Film and manufacturing method thereof

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 purposes such as decoration, and a method for producing the same. [Background technology]

[0002] Decorative films are used to decorate the interior and exterior of buildings, vehicles, etc. For example, decorative films are known that are made by laminating a polyvinyl chloride film with a printed layer and a transparent polyvinyl chloride film and then embossing the film. Various combinations of lamination and embossing can be used to create the textures of various materials, such as wood grain, metal, fabric, and marble.

[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 the surfaces of dry-finished wood, matte paint, etc. A method for forming decorative films with a low-gloss surface appearance by coating a surface layer with a resin containing fine particles or beads is known. These decorative films can be used for the exterior or interior of buildings, vehicle interiors, furniture, and the covering of articles, etc.

[0004] Patent Document 1 (JP 2011-255552 A) describes an embossed decorative sheet in which "an embossed decorative sheet is formed by embossing the surface of the decorative sheet, and a surface protective layer made of a curable resin containing synthetic resin beads is provided on the surface side of the decorative sheet, the embossing having an average amplitude of 15 to 50 μm, and the synthetic resin beads having an average particle size of 8 to 20 μm."

[0005] Patent Document 2 (WO 2008 / 129667) describes a decorative sheet comprising "a protective layer primarily composed of a transparent resin component provided on the surface of a printing layer provided on a printing sheet, wherein the protective layer comprises 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 wherein the gloss of the protruding surface of the first protective layer is lower than the gloss of the surface of the second protective layer."

[0006] Patent Document 3 (JP 2011-224962 A) describes a decorative sheet that is "a decorative sheet comprising at least a transparent resin layer, a gloss-adjusting layer, and a surface protection layer laminated together, and having a textured pattern formed on the surface, the textured pattern including recesses in which the gloss-adjusting layer is exposed in part or in whole."

[0007] Patent Document 4 (JP 2014-024318 A) describes "a decorative sheet having a picture pattern printed layer, a matte layer, and a top coat layer that forms a gloss pattern on a base sheet, wherein the base sheet contains a vinyl chloride resin and the top coat layer contains a thermosetting resin and a reactive silicone oil."

[0008] Patent Document 5 (JP 2015-199313 A) describes a "front and back matching gloss matte decorative sheet characterized by having a matte layer on one side of a transparent thermoplastic resin layer, a glossy negative pattern layer on the matte layer, and a pattern layer on the other side." [Prior art documents] [Patent documents]

[0009] [Patent Document 1] Japanese Patent Application Laid-Open No. 2011-255552 [Patent Document 2] International Publication No. 2008 / 129667 [Patent Document 3] Japanese Patent Application Laid-Open No. 2011-224962 [Patent Document 4] Japanese Patent Application Laid-Open No. 2014-024318 [Patent Document 5] Japanese Patent Application Laid-Open No. 2015-199313 Summary of the Invention [Problem to be solved by the invention]

[0010] Because surfaces that exhibit a low-gloss appearance tend to diffuse or irregularly reflect light, it is difficult to create a texture with irregularities on such a low-gloss surface. Even if a low-gloss surface is embossed, for example, the low gloss of the entire surface makes it difficult to distinguish the light and dark of the texture formed by the embossing, resulting in low texture visibility. This is more pronounced the lower the gloss of the low-gloss surface.

[0011] Furthermore, from an aesthetic point of view, it is sometimes desirable that the appearance of the texture does not change significantly when the low-gloss surface is observed at various viewing angles. Although it is possible to provide a low-gloss appearance with an uneven texture by printing a low-gloss pattern using matte ink directly on a high-gloss surface, such as a resin film having a smooth surface, light reflection may occur in areas where the matte ink is not printed or where the amount of matte ink printed is small, resulting in strong glare depending on the viewing angle.

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

[0013] The present disclosure provides films that have a high quality, low gloss appearance with minimal change in texture appearance when viewed at different viewing angles, and that have a tactile texture. [Means for solving the problem]

[0014] According to one embodiment, there is provided a film having an embossed surface layer, the surface layer comprising a low-gloss layer and a gloss printing pattern that partially covers the low-gloss layer, wherein (1) the 85-degree surface gloss of the surface layer is 5.0 GU or less on an in-plane average basis, (2) the Δ85-degree surface gloss, defined as the difference between the maximum in-plane value and the average in-plane value of the 85-degree surface gloss of the surface layer (= maximum in-plane value of 85-degree surface gloss - average in-plane value of 85-degree surface gloss), 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, the surface layer including a low gloss layer and a gloss print pattern partially covering the low gloss layer, the surface layer being formed by forming the gloss print pattern on the low gloss layer and then embossing the gloss print pattern.

[0016] According to another embodiment, there is provided a method for producing a film, comprising: forming a low-gloss layer on a substrate; forming a gloss printing pattern on the low-gloss layer so as to partially cover the low-gloss layer; and embossing the gloss printing pattern. [Effects of the Invention]

[0017] The films of the present disclosure have a high-quality, low-gloss appearance with minimal change in texture appearance when viewed from various viewing angles, and have a tactile texture, which allows them to impart designs such as realistic wood grain designs to the interior and exterior of buildings, vehicles, and the like.

[0018] It should be noted that the above description should not be considered as a disclosure of all embodiments of the present invention and all advantages associated with the present invention. [Brief explanation of the drawings]

[0019] [Figure 1] 1 is a schematic cross-sectional view of a film according to one embodiment. [Figure 2] FIG. 2 is a schematic cross-sectional view of a film according to another embodiment. [Figure 3] FIG. 2 is a schematic cross-sectional view of another embodiment of a film that is an overlaminate film. [Figure 4] FIG. 2 is a schematic cross-sectional view of another embodiment of a film that is a graphic laminate. [Figure 5A] 1 is a photograph of the film of Example 1, observed from the vertical direction of the surface layer side under a fluorescent lamp. [Figure 5B] 1 is a photograph of the film of Comparative Example 1, taken under fluorescent light from the vertical direction of the surface layer side. [Figure 6] Photographs of the films of Example 1 (left) and Comparative Example 1 (right) observed under fluorescent light at a viewing angle of about 30 degrees from the vertical direction of the surface layer side. [Figure 7A] This shows the visible light reflectance of the film of Example 1 at reflection angles of -80 degrees to 80 degrees when the incident light angle is 60 degrees. [Figure 7B] This shows the visible light reflectance of the film of Comparative Example 1 at reflection angles of -80 degrees to 80 degrees when the incident light angle is 60 degrees. DETAILED DESCRIPTION OF THE INVENTION

[0020] Representative embodiments of the present invention will be described in more detail below for the purpose of illustrating them, but the present invention is not limited to these embodiments.

