阅读说明：本技术 复合聚合物膜 (Composite polymer film ) 是由 S·刘 邓风华 J·N·鲁滨逊 M·泰勒 于 2018-09-26 设计创作，主要内容包括：复合膜包括：a)聚合物膜(例如聚酯)的自支撑层,b)在聚合物膜层上的任选的底漆层,其中底漆层包含PVdX(X为卤素)、丙烯酸类或乙烯基树脂；和c)在底漆层上的热封组合物层,其中热封组合物包含聚烯烃塑性体(POP)树脂和占热封组合物的至少20重量％的增粘剂。可以通过将在溶剂中的包含热封组合物的涂布组合物涂敷至聚合物膜上的底漆层或在不存在任选的底漆层下直接施用在聚合物膜上,然后蒸发溶剂来形成复合膜。可以将复合膜热封至容器或自支撑膜的表面。(The composite membrane includes: a) a self-supporting layer of a polymeric film (e.g., polyester), b) an optional primer layer on the polymeric film layer, wherein the primer layer comprises pvdf X (X is a halogen), an acrylic, or a vinyl resin; and c) a layer of a heat seal composition on the primer layer, wherein the heat seal composition comprises a polyolefin plastomer (POP) resin and at least 20% by weight of the heat seal composition of a tackifier. The composite film may be formed by applying a coating composition comprising the heat seal composition in a solvent to the primer layer on the polymeric film or directly on the polymeric film in the absence of the optional primer layer, and then evaporating the solvent. The composite film may be heat sealed to the surface of the container or self-supporting film.)

1. A composite membrane, comprising:

a) a self-supporting layer of a polymeric film (optionally, the polymeric film comprises a polar polymer and/or a polyolefin polymer), and further optionally oriented in at least one direction;

b) an optional primer layer on the polymeric film and between the polymeric film and heat seal layer (c), wherein the primer layer comprises a halogenated polyvinylidene polymer, an acrylic resin and/or a vinyl resin; and is

Wherein the heat-seal layer comprising a heat-seal composition is disposed on the optional primer layer in the presence of the optional primer layer or directly on the surface of the polymeric film in the absence of the optional primer layer (b),

wherein the heat seal layer composition comprises a polyolefin plastomer (POP) resin and a tackifier; and wherein

i. The tackifier is present in an amount of at least 20% by weight of the heat seal composition, the total weight of the heat seal composition being 100%; and is

The POP resin is present in an amount of no more than 80% by weight of the heat seal composition, the total weight of the heat seal composition being 100%; and wherein

The optional primer layer is present only when the polymeric film comprises polyolefin, and wherein the surface of the polymeric film in contact with the thermal layer (c) has been corona treated in the absence of optional primer layer (b).

2. The composite film of claim 1 wherein the heat seal composition further comprises an acrylic resin and/or a vinyl resin.

3. A composite film according to any preceding claim wherein the halogenated polyvinylidene polymer in the optional primer layer (b) comprises PVdX where X is halogen, preferably the halogenated polyvinylidene polymer consists of PVdX where X is halogen, preferably PVdX is a PVdC resin.

4. The composite film according to any preceding claim wherein the acrylic resin and/or vinyl resin present in the optional primer layer (b) and/or the heat seal layer (c) is selected from resins in the group of: c_1-4Alkyl vinyl acetate resin and C_1-4(meth) acrylic resins.

5. The composite film of claim 4 wherein the acrylic resin and/or vinyl resin is selected from the group consisting of: ethyl Acrylate (EA), Ethylene Vinyl Acetate (EVA), ethacrylic acid (EAA), and ethylmethacrylic acid (EMA).

6. A composite film according to any preceding claim wherein the adhesion promoter is an adhesion promoter resin which constitutes at least 25% by weight of the heat seal composition.

7. A composite film according to any preceding claim wherein the POP resin in the heat-seal layer (c) is selected from resins obtained and/or obtainable from at least one monomer of formula 1 and at least one other different polymer precursor selected from any one of the following I) to V):

CH₂CHR formula 1

Wherein R is H or C_1-10An alkyl group;

I. at least one different polymer precursor also represented by formula 1

At least one polymer precursor represented by formula 2

C_4-20α (alpha), omega (gamma) -diolefins, formula 2

At least one polymer precursor represented by formula 3

C_3-20α (alpha) -olefin, formula 3

At least one polymer precursor represented by formula 4

C_≥18A diene; -formula 4, and

v. at least one polymer precursor represented by formula 5

C_4-18Cyclic olefins (including norbornene) -formula 5.

8. The composite membrane according to claim 7, wherein formula 1 represents an ethylene monomer.

9. The composite film of claim 7, wherein the POP resin comprises at least one C_2-4A copolymer of an alkylene and at least one polymer precursor of any one of formulae 2 to 5.

10. The composite film of claim 7, wherein the POP resin comprises ethylene and/or propylene with at least one C_5-20Copolymers of olefinic hydrocarbons.

11. The composite film of claim 10, wherein the POP resin comprises ethylene and at least one C_6-15Copolymers of olefinic hydrocarbons.

12. The composite film of claim 11, wherein the POP resin comprises ethylene and at least one C_6-12Copolymers of olefinic hydrocarbons.

13. The composite film of claim 12, wherein the POP resin comprises ethylene and at least one linear monounsaturated C_6-10Copolymers of olefinic hydrocarbons.

14. The composite film of claim 13, wherein the POP resin is a copolymer of ethylene and 1-octene.

15. The composite film of any preceding claim, wherein the DSC melting point of the POP resin is less than 100 ℃.

16. Composite film according to any one of the preceding claims, wherein the number average molecular weight (M) of the POP resin_n) 5000 plus 50000 dalton.

17. The composite film of any preceding claim, wherein the amount of α (alpha) olefin comonomer in the POP resin is 5-85 mol% and the total amount of POP resin is 100 mol%.

18. A composite film according to any preceding claim wherein the POP resin is present in an amount of no more than 75% by weight of the heat seal composition, the heat seal composition total weight being 100%.

19. A composite film according to any preceding claim wherein the adhesion promoter is an adhesion promoter resin and is present in an amount of 25% by weight of the heat seal composition, the heat seal composition total weight being 100%.

20. The composite film of any preceding claim wherein the polymeric film layer is formed from a polar polymer and/or a polyolefin polymer.

21. The composite film of any preceding claim, wherein the polymeric film comprises a polyester or a polyolefin.

22. The composite film of claim 21 wherein the polymeric film comprises a biaxially oriented polyester film.

23. The composite film according to any one of the preceding claims, wherein the polymer film comprises at least one polymer selected from the group consisting of polypropylene (PP), Polyethylene (PE), polyglycolic acid (PGA), polylactic acid (P L A), polycaprolactone (PC L), Polyhydroxyalkanoate (PHA), Polyhydroxybutyrate (PHB), polyethylene adipate (PEA), polybutylene succinate (PBS), poly (3-hydroxybutyrate)-co-3-hydroxyvalerate) (PHBV), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), polyethylene furanoate (PEF), liquid crystalline aromatic polyesters such asPolyetheretherketone (PEEK), and/or any suitable mixtures, combinations, and copolymers thereof.

24. The composite film according to any preceding claim wherein the polymeric film comprises at least one polyester selected from the group consisting of P L A, PHB, PET, PEN, PEF, any suitable mixtures, combinations and copolymers thereof.

