JP7342396B2 - Decorative sheets and decorative parts - Google Patents

Description

TECHNICAL FIELD The present invention relates to a decorative sheet and a decorative member that have an impression of a bright color tone such as white and have an excellent three-dimensional effect.

Decorative members, in which a decorative sheet is bonded to an adherend, are generally used for interior and exterior materials of buildings, fittings such as doors and handrails, and decorative surface panels for cabinets and the like. Furthermore, among the decorative sheets, there is, for example, a laminated decorative sheet commonly referred to as a "doubling sheet" that is highly convenient for bonding to curved surfaces (see, for example, Patent Document 1).
Specifically, the doubling sheet disclosed in Patent Document 1 is prepared by printing a pattern layer on a colored sheet made of thermoplastic resin. Also, a transparent sheet of thermoplastic resin with a pattern layer printed on it is prepared. Next, the transparent sheet is laminated on the pattern layer of the colored sheet via an adhesive layer, that is, subjected to a doubling process, whereby a plurality of different patterns are overlapped to create a sheet with a design effect.

Special Publication No. 7-22989 Special Publication No. 45-24679

On the other hand, it has been conventionally known to use glittering ink containing pearlescent pigments (pearlescent pigments), metal foil powder pigments, etc. to construct patterns that exhibit glittering properties due to pearlescent or metallic luster. Glittering ink can be used alone or in combination with a wood grain pattern made of brownish low-brightness colors (dark colors) to reproduce the appearance of the shine of wood grain (the luster unique to wood grain boards). It was used in
For example, in Patent Document 1, the entire surface of a colored sheet is printed with glitter ink, and in Patent Document 2, although the substrate to be printed is assumed to be a wood base material, only the shiny area of the wood grain is printed with glitter ink. It is printed with .
In recent years, in addition to reproducing the shine of wood grain, there has been a demand for designs that combine glitter patterns with patterns of high brightness colors such as white.
When we attempted to manufacture such a decorative sheet with a doubling specification as typified by Patent Document 1, we encountered problems inherent in the doubling specification, such as registration of the glitter pattern layer and the high brightness pattern layer (image position However, mass production was not possible due to the difficulty of mass production. That is, in the invention of Patent Document 1, a glittering pattern layer (referred to as a "glossy ink layer" in the same document) that is solid all over the colored sheet (referred to as a "thermoplastic synthetic resin base sheet" in the same document) on a colored sheet (referred to as a "thermoplastic synthetic resin base sheet" in the same document) ) instead of a transparent sheet (referred to as a "transparent synthetic resin sheet" in the same document) as a pattern layer (referred to as a "woodgrain pattern printed layer" in the same document) to form a glittering pattern layer with a pattern localized within a plane. We prepared a two-layer sheet with a localized high-brightness color pattern layer instead of the 3D image layer, and attempted to laminate both sheets by dry lamination or heat fusion. However, it is difficult to register the pattern layers printed on separate sheets when laminating them, due to differences in dimensional expansion and contraction of each sheet over time, differences in behavior with respect to tension and heat during lamination, etc. This is because even if the positions of the image layers are aligned at one location, the positions of the pattern layers located at separate locations will shift.
In addition, in the doubling process, when the patterns to be superimposed are pale colors or bright colors, the detection of the pattern position itself, which is a prerequisite for improving the registration accuracy of the pattern, can be done by visual or optical detection. Both are difficult.
Therefore, as in Patent Document 2, a glitter pattern layer and a high brightness pattern layer are sequentially formed on one surface of the same base material (a resin sheet is used instead of the wood base material in the same document). I tried to print . However, it has still been difficult to mass-produce high-quality decorative sheets.
Furthermore, if registration is difficult, the reproducibility of the pattern will also be reduced, making it difficult to obtain the desired design.
In particular, it is difficult to enhance the desired design by overlapping designs that have a light tone such as white on the entire decorative sheet and use a light color such as glitter ink or white ink because the registration accuracy will be low.

Therefore, the present invention aims to improve the registration accuracy of a pattern that has an excellent three-dimensional effect when viewed in plan, while giving an impression of a bright color tone expressed by a high brightness color such as white and a glittering color such as metallic luster or pearlescent luster. To provide an expensive decorative sheet and decorative member.

As a result of intensive studies to solve the above problems, the present inventor found that the problems can be solved by the present invention described below.
That is, the present invention is as follows.

[1] It has a base material layer, a glittering ink pattern layer, and a high brightness hiding pattern layer in this order, and
A part of the right upper part of the base layer is covered with the glittering ink pattern layer or the high brightness hiding pattern layer,
The high-brightness hiding pattern layer covers a part of the area directly above the glittering ink pattern layer,
A decorative sheet, wherein the base layer has an L* value of 90 or less in the CIE (Commission Internationale de l'Eclairage) L*a*b* color system measured in accordance with JIS Z8781-4:2013.
[2] A decorative member including the decorative sheet and an adherend.

Advantageous Effects of Invention According to the present invention, a decorative sheet and a decorative member have high registration accuracy of a pattern that has an excellent three-dimensional effect in plan view while giving an impression of a bright color tone expressed by a high brightness color such as white and a glittering color. can be provided.

FIG. 1 is a schematic diagram showing a cross section of a decorative sheet of the present invention. FIG. 1 is a schematic diagram showing a cross section of a decorative sheet of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic plan view of a decorative sheet of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic plan view of a decorative sheet of the present invention.

