Cosmetic materials

Abstract

To provide a decorative material simultaneously realizing a tactile feeling and a low gloss feeling.SOLUTION: A decorative material includes a matte layer on a base material. The matte layer includes a binder resin, a resin particle and an inorganic particle. In a plane view of the decorative material, the matte layer has a first area not including the inorganic particle but including the resin particle, and a second area not including the resin particle but including the inorganic particle. If average thickness of the matte layer in the first area is T1 and average thickness of the matte layer in the second area is T2, T2<T1.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a cosmetic material. [Background technology]

[0002] Decorative materials may be attached to various components for decorative purposes. Examples of the various components include interior and exterior materials such as furniture and fittings; wall surfaces of buildings; indoor surfaces such as floors and ceilings; surfaces of fixtures such as waist walls, moldings, and lintels; outdoor surfaces such as exterior walls, roofs, door pockets, and eaves ceilings of buildings; surfaces of outdoor structures such as fences and walls; indoor or outdoor surfaces of fittings such as window frames, door frames, doors, and partitions; surfaces of furniture such as chests of drawers and cupboards; interior or exterior surfaces of vehicles such as automobiles, railway cars, ships, and aircraft; surfaces of various home appliances, office equipment, etc.

[0003] The basic layer structure of a decorative material is a layer structure having a pattern layer and a surface protection layer on a substrate. Decorative materials with this layer structure have a poor feel and many do not have the feel of natural wood such as veneer. However, in recent years, decorative materials aimed at improving the feel have been proposed (for example, Patent Documents 1 and 2). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2019-217740 [Patent Document 2] Japanese Patent Application Laid-Open No. 2004-262105 DISCLOSURE OF THE INVENTION [Problem to be solved by the invention]

[0005] The cosmetic material of Patent Document 1 imparts a tactile sensation to the cosmetic material by imparting an uneven shape to the surface of the cosmetic material through embossing. However, in embossing such as that of Patent Document 1, since an embossing plate needs to be produced for each desired uneven pattern, there is a problem that it is not suitable for the production of small-lot, multi-variety cosmetic materials.

[0006] The cosmetic material of Patent Document 2 has, on a base material, a specific first surface protection layer and a second resin layer containing synthetic resin beads having an average particle diameter of 10 to 30 μm, and the average film thickness of the portion excluding the synthetic resin beads protruding from the surface of the second surface protection layer is 3 to 6 μm. The cosmetic material of Patent Document 2 does not require the use of an embossing plate. However, although the cosmetic material of Patent Document 2 can impart a predetermined tactile sensation, it has insufficient low glossiness. That is, the cosmetic material of Patent Document 2 could not achieve both tactile sensation and low glossiness. When the low glossiness of the cosmetic material is insufficient, it becomes difficult to express the appearance of natural materials such as natural wood, and thus the design property of the cosmetic material cannot be enhanced.

[0007] The present invention has been made under such circumstances, and an object thereof is to provide a cosmetic material that achieves both tactile sensation and low glossiness.

Means for Solving the Problems

[0008] In order to solve the above problems, the present invention provides the following [1] to [8]. [1] A cosmetic material having a matte layer on a base material, The matte layer contains a binder resin, resin particles, and inorganic particles, When the cosmetic material is viewed in plan view, the matte layer has a first region containing the resin particles and not containing the inorganic particles, and a second region containing the inorganic particles and not containing the resin particles, When the average thickness of the matte layer in the first region is defined as T1 and the average thickness of the matte layer in the second region is defined as T2, a cosmetic material in which T2 < T1. [2] The cosmetic material according to [1], wherein T1 - T2 is 15 μm or more and 60 μm or less. [3] The decorative material according to [1] or [2], wherein the proportion of the resin particles whose tops are covered with the binder resin is 50% or more of all the resin particles in the first region. [4] The decorative material of [1] or [2], wherein the proportion of the resin particles whose tops are covered with the binder resin is less than 50% of all the resin particles in the first region. [5] The decorative material according to any one of [1] to [4], wherein when the average particle diameter of the resin particles is defined as D1, D1 is 20 μm or more and 70 μm or less. [6] The decorative material according to any one of [1] to [5], wherein when the average particle diameter of the inorganic particles is defined as D2, D2 is 5 μm or more and 20 μm or less. [7] The decorative material according to any one of [1] to [6], wherein the matte layer is provided on a portion of the substrate. [8] The decorative material according to any one of [1] to [7], which has a decorative layer between the substrate and the matte layer. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a decorative material that has both a pleasant feel and a low gloss. [Brief explanation of the drawings]

[0010] [Figure 1] 1 is a schematic cross-sectional view showing one embodiment of a decorative material of the present invention. [Figure 2] 1 is a schematic plan view showing one embodiment of a decorative material of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0011] [Decorative materials] The decorative material of the present invention is a decorative material having a matte layer on a substrate, the matte layer containing a binder resin, resin particles, and inorganic particles, and when the decorative material is viewed from above, the matte layer has a first region containing the resin particles but not the inorganic particles, and a second region containing the inorganic particles but not the resin particles, and when the average thickness of the matte layer in the first region is defined as T1 and the average thickness of the matte layer in the second region is defined as T2, <T1であるものである。

[0012] FIG. 1 is a schematic cross-sectional view showing one embodiment of a cosmetic material 100 of the present invention, and FIG. 2 is a schematic plan view showing one embodiment of a cosmetic material 100 of the present invention. The decorative material 100 in Fig. 1 has a matte layer 20 containing a binder resin 21, resin particles 22, and inorganic particles 23 on a substrate 10. When the decorative material 100 in Fig. 1 and Fig. 2 is viewed from above, the matte layer 20 has a first region R1 that contains resin particles but no inorganic particles, and a second region R2 that contains inorganic particles but no resin particles. The decorative material 100 in Fig. 1 and Fig. 2 has a plurality of first regions R1 and second regions R2. In the present invention, "planar view" means viewing the decorative material in a planar direction from the surface side of the decorative material. The surface side of the decorative material means the side having the matte layer relative to the substrate. For example, in the XYZ coordinate system shown in Figures 1 and 2, the plane represented by the X-axis direction and the Y-axis direction coincides with the surface of the decorative material, and "planar view" corresponds to viewing the surface of the decorative material from the Z-axis direction.

