In-line coated biaxially orientated polypropylene based antistatic multilayer films
Abstract
An antistatic film of acrylic / maleic base coated in line, multilayer and based on biaxially oriented polypropylene (BOPP) comprising: - a skin layer comprising a polypropylene or the polypropylene mixture with poly (ethylene-propylene) copolymer or poly (polypropylene) copolymer ( ethylene-co-propylene-co-butylene) and a thin antistatic layer coated on the surface line; wherein the thin in-line surface-coated antistatic layer comprises a mixture of: (1) acrylic matrix polymer or crosslinkable copolymers of maleic anhydride and (2) antistatic ionic agent based on complex binary systems that are selected from depoli (ethylene) imine) linear or branched s (PEIs) / oligo (acrylic acid), PEIs / (meth) acrylic copolymers, and water-soluble PEIs / copolymers of maleic anhydride with different comonomers; - two inner layers between the skin layer and the core layer and between the core layer and the outer layer, comprising a polypropylene or the polypropylene mixture with poly (ethylene-co-propylene) copolymer or poly (ethylene-co) copolymer -propylene-co-butylene), - a core layer between said two inner layers, comprising polypropylene, - a treated outer layer comprising a polypropylene or copolymer poly (ethylene-co-propylene) oterpolymer poly (ethylene-co-propylene) -co-butylene).

Term
0.9 yearsto projected expiry
Projected expiry 28 August 2027, counted from filing; an application has no term until it is granted.
- Priority and filed
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13 claims: 1 independent, 12 dependent
- 1ES 2 396 867 T3 REIVINDICACIONES 1. Un film antiestático de base acrílica/maleica recubierto en línea, multicapa y basado en polipropileno biaxialmente orientado (BOPP) que comprende:• una capa de piel que comprende un polipropileno o la mixtura de polipropileno con copolímero poli(etilenoco-propileno) o terpolímero poli(etileno-co-propileno-co-butileno) y una capa antiestático delgada recubierta en línea en la superficie;en donde la capa antiestático delgada recubierta en línea en la superficie comprende una mixtura de: (1) polímero de matriz acrílica o copolímeros reticulables de anhídrido maleico y (2) agente iónico antiestático basado en los sistemas binarios complejos que se seleccionan de poli(etilen-imina)s (PEIs) lineales o ramificadas/oligo(ácido acrílico), copolímeros PEIs/(met)acrílicos, y copolímeros PEIs/solubles en agua de anhídrido maleico con diferentes comonómeros;• dos capas internas entre la capa de piel y la capa de núcleo y entre la capa de núcleo y la capa externa, que comprenden un polipropileno o la mixtura de polipropileno con copolímero poli(etileno-co-propileno) o terpolímero poli(etileno-co-propileno-co-butileno), • una capa de núcleo entre dichas dos capas internas, que comprende polipropileno, • una capa externa tratada que comprende un polipropileno o copolímero poli(etileno-co-propileno) o terpolímero poli(etileno-co-propileno-co-butileno).
- 2El film de base acrílica/maleica antiestático recubierto en línea de acuerdo con la reivindicación 1, en donde los diferentes comonómeros se seleccionan de etileno, propileno, N-isopropilacrilamida, y N-vinil-2-pirrolidona.
- 3El film de base acrílica/maleica antiestático recubierto en línea de acuerdo con la reivindicación 1, en donde la al menos una capa delgada con recubrimiento antiestático comprende un adhesivo acrílico convencional y un aditivo polímero antiestático especial seleccionado de los grupos constituidos por mixturas polímeras formadoras de complejos de homo- o copolímeros de ácido (met)acrílico o copolímero hidrolizado alternante de anhídrido maleico y de poli(etilen-imina) lineal o ramificada con ratio de unidades amina/ácido carboxílico equivalente.
- 4El film antiestático de base acrílica/maleica recubierto en línea de acuerdo con la reivindicación 1, en donde la al menos una capa delgada con recubrimiento antiestático comprende una composición adhesiva especial seleccionada de los grupos constituidos por copolímero alternante soluble en agua de anhídrido maleico con αolefinas, preferiblemente etileno y propileno y comonómeros funcionales, preferiblemente N-isopropil-acrilamida, Nvinil-2-pirrolidona, y análogos, poli(etilenglicol) como reticulador y un catalizador soluble en agua, preferiblemente un catalizador de tipo carbamida.
- 5El film de base acrílica/maleica antiestático recubierto en línea de acuerdo con la reivindicación 1, en donde el espesor de recubrimiento que se aplica en línea tiene un grosor igual a o menor que 0,5 pm.
- 6El film de base acrílica/maleica antiestático recubierto en línea de acuerdo con la reivindicación 1, en donde el recubrimiento que se aplica en línea comprende un homopolímero o copolímero de ácido (met)acrílico que tiene un peso molecular medio (Mw) que es igual a o mayor que 1500 g/mol.
- 7El film de base acrílica/maleica antiestático recubierto en línea de acuerdo con la reivindicación 1, en donde el recubrimiento que se aplica en línea comprende un copolímero alternante de anhídrido maleico que tiene un peso molecular medio (Mn) que es igual a o mayor que 10.000 g/mol.
- 8El film de base acrílica/maleica antiestático recubierto en línea de acuerdo con la reivindicación 1, en donde el recubrimiento que se aplica en línea comprende una poli(etilen-imina) lineal o ramificada que tiene un peso molecular medio (Mn) que es igual a o mayor que 480 g/mol o 2000 g/mol, respectivamente.
- 9El film de base acrílica/maleica antiestático recubierto en línea de acuerdo con la reivindicación 1, en donde el recubrimiento que se aplica en línea comprende un reticulador de poli(etilen-glicol) que tiene un peso molecular medio (Mn) que es igual a o mayor que 420 g/mol.
- 10El film de base acrílica/maleica antiestático recubierto en línea de acuerdo con la reivindicación 1, en donde el espesor de la capa superficial de piel que se aplica por la técnica de recubrimiento en línea es igual a o mayor que 0,8 pm de grueso.
- 11El film de base acrílica/maleica antiestático recubierto en línea de acuerdo con la reivindicación 1, en donde la capa externa tratada comprende sílice y/o aditivos orgánicos antibloqueo y aditivos de deslizamiento/antiestáticos.
- 12El film de base acrílica/maleica antiestático recubierto en línea de acuerdo con la reivindicación 1, en donde las capas internas y la capa de núcleo comprenden mezcla madre blanca de TiO2, mezcla madre de deslizamiento/antiestática y mezcla madre de CaCO3 para producir un film sólido blanco o blanco cavitado de BOPP.
- 13El film de base acrílica/maleica antiestático recubierto en línea de acuerdo con la reivindicación 1, en donde la capa externa tratada se ha sometido a tratamiento en corona o a la llama o en plasma.
Independent claims13
130 paragraphs in 20 sections, as filed
ES 2 396 867 T3
DESCRIPTION
Inline coated biaxially oriented polypropylene based multilayer antistatic films
FIELD OF THE INVENTION
The present invention relates to the field of the manufacture and uses of plastics. More specifically, the present invention relates to inline coated multilayer polyolefin films exhibiting improved surface properties such as antistatic property, cold seal adhesion, slidability, wetting stress, printability, and excellent adhesion to various lamination glues.