25. The composite film of claim 24 wherein the polyester is selected from the group consisting of: PET, PEN and PEF.

26. The composite film of claim 25 wherein the polyester is selected from the group consisting of: PET and PEN.

27. The composite film of claim 26 wherein the polyester is PET.

28. The composite film of any preceding claim wherein the polymeric film layer is biaxially oriented.

29. A method of making a composite membrane according to any preceding claim comprising the steps of:

i. applying a coating composition comprising a heat seal composition in a solvent to an optional primer layer on the polymeric film or, in the absence of the optional primer layer, directly to the corona treated surface of the polymeric film prior to application

Evaporating the solvent, wherein the heat-seal composition comprises:

a polyolefin plastomer (POP) resin,

a tackifier present in an amount of at least 20% by weight of the heat seal composition, the total weight of the heat seal composition being 100%;

and optionally an acrylic resin and/or a vinyl resin.

30. A method of making the composite film of claim 23 wherein the polymer film comprises polyester.

31. A method of manufacturing a composite film according to claim 23 or 24 wherein the acrylic resin and/or vinyl resin is present in the optional primer layer (b) and/or in the heat seal layer (c), and wherein the acrylic resin and/or vinyl resin is selected from the group of: ethyl Acrylate (EA), Ethylene Vinyl Acetate (EVA), ethacrylic acid (EAA) and ethylmethacrylic acid (EMA), preferably EVA.

32. A method of bonding a polymeric film to a container or a self-supporting film comprising heat sealing the composite film of any one of claims 1 to 28 to a surface of the container or self-supporting film.

33. The method of claim 32, wherein the surface is a polyolefin surface.

34. The method of claim 33, wherein the surface is a surface of polypropylene (PP) or High Density Polyethylene (HDPE).

35. Use of a composite film according to any of claims 1 to 28 as a heat-sealable part of a packaging article and/or as a liner for a lid of a packaging article.

36. Use of a composite film according to claim 35 wherein the packaging article is a ovenable food container.

37. A packaging article comprising the composite film of any one of claims 1 to 28.

38. The packaging article of claim 37, which is a ovenable food container optionally comprising a polypropylene (PP) or High Density Polyethylene (HDPE) tray.

39. A packaging article which is a lid for a packaging article lined with a composite film according to any one of claims 1 to 22.

40. A filled packaging article sealed with a lid according to claim 39.

41. A method of filling a packaging article with a food or human and/or animal consumable liquid, comprising the steps of:

a. filling the article with the food or human and/or animal consumable liquid;

b. applying the cap of claim 39 to a filled article to reversibly seal the article.

Background

Polymeric films capable of being heat sealed to non-polar substrates are becoming increasingly important as more and more dietary manufacturers are turning to polypropylene (PP) trays for cost savings. Moreover, the market for induction seal gaskets for High Density Polyethylene (HDPE) and PP containers is steadily growing in the pharmaceutical and food industries. Ethylene Vinyl Acetate (EVA) resins have generally been used for such applications, but these tend to produce relatively weak seals to PP and HDPE, and this has limited applicability in many applications. Alternative heat-seal adhesives using conventional low density polyethylene have been described, but these tend to have a rather narrow operating temperature window for the heat-sealing process, and they cannot be applied to all polymeric substrates (e.g., cannot be applied to polyester substrates) by solvent-based coating because of their very poor solubility in common organic solvents. Therefore, polymer films with heat-sealable layers (e.g., polyester films) that address these issues would represent a welcome advance in packaging technology.

Disclosure of Invention

Broadly, one aspect of the invention provides a composite membrane comprising:

a) a self-supporting layer of a polymeric film, (optionally, the polymeric film comprises a polar polymer and/or a polyolefin polymer), and further optionally oriented in at least one direction),

b) an optional primer layer on the polymeric film and between the polymeric film and heat seal layer (c), wherein the optional primer layer comprises a halogenated polyvinylidene (halo polyvinylidene) polymer, an acrylic resin and/or a vinyl resin; and is

Wherein a heat-seal layer comprising the heat-seal composition is disposed on the optional primer layer in the presence, or directly on the surface of the polymeric film in the absence of the optional primer layer (b),

wherein the heat seal composition comprises a polyolefin plastomer (POP) resin and a tackifier; and wherein

(i) The tackifier is present in an amount of at least 20% by weight of the heat seal composition, the total weight of the heat seal composition being 100%; and is

(ii) The POP resin is present in an amount of no more than 80% by weight of the heat seal composition, the total weight of the heat seal composition being 100%; and wherein

(iii) The optional primer layer is present only when the polymeric film comprises polyolefin, and wherein in the absence of the optional primer layer (b), the surface of the polymeric film in contact with the thermal layer (c) has been corona treated.

The composite film may comprise a heat-seal composition further comprising an acrylic resin and/or a vinyl resin.

The composite film may comprise a halogenated polyvinylidene polymer comprising, more preferably consisting of, and most preferably consisting of, a pvdf resin wherein X is a halogen (e.g., X is chlorine), in an optional primer layer (b).

The composite film may comprise an acrylic resin and/or a vinyl resin present in the optional primer layer (b) and/or heat seal layer (c), the acrylic resin and/or vinyl resin being selected from: c_1-4Alkyl vinyl acetate resin and C_1-4(meth) acrylic resins, preferably selected from: ethyl Acrylate (EA), Ethylene Vinyl Acetate (EVA), ethacrylic acid (EAA), and ethylmethacrylic acid (EMA).

The composite film may comprise a POP resin in the heat seal layer (c), suitable POP resins being further defined herein.

The DSC melting point of the POP resin may be below 100 ℃.

Molecular weights (such as weight average molecular weight (M)) of the polymers and resins described herein_w) And number average molecular weight (M)_n) Can be determined by any suitable method known to those skilled in the art, such as by experiment (e.g., GPC, SEC, etc.) and/or by theoretical calculation. A measurement M is described in "Determination of Number Average and Weight Average molecular weights of Polymer Sample from Diffusion and Determination of location measurements in the solution" of Journal of Applied Polymer Science, volume 28, pages 2325 to 23339, Okabe and Matsuda_wAnd M_nThe article is incorporated herein by reference.

The amount of α (alpha) -olefin comonomer in the POP resin may be 5 to 85 mol% based on the total amount of the POP resin being 100 mol%.

The composite film may comprise a POP resin present in an amount of no more than 75% by weight, the total weight of the heat seal composition being 100%.

The composite film may comprise an adhesion promoter which is an adhesion promoter resin and preferably comprises at least 25% by weight of the heat seal composition, the total weight of the heat seal composition being 100%.

The composite film may comprise at least one polyester selected from the group consisting of polyethylene terephthalate (PET), polylactic acid (P L A), Polyhydroxybutyrate (PHB), polyethylene furan acid (PEF), and polyethylene naphthalate (PEN).

In another aspect of the invention, there is provided a method of preparing a composite membrane of the invention, the method comprising the steps of:

(i) the coating composition comprising the heat seal composition in a solvent is applied to a primer layer on a polymeric film (such as to a polar film, e.g., a polyester film) or, in the absence of an optional primer layer, directly to the surface of a corona-treated polymeric film, and then

(ii) Evaporating the solvent, wherein the heat seal composition comprises a polyolefin plastomer (POP) resin,

a tackifier resin present in an amount of at least 20% by weight, the heat-sealable composition being 100%, and optionally an acrylic resin and/or a vinyl resin, preferably an EVA resin.

Another aspect of the present invention provides a method of bonding a polymeric film to a container or a self-supporting film comprising heat sealing the composite film of the present invention described herein to a surface of the container or self-supporting film. The surface may be a surface of a polyolefin, such as polypropylene (PP) and/or High Density Polyethylene (HDPE). The heat sealable composite films of the present invention may be unprimed polyolefin films or primed polar films (e.g., primed polyester films) comprising the heat seal layer described herein thereon.

Drawings

Figure 1 shows the peel strength as a function of temperature at heat sealing of a composite film comprising a primed polyester film coated with a heat sealing composition heat sealed to an HDPE substrate according to the invention as compared to heat sealing of a prior art film with an extrusion coated EVA heat seal layer.

