Packaging materials including a barrier film

Abstract

The invention features a packaging material including a film having a barrier layer formed from an admixture containing a base polymer and a surface-modifying macromolecule. The invention also features containers made from the packaging materials and methods of storing a good.

Claims

1. A packaging material comprising a film, said film comprising a barrier layer formed from an admixture comprising a base polymer and a surface-modifying macromolecule, wherein the surface-modifying macromolecule is a polyurethane comprises fluorinated terminal groups.

2. The packaging material of claim 1, wherein WVTR of said barrier layer is less than 4.0 g/(m.sup.2.Math.day.Math.mil) at 38° C. and 90% RH.

3. The packaging material of claim 1, wherein WVTR of said barrier layer at least 20% lower than WVTR of said layer without said surface-modifying macromolecule.

4. The packaging material of claim 1, wherein said base polymer is a polyalkylene, a polyester, a polyamide, a polyurethane, or a polysaccharide, or a blend of thereof.

5. The packaging material of claim 4, wherein said base polymer is a polyalkylene or a polyester or a blend thereof.

6. The packaging material of claim 5, wherein said polyalkylene is a polyethylene, a polypropylene, polyvinyl chloride, polystyrene, ethylene vinyl alcohol, a cyclic olefin copolymer, or a cyclic olefin copolymer.

7. The packaging material of claim 6, wherein said polyalkylene is a polyethylene, a polypropylene, polyvinyl chloride, polystyrene, or ethylene vinyl alcohol.

8. The packaging material of claim 5, wherein said polyester is polyethylene terephthalate, polyethylene naphthalate, or polylactide.

9. The packaging material of claim 1, wherein said admixture comprises from 0.05% (w/w) to 10% (w/w) of said surface modifying macromolecule.

10. The packaging material of claim 1, wherein said film is formed by extrusion, calender rolling, casting, lamination, or solution deposition.

11. The packaging material of claim 1, wherein said film is formed by extrusion, calender rolling, or lamination.

12. The packaging material of claim 1, wherein said packaging material is a forming web or a non-forming web.

13. The packaging material of claim 1, wherein said packaging material comprises one and only one said barrier layer.

14. The packaging material of claim 1, wherein said barrier layer has a thickness equal to or less than 500 μm.

15. The packaging material of claim 14, wherein said barrier layer has a thickness equal to or less than 300 μm.

16. The packaging material of claim 15, wherein said barrier layer has a thickness equal to or less than 200 μm.

17. The packaging material of claim 1, wherein said barrier layer has a thickness equal to or greater than 10 μm.

18. The packaging material of claim 17, wherein said barrier layer has a thickness equal to or greater than 25 μm.

19. The packaging material of claim 1, wherein said barrier film is a multilayer film.

20. The packaging material of claim 19, wherein said packaging material comprises two or more said barrier layers, each said barrier layer formed from an admixture comprising a base polymer and a surface-modifying macromolecule.

21. The packaging material of claim 1, wherein said barrier film is a bilayer film.

22. The packaging material of claim 1, wherein said barrier film is a trilayer film.

23. The packaging material of claim 1, wherein said barrier film is a tetralayer film.

24. The packaging material of claim 1, wherein said barrier film is a single layer film.

25. The packaging material of claim 1, wherein said packaging material is a sterilizable packaging material.

26. A container comprising the packaging material of claim 1.

27. The container of claim 23, wherein said package is a primary package or a secondary package.

28. The container of claim 23, wherein said container is a pouch, a box, or an envelope.

29. The container of claim 23 further comprising a good.

30. The container of claim 29, wherein said good is a dry good.

31. The container of claim 29, wherein said good is a liquid good.

32. The container of claim 29, wherein said good is a food product or a pharmaceutical product.

33. A method of storing a good, comprising preparing the packaging material of claim 1 and arranging said good and a container comprising said packaging material so as to isolate said good from the environment external to said container.

34. The method of claim 33 further comprising forming said packaging material into said container prior to said arranging.

35. The method of claim 33 further comprising sealing said container after said arranging.

36. The method of claim 33 further comprising sterilizing said packaging material prior to said arranging.

37. The method of claim 33 further comprising sterilizing said packaging material after said arranging.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 shows a theoretical structure of Compound 1 (Z=2).

(2) FIG. 2 shows a theoretical structure of Compound 2.

(3) FIG. 3A shows a theoretical structure of Compound 3.

(4) FIG. 3B shows a theoretical structure of Compound 4.

(5) FIG. 4A shows a theoretical structure of Compound 5.

(6) FIG. 4B shows a theoretical structure of Compound 6.

(7) FIG. 5A shows a theoretical structure of Compound 7.

(8) FIG. 5B shows a theoretical structure of Compound 8.

(9) FIG. 6A shows a theoretical structure of Compound 9.

(10) FIG. 6B shows a theoretical structure of Compound 10.

(11) FIG. 7A shows a theoretical structure of Compound 11.

(12) FIG. 7B shows a theoretical structure of Compound 12.

(13) FIG. 8 shows a theoretical structure of Compound 13.

(14) FIG. 9 shows a theoretical structure of Compound 14.

(15) FIG. 10 shows a theoretical structure of Compound 15.

(16) FIG. 11 shows a theoretical structure of Compound 16.

(17) FIG. 12 shows a theoretical structure of Compound 17.

(18) FIG. 13 shows a theoretical structure of Compound 18.

(19) FIG. 14 shows a theoretical structure of Compound 19.

(20) FIG. 15 shows a theoretical structure of Compound 20.

(21) FIG. 16 shows a theoretical structure of Compound 21.