BACKGROUND OF THE INVENTION (PRIOR ART)
It is known that many thermoplastic polymer packaging materials, such as films, sheets, coatings, foams, and the like, exhibiting adequate flexibility and mechanical strength have a wide range of application areas in the food and non-food industries such as food packaging. food, agriculture, industrial packaging applications, medicine, pharmacy, electrical and electronic material industries, and the like.
The various goals of these materials, especially packaging films, including biaxially oriented polyolefin films, are: (1) have required surface properties such as antistatic properties, wetting stress, adequate adhesion, and slipperiness during operation under various conditions, (2) ensure that the films retain their optical properties (haze, gloss, opacity, etc.) and thermal (heat-sealing susceptibility, etc.) (3) ensuring that the films retain their tensile and mechanical properties necessary for the specified applications.
At present, antistatic films are produced by incorporating additives in the form of a masterbatch into the film during extrusion or by coating the film off-line after production with various types of organic antistatic additives such as ethoxylated amines, polyimines. , and the like, containing positively charged ions in their molecules, to prepare conventional film-forming thermoplastic polymers, such as polyolefins, flexible polyvinyl chloride, styrene polymers, polyesters, functional α-olefin copolymers, and the like.
There are a number of patent publications available related to in-line coated thermoplastic films, polyolefin thin antistatic films, cavitated heat sealable or non-heat sealable biaxially oriented polypropylene films containing various types of organic and inorganic additives, such as polyethylene glycol and its stearyl ether. , fatty acid monoesters with polyhydric alcohols, fatty acid monoglycerides, alcohol esters and amides or metal salts of saturated or unsaturated monocarboxylic fatty acids, low and high molecular weight amine and imine compounds, inorganic fillers and pigments, organic silicas and antiblocking agents, and the like. Fatty acid esters, ethoxylated alkylamines, diethanolamides, and ethoxylated alcohols are conventional nonionic antistatic agents used predominantly in polyolefin film compositions.
More specifically, a thermoplastic resin film laminate with antistatic property, as described in US Pat. 4,605,591, refers to a polyester film and a layer of polyester resin composition provided on at least one surface of the film, said composition (A) comprising a water-insoluble polyester copolymer or a mixture of aliphatic or alicyclic dicarboxylic acids and their derivatives of metal sulfonates (sulfphthalic acid and its isostructural analogs) with aliphatic glycols containing C2-8 and alicyclic glycols with C2 -8 and (B) inert inorganic particles such as fine calcium carbonate, kaolin, bentonite, zeolite and the like (the weight ratio of (A) / (B) = 100 / 0.5-3.0); Taking transparency and slidability into consideration, this invention's preferred use of natural and synthetic silicic acids. The composition also contained one or more ingredients selected from the group consisting of a water soluble silicone, a polyfunctional reactive compound, a poly (ethylene glycol) and its derivative (0.1-15% by weight), and an antistatic agent. This film laminate was preferably produced by an in-line coating method.
Although this invention recommended the possibility of film laminate production using other non-polar thermoplastic polymers, especially polyolefins, however this method is not applicable to polyolefins (polyethylene, polypropylene and α-olefin copolymers) since the surface of the films of these polymers is strongly hydrophobic and the formation of thin coatings from polar monomer systems on their surface is not possible without preliminary surface treatments (corona, plasma, flame and chemical treatments). The polyester laminating film according to this invention is a non-mono or multilayer, non-oriented or uniaxially oriented melt extruded film, and the resulting laminate is further uniaxially or biaxially oriented.
In patent EP 0505861 A2, a laminated film comprising 3-300 pm polyester film and at least one coating layer of 0.01-5.0 pm on one or both surfaces of said polyester film is disclosed. The thin covering film contained (a) a polymer having cationic nitrogen atoms in its main chain, (b) a binder polymer selected from the group consisting of polyesters, polyacrylics, polyurethanes, 2
ES 2 396 867 T3 chlorinated polymers and mixtures thereof, (c) a material selected from the group consisting of particles, lubricants and mixtures thereof, and (d) a crosslinker selected from the group consisting of melamine or epoxy crosslinking agents and their mixtures. Said coating film was formed by an in-line coating method. This laminated film is mono- or biaxially oriented, which is excellent in antistatic properties, adhesion and glidability. In EP 0172269 A2 a thermoplastic copolyester resin film laminate is disclosed comprising (A) a water insoluble polyester copolymer containing a dicarboxylic acid component mixed with a metal sulfonate group and a glycol component and (B ) inert particles; the weight ratio of (A) / (B) = 100 / 0.5-3.0. The film composition contained a water soluble silicone, a reactive polyfunctional compound, a poly (ethylene glycol) and its derivative and derivatives of phosphoric acid as the antistatic agents. The copolyester laminating film was preferably produced by in-line coating. According to patent EP 0362568 A2, antistatic polyester film is useful in various applications including magnetic recording media, graphic arts, presentations, packaging materials, construction materials, and so on. Various patent publications are cited that improve adhesion between the polymer base film surface and the coating surface using various polymer compositions for coating solutions. Such coatings include compositions based on poly (ethylene imine) (US patent 5,156,904), acrylic or methacrylic thermosetting materials (US patent 4,571,363), styreneanhydride maleic cross-linked copolymer (US patent 4,410,600), vinylidene chloride copolymer (US Patent 2,698,240), water dispersible copolyesters (US Patent 5,156,904), and analogous polymer coatings. Among such coatings, poly (ethylene imine) is widely used as a coating ingredient among various ionomeric and non-ionomeric thermoplastic films such as polyester or cellophane / polyethylene (US patent reissue No. 28554), polypropylene / other polymers (patent US 4,139,643), and analogous polymer systems. Oriented polymer films, preferably polyethylene terephthalate, coated with poly (ethylene imine) and / or polyamido-poly (ethylene imine) are disclosed in US Patent 5,156,904 and US Patent 5,453,326, respectively. , in which the poly (ethylene imine) is coated by an in-line method, that is, during the film manufacturing process, the polymer film is formed before the film is hardened by heating. The in-line coated film, when used to make a laminate with other polymers such as polyethylene or ionomer-type polymers, did not show any sign of delamination between the basic polymer film and the extrusion-coated polymer after 2 hours in hot water. 121 ° C at 0.1 N / mm<sup>2</sup> (US patent 5,156,904 and patent EP 0458147 A2). The oriented poly (ethylene terephthalate) film is coated in line with polyamido-poly (ethylene imine) to improve the antistatic properties of the film and its use for other packaging applications (US patent 5,453,326). In-line coated poly (polyethylene imine) film was used to make a laminate with other types of non-ionomeric or ionomeric polymers such as polyethylene or polyester, preferably polyethylene terephthalate (patent EP 0458147 A2). However, the above-mentioned patent inventions concerned the preparation of laminated film using only monolayer polymer matrix film and a group of polymeric antistatic agents containing polymer complexes containing cationic nitrogen, preferably soluble poly (ethylene imine). in water, with acids HCl or HBr. However, it is well known that the use of inorganic acid components in poly (ethylene-imine) complexes gives rise to certain difficulties in processing such as corrosion of the metal parts of the machinery and environmental problems since these components evaporate during processing. film formation process.