Figure 2 shows the peel strength results of tests similar to those shown in figure 1 when a polypropylene substrate was used in place of the HDPE substrate.

Detailed Description

The present invention provides composite films that provide excellent heat seal strength to a variety of substrates, including non-polar substrates such as polyolefin substrates, e.g., PP and HDPE. The composite films have a very broad temperature window for heat sealing to the substrate and provide them with the advantage that they can be applied by solvent-based coating. The composite film desirably has a low heat seal initiation temperature and provides a relatively constant peel strength as a function of heat seal temperature, as compared to films using conventional heat seal compositions. This allows for a shorter residence time during heat sealing, thereby facilitating process efficiency.

As used herein, the term "heat seal initiation temperature" is the temperature at which a peel strength of at least 350g force/inch (135N/m) is developed to the HDPE substrate when sealed at 80psi (552 kPa) for 1 second. The heat seal initiation temperature is the lowest temperature at which the sealing polymer is sufficiently melt flowable and melt bonded to adjacent layers in the seal. Below this temperature, the coating will have insufficient adhesive strength to the substrate. In many packaging line applications, a sealing temperature well above the heat seal initiation temperature is typically used to ensure adequate seal strength.

The heat seal initiation temperature of the composition of the composite film useful in the present invention is generally no greater than 265 ℃ F. (-129 ℃ C.) or 275 ℃ F. (-141 ℃ C.). Moreover, the composition of the composite film according to various embodiments of the present invention provides peel strength that varies little significantly over a wide range of sealing temperatures compared to typical extrusion coated products. The peel strength of the heat seal produced at 275 DEG F (141 ℃) is typically at least 70%, or at least 75%, or 80% or 85% or 90% of the peel strength produced at 400 DEG F (204 ℃).

Composite films according to the present invention typically provide peel strengths of at least 350g force/inch (135N/m), or at least 500, or greater than or equal to 700, or greater than or equal to 900, or greater than or equal to 925, or greater than or equal to 950, or greater than or equal to 975, or greater than or equal to 1000, or greater than or equal to 1025g force/inch (193N/m, 270N/m, 347N/m, 357N/m, 367N/m, 376N/m, 386N/m, and 396N/m, respectively) when applied to an HDPE substrate at 300 DEG F (149 ℃) and 80psi (552 kPa) for 1 second.

The inventors have found that due to the high tackifier content of the heat-seal compositions of the present invention, these heat-seal compositions cannot generally be applied by extrusion coating because of poor cold roll release. The present inventors have solved this problem by solvent coating the heat seal composition on a primed substrate comprising a primer layer on a polar polymer film, such as polyester. The heat seal composition may also be coated on an unprimed substrate, wherein the unprimed substrate comprises a polyolefin polymer film which may optionally be corona treated in place of using a primer coating, although it is still preferred to use a primer to provide improvements in the heat seal layer and polymer filmBecause it prevents delamination of the composite film under a wide range of conditions. The present invention also addresses the problem of thermal stability, which prevents certain types of tackifier resins from being used in extrusion coating. For example, tackifiers having a low softening point (e.g. tackifierC85 resin, softening point 82-88℃) may cause smoking under typical extrusion coating conditions.

The composite film of the present invention can be heat sealed to a container or a self-supporting film using a heat seal layer as a contact layer with the container or with the self-supporting film. The container may be preformed and the surface of the container to be bonded to the composite film may be made of any material. Suitable exemplary materials include glass-metal and polymers. Exemplary polymers include nylon and polyester, including polyesters that are not themselves heat sealable, such as polyethylene terephthalate (PET) homopolymer. Most particularly, the material may be HDPE or PP. If the composite film is heat-sealed to a self-supporting film instead, the self-supporting film having the composite film heat-sealed on its surface may be made of any of these same materials.

The composite film of the present invention comprises a self-supporting layer of polymeric film, an optional primer layer on the polymeric film (the primer layer being optional if the polymeric film is a corona-treated polyolefin film), and a heat seal layer on the primer layer or directly on the unprimed corona-treated polymeric film in the absence of the optional primer layer. Typically, all of these layers are coextensive.

The heat-seal layer comprises a heat-seal composition comprising one or more acrylic resins and/or vinyl resins, preferably EVA, EAA or EMA, more preferably EVA resins, one or more tackifiers (e.g., tackifier resins), and one or more polyolefin plastomer (POP) resins. Each of the components of the composite film will be discussed in detail herein, including a description of the components in the heat seal layer.

A further aspect of the present invention provides the use of a film of the present invention as described herein as a heat sealable component of a packaging article (e.g. a ovenable food container) and/or as a liner for the lid of a packaging article.

A further aspect of the present invention provides a packaging article comprising a composite film of the present invention as described herein, for example a packaging article comprising a ovenable food container (optionally comprising a HDPE or PP tray) and/or a lid for a packaging article lined with a composite film of the present invention as described herein.

Acrylic resin and/or vinyl resin

Acrylic and/or vinyl resins refer to a subset of resins that may be obtained and/or obtainable from at least one polymer precursor (i.e., which may itself be polymeric, e.g., oligomeric or monomeric) that contains activated unsaturation.

The term "activated unsaturated moiety" is used herein to denote a species (species) comprising at least one unsaturated carbon-carbon double bond that is chemically proximal to at least one activated moiety, preferably the activated moiety comprises any group that activates an ethylenically unsaturated double bond to add thereto via a suitable electrophilic group, suitably the activated moiety comprises an oxo, thio, (optionally organically substituted) amino, thiocarbonyl and/or carbonyl group (the latter two groups being optionally substituted by sulphur, oxygen or (optionally organically substituted) amino group), more suitably the activated moiety is a (thio) ether, (thio) ester and/or (thio) amide moiety most suitably the "activated unsaturated moiety" comprises an "unsaturated ester moiety" which denotes an organic species comprising one or more "hydrocarbylidene (thio) carbonyl (thio) oxy" and/or one or more "hydrocarbylidene (thio) -carbonyl (organic) amino" groups and/or derived moieties and/or derivatives thereof, for example including derivatives of methacrylic acid and/or derivatives thereof, including optionally substituted derivatives thereof, including derivatives thereof, such as α.

Acrylic and/or vinyl polymer precursors (such as acrylic and/or vinyl oligomers or monomers) suitable for use in preparing the acrylic and/or vinyl resins useful in the present invention may comprise one or more hydrophobic, hydrophilic, and/or partially hydrophilic polymer parents as a component that can be polymerized to form an acrylic polymer and/or vinyl polymer.

The hydrophobic polymer precursor may comprise, suitably consist essentially of, at least one hydrophobic polymer precursor comprising at least one activated unsaturated moiety, suitably at least one hydrophobic (meth) acrylate monomer, and/or an aryl alkylene (aryl alkylene) polymer precursor. As used herein, (meth) acrylate refers to acrylate and/or methacrylate moieties, and similarly herein (meth) acrylic acid refers to acrylic and/or methacrylic moieties.

The hydrophobic (meth) acrylate may comprise C_＞4A hydrocarbyl (meth) acrylate, and suitably C_＞4The hydrocarbyl moiety may be C_4-20A hydrocarbon group, more suitably C_4-14Alkyl, most suitably C_4-10Alkyl radicals, e.g. C_4-8An alkyl group. The hydrophobic (meth) acrylate may be selected from: isooctyl acrylate, 4-methyl-2-pentyl acrylate, 2-methylbutyl acrylate, isoamyl acrylate, sec-butyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, isodecyl methacrylate, isononyl acrylate, isodecyl acrylate, and/or mixtures thereof.

The aryl alkylene monomer may comprise styrene (optionally substituted with a hydrocarbyl group), and the optional hydrocarbyl group may be C_1-10A hydrocarbon group, more suitably C_1-4The alkyl aryl olefin monomer is selected from the group consisting of styrene, α -methyl styrene, vinyl toluene, t-butyl styrene, dimethyl styrene and/or mixtures thereof.

