Film and method for manufacturing the same

Abstract

To provide a film that has high-quality low glossy appearance with small changes of how a texture is seen even when observed at various view angles, and has palpable texture.SOLUTION: A film having an embossed surface layer, in which the surface layer includes a low glossy layer and a gloss printing pattern partially covering the low glossy layer, (1) 85-degree surface glossiness of the surface layer is 3.5GU or less in the in-plane average value, (2) Δ85-degree surface glossiness (=in-plane maximum value of 85-degree surface glossiness - in-plane average value of 85-degree surface glossiness) defined by a difference between the in-plane maximum value and the in-plane average value of 85-degree surface glossiness of the surface layer is 0.2 to 2.5, and (3) the surface roughness Ra of the embossed surface of the film is 3.5 μm or more.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present disclosure relates to a film that can be used for applications such as decoration and a method for manufacturing the same.

Background Art

[0002] Decorative films are used for the purpose of decorating the interior and exterior of buildings, vehicles, etc. For example, a decorative film in which a polyvinyl chloride film provided with a printing layer and a transparent polyvinyl chloride film are laminated and embossed is known. By various combinations of lamination and embossing, textures of various materials such as wood grain, metal, fabric, and marble can be expressed.

[0003] In recent years, there has been a demand for films that can be used for decorative purposes and have a lower gloss appearance that can reproduce surfaces such as dry-finished wood and matte painting. A method of forming a decorative film having a low-gloss appearance by coating a resin containing fine particles or beads as a surface layer is known. These decorative films can be used for building exterior or interior decoration, vehicle interior decoration, furniture, article surface decoration, etc.

[0004] Patent Document 1 (Japanese Patent Application Laid-Open No. 2011-255552) describes "an embossed decorative sheet in which an embossing process is applied to the surface of a decorative sheet, and a surface protection layer made of a curable resin containing synthetic resin beads is provided on the surface side of the decorative sheet, the embossing process having an average amplitude of 15 to 50 μm, and the synthetic resin beads being synthetic resin beads having an average particle size of 8 to 20 μm."

[0005] Patent Document 2 (International Publication No. WO2008 / 129667) describes "a decorative sheet in which a protective layer mainly composed of a transparent resin component is provided on the surface of a printing layer provided on a printing sheet, the protective layer comprising a first protective layer provided on the printing layer of the printing sheet and a second protective layer containing transparent or translucent spherical particles and provided at a predetermined portion on the first protective layer, and the gloss of the protruding surface of the first protective layer being lower than the gloss of the surface of the second protective layer."

[0006] Patent Document 3 (Japanese Unexamined Patent Application Publication No. JP2011-224962) describes "a decorative sheet in which at least a transparent resin layer, a gloss adjustment layer, and a surface protective layer are laminated and an uneven pattern is formed on the surface, the uneven pattern including concave portions in which part or all of the gloss adjustment layer is exposed."

[0007] Patent Document 4 (Japanese Unexamined Patent Application Publication No. JP2014-024318) describes "a decorative sheet having a pattern printing layer, a matte layer, and a top coat layer for forming a gloss difference pattern on a base sheet, the base sheet containing a vinyl chloride-based resin, and the top coat layer containing a thermosetting resin and a reactive silicone oil."

[0008] Patent Document 5 (Japanese Unexamined Patent Application Publication No. JP2015-199313) describes "a front-back synchronous gloss-matte decorative sheet characterized in that a matte layer is provided on one surface of a transparent thermoplastic resin layer, a gloss negative pattern layer is provided on the matte layer, and a pattern layer is provided on the other surface."

Prior Art Documents

Patent Documents

[0009]

Patent Document 1

Patent Document 2

Patent Document 3

[0010] Since a surface exhibiting a low gloss appearance has the property of light diffusion or irregular light reflection, it is difficult to express an uneven texture on such a low gloss surface. Even if, for example, embossing is applied to a low gloss surface, it is difficult to distinguish the light and dark of the texture formed by the embossing due to the low glossiness of the entire surface, and as a result, the visibility of the texture is reduced. This is more prominent as the glossiness of the low gloss surface is lower.

[0011] Also, from the viewpoint of aesthetics, it may be desired that when a low gloss surface is observed from various viewing angles, the appearance of the texture does not change significantly. By directly printing a low gloss pattern using matte ink on a high gloss surface, for example, a resin film having a smooth surface, it is possible to provide a low gloss appearance having an uneven texture. However, light reflection occurs in areas where the matte ink is not printed or the amount of matte ink printed is small, and strong glare may occur depending on the viewing angle.

[0012] Furthermore, in order to realize a realistic wood grain design or the like, it is desirable that the texture can be recognized not only visually but also tactilely.

[0013] The present disclosure provides a film having a high-quality low gloss appearance with little change in the appearance of the texture even when observed from various viewing angles, and having a texture that can be touched. [Means for Solving the Problems]

[0014] According to one embodiment, there is provided a film having an embossed surface layer, wherein the surface layer includes a low gloss layer and a gloss print pattern partially covering the low gloss layer, and (1) the 85-degree surface glossiness of the surface layer is 5.0 GU or less as an in-plane average value, (2) the Δ85-degree surface glossiness (= in-plane maximum value of the 85-degree surface glossiness - in-plane average value of the 85-degree surface glossiness) defined by the difference between the in-plane maximum value and the in-plane average value of the 85-degree surface glossiness of the surface layer is 0.2 to 2.5, and (3) the surface roughness Ra of the embossed surface of the film is 3.5 μm or more.

[0015] According to another embodiment, there is provided a film having an embossed surface layer, wherein the surface layer includes a low gloss layer and a gloss print pattern partially covering the low gloss layer, and the surface layer is formed by performing embossing from above the gloss print pattern after forming the gloss print pattern on the low gloss layer.

[0016] According to another embodiment, there is provided a method for manufacturing a film, including forming a low gloss layer on a substrate, forming a gloss print pattern partially covering the low gloss layer on the low gloss layer, and performing embossing from above the gloss print pattern.

Advantages of the Invention

[0017] The film of the present disclosure has a high-quality low gloss appearance with little change in the appearance of the texture when observed from various viewing angles, and has a texture that can be touched. Therefore, for example, a design such as a realistic wood grain design can be applied to the interior and exterior of buildings, vehicles, etc.

[0018] It should not be considered that the above description discloses all embodiments of the present invention and all advantages related to the present invention.

Brief Description of the Drawings

[0019]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5A

Figure 5B

Figure 6

Figure 7A

Figure 7B

Mode for Carrying Out the Invention

[0020] Hereinafter, it will be described in more detail for the purpose of exemplifying typical embodiments of the present invention, but the present invention is not limited to these embodiments.

[0021] In the present disclosure, "transparent" means that the total light transmittance of a certain material or article in the wavelength range of 400 to 700 nm is about 85% or more, "translucent" means that the total light transmittance of a certain material or article in the wavelength range of 400 to 700 nm is about 20% or more and less than about 85%, and "opaque" means that the total light transmittance of a certain material or article in the wavelength range of 400 to 700 nm is less than about 20%. The total light transmittance is determined in accordance with JIS K 7361-1:1997 (ISO 13468-1:1996).

[0022] The film has an embossed surface layer. The embossed surface layer imparts a tactile texture to the film. The surface layer includes a low gloss layer and a gloss print pattern that partially covers the low gloss layer. The area not covered by the gloss print pattern of the low gloss layer exhibits a matte appearance, and the surface glossiness of the area of the gloss print pattern is higher than that of the area not covered by the gloss print pattern. By using a gloss print pattern that partially covers the low gloss layer, the change in glossiness resulting from the cooperation of the uncovered area of the low gloss layer and the gloss print pattern is visually recognized by the observer as a texture (concavity and convexity). In this way, a texture visible even on the low gloss surface of the film can be formed.

[0023] In one embodiment, the film has the following characteristics. (1) The 85-degree surface glossiness of the surface layer is about 5.0 GU or less as an in-plane average value. (2) The Δ85-degree surface glossiness (= the in-plane maximum value of the 85-degree surface glossiness - the in-plane average value of the 85-degree surface glossiness) defined by the difference between the in-plane maximum value and the in-plane average value of the 85-degree surface glossiness of the surface layer is about 0.2 to about 2.5. (3) The surface roughness Ra of the embossed surface of the film is about 3.5 μm or more.

[0024] In another embodiment, the surface layer is formed by applying an embossing process from above the gloss print pattern after forming the gloss print pattern on the low gloss layer.

[0025] The low gloss layer can be formed, for example, by applying a matte coating composition containing a low gloss agent onto the base material layer and heating as necessary, or by kneading the low gloss agent into the resin and molding it into a film.

