JP7107133B2 - Decorative sheet and method for producing decorative sheet - Google Patents

Description

TECHNICAL FIELD The present invention relates to a decorative sheet and a method for manufacturing a decorative sheet.

Decorative sheets used for furniture, building materials, and the like are sometimes required to have a high-brightness metallic design. Conventionally, as a method of reproducing such a metallic design, a method of forming a vapor deposition film on a sheet that serves as a support, a method of forming a coating film by printing by combining particles with different particle sizes, and the like have been proposed. ing. Among these methods, the latter method has the advantage of being able to produce a decorative sheet at a lower cost than the method of forming a deposited film (see, for example, Patent Documents 1 and 2).

JP 2015-214031 A Japanese Utility Model Laid-Open No. 5-080746

In the above decorative sheet, improvement in brightness and adhesion of the outermost layer is required while maintaining low cost.

SUMMARY OF THE INVENTION An object of the present invention is to provide a decorative sheet and a method for producing a decorative sheet that have improved brightness and adhesion of the outermost layer while maintaining low cost.

The present invention solves the problems by means of the following solutions. In order to facilitate understanding, reference numerals corresponding to the embodiments of the present invention are used for description, but the present invention is not limited to these. Also, the configurations described with reference numerals may be improved as appropriate, and at least a part of them may be replaced with other configurations.

A first invention is a decorative sheet (1) in which a support (10) and a decorative layer (20) are laminated, wherein the decorative layer comprises large particle size metal flakes (22a) and small grains (22a). It has a metallic layer (22) made of a resin containing a plurality of metal scales (22b) having a diameter, and the metallic layer includes the large-diameter metal scales and the small-diameter scales on the surface layer opposite to the support. It relates to a decorative sheet mixed with metal scales of

A second invention is the decorative sheet according to the first invention, wherein the small-diameter metal scales are distributed in a large amount on the surface layer side opposite to the support in the thickness direction of the metallic layer.

A third invention is the decorative sheet according to the first or second invention, wherein the large-diameter metal scales are uniformly distributed in the thickness direction of the metallic layer and arranged in parallel along the layer direction. is doing.

A fourth invention is the decorative sheet according to any one of the first to third inventions, wherein the particle diameter of the small-diameter metal scales is 0.42 times the diameter of the large-diameter metal scales. The metallic layer contains 40 parts by mass or less of metal flakes per 100 parts by mass of resin.

A fifth invention is the decorative sheet according to any one of the first to fourth inventions, wherein the decorative layer comprises a pattern layer (23a) and a colored transparent layer on the surface of the metallic layer opposite to the support. It has at least one of the layers (23b).

A sixth invention is the decorative sheet according to any one of the first to fifth inventions, wherein the decorative layer has a protective layer (30) on the outermost surface opposite to the support.

A seventh invention is the decorative sheet according to any one of the first to sixth inventions, wherein the decorative layer has a colored opaque layer (21) on the support side surface of the metallic layer.

An eighth invention is a method for producing a decorative sheet according to any one of the first to seventh inventions, comprising non-leafing type large particle diameter metal scales and leafing type small diameter metal scales and a resin. and drying the coating film formed on the surface of the support to form the large-diameter metal scales on the surface layer opposite to the support. and a step of forming the metallic layer in which the metallic flakes having a small particle diameter are mixed.

ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the decorative sheet which improved the brightness|luminance and the adhesiveness of an outermost layer, and a decorative sheet can be provided, maintaining low cost.

It is a sectional view of decorative sheet 1 in an embodiment. 3 is a perspective view showing a layer structure of a metallic layer 22; FIG. FIG. 3 is a schematic diagram for explaining the relationship between the particle size D _S of small particle size scales 22b and the particle size D _L of large particle size scales 22a. FIG. 5 is a diagram illustrating evaluation results of Examples and Comparative Examples 1 and 2;

Embodiments of the present invention will be described below. Each drawing attached to this specification is a schematic diagram, and the shape, scale, length-to-width dimensional ratio, etc. of each part are changed or exaggerated from the actual ones in consideration of ease of understanding. Also, in each drawing, hatching indicating a cross section of a member is omitted.
Numerical values, shapes, material names, etc. described in this specification are examples as embodiments, and are not limited to these, and may be appropriately selected and used.