The hydrophilic monomer comprises, advantageously consists essentially of, at least one ethylenically unsaturated carboxylic acid (such as an acid having one ethylenic group and one or two carboxyl groups), the acid may be selected from acrylic acid (and oligomers thereof), β carboxyethyl acrylate, citraconic acid, crotonic acid, fumaric acid, itaconic acid, maleic acid, methacrylic acid, and mixtures thereof.

Partially hydrophilic polymer precursors may also be referred to as partially water soluble monomers and may suitably comprise at least one activated unsaturated moiety. Preferred partially hydrophilic monomers comprise at least one (meth) acrylic acid C_1-2The alkyl ester suitably consists essentially of it. More preferred partially hydrophilic monomers are selected from: methyl Acrylate (MA), Methyl Methacrylate (MMA), Ethyl Acrylate (EA) and mixtures thereof.

Examples of suitable Ethyl Acrylate (EA) resins are available from DuPont under the trade name2000 series of commercially available resins.

Ethylene-vinyl acetate (EVA) resins, also known as poly (ethylene-vinyl acetate) (PEVA), represent a class of copolymers formed from ethylene and vinyl acetate monomers. Vinyl Acetate (VA) has the following structure

Ethylene-acrylic acid (EAA) resins represent a class of copolymers formed from ethylene and Acrylic Acid (AA) monomers. Acrylic Acid (AA) has the following structure

Ethylene-methacrylic acid (EMA) resins represent a class of copolymers formed from ethylene and methacrylic acid (MAA) monomers. Methacrylic acid (MAA) has the following structure

Typically, the total amount of one or more acrylic and/or vinyl resins (such as EA, EAA, EVA, and/or EMA resins) in the heat seal composition of the heat seal layer is at least 15%, or at least 18%, or at least 20%, or at least 25%, or 30%, by weight of the heat seal composition, of acrylic and/or vinyl resin. Typically, up to 60%, or up to 55%, 50%, 45% or 40% of acrylic resin and/or vinyl resin is present in the heat-seal composition, the total weight of acrylic resin and/or vinyl resin being based on 100% of the total weight of the respective heat-seal composition (depending on the composition, acrylic resin and/or vinyl resin form part). EVA resin is a preferred vinyl resin, and is more preferably used in the aforementioned amount. The total amount of acrylic resin and/or vinyl resin present in the heat seal composition may be from 15% to 60%, preferably from 18% to 55%, more preferably from 20% to 50%, even more preferably from 25% to 45%, most preferably from 30% to 40%, or for example 18%, 23%, 30%, 34%, 36%, 54% or 60% by weight of the heat seal composition. All weights of acrylic and/or vinyl resins described herein are based on 100% of the total weight of the respective heat seal composition.

It will be appreciated that if any acrylic resin and/or vinyl resin is also present as a component of the optional primer layer, the amount of any such acrylic resin and/or vinyl resin primer layer component will be calculated separately and will not form part of the amount of acrylic resin and/or vinyl resin described herein, which may form part of the heat seal layer.

Ethylene Vinyl Acetate (EVA) polymers useful in the present invention contain 15 to 50 wt%, or 18 to 40 wt%, or 25 to 40 wt% vinyl acetate. Such EVA resins are available from DuPont under the trademark "DuPont(250, 420, 3180, 3185, 4031, 4260) commercially available under the trademark Celanese from Celanese(2810A、2821A、3325AC、4031AC)Commercially available under the trademark Arkema(28-05, 28-25, 28-40, 28-150, 33-25, 33-45, 40-55, 42-60) are commercially available.

The EVA resin may also be an EVA terpolymer. These terpolymers are terpolymers of ethylene, vinyl acetate and acrylic acid or methacrylic acid. Examples include4260. 4310 and 4320.

Tackifier

To provide a suitably low heat seal initiation temperature and a relatively constant peel strength with changes in heat seal temperature, the heat seal composition comprises a total amount of one or more tackifiers in an amount of at least 20% by weight of the heat seal composition, or at least 22%, 25%, 27%, or 30% by total weight of the heat seal composition. The tackifier may be a tackifier resin. However, it may be disadvantageous to include greater than 60% by weight of the total tackifier in a heat-seal composition for typical applications, since tackifiers tend to be relatively expensive compared to other components in the heat-seal composition, and tend to create coating blocking problems. Typically, the total amount of tackifier present in the heat-seal composition is at most 60%, or at most 55%, 50% or 45% by weight of the heat-seal composition. The total amount of tackifier present in the heat-seal composition may be from 20% to 60%, preferably from 22% to 60%, more preferably from 25% to 55%, even more preferably from 27% to 50%, most preferably from 30% to 45%, or such as 6%, 18%, 24%, 25%, 30% or 60% by weight of the heat-seal composition. All weights of the tackifiers described herein are based on the total weight of the heat seal composition being 100%.

Tackifiers (which may include tackifier resins) suitable for use in the present invention include, but are not limited to, synthetic and natural polyterpene, hydrocarbon resins, rosin and rosin ester resins, and combinations thereof. The tackifier resin may have a ring and ball softening point of 20 ℃ to 160 ℃, preferably 90 ℃ to 125 ℃. Number of tackifier resinsThe average molecular weight is generally at least 200 or 500 daltons, and typically at most 5000, 2000 or 1000 daltons, and thus typically may have a molar mass of from 200 to 5000, preferably from 500 to 1000 daltons, more preferably from 500 to 1000 daltons_n。

Natural polyterpene tackifier resins are based on natural and renewable raw materials including α -pinene, β -pinene and d-limonene examples include:

1)c resins (C85, C105, C115, C125, C135),F resins (F105, F115),Resin A (A25, A115, A125, A135),S resin (525, 585, 5115, 5125, 5135); all available from Pinova.

2)TR resins (A25L, 90, 105, 7115, 7125), all available from Arizona Chemical.

The hydrocarbon tackifier resin is made from petroleum-based raw materials as follows: aliphatic (C5), aromatic (C9), DCPD (dicyclopentadiene), or mixtures of these. Examples include:

1)Piccotac^TM1020、1095、1100、1115、6095E、8095；Picco^TM5120、5140、6100、2215；Regalite^TM51100、7125；Regalite^TMR1010、1100、9100,Regalrez^TM1018. 1094, 3102, 6108; all available from Eastman;

2)A100、B170、K100、M100、N295、U190、5100、D100. u185; all available from Nippon Zeon, japan;

3)Escorez^TM1102. 1304, 1315, 2203, 5300, 5320, 5340, 5400, 5415, 5600, 5615, 5690; all available from ExxonMobil;

4)86、95、98；w85, 90, 100, 110, 120, 130, 140; all available from Cray Valley.

Rosin ester tackifier resins are produced by the reaction between rosin acid and an alcohol. Rosin acids can be modified by hydrogenation or disproportionation. Typical commercial products are esters of methyl, triethylene glycol, glycerol and pentaerythritol. Examples include:

1)85、105；3085；A、H，9085、9100；esters 3, 5, 10; all available from Pinova;

2)Sylvalite^TMRE8OHP, RE85GB, RE100X L, RE 100L, 105L, 110L, RE25, 85, 98, all available from Arizona Chemical;

3)Foralyn^TM90、110、50201；Permalyn^TM2085. 5095, 3100, 5110, 6110; all available from Eastman.

Polyolefin plastomer (POP) resins

Typically, the heat seal composition comprises a total of at least 10 wt% of one or more polyolefin plastomer (POP) resins, or at least 15 wt% or 20 wt% POP resin, based on the weight of the heat seal composition. Typically, up to 60 wt.%, or up to 50 wt.%, 40 wt.%, or 30 wt.% POP resin may be present, based on the weight of the heat seal composition. The total amount of POP resin present in the heat seal composition may be from 10% to 60%, preferably from 10% to 50%, more preferably from 15% to 40%, most preferably from 20% to 30%, by weight of the heat seal composition. All weights of POP resin described herein are based on 100% of the total weight of the heat seal composition.

