Decorative material

Abstract

To provide a decorative material on which partial peel-off of ink disposed in a concavity is not noticeable.SOLUTION: A decorative material has a pattern layer on which pattern is drawn, an unevenness application layer that is stacked on the pattern layer and has an uneven pattern, and an ink layer formed of ink disposed in a concavity of the uneven pattern. When a site including the ink layer is a site A and a site not including the ink layer is a site B in plan view of the decorative material, color difference ΔE1 between the site A and the site B is 12 or less, and when a site seen through the pattern layer by removing the ink layer in the unevenness application layer in plan view of the decorative material is a site C, color difference ΔE2 between the site A and the site C is 3 or less.SELECTED DRAWING: Figure 2

Description

Technical Field

[0001] The present disclosure relates to decorative materials.

Background Art

[0002] Decorative materials are widely used as surface decorative materials for furniture, building materials, wall surfaces, the outer surfaces of household electrical appliances, the interior parts of vehicles such as cars, etc. Among them, there is a decorative material that expresses a predetermined texture by filling ink into recesses (grooves) provided on the surface (this is referred to as "wiping").

[0003] For example, Patent Document 1 discloses a decorative material in which ink is filled in embossed recesses. According to this, by filling the embossed recesses with ink by wiping, it is possible to obtain a synchronization between the shape of the embossed recesses and the pattern and color tone and a dulling effect to express a realistic feeling.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, there has been a problem that when the decorative material is used, the part filled with ink is removed due to wear, chipping, etc., and the difference in color tone between the part where the filled ink has disappeared and the other parts where the filled ink remains is prominent. The detachment of the filled ink in the recesses due to the use of the decorative material itself is inevitable to a certain extent.

[0006] Therefore, an object of the present disclosure is to provide a decorative material in which even if a part of the ink disposed in the recesses is detached, the detachment is not conspicuous.

Means for Solving the Problems

[0007] One aspect of the present disclosure is a decorative material including a pattern layer which is a layer on which a pattern is drawn, a concavo-convex imparting layer laminated on the pattern layer and having a concavo-convex pattern, and an ink layer formed of ink disposed inside a concave portion of the concavo-convex pattern. When the decorative material is viewed in plan view, when a portion including the ink layer is defined as portion A and a portion not including the ink layer is defined as portion B, a color difference ΔE1 between portion A and portion B is 12 or less, and when the decorative material is viewed in plan view and the ink in the concavo-convex imparting layer is removed to view the pattern layer to define the resulting portion as portion C, a color difference ΔE2 between portion A and portion C is 3 or less.

Advantages of the Invention

[0008] According to the decorative material of the present disclosure, even if a part of the ink layer and / or the concavo-convex imparting layer is missing due to, for example, abrasion, the missing part will not be conspicuous.

Brief Description of the Drawings

[0009]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Embodiments for Carrying Out the Invention

[0010] Hereinafter, each embodiment will be described with reference to the drawings. The present invention is not limited to these embodiments. In the drawings shown below, for the sake of clarity, the size and ratio of the members may be changed or exaggerated. Also, for the sake of visibility, the illustration of parts that are not necessary for the explanation and repeated reference numerals may be omitted.

[0011] 1. Form of the cosmetic material FIG. 1 is an enlarged view of a part of a cosmetic material 10 according to one embodiment, viewed in plan from the uneven-imparting layer 12 side (plan view). In FIG. 1 and the figures shown hereinafter, for the sake of convenience, arrows (x, y, z) indicating directions, that is, a coordinate system, are also shown as appropriate. Here, the xy direction is the in-plane direction of the cosmetic material 10, and the z direction is the thickness direction. Therefore, FIG. 1 is a view (viewed in plan) of the cosmetic material 10 seen particularly from the z direction on the uneven-imparting layer 12 side.

[0012] As can be seen from FIG. 1, in this embodiment, as a whole, the surface is configured to give the appearance of crack-like recesses existing on the surface, in a so-called "burned cedar" finish where the surface of a cedar wood board is burned and moderately carbonized. However, the aspects to be expressed in the present disclosure are not limited to the burned cedar finish, and normal wood grain finishes, tile joint or brickwork finishes with joints, stone grain finishes such as granite slab surfaces, cloth grain finishes with a large number of fibrous recesses, leather grain finishes with a large number of wrinkled recesses, etc. can also be targeted.