[0021] In this disclosure, "transparent" means that a material or article has a total light transmittance of about 85% or more in the wavelength range of 400 to 700 nm, "semi-transparent" means that a material or article has a total light transmittance of about 20% or more but less than about 85% in the wavelength range of 400 to 700 nm, and "opaque" means that a material or article has a total light transmittance of less than about 20% in the wavelength range of 400 to 700 nm. 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. Areas of the low-gloss layer that are not covered by the gloss print pattern have a matte appearance, and the surface gloss of the gloss print pattern area is higher than the surface gloss 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 gloss caused by the cooperation of the uncovered areas of the low-gloss layer and the gloss print pattern is visually perceived by an observer as texture (irregularities). In this way, a visible texture can be formed on the film even on a low-gloss surface.

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

[0024] In another embodiment, the surface layer is formed by forming a glossy print pattern on the low-gloss layer and then embossing the glossy print pattern.

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

[0026] In one embodiment, the low-gloss layer comprises a resin-containing binder, 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 ranges, the low-gloss layer can impart a low-gloss appearance to the film, and the low-gloss appearance can be maintained even after stretching. The film of this embodiment can be stretched to conform to the shape of the article to which it is attached. Furthermore, the low-gloss appearance can be maintained even when the low-gloss layer is provided with an uneven surface by embossing or other processes. The film of this embodiment can be provided with an uneven surface having a pattern such as wood grain, sand grain, cloth grain, or leather (cow, pig, etc.). Furthermore, the low-gloss appearance can be maintained even when a glossy printed pattern is provided on the low-gloss layer. The film of this embodiment can be provided with a printed pattern having a pattern such as wood grain, sand grain, cloth grain, leather (cow, pig, etc.), stone grain, concrete, or rust (a pattern resembling an oxide film formed on a metal surface).

[0027] A schematic cross-sectional view of a film according to one embodiment is shown in Figure 1. The film 100 in Figure 1 includes a surface layer 110 and optional components, such as a substrate layer 140 and an adhesive layer 150. The film 100 may be formed solely from the surface layer 110, i.e., the surface layer 110 itself may be a film. The surface layer 110 is embossed and includes a low-gloss layer 120 and a gloss print 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 approximately 4 µm or more and approximately 20 µm or less, and nanosilica particles 126.

[0028] Various resins can be used as the resin contained in the binder. In one embodiment, the binder includes a urethane resin. Various known urethane resins can be used as the urethane resin. The urethane resin can be obtained by drying or curing a urethane resin composition. The urethane resin composition may be aqueous or non-aqueous. Advantageously, the urethane resin is a cured product of a two-component urethane resin composition. Two-component urethane resin compositions are generally non-aqueous urethane resin compositions. By using a two-component urethane resin composition, other components of the low-gloss layer, such as resin beads, particularly urethane resin beads and nanosilica particles, form chemical bonds with the urethane resin during formation of the low-gloss layer, thereby preventing or suppressing the shedding of these particles and the bleeding of components from the low-gloss layer.

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

[0030] Examples of polyols that can be used include polyester polyols such as polycaprolactone diol and polycaprolactone triol; polycarbonate polyols such as cyclohexane dimethanol carbonate and 1,6-hexanediol carbonate; and combinations thereof. These polyols can impart transparency, weather resistance, strength, chemical resistance, and the like to the low-gloss layer. In particular, polycarbonate polyols can form low-gloss layers with high transparency and chemical resistance. From the viewpoint of imparting extensibility to the low-gloss layer without forming an excessively crosslinked structure, it is desirable for the polyol to be 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., as well as polymers (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 excessively crosslinked structure, the polyfunctional isocyanate is preferably 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); 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, and isomeric mixtures of these tolylene diisocyanates. aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, and 2,2'-diphenylmethane diisocyanate, as well as isomeric mixtures of these diphenylmethane diisocyanates (MDI); and araliphatic diisocyanates such as 1,3- or 1,4-xylylene diisocyanate or mixtures thereof (XDI), and 1,3- or 1,4-tetramethylxylylene diisocyanate or mixtures thereof (TMXDI).

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

[0034] The catalyst may be one generally used in the formation of urethane resins, such as di-n-butyltin dilaurate, zinc naphthenate, zinc octenate, triethylenediamine, etc. The amount of catalyst used may generally be about 0.005 parts by mass or more, or about 0.01 parts by mass or more, and 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 including the cellulose ester in the binder, the viscosity of the binder can be increased during the drying process, and the surface fluidity can be reduced, making it possible to uniformly apply the binder precursor containing the resin beads. Examples of the cellulose ester include cellulose acetate propionate and cellulose acetate butyrate.

[0036] Considering the solubility in a 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, and 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 temperature of use, the glass transition temperature (Tg) of the cellulose ester can generally be about 85° C. or higher, about 96° C. or higher, or about 101° C. or higher, and about 190° C. or lower, about 180° C. or lower, or about 160° C. or lower. 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 weight or more, about 10 parts by weight or more, or about 15 parts by weight or more, and about 35 parts by weight or less, about 30 parts by weight or less, or about 25 parts by weight or less, based on 100 parts by weight of the binder. By setting the amount of cellulose ester in the above range, the resin beads can be more uniformly dispersed in the low-gloss layer, thereby imparting a uniform low-gloss appearance to the film.