Polyolefin plastomer (POP) resins are polymers that combine the qualities of elastomers and plastics to provide thermoplastic processability with rubber-like properties. POP resins suitable for use in the present invention comprise ethylene and at least one C polymerized using a metallocene catalyst₃-C₂₀α (alpha) -olefins, preferably C₄-C₈α (alpha) -olefins examples of such resins and methods for their preparation are disclosed in US 4542199, US4752597, US4808561, US5189192 and US5349100, all of which are incorporated herein by reference for all purposes^TM、Versify^TMAnd Engage^TM(Dow Chemicals)、Queo^TM(Borealis)、Exact^TMAnd VistaMaxx^TM(ExxonMobil) is commercially available.

The POP resin used in the present invention is obtained or obtainable from at least one monomer of formula 1 and at least one other different polymer precursor selected from any one of the following I to V:

CH₂CHR formula 1

Wherein R is H or C_1-10Alkyl (and preferably, formula 1 represents a vinyl monomer):

I. at least one different polymer precursor also represented by formula 1

At least one polymer precursor represented by formula 2

C_4-20α (alpha), omega (gamma) -diolefins, formula 2

At least one polymer precursor represented by formula 3

C_3-20α (alpha) -olefin, formula 3

At least one polymer precursor represented by formula 4

C_≥18A diene; -formula 4, and

v. at least one polymer precursor represented by formula 5

C_4-18Cyclic olefins (including norbornene) -formula 5.

The useful POP resin for the present invention may be at least one C_2-4A copolymer of an alkylene (alkylene) and at least one polymer precursor of any one of formulae 2 to 5.

Preferred POP resins are ethylene and/or propylene, at least one C_5-20Copolymers of an alkylene (hydrocarbyl-ene), more preferably ethylene and at least one C_6-15Copolymers of olefinic hydrocarbons, even more preferably of ethylene and at least one C_6-12Copolymers of olefinic hydrocarbons, most preferably ethylene and at least one linear monounsaturated C_6-10Copolymers of olefinic hydrocarbons, for example, copolymers of ethylene and 1-octene.

Suitably, the POP resin used in the present invention is prepared using a suitable catalyst, more suitably a different catalyst to the ziegler-natta catalyst or the free radical initiator, most suitably selected from: metallocenes (such as complexes with zirconium, hafnium and/or vanadium), aluminoxanes, anionic, nonionic ligand systems with group 4 to 8 metals and/or chiral organometallic complexes.

The polyolefin plastomer resins used in the present invention may combine the qualities of elastomers and plastics, for example by exhibiting rubber-like properties for the processing capability of the plastics.POP resins currently commercially available are copolymers of ethylene and other olefins typically prepared with metallocene catalysts.by way of contrast, typical low density olefin polymers such as linear low density polyethylene (LL DPE); low density polyethylene (L DPE) and linear very low density polyethylene (V L DPE) are made by conventional Ziegler-Natta catalysts or free radical initiators.

Molecular weight, e.g., weight average molecular weight (also referred to as M), of the polymers or oligomers described herein_w) Or number average molecular weight (also referred to as M)_n) Can be calculated theoretically, and/or measured by any suitable conventional method, for example by Gel Permeation Chromatography (GPC), Gas Chromatography Mass Spectrometry (GCMS), and/or by Size Exclusion Chromatography (SEC) as known to those skilled in the art. GPC methods using polystyrene standards are preferred.

Weight average molecular weight (M) of POP plastomer for use in the present invention_w) Typically at least 3, or at least 5, or at least 12 or at least 15 kilodaltons, and at most 60, or at most 50, or at most 40 or at most 30 kilodaltons, M_wPreferably by GPC using polystyrene standards. Usefully, the POP plastomer has an M of 3-60 kilodaltons, or 5-50 kilodaltons, or 12-40 kilodaltons, or 15-30 kilodaltons_w。

Number average molecular weight (M) of POP plastomer for use in the present invention_n) Typically at least 5, or at least 15 kilodaltons and at most 50, or at most 30 kilodaltons, M_nPreferably by GPC using polystyrene standards. Usefully, the POP plastomer has an M of 5-50 kilodaltons or 15-30 kilodaltons_n。

The amount of α (alpha) -olefin comonomer in the plastomer is from 5 to 85 mole%, preferably from 10 to 25 mole%, more preferably from 10 to 30 mole%. the DSC melting point of the plastomer is typically below 100 ℃, or up to 70 ℃, which is typically at least 40 ℃, or at least 45 ℃, or 50 ℃ the tensile strength of the plastomer is typically from 1.0 to 20MPa, preferably from 5 to 10MPa [20in/min (-50.8 cm/min), ASTM D369 ].

Generally, POP resins suitable for use according to the present invention are soluble to a solids content of at least 10% in at least one of toluene, xylene, dichlorobenzene, trichlorobenzene, or mixtures of any of these with THF or ethyl acetate at 65 ℃ in each case. Typically, the resulting solution is clear.

Other ingredients

Slip additives are used to reduce the resistance of the composite membrane to sliding on itself or a component of the conversion apparatus. The most common slip additives in the coatings industry are long chain fatty acid amides such as erucamide and oleamide.

Typically, one or more slip agents, such as calcium stearate or fatty acid amides, e.g., available from Chemtura, are included in the heat seal compositionEZ andOR (9). If included, the one or more slip agents typically constitute in total at least 0.15% by weight of the heat seal composition, or at least 0.2%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, or 3.5% by weight of the heat seal composition.

The slip agents typically constitute up to 7% by weight of the composition, or up to 6.5%, 6%, 5.5%, 5% or 4.5% by weight of the heat seal composition. The total amount of slip agent present in the heat seal composition may be from 0.15% to 7%, preferably from 0.2% to 6.5%, more preferably from 0.5% to 6.5%, even more preferably from 1% to 6.5%, most preferably from 1.5% to 6.5%, or from 2% to 6%, or from 2.5% to 5.5%, or from 3% to 5%, or from 3.5% to 4.5%, or for example 1.5%, 1.7% or 2.5% by weight of the heat seal composition. All weights of slip agents described herein are based on 100% of the total weight of the heat seal composition.

Optional ingredients for the heat-sealable layer may include, among others, one or more of the following: anti-tack additives and/or matting agents, for example silica such as Syloid 244 or Syloid 620 (optionally present in an amount of 1% to 3%, preferably 1.5% to 2.5%, for example 1.5%; 2.2% or 2.5% by weight of the heat seal composition) available from Grace Davison; antifogging agents, e.g. sorbitan esters, such as ATMER available from Croda Polymer Additives^TM100, respectively; antistatic propertyAgents, e.g. glycerol esters, such as Atmer available from Croda Polymer Additives^TM129; UV absorbers, e.g. from Ciba477DW and1130; and pigments, e.g. titanium dioxide, such as Ti-Pure available from Chemours^TMR-101。

The heat-seal composition forms the heat-seal layer of the composite film of the present invention, and thus the same weight% of acrylic resin, vinyl resin, POP resin, tackifier, slip agent, and any other components thereof given herein in the heat-seal composition also correspond to the total weight by weight of those components wherein may be present in the heat-seal layer where the total weight of the heat-seal layer is 100%.

