JP7287016B2 - decorative material - Google Patents

Description

The present invention relates to a decorative material.

2. Description of the Related Art A decorative material having a metallic appearance is known as a decorative material used for decorating the surfaces of building materials, furniture, home electric appliances, and the like (Patent Document 1, etc.).

Patent Literature 1 proposes a decorative material in which a metal foil is vapor-deposited on a transparent resin layer having fine grooves on the back surface, and the transparent resin layer is attached to a substrate.

For a long time in Europe, there has been a tendency for furniture and the like containing metal members that have rusted over time to be prized as vintage or antique products.
In Japan as well, vintage and antique products have become more popular in recent years, and there is also demand for metallic decorative materials that express these designs.
However, since rust occurs spontaneously in irregular patterns, it is difficult to express the speckled pattern of rust naturally.
Conventionally, as in Patent Document 1, a decorative material that reproduces a metallic appearance by combining a printed pattern with a metal thin film layer and a hairline-like uneven pattern has been proposed. It is possible to reproduce the appearance of the rust speckled pattern to some extent by printing the speckled pattern.
However, in the real object with a metal surface partially having a mottled pattern, the appearance of the surface gloss appears to change depending on the combination of the incident direction of the illumination light and the viewing direction of the observer, and areas with and without rust. It is characterized by different tactile sensations depending on the area.
On the other hand, the appearance of the decorative material, which reproduces the metal surface with rust spots by printing, does not depend on the combination of the incident direction of the illumination light and the direction of the observer's line of sight, and the tactile sensation is monotonous regardless of the location. become something.
For this reason, a metallic decorative material that naturally expresses the appearance and feel of the mottled rust pattern has not been realized.

Japanese Patent Application Laid-Open No. 2001-001444

SUMMARY OF THE INVENTION An object of the present invention is to provide a metallic decorative material that naturally expresses the appearance and feel of a mottled rust pattern.

In order to solve the above problems, the present inventors provide the following [1].
[1] A decorative material having a resin base layer, a pattern layer, and a metal layer disposed on the inner layer side of the pattern layer, wherein the surface of the pattern layer side with respect to the metal layer, A parallel curve group concavo-convex pattern having a plurality of independent convex regions and concave regions surrounding the convex regions, wherein a large number of fine lines having a curved shape in plan view are arranged in parallel in the concave regions; and/or a decorative material comprising a multitude of parallel linear fine lines arrayed in parallel to each other and having an uneven pattern with parallel straight lines in plan view.

The decorative material of the present invention has a metallic tone that naturally expresses the appearance and feel of a mottled rust pattern, and can reproduce a vintage-like or antique-like design very satisfactorily.

It is an explanatory view of a cross section of a portion of the decorative material of one embodiment of the present invention. (It is an explanatory view of the cross section of the decorative material taken along a virtual cut plane that includes the virtual line AA' in FIG. 3 and is parallel to the thickness direction of the decorative material, that is, the Z-axis direction.) 1 is a photomicrograph (×120) in plan view of the decorative material of one embodiment of the present invention, taken from above the surface on the pattern layer side in a line-of-sight direction parallel to the thickness direction of the surface of the decorative material. FIG. 3 is a partially enlarged view of the photograph of FIG. 2; FIG. 3 is an explanatory view of the parallel curve group concavo-convex pattern in the same plane line of sight as in FIG. 2 ; FIG. 3 is an explanatory view of the uneven pattern of parallel straight lines in the same plane line of sight as in FIG. 2 ; FIG. 3 is an explanatory view of the uneven pattern of parallel straight lines in the same plane line of sight as in FIG. 2 ; FIG. 3 is an explanatory view of the uneven pattern of parallel straight lines in the same plane line of sight as in FIG. 2 ; FIG. 2 shows pattern data used to form a pattern layer in Examples. FIG. 2 is an explanatory diagram of the structure of fine lines forming the fine uneven pattern and various dimensions of the fine lines;

[Cosmetic material]
The decorative material 10 of the present invention, as shown in the cross-sectional view of FIG. A convex region 4 and a concave region 5 are provided on the surface on the pattern layer side with respect to the metal layer.
FIG. 1 shows a cut plane including the thickness direction of the decorative material 10 (the Z-axis direction in the same figure), which is cut along a virtual cut plane parallel to the ZX plane in the same figure.
Further, the appearance of the decorative material 10 looking down from the surface of the decorative material 10 on the pattern layer 2 side, that is, the angle θ formed by the thickness direction or the Z-axis in the figure and the line of sight direction L is 0°≦θ< The appearance looking down at 90° is called planar view. FIG. 2 and subsequent drawings show a plan view where the angle θ between the viewing direction L of the observer O and the thickness direction of the decorative material 10 (the Z-axis direction in these figures) is θ=0°. do.