[0013] For example, in the case of the burned cedar finish aspect, the ink layer 14 disposed inside the groove-like recess 13 can reproduce the shadows and three-dimensional effect due to cracks and steps, and thereby can well reproduce the appearance of cracks and steps on the surface of a surface-carbonized wood board such as burned cedar. In the case of the wood grain finish aspect, the groove-like recess 13 with the ink layer 14 disposed inside can reproduce the shadows and three-dimensional effect due to early wood and late wood in the annual rings, and thereby can well reproduce the appearance due to the annual rings of the wood grain. In the case of the tile joint or brickwork finish aspect, the recess 13 with the ink layer 14 disposed inside can reproduce the shadows and three-dimensional effect due to the steps and recesses at the joint parts of the tile joint or brickwork, and thereby can reproduce the appearance of the joint groove. In the case of the cloth-like pattern form, the groove-shaped recess 13 with the ink layer 14 disposed therein can reproduce the steps of knots, tangles, or tumor-like uneven portions where fiber bundles are intertwined (these are also referred to as "neps"), the shadows caused by the recesses, and further the three-dimensional effect, thereby reproducing the appearance of the recesses in the structure (texture) of the fiber aggregate. In the case of the leather-like grain form, the groove-shaped recess 13 with the ink layer 14 disposed therein can reproduce the steps of the wrinkled uneven portions of the leather, the shadows caused by the recesses, and further the three-dimensional effect, thereby reproducing the appearance of the wrinkled recesses on the leather surface.

[0014] FIG. 2 is an enlarged perspective view schematically showing a part of the decorative material 10 for explaining the form of the decorative material 10. Further, FIG. 3 shows a cross-sectional view in the thickness direction along III-III parallel to the x direction of FIG. 2. As can be seen from FIGS. 1 to 3, in this embodiment, the decorative material 10 includes a base material 11, a pattern layer 15 provided on one surface of the base material 11 (the upper surface in FIG. 3, that is, the surface on the + side in the z-axis direction in the coordinate system), an unevenness-imparting layer 12 disposed on the surface of the pattern layer 15 opposite to the base material 11, and an ink layer 14.

[0015] Hereinafter, each component will be described in more detail.

[0016] 1.1. Base Material The base material 11 is a sheet-like member that holds the unevenness-imparting layer 12, imparts strength to the decorative material 10, and has a function of maintaining the shape of the decorative material 10. Here, the form of the base material 11 may be any of a film, a sheet, and a plate. Generally, those with relatively thin thicknesses are sequentially referred to as a film, a sheet, and a plate. However, in this embodiment, the differences in the thickness forms of these base materials are neither essential nor important matters. Therefore, in this specification, any of the terms film, sheet, and plate may be appropriately read as other terms without changing the essence of the present invention or the interpretation of the claims.

[0017] In this embodiment, the base material 11 is made of a transparent resin. As the transparent resin, conventionally known materials for decorative materials can be used. These include, for example, polyolefin resins such as polyethylene, polypropylene, olefin-based thermoplastic elastomers, ionomers, acrylic resins such as polymethyl methacrylate and polybutyl methacrylate, thermoplastic polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene glycol-terephthalic acid-isophthalic acid copolymer, terephthalic acid-ethylene glycol-1,4-cyclohexanedimethanol copolymer, various polyester-based thermoplastic elastomers, thermoplastic urethane resins, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-based resins such as ethylene-vinyl chloride copolymer, polycarbonate resins, ABS resins (acrylonitrile-butadiene-styrene copolymer), thermoplastic resins such as styrene resins, thermosetting resins such as melamine resins, unsaturated polyester resins, epoxy resins, two-component curable urethane resins, or radiation-curable resins such as radical-polymerizable acrylate-based or cation-polymerizable epoxy-based monomers and prepolymers that are cured by ionizing radiation (ultraviolet rays, electron beams, etc.).

[0018] As described above, in this embodiment, the base material is made of a transparent resin, but it may be colored with a colorant. As the colorant, known ones can be used. In the case of so-called achromatic colors (white, black), for example, inorganic black pigments such as carbon black (ink) and iron black, organic black pigments (or dyes) such as azomethine azo black and perylene black, and white pigments such as titanium white, antimony white, and zinc white can be appropriately used alone or in a mixture of two or more. Note that gray can be obtained by mixing white and black. On the one hand, as the coloring agent for colored substances, for example, inorganic pigments such as lead yellow, titanium yellow, safflower, cadmium red, ultramarine, cobalt blue, etc., organic pigments or dyes such as quinacridone red, isoindolinone yellow, nickel azo complex, phthalocyanine blue, etc., metal pigments composed of flaky foil pieces such as aluminum and brass, and pearl luster (pearl) pigments composed of flaky foil pieces such as titanium dioxide-coated mica and basic lead carbonate, etc. can be appropriately used alone or in a mixture of two or more kinds.

[0019] There is no particular limitation on the thickness of the base material. However, in the case of a sheet-shaped base material or a film-shaped base material, for example, those with a thickness of about 20 μm or more and 1000 μm or less are used. In the case of a plate-shaped base material, for example, those with a thickness of about 1 mm or more and 20 mm or less are used.

[0020] 1.2. Concavo-convex imparting layer The concavo-convex imparting layer 12 imparts characteristics to the surface of the decorative material visually and tactilely by means of concavo-convexities. The concavo-convex pattern formed by the concavo-convex imparting layer 12 can be based on the pattern to be expressed (for example, the "charred cedar tone", "wood grain tone", "tile pasted tone", "brick stacked tone", "cloth texture tone", "skin texture tone", etc. as described above).

