JP2019059087A - Decorative film - Google Patents

Abstract

To provide a decorative film that has, on the surface thereof, a texture comprising real quality, or a three-dimensional convexoconcave corresponding to the design of various decorative films, as well as that is excellent in both elongation and bending characteristics.SOLUTION: The decorative film 10 having a texture comprises a base film layer 12, a printed layer 14 disposed on the base film layer 12, and a transparent protective layer 16 covering at least a part of the printed layer 14 and said transparent protective film 16 having a three-dimensional shape which is ink-jet printed with UV-curable transparent ink, and in which the transparent protective layer 16 at least partially has a thickness of 7 μm or more, has an elongation at break of 15% or more at 20°C, and does not crack in a 45 degree bending test.SELECTED DRAWING: Figure 1

Description

  The present disclosure relates to decorative films, and more particularly to decorative films having a texture.

  Decorative films are used to decorate the inner and outer walls of buildings. In recent years, in the construction and construction industry, there is an increasing demand for interior materials that exhibit a real texture. For example, in one way to make the design like wood grain or stone look more real, make the surface of the interior material uneven as those materials have, that is, a large asperity in the surface of the interior material It is desirable to provide. In addition, the design required for the decorative film is diversified, and there is also a demand for a decorative film having a three-dimensional uneven design on the surface according to the decorative design.

  Patent Document 1 (Japanese Patent Application Laid-Open No. 2014-100811) is characterized by “having a substrate, and a surface pattern layer formed by printing a pattern on the substrate using a transparent ink. "Laminate" is described.

  Patent Document 2 (Japanese Patent Application Laid-Open No. 2008-080650) has a constitution in which “a glitter colored layer, a pattern pattern layer, a transparent adhesive layer, a transparent resin layer and a transparent transparent protective layer are sequentially At least the glitter colored layer is described as a decorative sheet characterized by having a concavo-convex pattern formed by embossing.

  Patent Document 3 (Japanese Patent Application Laid-Open No. 2007-253506) is a decorative sheet having a design print layer on both sides of the front and back sides of a resin sheet, and the registration accuracy of the front and back patterns in the width direction and the longitudinal direction of the sheet is 0 A cosmetic sheet having an error within .08 mm is described.

  Patent Document 4 (Japanese Patent Application Laid-Open No. 2005-067175) "A flat pattern representing the appearance pattern in the (A) plane and the appearance of the concavo-convex shape formed by the concavo-convex surface of the cutting tone are The planer pattern is the appearance pattern of the concavo-convex surface by separately preparing each of the concavo-convex shading pattern expressed in FIG. Producing a synthetic concavo-convex surface pattern expressing pseudo three-dimensional feeling like a canopy, and (C) forming the composite concavo-convex surface pattern on the surface having no concavo-convex shape formed by the concavo-convex surface on the substrate. Thus, a method for producing a cosmetic material having a three-dimensional effect, in which a pseudo three-dimensional effect is imparted to the uneven surface of the cutting tone is described.

JP, 2014-10081, A JP 2008-080650 A Unexamined-Japanese-Patent No. 2007-253506 JP, 2005-067175, A

  When providing unevenness on the surface of the interior material using surface processing techniques such as embossing, the material constituting the interior material, for example, a polymer film, needs to have a thickness sufficiently larger than the height difference of the unevenness. However, when the polymer film is thickened to a certain extent, it becomes rigid and becomes difficult to handle during manufacturing, transportation and construction of the interior material, and the interior material does not sufficiently follow the curved surface or corner of the adherend, Problems may occur. Therefore, the height difference of the concavities and convexities which can be formed by embossing is not sufficient to give the decoration film a real texture or to give a three-dimensional design appearance matched to the pattern given to the decoration film. . In addition, since the interior material is often installed so as to cover the curved surface and the corner of the structure, it has sufficient elongation characteristics and bending characteristics, and can be installed without losing its appearance and strength. Is required.

  The present disclosure provides a decorative film having on its surface a texture with a real texture or three-dimensional asperities matched to the design of various decorative films, and that is excellent in both elongation and bending characteristics.

  According to one embodiment of the present disclosure, there is provided a base film layer, a print layer disposed on the base film layer, and a transparent protective layer covering at least a part of the print layer, the UV curable transparent layer. A decorative film having a texture, wherein the ink comprises an inkjet printed three-dimensional transparent protective layer, the transparent protective layer at least partially having a thickness of 7 μm or more, and the decorative film at 20 ° C. A decorative film is provided that has an elongation at break of 15% or more and does not crack in a 45 degree bend test.

  According to another embodiment of the present disclosure, there is provided a base film layer, a printing layer disposed on the base film layer, and a transparent protective layer covering at least a part of the printing layer, wherein the transparent protective layer is UV curable. Provided is a textured decorative film comprising a transparent ink and a three-dimensionally shaped transparent protective layer ink jet printed, wherein the UV curable transparent ink comprises 50% by mass or more of a monofunctional monomer. .