<Surface shape of decorative material>
As shown in FIGS. 2 and 3, the convex regions 4 and the concave regions 5 are composed of a plurality of independent convex regions 4 and concave regions 5 surrounding the convex regions.
In the recessed area 5, as shown in FIG. 4, a parallel curved line group concavo-convex pattern 7 formed by arranging a large number of fine lines 6 that are curved in plan view in parallel with each other, and/or , includes a group of parallel straight lines uneven pattern 7 in which a large number of linear fine lines are arranged parallel to each other.
The parallel curve group concavo-convex pattern and/or the parallel straight line group concavo-convex pattern may be a concavo-convex pattern formed by embossing, or a concavo-convex pattern formed by thick film printing such as silk screen printing (so-called raised printing). It's okay.
Hereinafter, the group of parallel curves and/or the group of parallel straight lines will also be collectively referred to as the group of parallel lines. In addition, uneven patterns having parallel line shapes in plan view are collectively referred to as fine uneven patterns.
In the present invention, the convex region 4 and the concave region 5 are provided with a difference in glossiness by providing the concave region 5 with a fine concave-convex pattern. In addition, as shown in FIGS. 4 to 7, the surface of the recessed regions 5 has a fine uneven pattern exhibiting a group of parallel straight lines and/or a group of parallel curves when viewed from above. is the angle of incidence of the illumination light, the line-of-sight direction of the observer O, and the extending direction of the group of parallel lines (in the case of a curve, the angle of the curve at the point where the curve touches the specific light ray and line-of-sight direction. tangential direction).
Since the light incident on the convex region is reflected in the vicinity of the regular reflection direction without being attenuated, much light reaches the human eye. On the other hand, the light incident on the recesses of the fine uneven pattern of the recessed area is attenuated by multiple reflection, but the predetermined reflected light reaches the human eye. Therefore, a person can perceive gloss based on the reflected light with respect to the convex areas and the concave areas, and since the gloss of the convex areas is stronger than that of the concave areas, the person can feel unevenness due to the gloss difference.
Regarding each recessed region, the extent to which light incident on the recesses of the fine uneven pattern is reflected in the regular reflection direction is determined when viewed from the extending direction of the grooves and when viewed from a direction perpendicular to the extending direction of the grooves. different in The reason for this is that the attenuation due to multiple reflection of the light incident on the concave portion is less when viewed from the extending direction of the groove. In this way, due to the existence of the recesses (grooves), the intensity of the reflected light from each recessed region differs depending on the observation direction, so that humans can perceive changes in gloss (changes in shading) of individual recessed regions depending on the observation direction. can feel.
In addition, by configuring the fine uneven pattern with a curved line group (for example, FIG. 4) or a polygonal line group (for example, FIGS. 6 and 7), a gloss difference is given in each recessed area. It is possible to further enhance the aforementioned effects. In addition, by configuring the fine uneven pattern with a group of parallel straight lines (for example, FIG. 5), it is possible to impart different gloss to adjacent recessed areas, further enhancing the above effects. can be done.
On the other hand, since there is no group of parallel lines in the area, the gloss on the surface of the convex area 4 does not depend on the angle of the group of parallel lines. It is determined only by the incident angle and the line-of-sight direction of the observer O.
Due to the gloss difference between the convex regions 4 and the concave regions 5, for example, the surface of a polycrystalline body such as the surface of a galvanized steel plate, that is, the crystal structure of a metal coated with a plurality of single crystals arranged without gaps on the plane. Realizes a natural expression of the appearance of the

The fine lines 6 forming the fine rugged pattern forming a group of parallel lines in a plan view are composed of the ridges _6H as shown in the cross-sectional view of FIG. A groove-like recessed line portion _6L is formed between two adjacent protruded line portions _6H . 9 is cut along a virtual cutting plane (ZX plane or a plane parallel thereto in the drawing) perpendicular to the extending direction of the fine wire 6 (the Y-axis direction in the drawing). It is a cross-sectional view. The width W _H of the _protruding portion 6 _H forming the fine line 6 is preferably 20 μm to 200 μm, more preferably 50 μm to 150 μm.
In this specification, the width of the ridge _6H of the fine line indicates an average value of measured values at arbitrary 10 points.
The pitch P of the fine lines 6 is preferably 70 μm to 400 μm, more preferably 150 μm to 300 μm. _Here , the pitch _of the fine lines _{6 is} the distance between adjacent fine lines _. have a relationship.
In this specification, the fine wire pitch P indicates the average value of the measured values at 10 arbitrary points.
By setting the width W _H of the fine line 6 to 50 μm to 150 μm and the pitch P of the fine line 6 to 150 μm to 300 μm, it is possible to adjust the glossiness while making the fine line 6 itself less visible.
In the fine uneven pattern, the ratio W _H /P of the width W _H of the protruding portion _6H to the pitch P, that is, the duty ratio of the uneven pattern is W _H /P=20/100 to 80. /100, and more preferably W _H /P=30/100 to 70/100.
The height of the ridges _6H forming the fine lines 6 forming the fine rugged pattern is preferably 15 μm to 150 μm, more preferably 30 μm to 80 μm, in the cross-sectional shape.
By setting the height to 30 μm to 80 μm, the appearance and feel of the metal crystal structure can be expressed more naturally.
The above pitch, width and height data are average values of measured values at arbitrary 10 points, and can be measured by a surface shape measuring device. The measurement length shall be 1 mm. A specific measuring method will be described later.

<Physical properties of concave region 5 and convex region 4>
A concave region 5 containing a fine uneven pattern and a convex region 4 not containing a fine uneven pattern exhibit different surface gloss.
The difference between the JIS Z8741: 1997 20-degree glossiness of the convex area 4 and the JIS Z8741: 1997 20-degree glossiness of the concave area 5 [20-degree glossiness of convex area 4-20-degree glossiness of concave area 5] is preferably 30 or more.
By setting the difference to 30 or more, the difference in glossiness between the concave region 5 and the convex region 4 becomes clear, making it easy to naturally express the mottled rust pattern. The difference is more preferably 40 or more and 200 or less, even more preferably 60 or more and 180 or less, and even more preferably 80 or more and 150 or less.
The 20 degree glossiness of the convex region 4 is preferably 100 or more and 300 or less. The 20-degree glossiness of the surface of the concave region 5 is preferably 30 or more and 100 or less.
In this specification, the 20-degree gloss indicates the average value of the measured values at 10 arbitrary points.

The concave region 5 including the fine uneven pattern preferably has an arithmetic mean roughness Ra of 7 μm to 50 μm, more preferably 10 μm to 40 μm, according to JIS B0601:2001. By setting the lower limit to 7 μm or more, it is possible to easily provide a low-gloss region that visually exhibits a low-gloss appearance. It is possible to suppress deterioration of designability due to excessive unevenness due to.
In this specification, Ra indicates the average value of measured values at 10 arbitrary points.

The difference between the JIS B0601:2001 arithmetic mean roughness Ra of the surface of the convex region 4 and the JIS B0601:2001 arithmetic mean roughness Ra of the surface of the concave region 5 [Ra of concave region 5 - Ra of convex region 4] is preferably 7 μm or more.
By setting the difference to 10 μm or more, more preferably 12 μm, the difference in glossiness between the concave region 5 and the convex region 4 can be easily increased, and the rust spot pattern can be easily expressed naturally. Further, if the difference in arithmetic mean roughness Ra is given to a certain extent or more, the above effect is saturated, and if the difference in arithmetic mean roughness Ra is increased more than necessary, the surface of the low gloss region will not be too rough and will be visually recognized as a mere irregular shape. Therefore, the difference is more preferably 50 μm or less, more preferably 30 μm or less.
The arithmetic mean roughness Ra of JIS B0601:2001 of the surface of the convex region 4 is preferably 1 μm to 5 μm.
Note that the arithmetic mean roughness Ra of JIS B0601:2001 is a value at a cutoff value of 0.8 mm.