[0039] Various resin beads can be used as the resin beads. The resin beads 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. Urethane resin beads have good affinity with binders containing resins, particularly binders containing urethane resins, and therefore have high adhesion to the binder. As a result, detachment of the urethane resin beads from the binder can be suppressed when the film is stretched or deformed. Crosslinked polyurethane particles obtained by suspension polymerization, seed polymerization, emulsion polymerization, or the like can be used as the urethane resin beads. Urethane resin beads have excellent flexibility, toughness, scratch resistance, and the like, and can impart these properties to the low-gloss layer.

[0041] The average particle size of the resin beads is about 4 μm or more and about 20 μm or less. The average particle size of the resin beads may be about 6 μm or more, or about 10 μm or more, or about 10 μm or less, or about 15 μm or less. If the average particle size of the resin beads is less than about 4 μm, whitening of the film surface due to light scattering is likely to occur. If the average particle size of the resin beads is more than about 20 μm, gloss is likely to occur, making it difficult to achieve low gloss. Resin beads having an average particle size within the above range can appropriately scatter light incident on the low gloss layer, thereby imparting low brightness, i.e., low gloss with little whiteness, to the low gloss layer. The average particle size of the resin beads is the particle size at 50% of the cumulative volume measured using a laser diffraction particle size distribution analyzer.

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

[0043] The presence of nanosilica particles in the binder further reduces the glossiness of the low-gloss layer, and also suppresses the change in low glossiness that tends to occur when the film is stretched using resin beads alone, effectively preventing whitening of the film.

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

[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, the use of small-sized nanosilica particles allows the nanosilica particles to be highly dispersed in the low-gloss layer. Even when the film is stretched, the small nanosilica particles remain dispersed in the stretched area, thereby suppressing loss of low gloss and effectively preventing film whitening. Nanosilica particles adjacent to resin beads may also function as a type of physical crosslinking point between the resin beads, particularly urethane resin beads, and the binder. The presence of nanosilica particles that can act as such physical crosslinking points prevents the resin beads from falling off when the film is stretched, effectively preventing film whitening. The average particle size of the nanosilica particles is a conversion value based on the specific surface area measured using the BET method.

[0046] In some embodiments, the nanosilica particles may be present in the low-gloss layer in an amount of about 5 parts by weight or more, about 10 parts by weight or more, or about 20 parts by weight or more, and about 120 parts by weight or less, about 110 parts by weight or less, or about 100 parts by weight or less, based on 100 parts by weight of the binder. By incorporating the nanosilica particles in the above range, the gloss of the low-gloss layer can be further reduced. By incorporating the nanosilica particles in the above range, the low-gloss appearance can be maintained even when the film is stretched, and an increase in brightness, i.e., whitening, can be prevented or suppressed, for example, when stretched 150%. By incorporating the nanosilica particles in the above range, excellent scratch resistance can be imparted to the low-gloss layer.

[0047] The low-gloss layer may further contain a silicone-modified polymer having a functional group reactive with an isocyanate or hydroxyl group. When finger grease adheres to a low-gloss surface, traces are easily observed. By incorporating a silicone-modified polymer having a functional group reactive with an isocyanate or hydroxyl group into the low-gloss layer, the fingerprint resistance of the low-gloss layer can be improved. The silicone-modified polymer can also reduce the coefficient of friction of the low-gloss layer, thereby imparting 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 or isocyanate group of the urethane resin or urethane resin beads contained in the binder, thereby bonding the silicone-modified polymer to the urethane resin or urethane resin beads. In this embodiment, bleeding of the silicone-modified polymer from the low-gloss layer can be prevented or suppressed.

[0048] Examples of silicone-modified polymers having functional groups reactive with isocyanate or hydroxyl groups include polyether-modified silicones, polyester-modified silicones, aralkyl-modified silicones, acrylic-modified silicones, silicone-modified polyacrylates, and urethane-modified silicones. Examples of functional groups reactive with isocyanate or hydroxyl groups of silicone-modified polymers include hydroxyl groups, amino groups having active hydrogen, isocyanate groups, epoxy groups, and acid anhydride groups. Because of their particularly excellent fingerprint resistance, the silicone-modified polymer is advantageously a silicone-modified polyacrylate. It is desirable for the silicone-modified polymer to have hydroxyl groups or isocyanate groups, particularly hydroxyl groups, which are highly reactive with isocyanate or hydroxyl groups.

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

[0050] The low-gloss layer may contain, as other optional components, fillers other than resin beads and nanosilica particles, and additives such as ultraviolet absorbers, light stabilizers, heat stabilizers, dispersants, plasticizers, flow improvers, leveling agents, flame retardants, etc. The individual and total amounts of these additives added 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 a flake filler 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 flake fillers include expandable graphite, aluminum foil powder pigments, glass flake powder pigments, and resin film foil powder pigments. The average particle size of the flake filler is the cumulative volume 50% particle size measured using a laser diffraction particle size distribution analyzer. The thickness of the flake filler may be about 0.5 μm to about 30 μm. The aspect ratio of the flake 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 for the binder. The cellulose ester can impart quick-drying properties, dry-to-touch properties, flow properties, leveling properties, etc. to the coating composition. The cellulose ester can also be used to adjust the viscosity of the coating composition.

[0054] The coating composition may further contain a silicone-modified polymer having a functional group capable of reacting with the above-mentioned isocyanate or hydroxyl group. The isocyanate or hydroxyl group of the silicone-modified polymer reacts with the hydroxyl or isocyanate group of the urethane resin composition or urethane resin beads, thereby bonding the silicone-modified polymer to the urethane resin or urethane resin beads. This prevents or suppresses bleeding of the silicone-modified polymer from the low-gloss layer. When using a silicone-modified polymer, it is advantageous from the standpoint of reactivity that the urethane resin composition be a two-component urethane resin composition.

[0055] The formulation of the coating composition is the same as that of the low-gloss layer containing the binder, resin beads, and nanosilica particles. The 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 calculated by converting 100 parts by mass of the binder precursor into 100 parts by mass.

[0056] To improve workability, coatability, etc., the coating composition may further contain solvents such as ketones such as methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, etc.; 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), dipropylene glycol monomethyl ether acetate, etc. The amount of 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 using a Brookfield viscometer with an appropriate spindle at 60 rpm.