<Cosmetic sheet>
[Schematic diagram showing a cross section of a decorative sheet]
The layers constituting the decorative sheet 1 of the present invention will be explained using FIG. 1.
FIG. 1 is a schematic diagram showing a cross section of an example of a decorative sheet of the present invention, which has a base material layer 11, a glittering ink pattern layer 12, and a high brightness hiding pattern layer 13 in this order, and A portion directly above the layer 11 is covered with a glitter ink pattern layer 12 or a high brightness hiding pattern layer 13, and a portion right above the bright ink pattern layer 12 is covered with a high brightness hiding pattern layer 13. Cover.
In addition, "high brightness" in "high brightness hiding pattern layer" refers to colors that are white or close to white and give a generally white impression, such as bright gray, bright pale green, bright pink, bright light blue, bright pale yellow, etc. means.

By laminating the base material layer 11, the glittering ink pattern layer 12, and the high-brightness hiding pattern layer 13 in this order, the entire decorative sheet gives an impression of a bright white tone, while the glittering ink pattern layer 13 is laminated in this order. Since the layer 12 is partially hidden by the high-brightness hiding pattern layer 13, the contrast of light due to the glitter and hiding properties creates a sense of depth depending on the viewing angle, making it possible to create a pattern with a pseudo three-dimensional effect. can. This type of design provides a three-dimensional effect that is superior to the design provided by conventional decorative sheets with a white color tone, such as gloss matte, surface roughness such as unevenness, and pattern formation using white ink. can be expected to give. In the conventional doubling process, both the bright ink and the high-brightness hiding ink are light-colored, making it difficult to register and match the colors of the patterns. Since the decorative sheet of the present invention can be directly printed with a pattern so as to have the above-mentioned layer structure, registration and color matching are easy and an excellent design can be obtained.

On the other hand, for example, if the decorative sheet is laminated in the order of the base material layer 11, the high-brightness hiding pattern layer 13, and the glittering ink pattern layer 12, the glossiness of the glittering ink pattern layer 12 will be too strong. , and since the decorative sheet has a bright white color tone, the entire decorative sheet has a shiny impression and a sense of depth is lost, making it difficult to create a pattern with a pseudo three-dimensional effect when viewed from above. becomes.

Furthermore, if the entire surface of the base layer 11 is coated with the glitter ink pattern layer 12 and the high brightness hiding pattern layer 13 in this order, the color tones of the base material layer 11 and the glitter ink pattern layer 12 will be almost the same. The viewer of the decorative sheet simply perceives the color tone of the high brightness opaque pattern layer 13 on the entire surface. On the other hand, in the decorative sheet 1 of the present invention, not the entire surface but a part of the base layer 11 is covered with the glittering ink pattern layer 12 or the high brightness hiding pattern layer 13, and By covering a part of the transparent ink pattern layer 12, not the entire surface, with the high brightness hiding pattern layer 13, the base material layer 11, the bright ink pattern layer 12, and the high brightness hiding pattern layer 13 are covered in a plan view. The surfaces of the three layers of the sexual pattern layer 13 can be visually recognized without the color tones being hidden by other layers. As a result, the decorative sheet can have a design appearance unique to the present invention, which is a pattern created by visually cooperating the tones and colors of each of the three layers.

Here, in the present invention, "in plan view" means viewing the decorative sheet of the present invention in a planar direction from the side of the high-brightness hiding pattern layer. A typical example of "planar view" is that each pattern layer of the decorative sheet 1 is formed by aligning the viewing direction with the vertical direction of the surface of the high-brightness hiding pattern layer (for example, the vertical direction in FIG. 1). This is a case where the side surface is visually observed, but the "planar view" in the present invention is not limited to this form, and the decorative sheet of the present invention is visually observed from the side of the high brightness hiding pattern layer in the originally expected line of sight direction. This includes any case where

Further, one aspect of a preferred embodiment of the decorative sheet of the present invention will be described using FIG. 2.
FIG. 2 is a schematic diagram showing a cross section of an example of a decorative sheet, in which the transparent ink pattern layer 14 is composed of one or more layers selected from the base material layer 11, the glittering ink pattern layer 12, and the high brightness hiding pattern layer 13. Cover at least a portion of the area directly above the area.
When the decorative sheet has a transparent ink pattern layer, the base material layer, the glittering ink pattern layer, the high brightness hiding pattern layer, and the transparent ink pattern layer are laminated in this order. Even if the transparent ink pattern layer 14 is located on the surface side of the bright ink pattern layer 12 and the high brightness hiding pattern layer 13 as shown in FIG. 2, and covers these pattern layers, In plan view, the three layers of the base layer 11, the glittering ink pattern layer 12, and the high-brightness hiding pattern layer 13 are visually recognizable, and the decorative sheet is excellent as in the case without the transparent ink pattern layer. A material having transparency and color tone that does not impede the ability to obtain a design with a three-dimensional effect is appropriately selected, and the transparency and color tone are adjusted as appropriate.
The transparent ink pattern layer may cover the entire surface of the base material layer, the glitter ink pattern layer, and the high brightness hiding pattern layer, and as shown in FIG. A portion directly above one or more layers selected from the highly concealable pattern layers may be covered. By partially having a transparent ink pattern layer, the reflection of light becomes more complex, making visual changes more likely to occur, and in combination with the glitter and bright white tone, a more delicate design appears on the decorative sheet. be able to.

[Schematic diagram in plan view of decorative sheet]
Furthermore, visual recognition of each of the three layers described above in plan view of the decorative sheet 1 of the present invention will be explained using FIG. 3.
FIG. 3 is a schematic plan view of an example of the decorative sheet 1 of the present invention. In a plan view of the decorative sheet, a region 133 is a region where a portion directly above the base material layer is covered with the high-brightness hiding pattern layer 13, and a region 134 is a region directly above the glitter ink pattern layer 12. This is the area covered with the high-brightness hiding pattern layer 13. That is, the regions 133 and 134 are visually recognized as the high-concealing, high-brightness concealing pattern layer 13 located on the outermost surface. In addition, the area 132 is a region where the glitter ink pattern layer 12 covers a part of the right upper part of the base material layer, and since the surface thereof is not covered with the high-hidden pattern layer 13, the glitter ink pattern layer It is visually recognized as 12. Further, the region 131 is a part of the base layer 11 that is not covered with either the glitter ink pattern layer 12 or the high brightness hiding pattern layer 13, and is visually visible as the base material layer 11 exposed on the outermost surface. Recognized. Therefore, in the decorative sheet shown in the schematic diagram of FIG. 3, in plan view, the three layers of the base layer 11, the glittering ink pattern layer 12, and the high brightness hiding pattern layer 13 are partially visually recognizable in a pattern. This enables the area of the three layers in plan view to be recognized as a pattern, and a design can be made to appear on the decorative sheet 1.
In the present invention, the term "area" refers to a portion (closed area).

