Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/10—Printing inks based on artificial resins
  • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C09D11/108—Hydrocarbon resins
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B44—DECORATIVE ARTS
  • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
  • B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
  • B44C1/10—Applying flat materials, e.g. leaflets, pieces of fabrics
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
  • Y10T428/31573—Next to addition polymer of ethylenically unsaturated monomer
  • Y10T428/31587—Hydrocarbon polymer [polyethylene, polybutadiene, etc.]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31801—Of wax or waxy material

Definitions

• the present invention relates to a film ink and multilayer product based on olefinic polymer, and also relates to decorated multilayer films and products.
• An ink is generally composed of one or more pigments and a binder for suspending, transporting, and fixing the pigment on the support that is to be covered, or the support on which the we want to print patterns.
• the choice of pigment and binder are essential because the pigment determines the coloring power of the ink and the binder determines not only the drying mode of the ink, but also the main characteristics (strength, adhesion %) of the ink layer thus obtained.
• the pigment-binder mixture is added additives to optimize the characteristics of the ink during and after its application. They are also used to facilitate the implementation of the ink and allow, among other things, to accelerate the drying, to improve the gloss, and / or to increase the resistance of the ink film.
• additives for ink there are in particular dispersing agents, anti-foaming agents, but also waxes, polymers, thickeners and plasticizers.
• Waxes of animal origin, vegetable or mineral, allow to change the surface condition of the ink film and mainly allow to increase the resistance to friction, abrasion and improve the slip coefficient of the ink layer.
• the polymers generally based on nitrocellulose or ethyl cellulose, make it possible to improve the properties of the ink layer, to improve its gloss and resistance. They also make it possible to improve the wetting of the pigments.
• the thickeners for their part, make it possible to correct the viscosity of the ink.
• the composition of an ink varies depending on the medium on which it will be applied and the desired result.
• the ink must have good intrinsic cohesion and good adhesion to the substrate. Not all inks can be applied to all media.
• the inks commonly used are not suitable for their application on plastic films or on multilayer products used in particular as decorative surface coatings.
• the printing on plastic films is difficult because, often, these films are made of non-polar polymers, and the application of an ink requires the prior installation of a coating, also called " primary ", or the use of a film surface treatment, such as a corona treatment, which has the disadvantage of introducing into the manufacturing process of such plastic films one or two additional steps.
• a multilayer product usually consists of a plastic film, also called substrate layer or support layer, on which is disposed another plastic film, also called top layer or layer wear.
• the wear layer which is usually transparent, has the function of protecting the decorative face due to its good resistance to mechanical and chemical attack that may occur under the normal conditions of use of such multilayer products.
• the support layer which has a decorative face on which the wear layer is applied.
• the adhesion between the layers of a multilayer product is a crucial point because it must be sufficient to meet the most demanding criteria, particularly in terms of traffic resistance of the final product is a floor covering.
• the polyolefinic film (or the polyolefinic support layer is a multilayer product) to be decorated must undergo a surface treatment before printing the decorative pattern. It may be the application of a "primary" or a physical treatment, in particular a corona treatment as described in document FR2836088.
• a multilayer product as described in FR2836088, an adhesion promoter must be applied to the decorative layer to improve the adhesion between the ink layer and the coating layer. 'wear.
• adhesion promoters mentioned in the document FR2836088 are solutions based on polyolefins, chlorinated polyolefins, hydroxyl functionalized chlorinated polyolefins or maleic anhydride or epoxy, solutions based on acrylic, crosslinked polyesters or solutions based on silanes.
• an alternative solution consists in using an adherent ink in which the adhesion promoter is an integral part of the ink.
• EP0604729 discloses an adhesive ink for printing on a support based on polyolefinic polymer to obtain woven or nonwoven products, in the form of fibers or films. This ink comprises a pigment, a binder, and an adhesion promoter.
• the binder is either polyvinyl alcohol or ethylene-vinyl acetate (EVA), compounds used for their ability to form a film, while the adhesion promoter is a compound selected from hydrocarbon resins, esters rosin or polyterpenes.