Polymer film

The polymer film used in the present invention may be any suitable polymer capable of forming a film prior to deposition of any coating or layer, and may therefore comprise: polyolefins [ e.g., polypropylene (PP) and/or Polyethylene (PE) ], polyurethanes, polyvinyl halides [ e.g., polyvinyl chloride (PVC) ], polar polymers, polyesters [ e.g., polyethylene terephthalate (PET) ], or other polyesters, polyamides [ e.g., nylon ], polyaryletherketones, and/or non-hydrocarbon polymers described herein); suitable combinations and/or mixtures thereof.

Preferably, the polymer film comprises a homopolymer, a crystalline polymer, and/or a polymer of randomly oriented amorphous, non-crystalline polymer chains.

Suitably, the polyolefin film used as the polymer film in the present invention may comprise one or more polyolefins [ e.g., polypropylene homopolymer, polyethylene homopolymer [ e.g., linear low density polyethylene (LL DPE) ] and/or polypropylene/polyethylene copolymer, optionally in one or more layers ] the constituent polymers and/or layers in the polymer film of the present invention may be oriented, blown, shrunk, stretched, cast, extruded, coextruded, and/or comprise any suitable mixtures and/or combinations thereof.

Polyolefin films may include, but are not limited to, polyethylene homopolymers, ethylene- α -olefin copolymers, polypropylene- α -olefin copolymers, polypropylene homopolymers, ethylene-vinyl acetate copolymers, ethylene-methacrylic acid copolymers and salts thereof, ethylene-styrene polymers, and/or blends of these polymers.

The polymer resins used to produce the polymer films of the present invention are generally commercially available in pellet form and can be melt blended or mechanically mixed by methods known in the art using commercially available equipment including rotating drums, mixers, and/or blenders. The resin may have blended therewith other additional resins as well known additives such as processing aids and/or colorants. Methods of making polymer films are well known and include the technique of casting the film into a sheet through a narrow slot die (die) and the blown film technique of expanding an extruded tube of molten polymer to the desired bubble diameter and/or film thickness. For example, to produce a polymer film, the resin and additives may be introduced into an extruder where the resin is melt plasticized by heating and then transferred into an extrusion die to form a film tube. Extrusion temperatures and die temperatures are generally dependent on the particular resin being processed, and suitable temperature ranges are generally known in the art or provided by the resin manufacturer in available technical bulletins. The processing temperature may vary depending on the selected processing parameters.

The polymer film of the present invention may be unoriented (cast film), and may be oriented preferably in at least one direction (uniaxial orientation), more preferably in two directions (biaxial orientation).

The orientation of the polymer film may be achieved by any suitable technique, for example, the polymer film may be oriented by simultaneous or sequential stretching in each of two mutually perpendicular directions by means of a stretching machine or by a combination of stretching rolls and a tenter frame, oriented in the MD and then expanded in a flat state by a process of stretching the film at a temperature above the glass transition temperature (Tg) of its constituent polymers, stretching the polymer film in a temperature above the TD, stretching the resulting oriented polymer film in a substantially improved stretching and stiffness properties.

The polymer film of the composite film is self-supporting and is preferably a biaxially oriented film, optionally a polar polymer or polyolefin. The polymer film may optionally comprise slip additives and/or antiblock additives.

As used herein, the term "polar polymer" means a polymer obtained and/or obtainable from at least one polymer precursor that itself comprises a polar moiety, and/or wherein said polymer comprises a repeating unit comprising a polar moiety. An example of such a polar moiety is a carbonyloxy moiety. Thus, the term polar polymer does not necessarily imply any common property of the resulting polymer or films made therefrom. Usefully, the polar polymer comprises a polyester polymer and/or a polyaryletherketone polymer.

Examples of polar polymers include polyaryletherketones, polyesters including or consisting of polyethylene terephthalate (PET), polylactic acid (P L A), Polyhydroxybutyrate (PHB), Polyfuranate (PEF), and/or polyethylene naphthalate (PEN), copolyesters comprising or consisting of repeat units of any of the foregoing (or any other polyester described herein), such as terephthalic acid, lactic acid, hydroxybutyric acid, furan acid, naphthalene dicarboxylic acid, and/or aliphatic dicarboxylic acids, and glycols, e.g., copolyesters of terephthalic acid, naphthalene dicarboxylic acid, and/or aliphatic dicarboxylic acids with glycols.

The polymeric film may have a shrinkage of less than 5% in length and/or width when exposed to boiling water for five seconds. The polymeric film may be a single layer of polymer that does not have any additional layers comprising any polymers (same or different) or does not have a metal layer on the surface opposite the surface bearing the primer and heat seal composition.

Polyolefins suitable for forming the self-supporting layer of the polymeric film used in the present invention may include any of the polyolefins described herein, which are capable of being formed into a film (filmable) alone (i.e., as a substantially pure polymer), and/or into a film in the form of a mixture and/or copolymer with other polymers, such as any of those described herein. Preferred polyolefin films are polypropylene (PP) and/or Polyethylene (PE), more preferably biaxially oriented polypropylene (BOPP) films.

Polyesters suitable for forming the self-supporting layer of the polymeric film used in the present invention may include any of the following, which are capable of being film-formed alone and/or in mixtures and/or copolymers with other polymers (such as any other polymer, e.g., polyesters described herein):

aliphatic polyester homopolymers such as polyglycolide or polyglycolic acid (PGA), polylactic acid (P L a), polycaprolactone (PC L), Polyhydroxyalkanoate (PHA), and/or Polyhydroxybutyrate (PHB).

Aliphatic polyester copolymers such as polyethylene adipate (PEA), polybutylene succinate (PBS) and/or poly (3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV).

Semi-aromatic polyester copolymers such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN) and/or polyethylene furan acid ester (PEF).

Aromatic polyester copolymers are obtained and/or obtainable, for example, by polycondensation of 4-hydroxybenzoic acid and 6-hydroxy-naphthalene-2-carboxylic acid and can be obtained from Kuraray under the trade name Vectran^TMA polymer was obtained.

Also suitable for use in the present invention are film-forming polar polymers such as Polyaryletherketones (PAEKs), for example from Victrex Plc under the registered trade markA commercially available Polyetheretherketone (PEEK).

Polyesters and/or polyaryletherketones suitable for use as polar polymer films in the present invention may include at least one polymer selected from aliphatic polyester homopolymers (such as PGA, P L A, PC L, PHA and/or PHB), aliphatic polyester copolymers (such as PEA, PBS and/or PHBV), semi-aromatic polyester copolymers (such as PET, PBT, PTT, PEN and/or PEF), aromatic polyester copolymers (such as Vectran)^TM) PEEK polymers (for example under the registered trademark)Commercially available ones) of any suitable mixtures, combinations, and copolymers thereof.

Preferred polymers suitable for use as the polar polymer film in the present invention include at least one polymer selected from the group consisting of PGA, P L A, PC L, PHA, PHB, PEA, PBS, PHBV, PET, PBT, PTT, PEN, PEF, poly (ethylene glycol terephthalate), poly (ethylene glycol terephthalate,PEEK and/or any suitable mixtures, combinations, and copolymers thereof.

More preferred polyesters suitable for use as the polymeric film in the present invention include at least one polyester selected from the group consisting of P L A, PHB, PET, PEN, PEF, any suitable mixtures, combinations and copolymers thereof.

Even more preferred polyesters suitable for use as polymer films in the present invention include at least one polymer selected from the group consisting of: PET, PEN and PEF.

Most preferred polyesters suitable for use as the polymeric film in the present invention include at least one polymer selected from the group consisting of: PET and PEN.

For example, polyesters suitable for use as polymer films in the present invention include at least one PET polymer.