(22) FIG. 17 shows a theoretical structure of Compound 22.

(23) FIG. 18 shows a theoretical structure of Compound 23.

(24) FIG. 19 shows a theoretical structure of Compound 24.

(25) FIG. 20 shows a theoretical structure of Compound 25.

(26) FIG. 21 shows a theoretical structure of Compound 26.

(27) FIG. 22A shows a theoretical structure of Compound 27.

(28) FIG. 22B shows a theoretical structure of Compound 28.

DETAILED DESCRIPTION

(29) In general, the present invention relates to packaging materials including a film containing a barrier layer formed from an admixture containing a base polymer and a surface-modifying macromolecule. The use of surface-modifying macromolecules in the packaging materials of the invention can be advantageous for two reasons: (1) the need for inclusion of a layer solely for enhancing the barrier properties of the packaging material is negated, and (2) the surface-modifying macromolecule may lower the coefficient of friction of the layer, thereby allowing for higher processing speed. Thus, the packaging materials of the invention include a film having at least one multifunctional layer, in which the base polymer provides one function (e.g., maintenance of a shape of the packaging material of the invention) and the surface-modifying macromolecule provides an additional function (e.g., enhancement of barrier properties of the base polymer). Without being bound by a theory, the enhancement of barrier properties in a layer formed from an admixture of a base polymer and a surface-modifying macromolecule is due to the migration of the surface-modifying macromolecule to the surface of the layer.

(30) The surface-modifying macromolecules can provide a base polymer with certain barrier properties that the base polymer otherwise lacks. Many base polymers are amenable to enhancement of the barrier properties by admixing the polymer with the surface-modifying macromolecule. Other base polymers that have acceptable barrier properties do not need admixing with surface-modifying macromolecules. Indeed, often these base polymers are used as dedicated barrier layers in multilayer films. Enhancing the barrier properties of other base polymers in a film using a surface-modifying macromolecule, thus, can help to eliminate the need for use of the base polymers solely for the purpose of providing the missing barrier properties. For example, PVdC is a base polymer that already possesses the requisite barrier properties (e.g., moisture barrier properties). However, processing PVdC is complicated by its corrosive effect on the manufacturing equipment. Therefore, surfaces contacting PVdC during manufacturing process must be protected by coating with PTFE, which increases the manufacturing costs. Thus, the use of surface-modifying macromolecules in admixture with a base polymer can remove the need for inclusion of a PVdC layer in a film used in a packaging material, thereby reducing the material expenditure and manufacturing complexity. Alternatively, in packaging applications requiring very high barrier properties (e.g., extremely low WVTR, OTR, or COTR), admixtures of base polymers (e.g., a barrier base polymer (e.g., a cyclic olefin copolymer (e.g., TOPAS®))) having barrier properties with the surface-modifying macromolecules may be used. Admixing a surface-modifying macromolecule with such barrier base polymer may enhance the desired barrier property (e.g., moisture barrier property) further. When very high barrier properties are desired in multilayer films (e.g., a bilayer, a trilayer, or a tetralayer film), the film may include a layer formed from a base polymer having high barrier properties (e.g., cyclic olefin copolymer, PVdC, or PCTFE) and a layer formed from another base polymer (e.g., a polyalkylene, a polyester, a polyamide, or a polysaccharide), provided that at least one layer in this multilayer film is formed from an admixture of a base polymer and a surface-modifying macromolecule. Thus, the selection of a base polymer for the packaging material of the invention can be carried out with the desired barrier property in mind.

(31) Films, Packaging Materials, and Containers

(32) The packaging materials of the invention may include films containing a barrier layer. The barrier layer can have acceptable barrier properties, such as moisture barrier properties (i.e., the layer reduces WVTR of the packaging material to an acceptable level), oxygen barrier properties (i.e., the layer reduces oxygen transmission rate (OTR) of the packaging material to an acceptable level), or carbon dioxide barrier properties (i.e., the layer reduces carbon dioxide transmission rate (COTR) of the packaging material to an acceptable level).

(33) The films of the invention may be single-layer or multilayer and may be prepared according to methods known in the art, e.g., extrusion (e.g., melt extrusion or blown film extrusion), or calender rolling. In particular, the multilayer films may be prepared by extrusion laminating, extrusion coating, or co-extrusion. One of the layers in the film may be a layer formed from an admixture of a base polymer and a surface-modifying macromolecule.

(34) The film alone can be a packaging material. Alternatively, a packaging material may be a combination of the film with other ingredients, e.g., a sheet material (e.g., cardboard or aluminum foil), handles, or a locking mechanism. Examples of locking mechanisms that can be included in the packaging materials of the invention are provided in U.S. Pat. Nos. 2,810,944; 7,029,178; and 5,138,750, the disclosures of which are incorporated herein by reference. The packaging material formed from a film of the invention and a sheet material may be prepared according to methods known in the art, e.g., lamination or extrusion coating.

(35) Containers of the invention can be assembled from the packaging materials according to methods known in the art. For example, the packaging material may be formed into a pouch, a box, or an envelope. Additional elements may be added to the container, such as print (e.g., by offset printing) and/or labels affixed to the container with adhesives. The container can be a primary package or a secondary package. Preferably, the container is a flexible package (e.g., a pouch (e.g., a vacuum packaging bag) or a blister pack).