[0026] In one embodiment, the low gloss layer includes a binder containing a resin, resin beads having an average particle size of about 4 μm or more and about 20 μm or less, and nanosilica particles. By including resin beads and nanosilica particles having an average particle size within the above range in the low gloss layer, a low gloss appearance can be imparted to the film, and the low gloss appearance can be maintained even after the film is stretched. The film of this embodiment can be stretched to conform to the shape of the article to be pasted. Also, even if unevenness is imparted to the low gloss layer by embossing or the like, the low gloss appearance can be maintained. The film of this embodiment can be provided with unevenness having patterns such as wood grain, sand grain, cloth grain, leather (cow, pig, etc.). Further, even if a gloss printing pattern is provided on the low gloss layer, the low gloss appearance can be maintained. The film of this embodiment can form a printing pattern having patterns such as wood grain, sand grain, cloth grain, leather (cow, pig, etc.), stone grain, concrete, rust pattern (a pattern like an oxide film is formed on the metal surface).

[0027] A schematic cross-sectional view of a film according to one embodiment is shown in FIG. 1. The film 100 in FIG. 1 includes a surface layer 110, and a base material layer 140 and an adhesive layer 150 which are optional components. The film 100 may be formed only of the surface layer 110, that is, the surface layer 110 itself may be the film. The surface layer 110 is embossed and includes a low gloss layer 120 and a gloss printing pattern 130 that partially covers the low gloss layer 120. The low gloss layer 120 includes a binder 122 containing a resin, resin beads 124 having an average particle size of about 4 μm or more and about 20 μm or less, and nanosilica particles 126.

[0028] As the resin contained in the binder, various resins can be used. In one embodiment, the binder contains a urethane resin. Various urethane resins known as urethane resins can be used. The urethane resin can be obtained by drying or curing a urethane resin composition. The urethane resin composition may be aqueous or non-aqueous. It is advantageous that the urethane resin is a cured product of a two-component urethane resin composition. The two-component urethane resin composition is generally a non-aqueous urethane resin composition. By using the two-component urethane resin composition, when forming a low gloss layer, other components of the low gloss layer, such as resin beads, particularly urethane resin beads, nano-silica particles, etc., can form chemical bonds with the urethane resin to prevent or suppress the dropout of these particles from the low gloss layer and the bleed-out of components.

[0029] The two-component urethane resin composition generally contains a polyol as the main component and a polyfunctional isocyanate as the curing agent, and optionally contains a catalyst and / or a solvent.

[0030] As the polyol, polyester polyols such as polycaprolactone diol and polycaprolactone triol; polycarbonate polyols such as cyclohexanedimethanol carbonate and 1,6-hexanediol carbonate, and combinations thereof can be used. These polyols can impart transparency, weather resistance, strength, chemical resistance, etc. to the low gloss layer. In particular, the polycarbonate polyol can form a low gloss layer having high transparency and chemical resistance. From the viewpoint of imparting extensibility to the low gloss layer without forming an excessive crosslinked structure, it is desirable that the polyol is a diol, and polyester diols and polycarbonate diols, particularly polycarbonate diols, can be advantageously used.

[0031] The OH value of the polyol can generally be about 10 mg / KOH or more, about 20 mg / KOH or more, or about 30 mg / KOH or more, and about 150 mg / KOH or less, about 130 mg / KOH or less, or about 120 mg / KOH or less.

[0032] Examples of polyfunctional isocyanates include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, araliphatic polyisocyanates, etc., and multimers (dimers, trimers, etc.) of these polyisocyanates, biuret-modified products, allophanate-modified products, polyol-modified products, oxadiazinetrione-modified products, carbodiimide-modified products, etc. From the viewpoint of imparting extensibility to the low gloss layer without forming an excessive crosslinked structure, it is desirable that the polyfunctional isocyanate be a diisocyanate. Such diisocyanates include aliphatic diisocyanates such as tetramethylene diisocyanate and hexamethylene diisocyanate (HDI); alicyclic diisocyanates such as isophorone diisocyanate, trans,trans-, trans,cis-, and cis,cis-dicyclohexylmethane-4,4'-diisocyanate and mixtures thereof (hydrogenated MDI); aromatic diisocyanates such as 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, and isomer mixtures of these tolylene diisocyanates (TDI), 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate and 2,2'-diphenylmethane diisocyanate, and isomer mixtures of these diphenylmethane diisocyanates (MDI); and araliphatic diisocyanates such as 1,3- or 1,4-xylylene diisocyanate or mixtures thereof (XDI), 1,3- or 1,4-tetramethylxylylene diisocyanate or mixtures thereof (TMXDI).

[0033] The equivalent ratio of polyol to polyisocyanate can generally be such that the polyisocyanate is about 0.6 equivalents or more, about 0.7 equivalents or more, about 2 equivalents or less, or about 1.2 equivalents or less per 1 equivalent of polyol.

[0034] Those generally used as catalysts for urethane resin formation, such as di-n-butyltin dilaurate, zinc naphthenate, zinc octenoate, triethylenediamine, etc. can be used. The amount of the catalyst used can generally be about 0.005 parts by mass or more, or about 0.01 parts by mass or more, about 0.5 parts by mass or less, or about 0.2 parts by mass or less based on 100 parts by mass of the two-component urethane resin composition.

[0035] The binder may further contain a cellulose ester. By incorporating the cellulose ester into the binder, the viscosity of the binder during the drying process can be increased and the surface fluidity can be decreased, so that it becomes possible to uniformly apply the binder precursor containing resin beads. Examples of the cellulose ester include cellulose acetate propionate and cellulose acetate butyrate.

[0036] Considering the solubility in the solvent, the number average molecular weight of the cellulose ester can generally be about 12,000 or more, about 16,000 or more, or about 20,000 or more, about 110,000 or less, about 100,000 or less, or about 90,000 or less. The number average molecular weight of the cellulose ester is determined by gel permeation chromatography (GPC) using standard polystyrene.

[0037] Considering the shape retention at the use temperature, the glass transition temperature (Tg) of the cellulose ester can generally be about 85°C or more, about 96°C or more, or about 101°C or more, about 190°C or less, about 180°C or less, or about 160°C or less. The glass transition temperature of the cellulose ester is determined using differential scanning calorimetry (DSC).

[0038] In some embodiments, the cellulose ester may be contained in the binder in an amount of about 5 parts by mass or more, about 10 parts by mass or more, or about 15 parts by mass or more, about 35 parts by mass or less, about 30 parts by mass or less, or about 25 parts by mass or less based on 100 parts by mass of the binder. By setting the blending amount of the cellulose ester within the above range, the resin beads can be uniformly dispersed by the low-gloss layer to impart a uniform low-gloss appearance to the film.

[0039] As resin beads, various resin beads can be used. The resin beads can form fine irregularities on the surface of the low gloss layer due to the presence of the beads, and can form a low gloss structure on the surface of the low gloss layer.

[0040] In one embodiment, the resin beads are urethane resin beads. Since urethane resin beads have good affinity with a binder containing a resin, particularly a binder containing a urethane resin, they have high adhesion to the binder. As a result, when the film is stretched or deformed, the detachment of the urethane resin beads from the binder can be suppressed. As the urethane resin beads, crosslinked polyurethane fine particles obtained by suspension polymerization, seed polymerization, emulsion polymerization, etc. can be used. The urethane resin beads are excellent in flexibility, toughness, scratch resistance, etc., and these properties can be imparted to the low gloss layer.

[0041] The average particle diameter of the resin beads is about 4 μm or more and about 20 μm or less. The average particle diameter of the resin beads may be about 6 μm or more, or about 10 μm or more, and may be about 10 μm or less, or about 15 μm or less. When the average particle diameter of the resin beads is less than about 4 μm, whitening of the film surface due to light scattering is likely to occur. When the average particle diameter of the resin beads exceeds about 20 μm, gloss is likely to occur, and it becomes difficult to obtain low glossiness. The resin beads having an average particle diameter within the above range can impart a low glossiness with low brightness, that is, little whiteness, to the low gloss layer by moderately scattering the light incident on the low gloss layer. The average particle diameter of the resin beads is the cumulative volume 50% particle diameter measured using a laser diffraction particle size distribution analyzer.

[0042] In some embodiments, the resin beads may be included in an amount of about 70 parts by mass or more, about 80 parts by mass or more, or about 100 parts by mass or more, and about 240 parts by mass or less, about 230 parts by mass or less, or about 200 parts by mass or less, based on 100 parts by mass of the binder, in the low gloss layer. If the blending amount of the resin beads is less than about 70 parts by mass, it is difficult to obtain low glossiness, and if it exceeds about 240 parts by mass, whitening is likely to occur. By setting the blending amount of the resin beads within the above range, a low gloss layer that exhibits low gloss over a wide viewing angle, for example, from 20 degrees to 85 degrees, can be obtained.

