25 microns, in order for the resulting gas barrier coating to have an OPC value of not more than 0 05 and a 20° gloss of at least 60% reflected light, filler (C) is preferably present in an amount ranging from about 5 to about 50 weight percent, more preferably in an amount ranging from about 6 to about 45 weight percent, and ev en more preferably from about 7 to about 40 weight ] ⁇ r Cen t These weight percentages are based upon the total solids weight of the gas barrier coating composition
  • filler (C) when the number mean particle diameter of filler (C) ranges from about 5 5 to less than 9 5 microns, and/or when the volume mean particle diameter ranges from about 8 to less than 14 microns, in order for the resulting coating composition to have an OPC value of not more than 0 05, filler (C) is preferably present in an amount ranging from about 12 to about 50 weight percent, more preferably in an amount ranging from about 15 to about 45 weight percent, and even more preferably from about 18 to about 40 weight percent. These weight percentages are based upon the total solids weight of the gas barrier coating composition. Any suitable platelet-type filler which has the aforementioned particle size distribution and which is compatible with the barrier coating composition described above can be used when practicing this embodiment of the invention.
  • fillers examples include: mica, vermiculite, clay, talc, micaeous iron oxide, silica, flaked metals, flaked graphite, flaked glass, flaked phthalocyanine, and the like.
  • mica due to its commercial availability.
  • Micas which can be used when practicing this invention include natural micas and synthetic micas.
  • natural micas include: muscovite ( 2 Al (Al 2 Si 6 0 2 o)(OH)4), phlogopite (K 2 (Mg,Fe2 -) 6 (Al Si6 ⁇ 20 )(OH.F) ), and biotite (K. 2 (Fe2,Mg)6(Al 2 Si50 2 o)(OH)4).
  • Examples of synthetic micas include: fluorophlogopite (K 2 Mg6Al 2 Si ⁇ 0 2 oF4) and barium disilicic (Ba 2 Mg6Al 2 Sig0 2 oF4).
  • the preferred, for the purposes of this invention is muscovite mica due to its commercial availability.
  • Gas barrier coatings of this invention can further include other additives known to those skilled in the art.
  • Some of the more common additives which can be present in the gas barrier coating include: pigments, silicones. surfactants, and/or catalysts for coating compositions which involve an epoxy-amine reaction. Each of these specific optional components will be discussed below.
  • the weight ratio of pigment to binder is typically not more than about 1 : 1 , preferably not more than about 0.3: 1 , and more preferably not more than about 0.1 : 1 .
  • the binder weight used in these ratios is the total solids weight of the polyamine-polvepoxide resin in the gas barrier coating.
  • silicones they may be included in the gas barrier coating to assist in wetting the thermoplastic, gas-permeable label material over which the barrier coating will be applied.
  • silicones which can be used for this purpose include various organosiloxanes such as polydimethylsiloxane, polymethylphenylsiloxane and the like. Specific examples of such include: SF-1023 silicone (a polymethylphenylsiloxane available from General Electric Co.), AF-70 silicone (a polydimethylsiloxane available from General Electric Co.), and DF- 100 S silicone (a polydimethylsiloxane available from Mazer Chemicals, a division of PPG Industries, Inc.). If employed, such silicones are typically added to the gas barrier coating in amounts ranging from about 0.01 to about 1.0 percent by weight based on total resin solids in the gas barrier coating.
  • surfactants they are typically included in the aqueous-based versions of the gas barrier coating.
  • surfactants that can be used for this purpose include any suitable nonionic or anionic surfactant. If employed, such surfactants are typically present in an amount ranging from about 0.01 to about 1 .0 percent by weight based on the total weight of the gas barrier coating.
  • catalysts they may be included in the gas barrier coating to aid in the reaction between polyamine (A) and polyepoxide (B).
  • any suitable catalyst that is used for epoxy-amine reactants can be employed when practicing this invention.
  • suitable catalysts include: dihydroxy aromatics (e.g., resorcinol), triphenyl phosphite, calcium nitrate and the like.