(36) Surface Modifying Macromolecules

(37) The surface-modifying macromolecules using in the packaging materials of the invention may be described by the structure of any one of formulae (I), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX), (X), (XI), and (XII) shown below.
(1) Formula (I):
F.sub.T—[B-A].sub.n—B—F.sub.T  (I)
wherein
(i) A includes hydrogenated polybutadiene, poly((2,2-dimethyl)-1,3-propylene carbonate), polybutadiene, poly(diethylene glycol)adipate, poly(hexamethylene carbonate), poly(ethylene-co-butylene), (neopentyl glycol-ortho phthalic anhydride) polyester, (diethylene glycol-ortho phthalic anhydride) polyester, (1,6-hexanediol-ortho phthalic anhydride) polyester, or bisphenol A ethoxylate;
(ii) B is a segment including a urethane; and
(iii) F.sub.T is a polyfluoroorgano group, and
(iv) n is an integer from 1 to 10.
(2) Formula (II):
F.sub.T—[B-(oligo)].sub.n—B—F.sub.T  (II)
wherein
(i) B includes a urethane;
(ii) oligo includes polypropylene oxide, polyethylene oxide, or polytetramethylene oxide;
(iii) F.sub.T is a polyfluoroorgano group; and
(iv) n is an integer from 1 to 10.
(3) Formula (III) or Formula (IV):

(38) ##STR00007##
wherein (i) A is an oligomeric segment containing an ether linkage, an ester linkage, a carbonate linkage, or a polyalkylene and having a theoretical molecular weight of from 500 to 5,000 Daltons (e.g., from 500 to 3,500 Daltons, from 500 to 2,000 Daltons, from 1,000 to 2,000 Daltons, or from 1,000 to 3,000 Daltons); (ii) B is a segment including a isocyanurate trimer or biuret trimer; B′, when present, is a hard segment including a urethane; (iii) each F.sub.T is a polyfluoroorgano group; and (iv) n is an integer between 0 to 10.
(4) Formula (V):
F.sub.T—[B-(Oligo)].sub.n—B—F.sub.T  (V)
wherein (i) Oligo is an oligomeric segment including polypropylene oxide, polyethylene oxide, or polytetramethyleneoxide and having a theoretical molecular weight of from 500 to 5,000 Daltons (e.g., from 500 to 3,000 Daltons, from 500 to 2,000 Daltons, from 1,000 to 2,000 Daltons, or from 1,000 to 3,000 Daltons); (ii) B is a segment formed from a diisocyanate; (iii) F.sub.T is a polyfluoroorgano group; and (iv) n is an integer from 1 to 10.
(5) Formula (VI):

(39) ##STR00008##
wherein (i) A is an oligomeric segment including polyethylene oxide, polypropylene oxide, polytetramethylene oxide, or a mixture thereof, and having a theoretical molecular weight of from 500 to 5,000 Daltons (e.g., from 500 to 3,000 Daltons, from 500 to 2,000 Daltons, from 1,000 to 2,000 Daltons, or from 1,000 to 3,000 Daltons); (ii) B is a hard segment including an isocyanurate trimer or biuret trimer; (iii) F.sub.T is a polyfluoroorgano group; and (iv) n is an integer from 0 to 10.
(6) Formula (VII):
F.sub.T—[B-(Oligo)].sub.n—B—F.sub.T  (VII)
wherein (i) Oligo is a polycarbonate polyol having a theoretical molecular weight of from 500 to 5,000 Daltons (e.g., from 500 to 3,000 Daltons, from 500 to 2,000 Daltons, from 1,000 to 2,000 Daltons, or from 1,000 to 3,000 Daltons); (ii) B is a segment formed from a diisocyanate; (iii) F.sub.T is a polyfluoroorgano group; and (iv) n is an integer from 1 to 10.
(7) Formula (VIM):

(40) ##STR00009##
wherein (i) A is an oligomeric segment including a polycarbonate polyol having a theoretical molecular weight of from 500 to 5,000 Daltons (e.g., from 500 to 3,000 Daltons, from 500 to 2,000 Daltons, from 1,000 to 2,000 Daltons, or from 1,000 to 3,000 Daltons); (ii) B is a segment including an isocyanurate trimer or biuret trimer; (iii) F.sub.T is a polyfluoroorgano group; and (iv) n is an integer from 0 to 10.
(8) Formula (IX):

(41) ##STR00010##
wherein (i) A includes a first block segment selected from polypropylene oxide, polyethylene oxide, polytetramethyleneoxide, or a mixture thereof, and a second block segment including a polysiloxane or polydimethylsiloxane, wherein A has a theoretical molecular weight of from 500 to 5,000 Daltons (e.g., from 1,000 to 5,000 Daltons, from 1,000 to 3,000 Daltons, from 2,000 to 5,000 Daltons, or from 2,500 to 5,000 Daltons); (ii) B is a segment including an isocyanurate trimer or biuret trimer; (iii) F.sub.T is a polyfluoroorgano group; and (iv) n is an integer from 0 to 10.
(9) Formula (X):
F.sub.T—[B-A].sub.n—B—F.sub.T  (X)
wherein (i) A is a segment selected from the group consisting of hydrogenated polybutadiene (HLBH) (e.g., HLBH), polybutadiene (LBHP) (e.g., LBHP), hydrogenated polyisoprene (HHTPI) (e.g., HHTPI), and polystyrene and has a theoretical molecular weight of from 750 to 3,500 Daltons (e.g., from 750 to 2,000 Daltons, from 1,000 to 2,500 Daltons, or from 1,000 to 3,500 Daltons); (ii) B is a segment formed from a diisocyanate; (iii) F.sub.T is a polyfluoroorgano group; and (iv) n is an integer from 1 to 10.
(10) Formula (XI):