FIG. 1 is a cross-sectional view of a decorative sheet 1 according to this embodiment.
As shown in FIG. 1, the decorative sheet 1 of this embodiment comprises a support 10, a decorative layer 20 and a protective layer 30. As shown in FIG.
The support 10 is a base member of the decorative sheet 1 . As the support 10, for example, various paper materials, plastic films, plastic sheets, woods, non-metallic inorganic ceramic materials, cloth silk, etc. are appropriately selected according to the application. Each of these materials may be used alone, but may also be a laminate of any combination, such as a composite of paper, a composite of paper and plastic film, and the like.

Examples of the paper material used as the support 10 include thin paper, kraft paper, and titanium paper. Acrylic resin, styrene-butadiene rubber, melamine resin, urethane resin, or the like may be further added to these paper materials (impregnated with resin after papermaking or filled during papermaking). For example, there are inter-paper reinforced paper, resin-impregnated paper, and the like.

In addition to these, there are various types of paper that are often used in the field of building materials, such as linter paper, paperboard, base paper for gypsum board, vinyl wallpaper base paper having a vinyl chloride resin layer on the surface of paper, and the like. Furthermore, coated paper, art paper, parchment paper, glassine paper, parchment paper, paraffin paper, Japanese paper, etc., which are used in the business field, ordinary printing, packaging, etc., can also be used. In addition, woven fabrics and non-woven fabrics of various fibers having paper-like appearance and properties can also be used as the support 10, although they are distinguished from these papers. Examples of various fibers include inorganic fibers such as glass fiber, asbestos fiber, potassium titanate fiber, alumina fiber, silica fiber and carbon fiber, and synthetic resin fibers such as polyester fiber, acrylic fiber and vinylon fiber.

Plastics used as the support 10 include those made of various synthetic resins. As the thickness form, various forms such as film, sheet, and plate can be applied. Examples of synthetic resins include polyethylene, polypropylene (PP), olefin resins such as polymethylpentene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, vinyl chloride-vinyl acetate copolymers, ethylene-vinyl acetate copolymers, Vinyl resins such as ethylene-vinyl alcohol copolymers, polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate, ethylene glycol-terephthalic acid-isophthalic acid copolymers, polymethyl methacrylate, polymethacryl Acrylic resins such as ethyl acetate and polybutyl acrylate, polyamide resins such as nylon 6 and nylon 66, cellulose triacetate and cellophane resins, polystyrene, polycarbonate resins, polyarylate resins, polyimide resins, and the like. be done.

Examples of wood used as the support 10 include veneers of various types of wood such as cedar, pine, cypress, oak, lauan, and teak, plywood, laminated wood, particle board, medium-density fiberboard (MDF), and the like. mentioned.
Ceramic-based nonmetallic inorganic materials used as the support 10 include, for example, gypsum, calcium silicate, cement, wood chip cement, ceramics, glass, enamel, baked tiles, and the like.
Examples of the fabric used as the support 10 include woven fabrics woven from natural fibers such as cotton, linen, and silk, and synthetic resin fibers such as polyester resin, acrylic resin, polyamide resin, and the like.

The thickness of the support 10 is not particularly limited. When a film or sheet made of plastic is used as the support 10, the thickness is, for example, about 20 to 150 μm, preferably 30 to 100 μm. When a paper material is used as the support 10, the basis weight is, for example, about 20 to 150 g/m ² , preferably about 30 to 100 g/m ² .

The decoration layer 20 is composed of a colored opaque layer 21, a metallic layer 22, and a pattern layer 23. - 特許庁
In the present embodiment, a configuration including a colored opaque layer 21, a metallic layer 22, and a pattern layer 23 as the decorative layer 20 will be described. , it is sufficient that at least the metallic layer 22 is provided.

The colored opaque layer 21 is a concealing layer that makes it difficult to see the base support 10 when the decorative sheet 1 is viewed from the protective layer 30 side. The colored opaque layer 21 is formed so that the color pigment is 100 parts by mass or more with respect to 100 parts by mass of the resin. The colored opaque layer 21 is formed to cover the entire surface of the support 10 and is colored white, gray, brown, or the like. Examples of the resin constituting the colored opaque layer 21 include acrylic resin, vinyl chloride-vinyl acetate copolymer (vinyl chloride), acrylic acid ester-vinyl chloride-vinyl acetate copolymer, and the like.

Further, the colored opaque layer 21 may be added with a coloring agent for coloring in a desired color and various additives as necessary. As the coloring agent and additive, those suitable for expressing the desired color, hiding property and various physical properties are appropriately selected and used from those exemplified in the description of the pattern layer 23 (described later).
The layer thickness (dry) of the colored opaque layer 21 is preferably 1 μm or more.