  • the components of a gas barrier coating i.e., polyamine (A) and polyepoxide (B), and filler (C) when present
  • a gas barrier coating i.e., polyamine (A) and polyepoxide (B), and filler (C) when present
  • the mixture can then be immediately applied to the thermoplastic, gas-permeable packaging material, or held for a period of time typically ranging from about 1 minutes to about 60 minutes prior to application to improve cure and/or clarity. This holding time can be reduced and/or eliminated when the initial polyamine is in the form of a polyamine adduct or when the solvent employed is 2-butoxyethanoI.
  • the gas barrier coating can be applied onto the labels and/or plastic closures by any conventional means known to those skilled in the art (e.g., spraying, rolling, dipping, brushing and the like). However, for the purposes of this invention, spray, rolling, and/or dipping applications are preferred.
  • the gas barrier coating After application of the gas barrier coating, it may be cured at temperatures as low as ambient temperature by allowing for a gradual cure over several hours to several days However, such low temperature curing is generally slower than desired for commercial production lines It is also not an efficient means of removing solvent from the cured barrier coating Therefore, in one embodiment, the gas barrier coating is cured by being heated at elevated temperatures as high as possible without distorting the thermoplastic, gas-permeable packaging material over which it is applied
  • curing temperatures typically range from about 55° C to about 1 10° C , and preferably from about 70° C to about 95° C At such curing temperatures, curing times will typically range from about 1 minute to about 60 minutes
  • a relatively “fast” solvent t e a solvent having -elatively high evaporation iate
  • curing temperatures typically range from about 35° C to about 70° C , and preferably from about 45° C to about 65° C At such curing temperatures curing times will typically range from about 0 5 minute to about 30 minutes
  • the gas barrier label employed when practicing this invention provides significantly improved gas barrier properties to the resulting plastic packaging container
  • this gas barrier label can easily be removed from the plastic packaging container by conventional recycling practices
  • a polyamine-polyepoxide gas barrier coating composition was prepared by stirring together the following material 23 5 weight percent GASKAMINE® 328S (a reaction product of metaxyly lenediamine and epichlorohyd ⁇ n which has been vacuum stripped to remove free MXDA, commercially available from Mitsubishi Gas Company). 72 8 weight percent of DOWANOL® PM (l-methoxy-2-propanol commercially available from Dow Chemical Company), 0.1 weight percent SF-1023 silicone surfactant from General Electric, 2.4 weight percent of cyclohexyl alcohol (with 2% water), and 1.3 weight percent of deionized water. The resulting homogeneous blend is hereinafter referred to as "Component 1 A.” All aforementioned weight percentages are based on the total weight of all components in Component 1A.
  • Component I B 75.0 weight percent of DEN-444 (an epoxy novolac resin having a glycidyl functionality of 3.6, commercially available from Dow Chemical Co.). and 25.0 weight percent of methyl ethyl ketone were stirred together.
  • the resulting homogeneous blend is hereinafter referred to as "Component I B.” All aforementioned weight percentages are based on the total weight of all components in Component IB.
  • Components 1 A and 1 B were blended together at a ratio of 3 : 1 by volume.
  • the resultant homogeneous blend is hereinafter referred to as "Coating 1 ".
  • Multilayer gas barrier labels were prepared by spray applying the gas barrier coating of this example onto one side of polypropylene label stock having an approximate film thickness of 2 mils, the coated side of the polypropylene label having been corona pretreated to facilitate adhesion.
  • the surface area of the label was 16.8 in ⁇ (42.6 cm ⁇ ).
  • Coated labels were cured for 8.5 minutes at 145° F. (63° C.) to yield a dry coating having a thickness ranging from about 0.2 to 0.5 mil.
  • the cured film of the gas barrier coating had a theoretical nitrogen content of about 7.1 weight percent.