It is well known that many acrylic and methacrylic polymers [Maltzer YL Water-Soluble polymer, Noves Data Co .: New Jersey, USA, 1981] and copolymers of maleic anhydride and its isostructural analogs (citraconic anhydrides, amides, esters and imides and itaconics) [Triverdi BC, Culberton BM Maleic anhydride, Plenum Press: New York, 1982; Rzaev ZMO Polymers and copolymers of maleic anhydride, Elm: Baku, 1984; Rzaev ZMO Prog. Polym. Sci., 2000; 25: 163; Rzaev ZMO et al. Eur. Polym. J. 2002; 38: 2143] are widely used as the effective ingredient in water-soluble or dispersed film-forming compositions, which are also useful for the production of surface coatings on various thermoplastic polymers, preferably in polar polymer systems. using inline coating processing. For example, US patent 4,410,600 discloses a biaxially oriented aromatic polyester film coated by an in-line method with a crosslinked functional poly (styrene-co-maleic anhydride) copolymer prior to thermosetting; said coated copolymer film still requires corona treatment before extrusion coating in a converter. The number of publications relating to the use of such functional water-soluble polymer film-forming systems for coating polyolefin film surfaces is significantly limited to the use of polymer compositions of the (meth) acrylic type, whereas for copolymers containing anhydrides and their various compositions, hardly any publications exist, including patent publications.
Various Japanese patent publications also refer to coated thermoplastic polymers, preferably polyester type polymers, in which an antistatic layer is coated on at least the single surface of basic films. The antistatic resin used is prepared by copolymerizing a component having a polyalkylene oxide in the side chain with a component having a quaternary amino group. The coated antistatic layer is stretched at least uniaxially (JP 2003-136641). JP 2002-012858 discloses a method for improving the antistatic properties of a thermoplastic film by using an antistatic agent exhibiting excellent antistatic behavior in low humidity conditions, capable of providing an excellent antistatic film in shade of color, and providing a coating-type antistatic film, as well as a coating-type antistatic film preparation method by an in-line coating method. The antistatic agent comprised (1) a compound that
ES 2 396 867 T3 includes a sulfonic acid or its salt in the molecule and (2) a polymer that includes a cationic group. The objective of another patent (patent JP 2001-026088) is to improve the adhesiveness, printability and other characteristics by providing a layer of easily wettable cover film on the single surface of a polyester film and adjusting the wetting tension of the other surface of the polyester film to a specified value (45 mN / m or more). As a method for forming the coating film layer, an in-line coating method in which a coating agent is applied to the polyester film before the orientation / crystallization is completed and the coated film is stretched at least unidirectionally to form a coated film preferably 0.001-1.0 pm. In the invention patent (JP 2004-345298) a polyester film for heat shrinkable packaging is disclosed which is excellent in solvent bonding properties and has sufficient solvent bonding properties even if an antistatic coating film is applied by a online coating method. Patent JP 5,320,391 refers to easily coated polyester improved in electrostatic property and characterized by having a primer layer comprising a composition containing (1) an easily adhesive polyester resin, (2) an antistatic agent having a sulfonic acid group and / or its group of metal salts in the molecule and (3) an acid compound having at least one carboxylic group or a free phenolic hydroxyl group on at least one face of a polyester film, and the method of producing the film by an in-line coating method. The purpose of the Jp 6,293,875 invention is to obtain a coating agent that has excellent slip properties and blocking resistance for a copolyester film and that exhibits adhesiveness to various coating materials by preparing a resin-water soluble copolyester composition. acrylic. This invention provides a polyester film coated with the coating agent dispersed in water and a method of manufacturing this film by an on-line technique. JP 6,099,559 disclosed a polyester film useful as a base film such as a film-processed product such as a magnetic recording medium, an X-ray photographic film, a telephone card, a diazo microfilm, etc. having excellent adhesive properties, blocking resistance and smoothness. This polyester-based film comprises a coating layer formed by fine inorganic particles of water-soluble or dispersible acrylic resin, (size 0.2 pm). The coating layer of this film is prepared by an in-line coating method. Tsunashima et al. (Toray Ind.) (Patent JP 11,198,228) developed the in-line coating method for water-soluble coating materials or the like that had satisfactory productivity and quality such as lack of thickness irregularities during the film manufacturing process, and the possibility of forming a film oriented simultaneously in two axes with an orientation speed of 10 ± 4% / min or more in both longitudinal and lateral directions. The oriented film obtained by this method includes a layer of coating material having a thickness of 0.005-0.5 pm on the surface of the film.
However, these invention patents predominantly comprised basic polymers of the polyester type and polyester or acrylic adhesive resin, and the films prepared are not mono- or multilayer. All the methods, even those developed in said patents, are not applicable to hydrophobic polyolefin films, especially for mono- or multilayer and biaxially oriented polypropylene films. On the other hand, any patent information about polypropylene-acrylic composition base film laminates having a combination of useful properties such as excellent antistatic, antiblocking, and physico-mechanical properties and other important parameters is limited only to information of suggestions without Detailed prototype and experimental technology results.
As is evident from the above-described patent publications, there are relatively few publications that describe polyolefin-based coated films, particularly polyolefin-based inline surfaces. All patent publications suffer from one or more of the following properties, such as that the film compositions are not mono- or multilayer, are not based on biaxially oriented polypropylene, are not heat sealable, or are not cavitated or colored having a combination of excellent antistatic performance properties with improved wetting stress, slip and anti-blocking properties, cold sealing and adhesive bonding ability and the like, that are kept for long periods of time.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 is a schematic representation of the formation of self-assembled and hyperbranched positive charge macrocomplexes as effective antistatic agents.
Fig. 2 is a general schematic for the production and processing technology of the disclosed films with a revised and improved in-line chemical coating unit.