[0021] The cross-sectional shape of the concave portion 13 forming the concavo-convex pattern is not particularly limited and can be appropriately set according to the desired mode. For example, it is possible by combining the cross-sectional shape of the concave portion (such as a triangle or a quadrilateral), the presence or absence of rounding at the outer and inner corners of the concave portion, the width of the concavo-convexity (the size in the x direction), the depth of the concavo-convexity (the size in the z direction), etc.

[0022] The material constituting the concavo-convex imparting layer 12 is transparent to such an extent that the pattern layer 15 can be seen directly or through the ink layer, and it is preferably at least one selected from two-component curable resins, thermoplastic resins, thermosetting resins, and radiation-curable resins.

[0023] Examples of the two-component curable resin include two-component curable urethane resins with a polyol compound as the main agent and an isocyanate compound as the curing agent, two-component curable epoxy resins, two-component curable urethane-modified acrylic resins, and two-component curable polyester resins.

[0024] Examples of the thermoplastic resin include acrylic resins, cellulose resins, urethane resins, vinyl chloride resins, polyester resins, polyolefin resins, polycarbonate, nylon, polystyrene, and ABS resins.

[0025] Examples of the thermosetting resin include acrylic resins, urethane resins, phenolic resins, urea resins, melamine resins, epoxy resins, unsaturated polyester resins, and silicone resins. A curing agent is added to the thermosetting resin as necessary.

[0026] The radiation-curable resin is a composition containing a compound having a radiation-curable functional group. Examples of the radiation-curable functional group include ethylenically unsaturated bond groups such as (meth)acryloyl group, vinyl group, and allyl group, and epoxy group and oxetanyl group. As the radiation-curable resin, a compound having an ethylenically unsaturated bond group is preferable. Further, from the viewpoint of suppressing damage to the resin layer during the production of the cosmetic sheet, as the radiation-curable resin, a compound having two or more ethylenically unsaturated bond groups is more preferable, and among them, a polyfunctional (meth)acrylate-based compound having two or more ethylenically unsaturated bond groups is even more preferable. As the polyfunctional (meth)acrylate-based compound, either a monomer or an oligomer can be used. The radiation refers to those having energy quanta capable of polymerizing or crosslinking molecules among electromagnetic waves or charged particle beams. Usually, ultraviolet rays (UV) or electron beams (EB) are used, but other electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion beams can also be used.

[0027] Among the polyfunctional (meth)acrylate-based compounds, examples of the bifunctional (meth)acrylate-based monomer include ethylene glycol di(meth)acrylate, bisphenol A tetraethoxydiacrylate, bisphenol A tetrapropoxydiacrylate, and 1,6-hexanediol diacrylate. Examples of the (meth)acrylate monomers having three or more functional groups include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol tetra(meth)acrylate, isocyanuric acid-modified tri(meth)acrylate, and the like. Further, the above (meth)acrylate monomers may be those having a modified part of the molecular skeleton, and those modified with ethylene oxide, propylene oxide, caprolactone, isocyanuric acid, alkyl, cycloalkyl, aromatic, bisphenol, etc. can also be used.

[0028] Examples of the polyfunctional (meth)acrylate oligomers include acrylate polymers such as urethane (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, and polyether (meth)acrylate. Urethane (meth)acrylate is obtained, for example, by the reaction of a polyhydric alcohol, an organic diisocyanate, and hydroxy (meth)acrylate. Also, preferred epoxy (meth)acrylates are (meth)acrylates obtained by reacting an aromatic epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, etc. having three or more functional groups with (meth)acrylic acid, (meth)acrylates obtained by reacting an aromatic epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, etc. having two or more functional groups with a polybasic acid and (meth)acrylic acid, and (meth)acrylates obtained by reacting an aromatic epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, etc. having two or more functional groups with phenols and (meth)acrylic acid. The above ionizing radiation curable resin can be used alone or in combination of two or more.

[0029] When the ionizing radiation curable resin is an ultraviolet curable resin, the composition preferably contains additives such as a photopolymerization initiator and a photopolymerization accelerator. As a photoinitiator, for example, in the case of a compound having an ethylenically unsaturated group, one or more selected from acetophenone, benzophenone, α-hydroxyalkylphenone, Michler's ketone, benzoin, benzyldimethyl ketal, benzoyl benzoate, α-acyl oxime ester, thioxanthones, etc. can be mentioned. The photopolymerization accelerator can reduce the polymerization inhibition by air during curing and increase the curing rate. As the photopolymerization accelerator, for example, one or more selected from isopentyl p-dimethylaminobenzoate, ethyl p-dimethylaminobenzoate, etc. can be mentioned.

[0030] These compositions may contain various additives such as fillers, matting agents, foaming agents, flame retardants, lubricants, antistatic agents, antioxidants, ultraviolet absorbers, light stabilizers, radical scavengers, soft components (such as rubber), etc. as required.

[0031] The thickness of the concavo-convex imparting layer 12 is not particularly limited, but is preferably larger than the depth of the concave portion. By making the thickness of the concavo-convex imparting layer 12 thicker than the depth of the concave portion, the durability of the surface of the decorative material can be improved.