[0058] The low gloss layer can be formed by coating the coating composition on the substrate by knife coating, bar coating, blade coating, doctor coating, roll coating, cast coating, or the like, and then heating to about 80°C to about 150°C as needed to dry and / or cure the composition.

[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. In this disclosure, the thickness of the low-gloss layer refers to the thickness of the thickest part, i.e., the maximum thickness.

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

[0061] The gloss printing pattern is used to provide a region on the low-gloss layer that is relatively glossier than the low-gloss layer, thereby imparting a visible texture to the film due to the difference in gloss from 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 glare due to changes in viewing angle, it is desirable that the gloss printing pattern be formed to a thickness that does not completely cover the unevenness formed by embossing.

[0062] In one embodiment, the gloss printing pattern is a pattern printed by a printing plate. Examples of printing by a printing plate include gravure printing, offset printing, letterpress printing, and screen printing. From the viewpoint of reducing the particle size of the printed gloss ink 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 ruling of the gravure plate is preferably 60 lpi or more, 80 lpi or more, or 100 lpi or more, 350 lpi or less, 200 lpi or less, or 175 lpi or less, from the viewpoint of reducing the particle size of the printed gloss ink and controlling the thickness of the gloss print pattern. The ruling of the gravure plate correlates with the printing volume of the gloss ink. By setting the ruling of the gravure plate to 100 lpi or more, a good balance can be achieved between the printing resolution and the printing volume of the ink. On the other hand, by setting the ruling of the gravure plate to 175 lpi or less, high-resolution printing can be applied, even with high solids ink.

[0064] The gloss ink may be a solvent-based, water-based, or UV-curable ink, with solvent-based ink being preferred from the standpoint of control of the amount of gloss ink printed and ease of use. The gloss ink may be transparent, translucent, or opaque, and may be colorless or colored.

[0065] In one embodiment, the gloss print pattern includes a gloss ink selected from the group consisting of acrylic ink, urethane ink, and vinyl chloride-vinyl acetate ink. Acrylic ink, urethane ink, and vinyl chloride-vinyl acetate ink are advantageously used from the viewpoint of versatility. In particular, acrylic ink and urethane ink are also favorable 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.), anti-fouling agents, weathering stabilizers, etc. for the purpose of reducing gloss or for other purposes, provided that it can form a printed pattern that is glossier than the low-gloss layer.

[0067] The thickness of the gloss print pattern is desirably thin enough to allow the presence of the gloss print pattern to be recognized from various viewing angles, but not to excessively increase the surface glossiness. Generally, when a solvent-based ink is used, the thickness 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 print pattern may be continuous or discontinuous. The gloss print pattern may be arranged to cover the entire surface of the film, or may be arranged to cover a portion or multiple portions of the film. Examples of print patterns include wood grain, stone grain, logos, pictures, letters, symbols, etc.

[0069] The surface layer is embossed, thereby providing the film with an embossed surface. Embossing can impart a tactile texture to the embossed surface of the film. Embossing can be performed under known conditions using an embossing roll having various designs or patterns. The embossing may be deeper than the thickness of the surface layer; for example, other layers, such as a substrate layer, below 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 making the maximum height Rz of the embossing about 40 μm or more, good tactility can be imparted, and by making it about 50 μm or more, clear tactility 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 making the maximum height Rz of the embossing about 100 μm or less, the embossed surface of the film can be easily cleaned.

[0071] In one embodiment, embossing can be performed after the formation of the low-gloss layer and the gloss print pattern. In this embodiment, both the low-gloss layer and the gloss print pattern are embossed. This allows the gloss print pattern to follow the uneven shape formed by embossing, effectively suppressing glare caused by changes in viewing angle.

[0072] In one embodiment, at least a part of the glossy print pattern is distributed on the bottom of the embossed surface layer, which can effectively suppress glare caused by changes in viewing angle.

[0073] The gloss print pattern and the embossed pattern may be synchronized, or may be partially or entirely mismatched. In one embodiment, the film includes a portion where the gloss print pattern and the embossed pattern are not synchronized. In this embodiment, the tactile texture formed by the embossing and the visible texture formed by the gloss print pattern can be formed separately and independently, thereby allowing for the expression of highly complex designs. For example, the tactile texture of a cross section of wood can be formed by the embossing, while the visible texture of a wood grain pattern can be formed by the gloss print pattern.

[0074] In one embodiment, the surface layer has the following characteristics (1) and (2). (1) The 85° surface gloss is approximately 5.0 GU or less on an in-plane average basis. (2) The Δ85° surface glossiness, defined as the difference between the maximum value of the 85° surface glossiness and the average value of the 85° surface glossiness, is approximately 0.2 to approximately 2.5 (= maximum value of the 85° surface glossiness - average value of the 85° surface glossiness). By keeping the 85-degree surface gloss at an average value of approximately 5.0 GU or less and the Δ85-degree surface gloss at approximately 2.5 or less, it is possible to suppress glare caused by changes in the viewing angle.By keeping the Δ85-degree surface gloss at approximately 0.2 or more, it is possible to ensure the visibility of the gloss print pattern and to express a delicate, three-dimensional design.

[0075] The in-plane average value of the 85-degree surface gloss 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. An in-plane average value of about 4.5 GU or less can achieve a better low-gloss appearance and improve designability, and an in-plane average value of about 3.5 GU or less can further improve designability. The in-plane average value of the 85-degree surface gloss 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° surface gloss 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° surface gloss to about 0.22 to about 2.3, it is possible to achieve a moderately low-gloss appearance and a good design through gloss printing. By setting the Δ85° surface gloss to about 0.25 to about 2.0, it is possible to achieve a good low-gloss appearance and further enhance the design through gloss printing.