Usually, the height difference between the concave region and the convex region is about 5 μm to 20 μm, preferably 7 μm to 15 μm.
When the thickness is 7 μm or more, the feeling of natural rust can be enhanced. can be suppressed.
The elevation difference can be calculated from the average height of the convex regions and the average depth of the concave regions on the entire surface of the decorative material.
In this specification, the average height of the convex regions and the average depth of the concave regions are the average values of measured values at arbitrary 10 points, and can be measured by a surface shape measuring device. The measurement length shall be 1 mm. A specific measuring method will be described later.

The area ratio of the concave region 5 and the convex region 4 in the face of the decorative material can be concave region:convex region=0.1:1 to 8:1, but concave region:convex region=3:1 to 8:1. It is preferably 7:1, and more preferably concave area:convex area=5:1 to 6:1.
The area of the independent convex regions 4 is preferably 0.1×10 ⁷ μm ² to 8×10 ⁷ μm ² , more preferably 1×10 ⁷ μm ² to 5×10 ⁷ μm ² .

<Concave area 5>
The recessed area 5 preferably includes dividing lines 8 that demarcate the recessed area to form two or more adjacent recessed areas, as shown in FIG.
The partition line has a width of 50 to 300 μm in a plan view shape viewed in a line of sight parallel to the thickness direction (in FIG. 3, the Z axis direction, that is, a line of sight looking down from the normal direction of the paper surface). is preferable, and a width of 80 to 200 μm is more preferable.
By setting the width to 80 to 200 μm, the crystal structure of the metal can be expressed more naturally.
In this specification, the width of the demarcation line indicates the average value of the measured values at 10 arbitrary points.
The demarcation lines preferably have a height of 15 μm to 150 μm, more preferably 40 μm to 100 μm in cross-sectional shape.
By setting the height to 40 μm to 100 μm, the crystal structure of the metal can be expressed more naturally.
In this specification, the height of the marking line is the average value of the measured values at 10 arbitrary points, and can be measured by a surface shape measuring device. The measurement length shall be 1 mm. A specific measuring method will be described later.
The recessed area 5 consists of a set of closed areas formed by boundaries between the adjacent projected areas 4 and partition lines 8 . The area of each closed region is preferably 1×10 ⁷ μm ² to 10×10 ⁷ μm ² , more preferably 3×10 ⁷ μm ² to 6×10 ⁷ μm ² .

<Lamination structure of decorative material>
The decorative material of the present invention is formed by laminating the resin substrate layer, the adhesive layer, the metal layer, and the pattern layer in order from the bottom, and examples thereof include the following lamination structures 1 to 9. "/" indicates the layer interface, and the right side indicates the viewer's side.
1. Resin substrate layer/metal layer/pattern layer (observer side)
2. Resin substrate layer/metal layer/pattern layer/transparent protective layer (observer side)
3. Resin substrate layer/metal layer/transparent protective layer/pattern layer (observer side)
4. Resin substrate layer/metal layer/transparent adhesive layer/pattern layer (observer side)
5. Resin substrate layer/metal layer/pattern layer/transparent protective layer (observer side)
6. Resin base layer/adhesive layer/metal layer/pattern layer (observer side)
7. Resin substrate layer/adhesive layer/metal layer/pattern layer/transparent protective layer (observer side)
8. Resin substrate layer/adhesive layer/metal layer/transparent protective layer/pattern layer (observer side)
9. Resin substrate layer/adhesive layer/metal layer/transparent adhesive layer/pattern layer/transparent protective layer (observer side)
When the metal layer is a vapor-deposited metal layer, it may also contain a resin substrate for vapor deposition on which the metal layer is laminated. When the vapor deposition resin substrate is located on the observer's side with respect to the metal layer, the vapor deposition resin substrate is made of a transparent resin substrate.

The above (1) is the laminated structure of FIG. In the configuration of (1) above (the configuration of FIG. 1), the decorative material 10 has the resin base material layer 1, the metal layer 3, and the pattern layer 2 in this order, and the surface on the pattern layer 2 side has the above-described convex region. 4 and a recessed area 5 .

The "transparent protective layer" of (2), (3), (5), (7), (8), and (9) above is a transparent (layer The "adhesive layer" or "transparent adhesive layer" of the above (4), (6) to (9) is a resin layer that protects and covers each layer such as the pattern layer and the metal layer on the back side of the In addition to the adhesive layer of the dry laminate, pre-deposition treatment layers such as so-called deposition anchor layers and deposition primer layers are also included.

<Resin substrate layer>
The material of the substrate constituting the resin substrate layer is not particularly limited, but in consideration of the ease of forming convex regions and concave regions by embossing, a thermoplastic resin sheet or a composite of a thermoplastic resin sheet and paper is used. body is preferred.

Specific examples of the resin constituting the thermoplastic resin sheet include polyethylene, polypropylene, ionomer, polyolefin resin such as olefinic thermoplastic elastomer, vinyl chloride resin, vinylidene chloride resin, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, chloride vinyl resins such as vinyl-vinyl acetate copolymers, polyethylene terephthalate, polybutylene terephthalate, ethylene glycol-terephthalic acid-isophthalic acid copolymers, polyester resins such as polyester thermoplastic elastomers, polymethyl (meth)acrylate, Polyethyl (meth)acrylate, methyl (meth)acrylate-butyl (meth)acrylate copolymer, methyl (meth)acrylate-butyl (meth)acrylate copolymer-2hydroxyethyl (meth)acrylate Examples include acrylic resins such as copolymers, polystyrene, acrylonitrile-butadiene-styrene copolymer (ABS resin), cellulose triacetate, and polycarbonate. Among these, polyolefin resins, vinyl chloride resins, polyester resins, or acrylic resins are preferable from the viewpoint of various physical properties such as weather resistance and water resistance, printability, moldability, and price. In this specification, "(meth)acrylic acid" is a notation meaning "acrylic acid or methacrylic acid".

A laminate of a plurality of substrates may be used for the resin substrate layer.

The thickness of the resin substrate layer is not particularly limited, but is preferably 20 to 500 μm, more preferably 40 to 300 μm, even more preferably 50 to 200 μm.