The metallic layer 22 is a layer that imparts a bright metallic design to the decorative sheet 1 . The metallic layer 22 is composed of large-diameter metal flakes 22a, small-diameter metal flakes 22b, and resin 22c serving as a binder. In the following description, the metal scales 22a with a large particle size are called "large size scales 22a", and the metal scales 22b with a small size are called "small size scales 22b". The layer structure of the metallic layer 22 will be described later.

The pattern layer 23 is composed of a pattern layer 23a and a colored transparent layer 23b.
The pattern layer 23a is a layer on which a design such as a pattern, pattern, or pattern is formed. The pattern layer 23a is formed so that the color pigment is 15 parts by mass or more with respect to 100 parts by mass of the resin. The resin constituting the pattern layer 23a is, for example, acrylic resin, vinyl chloride-vinyl acetate copolymer (vinyl chloride acetate) resin, urethane resin, polyamide resin, polyester resin, or two or more selected from these resins. A mixed composition, for example, a composition in which an acrylic resin and a vinyl chloride-vinyl acetate copolymer are mixed in an appropriate mass ratio in the range of 1:9 to 9:1. Further, the pattern layer 23a contains a coloring agent for coloring a desired color, and various additives (ultraviolet absorber, heat stabilizer, light stabilizer, surfactant, plasticizer, extender pigment, etc.) as necessary. ) etc. are added.

The colored transparent layer 23b is a transparent colored layer laminated on the pattern layer 23a. The colored transparent layer 23b is formed so that the color pigment is less than 15 parts by mass with respect to 100 parts by mass of the resin. As the colored transparent layer 23b, for example, a mixture of an acrylic resin and a coloring agent can be used. In this embodiment, an example in which the pattern layer 23a and the colored transparent layer 23b are provided as the pattern layer 23 will be described, but the pattern layer 23 is not limited to this, and the pattern layer 23a may be the only pattern layer 23a. Only the colored transparent layer 23b may be used.
The layer thickness (dry) of the pattern layer 23a including the pattern layer 23a and the colored transparent layer 23b is about 5 μm.

The protective layer 30 is a transparent layer for protecting the surface of the decorative sheet 1 (the surface opposite to the support 10 ), and covers the surface of the decorative layer 20 . Examples of the resin forming the protective layer 30 include durable resins such as thermosetting resins, thermoplastic resins, ionizing radiation curable resins, ultraviolet curable resins, and moisture curable resins. Among them, specific examples of thermosetting resins, thermoplastic resins and ionizing radiation-curable resins are listed below.
Thermosetting resins include, for example, epoxy resins, phenolic resins, urea resins, unsaturated polyester resins, melamine resins, alkyd resins, polyimide resins, silicone resins, hydroxyl-functional acrylic resins, carboxyl-functional acrylic resins, amide-functional Examples include copolymers and urethane resins.

Examples of thermoplastic resins include acrylic resins such as polymethyl (meth) acrylate and polyethyl (meth) acrylate, polyolefin resins such as polypropylene and polyethylene, polycarbonate resins, vinyl chloride resins, polyethylene terephthalate (PET), poly Examples include polyester resins such as butylene terephthalate (PBT) and polyethylene naphthalate (PEN), acrylonitrile-butadiene-styrene resins (ABS resins), acrylonitrile-acrylic acid ester resins, and the like.

The ionizing radiation curable resin is a resin that is crosslinked and cured by irradiation with electron radiation. Specifically, the ionizing radiation-curable resin includes a mixture of at least one of prepolymers, oligomers, monomers, etc. having polymerizable unsaturated bonds or epoxy groups in the molecule. Note that the ionizing radiation means, among electromagnetic waves and charged particle beams, those having energy quanta capable of polymerizing or cross-linking molecules, and generally ultraviolet rays, electron beams, and the like are used. Among the ionizing radiation curable resins, the electron beam curable resin can be solvent-free, does not require a photopolymerization initiator, and provides stable curing properties. Are suitable.