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

[0078] The in-plane average value of 85-degree surface glossiness is the average value of measurements taken at a total of five points: one point in the center of a sample measuring 200mm to 400mm vertically and 200mm to 400mm horizontally, and the center of each of the four areas divided through the center of the sample (divided into two vertically and two horizontally). At each measurement point, the 85-degree surface glossiness is measured using the following procedure. (1) Set a reference line in any direction that passes through the measurement point. (2) Measure the surface gloss at an angle of 85 degrees from the set reference line in six directions: 0 degrees, 30 degrees, 60 degrees, 90 degrees, 120 degrees, and 150 degrees. (3) The maximum value of the six measured directions is adopted as the value of that measurement point.

[0079] The maximum in-plane value of 85-degree surface gloss is measured by dividing a sample, measuring 200mm to 400mm vertically and 200mm to 400mm horizontally, into four regions (two vertically and two horizontally) passing through the center of the sample.The first measurement point is the location with the highest visual gloss, and the 85-degree surface gloss is measured using the following procedure. (1) Set a first reference line in any direction that passes through the first measurement point. (2) Measure the surface gloss at 85 degrees 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) The maximum value of the measured values ​​in the six directions is adopted as the value of the first measurement point. (4) A second reference line is set through the first measurement point in the direction of the angle at which the maximum value is measured, and a third reference line is set through the first measurement point in a direction perpendicular to the second reference line. (5) Two points on the second reference line 20 mm away from the first measurement point and two points on the third reference line 5 mm away from the first measurement point are designated as the second measurement points, for a total of four points, and the surface gloss is measured at an angle of 85 degrees in a direction parallel to the second reference line. (6) The maximum value of the values ​​measured at the first and second measurement points (maximum value of 5 points / area x 4 areas = 20 points) is adopted 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. A surface roughness Ra of about 3.5 μm or more of the embossed surface of the film can provide the film with good tactile feel. 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 making the maximum height Rz of the embossed surface of the film about 40 μm or more, good tactility can be imparted, and by making it about 50 μm or more, clear tactility 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 making the maximum height Rz of the embossed surface of the film about 100 μm or less, good cleanability can be imparted to the film.

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

[0083] In one embodiment, the surface layer has an in-plane average surface gloss of 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 surface gloss 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 surface gloss 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. When the in-plane average surface gloss of the surface layer is within the above ranges, reflection of light incident on the film at various angles is suppressed, allowing the decoration of the film or a decorative surface covered with the film (when the film is used as an overlaminate film) to be recognized from a wide range of viewing angles.

[0085] The in-plane average surface gloss values ​​at measurement angles of 20 degrees and 60 degrees are determined by the same procedure as described above for the in-plane average surface gloss value at 85 degrees, except that the measurement angles are 20 degrees and 60 degrees, respectively.

[0086] The film may further include a substrate layer as a substrate. The substrate layer may be extensible. The substrate layer may be made of 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.

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

[0088] The substrate layer may have a printed layer on one or both sides. The printed layer imparts design to the film. The printed layer can be formed using a printing technique such as inkjet printing, gravure printing, electrostatic printing, screen printing, or offset printing.

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

[0090] The thickness of the printed layer may vary, and 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 10 μm or less, or about 5 μm or less. When a 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. In this disclosure, the thickness of the printed layer refers to the thickness of the thickest part, i.e., the maximum thickness.

[0091] The printing layer may be continuous or discontinuous. The printing layer may be disposed so as to correspond to the entire surface of the base layer, or to correspond to a portion or a plurality of portions. The printing layer may cover the entire surface of the base layer. In one embodiment, the printing layer includes a printed area and a non-printed area. Examples of designs of the printing layer include wood grain, stone grain, logos, patterns, letters, symbols, etc.

[0092] The design of the print layer may or may not be synchronized with the gloss print pattern, but if it is synchronized, it is preferable in that it makes it easier to reproduce a design that is closer to the real thing.

[0093] In one embodiment, the printing layer can be printed using a printing plate. Examples of printing using a printing plate include gravure printing, offset printing, letterpress printing, and screen printing. When the design of the printing layer and the gloss print pattern are printed in synchronization, gravure printing and letterpress printing are preferred, and gravure printing is more preferred, from the viewpoint of controlling the printing plate.

[0094] When performing gravure printing in which the design of the printing layer and the gloss printing pattern are synchronized, it is desirable that the line count of the gravure plate be 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 standpoint of the particle size of the gloss ink of the gloss printing pattern.

[0095] In one embodiment, the substrate layer comprises a transparent polyvinyl chloride resin layer and a colored polyvinyl chloride resin layer. In the film of this embodiment, the transparent polyvinyl chloride resin layer supports or protects the colored polyvinyl chloride resin layer, thereby imparting durability to the decorative properties of the film. The film of this embodiment is suitable for use in applications such as being attached to the interior or exterior materials of buildings or vehicles. FIG. 2 shows a schematic cross-sectional view of film 100 of this embodiment. Film 100 comprises substrate layer 140 and substrate layer 142. The remaining configuration of film 100 is as described in FIG. 1.

[0096] The thickness of the substrate 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 substrate layer has two or more layers, the above thickness refers to the total thickness of the substrate layers.

[0097] In some embodiments, the tensile elongation of the base 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 of the base layer is a value calculated by preparing a sample having a width of 25 mm and a length of 150 mm, stretching the sample until it breaks using a tensile tester at a temperature of 20°C, a stretching speed of 300 mm / min, and a chuck gap of 100 mm, as follows: [chuck gap at break (mm) - chuck gap before stretching (mm) (= 100 mm)] / chuck gap before stretching (mm) (= 100 mm) × 100 (%).

[0098] The substrate layer may have an adhesive layer on the side opposite to the surface layer. The adhesive layer may be a commonly used solvent-based, emulsion-based, pressure-sensitive, heat-sensitive, heat-curable, or UV-curable adhesive, such as an acrylic-based, polyolefin-based, polyurethane-based, polyester-based, or rubber-based adhesive. The thickness of the adhesive layer may 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 applied to 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 release-treated surface using 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 produced by a method including forming a low-gloss layer on a substrate, forming a gloss print pattern on the low-gloss layer so as to partially cover the low-gloss layer, and embossing the gloss print pattern. The substrate may be a releasable liner or the above-mentioned substrate layer. When a releasable liner is used as the substrate, the liner can be removed after the above process to obtain a film consisting of only the surface layer.