[0032] 1.3. Ink layer The ink layer 14 is a part composed of ink disposed inside the concave portion 13. By using ink, a decorative material 10 having a different appearance and touch can be obtained compared to the case of only the concave portion 13.

[0033] The material of the ink constituting the ink layer 14 is not particularly limited, and known materials can be used. For example, those containing any one or two or more of a coloring pigment, a matting pigment, a dye, an ultraviolet absorber, etc. in a vehicle can be applied. The vehicle can be appropriately selected from various thermoplastic resins, thermosetting resins, and radiation effect type resins.

[0034] 1.4. Pattern layer The pattern layer 15 is a layer on which a desired pattern is expressed. In this embodiment, for example, it can be matched to the pattern expressed by the unevenness of the unevenness-imparting layer 12. However, it is not limited to this, and it may be a pattern with a different expression from the unevenness-imparting layer 12. As the pattern of the pattern layer 15, various patterns such as a wood grain pattern, a tile sticker or brick stack pattern with joints, a cloth pattern, a leather texture pattern, a stone texture pattern, a geometric pattern such as a stripe pattern or a checkered pattern, a floral pattern, a vine pattern, a thunder pattern, characters, symbols, numbers, etc. can be used. Examples of typical and design-expression-suitable combinations of the unevenness pattern of the unevenness-imparting layer 12 and the pattern of the pattern layer 15 include the combination of the unevenness pattern of the conduit grooves on a wood board and the wood grain pattern having the conduit grooves, the combination of the joint unevenness pattern of tile stickers or brick stacks and the pattern on the surface of tile stickers or brick stacks having joints, the combination of the unevenness pattern on the surface of a granite slab having cleavage planes of polycrystals and the surface pattern of the granite slab, the combination of the cloth unevenness pattern having a large number of fibrous recesses and the cloth pattern, the combination of the leather texture unevenness pattern having a large number of wrinkled recesses and the leather texture pattern, etc. In this embodiment, the pattern layer 15 is laminated on the surface of the base material 11 and the surface of the unevenness-imparting layer 12, and is disposed between the unevenness-imparting layer 12 and the base material 11.

[0035] The pattern layer 15 is formed by appropriately arranging colorants such as pigments and dyes so as to obtain the desired design. The pattern layer is formed by printing methods such as offset printing, flexographic printing, gravure printing, silk screen printing, spray printing, and inkjet printing, and transfer methods for transferring the printed pattern.

[0036] As the ink used for forming the pattern layer, a mixture obtained by appropriately mixing a colorant such as a pigment and a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, etc. in a binder resin is used. The binder resin is not particularly limited, and examples thereof include acrylic resins, styrene resins, polyester resins, urethane resins, chlorinated polyolefin resins, vinyl chloride-vinyl acetate copolymer resins, polyvinyl butyral resins, alkyd resins, petroleum resins, ketone resins, epoxy resins, melamine resins, fluorine resins, silicone resins, cellulose derivatives, rubber resins, and the like. These resins can be used alone or in combination of two or more.

[0037] The colorant is not particularly limited. When it is black and white, for example, inorganic black pigments such as carbon black (ink) and iron black, organic black pigments (or dyes) such as azomethine azo black and perylene black, and white pigments such as titanium white, antimony white, and zinc white can be appropriately used alone or in combination of two or more in a form suitable for reproducing the desired color of the pattern layer. When it is a color other than white and black, as pigments and dyes, for example, inorganic pigments such as lead yellow, titanium yellow, bengara, cadmium red, ultramarine blue, and cobalt blue, organic pigments or dyes such as quinacridone red, isoindolinone yellow, nickel azo complex, and phthalocyanine blue, metallic pigments composed of flaky foil pieces such as aluminum and brass, and pearl pigments composed of flaky foil pieces such as titanium dioxide-coated mica and basic lead carbonate are used. The pattern layer may contain additives such as antioxidants, ultraviolet absorbers, and light stabilizers.

[0038] From the viewpoint of favorably exhibiting the design property by the pattern, the thickness of the pattern layer is preferably 0.1 μm or more and 40 μm or less, more preferably 0.3 μm or more and 20 μm or less, and even more preferably 0.5 μm or more and 10 μm or less.

