JPWO2019230954A1 - Metal-like decoration member and metal-like decoration molded body using it - Google Patents

Abstract

Provided is a metal-like decorative member capable of imparting a high level of design. A metal-like decorative member having a protective layer and a brilliant printing layer containing a brilliant pigment and a binder resin in this order from the outer layer side, and satisfying the following condition 1. <Condition 1> Visible light is incident on the outer layer side surface of the metallic decorative member from an arbitrary azimuth at an elevation angle of 45 degrees. Let L * 1-25 be the L * value of the L * a * b * color system calculated from the spectral spectrum of the reflected light in the direction in which the elevation angle is tilted 25 degrees toward the incident light side from the specular reflection direction of the incident light. .. Visible light is incident on the outer layer side surface of the metallic decorative member from an azimuth angle opposite to the arbitrary azimuth angle at an elevation angle of 45 degrees. Let L * 2-25 be the L * value of the L * a * b * color system calculated from the spectral spectrum of the reflected light in the direction in which the elevation angle is tilted 25 degrees toward the incident light side from the specular reflection direction of the incident light. .. Under the above premise, the relationship with L * 1-25 and L * 2-25 satisfies the following equations (1) and (2) at least in some azimuth angles. L * 1-25> L * 2-25 (1) 1.0 <{(L * 1-25-L * 2-25) / L * 1-25} x 100 (2)

Description

The present invention relates to a metal-like decorative member and a metal-like decorative molded body using the same.

As a method of enhancing the design of materials such as automobiles, interior materials and exterior materials of buildings, furniture, etc., painting by spraying or the like is performed. _{However, painting has a large environmental load due to the solvent and a large CO 2} emission load based on electricity required in the drying and cooling processes. In addition, since the coating is performed a plurality of times (for example, in the case of a pearl-like coating, the primer, the undercoat, the intermediate coat, the topcoat color base, the pearl base, and the topcoat clear may be applied six times). And the series of drying steps is repeated, the above-mentioned problems tend to become serious, and the cost also increases. For this reason, in recent years, in the painting of automobiles, there has been a switch to painting of resin members that can reduce _{CO 2 emissions in the cooling process.}
However, when the resin member has a three-dimensional structure, uneven coating occurs in the coating of the resin member, and it is difficult to apply a beautiful coating.

As a method that can solve the above problem, for example, a decorative film provided with a bright layer formed by silk screen printing has been proposed (Patent Document 1).

Japanese Patent No. 5793908

The decorative film of Patent Document 1 can solve painting problems (environmental load due to solvent, CO ₂ emission load based on electricity required in drying and cooling steps).
However, since the decorative film of Patent Document 1 is based on a screen printing method, there is a problem that the entire process from coating by screen printing to bonding the boards is a sheet-fed method, which is inefficient and increases the cost. is there.
Further, the bright layer (layer containing the pearl pigment) obtained by the screen printing method as in Patent Document 1 lacks metallic luster, and there are many cases where the design property cannot be satisfied.

As a result of diligent studies, the present inventors have found that a high level of designability can be imparted by imparting anisotropy to the glittering property of the bright layer, and have solved the above-mentioned problems.

The present invention provides the following [1] to [2].
[1] A metal-like decorative member having a protective layer and a brilliant printing layer containing a brilliant pigment and a binder resin in this order from the outer layer side, and satisfying the following condition 1.
<Condition 1>
Visible light is incident on the outer layer side surface of the metallic decorative member from an arbitrary azimuth angle (azimuth angle a) at an elevation angle of 45 degrees. Let ^{L * a *} b ^{* L *} value of the color system be ^{L *} _1-25 calculated from the spectral spectrum of the reflected light in the direction in which the elevation angle is tilted 25 degrees toward the incident light side from the specular reflection direction of the incident light. ..
Visible light is incident on the outer layer side surface of the metallic decorative member from an azimuth angle (azimuth angle b) opposite to the arbitrary azimuth angle at an elevation angle of 45 degrees. Let ^{L * a *} b ^{* L *} value of the color system be ^{L *} _2-25 calculated from the spectral spectrum of the reflected light in the direction in which the elevation angle is tilted 25 degrees toward the incident light side from the specular reflection direction of the incident light. ..
^{Under the above premise, the relationship with L *} _1-25 and L ^* _2-25 satisfies the following equations (1) and (2) at least in some azimuth angles.
L ^* _1-25 > L ^* _2-25 (1)
1.00 <{(L ^* _1-25- L ^* _2-25 ) / L ^* _1-25 } x 100 (2)
[2] A metallic decorative molded body formed from the metallic decorative member according to the above [1].