  The decorative film of the present disclosure is three-dimensional to match the design of a textured or decorative film with a real texture provided by a three-dimensional transparent protective layer formed by inkjet printing a UV curable transparent ink. It has asperities on its surface and is excellent in both elongation and bending characteristics. Therefore, a decoration film can be used conveniently for uses, such as interior material of a building.

  It is to be understood that the above description should not be taken as disclosing all embodiments of the invention and all the advantages associated with the invention.

It is a schematic sectional drawing of the decoration film of one embodiment of this indication.

  Hereinafter, the present invention will be described in more detail for the purpose of illustrating representative embodiments of the present invention, but the present invention is not limited to these embodiments.

  In the present disclosure, "monofunctional monomer" means a compound having only one reactive double bond, and generally its molecular weight is less than 1000.

  In the present disclosure, “oligomer” means a compound having a plurality of units derived from a monomer, and generally, the molecular weight thereof is about 500 or more, or about 1000 or more. For example, the urethane acrylate oligomer is a compound having a plurality of units having a urethane bond and having an acrylate group.

  In the present disclosure, "texture" means a three-dimensional shape on a surface that can be visually or tactilely sensed by an observer.

  In the present disclosure, "transparent" means that the total light transmittance in the wavelength range of 400 to 700 nm of a certain material or article is about 85% or more, or about 90% or more. The total light transmittance is determined in accordance with JIS K 7361-1: 1997 (ISO 13468-1: 1996).

  In the present disclosure, “(meth) acrylic” means acrylic or methacrylic, “(meth) acryloyl” means acryloyl or methacryloyl, and “(meth) acrylate” means acrylate or methacrylate.

  The decorative film having the texture of the present disclosure is a base film layer, a print layer disposed on the base film layer, and a transparent protective layer covering at least a part of the print layer, the UV curable transparent film. The ink includes an ink jet printed three-dimensional transparent protective layer.

  In one embodiment, the transparent protective layer at least partially has a thickness of about 7 μm or more, and the decorative film has an elongation at break of about 15% or more at 20 ° C., and cracks in a 45 degree bending test. Absent. A transparent protective layer having a three-dimensional shape formed by inkjet printing of a UV curable transparent ink includes a portion having a thickness of about 7 μm or more, so that it is matched with the design of a texture or a decorative film with real texture Three-dimensional unevenness can be imparted to the surface of the decorative film. Since the decorative film has predetermined elongation at break and bending properties, its elongation and bending properties are suitable, for example, for interior applications of buildings.

  In another embodiment, the UV curable clear ink comprises about 50% by weight or more of monofunctional monomers. A transparent protective layer having a three-dimensional shape formed by inkjet printing of a UV curable transparent ink containing 50% by mass or more of a monofunctional monomer is three-dimensional according to the design of a textured or decorative film with real texture Irregularities can be imparted to the surface of the decorative film and are excellent in both elongation and bending properties.

  The decorative film of one embodiment of the present disclosure is shown in schematic cross section in FIG. The decorative film 10 includes a base film layer 12, a print layer 14 disposed on the base film layer 12, and a transparent protective layer 16 covering at least a part of the print layer 14. The transparent protective layer 16 has a three-dimensional shape obtained by inkjet printing of a UV curable transparent ink, and the three-dimensional shape of the transparent protective layer 16 imparts texture to the decorative film. Although FIG. 1 shows the printing layer 14 completely covered with the transparent protective layer 16, a part of the printing layer 14 may be exposed to the outside. The printing layer 14 and the transparent protective layer 16 may be continuous or discontinuous, respectively.

  As base film layer, various resins such as acrylic resin including polymethyl methacrylate (PMMA), polyurethane (PU), polyvinyl chloride (PVC), polycarbonate (PC), polyethylene (PE), polypropylene (PP), etc. Polyolefins, polyesters such as polyethylene terephthalate (PET), polyethylene naphthalate, fluorine resin, ethylene-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate Films comprising copolymers such as copolymers, acrylonitrile-butadiene rubber (NBR), acrylonitrile-butadiene-styrene copolymer (ABS), or mixtures thereof can be used.

  From the viewpoint of strength, impact resistance and the like, a film containing polyurethane, polyvinyl chloride, polyethylene terephthalate, acrylonitrile-butadiene-styrene copolymer or polycarbonate as the base film layer can be advantageously used. The base film layer can also function as a receptor layer for printing ink and / or as a protective layer that protects the adherend surface from external punctures, impacts and the like. When the base film layer is made to function as a receptor layer of a printing ink, it is advantageous that the base film layer is a polyvinyl chloride film or a polyurethane film in terms of printability, solvent resistance (eg, alcohol resistance), and the like. A polyvinyl chloride film can be advantageously used as a base film layer in terms of flame retardancy, flexibility and the like.