From the perspective of obtaining a more delicate design, the area of each area of the three layers of the base material layer, the bright ink pattern layer, and the high-brightness hiding pattern layer is determined by the size of the entire surface of the decorative sheet. Although it may depend on the situation, on the viewer side surface of the decorative sheet 1, as shown in FIG. The area ratio S12/S1 of the area S12 of 132 to the total area S1 of the decorative sheet 1, and the area ratio S13/S1 of the area S13 of the area covered with the high brightness hiding pattern layer 13 to the total area S1 of the decorative sheet 1. Then, the total area ratio (S12+S13)/S1 of the glitter ink layer 12 and the high brightness hiding pattern layer 13 that appear exposed on the outermost surface to the total area of the decorative sheet 1 is expressed as a percentage.
5%≦(S12+S13)×100/S1≦95%
can be in the range of In particular, from the point of view of providing a design appearance and ease of registration between each pattern layer,
10%≦(S12+S13)×100/S1≦50%
can be in the range of
Further, the area ratio S12/S13 between the area S12 of the region 132 where the glitter ink pattern layer 12 is exposed on the outermost surface and the area S13 of the region 133 where the high brightness hiding pattern layer 13 is exposed on the outermost surface is as follows:
2/8≦S12/S13≦8/2
It is preferable that
4/6≦S12/S13≦6/4
It is more preferable that

Although it is originally preferable to measure and calculate the area ratios S12/S13 and (S12+S13)×100/S1 over the entire surface of the decorative sheet, it is possible to measure and calculate the area ratios over the entire surface of the decorative sheet 1 within the required sufficient accuracy. If a numerical value representative of the ratio is obtained, the area ratio of the decorative sheet 1 is S12/S12 and (S12+S13)×100/ using the numerical value measured and calculated for a partial area of the entire surface of the decorative sheet 1. It can be S1.

In a plan view of the three layers of the base material layer, the bright ink pattern layer, and the high brightness hiding pattern layer, the size, area, and shape of each of the above regions may be the same or different, but it is more complex. It is preferable that they are different from the viewpoint of achieving a good design.

Further, visual recognition of each layer in a plan view when a transparent ink pattern layer is provided, which is one aspect of a preferred embodiment of the decorative sheet of the present invention, will be explained using FIG. 4.
FIG. 4 is a schematic plan view of an example of the decorative sheet 1 of the present invention. In a plan view of the decorative sheet 1, a region 144 is a region where the outermost surface of a part directly above the base material layer 11 is covered with the transparent ink pattern layer 14, and regions 147 and 148 are regions where the high brightness hiding pattern layer 13 A region 146 is a region in which a portion of the transparent ink pattern layer 14 covers a part of the transparent ink pattern layer 14 , and a region 146 is a region in which a portion directly above the glittering ink pattern layer 12 is covered with the transparent ink pattern layer 14 . Since the transparent ink pattern layer 14 is transparent, the base material layer 11 can be seen through the area 144, and the high brightness hiding pattern layer 13 can be seen through the areas 147 and 148 (the bright ink pattern layer 12 directly under the area 148). The color tone is hidden by the high-brightness concealing pattern layer 13 and is therefore not visible), but in the area 146, the glittering ink pattern layer 12 is visible.

When the transparent ink pattern layer 14 is colorless and transparent, it is possible to change the light diffusivity of the surface, and the area 144 has a different impression from the exposed area 141 of the base material layer 11 (for example, a more matte texture). Similarly, it is possible to give a different impression to the regions 146, 147, and 148 from the layer immediately below, and a more complex design can be created.
Furthermore, when the transparent ink pattern layer is colored and transparent, the region 144 can exhibit a hue different from that of the base material layer, and similarly, the regions 146, 147, and 148 are also different from the layer immediately below. It is possible to exhibit different hues, and more complex designs can be created.

Further, a region 143 is a region in which a portion directly above the base material layer 11 is covered with a high-brightness hiding pattern layer 13, and a region 145 is a region in which a portion directly above the glittering ink pattern layer 12 is covered with a high-brightness hiding pattern layer 13. This is the area covered by the pattern layer 13. That is, the area 143 and the area 145 are visually recognized as the high brightness opaque pattern layer 13. Further, the region 142 is a region where the glitter ink pattern layer 12 covers a part of the immediately upper part of the base material layer 11, and is visually recognized as the glitter ink pattern layer 12. Further, the region 141 is a part of the base material layer 11 that is not covered with any of the transparent ink pattern layer 14, the glittering ink pattern layer 12, and the high brightness hiding pattern layer 13, and is exposed on the outermost surface. It is visually recognized as the base material layer 11 that has been formed.

In a plan view of the four layers of the base layer, the bright ink pattern layer, the high brightness hiding pattern layer, and the transparent ink pattern layer, the size, area, and shape of each of the above regions may be the same or different. However, it is preferable that they are different from the viewpoint of achieving a more complex design.