According to the present invention, it is possible to provide a metal-like decorative member capable of imparting a high level of designability and a metal-like decorative molded body using the same.

It is sectional drawing which shows one Embodiment of the metal-like decoration member of this invention. It is sectional drawing which shows the other embodiment of the metal-like decoration member of this invention. It is a schematic diagram explaining the measurement method of condition 1. It is a schematic diagram explaining the measurement method of condition 1. It is a schematic diagram explaining an example of the printing method of a brilliant printing layer. It is a schematic diagram explaining an example of the arrangement of the bright pigment in a bright print layer.

[Metallic decoration material]
The metallic decorative member of the present invention comprises a protective layer and a brilliant printing layer containing a brilliant pigment and a binder resin in this order from the outer layer side, and satisfies the following condition 1.
<Condition 1>
Visible light is incident on the outer layer side surface of the metallic decorative member from an arbitrary azimuth angle (azimuth angle a) at an elevation angle of 45 degrees. Let ^{L * a *} b ^{* L *} value of the color system be ^{L *} _1-25 calculated from the spectral spectrum of the reflected light in the direction in which the elevation angle is tilted 25 degrees toward the incident light side from the specular reflection direction of the incident light. ..
Visible light is incident on the outer layer side surface of the metallic decorative member from an azimuth angle (azimuth angle b) opposite to the arbitrary azimuth angle at an elevation angle of 45 degrees. Let ^{L * a *} b ^{* L *} value of the color system be ^{L *} _2-25 calculated from the spectral spectrum of the reflected light in the direction in which the elevation angle is tilted 25 degrees toward the incident light side from the specular reflection direction of the incident light. ..
^{Under the above premise, the relationship with L *} _1-25 and L ^* _2-25 satisfies the following equations (1) and (2) at least in some azimuth angles.
L ^* _1-25 > L ^* _2-25 (1)
1.00 <{(L ^* _1-25- L ^* _2-25 ) / L ^* _1-25 } x 100 (2)

1 and 2 are cross-sectional views showing an embodiment of the metal-like decorative member of the present invention.
The metal-like decorative member 100 of FIGS. 1 and 2 has a protective layer 10 (transparent base material 11) and a brilliant printing layer 20 in this order from the outer layer side. Further, the metal-like decorative member 100 of FIGS. 1 and 2 has one or more layers selected from the coloring layer 30, the adhesive layer 50, and the resin plate 40 on the inner layer side of the brilliant printing layer 20. There is. The metal-like decorative member 100 of FIG. 2 has a colored layer 30A and a colored layer 30B as colored layers, and an adhesive layer 50 is located between the colored layer 30A and the colored layer 30B.

The metallic decorative member of the present invention needs to satisfy the following condition 1.
<Condition 1>
Visible light is incident on the outer layer side surface of the metallic decorative member from an arbitrary azimuth angle (azimuth angle a) at an elevation angle of 45 degrees. Let ^{L * a *} b ^{* L *} value of the color system be ^{L *} _1-25 calculated from the spectral spectrum of the reflected light in the direction in which the elevation angle is tilted 25 degrees toward the incident light side from the specular reflection direction of the incident light. ..
Visible light is incident on the outer layer side surface of the metallic decorative member from an azimuth angle (azimuth angle b) opposite to the arbitrary azimuth angle at an elevation angle of 45 degrees. Let ^{L * a *} b ^{* L *} value of the color system be ^{L *} _2-25 calculated from the spectral spectrum of the reflected light in the direction in which the elevation angle is tilted 25 degrees toward the incident light side from the specular reflection direction of the incident light. ..
^{Under the above premise, the relationship with L *} _1-25 and L ^* _2-25 satisfies the following equations (1) and (2) at least in some azimuth angles.
L ^* _1-25 > L ^* _2-25 (1)
1.00 <{(L ^* _1-25- L ^* _2-25 ) / L ^* _1-25 } x 100 (2)

As specified in Condition 1, the present invention specifies the invention ^{not by the L * value of the specularly reflected light but by the L *} value based on the reflected light at an angle deviating from the specular reflection direction. When humans look at the color of an object, it is said that they are looking at the object at an angle where there is no specularly reflected light. Therefore, it is said that the present invention, which defines the ^{L *} value based on the reflected light at an angle deviating from the specularly reflected light, as in the equations (1) and (2) of the condition 1, is consistent with the evaluation by the human eye. I can say.