[0013] <Base material> The form of the substrate is not particularly limited, and may include flat forms such as films, sheets, and plates, as well as three-dimensional forms such as polyhedrons, polygonal prisms, cylinders, spheres, and spheroids. Although films, sheets, and plates are often referred to as films, sheets, and plates in the order of relatively thinnest thickness, no distinction is made between these three in this specification unless otherwise specified.

[0014] Examples of materials constituting the substrate include resins, metals, non-metallic inorganic materials, fibrous materials, and wood-based materials, and can be appropriately selected depending on the application.

[0015] The substrate may be a single layer, or may be a laminate of two or more layers made of the above materials. When the substrate is a laminate of two or more layers, it is preferable that two or more layers of different materials are laminated, and the performance properties of the materials in each layer complement each other. Examples of substrates made of two or more layers are listed below as A to J. (A) Lamination of resin and wood-based materials (B) Lamination of resin and metal (C) Lamination of resin and fibrous material (D) Lamination of resin and non-metallic inorganic material (E) Lamination of Resin 1 and Resin 2 (F) Lamination of metal and wood-based materials (G) Lamination of metal and non-metallic inorganic material (H) Lamination of metal and fibrous material (I) Lamination of Metal 1 and Metal 2 (J) Lamination of non-metallic inorganic materials and fibrous materials

[0016] In the above E, resin 1 and resin 2 represent different types of resins (for example, resin 1 is an olefin resin and resin 2 is an acrylic resin). Also, in the above H, metal 1 and metal 2 represent different types of metals (for example, metal 1 is copper and metal 2 is chromium).

[0017] Furthermore, when the substrate is a laminate such as those A to J above, a layer (adhesive layer or the like) for strengthening adhesive strength may be provided between the constituent layers of the laminate.

[0018] Resins used for the substrate include various synthetic resins and natural resins, such as thermoplastic resins and cured products of curable resin compositions.

[0019] Examples of thermoplastic resins include olefin resins such as polyethylene, polypropylene, polymethylpentene, ionomers, and various olefin-based thermoplastic elastomers; vinyl chloride resins such as polyvinyl chloride, polyvinylidene chloride, and vinyl chloride-vinyl acetate copolymers; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene glycol-terephthalic acid-isophthalic acid copolymers, and polyester-based thermoplastic elastomers; acrylic resins such as polymethyl (meth)acrylate, polyethyl (meth)acrylate, polybutyl (meth)acrylate, and methyl (meth)acrylate-butyl (meth)acrylate copolymers; polyamide resins typified by nylon 6 or nylon 66; cellulose resins such as cellulose triacetate, cellophane, and celluloid; styrene resins such as polystyrene, acrylonitrile-styrene copolymers, and acrylonitrile-butadiene-styrene copolymers (ABS); polyvinyl alcohol, ethylene-vinyl acetate copolymers, ethylene-vinyl alcohol copolymers, polycarbonate resins, polyarylate resins, and polyimide resins. Examples of the curable resin composition include the thermosetting resin composition and the ionizing radiation curable resin composition exemplified for the matte layer described below. Natural resins include natural rubber, pine resin, and amber.

[0020] Examples of metals used for the substrate include aluminum or aluminum-containing alloys such as duralumin, iron or iron-containing alloys such as carbon steel and stainless steel, copper or copper-containing alloys such as brass and bronze, gold, silver, chromium, nickel, cobalt, tin, titanium, etc. Metal substrates that have been plated with these metals or the like can also be used.

[0021] Examples of non-metallic inorganic materials used for the substrate include non-ceramic ceramic materials such as cement, ALC (aerated lightweight concrete), gypsum, calcium silicate, and wood chip cement; ceramic ceramic materials such as porcelain, earthenware, glass, and enamel; and natural stones such as limestone, marble, granite, and andesite.

[0022] Examples of fibrous materials used for the substrate include tissue paper, kraft paper, fine paper, Japanese paper, titanium paper, linter paper, parchment paper, paraffin paper, parchment paper, glassine paper, wallpaper backing paper, paperboard and plasterboard base paper, and other papers; and woven or nonwoven fabrics made of fibers such as silk, cotton, linen, polyester resin fiber, acrylic resin fiber, glass fiber, and carbon fiber. Paper may further contain resins such as acrylic resin, styrene butadiene rubber, melamine resin, and urethane resin to increase the interfiber strength of the paper substrate or prevent fuzzing of the paper substrate. Examples of resin-added paper include interfiber reinforced paper and resin-impregnated paper. Furthermore, an example of a substrate in which a resin layer is laminated onto a fibrous material layer is wallpaper roll in which a resin layer such as a vinyl chloride resin layer, an olefin resin layer, or an acrylic resin layer is laminated onto the surface of wallpaper backing paper.

[0023] The substrate may contain additives as necessary. When the material constituting the substrate is a resin, examples of the additives include inorganic substances such as calcium carbonate and clay, flame retardants such as magnesium hydroxide, antioxidants, lubricants, foaming agents, ultraviolet absorbers, and light stabilizers. The content of the additives is not particularly limited as long as it does not impair processing characteristics, and can be set appropriately depending on the required characteristics, etc.

[0024] The shape and dimensions of the substrate are not particularly limited and may be appropriately selected depending on the intended use, desired performance properties and processability. When the substrate is a flat film, sheet, or plate, the thickness is a typical dimension in the design of the article. There are no particular restrictions on the thickness, but it is generally set to about 10 μm or more and 10 cm or less from the viewpoints of manufacturing processability, mechanical strength, ease of use and handling, and economic efficiency. In the case of a film or sheet, a thickness of about 20 μm or more and 300 μm or less is usually selected, and in the case of a plate, a thickness of about 1 mm or more and 2 cm or less is usually selected.