(42) ##STR00011##
wherein (i) A is hydrogenated polybutadiene (HLBH) (e.g., HLBH), polybutadiene (LBHP), hydrogenated polyisoprene (HHTPI), or polystyrene and has a theoretical molecular weight of from 750 to 3,500 Daltons (e.g., from 750 to 2,000 Daltons, from 1,000 to 2,500 Daltons, or from 1,000 to 3,500 Daltons); (ii) B is a segment including an isocyanurate trimer or biuret trimer; (iii) F.sub.T is a polyfluoroorgano group; and (iv) n is an integer from 0 to 10.
(11) Formula (XII):

(43) ##STR00012##
wherein (i) A is a polyester having a theoretical molecular weight of from 500 to 3,500 Daltons (e.g., from 500 to 2,000 Daltons, from 1,000 to 2,000 Daltons, or from 1,000 to 3,000 Daltons); (ii) B is a segment including an isocyanurate trimer or biuret trimer; (iii) F.sub.T is a polyfluoroorgano group; and (iv) n is an integer from 0 to 10.

(44) The surface modifying macromolecule of formula (I) can include B formed from a diisocyanate selected from 3-isocyanatomethyl-3,5,5-trimethyl-cyclohexylisocyanate; 4,4′-methylene bis(cyclohexyl isocyanate); 4,4′-methylene bis(phenyl isocyanate); toluene-2,4-diisocyanate; m-tetramethylxylene diisocyanate; and hexamethylene diisocyanate. The variable n may be 1 or 2. In certain embodiments, A is hydrogenated polybutadiene or poly((2,2-dimethyl)-1,3-propylene carbonate), and B is formed from 4,4′-methylene bis(cyclohexyl isocyanate). The surface modifying macromolecule of formula (I) may be used in admixture with a base polymer (e.g., polyalkylene (e.g., polyethylene, polypropylene, polyvinyl chloride, ethylene vinyl alcohol (EVOH), or polystyrene), polyester (e.g., poly(ethylene terephthalate) or polylactide), polyamide (e.g., PA6), or a polysaccharide (e.g., cellulose or cellulose acetate) to form a barrier layer (e.g., a moisture barrier layer) in the packaging materials of the invention. In some embodiments (e.g., embodiments related to pharmaceutical packaging materials), the surface modifying macromolecule of formula (I) (e.g., a compound of formula (I), in which A is hydrogenated polybutadiene or poly((2,2-dimethyl)-1,3-propylene carbonate), and B is formed from 4,4′-methylene bis(cyclohexyl isocyanate)) can be used in admixture with a base polymer, such as a polyethylene, a polypropylene, a polyvinyl chloride, or EVOH, to form a film (e.g., a monolayer or a bilayer) for a packaging material of the invention. In other embodiments (e.g., embodiments related to food packaging materials), the surface modifying macromolecule of formula (I) (e.g., a compound of formula (I), in which A is hydrogenated polybutadiene or poly((2,2-dimethyl)-1,3-propylene carbonate), and B is formed from 4,4′-methylene bis(cyclohexyl isocyanate)) can be used in admixture with a base polymer, such as a polyethylene, a polypropylene, a polyvinyl chloride, polystyrene, EVOH, polyethylene terephthalate, polylactide, or cellulose, to form a film (e.g., a monolayer or a bilayer) for a packaging material of the invention.

(45) The surface modifying macromolecule of formulae (III) and (IV) can include A that is an oligomeric segment containing hydrogenated polybutadiene (HLBH), poly((2,2-dimethyl)-1,3-propylene carbonate) (PCN), polybutadiene (LBHP), polytetramethylene oxide (PTMO), polypropylene oxide (PPO), (diethyleneglycol-orthophthalic anhydride) polyester (PDP), hydrogenated polyisoprene (HHTPI), poly(hexamethylene carbonate) (PHCN), poly((2-butyl-2-ethyl)-1,3-propylene carbonate), or A can be formed from hydroxylterminated polydimethylsiloxane (C22) or 1,12-dodecanediol. In the surface modifying macromolecule of formulae (III) and (IV), B is formed by reacting a triisocyanate (e.g., hexamethylene diisocyanate (HDI) biuret trimer, isophorone diisocyanate (IPDI) trimer, or hexamethylene diisocyanate (HDI) trimer) with a diol including the oligomeric segment A.

(46) In the surface modifying macromolecule of formula (V), B may be a segment formed from 3-isocyanatomethyl-3,5,5-trimethyl-cyclohexylisocyanate; 4,4′-methylene bis(cyclohexyl isocyanate); 4,4′-methylene bis(phenyl isocyanate); toluene-2,4-diisocyanate; m-tetramethylxylene diisocyanate; and hexamethylene diisocyanate. The variable n may be an integer from 1 to 3.

(47) In the surface modifying macromolecule of formula (VI), B is a segment formed by reacting a triisocyanate with a diol of A. The triisocyanate may be hexamethylene diisocyanate (HDI) biuret trimer, isophorone diisocyanate (IPDI) trimer, or hexamethylene diisocyanate (HDI) trimer. The variable n may be 0, 1, 2, or 3.

(48) In the surface modifying macromolecule of formula (VII), Oligo can include poly((2,2-dimethyl)-1,3-propylene carbonate) (PCN). B may be a segment formed from 3-isocyanatomethyl-3,5,5-trimethyl-cyclohexylisocyanate; 4,4′-methylene bis(cyclohexyl isocyanate); 4,4′-methylene bis(phenyl isocyanate); toluene-2,4-diisocyanate; m-tetramethylxylene diisocyanate; and hexamethylene diisocyanate. The variable n may be 1, 2, or 3. The surface modifying macromolecules of formula (VII) may be used in admixture with a base polymer (e.g., polyalkylene (e.g., polyethylene, polypropylene, polyvinyl chloride, ethylene vinyl alcohol (EVOH), or polystyrene), polyester (e.g., poly(ethylene terephthalate) or polylactide), polyamide (e.g., PA6), or a polysaccharide (e.g., cellulose or cellulose acetate) to form a barrier layer (e.g., a moisture barrier layer) in the packaging materials of the invention.