Next, the layer structure of the metallic layer 22 (decoration layer 20) will be described.
FIG. 2 is a perspective view showing the layer structure of the metallic layer 22. As shown in FIG. FIG. 2 conceptually shows the distribution of the large particle size scales 22a and the small particle size scales 22b in the metallic layer 22. As shown in FIG. The shape, arrangement, etc. of the large particle size scale 22a and the small particle size scale 22b are not limited to the example in FIG. In addition, in FIG. 2, the colored opaque layer 21 and the support 10 are illustrated by imaginary lines in order to facilitate understanding of the positional relationship of each scale in the metallic layer 22 .

As described above, the metallic layer 22 is composed of the large particle size scales 22a, the small particle size scales 22b, and the resin 22c serving as a binder.
The large particle size scale 22a and the small particle size scale 22b are made of metal. For example, metals with metallic luster such as aluminum, gold, silver, copper, tin, nickel, chromium, and brass can be used. As a typical example, aluminum particles are used because they have a good metallic luster, are inexpensive, and have a flat (that is, colorless) reflected light spectrum over the entire visible light band. Hereinafter, aluminum particles having a scale-like shape are referred to as aluminum pigments. Aluminum pigments are broadly classified into leafing type and non-leafing type. In this embodiment, the small-diameter scales 22b are leafing-type pigments. Also, the large-diameter scales 22a are non-leafing type pigments.

Leafing-type pigments have the property of floating on the surface side of the coating film (the side opposite to the support 10) during the process of drying after the coating film of the metallic layer 22 is formed. The small-diameter scales 22b made of leafing-type pigments are arranged in parallel on the surface layer opposite to the support 10 (hereinafter also referred to as "surface layer of the metallic layer 22") in the thickness direction of the metallic layer 22. As the leafing type pigment, it is preferable to use a high brightness type with enhanced brightness.

On the other hand, non-leafing type pigments have the property of uniformly dispersing in the coating film during the drying process when the coating film of the metallic layer 22 is formed. Most of the large-diameter scales 22a made of non-leafing type pigments are uniformly distributed in the thickness direction of the metallic layer 22 and arranged in parallel along the layer direction. Some of the large particle size scales 22a are arranged in parallel with the small particle size scales 22b on the surface layer of the metallic layer 22 .

Here, the relationship between the particle size D _S of the small particle size scales 22b and the particle size D _L of the large particle size scales 22a will be described.
FIG. 3 is a schematic diagram for explaining the relationship between the particle size D _S of the small particle size scales 22b and the particle size D _L of the large particle size scales 22a.

In FIG. 3, the range of the unit area of the coating film is indicated by a square frame whose one side is twice the particle size D _L of the large particle size scale 22a. When the thickness of the coating film of the metallic layer 22 is four times the thickness of the large particle size scales 22a, as shown in FIG. 3, the square frame is filled with up to four large size scales 22a. . On the other hand, since gaps are formed between the large-diameter scales 22a, only four large-diameter scales 22a give a conspicuous graininess.

The particle size D _S of the small particle size scales 22b is preferably less than 0.42 of the particle size D _L of the large particle size scales 22a in order to achieve both brightness and adhesion. Specifically, the particle size D _S of the small particle size scale 22b that fits in the gap is obtained by (√2−1), where the particle size D _L of the large particle size scale 22a is 1, and is approximately 0.42. Become. Therefore, by setting the particle size DS of the small particle size scales 22b to be less than 0.42 of the particle size _{D L of} the large particle size scales 22a, the gap between the large particle size scales 22a is reduced to the size of the small particle size scales 22b. can be almost filled with As shown in FIG. 3, the number of small-diameter scales 22b is four within a square (unit area) range of which one side is twice the diameter D _L of the large-diameter scales 11a. The particle diameter D _S of the small particle size scales 22b shown in FIG. 3 is 0.42 of the particle size D _L of the large particle size scales 22a, which is the maximum diameter that can fill the gaps between the large particle size scales 22a. . Thus, if the particle diameter D _S of the small particle size scales 22b is set to be less than 0.42 of the particle size D _L of the large particle size scales 22a, the small particle size scales 22b will fill the gaps between the large particle size scales 22a. Since it is possible to fill the gap, it is possible to suppress the decrease in adhesion while making the graininess less noticeable.