[0025] In order to improve adhesion to other layers constituting the decorative material, the substrate may be subjected to a surface treatment such as a physical surface treatment, such as an oxidation method or a roughening method, or a chemical surface treatment, on one or both sides of the substrate. Examples of oxidation methods include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone-ultraviolet treatment, etc. Examples of roughening methods include sandblasting, solvent treatment, etc. These surface treatments are appropriately selected depending on the type of substrate, but generally, corona discharge treatment is preferably used in terms of the effect of the surface treatment, operability, etc.

[0026] <Matte layer> The matte layer contains a binder resin, resin particles, and inorganic particles. When the decorative material is viewed from above, the matte layer has a first region containing resin particles but not inorganic particles, and a second region containing inorganic particles but not resin particles. Furthermore, when the average thickness of the matte layer in the first region is defined as T1 and the average thickness of the matte layer in the second region is defined as T2, T2 <T1である。

[0027] The decorative material of the present invention can achieve both a pleasant feel and a low gloss by virtue of the matte layer having the above-described configuration. That is, the decorative material of the present invention can reduce the gloss of the decorative material by virtue of the second region containing inorganic particles but not resin particles. Furthermore, the decorative material of the present invention can impart a pleasant feel to the decorative material because T1, which indicates the average thickness of the first region containing resin particles but not inorganic particles, is greater than T2, which indicates the average thickness of the second region containing inorganic particles but not resin particles.

[0028] On the other hand, if the matte layer does not have the above-mentioned structure, it is not possible to achieve both a good feel and a low gloss. First, if the matte layer does not contain inorganic particles but contains only resin particles, it is not possible to reduce the gloss of the decorative material. In addition, when the matte layer contains no resin particles but only inorganic particles, the matte layer turns white, and the design property deteriorates due to, for example, the visibility of the decorative layer deteriorating. Also, when the matte layer contains no resin particles but only inorganic particles, the gloss of the matte layer extremely decreases, and it may lack a natural texture. Further, since the inorganic particles have lower adhesion to the binder resin than the resin particles, they are more likely to fall off from the matte layer than the resin particles. Larger inorganic particles are more likely to fall off from the matte layer. Therefore, when the matte layer contains no resin particles but only inorganic particles, defects due to the falling off of the inorganic particles are likely to occur. Also, since the refractive index difference between the binder resin and the inorganic particles is relatively large, when the inorganic particles fall off from the matte layer, the gloss changes significantly. Also, even when the matte layer contains resin particles and inorganic particles, if it does not have the first region and the second region, the entire matte layer has a uniform composition, and the touch and gloss in the plane of the matte layer are made uniform. When the touch in the plane of the matte layer is made uniform, it may feel artificial and uncomfortable, or the touch (concavo-convex feeling) itself may decrease. Also, when the gloss in the plane of the matte layer is made uniform, it has an artificial texture, and it becomes difficult to express the appearance of natural materials such as natural wood. Also, even if it has the first region and the second region, if T2 < T1 is not satisfied, it is impossible to achieve both good touch and low gloss. For example, when T1 = T2, the touch cannot be improved. Also, when T1 < T2, larger inorganic particles are more likely to fall off from the matte layer, and defects are more likely to be noticeable.

[0029] Also, when using only inorganic particles, it can be said that it is difficult to achieve both good touch and low gloss for the following reasons. Inorganic particles such as silica for blending into ink are usually manufactured by a method of growing the particle size by synthesis. In the above-described manufacturing method by synthesis, it is possible to manufacture particles with a somewhat uniform particle size, but the maximum particle size remains at about 18 μm, and it is difficult to manufacture larger inorganic particles. Thus, it is difficult to obtain inorganic particles with a large particle size that can improve the touch. Another method for producing inorganic particles such as silica involves crushing large clumps of inorganic particles. While the aforementioned crushing method produces inorganic particles with large particle sizes, the particle size distribution is extremely broad, ranging from several tens of microns to several hundred microns. As a result, the properties of the material, such as tactile feel and low gloss, are unstable, making it unsuitable as an additive for ink.

[0030] T1, which indicates the average thickness of the matte layer in the first region, and T2, which indicates the average thickness of the matte layer in the second region, can be calculated, for example, from a cross-sectional photograph of the decorative material. Specifically, T1 and T2 can be calculated by the following steps (1) to (4). (1) Taking a cross-sectional photograph of the decorative material The cross-sectional photograph can be taken using, for example, a scanning electron microscope (SEM). (2) Extract each of the first regions R1 and each of the second regions R2 from the cross-sectional photograph. (3) In any first region R1 of the cross-sectional photograph, the thickness of the matte layer at the thickest point is defined as T1-n. Also, in any second region R2 of the cross-sectional photograph, the thickness of the matte layer at the thickest point is defined as T2-n. (4) Repeat steps (1) to (3) above until 20 T1-n locations and 20 T2-n locations are obtained. Then, define the average of the 20 T1-n locations as T1 and the average of the 20 T2-n locations as T2.

[0031] In the above (3), the thickness of the thickest part of the matte layer in any first region R1 of the cross-sectional photograph is defined as T1-n. However, the first region R1 of the cross-sectional photograph does not always cut through the center of the resin particle, but also includes parts that do not pass through the center of the resin particle. Therefore, T1-n can be said to contain thickness information of various parts of the first region R1. Therefore, T1 and T2 obtained in the above steps (1) to (4) can be said to represent the average thickness of the matte layer in the first region and the average thickness of the matte layer in the second region.

[0032] T1-T2 is preferably 15 μm or more and 60 μm or less, more preferably 25 μm or more and 50 μm or less, and even more preferably 30 μm or more and 45 μm or less. By setting T1-T2 to 15 μm or more, it is possible to improve the tactile feel, and by setting T1-T2 to 60 μm or less, it is possible to impart a moderate tactile feel that is natural for use as a surface material for general furniture and fittings and does not cause any problems in use.