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

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

[0103] In one embodiment, the low-gloss layer comprises 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. The low-gloss layer contains resin beads having an average particle size in the above range and nanosilica particles, imparting a low-gloss appearance to the overlaminate film. This embodiment provides a design appearance with a high contrast ratio, whereby visible light reflection in dark areas is suppressed. In other words, the dark areas appear darker, making the difference between light and dark more pronounced, providing a design appearance with a unique and vivid visual effect.

[0104] In one embodiment, the overlaminate film is stretchable. In this embodiment, the overlaminate film can be stretched to conform to the shape of the article to which it is attached. In some embodiments, the overlaminate film 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 Figure 3. The overlaminate film 200 in Figure 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 base film may be colored or colorless. The transparent resin base film may have a substantially smooth surface, or may have a structured surface that can be formed by surface processing such as embossing. By making the appearance or shape of the transparent resin base film as described above, a variety of decorative properties can be imparted to the overlaminate film.

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

[0109] The thickness of the transparent resin base 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 of the transparent resin base 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 of the transparent resin base film is a value calculated by preparing a sample having a width of 25 mm and a length of 150 mm, stretching the sample to break using a tensile tester at a temperature of 20°C, a stretching speed of 300 mm / min, and a chuck spacing of 100 mm, as follows: [chuck spacing at break (mm) - chuck spacing before stretching (mm) (= 100 mm)] / chuck spacing before stretching (mm) (= 100 mm) × 100 (%).

[0111] The transparent adhesive layer can be made of commonly used solvent-based, emulsion-based, pressure-sensitive, heat-sensitive, heat-curable, or UV-curable adhesives, such as acrylic, polyolefin-based, polyurethane-based, polyester-based, or rubber-based adhesives. 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 transparent adhesive layer has a total light transmittance in the wavelength range of 400 to 700 nm of about 85% or more, about 90% or more, or about 95% or more.

[0113] A liner may be applied to 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 release-treated surface using 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] One embodiment of the graphic laminate includes a resin-based film having a first surface and a second surface opposite the first surface, a graphic film including a print layer disposed on the first surface and an adhesive layer disposed on the second surface, and an overlaminate film of the present disclosure covering the print layer of the graphic film. By covering the print 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 print layer of the graphic film.

[0117] A schematic cross-sectional view of one embodiment of a graphic laminate is shown in Figure 4. The graphic laminate 400 of Figure 4 includes a graphic film 300 including a resin base film 340, a print layer 310, and an adhesive layer 350, and an overlaminate film 200 that covers the print layer 310 of the graphic film 300. The overlaminate film 200 is laminated onto the print layer 310 of the graphic film via a transparent adhesive layer 250. Figure 4 also shows a liner 360 that protects the adhesive layer 350.

[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 may have a structured surface that can be formed by surface processing such as embossing. By adjusting the appearance or shape of the resin base film as described above, a variety of decorative properties 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 transparent polyvinyl chloride resin layer supports or protects the colored polyvinyl chloride resin layer, thereby imparting durability to the graphic laminate. The graphic laminate of this embodiment is suitable for use in applications such as being 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 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 of the resin-based film is a value calculated by preparing a sample having a width of 25 mm and a length of 150 mm, stretching the sample to break using a tensile tester at a temperature of 20°C, a stretching speed of 300 mm / min, and a chuck spacing of 100 mm, as follows: [chuck spacing at break (mm) - chuck spacing before stretching (mm) (= 100 mm)] / chuck spacing before stretching (mm) (= 100 mm) × 100 (%).

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

[0124] The printing ink may be a solvent-based ink, a water-based ink or a UV-curable ink. The printing ink may be transparent, translucent or opaque, and may be colorless or colored.

[0125] The thickness of the printed layer may vary, and 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 10 μm or less, or about 5 μm or less. When a 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. In this disclosure, the thickness of the printed layer refers to the thickness of the thickest part, i.e., the maximum thickness.

[0126] The printing layer may be continuous or discontinuous. The printing layer may be arranged so as to correspond to the entire surface of the resin base film, or may be arranged so as to correspond to a portion or a plurality of portions. The printing layer may cover the entire surface of the resin base film. In one embodiment, the printing layer includes a printed area and a non-printed area. Examples of designs of the printing layer include wood grain, stone grain, logos, patterns, letters, symbols, etc.

[0127] In one embodiment, the printed layer is an inkjet printed layer. Inkjet printing allows for short-run, on-demand manufacturing.

[0128] The adhesive layer disposed on the second surface of the resin-based film can be a solvent-based, emulsion-based, pressure-sensitive, heat-sensitive, heat-curable, or UV-curable adhesive, commonly used in the form of acrylic, polyolefin, polyurethane, polyester, rubber, etc. 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 presented by the print layer and, if necessary, the resin-based film.

[0130] A liner may be applied to 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 release-treated surface using 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 interior materials such as walls, stairs, ceilings, pillars, and partitions of buildings such as buildings, condominiums, and houses, or as exterior materials such as exterior walls. It can also be used as interior or exterior materials for various vehicles such as railway cars, ships, airplanes, and automobiles including two-wheeled and four-wheeled vehicles. Furthermore, it can also be used as a covering material for various items such as road signs, signs, furniture, and electrical appliances. [Example]

[0132] The following examples illustrate specific embodiments of the present disclosure, but the present invention is not limited thereto. All parts and percentages are by weight unless otherwise specified. Numerical values ​​inherently contain errors resulting from measurement principles and measuring devices. Numerical values ​​are presented to the nearest significant digit with ordinary rounding applied.

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

[0134] [Table 1]

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

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

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

[0138] The surface gloss of the PET film was 139GU / 128GU / 101GU (20° / 60° / 85°) when JS1000A (white PVC film) was water-laminated on the opposite side of the PET film.