  The thickness of the base film layer may vary, but generally from about 10 μm or more, about 20 μm or more, or about 50 μm or more, about 500 μm or less, about 200 μm or less, or about 100 μm or less from the viewpoint of strength and handleability of the decorative film. It can be done. The thickness of the base film layer when the base film layer is not flat means the thickness of the thinnest portion of the base film layer. For example, the base film layer may be embossed. The embossing depth can generally be about 1 μm or more, about 2 μm or more, or about 5 μm or more, about 50 μm or less, about 20 μm or less, or about 10 μm or less, in the range less than the thickness of the base film layer.

  The base film layer may be transparent, translucent or opaque, and may be colorless or colored. In one embodiment, the base film layer is colored white. This embodiment is advantageous in terms of sharpness, color development, etc. of the image produced by the printing layer disposed directly or indirectly on the base film layer.

  The print layer is used to impart decorativeness or design to the decorative film with a pattern, a pattern or the like. The printing layer can be formed by printing on the base film layer directly or through another layer using a colorant such as toner, ink and the like. If the base film layer is transparent or translucent, a print layer can also be formed between the base film layer and the adhesive layer. The printing layer can be formed by using a printing technique such as gravure printing, electrostatic printing, screen printing, inkjet printing, offset printing and the like. As the printing ink, a solvent-based ink or a UV curable ink can be used.

  In one embodiment, the printing layer is an inkjet printing layer. In another embodiment, the printing layer is formed by inkjet printing using a UV curable ink. Ink jet printing, in particular ink jet printing with UV curable inks, enables on-demand production with short delivery times.

  The thickness of the print layer may vary, and generally can be about 1 μm or more, or about 2 μm or more, about 10 μm or less, or about 5 μm or less when a solvent-based ink is used. When a UV curable ink is used, it can be about 1 μm or more, or about 5 μm or more, about 50 μm or less, or about 30 μm or less.

  The print layer may be continuous or discontinuous. The print layer may be disposed to correspond to the entire surface of the decorative film, or may be disposed to correspond to a part or a plurality of parts.

  The transparent protective layer covers at least a part of the printing layer, and has a three-dimensional shape formed by inkjet printing a UV curable transparent ink.

  As a UV curable transparent ink used for the transparent protective layer, any of radical polymerization type and cationic polymerization type can be used. As a UV curable transparent ink, a polymerizable monomer and / or a polymerizable oligomer, a photopolymerization initiator, and other optional components (such as a light stabilizer, a polymerization inhibitor, a UV absorber, an antifoaming agent, an antifouling agent, etc.) Solvent-free inks can be used advantageously. A water-based ink or a solvent-based ink can also be used as the UV curable transparent ink.

  In one embodiment, the UV curable clear ink comprises about 50% by weight or more of monofunctional monomers. A common UV curable ink contains a relatively large amount of a polyfunctional monomer which becomes a crosslinking point in order to obtain sufficient curing with a short time ultraviolet irradiation, and the cured ink tends to be rigid and brittle. is there. In this embodiment, by using a large amount of about 50% by mass or more of a monofunctional monomer in the transparent protective layer, three-dimensional unevenness corresponding to the design of a textured or decorative film having a real texture is provided on the surface of the decorative film. While forming, both excellent elongation and bending properties can be imparted to the decorative film.

  In some embodiments, the UV curable clear ink comprises about 55 wt% or more, about 60 wt% or more, or about 65 wt% or more, about 90 wt% or less, about 85 wt% or less of the monofunctional monomer. 80 mass% or less is included.

  In one embodiment, the UV curable transparent ink is a radical polymerizable acrylic ink. A transparent protective layer formed using an acrylic ink is excellent in transparency, strength, weather resistance and the like, and is advantageous, for example, when a decorative film is used as an interior material.

  (Meth) acrylic monomers having a (meth) acryloyl group, such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isoamyl (meth) acrylate, as a monofunctional monomer used for an acrylic ink ) Acrylate, 2-methylbutyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate Alkyl (meth) acrylates such as cyclohexyl (meth) acrylate and isobornyl (meth) acrylate; phenoxyalkyl (meth) acrylates such as phenoxyethyl (meth) acrylate; methoxy group Alkoxyalkyl (meth) acrylates such as pill (meth) acrylate, 2-methoxybutyl (meth) acrylate, 2- (2-ethoxyethoxy) ethyl (meth) acrylate; glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate Cyclic ether-containing (meth) acrylates such as cyclic trimethylolpropane formal acrylate; hydroxyl-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate Acrylates; nitrogen-containing (meth) acryloyl compounds such as (meth) acrylamide and N, N-diethyl (meth) acrylamide; (meth) acrylic acid and the like. As monofunctional monomers, vinyl compounds such as vinyl acetate, vinyl propionate, styrene and vinyl toluene, unsaturated nitriles such as acrylonitrile and methacrylonitrile, and unsaturated such as crotonic acid, itaconic acid, fumaric acid, citraconic acid and maleic acid Carboxylic acid etc. are also mentioned. It is advantageous that the monofunctional monomer is a (meth) acrylic monomer having a (meth) acryloyl group in terms of strength, transparency, and adhesion with the base film layer or other layers constituting the decorative film, An acrylic monomer having an acryloyl group is more advantageous in terms of curing speed.