• EVA ethylene-vinyl acetate
• Such adhesive inks have the disadvantage of being of a complex formulation and not being sufficiently adherent to the polyolefinic support on which it is applied, because indeed, their formulation represents a compromise between homogeneity of ink and adhesion to the substrate, a compromise to the detriment of their adhesion property.
• the present invention aims at providing an ink which does not have the drawbacks of the state of the art.
• the present invention describes a polyolefinic polymer based printing ink comprising at least one pigment and a binder, said binder being an oxidized polyolefinic wax emulsified in water, said wax having a viscosity Brookfield less than 5000 mPa.s at 150 ° C. and an acidity level of between 28 and 32 mg KOH / g, said ink having a viscosity of less than 2000 mPa.s at 25 ° C.
• oxidized olefinic polymer denotes a polymer, prepared by polymerization of olefins from olefinic monomers, and which has undergone oxidative treatment.
• the ink comprises one or more of the following characteristics:
• the viscosity of said ink is between 300 and 1000 mPa.s at 25 ° C.
• the oxidized polyolefin wax is an ethylene homopolymer with a high oxidized density.
• the oxidized and emulsified polyolefin wax represents by weight between 35% and 96% of the total weight of the ink.
• the ink further comprises at least one additive selected from the group selected from the group consisting of an antifoam, a thickener and / or a surfactant.
• the present invention also discloses a support, based on high density ethylene polymer, decorated using the ink according to the invention wherein said ink is applied continuously or discontinuously on at least one face of said support.
• support means any support suitable for receiving an ink, in particular it may be a film. According to particular embodiments, the support comprises the following characteristic:
• the support further comprises mineral fillers.
• the present invention also discloses a multilayer product comprising a polyolefinic polymer-based support layer, and a polyolefinic polymer-based wear layer, wherein at least one face of said support layer and / or or said wear layer is covered with an ink comprising at least one pigment and a binder, said binder being an oxidized polyolefinic wax emulsified in water, said oxidized polyolefinic wax having a Brookfield viscosity of less than 5000 mPa.s at 150 ° C. and an acid content of between 28 and 32 mg KOH / g.
• the decorated multilayer product comprises one or more of the following features:
• the support layer is based on high density ethylene polymer.
• the support layer comprises mineral fillers.
• the wear layer comprises a layer based on a polymer of the ionomeric type.
• a layer based on polyurethane is applied to the wear layer.
• the multilayer product is used for the development of a floor covering and / or a wall covering.
• the present invention further discloses a method of manufacturing a multilayer product comprising a polyolefinic polymer-based support layer and a polyolefinic polymer-based wear layer, said process comprising the following steps :
• Corona treatment of one side of the support layer and / or the wear layer to be printed - Application on at least one face of the support layer and / or the wear layer of an ink comprising at least one pigment and a binder, said binder being an oxidized polyolefinic wax emulsified in water, said oxidized polyolefinic wax having a Brookfield viscosity of less than 5000 mPa.s at 150 ° C. and an acidity level of between 28 and 32 mg KOH / g,
• the method comprises one or more of the following features:
• the method further comprises a step of covering the wear layer with a polyurethane-based surface layer.
• the method further comprises a step of mechanical graining of the wear layer after its assembly to the support layer.
• Figure 1 shows a multilayer product decorated with the ink according to the invention.
• the oxidized polyolefinic waxes are known per se and are commercially available. These are generally polymers, homopolymers or copolymers, obtained by polymerization of olefinic monomers, which have undergone oxidation.
• the oxidized polyolefin wax used as binder in the ink according to the present invention is a polyolefinic polymer having a Brookfield viscosity of less than 5000 mPa.s at 150 ° C. and which has a degree of oxidation (which is expressed in terms of acidity) of between 28 and 32 mg KOH / g, preferably an average degree of oxidation of 30 mg KOH / g.
• the oxidation of the wax promotes the cohesion of the pigment in the ink and makes it possible to obtain an optimum adhesion between the ink and the film, or the polyolefinic support layer on the one hand, and the other on the other hand, between the ink and the wear layer for multilayer products.