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

[0140] Preparation of Low Gloss Layer Coating Composition A mixture of 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 was added. 59.5 g of 1-methoxy-2-propyl acetate was added to the mixture to adjust the solids content to 32.51% by mass, and the mixture was stirred for 3.5 minutes using a THINKY AR-250 centrifugal mixer (Thinky Corporation, Chiyoda-ku, Tokyo, Japan) to obtain a low-gloss layer coating composition.

[0141] Formation of a low gloss layer The transparent polyvinyl chloride film was heat-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 to heat cure, forming a low-gloss layer with a dry thickness of approximately 12 μm.

[0142] Example 1 The PET film laminated to a transparent polyvinyl chloride film with a low-gloss layer was peeled off. A gloss print pattern was formed on the low-gloss layer of the transparent polyvinyl chloride film by gravure printing using a wood grain A (133-line mixed pattern of straight and cross grain) gravure plate and gloss ink 1. The colored polyvinyl chloride film and the transparent polyvinyl chloride film were then placed so that the colored polyvinyl chloride film was in contact with the transparent polyvinyl chloride film, and the colored polyvinyl chloride film and the transparent polyvinyl chloride film were thermally laminated together so that the pattern A (wood grain) embossing roll came into contact with the gloss print pattern and low-gloss layer, resulting in a graphic film. Thermal lamination was performed under the following conditions. IR temperature: 600℃ Nip pressure: 0.2MPa Embossing roll temperature: 60℃ Take-off roll temperature: 170℃ Heat drum temperature: 130℃

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

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

[0145] Example 4 A graphic film was obtained in the same manner 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 manner as in Example 1, except that a matte print pattern identical to the gloss print 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 manner as in Example 1, except that the embossing roll was changed to pattern C (matt finish).

[0148] Comparative Example 3 A graphic film was obtained in the same manner as in Example 1, except that no glossy print pattern was formed.

[0149] Table 2 shows the manufacturing conditions and structures of the graphic films of Examples 1 to 4 and Comparative Examples 1 to 3.

[0150] [Table 2]

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

[0152] The in-plane average value of 85-degree surface glossiness was the average of the values ​​measured at a single point in the center of a sample measuring approximately 300 mm in length and 400 mm in width, and at the center of each of the four areas (divided into two vertically and two horizontally) passing through the center of the sample, for a total of five points. The 85-degree surface glossiness was measured at each measurement point using the following procedure. (1) Set a reference line in any direction that passes through the measurement point. (2) Measure the surface gloss at an angle of 85 degrees from the set reference line in six directions: 0 degrees, 30 degrees, 60 degrees, 90 degrees, 120 degrees, and 150 degrees. (3) The maximum value of the six measured directions is adopted as the value of that measurement point.

[0153] The maximum in-plane 85-degree surface gloss was measured using the following procedure, with the first measurement point being the location with the highest visual gloss for each of the four regions (two vertically and two horizontally) that were divided through the center of a sample measuring approximately 300 mm in length and 400 mm in width. (1) Set a first reference line in any direction that passes through the first measurement point. (2) Measure the surface gloss at 85 degrees 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) The maximum value of the measured values ​​in the six directions is adopted as the value of the first measurement point. (4) A second reference line is set through the first measurement point in the direction of the angle at which the maximum value is measured, and a third reference line is set through the first measurement point in a direction perpendicular to the second reference line. (5) Two points on the second reference line 20 mm away from the first measurement point and two points on the third reference line 5 mm away from the first measurement point are designated as the second measurement points, for a total of four points, and the surface gloss is measured at an angle of 85 degrees in a direction parallel to the second reference line. (6) The maximum value of the values ​​measured at the first and second measurement points (maximum value of 5 points / area x 4 areas = 20 points) was adopted as the in-plane maximum value.

[0154] Δ85 degree surface gloss The Δ85° surface gloss was determined by subtracting the in-plane average value of 85° surface gloss from the in-plane maximum value. If the Δ85° surface gloss is approximately 2.5GU or less, glare caused by changes in viewing angle can be suppressed. If the Δ85° surface gloss is 0.2GU or more, the pattern formed by the gloss printing pattern can be seen, and a delicate, 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, respectively, measured in accordance with JIS B 0601:2001, Line Roughness.

[0156] Slope from the approximate line of visible light reflectance The slope of the approximation line for the visible light reflectance of graphic films was measured using a GC5000 spectrogonal color difference meter (Nippon Denshoku Industries Co., Ltd., Bunkyo-ku, Tokyo, Japan). Specifically, visible light reflectance was measured at 5-degree intervals from a reflection angle of -80° to 80° when the incident light was 60°. The average reflectance from 400 to 800 nm at each angle was used to determine the visible light reflectance at that angle. Visible light reflectance was plotted over a reflection angle range of -80° to 80°, and the slope was calculated from the visible light reflectance at two adjacent measurement angles. A maximum slope of 3.5% ( / 5°) or greater indicates that a slight change in viewing angle from a certain viewing angle results in a large change in visible light reflectance, i.e., glare is observed at angles around that viewing angle.

[0157] exterior Those with low gloss overall and three-dimensional expression of the wood grain pattern were rated as good, and those with partial glare of gloss or no visible expression of the wood grain pattern were rated as poor.

[0158] tactile A graphic film approximately 10cm square with an embossed surface was placed on a flat surface, and the surface was evaluated by rubbing it with the pads of three or more fingers, including the index, middle, and ring fingers, around the center of the surface, moving back and forth twice over an interval of approximately 5cm in about one second, with a load of approximately 200g. If the embossed pattern had a direction (such as wood grain), the evaluation was made in the direction perpendicular to that direction. A film with a clearly perceptible uneven or rough surface was rated as "good," one with a perceptible uneven or rough surface was rated as "passable," and one with little perceptible uneven or rough surface was 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 observed under a fluorescent lamp from a vertical direction on the surface layer side, and FIG. 5B is a photograph of the film of Comparative Example 1 observed under a fluorescent lamp from a 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 fluorescent light at a viewing angle of about 30 degrees from the vertical direction of the surface layer side.