The resin substrate layer may be subjected to adhesion-enhancing treatment such as physical treatment or chemical surface treatment on one side or both sides thereof in order to improve adhesion with the layer provided thereon.

<Metal layer>
The metal layer is a layer made of a metallic material having metallic luster. Specifically, metal deposition layers and metal foils can be exemplified.

Any metal material can be used depending on the desired color tone of metallic luster, reflectance, and the like. Good luck. In general, aluminum is often used because of its reflectivity, workability, and cost. Aluminum is excellent in terms of suitability for vacuum deposition, and when used as a foil, it is excellent in terms of foil-manufacturing properties and lamination suitability (particularly strength and high tensile strength).

The metal deposition layer is formed by depositing a metal material on a resin base material for deposition or on a resin base material layer by a vacuum film forming method such as a vacuum deposition method or a sputtering method. Although the thickness depends on the type of metal material and the desired reflectance, it is usually 10 nm to 300 nm, and more often about 30 nm to 60 nm.

The resin substrate for vapor deposition may be arranged on the resin substrate layer side with respect to the metal layer, or may be arranged on the observer side (hereinafter also referred to as the surface) with respect to the metal layer. In the example shown in FIG. 1, a metal layer 3 made of a metal vapor deposition layer is formed on the surface of a vapor deposition resin base material made of a thermoplastic resin sheet, and the vapor deposition resin base material is a resin base material with respect to the metal layer. placed on the layer side. The resin base material for vapor deposition will be described later.

In forming the metal layer 3 , an anchor coat layer can be provided between the resin base material for vapor deposition and the metal layer 3 if the adhesion with the resin base material for vapor deposition is not sufficient. As this anchor coat layer, for example, an anchoring agent for metal adhesion made of an acrylic resin, a polyester resin, a polyurethane resin, or the like can be used.

A protective coating layer may be provided on the surface of the metal layer 3 in order to improve rust prevention and scratch resistance of the metal layer 3 . As the protective coat layer, for example, acrylic resin, polyester resin, polyurethane resin, melamine resin, or the like can be used.

When a metal foil is used as the metal layer 3, for example, a dry lamination or wet lamination method via an adhesive layer, a thermal lamination method in which fusion is performed by heat and pressure, or a method in which the resin constituting the resin base layer 1 is melted. It is laminated with the resin substrate layer 1 by an appropriate lamination method such as an extrusion lamination method in which the support is extruded onto a metal foil and then laminated, or a coating method in which the resin constituting the support is dissolved or dispersed in an appropriate solvent and applied. be.

If the metal foil is too thick, it will increase the weight of the decorative material, make it difficult to mold into various shapes, and cause abrasion of cutting blades and generation of cutting shavings during cutting. It is preferable that the thickness is as thin as the processing technology such as lamination allows.

<<Resin base material for vapor deposition>>
A vapor deposition resin substrate used for forming a metal layer by a method involving a temperature rise such as vacuum vapor deposition must have a certain thickness, preferably about 25 μm or more, usually about 25 μm to 70 μm.

When the resin substrate for vapor deposition is arranged on the observer side (hereinafter also referred to as the surface) with respect to the metal layer, the resin substrate for vapor deposition is required to have transparency or light diffusion and transmission properties. Here, the light diffusing and transmitting property means that the metallic luster of the metal layer is cloudy to the extent that it is moderated, but not completely shielded. The degree of light diffuse transmittance is represented by total light transmittance and haze value. For example, a vapor deposition resin substrate having a total light transmittance of 60% or more and a haze value of 60% or more does not completely block the metallic luster of the underlying metal layer, but is cloudy enough to soften it. It is suitable for expressing vintage-like or antique-like brightness while suppressing stickiness. In this specification, the total light transmittance is measured according to JIS K7361:1997. Moreover, in this specification, the haze value shall be measured based on JISK7136:2000.
When the resin base material for vapor deposition is disposed on the resin base material layer side with respect to the metal layer, the resin base material for vapor deposition may be a shielding material that does not transmit light.

It is desirable to use a thermoplastic resin as the resin base material for vapor deposition in order to obtain a decorative material having good post-processing properties such as molding. The type of thermoplastic resin is not particularly limited, and examples include polyolefin resins such as polyethylene and polypropylene, polyester resins such as polyethylene terephthalate, acrylic resins such as polymethyl methacrylate, styrene resins such as polystyrene and ABS, poly Vinyl chloride resin etc. can be used arbitrarily.

As a method for adjusting the light diffusion transmittance (total light transmittance and haze value) to the desired range, a method of embossing the surface of the resin substrate for vapor deposition or coating with a paint containing a matting agent is used. However, if a resin base material for vapor deposition whose surface has been roughened (formed with irregularities) by such a method is used, the irregularities may be filled with an adhesive when forming a metal layer. In addition, the light diffusibility may be lost, and air may be entrapped during the formation of the metal layer, which may cause a decrease in interlayer strength and design properties.

For example, by dispersing a light scattering agent composed of fine particles having a refractive index different from that of the resin that is the main component, light scattering transmittance can be imparted. Examples of the light scattering agent include inorganic particles such as titanium oxide, zinc oxide, calcium carbonate, barium sulfate, mica, talc, and kaolin, and synthetic resin particles such as nylon.

From various commercially available milky-white thermoplastic resin sheets or matte thermoplastic resin sheets, if desired, a sheet having appropriate total light transmittance and haze degree can be selected and used.

<Picture layer 2>
The pattern layer 2 preferably includes a transparent ink layer and a concealing colored ink layer.
As shown in FIG. 1, the pattern layer 2 may be arranged on the outer layer side of the metal layer 3, that is, not on the adherend B side, but on the observer O side, and the formation method and its support are particularly limited. Although not shown in FIG. 1, it is formed by direct printing on the surface of the metal layer 3 .
A print pattern is not particularly limited. For example, after a transparent ink layer is solidly coated on the entire surface of the metal layer 3, a concealing colored ink layer expressing a rust pattern can be overlaid and printed. It is also possible to print a transparent ink layer on part of the surface of the metal layer 3 and print a concealing colored ink layer on the remaining part.

<<Transparent ink layer>>
The transparent ink layer is formed for the purpose of expressing the color of a metal material such as tin (galvanized steel sheet).