[L ^* value]
As described above, the base material layer, the glittering ink pattern layer, and the high-brightness hiding pattern layer are visually observed as adjacent regions in a plan view. From the viewpoint of easily achieving excellent design, it is preferable that the three layers have different brightnesses.
That is, a plurality of regions are adjacent to each other in a plan view, and L in the CIE (Commission Internationale de l'Eclairage) L ^* a ^* b ^* color system is measured in accordance with JIS Z8781-4:2013 of one region. ^* value and the L ^* value of a region adjacent to the one region can be made into decorative sheets in which the values are different from each other as an example of an embodiment of the decorative sheet of the present invention.
The glittering ink pattern layer having the above L ^* value _{of the glittering ink pattern} layer 12 is preferably used in order to express glittering properties and reproduce ^a design appearance with an excellent three-dimensional effect of bright color tone in the present invention. is 70 or more, more preferably 80 or more, and is preferably 98 or less, more preferably 95 or less, since obtaining an extremely high L ^* value is difficult in terms of material acquisition and printing technology. . The above-mentioned L ^* value of the high _{brightness hiding pattern} layer 13 is also preferably 70 or more in order to reproduce the design appearance with bright color tone and excellent three-dimensional effect ⁱⁿ the present invention. , more preferably 80 or more, and preferably 98 or less, more preferably 95 or less.
Note that the above L ^* value of the base material layer is as described below.

[Base material layer]
The base material layer has an L ^* value of 90 or less in the CIE (Commission Internationale de l'Eclairage) L ^* a ^* b ^* color _system measured ⁱⁿ accordance with JIS Z8781-4:2013. It is.
In the decorative sheet of the present invention, since the pattern of the decorative sheet 1 is composed of at least three of the glittering ink pattern layer 12, the high brightness hiding pattern layer 13, and the base material layer 11, the three layers 11, The hue and saturation of the colors 12 and 13 are selected so that the three colors 11, 12, and 13 are different from each other to the extent that they can be visually distinguished from each other.
However, since the decorative sheet of the present invention has a bright white tone as a whole, the L ^* _{glittering ink pattern layer} and the L ^* _{high brightness hiding pattern layer} both have a high value of 70 or more, as described above. Selected as a high brightness color.
Therefore, when the L ^* _{base material layer} becomes larger, which corresponds to the brightness of the base material layer 11, specifically, when the above L ^* _{base material layer} exceeds 90, the brightness ink pattern layer 12 and the high brightness hiding property are used during printing. It becomes difficult to detect printing defects such as ink streaks and color unevenness that occur in the pattern layer 13, and the decorative sheet may be inferior in design. If the L ^* value of the base _material layer 11 is 90 or less, defects such as ink streaks and color unevenness that occur during printing will be easier to discover, and such defects can be addressed even during gravure printing, for example ^. A decorative sheet with an excellent design can be stably obtained. Furthermore, since the glitter ink pattern layer and the high-brightness hiding pattern layer laminated on the base material layer are pale in color, if the L ^* value of each layer is set in this way, the pattern woven by these pattern layers will be created as described above. becomes easier to visually recognize.
If the L ^* value of each layer is set as above, it will be easier to discover the above defects and obtain an excellent design, and from the viewpoint of making it easier to recognize the pattern of the pattern layer and expressing a pattern with a more three-dimensional effect. , L ^* _{of the base layer} is preferably 80 or less, more preferably 70 or less. Furthermore, the lower limit of the L ^* value of the base _layer 11 is not particularly limited and may be determined as appropriate depending on the desired design, but the decorative sheet as a ^whole gives an impression of a light tone such as white. From the viewpoint of providing the desired value, it is preferably 40 or more, more preferably 50 or more.

For example, types of colors ^for which the L ^* value of _{the base material layer} is 90 or less include ivory color, ecru color, chalk color, flesh color, beige, light blue, sky blue, white green, Preferred examples include young leaf color, light gray, and pink color. Further, as the color of the base material layer, these colors can be used alone or in combination of a plurality of colors.

For the base material layer, materials that are normally used as base materials for decorative sheets can be used without limitation, and for example, paper, a resin base material made of thermoplastic resin, nonwoven fabric, or a composite material thereof can be used. .
Examples of paper include thin paper, kraft paper, high-quality paper, linter paper, baryta paper, parchment paper, and Japanese paper. The basis weight of the paper is usually about 20 to 100 g/m ² . Further, the paper is not particularly limited as long as it satisfies the L ^* value described below and does not impair the effects of the present invention, but it may be impregnated with resin or colored. .

Examples of thermoplastic resins constituting the resin base material include polyolefin resins such as polypropylene and polyethylene; polyester resins; polycarbonate resins; acrylonitrile-butadiene-styrene resins (hereinafter also referred to as "ABS resins"); acrylic resins; Vinyl chloride resins such as vinyl chloride, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl chloride copolymer, and vinyl chloride-vinyl acetate-maleic acid copolymer are used. Among these, vinyl chloride resins, polyolefin resins, polyester resins, polycarbonate resins, and ABS resins are preferred, and vinyl chloride resins and polyolefin resins are particularly preferred, considering ease of handling, processing characteristics, and the like. In the present invention, these resins can be used alone or in combination.

Polyolefin resins are not particularly limited, and include, for example, polyethylene (low density, medium density, high density), polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, propylene-butene copolymer, ethylene-vinyl acetate. Examples include copolymers, ethylene-acrylic acid copolymers, ethylene-propylene-butene copolymers, and polyolefin thermoplastic elastomers. Among these, polyethylene (low density, medium density, high density), polypropylene, ethylene-propylene copolymer, and propylene-butene copolymer are preferred.
In addition, vinyl chloride resins include polyvinyl chloride (homopolymer of vinyl chloride monomer), chlorinated polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl chloride copolymer, vinyl chloride- Vinyl acetate-maleic acid copolymer and the like are preferred. Appropriate amounts of known additives such as plasticizers, heat stabilizers, extender pigments (or fillers), and ultraviolet absorbers can be added to these vinyl chloride resins, if necessary.