  In some embodiments, the monofunctional monomer is a cycloaliphatic (meth) acrylate such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, cyclic such as tetrahydrofurfuryl (meth) acrylate, cyclic trimethylol propane formal acrylate, etc. Ether-containing (meth) acrylate is included. Alicyclic (meth) acrylates and cyclic ether-containing (meth) acrylates can increase the surface hardness of the cured ink without losing the elongation and bending properties. The monofunctional monomer is a total of about 40 parts by mass or more, about 50 parts by mass or more, or about 60 parts by mass in total of the alicyclic (meth) acrylate and the cyclic ether-containing (meth) acrylate based on 100 parts by mass of the monofunctional monomer As mentioned above, about 100 mass parts or less, about 95 mass parts or less, or about 85 mass parts or less can be included.

  The polymerizable monomer may contain a polyfunctional monomer. The multifunctional monomer can function as a crosslinking agent to enhance the strength and durability of the transparent protective layer. In some cases, crosslinking with a polyfunctional monomer can improve the adhesion of the transparent protective layer to the base film layer or other layers of the decorative film.

  As a polyfunctional monomer used for acrylic ink, for example, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, cyclohexane dimethanol di ( Bifunctional (meth) acrylates such as meta) acrylate, diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate; glycerol tri (meth) acrylate, trimethylolpropane tri (meth) Acrylates, trifunctional (meth) acrylates such as pentaerythritol tri (meth) acrylate; ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate Rate, having four or more functional groups, such as pentaerythritol tetra (meth) acrylate (meth) acrylate can be used.

  In some embodiments, the UV curable clear ink comprises about 1 wt% or more, about 3 wt% or more, or about 5 wt% or more, about 50 wt% or less, about 40 wt% or less of the polyfunctional monomer. 30 mass% or less is included.

  As the polymerizable oligomer, for example, urethane acrylate, polyester acrylate, epoxy acrylate and the like can be used. By using the polymerizable oligomer, the printability of the UV curable transparent ink can be enhanced, and the adhesion of the transparent protective layer to the base film layer or the other layer of the decorative film can be enhanced. These polymerizable oligomers generally have two or more polymerizable functional groups, and can also be used as a crosslinking agent.

  In some embodiments, the UV curable clear ink comprises about 1 wt% or more, about 3 wt% or more, or about 5 wt% or more, about 30 wt% or less, about 25 wt% or less of the polymerizable oligomer. 20 mass% or less is included.

  As a photoinitiator, the well-known compound which induces the radical polymerization reaction of (meth) acrylate can be used. As the photopolymerization initiator, any of intramolecular cleavage type and hydrogen abstraction type can be used, and examples thereof include 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, 2-methyl-1- [4] 4- (Methylthio) phenyl] -2-morpholinopropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) -Butan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2,4,6-trimethyl benzoyl diphenyl phosphine oxide 2,6-Dimethyl benzoyl diphenyl phosphine oxide, benzoyl diethoxy phosphine oxide, (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl phosphine oxide, benzoin alkyl ether (eg, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, n-butyl benzoin ether, etc.) Methylbenzoyl formate, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, p-tert-butyl Trichloroacetophenone, p-tert-butyldichloroacetophenone, benzyl, acetophenone, thioxanthones (2-chlorothioxanthone, 2-methylthioxanthone, 2,4-diethylthioxanthone, 2,4- Diisopropylthioxanthone), camphorquinone, 3-ketocoumarin, anthraquinones (eg, anthraquinone, 2-ethylanthraquinone, α-chloroanthraquinone, 2-tert-butylanthraquinone, etc.), acenaphthene, 4,4'-dimethoxybenzyl, 4,4 '-Dichlorobenzyl and the like. Commercially available examples of photoinitiators include those sold under the tradenames of IRGACURE, DAROCURE, Bersicure, Bersicure, available from BASF Japan Ltd. The thermal initiator or the photoinitiator can be used alone or in combination of two or more.

  In some embodiments, the UV curable clear ink comprises about 0.1 wt% or more, or about 1 wt% or more, about 15 wt% or less, or about 10 wt% or less of the photoinitiator.

  The UV curable transparent ink may contain, as optional components, additives such as a light stabilizer, a polymerization inhibitor, a UV absorber, an antifoaming agent, and an antifouling agent.

  The UV curable transparent ink may further contain a reactive siloxane. By including a reactive siloxane in the UV curable transparent ink, the chemical resistance of the transparent protective layer, the bending properties of the decorative film, and the like can be enhanced. Examples of reactive siloxanes include silicone resins having (meth) acryloyl groups at side chains or ends, and siloxane-containing inorganic oxides whose surfaces are blocked with (meth) acryloyl groups. Examples of the siloxane-containing inorganic oxide include silica, silica-zirconia mixed oxide, silica-alumina mixed oxide and silica-titania mixed oxide. The surface hardness (for example, pencil hardness) can be further increased by using a siloxane-containing inorganic oxide whose surface is blocked by a (meth) acryloyl group.