[0039] 1.5. Regarding Color In this embodiment, it is configured such that the color difference ΔE between the surface on the unevenness-providing layer 12 side of the decorative material 10 and the pattern layer 15 falls within a predetermined range. Here, the color difference ΔE is the color difference ΔE in the "L * a * b * Color difference ΔE in the color space * abIt means "」". That is, L in two parts to be compared * a * b * the color distance in the color space is ΔE, and the colors in the two parts are respectively (L * 1, a * 1, b * 1), (L * 2, a * 2, b * 2). When expressed in this way, it is represented by the following formula. ΔE = {(L * 2 - L * 1) 2 + (a * 2 - a * 1) 2 + (b * 2 - b * 1) 2} 0.5

[0040] [Color difference between the ink part and the non-ink part] When the cosmetic material is viewed in plan view, as shown by A in FIG. 3, there is an ink part which is a predetermined range (part A) including the ink layer 14, and a non-ink part which is a predetermined range (part B) not including the ink layer 14 as shown by B. In this embodiment, the color difference ΔE between such part A and part B is defined as ΔE1, and it is assumed that ΔE1 is 12 or less. Such a color difference ΔE1 is obtained from the distance between the color in the L * a * b * color space of part A and the color in the L * a * b * color space of part B. The measurement of such a color difference is performed under the following measurement device and measurement conditions. · Measurement device: Spectrophotometer CM-3700A manufactured by Konica Minolta · Measurement conditions: Measurement method of regular reflection light SCI (Specular component Include including regular reflection light) · Light source: D65 · Field of view: 2° field of view · Measurement diameter φ 8mm · Wavelength range 360nm~740nm

[0041] [Color difference before and after removal of the concavo-convex layer] Furthermore, when the ink layer 14 in the concavo-convex layer 12 at site A is removed as shown in FIG. 4 and the pattern layer 15 can be seen through without passing through the ink layer 14, and the site is defined as site C, when the color difference ΔE between site A and site C is defined as ΔE2, ΔE2 is set to 3 or less. That is, the color of site C is the color of the pattern layer 15 visually recognized without passing through the ink layer 14. The removal of such a concavo-convex layer 12 reproduces a state in which the ink layer 14 in the concave portion of the concavo-convex layer 12 is lost due to surface wear during use of the decorative material 10. Such a color difference ΔE2 is obtained from the L at site A measured * a * b * color in the color space and the L at site C * a * b * The distance from the color in the color space is obtained by ΔE2. The measurement of such a color difference is performed under the same measurement apparatus and measurement conditions as described above. Also, the means for removing the ink layer 14 in the concavo-convex layer 12 to obtain site C is not particularly limited. For example, using a Taber abrasion tester in accordance with JIS K 7204, using a Taber abrasion tester model number 5130ABRASER manufactured by Toyo Seiki, with an abrasion wheel CS-10, a load of 9.8 N, and a rotational speed of 60 rpm, a method of removing part or all of the concavo-convex layer under the test conditions of 1000 rotations can be mentioned. When the ink layer 14 in the concavo-convex layer 12 can be completely removed, the number of rotations of the abrasion wheel may be less than 1000. Also, if the ink layer 14 cannot be completely removed even after 1000 rotations of the abrasion wheel, the number of rotations of the abrasion wheel is set to exceed 1000 until the ink layer 14 can be removed.

[0042] 1.6. Other layers In addition to the above, layers such as the following can be provided as necessary.

[0043] [Protective layer] In the decorative material, a protective layer may be further laminated on the unevenness-providing layer. Fig. 5 shows a cross-sectional view of the decorative material 10 having the protective layer 16. The protective layer 16 protects the decorative material from contamination and damage. Such a protective layer 16 can be composed of, for example, a transparent resin or transparent glass. When using a transparent resin, examples thereof include a layer made of a thermoplastic resin or a cured resin. In addition, when the unevenness-providing layer 12 alone can ensure surface durability performance such as sufficient stain resistance and scratch resistance in the intended use, the protective layer can be omitted.

[0044] Examples of the thermoplastic resin include acrylic resins such as polymethyl (meth)acrylate and polyethyl (meth)acrylate, polyolefin resins such as polypropylene and polyethylene, fluororesins such as polyvinyl fluoride and polyvinylidene fluoride, polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN), polycarbonate resin, vinyl chloride-based resin, acrylonitrile-butadiene-styrene resin (ABS resin), acrylonitrile-styrene-acrylic ester resin, etc. Note that “(meth)acrylic” means acrylic or methacrylic.

[0045] The layer made of the cured resin is a layer obtained by curing a curable resin composition, and the curable resin composition is a composition containing a curable resin. Examples of the curable resin composition include a thermosetting resin composition containing a thermosetting resin and an ionizing radiation curable resin composition containing an ionizing radiation curable resin. Examples of the thermosetting resin include unsaturated polyester resin, polyurethane resin (including two-component curable polyurethane), epoxy resin, aminoalkyd resin, phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, melamine-urea co-condensation resin, silicone resin, polysiloxane resin, etc. The thermosetting resin composition may contain, if necessary, components involved in the curing reaction of the thermosetting resin, such as a catalyst, a curing agent (including a crosslinking agent, a polymerization initiator, a polymerization accelerator, etc.). An ionizing radiation curable resin is a resin that undergoes a crosslinking polymerization reaction upon irradiation with ionizing radiation and changes into a three-dimensional polymer structure. Ionizing radiation is one of electromagnetic waves and charged particle beams that have energy quanta capable of polymerizing or crosslinking molecules. In addition to ultraviolet rays (UV) and electron beams (EB), it includes electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion beams. Usually, ultraviolet rays (UV) or electron beams (EB) are used. Among ionizing radiation curable resins, electron beam curable resins can be solvent-free, do not require a photoinitiator for photopolymerization, and stable curing properties can be obtained. As the ionizing radiation curable resin, for example, a composition containing one or more of monomers, oligomers, or prepolymers having a polymerizable unsaturated bond such as a (meth)acryloyl group that can be crosslinked by irradiation with ionizing radiation, an epoxy group, etc. in the molecule can be used.