(49) In the surface modifying macromolecule of formula (VIII), B is a segment formed by reacting a triisocyanate with a diol of A (e.g., the oligomeric segment). The triisocyanate may be hexamethylene diisocyanate (HDI) biuret trimer, isophorone diisocyanate (IPDI) trimer, or hexamethylene diisocyanate (HDI) trimer. The segment A can include poly((2,2-dimethyl)-1,3-propylene carbonate) (PCN) or poly(hexamethylene carbonate) (PHCN). The variable n may be 0, 1, 2, or 3. The surface modifying macromolecules of formula (VIII) may be used in admixture with a base polymer (e.g., polyalkylene (e.g., polyethylene, polypropylene, polyvinyl chloride, ethylene vinyl alcohol (EVOH), or polystyrene), polyester (e.g., poly(ethylene terephthalate) or polylactide), polyamide (e.g., PA6), or a polysaccharide (e.g., cellulose or cellulose acetate) to form a barrier layer (e.g., a moisture barrier layer) in the packaging materials of the invention.

(50) In the surface modifying macromolecule of formula (IX), B is a hard segment formed by reacting a triisocyanate with a diol of A. In segment A, the number of first block segments and second block segments can be any integer or non-integer to provide the approximate theoretical molecule weight of the soft segment. The segment A can include polypropylene oxide and polydimethylsiloxane. The triisocyanate may be hexamethylene diisocyanate (HDI) biuret trimer, isophorone diisocyanate (IPDI) trimer, or hexamethylene diisocyanate (HDI) trimer. The variable n may be 0, 1, 2, or 3. The surface modifying macromolecules of formula (IX) may be used in admixture with a base polymer (e.g., polyalkylene (e.g., polyethylene, polypropylene, polyvinyl chloride, ethylene vinyl alcohol (EVOH), or polystyrene), polyester (e.g., poly(ethylene terephthalate) or polylactide), polyamide (e.g., PA6), or a polysaccharide (e.g., cellulose or cellulose acetate) to form a barrier layer (e.g., a moisture barrier layer) in the packaging materials of the invention.

(51) In surface modifying macromolecule of formula (X), B is a segment formed from a diisocyanate and a diol including segment A. The segment A can include hydrogenated polybutadiene. The segment B may be formed from 3-isocyanatomethyl-3,5,5-trimethyl-cyclohexylisocyanate; 4,4′-methylene bis(cyclohexyl isocyanate); 4,4′-methylene bis(phenyl isocyanate); toluene-2,4-diisocyanate; m-tetramethylxylene diisocyanate; or hexamethylene diisocyanate. The variable n may be 1, 2, or 3. The surface modifying macromolecules of formula (X) may be used in admixture with a base polymer (e.g., polyalkylene (e.g., polyethylene, polypropylene, polyvinyl chloride, ethylene vinyl alcohol (EVOH), or polystyrene), polyester (e.g., poly(ethylene terephthalate) or polylactide), polyamide (e.g., PA6), or a polysaccharide (e.g., cellulose or cellulose acetate) to form a barrier layer (e.g., a moisture barrier layer) in the packaging materials of the invention.

(52) In the surface modifying macromolecule of formula (XI), B is a segment formed by reacting a triisocyanate with a diol of A. The segment A may be hydrogenated polybutadiene (HLBH) or hydrogenated polyisoprene (HHTPI). The triisocyanate may be hexamethylene diisocyanate (HDI) biuret trimer, isophorone diisocyanate (IPDI) trimer, or hexamethylene diisocyanate (HDI) trimer. The variable n may be 0, 1, 2, or 3. The surface modifying macromolecules of formula (XI) may be used in admixture with a base polymer (e.g., polyalkylene (e.g., polyethylene, polypropylene, polyvinyl chloride, ethylene vinyl alcohol (EVOH), or polystyrene), polyester (e.g., poly(ethylene terephthalate) or polylactide), polyamide (e.g., PA6), or a polysaccharide (e.g., cellulose or cellulose acetate) to form a barrier layer (e.g., a moisture barrier layer) in the packaging materials of the invention.

(53) In the surface modifying macromolecule of formula (XII), B is a segment formed by reacting a triisocyanate with a diol of A (e.g., polyester). The segment A may be poly(diethylene glycol)adipate, (neopentyl glycol-ortho phthalic anhydride) polyester, (diethylene glycol-ortho phthalic) anhydride polyester, or (1,6-hexanediol-ortho phthalic anhydride) polyester. The triisocyanate may be hexamethylene diisocyanate (HDI) biuret trimer, isophorone diisocyanate (IPDI) trimer, and hexamethylene diisocyanate (HDI) trimer. The variable n may be 0, 1, 2, or 3. The surface modifying macromolecules of formula (XII) may be used in admixture with a base polymer (e.g., polyalkylene (e.g., polyethylene, polypropylene, polyvinyl chloride, ethylene vinyl alcohol (EVOH), or polystyrene), polyester (e.g., poly(ethylene terephthalate) or polylactide), polyamide (e.g., PA6), or a polysaccharide (e.g., cellulose or cellulose acetate) to form a barrier layer (e.g., a moisture barrier layer) in the packaging materials of the invention.