The transparent ink layer contains, for example, a matting agent and a binder, and may also contain a luster pigment and a colorant as necessary.
The delustering agent can improve the texture of the rust by imparting a feeling of white turbidity to the rust. The matting agent is not particularly limited, and a wide range of known matting agents can be used. Examples of matting agents include inorganic particles such as silica, alumina, calcium carbonate, magnesium carbonate, aluminosilicate, and barium sulfate; resin (organic) particles such as acrylic beads, polyethylene, polyurethane resin, polycarbonate, polyamide (nylon), and the like. mentioned. The average particle size of the particles is preferably 0.5-20 μm, more preferably 0.5-10 μm. The amount of the matting agent added is preferably 10 to 80 parts by mass, more preferably 30 to 60 parts by mass, per 100 parts by mass of the binder. The shape of the particles is polyhedral, spherical, scaly, and the like. Among the above inorganic particles and organic particles, silica is preferred.
Luster pigments include pearl pigments and metal pigments. Among these, pearl pigments can easily suppress a decrease in the light transmittance of the glitter ink layer, so when a pattern layer exists under the glitter ink layer, the visibility of the pattern layer is less likely to be impaired. point.

A pearl pigment is a pigment capable of imparting pearl luster, and examples thereof include base particles coated with a metal oxide, basic lead carbonate, scaly foil pieces or powder such as shells such as pearl oysters. be done. Scale-like particles such as mica are preferable as the base particles whose surface is coated with a metal oxide. Metal oxides include oxides of metals such as titanium, iron, zirconium, silicon, aluminum and cerium. One type of metal oxide may be used alone, or two or more types may be used.
Specific examples of pearl pigments include scale-like foil pieces such as titanium dioxide-coated mica, iron oxide-coated mica, and mica coated with titanium dioxide and iron oxide. A pearl pigment may be used individually by 1 type, and may be used in combination of 2 or more types.

Examples of metal pigments include pigments composed of scale-like foil pieces of metals such as aluminum, brass, stainless steel, tin, zinc, copper, nickel, gold powder and silver, and alloys of these metals. A metal pigment may be used individually by 1 type, and may be used in combination of 2 or more types.

The average particle size of the glitter pigment is preferably 1 to 500 μm, more preferably 5 to 100 μm, from the viewpoint of imparting glitter and suppressing dropout of the glitter pigment.
From the same point of view, the ratio of [average particle size of glitter pigment/thickness of glitter ink layer] is preferably about 10 to 10,000, more preferably 100 to 1,000.

Examples of the binder for the transparent ink layer include cured products of thermoplastic resins and curable resin compositions, and cured products of curable resin compositions are preferable from the viewpoint of durability.
The cured product of the curable resin composition includes a cured product of a thermosetting resin composition and a cured product of an ionizing radiation-curable resin composition. From the viewpoint of adhesion to the layer adjacent to the glitter ink layer, a cured product of a thermosetting resin composition is preferred.

Thermosetting resin compositions for the transparent ink layer include thermosetting polyester resin compositions, epoxy resin compositions, thermosetting polyurethane resin compositions, aminoalkyd resin compositions, melamine resin compositions, guanamine resin compositions, A urea resin composition, a thermosetting acrylic resin composition, and the like are included. These thermosetting resin compositions contain monomers and/or prepolymers constituting each resin, and a curing agent or the like added as necessary.
As the ionizing radiation-curable resin composition for the glitter ink layer, the same ionizing radiation-curable resin composition as the ionizing radiation-curable resin composition for the transparent protective layer to be described later can be used.

The content of the bright pigment in the transparent ink layer is preferably 10 to 90 parts by mass, more preferably 50 to 80 parts by mass, based on 100 parts by mass of the binder. By setting the content of the bright pigment to 10 parts by mass or more, it is possible to easily achieve a sufficiently glossy feeling. It is possible to suppress that the visibility of is impaired.
From the same point of view, the thickness of the glitter ink layer is preferably 1 to 30 μm, more preferably 5 to 20 μm.

The transparent ink layer is formed by, for example, forming a transparent ink layer-forming coating liquid containing a material constituting the transparent ink layer on either one surface or both surfaces of the resin substrate for vapor deposition by general-purpose printing means such as gravure printing. can be done.

<<Concealing colored ink layer>>
The concealing colored ink layer is formed for the purpose of expressing rust scattered on the metal material.

The pattern layer may form a decoration layer by using only the concealing colored ink layer, but it is preferable to form the pattern layer in combination with the transparent ink layer.
When the transparent ink layer and the concealing colored ink layer are used in combination, the concealing colored ink layer is preferably formed under the transparent ink layer or formed so as not to overlap the transparent ink layer in the thickness direction.

The pattern of the concealing colored ink layer is preferably a random pattern in order to express a natural rust feeling.

The concealing colored ink layer is formed, for example, by printing such as gravure printing, silk screen printing, flexographic printing, and ink jet printing. More specifically, the concealing colored ink layer is formed by multi-color printing using normal process colors of yellow, red, blue, and black. It is also formed by multi-color printing, etc.

Examples of the ink used for forming the concealing colored ink layer include binders mixed with colorants such as pigments and dyes, extender pigments, solvents, stabilizers, plasticizers, catalysts, curing agents, and the like.
The binder is not particularly limited, and examples include acrylic resins, styrene resins, polyester resins, polyurethane resins, chlorinated polyolefin resins, vinyl chloride-vinyl acetate copolymer resins, polyvinyl butyral resins, alkyd resins, petroleum resins, Examples include 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.
Examples of coloring agents include carbon black (ink), iron black, titanium white, antimony white, yellow lead, titanium yellow, red iron oxide, cadmium red, ultramarine blue, inorganic pigments such as cobalt blue, quinacridone red, and isoindolinone yellow. , organic pigments such as phthalocyanine blue, or dyes.

The thickness of the concealing colored ink layer can be appropriately adjusted in the range of about 0.1 to 20 μm in consideration of the intended design properties. Additives such as antioxidants and ultraviolet absorbers may be contained in the concealing colored ink layer as long as the effects of the present invention are not impaired.