[0033] From the viewpoint of making it easier to set T1-T2 within the above range, T1 and T2 are preferably within the following ranges. T1 is preferably 20 μm or more and 70 μm or less, more preferably 25 μm or more and 65 μm or less, and even more preferably 30 μm or more and 60 μm or less. T2 is preferably 5 μm or more and 20 μm or less, more preferably 7 μm or more and 17 μm or less, and even more preferably 10 μm or more and 15 μm or less.

[0034] The number of first regions and second regions in the matte layer is not particularly limited. Since the resin particles and inorganic particles are sufficiently small and contained in a predetermined amount, the matte layer usually contains an infinite number of first regions and second regions.

[0035] The area ratio of the first region R1 to the second region R2 in the matte layer is preferably 1.0:2.0 to 2.0:1.0, and more preferably 1.0:1.3 to 1.3:1.0. By setting the area ratio within this range, it is easier to achieve a good balance between the feel and the matte finish.

[0036] The matte layer may have other regions in addition to the first region R1 and the second region R2. Examples of other regions include "regions of the entire matte layer that contain no resin particles or inorganic particles and contain only binder resin when the decorative material is viewed in a plan view" and "regions of the entire matte layer that contain both resin particles and inorganic particles when the decorative material is viewed in a plan view."

[0037] When the total area of the matte layer in a plan view of the decorative material is taken as 100, the sum of the areas of the first region R1 and the second region R2 is preferably 10 or more, more preferably 30 or more, and even more preferably 40 or more. By making the sum of the areas of the first region R1 and the second region R2 relative to the total area of the matte layer 10 or more, it is possible to easily achieve a good feel to the touch and a good matte finish. Furthermore, when the total area of the matte layer in a plan view of the decorative material is taken as 100, the sum of the areas of the first region R1 and the second region R2 is preferably 70 or less, more preferably 65 or less, and even more preferably 60 or less. By making the sum of the areas of the first region R1 and the second region R2 relative to the total area of the matte layer 70 or less, it becomes easier to synchronize the pattern of the matte layer with the pattern of the decorative layer. This makes it easier to link the visual design with the tactile feel.

[0038] In the cross-sectional view of Figure 1, among the resin particles in the first region, the tops of the particles on the left are covered with binder resin, while the tops of the particles on the right are not. Thus, the tops of the resin particles in the first region may or may not be covered with binder resin. Resin particles whose tops are covered with binder resin have a gentler uneven shape due to the resin particles, resulting in a slightly reduced tactile feel. However, since the entire resin particle is protected by the binder resin, they tend to have better scratch resistance. On the other hand, resin particles whose tops are not covered with binder resin are exposed, resulting in poor scratch resistance, but the uneven shape of each particle tends to directly affect the tactile feel in a positive way. If the average particle size of the resin particles is large or the amount of binder resin relative to the resin particles is small, the tops of the resin particles are less likely to be covered with binder resin.

[0039] Furthermore, the proportion of resin particles whose tops are covered with binder resin among all the resin particles in the first region is preferably 50% or more, more preferably 70% or more, and even more preferably 80% or more. By satisfying this constitution, it becomes easier to protect the entire particles with binder resin, and a decorative material with high scratch resistance can be obtained.

[0040] Of all the resin particles in the first region, the proportion of resin particles whose tops are covered with binder resin is preferably less than 50%, more preferably 30% or less, and even more preferably 20% or less. By satisfying this configuration, the uneven shape caused by each particle becomes more pronounced, and a cosmetic material with an even better feel can be obtained.

[0041] <Binder resin> Examples of binder resins include thermoplastic resins and cured products of curable resin compositions. Among these, cured products of curable resin compositions are preferred from the viewpoint of scratch resistance. That is, the binder resin preferably contains a cured product of a curable resin composition. Furthermore, the proportion of the cured product of the curable resin composition to the total amount of binder resin is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 90% by mass or more, and most preferably 100% by mass.

[0042] Examples of thermoplastic resins include acrylic resins, cellulose resins, urethane resins, vinyl chloride resins, polyester resins, polyolefin resins, polycarbonate, nylon, polystyrene, and ABS resins.

[0043] Examples of the cured product of the curable resin composition include a cured product of a heat-curable resin composition and a cured product of an ionizing radiation-curable resin composition. The cured product of a heat-curable resin composition is preferred in terms of surface performance such as scratch resistance and contamination resistance. The cured product of an ionizing radiation-curable resin composition is preferred in terms of excellent surface performance such as scratch resistance and contamination resistance, as well as excellent performance retention over time.

[0044] The thermosetting resin composition is a composition that contains at least a thermosetting resin and is a resin composition that is cured by heating. Examples of thermosetting resins include acrylic resins, urethane resins, phenolic resins, urea melamine resins, epoxy resins, unsaturated polyester resins, silicone resins, etc. In addition to these thermosetting resins, a curing agent, a curing catalyst, etc. are added to the thermosetting resin composition as needed.

[0045] Among thermosetting resin compositions, two-component curing compositions using a polyol-based resin as the base and an isocyanate-based compound as the curing agent are preferred. Examples of polyol-based resins include acrylic polyols and polyester polyols.

[0046] Representative examples of the ionizing radiation curable resin composition include an electron beam curable resin composition and an ultraviolet ray curable resin composition, and among these, an electron beam curable resin composition is preferred from the viewpoints of having less odor and being less likely to be discolored because a polymerization initiator is not required, etc. Furthermore, when the matte layer contains an ultraviolet ray absorber described later, an electron beam curable resin composition is preferred in that it is easier to increase the crosslink density of the matte layer and to improve the scratch resistance and contamination resistance.

[0047] The ionizing radiation curable resin composition is a composition containing a compound having an ionizing radiation curable functional group (hereinafter also referred to as "ionizing radiation curable compound"). The ionizing radiation-curable functional group is a group that crosslinks and cures upon irradiation with ionizing radiation, and preferred examples thereof include functional groups having an ethylenic double bond such as a (meth)acryloyl group, a vinyl group, and an allyl group. Further examples of the ionizing radiation-curable functional group include an epoxy group and an oxetanyl group. In this specification, the term "(meth)acryloyl group" refers to an acryloyl group or a methcroyl group, and the term "(meth)acrylate" refers to an acrylate or a methacrylate. Furthermore, ionizing radiation refers to electromagnetic waves or charged particle beams that have an energy quantum capable of polymerizing or crosslinking molecules. Typically, ultraviolet (UV) rays or electron beams (EB) are used, but it also includes other electromagnetic waves such as X-rays and gamma rays, and charged particle beams such as alpha rays and ion beams. Specifically, the ionizing radiation curable compound can be appropriately selected from polymerizable monomers and polymerizable oligomers (sometimes referred to as "polymerizable prepolymers") that have conventionally been used as ionizing radiation curable resins.