  In some embodiments, the UV curable clear ink comprises about 1 wt% or more, about 3 wt% or more, or about 5 wt% or more, about 15 wt% or less, about 12 wt% or less of the reactive siloxane. 10 mass% or less is included.

  The viscosity of the UV curable transparent ink can be about 5 mPa · s or more, or about 15 mPa · s or more, about 60 mPa · s or less, or about 50 mPa · s or less at 25 ° C., for example, 45 ° C. And at least about 5 mPa · s, at most about 20 mPa · s, or at most about 15 mPa · s. By setting the viscosity of the UV curable transparent ink in the above range, the ink fluidity at the time of ink droplet ejection is ensured, and the shape of the ink droplet is maintained at the time of ink droplet landing, and the three-dimensional shape is efficiently achieved. The transparent protective layer which it has can be formed.

  A UV curable transparent ink can be inkjet printed on the base film layer directly or through another layer, and cured by irradiation with ultraviolet light to form a transparent protective layer having a three-dimensional shape. The UV curable transparent ink may be printed to cover at least a portion of the print layer, or may be printed to cover the entire print layer. The thickness of the transparent protective layer may be increased by printing the UV curable transparent ink repeatedly locally or over a plurality of times.

  The thickness of the transparent protective layer may vary, but in some embodiments is at least partially about 7 μm or more, about 20 μm or more, or about 30 μm or more. By providing the transparent protective layer with a portion having a thickness of about 7 μm or more, it is possible to impart three-dimensional unevenness corresponding to the design of the textured or decorative film with a real texture to the surface of the decorative film.

  In some embodiments, the maximum thickness of the transparent protective layer is about 500 μm or less, about 300 μm or less, or about 100 μm or less. By setting the maximum thickness of the transparent protective layer to about 500 μm or less, the elongation characteristics and bending characteristics of the transparent protective layer can be made suitable.

  In some embodiments, the maximum height roughness Rz of the transparent protective layer is about 0.5 μm or more, about 1 μm or more, or about 1.5 μm or more, about 20 μm or less, about 15 μm or less, or about 10 μm or less . By setting the maximum height roughness Rz of the transparent protective layer in the above range, it is possible to impart three-dimensional unevenness corresponding to the design of the texture or decoration film having a real texture to the surface of the decoration film.

  In some embodiments, the total light transmittance of the transparent protective layer is about 90% or more, about 92% or more, or about 95% or more, and the haze is about 2% or less, about 1.5% or less, or about It is less than 1.0%. When the total light transmittance and haze are in the above range, the image provided by the print layer of the decorative film can be made clearer. The haze is determined in accordance with JIS K 7136: 2000 (ISO 14782: 1999).

（Ｔｇ_１：成分１のホモポリマーのガラス転移温度
Ｔｇ_２：成分２のホモポリマーのガラス転移温度
・・・
Ｔｇ_ｎ：成分ｎのホモポリマーのガラス転移温度
Ｘ_１：重合の際に添加した成分１のモノマーの質量分率
Ｘ_２：重合の際に添加した成分２のモノマーの質量分率
・・・
Ｘ_ｎ：重合の際に添加した成分ｎのモノマーの質量分率
Ｘ_１＋Ｘ_２＋・・・＋Ｘ_ｎ＝１） In some embodiments, the glass transition temperature (Tg) of the transparent protective layer is about 25 ° C. or more, or about 28 ° C. or more, about 40 ° C. or less, or about 35 ° C. or less. By making the glass transition temperature of a transparent protective layer into the said range, both the outstanding elongation characteristic and a bending characteristic can be provided to a decoration film. The glass transition temperature (Tg) of the transparent protective layer is determined by the following formula of FOX (Fox, TG, Bull. Am. Phys. Soc., Assuming that the transparent protective layer is formed of a copolymer of n types of monomers). It can be determined as a calculated glass transition temperature using 1 (1956), p. 123).

(Tg ₁ : Glass transition temperature of homopolymer of component 1 Tg ₂ : Glass transition temperature of homopolymer of component 2 ...
Tg _n : Glass transition temperature of homopolymer of component n X ₁ : Mass fraction of monomer of component 1 added in polymerization X ₂ : Mass fraction of monomer of component 2 added in polymerization ...
X _n : Mass fraction of monomer of component n added in polymerization X ₁ + X ₂ + ... + X _n = 1)

  The decorative film may further comprise an adhesive layer disposed on the base film layer opposite the print layer. An adhesive layer 18 is shown in FIG. 1 disposed on the base film layer 12 opposite the printing layer 14. The adhesive layer is generally formed using an adhesive of acrylic, polyolefin, polyurethane, polyester, rubber, etc., solvent type, emulsion type, pressure sensitive type, heat sensitive type, thermosetting type or UV curable type. can do.