• the polished olefinic wax used in the ink according to the invention is a high density ethylene homopolymer which has been oxidized by any suitable means.
• the oxidation can be done by reaction with oxygen, or an oxygen-containing gas, at temperatures ranging between 140 and 200 ° C. and at pressures ranging from 5 to 200 bars.
• the pigment used in the ink according to the invention may be any colored substance, mineral or organic, whatever the structure or nature. It may also be metal pigments, iridescent or pearls. It may also be mixtures of such pigments.
• the pigment is in the form of a powder, but may also be in any other suitable form, and may also be associated with a dispersant.
• the preparation of the ink is done conventionally, however, before the incorporation of the pigment, the wax is previously emulsified in water, the water portion varying between 55 and 75% by weight, of preferably the water portion being 65% by weight.
• the percentage of dry matter, ie solid oxidized wax in the emulsion varies from 25 to 45% by weight, preferably the percentage of solid oxidized wax is 35% by weight.
• the ink may further comprise one or more additives, for example an anti-aging compound. foam, a thickener, a surfactant, which are preferably added to the oxidized wax and emulsified before the incorporation of the pigment.
• the additive portion does not exceed 10% by weight of the final ink.
• the ink according to the invention has a viscosity of less than 2000 mPa.s at 25 ° C., advantageously the viscosity is between 300 and 1000 mPa.s at 25 ° C.
• the wax used is a high density polyethylene polymer (Solewax 403 from Ramvers) having an average acidity level of 30 mg KOH / g, and a viscosity of 3600 mPa.s. at 150 0 C, and which was emulsified in water.
• the emulsion comprises 55 to 75% by weight of water, advantageously 65% by weight of water.
• Tables 1 to 4 give examples of composition of an ink according to the invention.
• Table 1 Composition of a white ink.
• Table 2 Composition of a metallic ink.
• a white which comprises 70% of white pigment, the remaining 30% consisting of 90% water and 10% acrylic resin.
• the white ink itself can be used as a support for the printing of one or more colored and / or metallic inks, but it can also be mixed with one or more colored inks, for example table 3 inks.
• a mixture of white ink / colored ink, the percentage of colored ink represents by weight, preferably between 1 and 10% of the weight of the total mixture.
• the pigment used is aluminum coated with silicon dioxide (Stapa IL hydrolan Aluminum).
• a polyolefinic polymer-based support which may or may not be coated with white ink, but may itself be used as a support for printing one or more color inks , or a mixture of at least one colored ink with the white ink.
• a color ink (Table 3) according to the invention can be used to print a support based on polyolefinic polymer which may or may not be coated with a white ink or a metallic ink.
• the color ink can be used as described in Table 3, in a form that can be qualified "concentrated” to obtain a dark shade, or used in a "diluted” form, that is to say in the form of a mixture with the white ink, the metallic ink, or even the ink colorless (Table 4) to obtain lighter shades.
• a colorless ink (Table 4) may be used to coat a polyolefinic polymer-based support which may or may not be coated with a white, metallic or colored ink.
• the colorless ink, mixed with one or more "concentrated” colored inks (Table 3) can also be used to obtain "diluted” inks in order to obtain lighter shades.
• the proportion by weight of concentrated colored ink is between about 1% and about 16%.
• the percentage of oxidized and emulsified wax represents between about 35 and about 83% by weight of the total weight of a white ink, metallic or concentrated color and between about 86 and about 89% by weight of the total weight of a diluted color ink, and about 96% by weight of the total weight of a colorless ink.
• the percentage of dry matter of oxidized wax represents, by weight, between about 9% and about 37% of the total weight of a white, metallic or white ink. of concentrated color and between about 21% and about 40% by weight of the total weight of a diluted color ink, and about 43% by weight of the total weight of a colorless ink.
• the oxidized wax is emulsified in 65% of water, thus the percentage of dry matter of oxidized wax represents by weight between about 12% and about 29% of the total weight of the product. a white, metallic or colored ink concentrated and about 30% by weight of the total weight of a diluted color ink, and about 33% of the total weight of a colorless ink.