[0048] The ionizing radiation curable compound is preferably a compound having two or more ethylenically unsaturated bond groups, and more preferably a polyfunctional (meth)acrylate compound having two or more ethylenically unsaturated bond groups. The polyfunctional (meth)acrylate compound may be either a monomer or an oligomer.

[0049] Among the polyfunctional (meth)acrylate compounds, examples of bifunctional (meth)acrylate monomers include ethylene glycol di(meth)acrylate, bisphenol A tetraethoxydiacrylate, bisphenol A tetrapropoxydiacrylate, and 1,6-hexanediol diacrylate. Examples of trifunctional or higher (meth)acrylate monomers include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol tetra(meth)acrylate, and isocyanuric acid-modified tri(meth)acrylate. Examples of the polyfunctional (meth)acrylate oligomer include acrylate polymers such as urethane (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, and polyether (meth)acrylate.

[0050] Urethane (meth)acrylates can be obtained, for example, by reacting a polyhydric alcohol and an organic diisocyanate with a hydroxy (meth)acrylate.

[0051] Preferred epoxy (meth)acrylates are (meth)acrylates obtained by reacting a tri- or higher functional aromatic epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, or the like with (meth)acrylic acid; (meth)acrylates obtained by reacting a di- or higher functional aromatic epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, or the like with a polybasic acid and (meth)acrylic acid; and (meth)acrylates obtained by reacting a di- or higher functional aromatic epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, or the like with a phenol and (meth)acrylic acid.

[0052] The above ionizing radiation curable resins can be used alone or in combination of two or more.

[0053] When the ionizing radiation curable compound is an ultraviolet ray curable compound, the ionizing radiation curable resin composition preferably contains additives such as a photopolymerization initiator and a photopolymerization accelerator. The photopolymerization initiator may be one or more selected from acetophenone, benzophenone, α-hydroxyalkylphenone, Michler's ketone, benzoin, benzil dimethyl ketal, benzoyl benzoate, α-acyloxime ester, thioxanthones, and the like. The photopolymerization accelerator can reduce polymerization inhibition caused by air during curing and increase the curing rate, and examples thereof include one or more selected from p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid ethyl ester, etc.

[0054] Resin particles The resin particles may be formed from one or more of resins such as polymethyl methacrylate, polyacrylic-styrene copolymer, melamine resin, polycarbonate, polystyrene, polyvinyl chloride, benzoguanamine-melamine-formaldehyde condensate, silicone resin, fluorine-based resin, and polyester-based resin. Among these, polymethyl methacrylate particles are preferred. The resin particles are preferably spherical in shape.

[0055] When the average particle size of the resin particles is defined as D1, D1 is preferably 20 μm or more and 70 μm or less, more preferably 25 μm or more and 65 μm or less, and even more preferably 30 μm or more and 60 μm or less. By setting D1 to 20 μm or more, it is possible to improve the tactile feel. Also, by setting D1 to 20 μm or more, it is possible to easily form a first region that does not contain inorganic particles but contains resin particles. Also, by setting D1 to 70 μm or less, it is possible to easily prevent the resin particles from falling off the matte layer. Furthermore, the proportion of resin particles having an average particle diameter within ±20 μm is preferably 70% or more, more preferably 80% or more, even more preferably 90% or more, and most preferably 95% or more.

[0056] In this specification, the average particle size of resin particles and inorganic particles refers to the mass average value d50 measured in particle size distribution measurement by laser light diffraction method.

[0057] The content of the resin particles is preferably 5 to 35 parts by weight, more preferably 10 to 30 parts by weight, and even more preferably 15 to 25 parts by weight, per 100 parts by weight of the binder resin. By setting the content to 5 parts by weight or more, it is possible to improve the tactile feel. Furthermore, by setting the content to 35 parts by weight or less, it is possible to suppress an increase in gloss due to the resin particles, and to achieve a design with a natural texture.

[0058] 《Inorganic particles》 The inorganic particles include those formed from one or more inorganic substances such as silica, alumina, zirconia, and titania, among which silica is preferred. The shape of the inorganic particles may be spherical or irregular, but spherical particles are preferred.

[0059] When the average particle size of the inorganic particles is defined as D2, D2 is preferably 5 μm or more and 20 μm or less, more preferably 7 μm or more and 17 μm or less, and even more preferably 10 μm or more and 15 μm or less. By setting D2 to 5 μm or more, it is possible to easily reduce the gloss. Also, by setting D2 to 5 μm or more, it is possible to easily form a second region that does not contain resin particles but contains inorganic particles. Also, by setting D2 to 20 μm or less, it is possible to easily make T1 larger than T2, which makes it easier to improve the tactile feel. Furthermore, the proportion of inorganic particles having a particle size 20 μm or more larger than the average particle size is preferably 30% or less, more preferably 20% or less, even more preferably 10% or less, and most preferably 5% or less.

[0060] The content of inorganic particles is preferably 4 to 30 parts by mass, more preferably 7 to 25 parts by mass, and even more preferably 10 to 20 parts by mass, per 100 parts by mass of binder resin. Setting the content to 4 parts by mass or more makes it easier to reduce gloss. Setting the content to 30 parts by mass or less makes it easier to prevent a decrease in visibility due to whitening of the matte layer and to prevent a drastic decrease in gloss of the matte layer, which would impair the natural texture.