  The thickness of the adhesive layer can generally be about 3 μm or more, about 5 μm or more, or about 10 μm or more, about 100 μm or less, about 80 μm or less, or about 50 μm or less.

  In one embodiment, the adhesive layer is a pressure sensitive adhesive layer. For the purpose of adjusting the adhesion of the pressure sensitive adhesive layer, the pressure sensitive adhesive layer may comprise elastic microspheres comprising polyester, polystyrene, acrylic resin, polyurethane and the like.

  A liner may be disposed on the surface of the adhesive layer. Examples of liners include paper such as kraft paper, polymers such as polyethylene, polypropylene, polyester, cellulose acetate, and papers coated with these polymers. These liners may have surfaces that have been release treated with silicone, fluorocarbons, and the like. The thickness of the liner can generally be about 5 μm or more, about 15 μm or more, or about 25 μm or more, about 300 μm or less, about 200 μm or less, or about 150 μm or less.

  The adhesive layer may have a microstructured surface with communicating passages extending to the outer edge of the adhesive layer. When the decorative film is applied to the adherend, air bubbles caught between the decorative film and the adherend can be discharged to the outside through the communication path of the microstructured surface. In this embodiment, the liner may have a relief structure on its release surface corresponding to the microstructured surface of the adhesive layer. The liner may be the same as or different from that used in forming the microstructured surface of the adhesive layer.

  Other layers, for example, a decorative layer such as a metal layer, a receptor layer of printing ink, and the like may be laminated on the base film layer. These layers may be bonded by a bonding layer. The decorative layer may be disposed to correspond to the entire surface of the decorative film, or may be disposed to correspond to a part or a plurality of parts.

  The metal layer can be formed by depositing a metal such as indium, tin, chromium or the like on the base film layer or other layer of the decorative film by vapor deposition, sputtering or the like. It is also possible to form a pattern or picture using a metal mask or the like during deposition or sputtering. The thickness of the metal layer can vary, and can generally be about 5 nm or more, about 10 nm or more, or about 20 nm or more, about 10 μm or less, about 5 μm or less, or about 2 μm or less.

  Various resin films can be used as receptor layers for printing inks. Although it does not specifically limit as resin which comprises a receptor layer, Acrylic polymer, polyolefin, polyvinyl acetal, a phenoxy resin etc. can be used. The glass transition temperature of the resin forming the receptor layer can generally be about 0 ° C. or more and about 100 ° C. or less. By setting the glass transition temperature in the above range, a clear image can be obtained by transferring a toner or printing an ink without losing the flexibility of the entire decorative film. The thickness of the receptor layer can generally be about 2 μm or more, about 5 μm or more, or about 10 μm or more, about 50 μm or less, about 40 μm or less, or about 30 μm or less.

  The bonding layer for bonding the layers constituting the decorative film is generally a solvent type, an emulsion type, a pressure sensitive type, a thermal type, a thermosetting type, or an ultraviolet curing such as acrylic, polyolefin, polyurethane, polyester, and rubber. Includes a type of adhesive. The thickness of the bonding layer can generally be about 1 μm or more, about 2 μm or more, or about 5 μm or more, about 50 μm or less, about 40 μm or less, or about 30 μm or less.

  In one embodiment, the print layer has a print image pattern, the transparent protective layer has a three-dimensional shape pattern by inkjet printing, and the print image pattern and the three-dimensional shape pattern are in phase. The alignment of the printed image pattern and the three-dimensional shape pattern of the transparent protective layer can further enhance the texture from both the visual and tactile sides.

  The decorative film in which the three-dimensional shape pattern of the print image pattern and the transparent protective layer is synchronized, for example, provides image data of the print layer, and converts the image data of the print layer to grayscale to generate grayscale image data. And inverting the tone of the gray scale image data to generate the image data of the transparent protective layer, adjusting the tone curve of the image data of the transparent protective layer as necessary, and image data of the print layer Forming a printing layer on the base film layer by inkjet printing using a UV curable CMYK ink, and inkjet printing using a UV curable transparent ink based on image data of the transparent protective image Forming a transparent protective layer on the print layer.

  The step of forming the printing layer and the step of forming the transparent protective layer may be performed successively. The steps of forming the print layer and the step of forming the transparent protective layer may be performed in a single apparatus comprising a plurality of inkjet print heads. The inkjet printing apparatus can reciprocate the printed matter (for example, the film of the base film layer) so that the transparent protective layer can be formed by repeating the steps of forming the transparent protective layer a plurality of times to form the transparent protective layer having a large height difference of the surface irregularities. A transport device may be provided, and a plurality of ink jet print heads having a transparent protective layer may be provided.

  The three-dimensional shape pattern of the print image pattern and the transparent protective layer is obtained by arranging the inkjet print head of the print layer and the inkjet print head of the transparent protective layer in series in the inkjet printing device, and image data and transparency of the print layer obtained by the above method By printing the printing layer and the transparent protective layer successively based on the image data of the protective layer, respectively, more accurate synchronization can be achieved.