[0046] The thickness of the protective layer is not particularly limited, but can be 0.1 μm or more and 35 μm or less. When it is thin, the durability against bending etc. is high but the scratch resistance is weak, and when it is thick, it is strong against scratches and damage but weak against deformation such as bending and cracks may occur. Therefore, by setting the thickness within the above range, a well-balanced protective layer can be obtained. Therefore, it may be 1 μm or more and 10 μm or less.

[0047] [Adhesive layer] The decorative material may be provided with an adhesive layer (not shown) between at least one of each layer. The adhesive layer has a function of assisting the joining of each layer and can strengthen the joining of each layer. The adhesive layer is preferably at least one selected from two-component curable resins, thermoplastic resins, thermosetting resins, and ionizing radiation curable resins.

[0048] [Primer layer] The decorative material may be provided with a primer layer (not shown) between at least one of each layer. The primer layer has a function of assisting the joining of each layer and can strengthen the joining of each layer. As the primer layer, a resin that improves the adhesion of both layers facing each other with the primer layer in between can be appropriately selected, and there is no particular limitation.

[0049] 2. Effects, etc. According to the cosmetic materials 10 and 20 having the above-described configuration, by satisfying the regulations of ΔE1, which is the color difference between the ink portion and the non-ink portion, and ΔE2, which is the color difference before and after removing the unevenness-imparting layer, even if a part of the ink layer or a part of the unevenness-imparting layer detaches from the cosmetic material for some reason, the color difference from the surrounding is suppressed to be small, and the cosmetic material becomes one in which the detachment is not noticeable.

[0050] 3. Method for manufacturing a cosmetic material Next, an example of a method for manufacturing a cosmetic material will be described using the cosmetic material 10 as an example. However, the method for manufacturing the cosmetic material is not limited thereto. The manufacturing method described below includes a step of producing a manuscript image, a step of producing an image under the plate, a step of producing a plate, a step of forming a concave portion of the unevenness-imparting layer, and a step of filling the ink.

[0051] In the step of producing a manuscript image, a pattern in plan view (for example, a charred cedar pattern) to be expressed in the concave portion of the unevenness-imparting layer 12 is obtained and used as the manuscript image.

[0052] In the step of producing an image under the plate, a pattern in plan view to be expressed is obtained as image density (shading) and used as the image under the plate. Since the image under the plate is preferably digital data, when the manuscript image is not digital data, a method of reading the manuscript image with a scanner and performing AD conversion is used to obtain digital data in which pixels are arranged in a two-dimensional coordinate plane (x, y), and each pixel corresponds to a unique density value. Also, when the manuscript image has been designed using digital data from the beginning, such as using CAD, that digital data can be used. Then, by using a conversion program from density to unevenness for the digital data, patterns of each region as a binary image are generated and arranged on a two-dimensional virtual plane corresponding to the gradation image of the pattern, and an image under the plate is obtained as digital data.

[0053] In the step of manufacturing the plate, an embossing plate (molding die for decorative material) having a pattern of the planar shape formed by the concave portions 13 on the surface based on the image under the plate is manufactured. Specifically, the manufacturing process of the concavo-convex pattern consists of the following steps (1) to (5).

[0054] [(1) Shaded image data creation step] Using the graphic design drawing software "Photoshop" (registered trademark) manufactured by Adobe Systems, shaded image data with an 8-bit image shading gradation (256 gradations) in TIFF format and a resolution of 2540 dpi was created. This shaded image data is also referred to as concavo-convex pattern image data.

[0055] [(2) Metal roll preparation step] A metal roll 30 for embossing plate engraving as shown in FIG. 6 was prepared. The metal roll 30 is formed by plating a copper layer on the surface of a hollow iron cylinder having rotary drive shafts 31 at both axial ends. The surface of the metal roll 30 was polished with a grindstone to roughen it, and a process was performed to prevent a decrease in engraving efficiency due to specular reflection of the laser light for engraving.

[0056] [(3) Laser engraving step] As schematically shown in FIG. 6, using a laser direct engraving machine, the surface of the metal roll 30 prepared in step (2) is engraved based on the concavo-convex pattern image data created in step (1). As a result, an uneven shape having the same planar shape as the concavo-convex pattern formed by the concave portions 13 on the surface of the decorative material and an inverse concavo-convex relationship (the portion corresponding to the convex line of the decorative material is a concave line on the embossing plate surface) is formed. Therefore, the shape that the concavo-convex pattern in the embossing plate should have is a mode in which the concavo-convex relationship of the concavo-convex pattern formed by the concave portions 13 in the above-described decorative material is inverted, and the same can be considered. The metal roll 30 is driven by an electric motor via its rotary drive shaft 31 and rotates about the rotary drive shaft 31 as the central axis. The surface of the metal roll 30 is scanned with the laser beam P emitted from the laser head 32. In order to prevent the evaporated metal from becoming powder and remaining or adhering to the surface of the metal roll 30, laser beam irradiation is performed while spraying the etching liquid T from the etching liquid discharge port 33 onto the laser beam irradiation region on the surface of the metal roll 30.