[0043] The presence of the nanosilica particles in the binder can further reduce the glossiness of the low gloss layer. In addition, it is possible to suppress changes in low glossiness that are likely to occur when the film is stretched using only the resin beads, and effectively prevent whitening of the film.

[0044] As the nanosilica particles, for example, a silica sol obtained using water glass (sodium silicate solution) as a starting material can be used. The surface of the nanosilica particles may be modified using a surface treatment agent such as silane, alcohol, amine, carboxylic acid, sulfonic acid, phosphonic acid, titanate, or the like.

[0045] In some embodiments, the average particle size of the nanosilica particles is about 10 nm or more, about 20 nm or more, or about 30 nm or more, and about 100 nm or less, about 75 nm or less, or about 45 nm or less. Thus, by using nanosilica particles of a minute size, the nanosilica particles can be highly dispersed in the low gloss layer. Even when the film is stretched, the minute nanosilica particles are dispersed and remain in the stretched portion, so that the disappearance of the low gloss property is suppressed, and whitening of the film can be effectively prevented. The nanosilica particles present adjacent to the resin beads may also act as certain physical crosslinking points between the resin beads, particularly urethane resin beads and the binder. Due to the presence of the nanosilica particles that can act as such physical crosslinking points, the detachment of the resin beads when the film is stretched is suppressed, and whitening of the film can be effectively prevented. The average particle size of the nanosilica particles is a conversion value from the specific surface area measured using the BET method.

[0046] In some embodiments, the nanosilica particles may be included in an amount of about 5 parts by mass or more, about 10 parts by mass or more, or about 20 parts by mass or more, and about 120 parts by mass or less, about 110 parts by mass or less, or about 100 parts by mass or less based on 100 parts by mass of the binder in the low gloss layer. By setting the blending amount of the nanosilica particles within the above range, the glossiness of the low gloss layer can be further reduced. By setting the blending amount of the nanosilica particles within the above range, the low gloss appearance can also be maintained even when the film is stretched, and for example, when stretched by 150%, an increase in lightness, that is, whitening, can be prevented or suppressed. By setting the blending amount of the nanosilica particles within the above range, excellent scratch resistance can also be imparted to the low gloss layer.

[0047] The low gloss layer may further contain a silicone-modified polymer having a functional group capable of reacting with an isocyanate or a hydroxyl group. When fingerprint grease adheres to the low gloss surface, its traces are easily observable. By including a silicone-modified polymer having a functional group capable of reacting with an isocyanate or a hydroxyl group in the low gloss layer, the fingerprint resistance of the low gloss layer can be enhanced. The silicone-modified polymer can also reduce the coefficient of friction of the low gloss layer and impart scratch resistance due to sliding to the low gloss layer. The isocyanate or hydroxyl group of the silicone-modified polymer may react with the hydroxyl group or isocyanate group of the urethane resin or urethane resin beads contained in the binder, and the silicone-modified polymer may be bonded to the urethane resin or urethane resin beads. In this embodiment, bleeding out of the silicone-modified polymer from the low gloss layer can be prevented or suppressed.

[0048] As the silicone-modified polymer having a functional group capable of reacting with an isocyanate or a hydroxyl group, silicone-modified polymers such as polyether-modified silicone, polyester-modified silicone, aralkyl-modified silicone, acrylic-modified silicone, silicone-modified polyacrylate, and urethane-modified silicone can be used. Examples of the functional group capable of reacting with the isocyanate or hydroxyl group of the silicone-modified polymer include a hydroxyl group, an amino group having active hydrogen, an isocyanate group, an epoxy group, and an acid anhydride group. Since it is particularly excellent in fingerprint resistance, it is advantageous that the silicone-modified polymer is a silicone-modified polyacrylate. It is desirable that the silicone-modified polymer has a hydroxyl group or an isocyanate group, particularly a hydroxyl group, which has high reactivity with an isocyanate or a hydroxyl group.

[0049] In some embodiments, a silicone-modified polymer having a functional group reactive with an isocyanate or a hydroxyl group, such as a silicone-modified polyacrylate, may be included in the low-gloss layer in an amount of about 0.1 part by mass or more, about 0.5 part by mass or more, or about 1.0 part by mass or more, and about 15 parts by mass or less, about 12 parts by mass or less, or about 10 parts by mass or less based on 100 parts by mass of the binder. By setting the blending amount of the silicone-modified polymer within the above range, the fingerprint resistance and / or scratch resistance of the low-gloss layer can be further enhanced.

[0050] The low-gloss layer may contain, as other optional components, fillers other than resin beads and nanosilica particles, ultraviolet absorbers, light stabilizers, heat stabilizers, dispersants, plasticizers, flow improvers, leveling agents, flame retardants, and other additives. The individual and total blending amounts of these additives can be determined within a range that does not impair the properties required for the low-gloss layer.

[0051] In one embodiment, the low-gloss layer contains flaky fillers having an average particle size of more than about 30 μm and less than about 1000 μm within a range that does not impair the low-gloss appearance. Examples of the flaky fillers include expandable graphite, aluminum foil powder pigments, glass flake powder pigments, resin film foil powder pigments, and the like. The average particle size of the flaky filler is the cumulative volume 50% particle size measured using a laser diffraction particle size distribution analyzer. The thickness of the flaky filler may be about 0.5 μm to about 30 μm. The aspect ratio of the flaky filler may be about 1.0 to about 2000.

[0052] The low-gloss layer containing the binder, resin beads, and nanosilica particles described above can be formed using a coating composition containing a binder precursor containing a resin composition, resin beads having an average particle size of about 4 μm or more and about 20 μm or less, and nanosilica particles. In one embodiment, the resin composition is a urethane resin composition. In one embodiment, the resin beads are urethane resin beads.

[0053] The binder precursor may contain, in addition to the resin composition, the cellulose ester described above with respect to the binder. The cellulose ester can impart properties such as quick-drying property, touch-dry property, flowability, or leveling property to the coating composition. The cellulose ester can also be used for the purpose of adjusting the viscosity of the coating composition.

[0054] The coating composition may further contain the silicone-modified polymer having a functional group reactive with the above-described isocyanate or hydroxyl group. The isocyanate or hydroxyl group of the silicone-modified polymer can react with the hydroxyl group or isocyanate group of the urethane resin composition or urethane resin beads to bond the silicone-modified polymer to the urethane resin or urethane resin beads. Thereby, bleed-out from the low gloss layer of the silicone-modified polymer can be prevented or suppressed. When using the silicone-modified polymer, from the viewpoint of reactivity, it is advantageous that the urethane resin composition is a two-component urethane resin composition.

[0055] The formulation of the coating composition is as described for the low gloss layer containing the above-described binder, resin beads, and nanosilica particles. The formulation amounts of the cellulose ester, resin beads, nanosilica particles, and silicone-modified polymer having a functional group reactive with an isocyanate or hydroxyl group are applied by reading 100 parts by mass of the binder as 100 parts by mass of the binder precursor as a reference.

[0056] The coating composition may further contain solvents such as ketones such as methyl ethyl ketone, methyl isobutyl ketone, and acetylacetone; aromatic hydrocarbons such as toluene and xylene; alcohols such as ethanol and isopropyl alcohol; esters such as ethyl acetate and butyl acetate; and ethers such as tetrahydrofuran, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (1-methoxy-2-propyl acetate), and dipropylene glycol monomethyl ether acetate in order to improve workability, coating properties, etc. The blending amount of the solvent in the coating composition is generally about 20 parts by mass or more, or about 30 parts by mass or more, and about 60 parts by mass or less or about 50 parts by mass or less based on 100 parts by mass of the binder precursor.

[0057] The viscosity of the coating composition is generally about 20 mPa·s or more, about 50 mPa·s or more, or about 100 mPa·s or more, and about 1000 mPa·s or less, about 800 mPa·s or less, or about 600 mPa·s or less. The viscosity of the coating composition is measured at a rotational speed of 60 rpm using a B-type viscometer and selecting an appropriate spindle.

[0058] The low gloss layer can be formed by coating the coating composition on a substrate by knife coating, bar coating, blade coating, doctor coating, roll coating, cast coating, etc., and heating it to about 80°C to about 150°C as necessary for drying and / or curing.