[0061] The difference between D1, which indicates the average particle size of the resin particles, and D2, which indicates the average particle size of the inorganic particles, is preferably set within a predetermined range so as to easily achieve both a good touch and a low gloss feel. Specifically, the difference (D1-D2) is preferably 15 μm or more and 60 μm or less, more preferably 25 μm or more and 50 μm or less, and even more preferably 30 μm or more and 45 μm or less.

[0062] The resin particles and inorganic particles are preferably used in a predetermined ratio to easily achieve both a good feel and a low gloss. Specifically, the content of the inorganic particles is preferably 40 parts by mass or more and 200 parts by mass or less, more preferably 50 parts by mass or more and 150 parts by mass or less, and even more preferably 60 parts by mass or more and 110 parts by mass or less, relative to 100 parts by mass of the resin particles.

[0063] The matte layer is preferably provided on one surface of the substrate, and is preferably located on the outermost surface in the thickness direction of the decorative material. The matte layer may be present on a portion of the substrate, or may be present on the entire surface of the substrate. When the matte layer is present on a portion of the substrate, areas with the matte layer and areas without the matte layer are formed within the surface of the decorative material, which allows for a contrast in gloss within the surface and makes it easier to impart a three-dimensional effect. In addition to this point, the areas with the matte layer are more easily visible as recessed compared to areas without the matte layer.

[0064] The matte layer may contain additives as needed, such as antioxidants, ultraviolet absorbers, light stabilizers, and silicone oils.

[0065] The matte layer can be formed, for example, by applying, drying, and curing a matte layer ink containing materials constituting the matte layer (binder resin, resin particles, inorganic particles, etc.) and a solvent added as needed, onto a substrate.

[0066] <Other layers> The decorative material may have layers other than the substrate and the matte layer, such as a decorative layer, a primer layer, and an adhesive layer.

[0067] Decorative Layer The decorative material may have a decorative layer to improve the design. From the viewpoint of improving the weather resistance of the decorative layer, the decorative layer is preferably located closer to the substrate. Specifically, the decorative layer is preferably disposed between the substrate and the matte layer. Furthermore, when a primer layer (described later) is disposed between the substrate and the matte layer, the decorative layer is preferably disposed between the substrate and the primer layer. The decorative layer may be formed on the entire surface of the decorative material, or may be formed on only a part of the surface.

[0068] Examples of the decorative layer include a colored layer formed by applying ink in a solid manner, a patterned layer formed by printing ink as a pattern, and a thin metal film. Examples of patterns (designs) that can be expressed by the decorative layer include wood grain patterns such as tree rings and vessel grooves on the surface of wooden boards; stone grain patterns on the surface of stone slabs such as marble and granite; fabric grain patterns on the surface of fabric; leather grain patterns on the surface of leather; tile patterns including grooves; brickwork patterns including grooves; sand grain patterns; pear-skin patterns; patterns consisting of an arrangement of multiple concave and convex stripes extending in parallel directions (so-called ``line-like concave and convex patterns'' or ``ray-carved patterns''); and abstract patterns such as geometric patterns, letters, figures, polka dots, and floral designs.

[0069] The ink used for the colored layer and the design layer is a mixture of a binder resin with an appropriate amount of a colorant such as a pigment or dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, an ultraviolet absorber, a light stabilizer, etc. The binder resin for the colored layer and the design layer is not particularly limited, and examples thereof include urethane resin, acrylic polyol resin, acrylic resin, ester resin, amide resin, butyral resin, styrene resin, urethane-acrylic copolymer, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-acrylic copolymer resin, chlorinated propylene resin, nitrocellulose resin, cellulose acetate resin, etc. In addition, various types of resins can be used, such as one-component curing resins and two-component curing resins containing a curing agent such as an isocyanate compound.

[0070] The colorant is not particularly limited, and examples thereof include inorganic pigments such as carbon black (ink), iron black, titanium white, antimony white, yellow lead, titanium yellow, red iron oxide, cadmium red, ultramarine blue, and cobalt blue; organic pigments or dyes such as quinacridone red, isoindolinone yellow, nickel azo complex, phthalocyanine blue, and azomethine azo black; metal pigments consisting of flaky flakes of aluminum, brass, or the like; and pearlescent pigments consisting of flaky flakes of titanium dioxide-coated mica, basic lead carbonate, or the like. The content of the colorant is not particularly limited, as it varies depending on the pattern, color, and density of the decorative layer, as well as the material of the colorant. That is, the content of the colorant may be freely selected as appropriate, taking into consideration the above-mentioned factors. For example, the content of the colorant is preferably 20 to 500 parts by mass, more preferably 50 to 300 parts by mass, and even more preferably 70 to 200 parts by mass, per 100 parts by mass of the resin constituting the colored layer and the pattern layer.

[0071] The color layer and the design layer may contain additives such as ultraviolet absorbers, light stabilizers, and colorants. The thickness of the colored layer and the patterned layer may be selected appropriately depending on the desired pattern, but from the viewpoint of concealing the base color of the adherend and improving the design, it is preferably 0.5 μm or more and 20 μm or less, more preferably 1 μm or more and 10 μm or less, and even more preferably 2 μm or more and 5 μm or less.

[0072] Examples of metal thin films include thin films of simple metal elements such as gold, silver, copper, tin, iron, nickel, chromium, and cobalt, and thin films of alloys containing two or more of the above metal elements. Examples of alloys include brass, bronze, and stainless steel. The metal thin film can have a thickness of about 0.1 μm to 1 μm.

[0073] <Primer layer> The decorative material may have a primer layer to improve adhesion between the substrate and the matte layer.