SUMMARY OF THE INVENTION
It is an object of the present invention to design and prepare a multilayer structure, preferably an A / B / C / D / E structure having at least one thin layer of antistatic coated skin (A), two inner layers (B) and (D ), a basic core layer (C) and an outer layer (E) for biaxially oriented polyolefin-based films, preferably polypropylene-based films that exhibit advantageous properties such as antistatic, antiblocking, slip, cavitation, non-heat sealable or heat sealable and improved wetting stress, compared to known and commercial films based on polypropylene with similar compositions. To improve the antistatic properties of the films, the composition of the coated skin layer (A) contains a
ES 2 396 867 T3 mixture of acrylic matrix polymer or crosslinkable copolymers of maleic anhydride and its isostructural analogs and an ionic antistatic agent based on complex binary systems such as linear poly (ethylene-imine) (PEIs) / oligo (acrylic acid) copolymers or branched and (meth) acrylic copolymers or PEIs / water-soluble copolymers of maleic anhydride [poly (MA-co-comonomer)] with different comonomers, preferably with ethylene, propylene, N-isopropylacrylamide, N-vinyl-2-pyrrolidone and analogous comonomers (Fig. 1), polypropylene homopolymer, donor-acceptor interaction or interaction of hydrogen bonds in the usual combination of binary systems in the composition of said layer that provide a significant increase in positive charge in primary, secondary and tertiary amine groups, and therefore exhibiting excellent antistatic properties. It is a known fact that hydrolyzed copolymers containing strong hydrogen bond structure anhydrides easily form macro-complexes assembled with PEI by non-covalent interaction COO '.<sup>+</sup>HN- between the free carboxylic groups of the acid unit and the amine groups of the PEI (Razaev ZMO et al. J. Appl. Polym. Sci. 2007; 102: 5841). Two internal layers (B) and (D) of said mono- or multilayer structure comprise 100% polypropylene or the mixture of polypropylene with poly (ethylene-co-propylene) copolymer or poly (ethylene-co-propylene-co-butylene terpolymer ) or polypropylene, white TiO2 masterbatch to produce a solid white BOPP film, slip / antistatic masterbatch and CaCO3 masterbatch to produce a cavitated white BOPP film. (C) The core layer with composition similar to layers (B) and (D) consists of polypropylene or a non-ionic / slip antistatic masterbatch and CaCO3 or white TiO2 masterbatch. The outer layer (E) consists of polypropylene or poly (ethylene-co-propylene) copolymer or poly (ethylene-co-propylene-co-butylene) terpolymer, silica and organic antiblocking masterbatches, and antistatic slip / non-ionic masterbatch). The outer layer (E) can be treated by corona, plasma or flame discharge methods or can be used without treatment depending on the end use of the film. The compositions and components of the layers for various types of polypropylene based film with a coated surface layer of the present invention are presented below with examples and in the Tables.
Additional multilayer films which are based on polypropylene are known from WO 99/07553 and TR 2000 02164A2.
The present invention is a surface-coated antistatic film that is a multilayer film, biaxially oriented and produced from terpolymers based on polyolefins, preferably polypropylene and poly (ethylene-co-propylene-co-butylene) [poly (E-co-P- co-B) s] with content different from units E and B. A thin surface coating with an approximate thickness of 0.05-2.0 pm formed (a) by a mixture of acrylic matrix polymer or cross-linked polyethylene glycol (PEG) copolymers, maleic anhydride and its isostructural analogs and an ionic antistatic agent based on complex binary systems such as linear or branched poly (ethylene-imine) (PEIs) / oligo (acrylic acid) and (meth) acrylic copolymers or PEIs / soluble copolymers in water of maleic anhydride (poly (MA-co-comonomer) with different comonomers, preferably with ethylene, propylene, Nisopropylacrylamide, N-vinyl-2-pyrrolidone and analogous comonomers and (b) by one of the conventional acrylic adhesive compositions (Rogers Int. Inc., Greenville SC, USA) which are modified with said polymer / polymer binary complex system as antistatic agent. The surface coated antistatic multilayer films of the invention are produced by improved in-line production, processing and coating technology. The present invention is useful for food and agricultural packaging applications as well as other specialty and unconventional packaging applications.
The following examples of the present invention illustrate the properties for the preparation of surface-coated, polypropylene-based multilayer antistatic films having different compositions.
EXAMPLE 1
A first example of an in-line surface coated multilayer film (A / B / C / D / E) having excellent antistatic properties comprises: (A) a 0.1 pm surface corona treated and line coated on a surface of a 0.9 pm skin layer containing 90% by weight of propylene homopolymer, 10% by weight of a polymer mixture acrylic matrix and ionic antistatic agent based on complex binary systems such as poly (ethylene-imine) s linear or branched PEIs [LPEI or (BPEI) / oligo (acrylic acid)], (B) inner layer of 2, 0 pm containing 100% by weight of polypropylene, (C) 22.0 pm core layer containing 100% by weight polypropylene, (D) 2.0 pm inner layer containing 100% polypropylene by weight, (E) outer surface corona treated layer of 1 0 pm containing 98.5% by weight of polypropylene. Prior to biaxial stretching and in-line coating, the skin layer (A) receives two corona or flame treatments to provide the best adhesion between the surface of the polypropylene-based matrix polymer and the acrylic base-line coated system. . The outer layer (E) is also corona or flame treated for further printing and labeling purposes. The film was prepared using the flat twin screw Tenter extrusion system with excellent capacity for mixing and simultaneous or sequential stretching, provided with a cooled corona system and improved in-line coating for effective modification / hydrophilization of the surface of the films, 3 or 4 satellite coextruders, flat die, cooling roller, water vaporization and recirculation lines.
EXAMPLE 2
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A second example of a multilayer film coated in line on the surface (A / B / C / D / E) that has excellent antistatic properties comprises: (A) A layer of 0.1 pm surface area corona treated and in-line coated on a 0.9 pm surface containing 90% by weight of polypropylene homopolymer or poly (ethylene-co-propylene-co-terpolymer). -butylene), 10% by weight of a mixture of acrylic matrix polymer and ionic antistatic agent based on complex binary systems such as poly (ethylene-imine) s linear or branched PEIs [LPEI or (BPEI) / oligo (acrylic acid )], (B) a 3.0 pm inner layer containing 85% by weight of polypropylene, 15% by weight of white TiÜ2 pigment, (C) a 30 pm core layer containing 85% by weight of polypropylene homopolymer, 15% by weight CaCO masterbatch<sub>3</sub> cavitant, (D) a 3.0 pm inner layer containing 95 wt% polypropylene, 5 wt% TiÜ2 white pigment and (E) 1.0 pm surface corona treated outer layer containing 100 % by weight of polypropylene or the poly (ethylene-copropylene-co-butylene) terpolymer. Prior to biaxial stretching and in-line coating, the skin layer (A) receives two corona or flame treatments to provide the best adhesion between the surface of the polypropylene-based matrix polymer and the acrylic base-line coated system. . The outer layer (E) also receives corona or flame treatment for further printing and labeling purposes. The film prepared by using the flat twin screw Tenter extrusion system with excellent capacity for mixing and simultaneous or sequential stretching, is supplied with a cooled crown and an improved in-line coating system for effective surface modification / hydrophilization of the films, 3 or 4 satellite coextruders, flat die, cooling roller, water vaporization and recirculation lines.
EXAMPLE 3
A third example of a multilayer film coated in line on the surface comprises the same structure, thickness and composition as in Example 1 with the following changes: the line-coated skin layer (A) having 1.0 pm thickness comprises 10% by weight of a mixture of crosslinkable copolymers maleic anhydride and ionic antistatic agent based on complex binary systems such as poly (ethylene-imine ) linear or branched (LPEI or BPEI / oligo (acrylic acid) having an average molecular weight (Mn) that is equal to or greater than 480 g / mol or 2000 g / mol, respectively.
EXAMPLE 4
A fourth example of a multilayer film coated in line on the surface comprises the same structure of thickness and composition as in Example 1 with the following changes: the layer of skin coated in line (A) comprises 10% by weight of a mixture of PEIs / water soluble copolymers of maleic anhydride with a ratio of equivalent amine / carboxylic acid units having an average molecular weight (Mn) that is equal to or greater than 10,000 g / mol.