[0059] The thickness of the low gloss layer can be, for example, about 3 μm or more, about 5 μm or more, or about 10 μm or more, and about 50 μm or less, about 30 μm or less, or about 20 μm or less. The thickness of the low gloss layer in the present disclosure means the thickness of the thickest part, that is, the maximum thickness.

[0060] In some embodiments, the low gloss layer is transparent or translucent. In these embodiments, the total light transmittance of the low gloss layer in the wavelength range of 400 to 700 nm may be about 80% or more, about 85% or more, or about 90% or more. In these embodiments, decorations such as printing applied to the substrate can be visually recognized through the low gloss layer.

[0061] The gloss printing pattern is used to provide a visible texture to the film due to the difference in glossiness from the low gloss layer by providing a region that is relatively glossier than the low gloss layer partially on the low gloss layer. The gloss printing pattern can be formed on the low gloss layer using known gloss inks and printing techniques. From the perspective of suppressing the glare caused by the change in the viewing angle, it is desirable that the gloss printing pattern be formed with a thickness such that it does not completely cover the unevenness formed by embossing.

[0062] In one embodiment, the gloss printing pattern is a printing pattern by a printing plate. Examples of printing by a printing plate include gravure printing, offset printing, letterpress printing, and screen printing. From the perspective of reducing the particle size of the gloss ink to be printed and controlling the thickness of the gloss printing pattern, gravure printing and letterpress printing are preferred, and gravure printing is more preferred.

[0063] In the case of gravure printing, the number of lines of the gravure plate is desirably 60 lines or more, 80 lines or more, or 100 lines or more, and 350 lines or less, 200 lines or less, or 175 lines or less from the perspective of reducing the particle size of the gloss ink to be printed and controlling the thickness of the gloss printing pattern. The number of lines of the gravure plate is correlated with the printing amount of the gloss ink. By setting the number of lines of the gravure plate to 100 lines or more, it is possible to achieve a high balance between the fineness of printing and the printing amount of the ink. On the other hand, by setting the number of lines of the gravure plate to 175 lines or less, it is possible to apply high-definition printing assuming high-solid ink as well.

[0064] As the gloss ink, a solvent-based, water-based or UV-curable ink can be used, and from the viewpoints of controlling the amount of the gloss ink to be printed and workability, it is desirable that the ink be a solvent-based ink. The gloss ink may be transparent, translucent, or opaque, and may be colorless or colored.

[0065] In one embodiment, the gloss printing pattern includes a gloss ink selected from the group consisting of an acrylic ink, a urethane ink, and a vinyl chloride-vinyl acetate ink. The acrylic ink, the urethane ink, and the vinyl chloride-vinyl acetate ink are advantageously used from the viewpoint of versatility. In particular, the acrylic ink and the urethane ink are also good from the viewpoint of durability.

[0066] The gloss ink may or may not contain additives such as fillers (e.g., inorganic beads, resin beads, etc.), antifouling agents, weather stabilizers, etc. for low gloss or other purposes, provided that it can form a printing pattern having a higher gloss than the low gloss layer.

[0067] The thickness of the gloss printing pattern is desirably thin to such an extent that the presence of the gloss printing pattern can be recognized from various viewing angles without excessively increasing the surface glossiness. Generally, when a solvent-based ink is used, it can be about 0.1 μm or more, about 0.2 μm or more, or about 0.3 μm or more, and about 5 μm or less, about 3 μm or less, or about 2 μm or less.

[0068] The gloss printing pattern may be continuous or discontinuous. The gloss printing pattern may be arranged to correspond to the entire surface of the film, or may be arranged to correspond to a part or a plurality of parts. Examples of the printing pattern include a wood grain, a stone grain, a logo, a pattern, characters, symbols, etc.

[0069] The surface layer is embossed, whereby the film has an embossed surface. The embossing can impart a tactile texture to the embossed surface of the film. The embossing can be performed under known conditions using an embossing roll having various patterns or designs. The embossing may be deeper than the thickness of the surface layer. For example, other layers such as a substrate layer beneath the surface layer may be embossed together with the surface layer.

[0070] The maximum height Rz of the embossing can generally be about 30 μm or more, about 40 μm or more, or about 50 μm or more. By setting the maximum height Rz of the embossing to about 40 μm or more, good touch feel can be imparted, and by setting it to about 50 μm or more, distinct touch feel can be imparted. The maximum height Rz of the embossing can generally be about 200 μm or less, about 150 μm or less, or about 100 μm or less. By setting the maximum height Rz of the embossing to about 100 μm or less, good cleanability can be imparted to the embossed surface of the film.

[0071] In one embodiment, the embossing can be performed after the formation of the low gloss layer and the gloss printing pattern. In this embodiment, both the low gloss layer and the gloss printing pattern are embossed. Thereby, the gloss printing pattern can be made to follow the uneven shape formed by the embossing, and the glare due to the change in the viewing angle can be effectively suppressed.

[0072] In one embodiment, at least a part of the gloss printing pattern is distributed at the bottom of the embossed surface layer. Thereby, the glare due to the change in the viewing angle can be effectively suppressed.

[0073] The gloss printing pattern and the embossing pattern may be in sync, or may not be in sync, either partially or entirely. In one embodiment, the film includes portions where the gloss printing pattern and the embossing pattern are not in sync. In this embodiment, the tactile texture by embossing and the visible texture by the gloss printing pattern can be formed separately and independently, thereby expressing a highly complex design. For example, while forming a tactile texture of a cross-section of a tree by embossing, a visible texture of a wood grain pattern can be formed by the gloss printing pattern.

[0074] In one embodiment, the surface layer has the following characteristics (1) and (2). (1) The 85-degree surface glossiness has an in-plane average value of about 5.0 GU or less. (2) The Δ85-degree surface glossiness (= the in-plane maximum value of the 85-degree surface glossiness - the in-plane average value of the 85-degree surface glossiness) defined by the difference between the in-plane maximum value and the in-plane average value of the 85-degree surface glossiness is about 0.2 to about 2.5. When the 85-degree surface glossiness has an in-plane average value of about 5.0 GU or less and the Δ85-degree surface glossiness is about 2.5 or less, the glare due to the change in the viewing angle can be suppressed. When the Δ85-degree surface glossiness is about 0.2 or more, the visibility of the gloss printing pattern can be ensured, and a delicate and three-dimensional design can be expressed.

[0075] The in-plane average value of the 85-degree surface glossiness is preferably about 4.5 GU or less, more preferably about 3.5 GU or less, and even more preferably about 2.7 GU or less. When the in-plane average value is about 4.5 GU or less, a better low-gloss appearance can be obtained, and the design property can be enhanced. When it is about 3.5 GU or less, the design property can be further enhanced. The in-plane average value of the 85-degree surface glossiness can generally be about 0.1 GU or more, about 0.2 GU or more, or about 0.5 GU or more.

[0076] The Δ85-degree surface glossiness is preferably about 0.22 to about 2.3, more preferably about 0.25 to about 2.0, and even more preferably about 0.3 to about 1.5. By setting the Δ85-degree surface glossiness to about 0.22 to about 2.3, a moderate low-gloss appearance and a good design by gloss printing can be expressed. By setting the Δ85-degree surface glossiness to about 0.25 to about 2.0, the design property can be further enhanced by a good low-gloss appearance and gloss printing.

[0077] The measurement of the 85-degree surface glossiness is performed using a portable gloss meter BYK Gardner Micro-Tri-Gloss (Big Chemie Japan Co., Ltd., Shinjuku-ku, Tokyo, Japan) according to the following procedure.

[0078] The in-plane average value of the 85-degree surface glossiness is the average value of the measured values at a total of five points, including one point at the center of a sample with a length of 200 mm to 400 mm and a width of 200 mm to 400 mm, and the centers of each region obtained by dividing the sample into four parts (two vertical divisions and two horizontal divisions) through the center of the sample. At each measurement point, the 85-degree surface glossiness is measured according to the following procedure. (1) Set a reference line in an arbitrary direction passing through the measurement point. (2) Measure the 85-degree surface glossiness in six directions at angles of 0 degrees, 30 degrees, 60 degrees, 90 degrees, 120 degrees, and 150 degrees from the set reference line. (3) Adopt the maximum value among the measured values in the six measured directions as the value at that measurement point.