3 and 4 are schematic views illustrating a method for measuring ^{L *} _1-25 and L ^* _2-25.
First, as shown in FIG. 3, visible light is incident on the outer layer side surface of the metal-like decorative member 100 from an arbitrary azimuth angle (azimuth angle a) at an elevation angle of 45 degrees. The solid arrow in FIG. 3 corresponds to the incident light. Then, based on the spectral spectrum of the reflected light in the direction in which the elevation angle is tilted 25 degrees toward the incident light side from the specular reflection direction of the incident light, the L ^* value (L ^* _1-25 ) of the ^{L *} a ^* b ^{* color system} Is calculated. The single-point chain line arrow in FIG. 3 corresponds to the regular reflected light, and the dotted arrow in FIG. 3 corresponds to the reflected light in the direction in which the elevation angle is inclined by 25 degrees from the regular reflection direction to the incident light side.
Next, visible light is incident from an azimuth angle (azimuth angle b) opposite to the arbitrary azimuth angle at an elevation angle of 45 degrees. Then, based on the spectral spectrum of the reflected light in the direction in which the elevation angle is tilted 25 degrees toward the incident light side from the specular reflection direction of the incident light, the L ^* value (L ^* _2-25 ) of the ^{L *} a ^* b ^{* color system} Is calculated.
FIG. 4 is a perspective view showing an example of the opposite azimuth angles. For example, in FIG. 4, the arrow from the upper right to the center (azimuth b) and the arrow from the lower left to the center (azimuth a) are located on a straight line. In the present specification, the directions opposite to each other with the coordinate center in the plane are referred to as opposite azimuths.

When the metal-like decoration member has light transmission as a whole, a transparent adhesive layer and a light-shielding plate are placed on the inner layer side of the metal-like decoration member in order to suppress reflection on the inner layer side of the metal-like decoration member. It is preferable to prepare a sample in which (for example, a black plate) is laminated and measure the conditions 1 and 2. At that time, the difference in refractive index between the inner layer side surface of the metal-like decorative member and the transparent adhesive layer, and the difference in refractive index between the transparent adhesive layer and the resin of the light-shielding plate shall be 0.10 or less, respectively. Is preferable. Further, the light-shielding plate preferably has a total light transmittance of 0%.
On the other hand, when the metal-like decoration member does not have light transmission as a whole, the measurement of condition 1 and condition 2 may be performed using the metal-like decoration member itself.
For L ^* _1-25 , L ^* _2-25 , L ^* _1-45 and L ^* _2-45 , it is preferable to measure with the light source as D65 and the field of view as a 10-degree field of view. L ^* _1-25 , L ^* _2-25 , L ^* _1-45 and L ^* _2-45 are, for example, part numbers "MA-68II", "MA94", etc. of multi-angle spectrophotometers manufactured by X-Rite. Can be measured with.

In condition 1, the formula (1) shows that the brilliance is anisotropic.
When L ^* _1-25 and L ^* _2-25 are the same and do not satisfy the formula (1), the anisotropy of brilliance does not appear, so that the metallic luster cannot be improved.

In condition 1, the formula (2) indicates the degree of anisotropy of brilliance. More specifically, the formula (2) shows that the amount of light reflected by the brilliant printing layer is larger on the azimuth a side than on the azimuth b side by a predetermined ratio or more. ..
When the formula (2) is not satisfied, the degree of anisotropy of brilliance is insufficient, and the metallic luster cannot be improved.
On the other hand, when the equation (2) is satisfied, the ratio of the reflected light to the azimuth angle a side can be increased, so that the L ^* value (L ^* _1-25 ) on the azimuth angle a side can be increased. The metallic luster can be increased. Further, when the equation (2) is satisfied, the appearance from the azimuth angle a side and the appearance from the azimuth angle b side can be different.
As described above, when the equation (2) is satisfied, a high level of metallic luster and a change in appearance depending on the direction can be imparted, so that an extremely high level of designability can be imparted.

In the present specification, L ^* _1-25 , L ^* _2-25 , L ^* _1-45 and L ^* _2-45 shall mean the average value measured at 10 points at the same azimuth angle.

In the formula (2), "{(L ^* _1-25- L ^* _2-25 ) / L ^* _1-25 } x 100" is preferably 1.50 or more, and preferably 2.00 or more. More preferably, it is more preferably 4.00 or more, and even more preferably 5.00 or more.
In addition, in order to suppress the deterioration of the design due to the reflection being too biased toward the azimuth angle a side, "{(L ^* _1-25- L ^* _2-25 ) / L ^* _1-25 } x 100" is 30. It is preferably 0.00 or less, more preferably 20.00 or less, and even more preferably 15.00 or less.