EXAMPLE 5
A fifth example of a surface line coated multilayer film comprises the same thickness and composition structure as in Example 1 with the following changes: the line coated skin layer (A) having 1.0 pm thickness comprises 10% by weight of a PEIs / (meth) acrylic copolymer mixture with a ratio of equivalent amine / carboxylic acid units having a mean molecular weight (M<sub>w</sub>) which is equal to or greater than 1500 g / mol.
EXAMPLE 6
A sixth example of a multilayer film coated in line on the surface comprises the same structure, thickness and composition as in Example 1 with the following changes: (A) a 0.1 pm skin layer corona treated on the surface and line coated on a 0.9 pm surface containing 90% by weight of propylene homopolymer, 10% by weight of a polymer mixture acrylic matrix and ionic antistatic agent based on complex binary systems such as poly (ethylene-imine) s linear or branched PEIs [LPEI or (BPEI) / oligo (acrylic acid)], the core layer (C) having 24 µm thickness comprises 85% by weight of propylene homopolymer and 15% by weight of white pigment TiO2. E) a 1.0 µm surface corona treated outer layer containing 100% by weight of polypropylene or poly (ethylene-co-propylene-cobutylene) terpolymer.
COMPARATIVE EXAMPLE
A comparative example of an inline coated multilayer film (A / B / C / D / E) having excellent antistatic properties comprises: (A) a 1.0 pm skin layer containing 98.5% by weight of propylene homopolymer and 1.5% by weight of polypropylene-based antiblock masterbatch (containing 5% of inorganic additive based on silica) , (B) a 2.0 pm inner layer containing 100% by weight polypropylene, (C) a 22.0 pm core layer containing 98% by weight polypropylene and 2% by weight antistatic masterbatch based on polypropylene (containing 15% ethoxylated amine additive), (D) a 2.0 pm inner layer containing 100 wt% polypropylene, (E) a 1.0 pm corona treated surface outer layer containing 97.5 wt% polypropylene and 2.5 wt% polypropylene based antiblock masterbatch (containing 5% inorganic additive based on silica). Before biaxial stretching and in-line coating, the skin layer (A) receives
ES 2 396 867 T3 two corona or flame treatments in order to provide the best adhesion between the surface of the polypropylene based matrix polymer and the acrylic base line coated system. The outer layer (E) is also corona or flame treated for further printing and labeling purposes. The film prepared using the flat twin screw Tenter extrusion system with excellent mixing and simultaneous or sequential stretching capacity, 5 supplied with a cooled crown and 3 or 4 satellite co-extruders, flat die, cooling roll, water vaporization and recycling lines.
TABLE 1
<td colspan="8">Compositions for the in-line coated films of the present invention.</td>
<td rowspan="2">Individual Components</td><td>Ex-1</td><td>Ex-2</td><td>Ex-3</td><td>Ex-4</td><td>Ex-5</td><td>Ex-6</td><td>Comparative Film</td>
<td>Content (% weight)</td><td>Content (% weight)</td><td>Content (% weight)</td><td>Content (% weight)</td><td>Content (% weight)</td><td>Content (% weight)</td><td>Content (% weight)</td>
<td>Isotactic polypropylene (homopolymer)</td><td> 99,635</td><td> 85,334</td><td> 99,635</td><td> 99,635</td><td> 99,635</td><td> 84,926</td><td> 99,745</td>
<td>Poly [propylenecoethylene (1.2-5.4%) co-1-butene (2.814.6%)]</td><td> 0,000</td><td> 5,000</td><td> 0,000</td><td> 0,000</td><td> 0,000</td><td> 6,333</td><td> 0,000</td>
<td>Calcium carbonate -cavitant agent</td><td> 0,000</td><td> 8,289</td><td> 0,000</td><td> 0,000</td><td> 0,000</td><td> 0,000</td><td> 0,000</td>
<td>Titanium dioxide white pigment</td><td> 0,000</td><td> 1,105</td><td> 0,000</td><td> 0,000</td><td> 0,000</td><td> 8,400</td><td> 0,000</td>
<td>Tetrakis-methane - antioxidant</td><td> 0,004</td><td> 0,004</td><td> 0,004</td><td> 0,004</td><td> 0,004</td><td> 0,004</td><td> 0,004</td>
<td>Stabilizing aryl phosphide</td><td> 0,004</td><td> 0,004</td><td> 0,004</td><td> 0,004</td><td> 0,004</td><td> 0,004</td><td> 0,004</td>
<td>Silica-based antiblocking agent</td><td> 0,000</td><td> 0,000</td><td> 0,000</td><td> 0,000</td><td> 0,000</td><td> 0,000</td><td> 0,007</td>
<td>Additive based on ethoxylated amine</td><td> 0,000</td><td> 0,000</td><td> 0,000</td><td> 0,000</td><td> 0,000</td><td> 0,000</td><td> 0,240</td>
<td>Material of coating 1</td><td> 0,357</td><td> 0,263</td><td> 0,000</td><td> 0,000</td><td> 0,000</td><td> 0,333</td><td> 0,000</td>
<td>Material of coating 2</td><td> 0,000</td><td> 0,000</td><td> 0,357</td><td> 0,000</td><td> 0,000</td><td> 0,000</td><td> 0,000</td>
<td>Material of coating 3</td><td> 0,000</td><td> 0,000</td><td> 0,000</td><td> 0,357</td><td> 0,000</td><td> 0,000</td><td> 0,000</td>
<td>Material of coating 4</td><td> 0,000</td><td> 0,000</td><td> 0,000</td><td> 0,000</td><td> 0,357</td><td> 0,000</td><td> 0,000</td>
<td colspan="8">Coating Material 1: Mixture of acrylic matrix polymer and ionic antistatic agent based on complex binary systems such as linear or branched poly (ethylene-imine) s PEIs [LPEI or (BPEI) / oligo (acrylic acid)] Coating Material 2: Mixture of crosslinkable copolymers maleic anhydride and ionic antistatic agent based on complex binary systems such linear or branched poly (ethylene-imine) (LPEI or BPEI / oligo (acrylic acid) having average molecular weight (M „) Which is equal to or greater than 480 g / mol or 2000 g / mol, respectively. Coating Material 3: Mixture of PEIs / water-soluble copolymers of maleic anhydride with a ratio of equivalent amine / carboxylic acid units having average molecular weight (M<sub>n</sub>) which is equal to or greater than 10,000 g / mol. Coating Material 4: PEIs / (meth) acrylic copolymer mixture with ratio of equivalent amine / carboxylic acid units having average molecular weight (M<sub>w</sub>) which is equal to or greater than 1500 g / mol.</td>