[0079] For the in-plane maximum value of the 85-degree surface glossiness, for each region obtained by dividing (two vertical divisions and two horizontal divisions) through the center of a sample with a length of 200 mm to 400 mm and a width of 200 mm to 400 mm, visually identify the location with the highest glossiness as the first measurement point, and measure the 85-degree surface glossiness according to the following procedure. (1) Set a first reference line in an arbitrary direction passing through the first measurement point. (2) Measure the 85-degree surface glossiness in six directions at angles of 0 degrees, 30 degrees, 60 degrees, 90 degrees, 120 degrees, and 150 degrees from the set first reference line. (3) Adopt the maximum value among the measured values in the six measured directions as the value at the first measurement point. (4) Set a second reference line in the direction of the angle at which the maximum value was measured passing through the first measurement point, and set a third reference line in the direction passing through the first measurement point and orthogonal to the second reference line. (5) Set a total of four points, two points 20 mm away from the first measurement point on the second reference line and two points 5 mm away from the first measurement point on the third reference line, as the second measurement points, and measure the surface glossiness at 85 degrees in a direction parallel to the second reference line. (6) Adopt the maximum value among the values measured for the first measurement point and the second measurement points (the maximum value of 5 points / region × 4 regions = 20 points) as the in-plane maximum value.

[0080] In one embodiment, the surface roughness Ra of the embossed surface of the film is about 3.5 μm or more. By having the surface roughness Ra of the embossed surface of the film be about 3.5 μm or more, good touch feeling can be imparted to the film. Depending on the application and design, the surface roughness Ra of the embossed surface of the film can be about 5.0 μm or more, or about 10 μm or more. The surface roughness Ra of the embossed surface of the film can generally be about 50 μm or less, or about 30 μm or less.

[0081] The maximum height Rz of the embossed surface of the film can generally be about 30 μm or more, about 40 μm or more, or about 50 μm or more. By setting the maximum height Rz of the embossed surface of the film to about 40 μm or more, good touch feeling can be imparted, and by setting it to about 50 μm or more, distinct touch feeling can be imparted. The maximum height Rz of the embossed surface of the film can generally be about 200 μm or less, about 150 μm or less, or about 100 μm or less. By setting the maximum height Rz of the embossed surface of the film to about 100 μm or less, good cleanability can be imparted to the film.

[0082] The surface roughness Ra and the maximum height Rz are the arithmetic mean roughness and the maximum height measured in accordance with the line roughness of JIS B 0601:2001, respectively.

[0083] In one embodiment, the in-plane average value of the surface glossiness of the surface layer is about 5.0 GU or less, about 3.5 GU or less, about 2.7 GU or less, or about 1.0 GU or less when the measurement angle is 60 degrees.

[0084] In one embodiment, the in-plane average value of the surface glossiness of the surface layer is about 1.4 GU or less at 20 degrees, about 5.0 GU or less at 60 degrees, and about 5.0 GU or less at 85 degrees. In some embodiments, the in-plane average value of the surface glossiness of the surface layer is about 1.4 GU or less at 20 degrees, about 3.5 GU or less at 60 degrees, and about 3.5 GU or less at 85 degrees, or about 1.3 GU or less at 20 degrees, about 2.7 GU or less at 60 degrees, and about 2.7 GU or less at 85 degrees. By having the in-plane average value of the surface glossiness of the surface layer be a combination within the above ranges, the reflection of light incident on the film at various angles can be suppressed, and the decoration of the film or the decorative surface covered by the film (when the film is used as an overlaminate film) can be recognized from a wide viewing angle.

[0085] The in-plane average values of the surface glossiness at a measurement angle of 20 degrees and a measurement angle of 60 degrees are each determined by the same procedure as the method described above for the in-plane average value of the surface glossiness at 85 degrees, except that the measurement angle is 20 degrees or 60 degrees.

[0086] The film may further include a base material layer as a base material. The base material layer may be stretchable. As the base material layer, at least one resin layer selected from the group consisting of polyvinyl chloride, polyurethane, polyethylene, polypropylene, vinyl chloride-vinyl acetate resin, acrylic resin, cellulose resin, ionomer resin, silicone resin, and fluororesin can be used.

[0087] The base material layer may be colored or colorless. The base material layer may be opaque, translucent, or transparent. The base material layer may have a substantially smooth surface or a structured surface that can be formed by surface processing such as embossing. By making the appearance or shape of the base material layer as described above, various decorative properties can be imparted to the film.

[0088] The base material layer may be provided with a printing layer on one side or both sides. The printing layer imparts design properties to the film. The printing layer can be formed by using printing technologies such as inkjet printing, gravure printing, electrostatic printing, screen printing, and offset printing.

[0089] As the printing ink, solvent-based ink, water-based ink, or UV-curable ink can be used. The printing ink may be transparent, translucent, or opaque, and may be colorless or colored.

[0090] The thickness of the printing layer can vary. Generally, when using solvent-based ink, it can be about 0.1 μm or more, about 0.2 μm or more, or about 0.3 μm or more, and about 10 μm or less, or about 5 μm or less. When using UV-curable ink, it can be about 1 μm or more, or about 5 μm or more, and about 50 μm or less, or about 30 μm or less. The thickness of the printing layer in the present disclosure means the thickness of the thickest part, that is, the maximum thickness.

[0091] The printing layer may be continuous or discontinuous. The printing layer may be arranged to correspond to the entire surface of the base material layer, or may be arranged to correspond to a part or a plurality of parts. The printing layer may cover the entire surface of the base material layer. In one embodiment, the printing layer includes a printed area and a non-printed area. Examples of the design of the printing layer include wood grain, stone grain, logo, pattern, character, symbol, etc.

[0092] The design of the printing layer may or may not be synchronized with the gloss printing pattern. When they are synchronized, it is preferable in terms of being able to easily reproduce a design closer to the real object.

[0093] In one embodiment, the printing layer can be printed by a printing plate. Examples of printing by a printing plate include gravure printing, offset printing, letterpress printing, and screen printing. When printing while synchronizing the design of the printing layer and the gloss printing pattern, from the perspective of printing plate control, gravure printing and letterpress printing are preferable, and gravure printing is more preferable.

[0094] When performing gravure printing in which the design of the printing layer is synchronized with the gloss printing pattern, the line number of the gravure plate is desirably 60 lines or more, 80 lines or more, or 100 lines or more, and 350 lines or less, 200 lines or less, or 175 lines or less from the viewpoint of the particle size of the gloss ink of the gloss printing pattern.

[0095] In one embodiment, the base material layer includes a transparent polyvinyl chloride resin layer and a colored polyvinyl chloride resin layer. In the film of this embodiment, the colored polyvinyl chloride resin layer is supported or protected by the transparent polyvinyl chloride resin layer, and durability can be imparted to the decorativeness of the film. The film of this embodiment can be suitably used, for example, for applications such as being attached to interior or exterior materials of buildings or vehicles. FIG. 2 shows a schematic cross-sectional view of the film 100 of this embodiment. The film 100 includes a base material layer 140 and a base material layer 142. Other configurations of the film 100 are as described in FIG. 1.

[0096] The thickness of the base material layer can be, for example, about 25 μm or more, about 50 μm or more, or about 80 μm or more, and about 5 mm or less, about 1 mm or less, or about 0.5 mm or less. When the base material layer is two or more layers, the above thickness means the total thickness of the base material layer.

[0097] In some embodiments, the tensile elongation rate of the base material layer is about 10% or more, about 20% or more, or about 30% or more, and about 400% or less, about 350% or less, or about 300% or less. The tensile elongation rate of the base material layer is calculated by [chuck interval at break (mm) - chuck interval before elongation (mm) (= 100 mm)] / chuck interval before elongation (mm) (= 100 mm) × 100 (%) when a sample with a width of 25 mm and a length of 150 mm is prepared, and the sample is elongated until it breaks using a tensile testing machine at a temperature of 20 ° C., a tensile speed of 300 mm / min, and a chuck interval of 100 mm.

[0098] The base material layer may have an adhesive layer on the side opposite to the surface layer. As the adhesive layer, solvent-based, emulsion-based, pressure-sensitive, heat-sensitive, thermosetting, or ultraviolet-curable adhesives such as acrylic, polyolefin, polyurethane, polyester, and rubber-based adhesives that are commonly used can be used. The thickness of the adhesive layer can generally be about 5 μm or more, about 10 μm or more, or about 20 μm or more, and about 100 μm or less, about 80 μm or less, or about 50 μm or less.

[0099] A liner may be provided on the surface of the adhesive layer. Examples of the liner include paper; plastic materials such as polyethylene, polypropylene, polyester, and cellulose acetate; and paper coated with such plastic materials. These liners may have a surface subjected to a release treatment with silicone or the like. The thickness of the liner is generally about 5 μm or more, about 15 μm or more, or about 25 μm or more, and about 500 μm or less, about 300 μm or less, or about 250 μm or less.

[0100] The film can be manufactured by a method including forming a low-gloss layer on the base material, forming a gloss printing pattern on the low-gloss layer that partially covers the low-gloss layer, and performing embossing from above the gloss printing pattern. The base material may be a peelable liner or the above-described base material layer. When a peelable liner is used as the base material, the liner can be removed after the above steps to obtain a film consisting only of the surface layer.