The shape of metal flakes is expressed by the major axis (average particle diameter D ₅₀ ) and the minor axis (average particle thickness).
The average particle size can be measured by a microscope method, a sieving method, a sedimentation method, a Coulter counter method, a laser light scattering/diffraction method, or the like.
Also, the average particle thickness can be indirectly calculated by the following formula (1) by measuring the water surface diffusion area according to the JIS method (JIS K5906:1998).
Average particle thickness (μm) =
10,000/[Density of pigment×Diffusion area of water surface (cm ² /g)] Formula (1)

Also, the number ws of the small-diameter scales 22b to be added can be calculated by the following formula (2). In addition, in the description of the formulas shown below, the reference numerals of the members are appropriately omitted.
Addition number ws of small-diameter scales 22b =
[Number of parts of resin (= 100)] x [Volume V _s of small particle size scales in coating film] x [Density dp of aluminum scales]
/(([unit coating volume V _c ]−[volume of large particle size scales in coating film V _L ]−V _s )×[resin density dm]) Equation (2)

In the coating film _per unit area (unit _coating film) _shown in FIG. , expressed as follows:
V _s =π/4×[Diameter D _S of small particle size scales] ² ×[Thickness ts of small particle size scales]×[Number per unit area (=4)]
_{V c} = [square area with a diameter twice the diameter of the large-diameter scale DL] × [coating thickness tc]
V _L =π/4× _DL ² ×tc
Also, the number ws of the small-diameter scales to be added can be calculated by the following formula (3).
Addition number ws of small particle size scales =
100×dp/dm×(π×DS ² × _ts )
/(4×DL ² × _tc −tc×π/4×DL ² _−π × _DS ² ×ts)
... formula (3)

In this embodiment, the density dp of the aluminum flakes is approximately 2.5 g/cm ³ . Also, the resin density dm is about 1.2 to 1.4 g/cm ³ . The particle size D _S of small particle size scales and the particle size D _L of large particle size scales are the values of the selected material. Also, the thickness ts of the small-diameter scales is a value calculated from the water surface diffusion area of the selected material. Therefore, by setting the coating thickness tc of the metallic layer 22 arbitrarily, the number ws of small-diameter scales to be added can be determined. The coating thickness tc is desirably set at tc≧4× _tL .

In the metallic layer 22, the mixing ratio of the metal scales to the resin 22c is preferably 40 parts by mass or less for 100 parts by mass of the resin 22c. Also, the lower limit of the mixing ratio of the metal flakes is preferably 20 parts by mass or more in consideration of the limits of brightness and coating amount. In the metallic layer 22, when the total addition amount of the large particle size scales 22a and the small particle size scales 22b is 40 parts by mass or less, and the large particle size scales 22a are 35 (-40) parts by mass, the resin 22c and the large particle size The area (volume) ratio of the scales 22a is about 4:1. According to this, when one layer of coating having the same thickness as the thickness of the large particle size scale 22a is applied, the large particle size scale _22a is 1 in the square shown in FIG. It is a calculation that fits. Therefore, when four layers of the coating film having the same thickness as the thickness of the large-diameter scales 22a are applied, as shown in FIG. become.

The resin 22c is not particularly limited as long as it can be used as a binder. Examples include acrylic resin, vinyl chloride-vinyl acetate copolymer (vinyl chloride), acrylic resin and vinyl chloride-vinyl acetate copolymer and the like. As the resin 22c, one or a combination of two or more of these materials is used. Also, a coloring pigment, a coloring dye, or the like is added to the resin 22c.

A paint obtained by mixing the large particle size scales 22a, the small particle size scales 22b, the resin 22c, and the solvent is applied to the surface of the support 10 (the colored opaque layer 21) by a method such as gravure printing, offset printing, or screen printing. ,dry. As a result, the metallic layer 22 having a layer structure (see FIG. 2) in which the large-diameter scales 22a and the small-diameter scales 22b are mixed can be formed on the surface layer opposite to the support 10. FIG.
The layer thickness (dry) of the metallic layer 22 can be set to about 1 μm to 10 μm. For example, it is about 3 to 5 μm.

EXAMPLES Next, the present invention will be described in more detail with reference to examples and comparative examples. However, the present invention is by no means limited to the following examples.
In Examples and Comparative Examples 1 and 2, which will be described later, "leafing type aluminum flakes" correspond to the small particle diameter flakes 22b of the embodiment. A "non-leafing type aluminum scale" corresponds to the large-diameter scale 22a of the embodiment. Comparative Example 1 shows an example in which non-leafing type aluminum flakes are used as the small particle size flakes 22b.