ES 2 396 867 T3
Table 2
<td>COMPARATIVE FILM (28 pm) BOpP film not heat sealable</td><td>Homopolymer 98.5% Antiblock Masterbatch 1.5% (Thickness: 1 pm)</td><td>100% homopolymer (Thickness: 2 pm)</td><td>Homopolymer 98%</td><td>2% antistatic masterbatch (Thickness: 22.0 pm)</td>
<td>EXAMPLE-6 (30 pm) Heat sealable white bOpP film</td><td>Terpolymer 90% Cover material 1 10% (Thickness: 1 pm)</td><td>Homopolymer 100 % (Thickness: 2 pm)</td><td>LO 00 OR Φ AND or Q_ OR AND 0 X</td><td>15% white masterbatch (TiO2) (Thickness: 24.0 pm)</td>
<td>EXAMPLE - 5 (28 pm) Non-heat sealable inline coated bOpP film</td><td>Homopolymer 90% Coating material 4 10% (Thickness: 1 pm)</td><td>Homopolymer 100 % (Thickness: 2 pm)</td><td>0 0 0 Φ 0 Q_ OR AND 0 T</td><td>AND ZL Or cxf CXI 0 (Λ Φ Q_ (Λ LJ ¿</td>
<td>EXAMPLE-4 (28 pm) Non-heat sealable in-line coated bOpP film</td><td>Homopolymer 90% Coating material 3 10% (Thickness :) 1 pm)</td><td>Homopolymer 100 % (Thickness: 2 pm)</td><td>0 0 0 Φ Ε, ο 0 Q_ OR AND 0 T</td><td>'E ZL Or cxf CXI 0 (Λ Φ Q_ (Λ LJ ¿</td>
<td>EXAMPLE-3 (28 pm) Non-heat sealable in-line coated bOpP film</td><td>Homopolymer 90% Coating material 2 10% (Thickness: 1 pm)</td><td>Homopolymer 100 % (Thickness: 2 pm)</td><td>0 0 0 Φ Ε, ο 0 Q_ OR AND 0 T</td><td>'E ZL OR cxf CXI 0 (Λ Φ Q_ (Λ LJ</td>
<td>EXAMPLE-2 (38 pm) Opaque cavitated line coated bOpP film</td><td>Terpolymer 90% Cover material 1 10% (Thickness: 1 pm)</td><td>Homopolymer 85% White Masterbatch (TO2) 15% (Thickness: 3 pm)</td><td>θ ' LO 00 OR Φ AND or Q_ OR AND 0 X</td><td>Cavitation Master Mix (CaCO3) 15% (Thickness: 30 pm)</td>
<td>EXAMPLE 1 (28 pm) Non-heat sealable inline coated bOpP film</td><td>Homopolymer 90% Coating material 1 10% (Thickness: 1 pm)</td><td>Homopolymer 100 % (Thickness: 2 pm)</td><td>0 0 0 Φ Ε, ο 0 Q_ OR AND 0 T</td><td>E ZL OR cxf CXI 0 (Λ Φ Q_ (Λ LJ</td>
<td>Layers</td><td>Φ ~ O _ ω φ £ - Qo</td><td>or. E ω φ O .E</td><td colspan="2">Φ <sub>Λ </sub>Ό <sup>0</sup>05 -7T q., 2 rd ¿O <sup>c</sup></td>
ES 2 396 867 T3 (continued)
<td>COMPARATIVE FILM (28 pm) Non-heat sealable BOPP film</td><td>100% homopolymer (Thickness: 2 pm)</td><td>Homopolymer 97.5% Masterbatch Antiblocking masterbatch 2.5% (Thickness: 1 pm) Surface treatment: Corona or flame treatment</td>
<td>EXAMPLE-6 (30 pm) Heat sealable white BOPP film</td><td>Homopolymer 100 % (Thickness: 2 pm)</td><td>100% terpolymer (Thickness: 1 pm) Surface treatment: Corona or flame treatment</td>
<td>EXAMPLE - 5 (28 pm) Non-heat sealable in-line coated BOPP film</td><td>Homopolymer 100 % (Thickness: 2 pm)</td><td>Homopolymer 100% (Thickness: 1 pm) Surface treatment: Corona or flame treatment</td>
<td>EXAMPLE-4 (28 pm) Non-heat sealable in-line coated BOPP film</td><td>Homopolymer 100 % (Thickness: 2 pm)</td><td>Homopolymer 100 % (Thickness: 1 pm) Surface treatment: Corona or flame treatment</td>
<td>EXAMPLE-3 (28 pm) Non-heat sealable in-line coated BOPP film</td><td>Homopolymer 100 % (Thickness: 2 pm)</td><td>Homopolymer 100 % (Thickness: 1 pm) Surface treatment: Corona or flame treatment</td>
<td>EXAMPLE-2 (38 pm) Opaque cavitated line coated BOPP film</td><td>Homopolymer 95% White 5% Masterbatch (TiO2) (Thickness: 3 pm)</td><td>100% Terpolymer (Thickness: 1 pm) Surface treatment: Corona or flame treatment</td>
<td>EXAMPLE 1 (28 pm) Non-heat sealable inline coated BOPP film</td><td>Homopolymer 100 % (Thickness: 2 pm)</td><td>Homopolymer 100 % (Thickness: 1 pm) Surface treatment: Corona or flame treatment</td>
<td>Layers</td><td>Inner layer</td><td>Outer layer</td>
ES 2 396 867 T3
The thickness of the surface skin layer of the line-coated antistatic acrylic / maleic-based film developed in this invention is equal to or greater than 0.8 pm in thickness, the coating thickness that is applied in-line being equal to or less than 0 , 5 pm as in examples 1 to 6.
One aspect of the present description is the possibility of producing the films in the form of monooriented and biaxially oriented polyolefin, preferably mono- or multilayer films based on polypropylene having at least one surface covered with an antistatic adhesive layer by using a combination of
a) a twin screw flat Tenter extrusion system with excellent capacity for simultaneous or sequential mixing and drawing, a main extruder with 3 or 4 satellite co-extruders, flat die, cooling roll and water bath, orientation units in machine direction and cross direction, recycle line, corona and / or flame treatment units, and winding unit;
b) an in-line coating application system, supplied with tension rollers, engraving roller, dual cooled corona units and water vaporization line for effective surface modification / hydrophilization and to significantly improve tension and antistatic properties wetting of the films.
The flat Tenter extrusion film line is one that produces conventional biaxially oriented polypropylene films with industrially acceptable properties. However, this technology does not allow the production of films having improved and long-lasting slip, antistatic, wetting stress, optical and the like. With the use of masterbatches containing conventional migratory additives, the mentioned properties face changes over periods of aging and exploitation.