[0101] The film may be a graphic film or an overlaminate film applied to a decorative surface.

[0102] An overlaminate film according to one embodiment includes a transparent resin-based film having a first surface and a second surface opposite to the first surface, a surface layer disposed on the first surface of the transparent resin-based film, and a transparent adhesive layer disposed on the second surface of the transparent resin-based film. The surface layer has a low-gloss layer and a gloss printing pattern. The surface layer, the low-gloss layer, and the gloss printing pattern are as described above.

[0103] In one embodiment, the low gloss layer includes a binder containing a resin, resin beads having an average particle size of about 4 μm or more and about 20 μm or less, and nanosilica particles. By including resin beads and nanosilica particles with an average particle size within the above range in the low gloss layer, a low gloss appearance is imparted to the overlaminate film. In this embodiment, a design appearance with a high contrast ratio is provided in which visible light reflection in the dark portions is suppressed. In other words, since the dark portions are visually recognized as darker, a unique and clearer visual effect with a more prominent difference between light and dark can be provided.

[0104] In one embodiment, the overlaminate film is stretchable. The overlaminate film of this embodiment can be stretched to conform to the shape of the article to which it is adhered. The overlaminate films of some embodiments can maintain a low gloss appearance after stretching.

[0105] A schematic cross-sectional view of an overlaminate film according to one embodiment is shown in FIG. 3. The overlaminate film 200 in FIG. 3 includes a transparent resin base film 240, a surface layer 210 including a low gloss layer 220 and a gloss print pattern 230, and a transparent adhesive layer 250, and may include a liner 260 that protects the transparent adhesive layer 250. The low gloss layer 220 includes a binder 222 containing a resin, resin beads 224 having an average particle size of about 4 μm or more and about 20 μm or less, and nanosilica particles 226.

[0106] Various resin films can be used as the transparent resin base film. The transparent resin base film may be stretchable. As the transparent resin base film, at least one resin film selected from the group consisting of polyvinyl chloride, polyurethane, polyethylene, polypropylene, vinyl chloride-vinyl acetate resin, acrylic resin, cellulose resin, ionomer resin, silicone resin, and fluororesin can be used.

[0107] The transparent resin-based film may be colored or colorless. The transparent resin-based film may have a substantially smooth surface or a structured surface that can be formed by surface treatment such as embossing. By making the appearance or shape of the transparent resin-based film as described above, various decorative properties can be imparted to the overlaminate film.

[0108] In one embodiment, the total light transmittance of the transparent resin-based film in the wavelength range of 400 to 700 nm is about 85% or more, about 90% or more, or about 95% or more.

[0109] The thickness of the transparent resin-based film can be, for example, about 25 μm or more, about 50 μm or more, or about 80 μm or more, and about 5 mm or less, about 1 mm or less, or about 0.5 mm or less.

[0110] In some embodiments, the tensile elongation rate of the transparent resin-based film is about 10% or more, about 20% or more, or about 30% or more, and about 400% or less, about 350% or less, or about 300% or less. The tensile elongation rate of the transparent resin-based film is calculated by [distance between chucks at break (mm) - distance between chucks before elongation (=100 mm)] / distance between chucks before elongation (=100 mm) × 100 (%) when a sample with a width of 25 mm and a length of 150 mm is prepared, and the sample is elongated until it breaks using a tensile testing machine at a temperature of 20°C, a tensile speed of 300 mm / min, and a chuck interval of 100 mm.

[0111] As the transparent adhesive layer, generally used solvent-based, emulsion-based, pressure-sensitive, heat-sensitive, thermosetting, or ultraviolet-curable adhesives such as acrylic, polyolefin, polyurethane, polyester, and rubber-based adhesives can be used. The thickness of the transparent adhesive layer can generally be about 5 μm or more, about 10 μm or more, or about 20 μm or more, and about 100 μm or less, about 80 μm or less, or about 50 μm or less.

[0112] In one embodiment, the total light transmittance of the transparent adhesive layer in the wavelength range of 400 to 700 nm is about 85% or more, about 90% or more, or about 95% or more.

[0113] A liner may be provided on the surface of the transparent adhesive layer. Examples of the liner include paper; plastic materials such as polyethylene, polypropylene, polyester, and cellulose acetate; and paper coated with such plastic materials. These liners may have a surface subjected to a release treatment with silicone or the like. The thickness of the liner is generally about 5 μm or more, about 15 μm or more, or about 25 μm or more, and about 500 μm or less, about 300 μm or less, or about 250 μm or less.

[0114] In one embodiment, the total light transmittance of the overlaminate film in the wavelength range of 400 to 700 nm is about 75% or more, about 80% or more, or about 85% or more.

[0115] The thickness of the overlaminate film can generally be about 20 μm or more, about 50 μm or more, or about 80 μm or more, and about 500 μm or less, about 250 μm or less, or about 150 μm or less. The thickness of the overlaminate film means the maximum thickness within the film plane and does not include the thickness of the liner.

[0116] A graphic laminate of one embodiment includes a resin-based film having a first surface and a second surface opposite to the first surface, a printing layer disposed on the first surface, an adhesive layer disposed on the second surface, and an overlaminate film of the present disclosure that covers the printing layer of the graphic film. By covering the printing layer of the graphic film with the overlaminate film of the present disclosure, a low-gloss appearance can be imparted to the decorative surface represented by the printing layer of the graphic film.

[0117] A schematic cross-sectional view of a graphic laminate according to an embodiment is shown in FIG. 4. The graphic laminate 400 in FIG. 4 includes a graphic film 300 including a resin base film 340, a printing layer 310, and an adhesive layer 350, and an overlaminate film 200 that covers the printing layer 310 of the graphic film 300. The overlaminate film 200 is laminated on the printing layer 310 of the graphic film via a transparent adhesive layer 250. In FIG. 4, a liner 360 that protects the adhesive layer 350 is shown.

[0118] Various resin films can be used as the resin base film of the graphic film. The resin base film may be stretchable. As the resin base film, at least one resin film selected from the group consisting of polyvinyl chloride, polyurethane, polyethylene, polypropylene, vinyl chloride-vinyl acetate resin, acrylic resin, cellulose resin, ionomer resin, silicone resin, and fluororesin can be used.

[0119] The resin base film may be colored or colorless. The resin base film may be opaque, translucent, or transparent. The resin base film may have a substantially smooth surface or a structured surface that can be formed by surface treatment such as embossing. By making the appearance or shape of the resin base film as described above, various decorativeness can be imparted to the graphic laminate.

[0120] In one embodiment, the resin base film includes a transparent polyvinyl chloride resin layer and a colored polyvinyl chloride resin layer. In the graphic laminate of this embodiment, the colored polyvinyl chloride resin layer is supported or protected by the transparent polyvinyl chloride resin layer, and durability can be imparted to the graphic laminate. The graphic laminate of this embodiment can be suitably used, for example, for applications where it is attached to interior or exterior materials of buildings or vehicles.

[0121] The thickness of the resin-based film can be, for example, about 25 μm or more, about 50 μm or more, or about 80 μm or more, and about 5 mm or less, about 1 mm or less, or about 0.5 mm or less.

[0122] In some embodiments, the tensile elongation rate of the resin-based film is about 10% or more, about 20% or more, or about 30% or more, and about 400% or less, about 350% or less, or about 300% or less. The tensile elongation rate of the resin-based film is calculated by [the chuck interval at break (mm) - the chuck interval before elongation (= 100 mm)] / the chuck interval before elongation (= 100 mm) × 100 (%) when a sample with a width of 25 mm and a length of 150 mm is prepared, and the sample is elongated until it breaks using a tensile testing machine at a temperature of 20 °C, a tensile speed of 300 mm / min, and a chuck interval of 100 mm.

[0123] The printing layer disposed on the first surface of the resin-based film imparts design characteristics to the graphic film. The printing layer can be formed on the first surface of the resin-based film by using printing techniques such as inkjet printing, gravure printing, electrostatic printing, screen printing, offset printing, etc.

[0124] As the printing ink, solvent-based ink, water-based ink, or UV-curable ink can be used. The printing ink can be transparent, translucent, or opaque, and can be colorless or colored.

[0125] The thickness of the printing layer can vary. Generally, when solvent-based ink is used, it can be about 0.1 μm or more, about 0.2 μm or more, or about 0.3 μm or more, and about 10 μm or less, or about 5 μm or less. When UV-curable ink is used, it can be about 1 μm or more, or about 5 μm or more, and about 50 μm or less, or about 30 μm or less. The thickness of the printing layer in the present disclosure means the thickness of the thickest part, that is, the maximum thickness.