[0057] [(4) Electrolytic polishing process] After washing the etching liquid, electrolytic polishing is performed to remove the metal residue adhering to the surface of the metal roll 30.

[0058] [(5) Chromium plating process] After the process (4), a chromium layer with a thickness of 10 μm is formed on the surface of the metal roll by plating.

[0059] As described above, a plate (a molding die for a decorative material, an embossing plate in this embodiment) having a concavo-convex shape on its surface in which the concavo-convexity of the concavo-convex pattern formed by the concave portions 13 on the surface of the concavo-convex imparting layer 12 is reversed can be obtained.

[0060] Next, in the step of forming the concave portions of the concavo-convex imparting layer, if an embossing process is performed on the material to be the concavo-convex imparting layer using the produced plate (embossing plate), the recesses 13 can be obtained. The embossing process may be performed by an appropriate known method and is not particularly limited. Representative methods of embossing are as follows, for example. The material to be the concavo-convex imparting layer is heated and softened, and an embossing plate is pressed against its surface to form the concavo-convex pattern on the surface of the embossing plate on the surface of the resin sheet. Then, the resin sheet is cooled and solidified to fix the concavo-convex pattern on the resin sheet. After that, the resin sheet with the concavo-convex pattern formed thereon is released from the embossing plate. Here, various embossing processes will be further described. For example, there are methods as follows from (A) to (E).

[0061] (A) The resin sheet as the base material is heated and softened, and an embossing plate is pressed against it for embossing. By thermally fusing a resin sheet (base material) that becomes the surface sheet and a resin sheet (second base material) that serves as the base sheet under heat pressure when pressing the embossing plate, embossing is performed by the doubling embossing method that simultaneously performs embossing and lamination. (C) A resin sheet (base material) to be the surface sheet is melt-extruded from a T-die and brought into contact with a cylindrical embossing plate that also serves as a cooling roller to perform embossing simultaneously with the film formation of the surface sheet. At this time, a resin sheet (second base material) that serves as the base sheet inserted on the back side of the surface sheet is thermally fused to perform doubling embossing simultaneously with the film formation. (D) As disclosed in Japanese Patent Application Laid-Open No. 57-87318, Japanese Patent Application Laid-Open No. 7-32476, etc., an uncured liquid substance of a radiation-curable resin is applied to the surface of a cylindrical embossing plate. Further, radiation is irradiated in a state where a base sheet made of a resin sheet or the like is overlaid thereon to cure the uncured liquid substance into a cured product. At that time, after adhering the cured product to the base sheet, it is released from the embossing plate, and a base material composed of the base sheet and the cured product on the base sheet is used to perform embossing on the base material. (E) An impregnated paper impregnated with an uncured product of a thermosetting resin such as melamine resin on paper such as titanium paper is placed on a backing material such as core paper or plywood, and the plurality of layers placed are thermally press-molded to integrate the layers into a thermosetting resin decorative material. At that time, by inserting an embossing plate on the surface side of the impregnated paper, embossing is performed simultaneously with the thermal press on the surface when the thermosetting resin is impregnated and cured to form a decorative material.

[0062] Typically, a thermoplastic resin is used as the material for the base material used in the embossing methods (A) to (C). Typically, a radiation-curable resin is used as the material for the base material used in the embossing method (D). Typically, a thermosetting resin is used as the material for the base material used in the embossing method (E).

[0063] In the step of filling the ink, the ink is filled into the recesses 13 formed on the surface of the unevenness-providing layer 12, and the ink is arranged in the recesses 13 with a desired thickness distribution to form the ink layer 14. This is done by supplying the ink (in an uncured state), which is the material to become the ink layer 14, to the surface of the unevenness-providing layer 12 on the side where the recesses 13 are formed, by a coating method such as the curtain flow coating method or the roll coating method, and then scraping the excess ink outside the recesses 13 (wiping it) with a doctor blade, squeegee, sponge roller, etc. The method itself of filling and arranging such ink into the recesses is a method known as the so-called "wiping" method.

[0064] The uses of the decorative material described above are not particularly limited. For example, interior materials for buildings such as walls, floors, and ceilings, exterior materials for buildings such as building exteriors, roofs, doors, fences, and walls, fittings such as doors, window frames, and door frames, surface materials for trim members such as moldings, baseboards, and handrails, surface materials for the casings of household appliances such as televisions and refrigerators and office equipment such as copiers, surface materials for furniture such as wardrobes, surface materials for containers such as boxes and resin bottles, interior or exterior materials for vehicles, interior or exterior materials for ships, etc.