Primer layer

If present, the optional primer layer may comprise a halogenated polyvinylidene polymer (such as a pvdf polymer, where X is a halogen), preferably a polyvinylidene chloride polymer (e.g., where X is chlorine, i.e., PVdC) and/or an acrylic polymer and/or a vinyl polymer (preferably an EVA polymer). Useful acrylic and/or vinyl polymers for inclusion in the primer layer are those described herein for inclusion in the heat seal layer, which allows the heat seal layer to adhere sufficiently to the primer layer to resist delamination. Ethylene-acrylic acid (EAA) and/or ethylene-methacrylic acid (EMA) primers may also be used. Alternatively, if the self-supporting layer of the polymer film is a corona treated polyolefin film, the primer layer may not be present, and thus the surface of the polyolefin film has been sufficiently activated so that the heat-sealable composition can be applied directly to the unprimed polyolefin film and firmly adhered to it.

A primer composition comprising a suitable amount of halogenated polyvinylidene, acrylic and/or vinyl resin therein may be applied to the self-supporting layer of the polymeric film used to prepare the composite film of the present invention. Thus, the optional primer layer may also comprise any halogenated polyvinylidene polymer, acrylic resin, and/or vinyl resin in any suitable mixture thereof, in any suitable proportion or amount.

The total amount of acrylic resin and/or vinyl resin that may be present in the primer layer may be the same as the amounts given herein for the acrylic resin and/or vinyl resin present in the heat seal layer, with the remainder of the primer layer being the pvdf component. Preferably, the primer layer comprises, more preferably consists of, a halogenated polyvinylidene polymer (e.g. a PVdC polymer), an acrylic resin and/or a vinyl resin (such as EVA), even more preferably PVdC and/or EVA, most preferably PVdC.

Where the primer composition comprises an acrylic resin and/or a vinyl resin, although the amounts of these components (expressed as weight percentages based on the total weight of the primer composition or layer at 100%) may correspond to the total weight of acrylic resin and/or vinyl resin by weight given herein for the amounts present in the heat seal composition or layer, it is understood that the amount of acrylic resin and/or vinyl resin that may be present in each of the primer layer and/or heat seal layer is calculated separately and independently.

Coating (heat sealing and/or primer) compositions and methods

The above components may be applied to a polymeric film such as a polyester substrate from a solution of an organic solvent or mixture thereof. The coating composition may be applied using any conventional coating method, such as spray coating, roll coating, slot coating, meniscus coating, dip coating, wire bar coating, air knife coating, curtain coating, knife coating, forward gravure, reverse gravure, and the like. The coating is then allowed to dry.

A further aspect of the present invention provides a packaging article which is a lid for a packaging article lined with the composite film of the present invention as described herein.

A further aspect of the invention provides a filled packaging article sealed with a lid of the invention as described herein.

Yet another aspect of the present invention provides a method of filling a packaging article with a food or human and/or animal consumable liquid, comprising the steps of:

a) filling the article with food or human and/or animal consumable liquid;

b) the cap of the present invention is applied to the filled article to reversibly seal the article.

As used herein, the plural forms of terms shall be read to include the singular forms and vice versa, unless the context clearly dictates otherwise.

The term "comprising" as used herein is to be understood as meaning that the following list is not exhaustive and may or may not include any other suitable items, such as one or more further features, components, ingredients and/or substituents, as appropriate.

The terms "consisting", "consisting of and/or" being "as used herein shall be understood to mean that the following list is essentially exhaustive, and therefore it typically includes the listed components as its main components, and thus may, for example, exclude other additional items.

As used herein, "major component" (or synonym thereof) is understood to mean a proportion in which any other elements or additives present have no substantial effect on the properties of the component, and thus the major component may be present in a portion of at least 50%, preferably at least 60%, more preferably at least 70%, most preferably at least 80%, especially at least 90%, most especially about 99% of the relevant whole.

The terms "effective," "acceptable," "active," and/or "suitable" (e.g., with respect to any process, use, method, application, preparation, product, material, formulation, compound, monomer, oligomer, polymer precursor, and/or polymer of the present invention and/or described herein where appropriate) are understood to mean providing the desired properties, if used in the correct manner, to the subject to which they are added and/or incorporated to provide those features of and/or used in the present invention that are utilizable as described herein. Such utilization may be direct, such as where the material has the desired properties for the aforementioned use, and/or indirect, such as where the material has use as a synthetic intermediate and/or diagnostic tool in the preparation of other materials that are directly utilized. These terms as used herein also mean that the functional group is compatible with making an effective, acceptable, reactive, and/or suitable end product.

Preferred uses of the present invention include one or more uses of the film as a heat sealable component of a packaging article, such as a lid, such as a bakeable tray for food products and/or a liner for a lid of a packaging article.

In the discussion of the invention herein, unless stated to the contrary, the disclosure of alternative values for the upper and lower limits of a permissible range of parameters plus an indication that one of the stated values is more preferred than the other should be read as implicitly stating that each intermediate value of the parameter between the more preferred and less preferred of the alternative values is itself better than the less preferred value and is better than each less preferred value and the intermediate value.

For all upper and/or lower boundary values for any parameter given herein, the boundary value is included in the value for each parameter. It is also to be understood that all combinations of preferred and/or intermediate minimum and maximum boundary values for the parameters described herein in various embodiments of the invention may also be used to define alternative ranges for each parameter in various other embodiments and/or preferred versions of the invention, whether or not such combinations of values are specifically disclosed herein.

Thus, for example, reference herein to a substance in an amount (e.g., in mass and/or weight%) from 0 to "x" is intended to encompass (unless the context clearly indicates otherwise) two alternatives, the first broader alternative being that the substance may optionally be absent (when the amount is zero), or present only in the lowest amount that is below the amount detectable. A second preferred alternative (expressed as a lower zero amount within the range of the amount of a substance) means that the substance is present, with zero indicating that the lower amount is a very small trace amount, e.g., any amount sufficient to be detected by suitable conventional analytical techniques, more preferably with zero indicating that the lower limit of the amount of the substance is greater than or equal to 0.001 wt.% (calculated as described herein).

It should be understood that the sum of any amount expressed as a percentage herein cannot (allow for rounding errors) exceed 100%. For example, where rounding errors are permissible, the sum of all components comprised by a composition of the invention (or a portion thereof) when expressed as a weight (or other) percentage of the composition (or the same portion thereof) can total 100%. However, where a list of components is not exhaustive, the sum of the percentages of each of these components may be less than 100% to allow for a certain percentage to be used in additional amounts for any additional components not specifically described herein.

The term "substantially" as used herein may refer to a quantity or entity to imply a greater quantity or proportion. When used in the context of "substantially" it is understood to mean a proportion of at least 80%, preferably at least 85%, more preferably at least 90%, most preferably at least 95%, especially at least 98%, for example about 100% of the relevant whole in number (in relation to any number or entity referred to in the context of the specification). Similarly, the term "substantially free" may similarly mean that the quantity or entity to which it relates comprises no more than 20%, preferably no more than 15%, more preferably no more than 10%, most preferably no more than 5%, especially no more than 2%, for example about 0% of the relevant whole.

The terms "optional substituent" and/or "optionally substituted" as used herein (unless followed by a list of other substituents) denote one or more of the following groups (or substituted by such groups): carboxy, sulfo, formyl, hydroxy, haloamino, imino, nitrilo, mercapto, cyano, nitro, methyl, methoxy, and/or combinations thereof. These optional groups include all chemically possible combinations of identical moieties of a plurality (preferably two) of the aforementioned groups (e.g., amino and sulfonyl, which if directly linked to each other represents a sulfonamide group). Preferred optional substituents include carboxy, sulfo, hydroxy, amino, mercapto, cyano, methyl, chloro, fluoro, trihalomethyl and/or methoxy.