[0074] The primer layer is mainly composed of a binder resin, and may contain additives such as an ultraviolet absorber and a light stabilizer, if necessary. Preferred examples of binder resins include urethane resins, acrylic polyol resins, acrylic resins, ester resins, amide resins, butyral resins, styrene resins, urethane-acrylic copolymers, polycarbonate-based urethane-acrylic copolymers (urethane-acrylic copolymers derived from polymers (polycarbonate polyols) having carbonate bonds in the polymer main chain and two or more hydroxyl groups at the terminals and side chains), vinyl chloride-vinyl acetate copolymer resins, vinyl chloride-vinyl acetate-acrylic copolymer resins, chlorinated propylene resins, nitrocellulose resins (nitrocellulose), and cellulose acetate resins. These may be used alone or in combination. Furthermore, the binder resin may be a resin obtained by adding a curing agent such as an isocyanate-based curing agent or an epoxy-based curing agent to the resin and crosslinking and curing the resin. Among these, a polyol-based resin such as an acrylic polyol resin is preferably crosslinked and cured with an isocyanate-based curing agent, and an acrylic polyol resin is more preferably crosslinked and cured with an isocyanate-based curing agent.

[0075] The primer layer preferably contains an ultraviolet absorber and / or a light stabilizer to further improve weather resistance. General-purpose ultraviolet absorbers and light stabilizers can be used.

[0076] The thickness of the primer layer is preferably 0.01 μm or more and 10 μm or less, more preferably 0.7 μm or more and 8 μm or less, and even more preferably 1.0 μm or more and 6 μm or less.

[0077] 《Adhesive layer, adherend》 The decorative material may have an adhesive layer on the surface of the substrate opposite the matte layer, and the decorative material may have an adherend on the surface of the adhesive layer opposite the substrate.

[0078] The adhesive used in the adhesive layer is not particularly limited, and known adhesives can be used, and preferred examples include heat-sensitive adhesives and pressure-sensitive adhesives. Examples of resins used in the adhesive constituting this adhesive layer include acrylic resins, polyurethane resins, vinyl chloride resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymer resins, styrene-acrylic copolymer resins, polyester resins, and polyamide resins, and these can be used alone or in combination. Two-component curing polyurethane adhesives and polyester adhesives using an isocyanate compound or the like as a curing agent can also be used. The adhesive layer may also contain a pressure-sensitive adhesive, which may be appropriately selected from acrylic, urethane, silicone, rubber, and other pressure-sensitive adhesives.

[0079] The adhesive layer can be formed by applying the above resin in a coatable form such as a solution or emulsion by means of gravure printing, screen printing, or reverse coating using a gravure plate, and then drying the applied resin. The thickness of the adhesive layer is not particularly limited, but from the viewpoint of obtaining excellent adhesiveness, it is preferably from 1 μm to 100 μm, more preferably from 5 μm to 50 μm, and even more preferably from 10 μm to 30 μm.

[0080] Examples of the substrate include wooden components used as plates or three-dimensional articles, such as wood veneers made from various types of wood such as cedar, cypress, pine, and lauan, wood plywood, particle board, MDF (medium-density fiberboard), and wood fiberboards such as laminated lumber; metal components used as plates or steel plates, three-dimensional articles, or sheets, such as iron or aluminum; ceramic components used as plates or three-dimensional articles, such as glass, ceramics such as porcelain, non-cement ceramic materials such as gypsum, and non-ceramic ceramic materials such as ALC (aerated lightweight concrete) board; and resin components used as plates, three-dimensional articles, or sheets, such as acrylic resin, polyester resin, polystyrene, polypropylene and other polyolefin resins, ABS (acrylonitrile-butadiene-styrene copolymer) resin, phenolic resin, vinyl chloride resin, cellulose resin, and rubber.

[0081] <Application> The decorative material of the present invention can be used for various purposes, including the following (1) to (9): (1) Surface materials for interior walls, floors, ceilings, etc. of buildings such as houses, offices, stores, hospitals, and clinics. (2) Surface materials for exterior parts such as exterior walls, roofs, eaves ceilings, door pockets, etc. of buildings such as houses, offices, stores, hospitals, and clinics. (3) Surface materials for building fixtures such as windows, window frames, doors, and door frames (interior or exterior parts); surface materials for fixture accessories (handles, etc.); surface materials for building fixture jigs. (4) Surface materials for fixtures such as handrails, waist walls, moldings, thresholds, lintels, and top boards. (5) Surface materials for outdoor (exterior) parts such as fences, gates, drying rack pillars and handrails. (6) Surface materials for furniture such as chests of drawers, desks, chairs, cupboards, kitchen sinks, etc.; surface materials for furniture accessories (handles, etc.); surface materials for furniture fixtures. (7) Surface materials for the housings of various home appliances such as television receivers, radio receivers, refrigerators, microwave ovens, washing machines, electric fans, and air conditioners; surface materials for accessories of home appliances (handles, switches, touch panels, etc.); surface materials for fixtures of home appliances. (8) Surface materials for office automation equipment such as electronic copying machines, facsimiles, printers, personal computers, and other computing equipment; surface materials for the housings of various office automation equipment such as ATM machines at financial institutions such as banks and post offices; surface materials for accessories of various office automation equipment (keyboards, touch panels, etc.); surface materials for jigs of various office automation equipment. (9) Surface materials for the interior or exterior parts (walls, floors, ceilings, handrails, supports, control panels, levers, handles, steering wheels, and other control equipment) of vehicles such as automobiles, railway cars, ships, and aircraft. [Example]

[0082] Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples in any way.

[0083] 1. Measurement and Evaluation The decorative materials of the Examples and Comparative Examples were measured and evaluated as follows. The atmosphere during each measurement and evaluation was a temperature of 23±5°C and a humidity of 40 to 65%. Before each measurement and evaluation, the target sample was exposed to the above atmosphere for 30 minutes or more before measurement and evaluation. The results are shown in Table 1.

[0084] 1-1.Tactile sensation Twenty subjects evaluated the tactile sensation of the cosmetic materials obtained in the Examples and Comparative Examples. The 20 subjects consisted of five subjects each in their 20s, 30s, 40s, and 50s. Each subject touched the surface of the matte layer of the cosmetic material with the pad of the index finger of their dominant hand and evaluated whether the tactile sensation was high or low. The tactile sensation was evaluated based on whether or not there was a strong sense of unevenness and whether or not the sensation felt natural and not like an artificial object. Table 1 shows the results of the compiled tactile sensation evaluations, classified according to the following criteria. A: More than 18 out of 20 people answered that the tactile sensation was high. B: Between 15 and 17 out of 20 people answered that the tactile sensation was high. C: Between 11 and 14 out of 20 people answered that the tactile sensation was high. D: Fewer than 10 out of 20 people answered that the tactile sensation was high.