Further, a coloring agent can be used for the resin base material in order to satisfy the above-mentioned L ^* value.
As the pigment of the coloring agent, either an inorganic pigment or an organic pigment can be used as long as it can satisfy the L ^* value described below.
Examples of colorant pigments include inorganic pigments such as carbon black, iron black, yellow lead, titanium yellow, Bengara, cadmium red, ultramarine blue, cobalt blue, titanium oxide (titanium white), lead white, and antimony white, and azomethine. azomethine-based, perylene-based, perinone-based, disazo-based, polyazo-based, nickel-azo-based, quinacridone-based, isoindoline-based, isoindolinone-based, phthalocyanine-based, aniline-based, diketopyrrolopyrrole-based, dioxazine-based, etc. Preferred examples include organic pigments or dyes, metal pigments made of flaky foils such as aluminum and brass, mica coated with titanium dioxide, and pearlescent pigments made of flaky foils such as basic lead carbonate. These pigments can be used alone or in combination.

(thickness)
Although the thickness of the base material layer is not limited, it may generally be about 25 to 500 μm, preferably 80 to 500 μm, more preferably 80 to 300 μm, and even more preferably 80 to 200 μm.

[Glitter ink pattern layer]
(Glitter pigment)
The glitter ink pattern layer 12 preferably contains, for example, a glitter pigment and a binder.
Examples of bright pigments include pearl pigments and metal pigments. Among these, pearl pigments have moderate glittering properties, and have higher light transmittance (that is, lower hiding properties) than metal pigments, and the color tone of the base layer 11 directly below the glittering ink pattern layer 12 is similar to that of decorative sheets. This is advantageous in that it is easier to create a pattern with a three-dimensional effect by reflecting it in the design appearance.

Pearl pigments are pigments that can impart pearlescent luster, and include, for example, base particles whose surfaces are coated with metal oxides, basic lead carbonate, mica, shells such as mother-of-pearl, etc., in the form of scales (i.e. foils). flaky) particles. In particular, from the viewpoints of durability, mass productivity, cost, and good glitter, scaly particles whose surfaces are coated with a metal oxide are preferably used. The base particles are preferably scaly particles such as mica. Examples of 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 in combination.
Specific examples of pearlescent pigments include titanium dioxide-coated mica, iron oxide-coated mica, titanium dioxide- and iron oxide-coated mica, and the like. One type of pearl pigment may be used alone, or two or more types may be used in combination.

Examples of the metal pigment include pigments made of scaly particles of metals such as aluminum, brass, stainless steel, tin, zinc, copper, nickel, gold, and silver, and alloys of these metals. One type of metal pigment may be used alone, or two or more types may be used in combination.
The average particle diameter of the glitter pigment is preferably from 1 to 500 μm, more preferably from 5 to 100 μm, from the viewpoint of imparting glitter and suppressing shedding of the glitter pigment.

(binder)
Examples of the binder include thermoplastic resins and cured products of curable resin compositions, and from the viewpoint of durability, cured products of curable resin compositions are preferred.
Examples of the cured product of the curable resin composition include a cured product of a thermosetting resin composition and a cured product of an ionizing radiation-curable resin composition.
Examples of the thermosetting resin composition include a polyester resin composition, an epoxy resin composition, a polyurethane resin composition, an aminoalkyd resin composition, a melamine resin composition, a guanamine resin composition, a urea resin composition, and a thermosetting acrylic composition. Examples include resin compositions. These thermosetting resin compositions contain monomers and/or prepolymers constituting each resin, and a curing agent added as necessary.
As the ionizing radiation curable resin composition, the same one as the ionizing radiation curable resin composition of the transparent ink pattern layer described below can be used.

(Content)
The content of the glitter pigment in the glitter ink pattern layer is preferably 10 to 90 parts by weight, more preferably 50 to 80 parts by weight, based on 100 parts by weight of the binder. By setting the content of the glittering pigment within the above-mentioned preferred range, it is possible to sufficiently facilitate the appearance of a pattern having a three-dimensional effect.
(thickness)
The thickness of the glitter ink pattern layer is preferably 1 to 30 μm from the viewpoint of making it easy to sufficiently create a pattern with a three-dimensional effect.

(pictorial pattern)
The pattern of the glittering ink pattern layer may be determined as appropriate so that the desired design results from the combination with the pattern of the high brightness opaque pattern layer, which will be described later.
Patterns include, for example, wood grain patterns, stone grain patterns, cloth grain patterns, sand grain patterns, tiling or brickwork surface patterns including grooves, leather grain patterns, or polygons such as triangles, squares, hexagons, etc. Examples include geometric patterns and abstract patterns including shapes such as circles, ovals, heart shapes, floral patterns, striped patterns, arabesque patterns, thunder patterns, dragon patterns, and turtle shell patterns. Among these patterns, stone grain patterns or geometric patterns, such as a polycrystalline stone pattern appearing on the cleavage plane of a granite plate, are preferable from the viewpoint of easily creating a three-dimensional effect on the decorative sheet.

(Printing means)
For example, the glitter ink pattern layer is formed by applying a coating liquid for forming a glitter ink pattern layer containing the material constituting the glitter ink pattern layer to plate printing such as gravure printing, offset printing, flexo printing, silk screen printing, or inkjet printing. It can be formed by general-purpose printing means such as plateless printing.

[High brightness hiding pattern layer]
(white hiding pigment)
The high-brightness concealing pattern layer 13 gives an impression of high brightness and bright tone such as white color to the entire decorative sheet, and further hides the color tone of the bright ink pattern layer 12 immediately below, so that the bright ink pattern layer 12 is different from the bright one. It is preferable to contain a white hiding pigment from the viewpoint of imparting a different appearance and expressing a three-dimensional effect by the combination of the appearances of both adjacent pattern layers 12 and 13.
The high brightness opaque pattern layer can have white opaque properties and light diffusing properties, and is preferably formed using a coating liquid containing a white opaque pigment and a binder. In addition, a coloring agent as a color tone adjusting agent may also be added to prevent the binder from changing over time or becoming colored due to a decrease in light resistance.