As used herein, the synonymous terms "organic substituent" and "organic group" (also abbreviated herein as "organic") refer to any monovalent or multivalent moiety (optionally attached to one or more other moieties) that comprises one or more carbon atoms and optionally one or more other heteroatoms. Organic groups may include organoheteryl groups (also referred to as organoelement groups) which comprise monovalent groups containing carbon, and thus they are organic, but they possess their free valences on atoms other than carbon (e.g., organothio groups). The organic group may alternatively or additionally comprise an organic group, including any organic substituent having a free valence at a carbon atom, regardless of the type of functional group. The organic group may also include a heterocyclic group including a monovalent group formed by removing a hydrogen atom from any one of the ring atoms of the heterocyclic compound: (Cyclic compounds have at least two atoms of different elements as members of the ring, in which case one element is carbon). Preferably, the non-carbon atoms in the organic group are selected from: hydrogen, halogen, phosphorus, nitrogen, oxygen, silicon and/or sulfur, more preferably selected from hydrogen, nitrogen, oxygen, phosphorus and/or sulfur.

Most preferred organic groups include one or more of the following carbon-containing moieties: alkyl, alkoxy, alkanoyl, carboxyl, carbonyl, formyl and/or combinations thereof; optionally in combination with one or more of the following heteroatom containing moieties: oxo, thio, sulfinyl, sulfonyl, amino, imino, nitrilo, and/or combinations thereof. Organic groups include all chemically possible combinations of identical moieties of a plurality (preferably two) of the aforementioned carbon-containing and/or heteroatom-containing moieties (e.g., alkoxy and carbonyl, representing alkoxycarbonyl groups if directly attached to each other).

The term "hydrocarbyl" as used herein is a subset of organic groups and denotes any monovalent or multivalent moiety (optionally linked to one or more other moieties) that consists of one or more hydrogen atoms and one or more carbon atoms, and that may comprise one or more saturated, unsaturated, and/or aromatic moieties. The hydrocarbyl group may comprise one or more of the following groups. Hydrocarbyl groups include monovalent groups formed by removing a hydrogen atom from a hydrocarbon (e.g., alkyl groups). Alkylene groups include divalent groups formed by removing two hydrogen atoms from a hydrocarbon, the free valences of which do not participate in a double bond (e.g., alkylene). Hydrocarbylene (hydrocarbylene) includes a divalent group formed by removing two hydrogen atoms from the same carbon atom of a hydrocarbon (which may be referred to as "R")₂C ═ represents), its free valency participating in a double bond (e.g., an alkanyl group).Hydrocarbynyl (hydro-carbyldyne) includes a trivalent radical formed by removing three hydrogen atoms from the same carbon atom of a hydrocarbon (which may be represented by "RC ≡"), the free valence of which participates in a triple bond (e.g. an alkanyl radical). The hydrocarbyl group may also contain saturated carbon-carbon single bonds (e.g., in alkyl groups); unsaturated carbon-carbon double and/or triple bonds (e.g., in alkenyl and alkynyl groups, respectively); aromatic groups (e.g., in aryl groups) and/or combinations thereof within the same moiety and which may be substituted with other functional groups as indicated.

The term "alkyl" or its equivalent (e.g., "alk") as used herein may be conveniently replaced, where appropriate and unless the context clearly dictates otherwise, by terms including, for example, any other hydrocarbon group described herein (e.g., including double bonds, triple bonds, aromatic moieties (such as alkenyl, alkynyl and/or aryl, respectively) and/or combinations thereof (e.g., aralkyl), as well as any polyvalent hydrocarbon species linking two or more moieties (such as a divalent hydrocarbylene species, e.g., alkylene).

Any radical, substituent, group or moiety mentioned herein may be a multivalent or monovalent species, but is preferably a monovalent species (e.g., a divalent hydrocarbylene moiety (such as an alkylene moiety) linking two other moieties), unless otherwise indicated or clearly excluded from the context. However, such monovalent or multivalent species may also include optional substituents, if indicated herein. A group comprising a chain of three or more atoms represents a group wherein the entire chain or a portion of the chain may be linear, branched and/or form a ring (including spiro and/or fused rings). Specifying the total number of particular atoms for a particular substituent, e.g. C_1-NRepresents an organic moiety comprising from 1 to N carbon atoms. In any of the formulae herein, if one or more substituents are not indicated as being attached to any particular atom of a moiety (e.g., at a particular position along a chain or ring), the substituent may replace any H and/or may be located at any available position on the moiety that is chemically suitable and/or effective.

Preferably, any of the organic groups listed herein comprise from 1 to 36 carbon atoms, more preferably from 1 to 18. Even more preferred is a number of carbon atoms in the organic group of from 1 to 12, more preferred from 1 to 10, even more preferred from 1 to 6, for example from 1 to 4 carbon atoms.

Chemical terms as used herein including the features given in parentheses (except IUAPC nomenclature for explicitly identified compounds), such as (alkyl) acrylates, (meth) acrylates and/or (co) polymers-meaning that the part in parentheses is optional as described above and below, so for example the term (meth) acrylate stands for methacrylate and acrylate.

Substituents on the repeating units of the polymers and/or oligomers may be selected to improve the compatibility of the materials with the polymers and/or resins into which they may be formulated and/or incorporated for use as described herein. The size and length of the substituents may therefore be selected to optimise physical entanglement or co-location with the resin, or they may or may not contain other reactive entities which are capable of chemically reacting and/or cross-linking with these other resins, if appropriate.

As described herein, certain moieties, species, groups, repeat units, compounds, oligomers, polymers, materials, mixtures, compositions and/or formulations which comprise and/or are used in some or all of the present invention may exist in one or more different forms (such as isomeric and/or physical forms) including any of those in the following non-exhaustive list:

stereoisomers (such as enantiomers (e.g. E and/or Z forms), diastereomers and/or geometric isomers); tautomers (e.g., keto and/or enol forms), conformers, salts, zwitterions, complexes (such as chelates, clathrates, crown compounds, cryptands/cryptates, clathrates, intercalation compounds, interstitial compounds, ligand complexes, organometallic complexes, non-stoichiometric complexes, pi-adducts, solvates, and/or hydrates); isotopically substituted forms, polymeric configurations [ such as homopolymers or copolymers, random, graft and/or block polymers, linear and/or branched polymers (e.g. star and/or side branched), hyperbranched polymers (such as those of the type described in WO 93/17060), cross-linked and/or network polymers, polymers obtainable from di-and/or tri-valent repeat units, dendrimers (dendrimers), polymers of different tacticity (e.g. isotactic, syndiotactic or atactic polymers) ]; polymorphs (such as interstitial forms, crystalline forms, and/or amorphous forms), different phases, solid solutions; and/or combinations thereof and/or mixtures thereof, if possible. The present invention includes and/or uses all such effective forms (e.g., as defined herein).

Other conventional terms from polymer science, such as polymers, monomers, oligomers, etc., as used herein, shall have those meanings as suggested by IUPAC and are defined as Pure appl. chem., vol 68, p. 12 2287-2311, 1996, the contents of which are incorporated herein by reference. Unless the context clearly indicates otherwise, the terms "resin" and "polymer" are used interchangeably herein, and thus, for example, the terms acrylic resin and vinyl resin also refer to acrylic polymer and vinyl polymer, respectively, and vice versa.

The structural formulae herein may represent a polymer mixture or a series of discrete compounds. If the formulae herein represent monodisperse species (such as compounds), the values of any numerical variables represented therein (such as "n" and the like, for example representing the number of repeating units) are independently integers (or zero, if the context permits) within the specified range. If the formula represents the average structure of a number of discrete species present in a polydisperse oligomer and/or polymer mixture, the numerical values of any variable shown in the formula can be real, non-integer numbers with a specified range.

It is appreciated that certain features of the invention, which are, for clarity, described in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features of the invention which are, for brevity, described in the context of a single embodiment, may also be provided separately or in any suitable subcombination. Many other variant embodiments of the invention will be apparent to those skilled in the art and such variants are envisaged within the broad scope of the invention.

Other aspects of the invention and preferred features thereof are set out in the claims herein.

Detailed Description