[0126] The printing layer may be continuous or discontinuous. The printing layer may be arranged to correspond to the entire surface of the resin-based film, or may be arranged to correspond to a part or a plurality of parts. The printing layer may cover the entire surface of the resin-based film. In one embodiment, the printing layer includes a printed area and a non-printed area. Examples of the design of the printing layer include wood grain, stone grain, logo, pattern, character, symbol, and the like.

[0127] In one embodiment, the printing layer is an inkjet printing layer. Inkjet printing enables short-turnaround on-demand manufacturing.

[0128] As the adhesive layer disposed on the second surface of the resin-based film, generally used solvent-based, emulsion-based, pressure-sensitive, heat-sensitive, thermosetting or ultraviolet-curable adhesives such as acrylic, polyolefin, polyurethane, polyester, rubber-based adhesives can be used. The thickness of the adhesive layer can generally be about 5 μm or more, about 10 μm or more, or about 20 μm or more, and about 100 μm or less, about 80 μm or less, or about 50 μm or less.

[0129] The adhesive layer may be colored or colorless. The adhesive layer may be opaque, translucent or transparent. In one embodiment, the adhesive layer is a white adhesive layer containing a pigment such as titanium oxide. The white adhesive layer can enhance the clarity of the design shown by the printing layer and, if necessary, the resin-based film.

[0130] A liner may be provided on the surface of the adhesive layer. Examples of the liner include paper; plastic materials such as polyethylene, polypropylene, polyester, and cellulose acetate; and paper coated with such plastic materials. These liners may have a surface subjected to a release treatment with silicone or the like. The thickness of the liner is generally about 5 μm or more, about 15 μm or more, or about 25 μm or more, and about 500 μm or less, about 300 μm or less, or about 250 μm or less.

[0131] The use of the film of the present disclosure is not particularly limited. For example, the film of the present disclosure can be used as an interior material such as walls, stairs, ceilings, columns, partitions, etc. or an exterior material such as exterior walls of buildings such as buildings, condominiums, and houses. Further, it can be used as an interior material or an exterior material of various vehicles such as railway vehicles, ships, airplanes, and automobiles including two-wheel and four-wheel vehicles. Furthermore, it can also be used as a surface material for all kinds of articles such as road signs, signboards, furniture, and electrical appliances.

Examples

[0132] In the following examples, specific embodiments of the present disclosure are illustrated, but the present invention is not limited thereto. All parts and percentages are by mass unless otherwise specified. Numerical values include errors essentially caused by the measurement principle and the measuring device. Numerical values are shown as significant figures with normal rounding.

[0133] The materials, reagents, etc. used in this example are shown in Table 1.

[0134]

Table 1

[0135] The surface glossiness of the gloss ink 1 (urethane resin ink) solid-printed on the PET film was 105 GU / 108 GU / 101 GU (20 degrees / 60 degrees / 85 degrees) when JS1000A (white PVC film) was water-laminated on the opposite side of the PET film.

[0136] The surface glossiness of the gloss ink 2 (acrylic resin ink) solid-printed on the PET film was 104 GU / 106 GU / 98 GU (20 degrees / 60 degrees / 85 degrees) when JS1000A was water-laminated on the opposite side of the PET film.

[0137] The surface glossiness of the matte ink solid-printed on the PET film was 1.9 GU / 3.8 GU / 6.8 GU (20 degrees / 60 degrees / 85 degrees) when JS1000A (white PVC film) was water-laminated on the opposite side of the PET film.

[0138] When JS1000A (white PVC film) was water laminated on the opposite side of the PET film, the surface glossiness of the PET film was 139 GU / 128 GU / 101 GU (20 degrees / 60 degrees / 85 degrees).

[0139] The surface glossiness (20 degrees / 60 degrees / 85 degrees) was measured using a portable gloss meter BYK Gardner Micro - Tri - Gloss (Big Chemie Japan Co., Ltd., Shinjuku - ku, Tokyo, Japan).

[0140] Preparation of Low - Gloss Layer Coating Composition 15.0 g of Art pearl CE - 800T, 8.4 g of T5652, 15.0 g of MIBK ST L, 2.1 g of CAB - 381 - 20, 2.52 g of D110N, and 1.2 g of SILCLEAN 3700 were mixed. 59.5 g of 1 - methoxy - 2 - propyl acetate was added to the mixture to adjust the solid content to 32.51 mass%. Then, using a planetary centrifugal stirrer THINKY AR - 250 (Shinki Co., Ltd., Chiyoda - ku, Tokyo, Japan), the mixture was stirred for 3.5 minutes to obtain a low - gloss layer coating composition.

[0141] Formation of Low - Gloss Layer A transparent polyvinyl chloride film was thermally laminated onto the PET film. The low - gloss layer coating composition was applied onto the transparent polyvinyl chloride film using a knife coater with a gap of 40 μm, placed in an oven at 65 °C for 2 minutes to remove the solvent from the coating layer, and then placed in an oven at 120 °C for 5 minutes for thermal curing to form a low - gloss layer with a dry thickness of approximately 12 μm.

[0142] Example 1 The PET film laminated to the transparent polyvinyl chloride film having a low gloss layer was peeled off. A gloss printing pattern was formed on the low gloss layer of the transparent polyvinyl chloride film by gravure printing using a gravure plate of Wood Grain A (a mixed pattern of plank and square grain, 133 lines) and Gloss Ink 1. Thereafter, the colored polyvinyl chloride film and the transparent polyvinyl chloride film were arranged so that the colored polyvinyl chloride film was in contact with the transparent polyvinyl chloride film, and the embossing roll of Pattern A (wood grain pattern), the gloss printing pattern, and the low gloss layer were in contact with each other, and the colored polyvinyl chloride film and the transparent polyvinyl chloride film were thermally laminated to obtain a graphic film. The thermal lamination was performed under the following conditions. IR temperature: 600 °C Nip pressure: 0.2 MPa Embossing roll temperature: 60 °C Take-off roll temperature: 170 °C Heat drum temperature: 130 °C

[0143] Example 2 A graphic film was obtained in the same procedure as in Example 1, except that the gravure plate was changed to Wood Grain B (walnut pattern, 120 lines).

[0144] Example 3 A graphic film was obtained in the same procedure as in Example 1, except that the embossing roll was changed to Pattern B (sand texture pattern).

[0145] Example 4 A graphic film was obtained in the same procedure as in Example 1, except that Gloss Ink 1 was changed to Gloss Ink 2.

[0146] Comparative Example 1 A graphic film was obtained in the same procedure as in Example 1, except that a matte printing pattern identical to the gloss printing pattern was printed using matte ink on a transparent polyvinyl chloride film having no low gloss layer.

[0147] Comparative Example 2 A graphic film was obtained in the same procedure as in Example 1, except that the embossing roll was changed to Pattern C (pear skin texture pattern).

[0148] Comparative Example 3 A graphic film was obtained in the same procedure as in Example 1, except that a gloss print pattern was not formed.

[0149] The production conditions and structures of the graphic films of Examples 1 to 4 and Comparative Examples 1 to 3 are shown in Table 2.

[0150]

Table 2

[0151] Gloss at 85 degrees (in-plane average value and in-plane maximum value) The gloss at 85 degrees was measured using a portable gloss meter BYK Gardner Micro-Tri-Gloss (Big Chemie Japan Co., Ltd., Shinjuku-ku, Tokyo, Japan) in the following procedure.

[0152] The in-plane average value of the gloss at 85 degrees was defined as the average value of the measured values at a total of 5 points, including one point at the center of a sample measuring approximately 300 mm in length and approximately 400 mm in width and the centers of each region obtained by dividing the sample into 4 parts (2 parts in the longitudinal direction and 2 parts in the transverse direction) through the center of the sample. At each measurement point, the gloss at 85 degrees was measured in the following procedure. (1) Set a reference line in an arbitrary direction passing through the measurement point. (2) Measure the gloss at 85 degrees in 6 directions at angles of 0 degrees, 30 degrees, 60 degrees, 90 degrees, 120 degrees, and 150 degrees from the set reference line. (3) Adopt the maximum value among the measured values in the 6 measured directions as the value at that measurement point.