[0085] 1-2.Low gloss Twenty subjects evaluated the low gloss of the cosmetic materials obtained in the Examples and Comparative Examples. The 20 subjects consisted of five subjects each in their 20s, 30s, 40s, and 50s. Each subject visually observed the matte layer side of the cosmetic material and evaluated the low gloss of the area with the matte layer. The evaluation was carried out under fluorescent lighting in a room with external light blocked. The evaluation criterion for low gloss was whether or not the difference in gloss between the area with the matte layer and the area without it was sufficiently perceived. Table 1 shows the results of the compiled evaluation of low gloss, classified according to the following criteria. A: More than 18 out of 20 people answered that the gloss was low. B: Between 15 and 17 out of 20 people answered that the gloss was low. C: Between 11 and 14 out of 20 people answered that the gloss was low. D: Fewer than 10 out of 20 people answered that the gloss was low.

[0086] 1-3.T1 and T2 Following steps (1) to (4) of the specification, cross-sectional photographs of the decorative materials of the examples were taken using a scanning electron microscope (SEM), and T1, which indicates the average thickness of the matte layer in the first region, and T2, which indicates the average thickness of the matte layer in the second region, were calculated.

[0087] 2. Preparation of decorative materials [Example 1] Colored base paper for building materials ("CHPS45 (model number)", basis weight: 45 g / m 2 The substrate was a 5 μm thick wood grain patterned paper (manufactured by Tenma Tokushu Paper Co., Ltd.). A resin composition containing titanium white, red iron oxide, and yellow lead as colorants, and a mixed resin of acrylic resin and urethane resin as a binder, was applied by gravure printing to the surface of the substrate that had been treated for easy adhesion. Next, a wood grain patterned layer was formed on the colored layer using a resin composition containing soluble nitrocellulose as a binder and a colorant mainly composed of red iron oxide. A decorative layer was formed on the substrate by the colored layer and the patterned layer. Next, a primer layer ink containing a two-component curing resin (main component: acrylic polyol, curing agent: hexamethylene diisocyanate) was applied to the entire surface of the decorative layer and dried to form a primer layer with a thickness of 5 μm. Next, ink 1 for matte layer having the following formulation was applied to a part of the primer layer and dried to form a matte layer. The solid content of ink 1 for matte layer was about 4 g / m 2 Thereafter, heat curing was carried out at 70°C for 24 hours, and the decorative material of Example 1 was obtained.

[0088] <Matte layer ink 1> ·Two-component curable resin 100 parts by mass (Base: acrylic polyol, hardener: hexamethylene diisocyanate) ·Resin particles 19 parts by mass (spherical polymethyl methacrylate particles, average particle size 50 μm) ·Inorganic particles 14 parts by mass (spherical silica particles, average particle size 12 μm) Appropriate amount of solvent

[0089] [Example 2] A decorative material of Example 2 was obtained in the same manner as in Example 1, except that the resin particles in the matte layer ink 1 were changed to spherical polymethyl methacrylate particles having an average particle diameter of 30 μm.

[0090] [Example 3] A decorative material of Example 3 was obtained in the same manner as in Example 1, except that in the matte layer ink 1, the amount of resin particles added was changed to 22 parts by mass and the amount of inorganic particles added was changed to 11 parts by mass.

[0091] [Comparative Example 1] A decorative material of Comparative Example 1 was obtained in the same manner as in Example 1, except that the resin particles were removed from the matte layer ink 1 and the amount of inorganic particles added was changed from 14 parts by mass to 27 parts by mass.

[0092] Comparative Example 2 A decorative material of Comparative Example 2 was obtained in the same manner as in Example 1, except that the inorganic particles were removed from the matte layer ink 1 and the amount of resin particles added was changed from 19 parts by mass to 37 parts by mass.

[0093] [Table 1] [Explanation of symbols]

[0094] 100: Cosmetic materials 10: Base material 20: Matte layer 21: Binder resin 22: Resin particles 23: Inorganic particles R1: 1st area R2: 2nd area

Claims

1. A decorative material having a matte layer on a substrate, the matte layer contains a binder resin, resin particles, and inorganic particles; the resin particles are formed from one or more of polymethyl methacrylate, polyacrylic-styrene copolymer, melamine resin, polycarbonate, polystyrene, polyvinyl chloride, benzoguanamine-melamine-formaldehyde condensate, silicone resin, and polyester-based resin; When the decorative material is viewed from above, the matte layer has a first region that does not contain the inorganic particles but contains the resin particles, and a second region that does not contain the resin particles but contains the inorganic particles, When the average thickness of the matte layer in the first region is defined as T1 and the average thickness of the matte layer in the second region is defined as T2, T2<T1; When the average particle diameter of the resin particles is defined as D1 and the average particle diameter of the inorganic particles is defined as D2, D2 is 7 μm or more and 20 μm or less, and D1-D2 is 25 μm or more and 60 μm or less.

2. The decorative material according to claim 1, wherein the ratio of the resin particles whose tops are covered with the binder resin to all the resin particles in the first region is 50% or more.

3. The decorative material according to claim 1 , wherein the ratio of the resin particles whose tops are covered with the binder resin to all the resin particles in the first region is less than 50%.

4. The decorative material according to any one of claims 1 to 3, wherein when the average particle diameter of the resin particles is defined as D1, D1 is 30 µm or more and 70 µm or less.

5. The decorative material according to any one of claims 1 to 4, wherein the matte layer is provided on a portion of the substrate.

6. The decorative material according to any one of claims 1 to 5, further comprising a decorative layer between the substrate and the matte layer.

7. The decorative material according to any one of claims 1 to 6, wherein the constituent material of the substrate is at least one material selected from the group consisting of resins and fibrous materials.

8. A decorative material described in any one of claims 1 to 4, 6 and 7, having the matte layer on the entire surface of one side of the substrate.

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