<Transparent protective layer>
The decorative material may have a transparent protective layer in order to improve scratch resistance.
Although not shown, the transparent protective layer is a layer that is laminated on the surface of the metal layer 3 and the pattern layer 2 on the viewer O side as necessary, and does not completely block the metallic luster of the metal layer, but it is cloudy to the extent that it is softened. It may be a material having a light diffusive transmission property. The degree of light diffuse transmittance is represented by total light transmittance and haze value.
For example, a transparent protective layer having a total light transmittance of 60 to 90% and a haze value of 60 to 90% does not completely block the metallic luster of the underlying metal layer, but is cloudy enough to soften it. It is suitable for expressing vintage-like or antique-like brightness while suppressing stickiness.
In this specification, the total light transmittance is measured according to JIS K7361:1997. Moreover, in this specification, the haze value shall be measured based on JISK7136:2000.
As a method for adjusting the light diffusion transmittance (total light transmittance and haze value) to a desired range, a method of applying embossing to the surface of the transparent protective layer or a method of applying a coating with a paint containing a matting agent. However, if a light-transmitting resin sheet whose surface is roughened (formed with irregularities) is used by such a method, the irregularities are filled with an adhesive when forming a metal layer. In some cases, the light diffusibility may be lost, and air may be entrapped when forming the metal layer, which may cause a decrease in interlayer strength and design properties.
For example, by dispersing a light scattering agent composed of fine particles having a refractive index different from that of the resin that is the main component, light scattering transmittance can be imparted. Examples of the light scattering agent include inorganic particles such as titanium oxide, zinc oxide, calcium carbonate, barium sulfate, mica, talc, and kaolin, and synthetic resin particles such as nylon.
From various commercially available milky-white thermoplastic resin sheets or matte thermoplastic resin sheets, if desired, a sheet having appropriate total light transmittance and haze degree can be selected and used.

The transparent protective layer is preferably composed of a cured product of a resin composition containing a thermoplastic resin or a curable resin (curable resin composition), or a mixture thereof.
Thermoplastic resins are preferable because they facilitate the formation of convex regions and concave regions on the surface of the decorative material. On the other hand, the cured product of the curable resin composition is suitable because of its excellent scratch resistance.

Examples of the thermoplastic resin include those exemplified as the resin constituting the thermoplastic resin sheet that is the resin substrate layer 1 . Among these, polyolefin-based resins are preferable from the viewpoint of handleability and processability.

As the curable resin used for forming the transparent protective layer, in addition to thermosetting resins such as two-component curable resins, ionizing radiation curable resins and the like are preferably used. A so-called hybrid type, in which a radiation curable resin and a thermosetting resin are used in combination, or a curable resin and a thermoplastic resin are used in combination, may also be used.
As the curable resin, an ionizing radiation curable resin is preferable from the viewpoint of increasing the cross-linking density of the resin constituting the transparent protective layer and obtaining excellent surface properties such as scratch resistance and weather resistance, and is also easy to handle. From this point of view, an electron beam curable resin is more preferable.

The ionizing radiation-curable resin is a resin that is crosslinked and cured by irradiation with ionizing radiation, and has an ionizing radiation-curable functional group. Here, the ionizing radiation-curable functional group is a group that is cross-linked and cured by irradiation with ionizing radiation, and preferably includes a functional group having an ethylenic double bond such as a (meth)acryloyl group, a vinyl group, and an allyl group. be done. In addition, ionizing radiation means, among electromagnetic waves or charged particle beams, those having energy quanta capable of polymerizing or cross-linking molecules, and usually ultraviolet (UV) or electron beam (EB) is used. Electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion beams are also included.
As the ionizing radiation-curable resin, specifically, it is possible to appropriately select and use from polymerizable monomers and polymerizable oligomers conventionally used as ionizing radiation-curable resins.

As the polymerizable monomer, a (meth)acrylate monomer having a radically polymerizable unsaturated group in the molecule is preferable, and a polyfunctional (meth)acrylate monomer is particularly preferable. As used herein, "(meth)acrylate" means "acrylate or methacrylate".
Examples of polyfunctional (meth)acrylate monomers include (meth)acrylate monomers having two or more ionizing radiation-curable functional groups in the molecule and having at least a (meth)acryloyl group as the functional group, Acrylate monomers having an acryloyl group are preferred from the viewpoint of obtaining surface properties such as better scratch resistance and weather resistance.
From the viewpoint of obtaining better surface properties such as scratch resistance and weather resistance, the number of functional groups is preferably 2 or more, and the upper limit is preferably 8 or less, more preferably 6 or less, still more preferably 4 or less, and particularly preferably 3. It is below. These polyfunctional (meth)acrylates may be used alone or in combination.
Polymerizable (meth)acrylate monomers include, for example, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth) Acrylate, caprolactone-modified dicyclopentenyl di(meth)acrylate, ethylene oxide-modified phosphate di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, dipentaerythritol tri(meth) Acrylate, dipentaerythritol hexa(meth)acrylate and the like.

Polymerizable oligomers include, for example, (meth)acrylate oligomers having two or more ionizing radiation-curable functional groups in the molecule and at least (meth)acryloyl groups as the functional groups. Examples thereof include urethane (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, polyester (meth)acrylate oligomers, polyether (meth)acrylate oligomers, polycarbonate (meth)acrylate oligomers, and acrylic (meth)acrylate oligomers.
Furthermore, as polymerizable oligomers, there are also highly hydrophobic polybutadiene (meth)acrylate oligomers having (meth)acrylate groups in the side chains of polybutadiene oligomers, and silicone (meth)acrylate oligomers having polysiloxane bonds in the main chain. , Aminoplast resin modified aminoplast resin with many reactive groups in a small molecule (meth)acrylate oligomer, or novolac type epoxy resin, bisphenol type epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc. There are oligomers having cationic polymerizable functional groups.

These polymerizable oligomers may be used alone or in combination. Urethane (meth)acrylate oligomer, epoxy (meth)acrylate oligomer, polyester (meth)acrylate oligomer, polyether (meth)acrylate oligomer, polycarbonate (meth)acrylate from the viewpoint of obtaining better surface properties such as scratch resistance and weather resistance. Acrylate oligomers and acrylic (meth)acrylate oligomers are preferred, and urethane (meth)acrylate oligomers and polycarbonate (meth)acrylate oligomers are more preferred.