Examples of the white hiding pigment include particles of titanium oxide white, lead white, antimony white, aluminum oxide white, titanium dioxide-coated mica, zinc white, and the like. Among these white hiding pigments, titanium oxide white is preferred from the viewpoint of whiteness and hiding power. These white hiding pigments may be used alone or in combination of two or more.
There are anatase type, brookite type, and rutile type of titanium oxide, and any of them can be used, but the rutile type is preferable in consideration of excellent hiding power (color development) and weather resistance. Rutile-type titanium oxide has low photocatalytic activity, so even when used in an environment exposed to direct sunlight, photocatalytic reactions are less likely to occur, the effect of photocatalytic reactions on weather resistance is reduced, and weather resistance is improved. Moreover, from the viewpoint of further reducing the photocatalytic activity of titanium oxide, it is preferable to use titanium oxide particles as a white pigment whose surfaces are coated with a substance that blocks photocatalytic activity. Preferred examples of substances that block such photocatalytic activity include compounds containing metal atoms such as silicon, aluminum, and zirconium. Typical examples of compounds include oxides, such as silicon oxide such as silica, aluminum oxide, and zirconium. Preferred examples include zirconium.

The average particle size of the primary particles of the white hiding pigment is preferably 0.02 to 3.0 μm, more preferably 0.15 to 3.0 μm, and still more preferably 0.1 to 3.0 μm. When the average particle size of the white hiding pigment is within the above range, high hiding power and good color development can be obtained, resulting in an excellent design.

(binder)
As the binder, the same binder as mentioned above in the glitter ink pattern layer can be used.
(Content)
The content of the white hiding pigment in the high brightness hiding pattern layer is preferably 10 to 300 parts by weight, more preferably 50 to 250 parts by weight, based on 100 parts by weight of the binder. By setting the content of the glittering pigment within the above-mentioned preferred range, a pattern with excellent whiteness and concealing properties and a three-dimensional effect can be easily produced. Further, within the above preferred range, the stability of the high brightness hiding pattern layer and the durability of the formed coating film are also good.

(Other pigments)
The high brightness opaque pattern layer may contain other pigments in addition to the white opaque pigment as long as they do not impair the effects of the present invention. As other pigments, the same pigments as the above-mentioned coloring agent can be used in the base layer.
(Hue adjuster)
Furthermore, a hue adjusting agent may be added to the high brightness hiding pattern layer. The hue adjusting agent has the function of adjusting the whiteness of the high-brightness opaque pattern layer, and also has the function of further increasing the opacity.
As the hue modifier, any known material can be used without particular limitation, and examples thereof include quinone type, azo type, triarylmethane type, cyanine type, phthalocyanine type, and indigo type. These hue modifiers may be used alone or in combination of two or more.

(fluorescent brightener)
Further, a fluorescent whitening agent can be added to the high brightness hiding pattern layer. As the fluorescent whitening agent, known compounds having a fluorescent whitening effect such as stilbenzene compounds, pyrazoline compounds, etc. can be used.
(filling material)
In addition, the high brightness hiding pattern layer contains inorganic fillers such as silica, alumina, clay, talc, calcium carbonate or barium sulfate, acrylic resin, epoxy resin, polyurethane resin, phenol resin, melamine resin, benzoguanamine resin, and fluororesin. Alternatively, a filler of resin particles (plastic pigments) such as silicone resin can be added to improve the hiding property.

(thickness)
From the viewpoint of sufficiently facilitating the appearance of a pattern having a three-dimensional effect, the thickness of the high brightness hiding pattern layer is preferably 1 to 30 μm.
(pictorial pattern)
The pattern of the high-brightness opaque pattern layer may be determined as appropriate so that the design resulting from the combination with the pattern of the glittering ink pattern layer described above will be the desired one. The pattern may be similar to the pattern described above in the glitter ink pattern layer.
(Printing means)
The high-brightness opaque pattern layer can be formed, for example, by using a coating liquid for forming a high-brightness opaque pattern layer containing a material constituting the high-brightness opaque pattern layer using a general-purpose printing method such as the above-mentioned gravure printing.

[Transparent ink pattern layer]
As described above, the transparent ink pattern layer 14 is formed directly from the portion exposed on the outermost surface of one or more layers selected from the base material layer 11, the glittering ink pattern layer 12, and the high brightness hiding pattern layer 13. It is preferable to cover at least a part of the upper part, and also to cover the entire area directly above one or more layers selected from the base material layer, the glitter ink pattern layer, and the high brightness hiding pattern layer. is more preferable.

(resin)
The transparent ink pattern layer preferably contains resin as a main component. Here, the main component means that the resin is contained in an amount of 50% by mass or more based on the total solid content constituting the transparent ink pattern layer, preferably 70% by mass or more, more preferably 90% by mass or more, and still more preferably It is 98% by mass or more.
Examples of the resin for the transparent ink pattern layer include thermoplastic resins and cured products of curable resin compositions. Among these, when durability such as scratch resistance, solvent resistance, and stain resistance is particularly required, cured products of curable resin compositions are preferred, and among these, cured products of ionizing radiation-curable resin compositions are preferred. Among these, a cured product of an electron beam curable resin composition is preferred.
As the thermosetting resin composition for the transparent ink pattern layer, the same thermosetting resin composition as exemplified as the binder for the glittering ink pattern layer can be used.

The ionizing radiation-curable resin composition is a composition containing a compound (ionizing radiation-curable compound) that is cured by irradiation with ionizing radiation. Ionizing radiation refers to electromagnetic waves or charged particle beams that have energy quanta that can polymerize or crosslink molecules, and ultraviolet (UV) or electron beam (EB) are usually used, but other types include X-rays. Electromagnetic waves such as γ rays, α rays, and charged particle beams such as ion beams can also be used.