  The printed image pattern and the three-dimensional shape pattern of the transparent protective layer may be repeated in one decorative film or may be a non-repeated pattern. By using inkjet printing, not only repetitive patterns but also non-repeating patterns can be easily formed. In embossing using an embossing roll, it is not possible to form a non-repeating three-dimensional shape pattern longer than the outer circumference of the embossing roll. By making the pattern non-repetitive, it is possible to increase the degree of freedom in design of the design, and to produce a decorative film having a one-piece design.

  In some embodiments, the decorative film has an elongation at break of at least about 15%, at least about 20%, or at least about 30% at 20 ° C. and does not crack in a 45 degree bend test. Elongation at break is determined by cutting the decorative film to a length of about 150 mm and a width of 25 mm to prepare a sample, and using a tensile tester, performing a tensile test at a test length of 100 mm, a tensile speed of 300 mm / min, at 20 ° C. can do. In the 45-degree bending test, the decorative film was cut into a length of about 150 mm and a width of 25 mm to prepare a sample, and the sample was attached to an aluminum plate (A5052) having a length of 170 mm, a width of 30 mm and a thickness of 5 mm and left overnight After that, the aluminum plate to which the sample is attached is bent at 45 degrees using a coating film bending tester under the conditions of a mandrel diameter of 3 mm and an auxiliary plate thickness of 3 mm according to JIS K 5600-5-1: 1999. It can be carried out by visually observing the presence or absence of cracks in the bent portion.

  In one embodiment, the pencil hardness of the decorative film is 2B or more, B or more, or HB or more when measured in accordance with JIS K 5600-5-4: 1999. When the pencil hardness of the decorative film is in the above range, the deterioration of the surface of the decorative film due to damage can be prevented.

  The total thickness of the decorative film can generally be about 50 μm or more, about 60 μm or more, or about 70 μm or more, about 700 μm or less, about 600 μm or less, or about 500 μm or less. The total thickness of the decorative film does not include the thickness of the liner.

  The decorative film can be adhered to the surface of various adherends, and can be applied to, for example, concrete, glass, painted board, flooring material, wallpaper, gypsum board and the like. The adherend may be part of a building structure, such as a wall, a window, a floor, a ceiling, a pillar or the like.

  Although specific embodiments of the present disclosure are illustrated in the following examples, the present invention is not limited thereto. All parts and percentages are by weight unless otherwise stated.

The materials and reagents used in this example are shown in Table 1.

<Evaluation method>
1. Maximum surface depth The maximum depth of the decorative film surface is measured using a digital microscope DSX510 (Olympus Corporation, Shinjuku-ku, Tokyo, Japan). Select the location with the highest elevation difference from the profile, and measure it as the surface maximum depth.

2. Texture observation When the decoration film is observed at an angle of 10 degrees from the vertical direction of the film surface, it is compared with 3M (registered trademark) Dinocx (registered trademark) film TE-1650 (3M Japan Co., Ltd., Shinagawa Ward, Tokyo, Japan) Good when the texture is visible. The case where the texture is not visually recognized because the height difference of the surface unevenness is smaller than that of TE-1650 is regarded as a defect.

3. Elongation at break and yield point The decorative film is cut into a length of about 150 mm and a width of 25 mm to prepare a sample. Using a tensile tester (Tensilon universal tester, model number: RTC-1210A, A & D Co., Ltd., Toshima-ku, Tokyo, Japan), a tensile test is performed at a test length of 100 mm, a tensile speed of 300 mm / min, and 20 ° C. Measure the elongation at break and the yield point.

4.45 degree bending test A decorative film is cut into a length of about 150 mm and a width of 25 mm to prepare a sample. After peeling the liner, the sample is attached to an aluminum plate (A5052) having a length of 170 mm, a width of 30 mm and a thickness of 5 mm. After standing overnight, the aluminum plate to which the sample is attached is subjected to a PI-801 coating film bending tester under conditions of a mandrel diameter of 3 mm and an auxiliary plate thickness of 3 mm in accordance with JIS K 5600-5-1: 1999. Bend at 45 degrees using (Tester Industry Co., Ltd., Miyoshi-cho, Iruma-gun, Saitama Prefecture, Japan). The case where cracks, breakage and peeling from the aluminum plate are not visible in the decorative film in the bent portion is regarded as good, and any one of cracks, breakage or peeling from the aluminum plate is regarded as defective.

5. Chemical resistance Attach the decorative film to a 5 mm thick acrylic resin substrate. After 2 hours, the sample is immersed in ethanol, 10% aqueous NaOH or 10% hydrochloric acid for 25 hours. After pulling up the sample from these chemicals, observe the surface of the test piece visually. The case where no abnormality is visually recognized on the surface is regarded as good for all the chemicals, and the case where an abnormality such as corrosion or discoloration is visually recognized for one or more chemicals is regarded as bad.