(54) For any of the surface modifying macromolecules of the invention formed from a diisocyanate, the diisocyanate may be 3-isocyanatomethyl-3,5,5-trimethyl-cyclohexylisocyanate; 4,4′-methylene bis(cyclohexyl isocyanate) (HMDI); 2,2′-, 2,4′-, and 4,4′-methylene bis(phenyl isocyanate) (MDI); toluene-2,4-diisocyanate; aromatic aliphatic isocyanate, such 1,2-, 1,3-, and 1,4-xylene diisocyanate; meta-tetramethylxylene diisocyanate (m-TMXDI); para-tetramethylxylene diisocyanate (p-TMXDI); hexamethylene diisocyanate (HDD; ethylene diisocyanate; propylene-1,2-diisocyanate; tetramethylene diisocyanate; tetramethylene-1,4-diisocyanate; octamethylene diisocyanate; decamethylene diisocyanate; 2,2,4-trimethylhexamethylene diisocyanate; 2,4,4-trimethylhexamethylene diisocyanate; dodecane-1,12-diisocyanate; dicyclohexylmethane diisocyanate; cyclobutane-1,3-diisocyanate; cyclohexane-1,2-diisocyanate; cyclohexane-1,3-diisocyanate; cyclohexane-1,4-diisocyanate; methyl-cyclohexylene diisocyanate (HTDI); 2,4-dimethylcyclohexane diisocyanate; 2,6-dimethylcyclohexane diisocyanate; 4,4′-dicyclohexyl diisocyanate; 2,4′-dicyclohexyl diisocyanate; 1,3,5-cyclohexane triisocyanate; isocyanatomethylcyclohexane isocyanate; 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane; isocyanatoethylcyclohexane isocyanate; bis(isocyanatomethyl)-cyclohexane; 4,4′-bis(isocyanatomethyl)dicyclohexane; 2,4′-bis(isocyanatomethyl)dicyclohexane; isophoronediisocyanate (IPDI); 2,4-hexahydrotoluene diisocyanate; 2,6-hexahydrotoluene diisocyanate; 3,3′-dimethyl-4,4′-biphenylene diisocyanate (TODD; polymeric MDI; carbodiimide-modified liquid 4,4′-diphenylmethane diisocyanate; para-phenylene diisocyanate (PPDI); meta-phenylene diisocyanate (MPDI); naphthylene-1,5-diisocyanate; 2,4′-, 4,4′-, or 2,2′-biphenyl diisocyanate; polyphenyl polymethylene polyisocyanate (PMDI); mixtures of MDI and PMDI; mixtures of PMDI and TDI; dimerized uretdione of any isocyanate described herein, such as uretdione of toluene diisocyanate, uretdione of hexamethylene diisocyanate, or a mixture thereof; or a substituted or isomeric mixture thereof.

(55) For any of the surface modifying macromolecules of the invention formed from an isocyanate trimer, the isocyanate trimer can be hexamethylene diisocyanate (HDI) biuret or trimer, isophorone diisocyanate (IPDI) trimer, hexamethylene diisocyanate (HDI) trimer; 2,2,4-trimethyl-1,6-hexane diisocyanate (TMDI) trimer; a trimerized isocyanurate of any isocyanates described herein, such as isocyanurate of toluene diisocyanate, trimer of diphenylmethane diisocyanate, trimer of tetramethylxylene diisocyanate, or a mixture thereof; a trimerized biuret of any isocyanates described herein; modified isocyanates derived from the above diisocyanates; or a substituted or isomeric mixture thereof.

(56) The surface modifying macromolecule can include the group F.sub.T that is a polyfluoroalkyl having a theoretical molecular weight of between 100-1,500 Da. For example, F.sub.T may be CF.sub.3(CF.sub.2).sub.rCH.sub.2CH.sub.2— wherein r is 2-20, and CF.sub.3(CF.sub.2).sub.s(CH.sub.2CH.sub.2O).sub.χ, where χ is 1-10 and s is 1-20. Alternatively, F.sub.T may be CH.sub.mF.sub.(3-m)(CF.sub.2).sub.rCH.sub.2CH.sub.2— or CH.sub.mF.sub.(3-m)(CF.sub.2).sub.s(CH.sub.2CH.sub.2O).sub.χ—, where m is 0, 1, 2, or 3; χ is an integer between 1-10; r is an integer between 2-20; and s is an integer between 1-20. In certain embodiments, F.sub.T is 1H,1H,2H,2H-perfluoro-1-decanol; 1H,1H,2H,2H-perfluoro-1-octanol; 1H,1H,5H-perfluoro-1-pentanol; or 1H,1H-perfluoro-1-butanol, or a mixture thereof. In particular embodiments, F.sub.T is (CF.sub.3)(CF.sub.2).sub.5CH.sub.2CH.sub.2O—, (CF.sub.3)(CF.sub.2).sub.7CH.sub.2CH.sub.2O—, (CF.sub.3)(CF.sub.2).sub.5CH.sub.2CH.sub.2O—, CHF.sub.2(CF.sub.2).sub.3CH.sub.2O—, or (CF.sub.3)(CF.sub.2).sub.2CH.sub.2O—.

(57) The surface-modifying macromolecules can be prepared according to methods described herein or in U.S. Pat. No. 6,127,507, or in the U.S. pre-grant publication Nos. 2008/0228253 and 2012/0148774; the disclosures of which are incorporated herein in their entirety.