The ionizing radiation-curable compound can be appropriately selected from commonly used polymerizable monomers, polymerizable oligomers, or prepolymers.
As the polymerizable monomer, (meth)acrylate monomers having a radically polymerizable unsaturated group in the molecule are suitable, and polyfunctional (meth)acrylate monomers are particularly preferred.
The polyfunctional (meth)acrylate monomer may be any (meth)acrylate monomer having two or more ethylenically unsaturated bonds in the molecule, such as diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, Preferred examples include trimethylolpropane tri(meth)acrylate, trimethylolpropane ethylene oxide tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. It will be done. These (meth)acrylate monomers may be used alone or in combination of two or more.
In addition, "(meth)acrylate" here means acrylate or methacrylate.

The number of functional groups in the polyfunctional (meth)acrylate monomer is preferably 2 or more, preferably 2 to 8, more preferably 3 to 6 from the viewpoint of obtaining excellent surface protection properties.

Next, as polymerizable oligomers, oligomers having radically polymerizable unsaturated groups in the molecule, such as urethane (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, polyester (meth)acrylate oligomers, polyether (meth)acrylate Preferred examples include (meth)acrylate oligomers such as oligomers and acrylic (meth)acrylate oligomers, and these oligomers may be used alone or in combination of two or more.
Among the above polymerizable (meth)acrylate oligomers, polyfunctional urethane (meth)acrylate oligomers are preferred. This is because the polyfunctional urethane (meth)acrylate oligomer can provide excellent surface protection properties and can also suppress shrinkage of the decorative sheet during the manufacturing process.
The number of functional groups in the polyfunctional (meth)acrylate oligomer is not particularly limited as long as it is 2 or more, but from the viewpoint of surface protection properties and suppression of shrinkage during production, it is preferably 2 to 8, more preferably 2 to 6.

Further, the weight average molecular weight (weight average molecular weight in terms of polystyrene measured by GPC method) of the polyfunctional (meth)acrylate oligomer is preferably 1,000 to 20,000, and preferably 1,000 to 10,000. It is more preferable.

As the ionizing radiation-curable compound, monofunctional (meth)acrylate may be used in order to adjust the hardness and viscosity of the ionizing radiation-curable resin composition.
Examples of monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, and cyclohexyl (meth)acrylate. ) acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isobornyl (meth)acrylate, and the like. These monofunctional (meth)acrylates may be used alone or in combination of two or more.

When an ultraviolet curable compound is used as the ionizing radiation curable compound, it is desirable to add about 0.1 to 5 parts by weight of a photopolymerization initiator to 100 parts by weight of the ultraviolet curable compound. The photopolymerization initiator can be appropriately selected from conventionally used initiators, and is not particularly limited. Preferred examples include agents.
Further, as the photosensitizer, for example, p-dimethylbenzoic acid ester, tertiary amines, thiol-based sensitizers, etc. can be used.

The ionizing radiation curable compound is preferably electron beam curable. In the case of electron beam curability, it is possible to use no solvent, which is more preferable from an environmental and health perspective, and does not require a photopolymerization initiator, resulting in a cured product with stable curing characteristics and good weather resistance. Because you can get it.

(thickness)
The thickness of the transparent ink pattern layer may be any thickness that can provide a desired design, and is preferably 1 to 30 μm.
(pictorial pattern)
The pattern of the transparent ink pattern layer may be determined as appropriate so that the desired design results from the combination of the glittering ink pattern layer and the high brightness opaque pattern layer described above. The pattern may be similar to the pattern described above in the glitter ink pattern layer.
(Printing means)
The transparent ink pattern layer can be formed, for example, by using a coating liquid for forming a transparent ink pattern layer containing a material constituting the transparent ink pattern layer, using a general-purpose printing method such as the above-mentioned gravure printing.

<Cosmetic parts>
The decorative member of the present invention includes the decorative sheet of the present invention described above and an adherend.
Specifically, the surface of the adherend that requires decoration and the surface of the decorative sheet on the base material layer side are stacked so as to face each other. That is, the decorative member of the present invention has at least an adherend, a base material layer, a glittering ink pattern layer, and a high brightness opaque pattern layer in this order.

(adherent material)
The adherend material may be appropriately selected depending on the application, and examples include plate materials such as flat plates and curved plates made of various materials, three-dimensional articles, sheets (or films), and the like. For example, wood veneers made of various types of wood such as cedar, cypress, pine, and lauan, wood plywood, particle board, wood fiberboard such as MDF (medium density fiberboard), and wood materials used as three-dimensional objects. ; Metal members used as iron, aluminum plates, steel plates, three-dimensional objects, sheets, etc.; Ceramics such as glass and ceramics, non-cement ceramic materials such as plaster, non-ceramic materials such as ALC (Lightweight Aerated Concrete) plates; Ceramic materials used as plate materials and three-dimensional articles; polyolefin resins such as acrylic resin, polyester resin, polystyrene resin, and polypropylene, ABS (acrylonitrile-butadiene-styrene copolymer) resin, phenolic resin, vinyl chloride Examples include plate materials such as resin, cellulose resin, and rubber, three-dimensional articles, and resin members used as sheets. These members may be used alone or in combination of two or more.

The thickness of the adherend may be appropriately selected depending on the application and material, and is preferably 0.1 to 10 mm, more preferably 0.3 to 5 mm, and even more preferably 0.5 to 3 mm.

(Method for manufacturing decorative parts)
The method of laminating the decorative sheet onto various adherends is not particularly limited, and for example, a method of adhering the sheet to the adherend with an adhesive may be employed. The adhesive may be appropriately selected from known adhesives depending on the type of adherend. Examples include polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, ionomer, as well as urethane resin, epoxy resin, natural rubber, and various synthetic rubbers.