Condition 1 may be satisfied at least in some azimuth angles. That is, if condition 1 is satisfied at least in a part of the azimuth angles, the designability at the azimuth angle becomes good, and the metal-like decorative member having a high degree of designability can be obtained.
Further, it is preferable that the azimuth angle a is parallel to the flow direction of the metal-like decoration member. The flow direction of the metal-like decoration member refers to the flow direction of the machine when the metal-like decoration member is continuously produced. The term "parallel" means that the angle formed by the azimuth a and the flow direction of the metal-like decoration member is within 10 degrees, preferably within 5 degrees, and more preferably within 1 degree.

It is preferable that the metallic decorative member of the present invention further satisfies the following condition 2.
<Condition 2>
Visible light is incident on the outer layer side surface of the metallic decorative member from an arbitrary azimuth angle (azimuth angle a) at an elevation angle of 45 degrees. Let ^{L * a *} b ^{* L *} value of the color system be ^{L *} _1-45 calculated from the spectral spectrum of the reflected light in the direction in which the elevation angle is tilted 45 degrees toward the incident light side from the specular reflection direction of the incident light. ..
Visible light is incident on the outer layer side surface of the metallic decorative member from an azimuth angle (azimuth angle b) opposite to the arbitrary azimuth angle at an elevation angle of 45 degrees. Let ^{L * a *} b ^{* L *} value of the color system be ^{L *} _2-45 calculated from the spectral spectrum of the reflected light in the direction in which the elevation angle is tilted 45 degrees toward the incident light side from the specular reflection direction of the incident light. ..
^{Under the above premise, the relationship between L *} _1-25 , L ^* _2-25 , L ^* _1-45 and L ^* _2-45 is related to the following equations (1) and (1) at least in some azimuth angles. 3) is satisfied.
L ^* _1-25 > L ^* _2-25 (1)
1.00 <(L ^* _1-25 / L ^* _1-45 ) / (L ^* _2-25 / L ^* _2-45 ) (3)

Of formula (3) is the condition 2, and the rate of change of L ^* value at the time of changing the elevation angle in azimuth a side, and the rate of change of L ^* value at the time of changing the elevation angle in azimuth b side is different It means that. Therefore, by satisfying the condition (2), the appearance from the azimuth a side and the appearance from the azimuth b side can be made different, and the design can be made more advanced. ..
The “(L ^* _1-25 / L ^* _1-45 ) / (L ^* _2-25 / L ^* _2-45 )” of the formula (3) is preferably 1.02 or more, and 1.03 or more. Is more preferable.
^{“(L *} _1-25 / L ^* _1-45 ) / (L ^* _2-25 / L ^* _2-45 )” in equation (3) suppresses excessive brightness changes and gives a calm design. From the viewpoint of the above, it is preferably 1.30 or less, more preferably 1.20 or less, and further preferably 1.15 or less.

<Protective layer>
The protective layer is a layer arranged on the outer layer side of the brilliant printing layer for the purpose of imparting scratch resistance to the metal-like decorative member.

Examples of the protective layer include a single layer of a transparent base material, a single layer of a transparent resin layer, and a plurality of layers of a transparent base material and a transparent resin layer. The protective layer preferably contains a transparent base material from the viewpoint of scratch resistance and handleability.
As for the protective layer, the haze of JIS K7136: 2000 is preferably 5% or less, more preferably 3% or less, and further preferably 1% or less.
Further, the protective layer preferably has a total light transmittance of JIS K7361-1: 1997 of 85% or more, and more preferably 90% or more.

<< Transparent base material >>
Examples of the transparent base material as an example of the protective layer include polyolefin resins such as polyethylene and polypropylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, and vinyl such as ethylene-vinyl alcohol copolymer. Resins, polyester resins such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, acrylic resins such as poly (meth) methyl acrylate, poly (meth) ethyl acrylate, styrene resins such as polystyrene, nylon 6 or Examples thereof include a plastic film made of a resin such as a polyamide resin represented by nylon 66 and the like.
Among these transparent substrates, an acrylic resin film which is excellent in light resistance and moldability, has excellent transparency due to its low refractive index, and is inconspicuous in scratches is preferable. Further, among the acrylic resin films, the acrylic resin film containing rubber particles is preferable in that the moldability can be improved.

The transparent base material may be one that has been subjected to an easy-adhesion treatment such as a physical treatment and a chemical treatment in order to improve the adhesiveness with the glittering printing layer. Further, in order to improve the adhesiveness, the transparent base material may have an easy-adhesion layer on the plastic film.
Further, the transparent base material may contain additives such as an ultraviolet absorber and a light stabilizer.