From the viewpoint of obtaining better surface properties such as scratch resistance and weather resistance, the number of functional groups of these polymerizable oligomers is preferably 2 or more, and the upper limit is preferably 8 or less, more preferably 6 or less, and still more preferably. 4 or less, more preferably 3 or less.

The weight-average molecular weight of these polymerizable oligomers is preferably 2,500 or more, more preferably 3,000 or more, and even more preferably 3,500 or more, from the viewpoint of obtaining better surface properties such as scratch resistance and weather resistance. . Moreover, as an upper limit, 15,000 or less are preferable, 12,500 or less are more preferable, and 11,000 or less are still more preferable. Here, the weight average molecular weight is the average molecular weight measured by GPC analysis and converted with standard polystyrene.

For the ionizing radiation-curable resin, a monofunctional (meth)acrylate can be appropriately used together with the polyfunctional (meth)acrylate and the like for the purpose of decreasing the viscosity. These monofunctional (meth)acrylates may be used alone or in combination.

From the viewpoint of improving surface properties such as scratch resistance and weather resistance, the ionizing radiation-curable resin preferably contains a polymerizable oligomer. The content of the polymerizable oligomer in the ionizing radiation-curable resin is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and even more preferably 100% by mass.

When the transparent protective layer is formed from a thermoplastic resin, the thickness of the transparent protective layer is preferably 10 to 150 μm, more preferably 30 to 100 μm, from the viewpoint of processability of the convex regions and concave regions by embossing. is more preferable. On the other hand, when the transparent protective layer is formed from a cured product of a curable resin composition, the thickness is preferably 2 to 15 μm, and 4 to 10 μm, from the viewpoint of the balance between scratch resistance and suppression of cracks during molding. It is more preferable to have

<Primer layer>
The decorative material of the present invention may have a primer layer between each layer in order to improve the adhesion between each layer.
It is preferable that the primer layer contains resin as a main component. Resins for the primer layer include ester resins, urethane resins, acrylic resins, polycarbonate resins, vinyl chloride-vinyl acetate copolymers, and the like. Also, the resin of the primer layer may be a two-liquid curing resin. Among these resins, two-liquid curing resins are preferable from the viewpoint of adhesion.
The two-component curable resin is not particularly limited as long as it is a resin that is cured by adding a curing agent to the main component. Urethane resin is preferred.
The thickness of the primer layer is usually about 0.5-20 μm, preferably 1-10 μm.

<Application of decorative material>
The decorative material of the present invention can be used for various purposes as it is, as a laminated body attached to an adherend, or after being subjected to a predetermined molding process or the like to the decorative material or laminated body.
Various applications include interior materials for buildings such as walls, ceilings, and floors; fittings such as window frames, doors, and handrails; furniture such as chests, desks, dining tables, and cupboards; Examples include interior materials such as doors, exterior materials, and the like.

Examples of adherend materials include wood veneer, wood plywood, particle board, MDF (medium density fiberboard), laminated wood and other wood boards; gypsum boards such as gypsum boards and gypsum slag boards; calcium silicate boards and asbestos slate. Boards, lightweight foamed concrete boards, hollow extruded cement boards, and other cement boards; pulp cement boards, asbestos cement boards, wood chip cement boards, and other fiber cement boards; ceramics boards, such as pottery, porcelain, earthenware, glass, and enamel; iron plates, zinc Metal plates such as plated steel plates, polyvinyl chloride sol-coated steel plates, aluminum plates, copper plates; thermoplastic resin plates such as polyolefin resin plates, acrylic resin plates, ABS plates, and polycarbonate plates; phenol resin plates, urea resin plates, unsaturated polyester resin plates Plates, thermosetting resin plates such as polyurethane resin plates, epoxy resin plates, and melamine resin plates; Fiber non-woven fabrics, fabrics, paper, and other various fibrous base materials impregnated and cured to form composites, so-called FRP boards, etc. These may be used alone, and two or more of these may be laminated as composite substrates. may be used.

<Method for Forming Protruding Regions and Concave Regions>
The convex regions 4 and the concave regions 5 of the decorative material of the present invention can be formed, for example, by shaping with an embossing plate engraved with a laser beam, a diamond needle, or the like.

How to measure height data:
Height data (herein, "height and/or depth of fine line 6", "height of convex region, depth of concave region", "height and/or depth of demarcation line 8") ) can be measured using a surface shape measuring device. Examples of the surface shape measuring device include a white interference optical microscope (e.g., Zygo NewView 6300 type), an atomic force microscope (e.g., Shimadzu Corporation SPM-9500 type), a laser microscope (e.g., Keyence VK -X1000) and the like.
A probability distribution of height data in the measurement range can be acquired by the surface profile measuring device.
In this specification, "height" and "depth" are values with the average value of the height data as a reference (height 0).

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited by these examples.

1. Evaluation 1-1. Surface shape (fine line <width, pitch, height>, division line <width, height>, Ra, glossiness (20°)
Fine lines <width, pitch, height> and demarcation lines <width, height> were measured using a laser microscope (Keyence VK-X1000) as a surface shape measuring device. The measurement length was 1 mm.
Ra was measured according to JIS B0601:2001.
Glossiness was measured according to JIS Z8741:1997.
All data in the table are average values of measured values at arbitrary 10 points.
1-2. Natural Appearance For the decorative materials obtained in Examples and Comparative Examples, 20 arbitrary adults were asked to visually evaluate the presence or absence of the natural appearance of the rust spots under the illumination of a fluorescent lamp.
A: More than 18 people answered that the product had a natural appearance.
B: 15 to 17 people answered that it had a natural appearance.
C: 14 or less people answered that the product had a natural appearance.
1-3. Natural Tactile Feel Regarding the decorative materials obtained in Examples and Comparative Examples, 20 random adults were asked to evaluate the presence or absence of a natural tactile feel with respect to the mottled rust pattern.
A: More than 18 people answered that it had a natural tactile sensation.
B: 15 to 17 people answered that it had a natural feel.
C: There were 14 or less persons who answered that there was a natural tactile sensation.