(Example)
As the support 10, a 50 μm PET film (“A4300” manufactured by Toyobo Co., Ltd.) was prepared. Further, as an ink containing an aluminum pigment, a composition obtained by mixing an acrylic resin and a vinyl chloride-vinyl acetate copolymer (“KaXZ” manufactured by Showa Ink Kogyo Co., Ltd.) was added with a particle size of 10 μm (thickness of 0.17 μm). ) Leafing type aluminum flakes (“0870TS” manufactured by Toyo Aluminum Co., Ltd.) are added so as to be 1.5 parts by mass with respect to 100 parts by mass of resin, and a non-leafing with a particle size of 25 μm (thickness 0.40 μm) A gravure ink was prepared by adding aluminum flakes (“MG600” manufactured by Toyo Aluminum Co., Ltd.) of the type 36 parts by mass with respect to 100 parts by mass of the resin. This gravure ink was printed on one surface of the support 10 to form a decorative layer 20 (metallic layer only) having a thickness of 3 μm, thereby producing a decorative sheet of the example.

(Comparative example 1)
The leafing type aluminum scale was changed to a non-leafing type aluminum scale ("260M-S" manufactured by Toyo Aluminum Co., Ltd.) with a particle size of 9 μm (thickness 0.15 μm), and this aluminum scale was added to 100 parts by mass of the resin. A decorative sheet of Comparative Example 1 was produced under the same conditions as in the above Example, except that the amount of addition was 1.1 parts by mass.
(Comparative example 2)
The leafing type aluminum flakes were changed to aluminum flakes (“30T” manufactured by Toyo Aluminum Co., Ltd.) with a particle diameter of 15 μm (thickness of 0.13 μm), and the aluminum flakes were added at 1.7 parts by weight per 100 parts by weight of the resin. was added so that Moreover, the non-leafing type aluminum flakes were changed to have a particle size of 33 μm (thickness of 0.73 μm). Except for this, a decorative sheet of Comparative Example 2 was produced under the same conditions as in the above Example.

The three types of decorative sheets described above were evaluated for the cross section and adhesion of the metallic layer.
A cross-section of the metallic layer was photographed with a SEM (Scanning Electron Microscope) and evaluated with the SEM image. In the SEM image, when the small-diameter scales were arranged in parallel with the outermost layer of the metallic layer (the outermost layer on the side opposite to the support), it was rated as "◯", and the other cases were rated as "x".

In the adhesion test, the sample decorative sheet was fixed on a table and tested by the cross-cut method according to JIS K5600-5-6. In the adhesion test, the presence or absence of peeling of the metallic layer from the decorative material was observed. The classification of the test results was 0 (no peeling) or 1 (within 5% peeling) as "O", and otherwise as "X".
FIG. 4 shows the evaluation results of each of the above test items for the decorative sheets of Examples and Comparative Examples 1 and 2. FIG. FIG. 4 is a diagram for explaining the evaluation results of Examples and Comparative Examples 1 and 2. FIG.

(Evaluation results)
In the SEM image of the decorative sheet of the example, it was observed that the small-diameter scales were arranged in parallel with the outermost layer of the metallic layer, and it was confirmed that the luminance was improved. Moreover, it was confirmed that the decorative sheets of Examples had excellent adhesion, with no peeling observed in the outermost layer of the decorative layer. Although not included in the evaluation items, it was confirmed that the decorative sheet of the example had improved specularity of the decorative layer and improved unevenness (graininess) due to the uneven distribution of the aluminum flakes.

The decorative sheet of Comparative Example 1 yielded the same results as those of Examples with respect to adhesion. However, in the decorative sheet of Comparative Example 1, it was confirmed that the small-diameter scales were not arranged in parallel on the outermost layer of the metallic layer. This is presumably because, in the decorative sheet of Comparative Example 1, both the small-diameter scales and the large-diameter scales were non-leafing type, so that the small-diameter scales were dispersed in the coating film. As described above, in the decorative sheet of Comparative Example 1, since the small-diameter scales were not arranged in parallel on the outermost layer of the metallic layer, the same brightness as that of Examples could not be obtained.

As for the decorative sheet of Comparative Example 2, the same results as those of Examples were obtained with respect to the layer structure of the metallic layer. However, peeling of the decorative layer was observed in the decorative sheet of Comparative Example 2, confirming that the adhesiveness was low. This is because, in the decorative sheet of Comparative Example 2, since the particle size of the small particle size scales was increased, a large amount of the small particle size scales and the large particle size scales were mixed in the outermost layer of the metallic layer. It is considered that the adhesiveness in the surface layer decreased. In Comparative Example 2 (FIG. 4), the values in parentheses indicate the values when the particle diameter of the large-diameter scales is 25 μm, which is the same as in the example.
From the above results, it is clear that the decorative sheets of Examples are excellent in both brightness and adhesion of the outermost layer, provided that the cost is low compared to the method of forming a vapor deposition film as a decorative layer.