In accordance with the present description, an improved version of the in-line coating system was developed and integrated into a biaxially oriented standard flat Tenter polypropylene processing and manufacturing line by making the following important changes to in-line coating processing:
1) taking into consideration that polypropylene surfaces are hydrophobic with lower intrinsic wetting stress values (21-31 dynes / cm) compared to polyester surfaces that have intrinsically higher wetting stress levels (40-42 dynes / cm) which are widely used in in-line coating technology, Double cooled corona units are adopted in the in-line coating system to ensure that the wetting stress level of the polypropylene film surface is adequate enough to allow the water-based coatings to adhere to the surface;
2) In the standard BOPP production process, the tension between MDO and TDO is precisely controlled to avoid film breakage and poor quality production, although the coating unit in line between them leads to increased tension and imprecise control. of tension. With this the new support system of the last MDO rollers is changed and a new control system is supplied to the system in order to achieve the precise control of the tension;
3) It is well known that polypropylene structures have inferior heat resistance properties compared to polyester structures. Therefore, in corona treatment systems in BOPP film manufacturing processes, the heat generated during the corona discharge unit should be offset by cooling rollers. Since the corona power used in the in-line coating system is high, being approximately 30-40 kW, the corona rollers adopted for the in-line coating system are cooled by an additional cooling system in order to avoid overheating of the film;
4) It is also well known that one of the most important parameters in the in-line coating system is the achievement of a homogeneous distribution and even a coating thickness along the entire length of the web, since the MDO-stretched coated film has to undergo TDO stretching between 1: 8 and 1:10, and the thickness of the coatings has to be controlled in a very sensitive control unit. Therefore, the new coating thickness controller unit using a Gauge β or X-ray system is mounted on the in-line coating system;
5) The engraving pattern for polyester and polypropylene are different for each substrate. For the film of the present invention, different cell angle, line (number of cells / inch<sup>2</sup>) and cell volume depending on the composition and concentration of the coating material are used in the in-line coating process;
6) The dryer, in this case the TDO preheating section, must have sufficient thermal capacity in order to dry and remove water from the coated film. To achieve the desired drying temperature of 180-190 ° C (with in-line coating) instead of 160-170 ° C (for standard uncoated production), the thermal capacity of the TDO preheating section is increased.
According to the present description, the technological aspects developed for the production and processing of said films are:
a) Biaxially oriented mono- or multilayer polypropylene film technology,
b) a twin screw flat Tenter extrusion system provided with excellent simultaneous or sequential stretching and mixing capabilities, a main extruder with 3 or 4 satellite co-extruders, flat die, cooling roll and water bath, orienting units machine direction and cross direction, recycle line, corona and / or flame treatment units, winding unit,
ES 2 396 867 T3
c) an in-line coating application system provided with tension rollers, embossing roller, dual cooled corona units, and water vaporization line for effective surface modification / hydrophilization and to significantly improve the tensile and antistatic properties of wetting of the films.
Alternatively, the outer layer (E) of the prepared biaxially oriented films can be treated in a known manner such as plasma or flame or, more preferably, by corona electrical discharge. The general scheme for the production technology and the improved processing of the films is depicted in Fig. 2.
Another aspect of the present invention consists of using new functional copolymer systems using as basic polymers, that is to say, water-soluble copolymers containing anhydride and their PEI macrocomplexes in the compositions of the surface coatings and polymeric antistatic agents; linear and branched PEIs have the following mean characteristics: average molecular weight Mn = 425 g / mol, viscosity η = 200 cP at 25 ° C and density d = 1.07 g / cm<sup>3</sup> (for linear PEI) and Mn = 1800, M<sub>w</sub> = 2000 g / mol and density d = 1.08 g / cm<sup>3 </sup>(for branched PEI). The use of copolymers containing anhydride and homo- and copolymers of (meth) acrylic acid easily crosslinked by poly (ethylene glycol) (PEG) in the aqueous medium at 85-110 ° C without any catalyst and at room temperature in the presence of catalyst of water soluble carbamide type (as in Devrim Y., Rzaev ZMO et al. Macromol. Chem. Phys. 2007; 208: 175). The physical state of the PEGs used changes from liquid to crystalline powder; having different molecular weights (Mn = 200, 420, 950 and 8000 g / mol) they are used as a crosslinker, whose intermolecular links also improve the antistatic properties of the films. Both the aforementioned crosslinkable copolymer systems and the hyperbranched copolymer / PEI macrocomplexes (Fig. 1) exhibit better film-forming properties and excellent antistatic activity, respectively. Conventional acrylic adhesives can also be integrated to be used in the in-line surface coating process.
It is a further object of the present invention to expand the field of application of said films of said coated films useful for conventional applications that include the food industry and non-food industries such as food packaging, agriculture, industrial wrapping applications, medicine, pharmacy , electrical and electronic equipment industry, and the like.
Some important properties of the films prepared according to the present invention are summarized in Table 3.
ES 2 396 867 T3
Table 3
<td></td><td>COMPARATIVE FILM (28 pm) BOpP film not heat sealable</td><td> 28</td><td> 39,2</td><td> 0,91</td><td></td><td> 38</td><td>* * IT CD</td><td>co</td><td> 85</td><td></td><td></td>
<td rowspan="9">Physical and mechanical characteristics and surface properties of the multilayer BOPP films of the present invention</td><td>EXAMPLE-6 (30 pm) Heat sealable white BOPP film</td><td> 30</td><td> 34</td><td> 86'0</td><td></td><td> 42</td><td>* Or</td><td></td><td> 55</td><td> 65</td><td> 35</td>
<td>EXAMPLE-5 (28 pm) Non-heat sealable in-line coated BOPP film</td><td> 28</td><td> 39,2</td><td> 0,91</td><td></td><td> 42</td><td>* Or</td><td> 0,4</td><td> 100</td><td></td><td></td>
<td>EXAMPLE-4 (28 pm) Non-heat sealable in-line coated BOPP film</td><td> 28</td><td> 39,2</td><td> 0,91</td><td></td><td> 42</td><td>* or</td><td> 0,4</td><td> 100</td><td></td><td></td>
<td rowspan="2">EXAMPLE-3 (28 pm) Non-heat sealable in-line coated BOPP film</td><td></td><td></td><td></td><td rowspan="4">SURFACE AND OPTICAL PROPERTIES</td><td></td><td></td><td></td><td></td><td></td><td></td>
<td> 28</td><td> 39,2</td><td> 0,91</td><td> 42</td><td>* or</td><td> 0,4</td><td> 100</td><td></td><td></td>
<td>EXAMPLE-2 (38 pm) Opaque cavitated line coated BOPP film</td><td> 38</td><td> 39,3</td><td> 0,67</td><td> 42</td><td>* or</td><td></td><td> 90</td><td> 75</td><td> 30</td>
<td>EXAMPLE-1 (28 pm) Non-heat sealable in-line coated BOPP film</td><td> 28</td><td> 39,2</td><td> 0,91</td><td> 42</td><td>* or</td><td> 0,4</td><td> 100</td><td></td><td></td>
<td>UNIT</td><td>E ZL</td><td>CD AND</td><td>T) AND or CD</td><td></td><td>dynes / cm</td><td>Seconds</td><td>sp</td><td>sp</td><td>sp</td><td>sp θ '</td>
<td>Parameters</td><td>Thickness</td><td>Elastic limit</td><td>Density</td><td></td><td>Voltage Moistening</td><td>Static decay time</td><td>Turbidity</td><td>Brightness</td><td>Opacity</td><td>Light transmission</td>
<td></td><td>Method of Test</td><td>ASTM D 374</td><td>ASTM D 4321</td><td>ASTM D1505</td><td></td><td>ASTM D 2578</td><td>ASTM D257</td><td>ASTM D1003</td><td>ASTM D 2457</td><td>DIN 53146</td><td>ASTM D 1746</td>
ES 2 396 867 T3 (Continued)
<td rowspan="11">MECHANICAL AND THERMAL PROPERTIES</td><td> 166</td><td> 306</td><td> 159</td><td> 59</td><td></td><td>CXI</td><td></td><td rowspan="11">* 0 means the electrostatic charge on the coated surface of the immediately discharged film and without any static build-up on the surface. The same values are taken after production and after an aging time of 10 days. ** the comparative film includes the migratory antistatic agent, and this value is taken after an aging time of 10 days.</td>
<td> 148</td><td> 227</td><td> 166</td><td> 63</td><td>CO</td><td>CXI</td><td> 105-145</td>
<td> 172</td><td> 305</td><td> 174</td><td> 55</td><td></td><td>CXI</td><td></td>
<td> 169</td><td> 293</td><td> 162</td><td> 59</td><td></td><td>CXI</td><td></td>
<td> 173</td><td> 287</td><td> 167</td><td> 62</td><td></td><td>CXI</td><td></td>
<td> 79</td><td> 137</td><td> 98</td><td> 40</td><td>CO</td><td> -</td><td></td>
<td> 165</td><td> 298</td><td> 155</td><td> 58</td><td></td><td>CXI</td><td></td>
<td>MD</td><td>TD</td><td>MD</td><td>TD</td><td>MD</td><td>TD</td><td></td>
<td colspan="2">CN AND E z</td><td colspan="2"></td><td colspan="2"></td><td>or or</td>
<td colspan="2">Tensile strength</td><td colspan="2">Elongation at break</td><td colspan="2">Thermal shrinkage</td><td>Heat seal interval</td>
<td colspan="2">ASTM D 882</td><td colspan="2">ASTM D 882</td><td colspan="2">ASTM D 2732</td><td>00 00 LL 1— ω <</td>
ES 2 396 867 T3
The examples and the comparative film have been tested for wetting tension and adhesion quality against water-based and UV-based inks, as both ink systems are widely used in industry and standard BOPP films are lacking. of adequate adhesion to these ink systems.