2. Production of embossed plate The surface of a metal roll for embossed engraving (a copper layer is plated on the surface of a hollow iron cylinder) is applied to the previously created image data for forming an uneven pattern using a laser beam direct engraving machine. Sculpted based on As a result, a concave-convex pattern having the same planar shape as the concave-convex pattern on the surface of the decorative material and having a reverse concave-convex pattern (the portion corresponding to the convex of the decorative material becomes concave on the embossed plate surface) was formed on the surface. After washing the engraving liquid, electropolishing was performed to remove metal residue adhering to the surface of the metal roll. Finally, a chromium layer having a thickness of 10 μm was formed on the surface of the metal roll by plating. Here, the uneven pattern means a pattern including concave areas, convex areas, demarcation lines, and fine lines.

3. Preparation of decorative material [Example 1]
A biaxially stretched polyethylene terephthalate substrate having a thickness of 10 μm was used as a resin substrate for vapor deposition. A metal layer was formed by vapor-depositing aluminum on a resin base material for vapor deposition. Pattern data as shown in FIG. 8 was printed on the deposition surface by gravure printing to form a pattern layer. As the binder resin and colorant for the ink, the following resin systems were used.
(Sepia concealing colored ink)
Binder resin: A mixture of a vinyl chloride-vinyl acetate copolymer and an acrylic resin in a mass ratio of 1:1.
Colorant: Azo-based pigment and carbon black (silica-containing transparent ink)
Binder resin: A mixture of a vinyl chloride-vinyl acetate copolymer and an acrylic resin in a mass ratio of 1:1.
Colorant: Silica Particles A polyvinyl chloride sheet having a thickness of 100 μm was used as a resin substrate layer.
The non-deposited surface of the resin base material for vapor deposition on which the metal layer and the pattern layer are formed, and the resin base layer are superimposed and heated and pressurized together with the embossing plate prepared in "2" above to bond them together. The surface was embossed and unevenly processed to obtain a decorative material of Example 1 having an uneven pattern on the surface as shown in the cross-sectional view of FIG. 1 and the plan view of FIG.
Table 1 shows the surface shape of the obtained decorative material. The surface shape was evaluated by the method described above.
[Example 2]
The resin substrate for vapor deposition on which the metal layer and the pattern layer were formed and the resin substrate layer were laminated using a polyester adhesive, and then reheated to press the embossing plate, except that the resin substrate was reheated and pressed against the embossing plate. A decorative material of Example 2 was obtained in the same manner.
[Example 3]
A decorative material of Example 3 was obtained in the same manner as in Example 1, except that only the concealing colored ink was used for the pattern layer.
[Example 4]
Example 4 in the same manner as in Example 1, except that only the transparent ink was used for the pattern layer.
was obtained.
[Example 5]
A decorative material of Example 5 was obtained in the same manner as in Example 1, except that embossing plates having different widths, pitches and heights of the fine lines and division lines were used.
[Example 6]
A decorative material of Example 6 was obtained in the same manner as in Example 1, except that embossing plates having different widths, pitches and heights of the fine lines and division lines were used.
[Comparative Example 1]
A decorative material of Comparative Example 1 was obtained in the same manner as in Example 1 except that the embossing plate was not pressed when the resin base material for vapor deposition on which the metal layer and the pattern layer were formed and the resin base material layer were bonded together. rice field.
[Comparative Example 2]
A decorative material of Comparative Example 2 was obtained in the same manner as in Example 1, except that the pattern layer was not printed on the vapor deposition sheet.
[Comparative Example 3]
A decorative material of Comparative Example 3 was obtained in the same manner as in Example 1, except that an embossing plate having no convex regions was used.
[Comparative Example 4]
A decorative material of Comparative Example 4 was obtained in the same manner as in Example 1, except that an embossing plate having no fine lines in the recessed regions was used.

As shown in Table 1, it was confirmed that the decorative material of the example can express a metallic tone that naturally expresses the appearance and feel of the mottled rust pattern.

1: Resin base layer 2: Pattern layer 3: Metal layer 4: Convex area 5: Concave area 6: Fine line 6 _H : Convex section 6 _L : Concave section 7: Parallel curve group concavo-convex pattern and/or parallel straight line Group uneven pattern 8: Division line 9: Adhesive layer 10: Decorative material B: Adherend material L: Line of sight O of observer O: Observer

Claims (12)

A decorative material comprising a resin base layer, a pattern layer, and a metal layer disposed on the inner layer side of the pattern layer,
having a plurality of independent convex regions and concave regions surrounding the convex regions on the surface on the pattern layer side with respect to the metal layer;
In the concave region, a parallel curve group concavo-convex pattern in which a large number of fine lines having a curved shape in a plan view are arranged parallel to each other, and/or a large number of fine lines having a straight shape in a plan view are arranged parallel to each other. A planar view shape comprising a parallel straight line group uneven pattern,
The decorative material , wherein the pattern layer includes a concealing colored ink layer . 2. The decorative material according to claim 1, wherein said uneven pattern of group of parallel curves and/or said uneven pattern of group of parallel straight lines is an embossed pattern formed by embossing. 2. The decorative material according to claim 1, wherein said uneven pattern of group of parallel curves and/or said uneven pattern of group of parallel straight lines is a printed pattern formed by printing. The decorative material according to any one of claims 1 to 3, wherein the concave region and the convex region have different glosses. The decorative material according to any one of claims 1 to 4, comprising a dividing line that divides the recessed area to form two or more adjacent recessed areas. 6. The decorative material according to claim 5, wherein the dividing line has a width of 80 μm to 200 μm in a plan view observed in a line-of-sight direction parallel to the thickness direction of the resin base material layer. 7. The decorative material according to claim 5, wherein said demarcation line has a height of 15 μm to 150 μm in cross section. The decorative material according to any one of claims 1 to 7, wherein the resin substrate layer, the transparent adhesive layer, the metal layer, the pattern layer, and the transparent protective layer are laminated in this order from the bottom. The decorative material according to any one of claims 1 to 8, wherein the pattern layer includes a transparent ink layer and the concealing colored ink layer. The decorative material according to any one of claims 1 to 9, wherein the metal layer is a metal deposition layer. The metal vapor deposition layer is formed by forming a film on the surface of the resin base material for vapor deposition,
The decorative material according to claim 10, wherein the resin base material for vapor deposition is closer to the resin base material layer than the metal layer is. 2. The decorative material according to claim 1, wherein the height difference between said concave region and said convex region is 7 μm to 15 μm.

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