(58) Other Uses

(59) While the invention described above is related to packaging materials in relation to packaging pharmaceutical and food products, the invention also features “specialty chemical packaging” or “electronic barrier films.”

(60) Specialty chemical packaging materials are the materials including a film containing a barrier layer formed from an admixture of a base polymer and a surface-modifying macromolecule. The films in specialty chemical packaging materials of the invention may have barrier properties against reactive atmospheric gases (e.g., water vapor, oxygen, or carbon dioxide) or a compound, which is intended to be stored in a container formed from the specialty chemical packaging. Unlike the packaging materials of the invention that can be used for pharmaceutical and food packaging, the specialty chemical packaging material (e.g., a layer within the specialty chemical packaging material) is not required to be acceptable for use as a pharmaceutical or food packaging. Instead, the specialty chemical packaging material of the invention can be that material which is inert to the compound stored in the container formed from the specialty chemical packaging material and has the barrier properties against this compound. When the stored compound is a compound that is reactive with atmospheric gases, such as water, oxygen, or carbon dioxide, the specialty chemical packaging material (e.g., a layer within the specialty chemical packaging material) of the invention may also have barrier properties against the atmospheric gas (e.g., moisture barrier properties, oxygen barrier properties, or carbon dioxide barrier properties). The base polymers that may be used in the specialty chemical packaging materials are same as those described above. The preparation of specialty chemical packaging materials and films therefor can be performed using methods described herein.

(61) Electronic barrier film is the film containing a barrier layer formed from an admixture of a base polymer and a surface-modifying macromolecule. The electronic barrier film can be used to secure an oily product (e.g., an insulating oil, such as a refined mineral oil) on or in proximity of an electronic device or a portion thereof. Additionally or alternatively, the electronic barrier films can be used to decrease the exposure of an electronic device (e.g., a semiconductor) or a portion thereof to the environmental hazards, such as moisture or oxygen. The electronic barrier films of the invention may have barrier properties against atmospheric gases (e.g., water vapor, oxygen, or carbon dioxide) or oil (e.g., a hydrocarbon or a fatty acid ester). Unlike the packaging materials of the invention that can be used for pharmaceutical and food packaging, the electronic barrier film (e.g., a layer within the electronic barrier film) is not required to be acceptable for use as a pharmaceutical or food packaging. Instead, the electronic barrier film of the invention can be that material which the barrier properties against long chain hydrocarbons (e.g., hydrocarbon having more than 6 carbon atoms) and/or fatty acid esters and/or certain atmospheric gases (e.g., water vapor, oxygen, or carbon dioxide). The base polymers that may be used in the electronic barrier films of the invention are same as those described above. The preparation of electronic barrier films of the invention can be performed using methods described herein.

(62) The following examples are meant to illustrate the invention. They are not meant to limit the invention in any way.

EXAMPLES

(63) Surface-modifying macromolecules of any one of formulae (I), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX), (X), (XI), and (XII) can be prepared as described in U.S. Pat. Nos. 6,127,507; 8,071,683; and 8,318,867; and in U.S. pre-grant publication Nos. 2008/0228253 and 2012/0148774. FIGS. 1-22 show exemplary surface-modifying macromolecules that were prepared in accordance with procedures described herein or in U.S. Pat. Nos. 6,127,507; 8,071,683; and 8,318,867; and in U.S. pre-grant publication Nos. 2008/0228253 and 2012/0148774.

Example 1—Preparation of Surface Modifying Macromolecules

(64) ##STR00013##

(65) Compound 4:

(66) all glassware used for the synthesis was dried in an oven at 110° C. overnight. To a 3-necked 1000 ml oven dried flask equipped with a stir bar was added 175 g (72 mmol) of hydrogenated-hydroxyl terminated polybutadiene (HLBH diol, MW=2000). The flask with the diol was degassed overnight and then purged with dry N.sub.2. A 1000 mL graduated cylinder was filled with 525 mL anhydrous toluene, sealed by a rubber septa and purged with dry N.sub.2. The toluene was transferred to the 3-necked flask via a double-edged needle and the diol stirred vigorously to dissolve in the solvent. The flask was placed in an oil bath at 65-70° C. At this time, 39.70 g (151 mmol) of 4,4′-methylene bis(cyclohexyl isocyanate) (HMDI) was added to a degassed 250 ml flask equipped with a stir bar. To this flask was added 150 ml of anhydrous Toluene from a degassed, N.sub.2 purged 250 ml septa-sealed cylinder also using a double-edged needle and the mixture was stirred to dissolve the HMDI in the solvent. To a degassed 50 ml round bottom flask was added 8.75 g (5.00% w/w based on diol) of the bismuth carboxylate catalyst followed by 26 ml of toluene to dissolve the catalyst. The HMDI solution was transferred to the 1000 ml flask containing the diol using a double-edged needle. The bismuth catalyst solution was added (20 ml) immediately following the addition of the HMDI. The reaction mixture was allowed to stir for 5 h at 70° C. to produce a HMDI-HLBH prepolymer.

(67) In another 50 ml round bottom flask 74.95 g (180 mmol) of C8-FOH (1H,1H,2H,2H-perfluoro-1-octanol) was added, capped with a septa, degassed and then purged with N.sub.2. This was added to the 1000 ml flask containing prepolymer solution via a double-edged needle. All additions and transfers were conducted carefully in an atmosphere of dry N.sub.2 to avoid any contact with air. The resulting mixture was heated to 45° C. for 18 hours to produce Compound 4 with the end-capped C8-FOH. The Compound 4 solution was allowed to cool to ambient temperature and at this point is milky in color. The milky solution was precipitated in MeOH (methanol). The polymer was washed repeatedly with 2 more MeOH washes to form a white viscous material with dough-like consistency. This viscous, semi-solid material was washed twice in THF/EDTA (ethylene diamine tetraacetic acid) to remove residual catalyst followed by two more successive washes in THF/MeOH to remove unreacted monomers, low molecular weight byproducts, and catalyst residues. The Compound 4 was first dried in a flow oven from at 40-120° C. in a period of 10 h gradually raising the temperature and finally dried under vacuum at 120° C. (24 h) and stored in a desiccator as a colorless rubbery semi-solid. The structure of Compound 4 is shown in FIG. 3B (Z=1).