Table-4
Ink Adhesion Test Results (Ink Adhesion: 1-5, with 5 being the optimal adhesion)
<td rowspan="2">Film Type</td><td colspan="2">WB FLEXO INK</td><td colspan="2">UV FLEXO INK</td>
<td>Immediately</td><td>24 hours</td><td>Immediately</td><td>24 hours</td>
<td>Example -1,2 and 6</td><td> 5</td><td> 5</td><td> 1</td><td> 1</td>
<td>Example - 3</td><td> 4</td><td> 5</td><td> 1</td><td> 2</td>
<td>Example - 4</td><td> 4</td><td> 5</td><td> 1</td><td> 1</td>
<td>Example - 5</td><td> 4</td><td> 5</td><td> 1</td><td> 1</td>
<td>Comparative Film</td><td> 2</td><td> 3</td><td> 0</td><td> 0</td>
<td rowspan="2">Film Type</td><td colspan="2">UV OFFSET INK</td><td colspan="2">UV TYPOGRAPHIC PRINTING INK</td>
<td>Immediately</td><td>24 hours</td><td>Immediately</td><td>24 hours</td>
<td>Example -1,2 and 6</td><td> 4</td><td> 4,5</td><td> 3</td><td> 3,5</td>
<td>Example - 3</td><td> 3</td><td> 4</td><td> 2</td><td> 2,5</td>
<td>Example - 4</td><td> 4</td><td> 4</td><td> 3</td><td> 3</td>
<td>Example - 5</td><td> 3</td><td> 3,5</td><td> 2</td><td> 3</td>
<td>Comparative Film</td><td> 1</td><td> 3</td><td> 1</td><td> 1,5</td>
Another aspect of the present invention is the use of various combinations of organic and inorganic additives to enable the production of different types of mono- or multilayer surface-coated films based on biaxially oriented polypropylene such as transparent, non-heat sealable, white labels. cavitated non-heat sealable, white cavitated heat sealable, and the like using the above-described improved version of surface-coated mono- or multilayer antistatic thin film production and processing technology including chemical modification of the surface of the films by an in-line coating method.
Advantages of the acrylic / maleic-based antistatic films described in this present invention and their manufacturing and processing technology are:
(1) An assembled structure of macrocomplexes is provided with a higher degree of positive charges on the macromolecules with excellent antistatic properties over a long operating time combined with other important properties of films such as slidability, antiblocking, improved wetting tension, sealing adhesion. cold and for different types of laminating adhesives, etc., (2) all the functional polymer components described in the surface-coated compositions relative to the class of water-soluble bioengineered polymer systems, and therefore the film production and processing technology is environmentally friendly chemical technology, (3) the improved coating processing technology allows this method to be applied to the manufacture of a wide range of biaxially oriented mono- or multilayer polyolefin-based films and their laminates with various thermoplastic and thermosetting polar materials, (4) the possibility of expanding the field of conventional applications. The films described are also useful for special application as a new generation of antibacterial and antifog films due to the positively charged surface of the particles.
The acrylic / maleic based inline coated antistatic film developed in this invention can be antibacterial or antifog or antimicrobial or degradable or biodegradable or low SIT or a combination thereof.
The antistatic and coated film on an acrylic / maleic base line developed can be a film based on biaxially oriented monolayer polypropylene (BOPP) comprising: a single layer with a polypropylene or the mixture of polypropylene with poly (ethylene-co-propylene) copolymer or poly (ethylene-co-propylene-co-butylene) terpolymer and a thin antistatic layer coated in line on the surface.
Contents20
2 sheets
Sheet 1 Sheet 2
8 members in 4 offices
Priority claims4
| Document | Office | Kind | Date |
|---|---|---|---|
| 2007000083 | Türkiye | W | |
| 2007000083 | Türkiye | W | |
| PCTTR2007000083 | – | – | – |
| WO2007TR00083 | – | – | – |
Members8
| Document | Office | Kind | |
|---|---|---|---|
| WO2009029058A1 | World Intellectual Property Organization (WIPO) | A1 | |
| EP2237952A1 | European Patent Office (EPO) | A1 | |
| EP2237952B1 | European Patent Office (EPO) | B1 | |
| ES2396867T3This record | Spain | T3 | |
| PL2237952T3 | Poland | T3 | |
| EP2237952B2 | European Patent Office (EPO) | B2 | |
| ES2396867T5 | Spain | T5 | |
| PL2237952T5 | Poland | T5 |
Numbers
- Publication
- 2396867
- Publication, DOCDB
- 2396867
- Publication, EPODOC
- ES2396867T
- Application
- 7835595
- Application, DOCDB
- 07835595
- Application, EPODOC
- ES20070835595T
Titles2
- Spanish
- Películas multicapa antiestáticos basadas en polipropileno biaxialmente orientado con recubrimiento en línea
- English
- Multi-layer antistatic films based on biaxially oriented polypropylene with in-line coating
Classification
- CPC, 12
- B32B27/32
- B29C59/10
- B32B27/08
- B32B2255/10
- B32B2255/26
- B32B2307/518
- B32B2307/7145
- B32B2307/7163
- B32B2439/70
- C08J2323/08
- C08J2323/16
- C08J2433/06
- IPC, 4
- B32B27 32
- B29C59 10
- C08J7 04
- H01T19 00