  • Coated labels were affixed to uncoated 330 milliliter PET soft drink bottles.
  • the full brim volume capacity of the bottle is 350 ml: and the bottle ' s surface area is 40 in- 1 - ( 102 cm2).
  • the coated labels were affixed to the uncoated PET containers by rapping the label around the outer wall of the container and securing the label with tape to simulate the normal commercial practice of using a thin bead of adhesive to secure a label to a container.
  • Coated label (1-A) was affixed with the barrier coating side on the outside with the uncoated thermoplastic polymer layer adjacent the PET bottle surface, the PET bottle having been provided with a 28 millimeter coated closure: coated label (1-B) was .
  • the PET bottle Tixed with the barrier coating side on the inside, adjacent to the PET bottle surface, the PET bottle having been provided with a 28 millimeter coated closure.
  • the top outer surface of polypropylene screw-top bottle closures were coated with about 1 mil of the aforementioned barrier coating, or left uncoated.
  • the barrier coating was cured for about 10 minutes at 145°F. (63°C). After carbonation tieatment of the test bottles, the closures were then screwed onto the test bottles.
  • Bottles with coated and uncoated labels were carbon dioxide treated by filling each bottle with the following mixture: 330 milliliters of water at 40°F. (5°C); 6.9 g. sodium carbonate (anhydride): and 10.0 g. citric acid dihydrate. Filled containers were quickly capped and gently agitated to mix ingredients. This mixture provided a level of carbonation equivalent to about 4.2 volumes of carbon dioxide. All sealed samples were conditioned by being stored for 2 days at about 70°F. (21 °C.) at approximately 50% relative humidity prior to testing.
  • Example 1 illustrates the improved carbon dioxide permeability results of PET soft drink bottles demonstrated by the application of the polyamine-polyepoxide gas barrier coating designated in Example 1 as Coating 1 onto the top outer surface of typical polypropylene screw-top plastic bottle closures in conjunction with the multilayer gas barrier label of the present inv ention
  • Multilayer barrier labels were prepared by spray applying the gas barrier coating of Example 1 onto one side of polypropylene label stock having an approximate film thickness of 2 mils, the coated side of the polypropylene label having been corona pretreated to facilitate adhesion
  • the surface area of the label was 19 7 ⁇ n ⁇ (49 8 cm ⁇ )
  • Coated labels were cured for 8 5 minutes at 145° F (63° C ) to yield a dry coating having a thickness ranging from about 0 2 to 0 5 mil
  • the cured film of the gas barrier coating had a theoretical nitrogen content of about 7 1 weight percent Labels so prepared were aged for a period of one eek at approximatelv 7 0° F (23°C ) at approximatelv 50% relati e humiditv prior to attaching to test bottles
  • Coated and uncoated labels were affixed to uncoated twelve ounce (355 millihters) PET soft drink bottles The full brim volume of the bottle is 13 ounces (390 ml), and the bottle s surface area is 45 lii ⁇ (1 14 cm ⁇ )
  • the labels were affixed to the uncoated PET containers by rapping the label around the outer wall of the container and securing the label with tape to simulate the normal commercial practice of using a thin bead of adhesive to secuie a label to a container Container (2-A) was an uncoated PET bottle with no label and an uncoated closure Container (2-B) was an uncoated PET bottle with an uncoated label and an uncoated closure Container (3-A) was an uncoated PET bottle with the multilayer gas barrier label of the present invention, affixed such that the gas barrier coating, Coating 1 of Example 1 , was adjacent the PET bottle surface, the PET bottle having been provided with a closure
  • Bottles with coated and uncoated labels were carbon dioxide treated by filling each bottle with the following mixture: 375 milliliters of water at 40° F. (5°C): 7.7 g. sodium carbonate; and 1 1.0 g. citric acid. Filled containers were quickly capped and gently agitated to mix ingredients. This mixture provided a level of carbonation equivalent to about 4.2 volumes of carbon dioxide. All sealed samples were conditioned by being stored for 2 days at about 70° F. (21° C.) at approximately 50% relative humidity prior to testing.