(68) Compound 1:

(69) the reaction was carried out as described for Compound 4 using 180 g (74 mmol) Hydrogenated-hydroxyl terminated polybutadiene (HLBH diol, MW=2000) and 30.14 g (115 mmol) of 4,4′-methylene bis(cyclohexyl isocyanate) (HMDI) to form the prepolymer. The prepolymer was end-capped with 40.48 g (111.18 mmol) of 1H,1H,2H,2H-perfluoro-1-octanol (C8-FOH) to form Compound 1 as a colorless rubbery semi-solid. As described above, the couplings were carried out in the presence of bismuth carboxylate catalyst and the Compound 1 was washed similarly to Compound 4 and dried prior to use. The structure of Compound 1 is shown in FIG. 1 (Z=2).

(70) The properties of Compound 4 and Compound 1 are shown in Table 2.

(71) TABLE-US-00001 TABLE 2 Properties Test Method Compound 4 Compound 1 Appearance Visual Rubbery semi-solid Rubbery semi-solid Theo. MW Calc. from Structure 3785 Da 6372 Da Elemental Composition Elemental Analysis (%) C 75.27 77.93 for Bi (ppm) H 11.98 12.41 N 1.45 1.44 F 8.26 6.51 Bi 12 ppm 56 ppm T.sub.d, Thermal Degradation TGA, High Res First Onset at First Onset at temp (N.sub.2) TA Q500 5% wt loss, 5% wt loss, 326° C. 319° C. Glass Transition DSC, TA Q100 −44.27° C. −45.54° C. Temperature, T.sub.g (N.sub.2, Second heating)

(72) Compound 2:

(73) the reaction was carried out as described for Compound 4, except the solvent was changed from toluene to DMAC. Here, 100 g (100 mmol) poly((2,2-dimethyl)-1,3-propylene carbonate)diol (PCN, MW 1000) and 40.7 g (155 mmol) of 4,4′-methylene bis(cyclohexyl isocyanate) (HMDI) to form the prepolymer. The prepolymer was end-capped with 45.5 g (125 mmol) of 1H,1H,2H,2H-perfluoro-1-octanol (C8-FOH) to form Compound 2. The work-up after the reaction and the subsequent washing procedures are modified from Compound 4 as follows. The SMM from the reaction mixture in DMAC was precipitated in distilled water, and washed successively in IPA/EDTA (Isopropanol/ethylene diamine tetraacetic acid) solution followed by another wash in IPA/hexanes to remove unreacted monomers, low molecular weight byproducts and catalyst residues to yield Compound 2 as a white amorphous powder. As described above, the couplings were carried out in the presence of bismuth carboxylate catalyst and dried under vacuum prior to use. The structure of Compound 2 is shown in FIG. 2. Alternatively, a surface-modifying macromolecule, as shown in FIG. 2 with the exception that Z=1, can be prepared according to the procedure described herein for Compound 2 with adjusted stoichiometry.

Example 2—Preparation of Films

(74) The films of the invention can be prepared from a base polymer and a surface modifying macromolecule according to methods known in the art and described herein. Samples of certain films of the invention were prepared from Dowlex 2244G LLDPE with Compound 1 or Compound 4, such that the content of the surface modifying macromolecule in the film was 4%. Another film was prepared from Dowlex 2244G LLDPE without including a surface modifying macromolecule.

Example 3—Water Vapor Transmission Rate of Films of the Invention

(75) The water vapor transmission rate (WVTR) test was performed on the samples prepared in Example 2 on MOCON Permatran-W 3/33 instrument at 38° C. (100° F.). The protocol for WVTR test was in accordance with ASTM F-1249. The test gas was water vapor (90% RH), and the carrier gas was dry nitrogen (0% RH). The samples were masked to 5 cm.sup.2. The replicate experiments were performed on duplicate samples of the same film. The test results are shown in Table 3.

(76) TABLE-US-00002 TABLE 3 Thickness WVTR, g/(m.sup.2 .Math. day .Math. mil) Sample Average, mil Experiment 1 Experiment 2 Average LLDPE 1.3 7.55 7.51 7.53 LLDPE + 2.6 3.49 3.57 3.53 Compound 4 LLDPE + 2.8 2.99 2.99 2.99 Compound 1

(77) Water vapor transmission rate (WVTR) test can be performed in accordance with ASTM F-1249 on films prepared (e.g., by extrusion) from an admixture of a base polymer (e.g., a polyalkylene) and a surface-modifying macromolecule (e.g., any one of Compounds 1-28).

Other Embodiments

(78) Various modifications and variations of the described materials and methods of use of the invention will be apparent to those skilled in the art without departing from the scope and spirit of the invention. Although the invention has been described in connection with specific embodiments, it should be understood that the invention as claimed should not be unduly limited to such specific embodiments. Indeed, various modifications of the described modes for carrying out the invention that are obvious to those skilled in the art are intended to be within the scope of the invention.

(79) Other embodiments are in the claims.