• compositions of Tables 1 to 4 have an adhesion greater than 50N / 50mm in a peel strength test carried out according to European Standard EN431.
• the white ink comprising 57.4% by weight of emulsified oxidized wax, a metal ink containing about 71% by weight of emulsified oxidized wax and a colored ink concentrated to about 35% emulsified oxidized wax, have good adhesion. polyolefinic support while having a sufficient aesthetic appearance.
• the plastic films, or the multilayer product support layers, decorated using one or more inks according to the invention, are preferably films, or support layers, based on ethylene polymer. high density. Preferably, these films are obtained by lamination or calendering.
• the support layer 1 of a multilayer product may be a so-called compact layer or foam. It may comprise organic and / or mineral fillers intended to confer on it particular mechanical properties; It may be for example calcium carbonate or magnesium, calcium sulfate, carbonate or barium sulfate, kaolin, fumed silica, expanded graphite, or fiberglass.
• the support layer is of low density polyethylene and comprises calcium carbonate and a glass veil 2.
• the ink according to the present invention may be applied to at least one surface of the film, the support layer 1 or the wear layer 3, polyolefinic by any suitable means.
• the ink is applied by heliography, flexography or screen.
• the application may be continuous, over the entire surface of the film, the support layer 1 or the wear layer 3, or discontinuously, on only a portion of the surface of the film, the support layer 1 or the wear layer 3.
• the ink layer 2 colored, metallic, white or colorless, has the advantage of being itself a support for printing an additional pattern.
• the film, the support layer 1 or the wear layer 3, thus decorated undergoes drying, for example by forced air, for example at a temperature that can be between 20 and 100 ° C.
• the wear layer 3 of a multilayer product may be a monolayer or a multilayer of polymer and may be developed based on any suitable polymer to give it good resistance to mechanical and chemical attack that occur under the conditions normal use of such surface coatings.
• the wear layer may comprise an ionomer type polymer layer, ionic link copolymers comprising an olefinic chain containing carboxylic side groups, partially or completely neutralized with cations which may be metal cations or amine cations.
• the ionomeric polymer is an ethylenic co-polymer.
• the wear layer 3 is preferably transparent and its thickness is generally at least 10 .mu.m, preferably 200 .mu.m, but it can vary depending on different parameters such as the material used for the preparation of the coating layer. wear 3 but also depending on the applications to which the multilayer product is intended.
• the support layer 1 is made by calendering and the wear layer 3 is manufactured by blow-extrusion.
• the wear layer 3 is applied for example hot, preferably at a temperature between 110 and 120 0 C, and particularly preferably at 115 0 C, on the support layer 1 whose surface has been previously warmed, for example by IR.
• the adhesion between the wear layer 3 and the support layer 1 is produced for example by passing the multilayer product in an oven at 160 ° C. for three minutes.
• the wear layer 3 is covered with a polyurethane-based surface layer 4 in order to reinforce the resistance to abrasion wear.
• the multilayer product may undergo mechanical graining.
• the support layer 1 or the wear layer 3 of a multilayer product may contain various additives, in particular to improve or modify the mechanical properties of the final decorated multilayer product.
• the films decorated with the ink according to the present invention are used as packaging, and the decorated multilayer products are used as wall or floor coverings.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Inks, Pencil-Leads, Or Crayons (AREA)
• Laminated Bodies (AREA)

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• 2007
  • 2007-05-25 EP EP20070010461 patent/EP1995057A1/de not_active Withdrawn
• 2008
  • 2008-05-22 EP EP08758698A patent/EP2150410A2/de not_active Withdrawn
  • 2008-05-22 RU RU2009143076/05A patent/RU2470969C2/ru not_active IP Right Cessation
  • 2008-05-22 CA CA2687897A patent/CA2687897C/fr not_active Expired - Fee Related
  • 2008-05-22 WO PCT/EP2008/004099 patent/WO2008145299A2/fr not_active Ceased
• 2009
  • 2009-11-16 US US12/619,132 patent/US9657188B2/en not_active Expired - Fee Related

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