[0163] Figure 7A shows the visible light reflectance of the film of Example 1 at a reflection angle of -80 degrees to 80 degrees when the incident light angle is 60 degrees, and Figure 7B shows the visible light reflectance of the film of Comparative Example 1 at a reflection angle of -80 degrees to 80 degrees when the incident light angle is 60 degrees. While no peak is observed in Example 1, a peak is observed at a reflection angle of 60 degrees in Comparative Example 1. This peak indicates strong glare when observed at a reflection angle of 60 degrees. Therefore, the film of Example 1 does not exhibit glare at any viewing angle, achieving an overall stable, low-gloss appearance. Note that, because measurements cannot be obtained at -60 degrees, where the light source and detector angles coincide, both Figures 7A and 7B show a discontinuity at a reflection angle of -60 degrees.

[0164] It will be apparent to those skilled in the art that various modifications and variations can be made to this invention without departing from the scope and spirit of the invention. Some embodiments of the present invention are described below. [Aspect 1] A film having an embossed surface layer, the surface layer includes a low-gloss layer and a gloss printing pattern that partially covers the low-gloss layer; (1) The surface layer has an in-plane average 85-degree surface gloss of 5.0 GU or less, (2) The Δ85° surface glossiness (=maximum value of 85° surface glossiness−average value of 85° surface glossiness) defined as the difference between the maximum value of the 85° surface glossiness and the average value of the 85° 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. film. [Aspect 2] 2. The film of embodiment 1, wherein the embossed surface of the film has a maximum height Rz of 30 μm or more. [Aspect 3] 3. The film of any one of embodiments 1 or 2, wherein both the low gloss layer and the gloss printed pattern are embossed. [Aspect 4] A film according to any one of Aspects 1 to 3, wherein at least a portion of the gloss print pattern is distributed on a bottom portion of the embossed surface layer. [Aspect 5] The film according to any one of embodiments 1 to 4, comprising a portion where the gloss print pattern and the embossing pattern are not synchronized. [Aspect 6] Aspect 6. The film of any one of aspects 1 to 5, wherein the gloss print pattern comprises a gloss ink selected from the group consisting of an acrylic ink and a urethane ink. [Aspect 7] The film according to any one of aspects 1 to 6, wherein the gloss print pattern is a print pattern produced by a printing plate. [Aspect 8] The film of any one of aspects 1 to 7, wherein the low-gloss layer comprises a binder containing a resin, resin beads having an average particle size of 4 μm or more and 20 μm or less, and nanosilica particles. [Aspect 9] 9. The film of embodiment 8, wherein the nanosilica particles have an average particle size of 10 nm or more and 100 nm or less. [Aspect 10] 10. The film of any one of claims 8 or 9, wherein the low-gloss layer comprises 5 parts by weight or more and 120 parts by weight or less of the nanosilica particles, based on 100 parts by weight of the binder. [Aspect 11] Aspect 11. The film according to any one of aspects 8 to 10, wherein the low-gloss layer comprises 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. [Aspect 12] 12. The film of any one of aspects 8 to 11, wherein the binder comprises a urethane resin. [Aspect 13] 13. The film of embodiment 12, wherein the urethane resin comprises a cured product of a two-component urethane resin composition. [Aspect 14] The film according to any one of aspects 8 to 13, wherein the resin beads are urethane resin beads. [Aspect 15] 15. The film of any one of embodiments 8 to 14, wherein the binder further comprises a cellulose ester. [Aspect 16] A film having an embossed surface layer, the surface layer includes a low-gloss layer and a gloss printing pattern that partially covers the low-gloss layer; A film, wherein the surface layer is formed by forming the gloss print pattern on the low-gloss layer, and then embossing the gloss print pattern. [Aspect 17] 17. The film of any one of embodiments 1 to 16, wherein the film is a graphic film. [Aspect 18] 17. The film of any one of embodiments 1 to 16, wherein the film is an overlaminate film that is applied to a decorative surface. [Aspect 19] forming a low gloss layer on a substrate; forming a gloss print pattern on the low-gloss layer so as to partially cover the low-gloss layer; embossing the gloss print pattern; A method for producing a film, comprising: [Explanation of symbols]

[0165] 100 Film 110, 210 surface layer 120, 220 low gloss layer 122, 222 binder 124, 224 resin beads 126, 226 Nanosilica particles 130, 230 gloss print pattern 140, 142 Base material layer 150 Adhesive layer 200 Overlaminate Film 240 transparent resin-based 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, the surface layer includes a low-gloss layer and a gloss printing pattern that partially covers the low-gloss layer; (1) The surface layer has an in-plane average 85-degree surface gloss of 5.0 GU or less, (2) The Δ85° surface glossiness (Δ85° surface glossiness) defined as the difference between the maximum value and the average value of the 85° surface glossiness of the surface layer (= the maximum value of the 85° surface glossiness - the average value of the 85° surface glossiness) is 0.2 to 2.5, (3) The surface roughness Ra of the embossed surface of the film is 3.5 μm or more, and the low-gloss layer contains a binder containing a resin, resin beads having an average particle size of 4 μm or more and 20 μm or less, and nanosilica particles, A film in which the increase in visible light reflectance (%) at an incident light angle of 60 degrees is less than 3.5 per 5 degrees of reflection angle in the range of reflection angles from -80 degrees to 80 degrees.

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. 3. The film of claim 1, 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 printing pattern is distributed on the bottom of the low gloss layer of the embossed surface layer.

5. The film of any one of claims 1 to 4, comprising areas where the gloss print pattern and the embossed pattern are not synchronized.

6. The film of any one of claims 1 to 5, wherein the gloss print pattern comprises 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 produced by a printing plate.

8. The film according to any one of claims 1 to 7, wherein the low-gloss layer contains 5 parts by mass or more and 120 parts by mass or less of the nanosilica particles based on 100 parts by mass of the binder.

9. The film according to any one of claims 1 to 8, 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.

10. The film according to any one of claims 1 to 9, wherein the binder comprises a urethane resin.

11. The film according to any one of claims 1 to 10, wherein the resin beads are urethane resin beads.

12. The film of any one of claims 1 to 11, wherein the binder further comprises a cellulose ester.

Images