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Abstract

L'invention concerne un conteneur d'emballage en plastique conçu pour conserver des produits gazéifiés et/ou sensibles à l'oxygène qui comporte: (a) un corps plastique présentant une ouverture permettant le passage du produit gazéifié et/ou sensible à l'oxygène, (b) une fermeture rendant étanche l'ouverture du récipient et (c) une étiquette recouvrant au moins 30 % de la surface extérieur du corps de l'emballage plastique, la fermeture et/ou l'étiquette présentant des propriétés d'étanchéité aux gaz renforcées. L'étiquette étanche aux gaz comporte: (a) une couche de matière d'étiquette thermoplastique, perméable au gaz, et (b) une couche de matière thermodurcissable étanche aux gaz. Lorsqu'on utilise une étiquette étanche aux gaz, sa couche étanche aux gaz est en contact étroit avec la surface extérieure du récipient. La fermeture étanche aux gaz comporte: (a) un corps de fermeture thermoplastique, perméable au gaz, et (b) une couche de matière thermodurcissable étanche aux gaz. La matière thermodurcissable étanche aux gaz utilisée dans la fabrication de la couche étanche aux gaz de l'étiquette et/ou de la fermeture comporte le produit de réaction d'une polyamine (A) et d'un polyépoxyde (B), dans lequel la polyamine (A) comprend au moins: (a) une polyamine initiale; (b) un produit d'addition amine-époxyde non gélifié présentant des hydrogènes d'amines actifs et qui est le produit de réaction de la polyamine initiale et d'au moins: (i) de l'épichlorhydrine et (ii) d'un polyépoxyde présentant plusieurs groupes glycidyliques liés à un élément aromatique; ou (c) une polyamine initiale que l'on a fait réagir avec du formaldéhyde et un phénol R?5-OH, R5¿ étant un groupe aromatique ou un groupe aromatique fondu pouvant contenir des substituants alkyle de 1 à 4 atomes de carbone.
PCT/US1998/016839 1997-09-10 1998-08-12 Recipients d'emballage en plastique avec proprietes d'etancheite aux gaz ameliorees WO1999012820A1 (fr)

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AU89059/98A AU8905998A (en) 1997-09-10 1998-08-12 Plastic package containers having improved gas barrier properties

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US08/926,963 1997-09-10

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001060701A3 (fr) * 2000-02-16 2002-03-07 Ppg Ind Ohio Inc Compositions de barriere contre les gaz aux proprietes de barriere ameliorees
EP1375575B1 (fr) * 2002-06-25 2006-08-23 Mitsubishi Gas Chemical Company, Inc. Système de carburant ayant une excellente propriété de barrière contre l'essence
EP1634811A4 (fr) * 2003-06-13 2008-07-30 Akihide Mori Recipient depliable
EP1541489A4 (fr) * 2002-06-25 2009-06-03 Mitsubishi Gas Chemical Co Conteneurs etanches aux gaz
DE102019132058A1 (de) * 2019-11-27 2021-05-27 Krones Ag Behälterbehandlungsmaschine zur Behandlung von Kunststoffbehältern

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Cited By (8)

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Publication number Priority date Publication date Assignee Title
WO2001060701A3 (fr) * 2000-02-16 2002-03-07 Ppg Ind Ohio Inc Compositions de barriere contre les gaz aux proprietes de barriere ameliorees
AU766769B2 (en) * 2000-02-16 2003-10-23 Ppg Industries Ohio, Inc. Gas barrier compositions having improved barrier properties
EP1375575B1 (fr) * 2002-06-25 2006-08-23 Mitsubishi Gas Chemical Company, Inc. Système de carburant ayant une excellente propriété de barrière contre l'essence
CN100341750C (zh) * 2002-06-25 2007-10-10 三菱瓦斯化学株式会社 具有汽油屏蔽性能的燃料系统
EP1541489A4 (fr) * 2002-06-25 2009-06-03 Mitsubishi Gas Chemical Co Conteneurs etanches aux gaz
US8389082B2 (en) 2002-06-25 2013-03-05 Mitsubishi Gas Chemical Company, Inc. Fuel system having excellent gasoline barrier property
EP1634811A4 (fr) * 2003-06-13 2008-07-30 Akihide Mori Recipient depliable
DE102019132058A1 (de) * 2019-11-27 2021-05-27 Krones Ag Behälterbehandlungsmaschine zur Behandlung von Kunststoffbehältern

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