Although the embodiments of the present invention have been described above, the present invention is not limited to the above-described embodiments, and various modifications and changes such as the modified embodiments described later are possible. included within the technical scope of Moreover, the effects described in the embodiments are merely enumerations of the most suitable effects resulting from the present invention, and are not limited to those described in the embodiments. Although the above-described embodiment and modified embodiments described later can be used in combination as appropriate, detailed description thereof will be omitted.

(deformed form)
In the embodiment, an example in which an aluminum pigment is used as a preferable material for the large-diameter scales 22a and the small-diameter scales 22b that form the metallic layer 22 has been described, but the present invention is not limited to this. The material of the large particle size scales 22a and the small particle size scales 22b may be other metal materials (for example, iron, copper, nickel, etc.) or alloy materials thereof.
The decorative sheet 1 of the embodiment can be used alone, but may be used by forming an adhesive layer on the back side of the support 10 (the side opposite to the decorative layer 20) and attaching it to the surface of a plate. The plate material to which the decorative sheet 1 is attached includes, for example, a plate made of materials such as inorganic material, wood, and resin, and a wall. Among these, examples of inorganic materials include stone materials, concrete, glass, and metals. Also, the plate material may be a pottery (ceramic composition) such as ceramics made of an inorganic material.

REFERENCE SIGNS LIST 1 decorative sheet 10 support 20 decorative layer 21 colored opaque layer 22 metallic layer 22a large particle size metal flakes (large particle size flakes)
22b Small particle size metal scales (small particle size scales)
22c resin 23 pattern layer 23a pattern layer 23b colored transparent layer 30 protective layer

Claims (9)

A decorative sheet in which a support and a decorative layer are laminated,
The decorative layer has a metallic layer made of a resin containing a plurality of large-diameter metal scales and small-diameter metal scales,
In the metallic layer, the large-diameter metal scales and the small-diameter metal scales are mixed in a surface layer opposite to the support ,
The small particle size metal scales are leafing type and have a particle size of 10 μm or less,
The particle size of the small particle size metal scales is less than 0.42 times the particle size of the large particle size metal scales.
cosmetic sheet. The decorative sheet according to claim 1,
The metallic layer contains 40 parts by mass or less of metal flakes per 100 parts by mass of resin.
cosmetic sheet. A decorative sheet in which a support and a decorative layer are laminated,
The decorative layer has a metallic layer made of a resin containing a plurality of large-diameter metal scales and small-diameter metal scales,
In the metallic layer, the large-diameter metal scales and the small-diameter metal scales are mixed in a surface layer opposite to the support,
The particle size of the small particle size metal scales is less than 0.42 times the particle size of the large size metal scales,
The metallic layer contains 40 parts by mass or less of metal flakes per 100 parts by mass of resin.
cosmetic sheet. The decorative sheet according to any one of claims 1 to 3 ,
The small-diameter metal scales are mostly distributed on the surface layer side opposite to the support in the thickness direction of the metallic layer.
cosmetic sheet. The decorative sheet according to any one of claims 1 to 4 ,
The large-diameter metal scales are uniformly distributed in the thickness direction of the metallic layer and arranged in parallel along the layer direction.
cosmetic sheet. The decorative sheet according to any one of claims 1 to 5 ,
The decorative layer has at least one of a pattern layer and a colored transparent layer on the surface of the metallic layer opposite to the support,
cosmetic sheet. The decorative sheet according to any one of claims 1 to 6 ,
The decorative layer has a protective layer on the outermost surface opposite to the support,
cosmetic sheet. The decorative sheet according to any one of claims 1 to 7 ,
The decorative layer has a colored opaque layer on the surface of the metallic layer on the side of the support,
cosmetic sheet. A method for manufacturing a decorative sheet according to any one of claims 1 to 8 ,
a step of forming on the surface of the support a coating film obtained by mixing non-leafing type large particle size metal scales and leafing type small size metal scales with a resin;
The coating film formed on the surface of the support is dried to form the metallic layer in which the large-diameter metal scales and the small-diameter metal scales are mixed on the surface layer opposite to the support. and
A method for manufacturing a decorative sheet comprising

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