6. Pencil hardness A decorative film is attached to an aluminum plate (A5052) to prepare a sample. Using the obtained sample, the scratch hardness by the pencil method is evaluated in accordance with JIS 5600-5-4: 1999. Record the hardness of the hardest pencil for which no scratch marks could be identified visually.

7. Thickness of Transparent Protective Layer The thickness of the transparent protective layer is measured using a thickness measuring device PC-465N (Tester Sangyo Co., Ltd., Miyoshi-cho, Iruma-gun, Saitama Prefecture, Japan). A sample is held between a measurement stand and a measurement probe and measured three times, and the average value is determined. The total thickness of the transparent protective layer and the base film layer is measured, and the thickness of the base film layer is subtracted to obtain the thickness of the transparent protective layer.

Preparation of UV-Curable Transparent Inks A to G
The components shown in Table 2 were mixed to prepare UV curable transparent inks A to G. The numerical values in Table 2 are the blending amounts (parts by mass) of each component. The calculated glass transition temperature was determined using the formula of FOX based on the components and composition of the UV curable transparent ink.

<Example 1>
Using an inkjet printer UJF-3042FX (MIMAKI ENGINEERING CO., LTD., Tomi city, Nagano Prefecture, Japan), on ControlTac (registered trademark) graphic film 180-10 inkjet material (3M Japan Co., Ltd., Shinagawa-ku, Tokyo, Japan) Then, the UV curable transparent ink A was printed with a transparent carbon fiber pattern having a texture to produce the decorative film of Example 1. The device profile of the inkjet printer was set to color management off, 600 × 720 dpi, VD (dot size variable mode), 100% ink limit, and 6 printing times.

<Examples 2 to 5>
The decorative films of Examples 2 to 5 were produced in the same manner as Example 1 except that the number of printings was changed to form a thicker transparent protective layer.

Comparative Example 1
The decorative film of Comparative Example 1 was prepared in the same manner as Example 1, except that the commercially available UV curable transparent ink LH-100 (MIMAKI ENGINEERING CO., LTD., Tomi city, Nagano Japan) was used instead of the UV curable transparent ink A. Was produced. LH-100 is composed of multifunctional acrylate monomers such as hexamethylene diacrylate.

Comparative Example 2
A decorative film of Comparative Example 2 was produced in the same manner as Example 1 except that the UV curable transparent ink B was used instead of the UV curable transparent ink A.

Examples 6 and 7
The decorative films of Examples 6 and 7 were produced in the same manner as in Example 1 except that UV-curable transparent inks C and D were used instead of the UV-curable transparent ink A.

<Example 8>
A decorative film of Example 8 was produced in the same manner as in Example 1 except that the UV curable transparent ink E was used instead of the UV curable transparent ink A.

<Examples 9 and 10>
A decorative film of each of Examples 9 and 10 was produced in the same manner as Example 1, except that UV curable transparent inks F and G containing a reactive polysiloxane were used instead of the UV curable transparent ink A.

  The results of evaluating Examples 1 to 10 and Comparative Examples 1 and 2 are shown in Table 3.

10 Decorative Film 12 Base Film Layer 14 Printed Layer 16 Transparent Protective Layer 18 Adhesive Layer

Claims (10)

A base film layer,
A printing layer disposed on the base film layer;
A transparent protective layer covering at least a part of the print layer, wherein the UV curable transparent ink comprises an inkjet printed three-dimensional transparent protective layer and a decorative film having a texture,
The transparent protective layer at least partially has a thickness of 7 μm or more,
The decorative film has an elongation at break of 15% or more at 20 ° C. and does not crack in a 45 degree bending test. A base film layer,
A printing layer disposed on the base film layer;
A transparent protective layer covering at least a part of the print layer, wherein the UV curable transparent ink comprises an inkjet printed three-dimensional transparent protective layer and a decorative film having a texture,
The decorative film, wherein the UV curable transparent ink contains 50% by mass or more of a monofunctional monomer.   The decorative film according to claim 2, wherein the monofunctional monomer has a (meth) acryloyl group.   The decorative film according to any one of claims 1 to 3, further comprising an adhesive layer disposed on the base film layer opposite to the print layer.   The decorative film according to any one of claims 1 to 4, wherein the pencil hardness of the decorative film is 2B or more when measured in accordance with JIS K 5600-5-4: 1999.   The decorative film according to any one of claims 1 to 5, wherein the total light transmittance of the transparent protective layer is 90% or more and the haze is 2% or less.   The decorative film according to any one of claims 1 to 6, wherein the glass transition temperature of the transparent protective layer is 25 ° C to 40 ° C.   The decorative film according to any one of claims 1 to 7, wherein the base film layer is a polyvinyl chloride film.   The decorative film according to any one of claims 1 to 8, wherein the UV curable transparent ink comprises a reactive siloxane.   The said printed layer has a printing image pattern, The said transparent protective layer has a three-dimensional-shaped pattern by inkjet printing, The said printing image pattern and the said three-dimensional-shaped pattern are synchronized. The decoration film as described in any one.

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