[0153] The in-plane maximum value of the gloss at 85 degrees was visually determined to be the location with the highest gloss in each region obtained by dividing the sample measuring approximately 300 mm in length and approximately 400 mm in width into 4 parts (2 parts in the longitudinal direction and 2 parts in the transverse direction) through the center of the sample, and the gloss at 85 degrees was measured at the first measurement point in the following procedure. (1) Set a first reference line in an arbitrary direction passing through the first measurement point. (2) Measure the 85-degree surface glossiness in six directions where the angles from the set first reference line are 0 degrees, 30 degrees, 60 degrees, 90 degrees, 120 degrees, and 150 degrees. (3) Adopt the maximum value among the measured values in the six directions as the value of the first measurement point. (4) Set a second reference line in the direction of the angle where the maximum value was measured passing through the first measurement point, and also set a third reference line in the direction perpendicular to the second reference line passing through the first measurement point. (5) Take a total of four points, two points 20 mm away from the first measurement point on the second reference line and two points 5 mm away from the first measurement point on the third reference line, as the second measurement points, and measure the 85-degree surface glossiness in the direction parallel to the second reference line. (6) Adopt the maximum value among the values measured for the first measurement point and the second measurement point (the maximum value of 5 points / area × 4 areas = 20 points) as the in-plane maximum value.

[0154] Δ85-degree surface glossiness The Δ85-degree surface glossiness was determined by subtracting the in-plane average value from the in-plane maximum value of the 85-degree surface glossiness. If the Δ85-degree surface glossiness is about 2.5 GU or less, the flickering due to the change in the viewing angle can be suppressed. If the Δ85-degree surface glossiness is 0.2 GU or more, the pattern formed by the gloss printing pattern can be visually recognized, and a delicate and three-dimensional design can be expressed.

[0155] Surface roughness Ra and maximum height Rz The surface roughness Ra and maximum height Rz of the embossed surface of the graphic film were measured using a digital microscope DSX510 (Olympus Corporation, Shinjuku-ku, Tokyo, Japan). The surface roughness Ra and maximum height Rz are the arithmetic mean roughness and maximum height measured in accordance with the line roughness of JIS B 0601:2001, respectively.

[0156] Slope from the approximate line of visible light reflectance The slope of the approximate line of the visible light reflectance of the graphic film was measured using a spectroscopic angular difference meter GC5000 (Nippon Denshoku Industries Co., Ltd., Bunkyo-ku, Tokyo, Japan). Specifically, the visible light reflectance at a reflection angle of -80 degrees to 80 degrees when the incident light was 60 degrees was measured at 5-degree intervals, and the reflectance from 400 to 800 nm at each angle was averaged to obtain the visible light reflectance at that angle. The visible light reflectance was graphed over the range of a reflection angle of -80 degrees to 80 degrees, and the slope was calculated from the visible light reflectances at two adjacent measurement angles. When the maximum value of the slope is 3.5 (% / 5 degrees) or more, it means that the visible light reflectance changes greatly when the viewing angle changes slightly from a certain viewing angle, that is, flickering is observed at angles around that viewing angle.

[0157] Appearance Those with a low gloss overall and a three-dimensional expression of the wood grain pattern were rated as good, while those with partial gloss flickering or those where the expression of the wood grain pattern could not be visually recognized were rated as poor.

[0158] Tactility A graphic film with embossing on the entire surface with a size of about 10 cm square was placed flat, and it was evaluated by rubbing and touching the vicinity of the center on the surface side with the fingertips of three or more fingers including the index finger, middle finger, and ring finger at a load of about 200 g at a speed of reciprocating about 5 cm intervals twice in about 1 second. For those with a directionality (such as wood grain lines) in the embossing pattern, the evaluation was performed in a direction perpendicular to that direction. Those who clearly felt the unevenness or roughness on the surface were rated as good, those who could feel the unevenness or roughness on the surface were rated as acceptable, and those who hardly felt the unevenness or roughness on the surface were rated as poor.

[0159] The evaluation results of the graphic film are shown in Table 3.

[0160]

Table 3

[0161] FIG. 5A is a photograph of the film of Example 1 when observed under a fluorescent lamp from the vertical direction on the surface layer side, and FIG. 5B is a photograph of the film of Comparative Example 1 when observed under a fluorescent lamp from the vertical direction on the surface layer side.

[0162] FIG. 6 is a photograph of the films of Example 1 (left) and Comparative Example 1 (right) when observed under a fluorescent lamp at a viewing angle of about 30 degrees from the vertical direction on the surface layer side.

[0163] FIG. 7A shows the visible light reflectance of the film of Example 1 with an incident light of 60 degrees at a reflection angle from -80 degrees to 80 degrees, and FIG. 7B shows the visible light reflectance of the film of Comparative Example 1 with an incident light of 60 degrees at a reflection angle from -80 degrees to 80 degrees. In Example 1, no peak is observed, while in Comparative Example 1, a peak is observed at a reflection angle of 60 degrees. This peak means a strong glare when observed at a reflection angle of 60 degrees. Therefore, in the film of Example 1, glare does not occur at any viewing angle, and a stable low gloss appearance is achieved as a whole. In these measurements, since the measurement value at -60 degrees where the angles of the light source and the detector coincide cannot be obtained, both FIG. 7A and FIG. 7B are discontinuous at a reflection angle of -60 degrees.

[0164] It is obvious to those skilled in the art that various improvements and modifications of the present invention can be made without departing from the scope and spirit of the present invention.

Explanation of Signs

[0165] 100 Film 110, 210 Surface layer 120, 220 Low gloss layer 122, 222 Binder 124, 224 Resin beads 126, 226 Nano silica particles 130, 230 Gloss printing pattern 140, 142 Base material layer 150 Adhesive layer 200 Overlaminate film 240 Transparent resin base film 250 Transparent adhesive layer 260, 360 Liner 300 Graphic film 310 Printing layer 340 Resin-based film 350 Adhesive layer 400 Graphic laminate

Claims

1. A film having an embossed surface layer, wherein the surface layer includes a low gloss layer and a gloss print pattern that partially covers the low gloss layer, (1) the 85-degree surface glossiness of the surface layer is 5.0 GU or less as an in-plane average value, (2) the Δ85-degree surface glossiness (=the in-plane maximum value of the 85-degree surface glossiness - the in-plane average value of the 85-degree surface glossiness) defined by the difference between the in-plane maximum value and the in-plane average value of the 85-degree surface glossiness of the surface layer is 0.2 to 2.5, (3) the surface roughness Ra of the embossed surface of the film is 3.5 μm or more, a film.

2. The film according to claim 1, wherein the maximum height Rz of the embossed surface of the film is 30 μm or more.

3. The film according to any one of claims 1 or 2, wherein both the low gloss layer and the gloss print pattern are embossed.

4. The film according to any one of claims 1 to 3, wherein at least a part of the gloss print pattern is distributed at the bottom of the embossed surface layer.

5. The film according to any one of claims 1 to 4, including a portion where the gloss print pattern and the embossing pattern are not in sync.

6. The film according to any one of claims 1 to 5, wherein the gloss print pattern includes a gloss ink selected from the group consisting of acrylic ink and urethane ink.

7. The film according to any one of claims 1 to 6, wherein the gloss print pattern is a print pattern by a printing plate.

8. The film according to any one of claims 1 to 7, wherein the low gloss layer includes a binder containing a resin, resin beads having an average particle size of 4 μm or more and 20 μm or less, and nano silica particles.

9. The film according to claim 8, wherein the average particle size of the nano silica particles is 10 nm or more and 100 nm or less.

10. The film according to any one of claims 8 or 9, wherein the low gloss layer contains 5 parts by mass or more and 120 parts by mass or less of the nano silica particles based on 100 parts by mass of the binder.

11. The film according to any one of claims 8 to 10, wherein the low gloss layer contains 70 parts by mass or more and 240 parts by mass or less of the resin beads based on 100 parts by mass of the binder.

12. The film according to any one of claims 8 to 11, wherein the binder contains a urethane resin.

13. The film according to claim 12, wherein the urethane resin contains a cured product of a two-component urethane resin composition.

14. The film according to any one of claims 8 to 13, wherein the resin beads are urethane resin beads.

15. The film according to any one of claims 8 to 14, wherein the binder further contains a cellulose ester.

16. A film having an embossed surface layer, wherein the surface layer includes a low gloss layer and a gloss printing pattern that partially covers the low gloss layer, The film, wherein the surface layer is formed by performing embossing from above the gloss printing pattern after forming the gloss printing pattern on the low gloss layer.

17. The film according to any one of claims 1 to 16, wherein the film is a graphic film.

18. The film according to any one of claims 1 to 16, wherein the film is an overlaminate film applied to a decorative surface.

19. Forming a low gloss layer on a substrate, Forming a gloss printing pattern that partially covers the low gloss layer on the low gloss layer, Performing embossing from above the gloss printing pattern, A method for manufacturing a film, comprising:

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