Decorative components include, for example, interior materials of buildings such as walls, ceilings, and floors; fittings and fixtures such as window frames, doors, handrails, corrals, and ceilings; furniture such as chests of drawers, desks, and cupboards; and video and audio. It can be preferably used as a casing or a component of appliances, home appliances such as refrigerators, and various OA equipment.

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

[Measuring method]
(Measurement of L ^* value)
The L ^* value of the decorative sheets obtained in each example described below was measured by the following method.
When the decorative sheet before providing the transparent ink pattern layer is viewed from the high-brightness opaque pattern layer side, (1) base material layer, (2) bright ink pattern layer, and (3) high-brightness opaque pattern layer are shown. In each area, use a spectrocolorimeter/colorimeter ("CM-700d" (model number), manufactured by Konica Minolta, Inc.) to measure 10 arbitrary points on each of the layers (1) to (3) above of the decorative sheet. Irradiate the surface with light (D65 light source) at an incident angle of 10 degrees, measure the total reflected light (specular reflected light + diffuse reflected light) at a viewing angle of 2 degrees, a measurement diameter of 3 mm, and calculate the average value for each area. It was taken as L ^* value.

[Example 1]
(Decorative sheet: base material layer + bright ink pattern layer + high brightness hiding pattern layer)
The base material layer 11 is a polypropylene resin colored beige by adding a pigment made by mixing titanium white, Bengara, yellow lead, and phthalocyanine blue (L ^* (L ^* _{base material layer} ) is 90, a ^* (a ^* _{base material layer} ) is 0, b ^* (L ^* _{base material layer} ) is 7, thickness: 100 μm), and a geometric pattern is formed so as to cover a part of the right upper part of the base material layer in plan view. A coating liquid for forming a glitter ink pattern layer 12 having the following formulation was applied using a gravure printing method and dried to form a glitter ink pattern layer 12 having a thickness of 3 μm.
Next, a coating liquid for forming a high-brightness opaque pattern layer 13 having the following formulation is gravure printed in a geometric pattern so as to cover a portion of the base layer 11 and the right upper part of the glitter ink pattern layer 12 in a plan view. A decorative sheet was obtained by coating and drying to form a high brightness concealing pattern layer 13 having a thickness of 2 μm.
<Coating liquid for forming glitter ink pattern layer>
・Pearl pigment (white pearl consisting of titanium dioxide-coated mica scale particles, particle size 25 μm): 35 parts by mass ・Acrylic resin (binder): 65 parts by mass ・Dilution solvent: appropriate amount <Coating liquid for forming a high brightness shielding pattern layer ＞
・Polyester resin (binder): 33 parts by mass ・Isocyanate curing agent: 15 parts by mass ・White pigment consisting of rutile-type titanium oxide particles (particle size 2.5 μm): 75 parts by mass ・Dilution solvent: Appropriate amount (design evaluation)
The L ^* value of each region of the obtained decorative sheet was measured using the method described above, and the values were as follows.
(1) Area of base material layer: L ^* value 90
(2) Area of bright ink pattern layer: L ^* value 89
(3) Area of high brightness hiding pattern layer: L ^* value 87
Moreover, the obtained decorative sheet had an impression of a white-based bright color tone, and had a design that had a pseudo three-dimensional effect in plan view.

The decorative sheet of the present invention is useful in that it has an impression of a bright white tone, has excellent three-dimensional effect in plan view, and can have an extremely good design.

1. Decorative sheet 11. Base material layer 12. Glitter ink pattern layer 13. High brightness hiding pattern layer 14. transparent ink pattern layer

Claims (7)

It has a base material layer, a glittering ink pattern layer, and a high brightness hiding pattern layer,
a region (1) in which the glittering ink pattern layer covers a part of the base layer directly above the base material layer, and the high brightness hiding pattern layer is not formed directly above the glittering ink pattern layer;
another part directly above the base material layer is covered with the high-brightness hiding pattern layer, and an area (2) in which the glittering ink pattern layer is not formed;
A region (3) in which the glittering ink pattern layer covers another part directly above the base material layer, and the high brightness hiding pattern layer covers directly above the glittering ink pattern layer. and,
an area (4) in which the base material layer is not covered by either the glittering ink pattern layer or the high-brightness hiding pattern layer;
has
The L ^* value of the high brightness hiding pattern layer is 70 or more,
A decorative sheet in which the base layer has an L ^* value of 40 or more and 90 or less in the CIE (Commission Internationale de l'Eclairage) L ^* a ^* b ^* color system measured in accordance with JIS Z8781-4:2013. 2. The transparent ink pattern layer further covers at least a portion of the layer directly above one or more layers selected from the base material layer, the glittering ink pattern layer, and the high-brightness hiding pattern layer. cosmetic sheet. The cosmetic according to claim 2, wherein the transparent ink pattern layer covers the entire area immediately above one or more layers selected from the base material layer, the glitter ink pattern layer, and the high brightness hiding pattern layer. sheet. The decorative sheet according to any one of claims 1 to 3, wherein the high brightness opaque pattern layer contains a white opaque pigment. The plurality of regions (1) to (4) are adjacent to each other in plan view, and the CIE (Commission Internationale de l'Eclairage) L ^* a ^* b measured in accordance with JIS Z8781-4:2013 of one region. ^The decorative sheet according to any one of claims 1 to 4, wherein the L ^* value in the color system and the L ^* value of the area adjacent to the one area are different from each other. The decorative sheet according to any one of claims 1 to 5, wherein the base material layer, the glittering ink pattern layer, and the high-brightness hiding pattern layer are visually recognizable in plan view. A decorative member comprising the decorative sheet according to any one of claims 1 to 6 and an adherend.