[0065] 4. Examples In the examples, a decorative material was created based on the layer structure of the decorative material 10 described above, and tests were conducted by changing ΔE1 and ΔE2.

[0066] [Base material] · Material: Polypropylene · Thickness: 60 μm · Color: Brown

[0067] [Pattern layer] · Material: For the wood grain pattern (Example 1 and Comparative Example 1), a urethane / acrylic resin with valve pattern as the main pigment, and titanium white, lead yellow, and carbon black were added thereto. For the metallic pattern (Example 2 and Comparative Example 2), a urethane / acrylic resin with valve pattern, aluminum flaky foil pieces, lead yellow, and carbon black were added as pigments. · Thickness: 1 μm · Pattern: Examples 1 and 1 have the wood grain pattern on the surface of the charred cedar board Example 2 and Comparative Example 2 have a hairline-finished metal handle (see Table 1).

[0068] [Convexity and concavity imparting layer] · Material: Polypropylene · Thickness: 80 μm · Color: Colorless and transparent · Convexity and concavity pattern: In Example 1 and Comparative Example 1, the convexity and concavity pattern is formed by taking a mold of the charred cedar board surface, and in Example 2 and Comparative Example 2, the convexity and concavity pattern is formed by taking a mold of the hairline-finished metal surface.

[0069] [Ink layer] · Colorant 1: Medium (colorless and transparent acrylic urethane resin without pigment addition) · Colorant 2: Color... India ink, Material... Add a black pigment composed of carbon black (India ink) to an acrylic urethane resin · Blending ratio: See Table 1

[0070] [Measurement of ΔE1] For each of the obtained decorative materials of Examples and Comparative Examples, when viewed in plan view, the color difference ΔE1 between the ink part (part A) containing the ink layer in the concave part and the non-ink part (part B) not containing such an ink layer was measured under the following measuring apparatus and measuring conditions. · Measuring apparatus: Spectrophotometer CM-3700A manufactured by Konica Minolta · Measuring conditions: Measuring method of regular reflection light SCI (Specular component Include including regular reflection light) · Light source: D65 · Field of view: 2° field of view · Measuring diameter φ: 8 mm · Wavelength range 360 nm to 740 nm

[0071] [Measurement of ΔE2] [Removal of convexity and concavity imparting layer] The removal of the concavo-convex imparting layer reproduces the state in which the ink layer in the concave portion of the concavo-convex imparting layer is lost due to surface wear during the use of the decorative material, and was carried out by a Taber abrasion test in accordance with JIS K 7204. As the Taber abrasion tester, Model No. 5130 ABRASER manufactured by Toyo Seiki was used, and the abrasion wheel was CS-10, the load was 9.8 N, and the test was carried out under the test conditions of a rotational speed of 60 rpm and a number of rotations of 1000 rotations. <Measurement of ΔE2> Regarding the decorative materials of each example and comparative example, for the portion C where the ink layer in the portion A of the concavo-convex imparting layer was removed and the pattern layer was exposed so as to be visible without passing through the ink layer, the color difference ΔE2 between the corresponding portion A and portion C was measured under the same measuring device and measuring conditions as those for measuring the color difference ΔE1 described above.

[0072] [Evaluation] Regarding the decorative materials of each example and comparative example, the change in the design appearance between the test pieces before and after removing the concavo-convex imparting layer was visually evaluated. Such visual evaluation was carried out by 10 subjects visually comparing the same test pieces, and when the number of people who judged that the change in the design appearance of the test pieces before and after removing the concavo-convex imparting layer was unrecognizable or recognizable but slight was 5 or more, which was a majority, it was evaluated as "good", and when the number of people who judged that the change was unrecognizable or recognizable but slight was less than 4 (including the case of 0 people), it was evaluated as "bad".

[0073] [Results] The results of Example 1, Example 2, Comparative Example 1, and Comparative Example 2 are shown in Table 1. Table 1 also shows the blending ratio (mass%) of the colorant.

[0074]

Table 1

[0075] As can be seen from Table 1, good results could be obtained by changing the values of ΔE1 and ΔE2.

Explanation of Signs

[0076] 10 Decorative material 11 Base material 12 Concave-Convex Imprinting Layer 13 Concave Portion 14 Ink Layer 15 Pattern Layer

Claims

**Claim 1** A decorative material, comprising: a pattern layer which is a layer on which a pattern is drawn; a concavo-convex imparting layer laminated on the pattern layer and having a concavo-convex pattern; and an ink layer made of ink disposed inside a concave portion of the concavo-convex pattern. When the cosmetic material is viewed in a plan view, when the part including the ink layer is defined as part A and the part not including the ink layer is defined as part B, the color difference ΔE between part A and part B １ is 12 or less, and When the cosmetic material is viewed in plan view and the part where the ink in the concavo-convex imparting layer is removed to see through the pattern layer is defined as part C, the color difference ΔE between part A and part C ２ is 3 or less. The decorative material.

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