The thickness of the transparent substrate is preferably 50 to 250 μm, more preferably 60 to 200 μm, and even more preferably 70 to 150 μm from the viewpoint of the balance between moldability and protection of the glittering printed layer. ..
The thickness of the transparent substrate can be measured, for example, by observing a vertical cross section with an electron microscope or the like.
In addition, in this specification, AA to BB means that it is AA or more and BB or less.

<< Transparent resin layer >>
The transparent resin layer, which is an example of the protective layer, preferably contains a cured product of the curable resin composition from the viewpoint of scratch resistance. Examples of the cured product of the curable resin composition include a cured product of the thermosetting resin composition and a cured product of the ionizing radiation curable resin composition, and among these, the cured product of the ionizing radiation curable resin composition is preferable.

The thermosetting resin composition is a composition containing at least a thermosetting resin, and is a resin composition that is cured by heating. Examples of the thermosetting resin include acrylic resin, urethane resin, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, and silicone resin. In the thermosetting resin composition, a curing agent is added to these curable resins as needed.

The ionizing radiation curable resin composition is a composition containing a compound having an ionizing radiation curable functional group (hereinafter, also referred to as “ionizing radiation curable compound”). Examples of the ionizing radiation curable functional group include an ethylenically unsaturated group such as a (meth) acryloyl group, a vinyl group and an allyl group, and an epoxy group and an oxetanyl group.
As the ionizing radiation curable resin, a compound having an ethylenically unsaturated bond group is preferable. Further, from the viewpoint of suppressing damage to the resin layer in the process of manufacturing the metal-like decorative member, as the ionizing thermosetting resin, a compound having two or more ethylenically unsaturated bonding groups is more preferable, among others. , A polyfunctional (meth) acrylate compound having two or more ethylenically unsaturated bonding groups is more preferable. As the polyfunctional (meth) acrylate compound, either a monomer or an oligomer can be used.
Note that ionizing radiation means electromagnetic waves or charged particle beams that have energy quanta capable of polymerizing or cross-linking molecules, and usually ultraviolet rays (UV) or electron beams (EB) are used. Electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion rays can also be used.

The thickness of the transparent resin layer, which is an example of the protective layer, is preferably 0.5 to 30 μm, more preferably 1 to 20 μm, and further preferably 3 to 10 μm.

<Glittering print layer>
The brilliant printing layer is located on the inner layer side of the protective layer and plays a role of imparting a metallic luster to the metallic decorative member. The glitter printing layer contains a glitter pigment and a binder resin.

The brilliant printing layer may be formed in a part of the region visible from the outer layer side of the metal-like decorative member, but is preferably formed on the entire surface.
The brilliant printing layer can be formed, for example, by printing on a material to be coated (for example, a transparent base material as a protective layer, a colored film as a colored layer described later) with an ink for a brilliant printing layer. .. The ink for the glitter printing layer usually contains a vehicle composed of a binder resin or a solvent as a main component, and an ink in which a glitter pigment and, if necessary, a colorant such as a dye or a pigment are added and mixed is used. Be done.
The printing method is not particularly limited, but comma coater printing is preferable from the viewpoint of facilitating the satisfaction of the formulas (1) to (3).

FIG. 5 is a schematic diagram showing an example of comma coater printing. In FIG. 5, the arrow of the coating roll 202 indicates the rotation direction of the coating roll 202. Further, another arrow in FIG. 5 indicates the flow direction of the material to be coated 205 (in other words, the flow direction of the coating device in FIG. 5).
In FIG. 5, it is considered that the bright pigments are arranged in the liquid pool 203 of the ink for the bright printing layer at each location of the liquid pool 203 as shown in (A) to (C) below.
(A) In most regions of the liquid pool 203, the bright pigments are randomly arranged with respect to the liquid surface 204.
(B) In the region near the material to be coated 205, the bright pigment is pulled by the flow of the material to be coated 205 and is arranged substantially parallel to the material to be coated 205.
(C) In the region near the comma roll 201 (particularly, the region near the comma roll 201 where the distance between the comma roll 201 and the coating roll 202 is narrow), the bright pigment follows the curved surface of the comma roll 201. They are arranged in the same direction. More specifically, since the comma roll 201 itself does not move, the brilliant print layer ink in the region near the comma roll 201 has a pulling force more than the brilliant print layer ink in the region near the material 205 to be coated. Is weak. Therefore, the bright pigments in the vicinity of the material to be coated are arranged substantially parallel to the material to be coated, whereas the bright pigments in the vicinity of the surface of the bright printing layer have a predetermined orientation (commaroll 201). It is considered that they are arranged at an angle (inclination of the curved surface).

From the above (A) to (C), the brilliant print layer ink adhering to the material to be coated 205 is likely to be arranged at least in the vicinity of the surface so as to be inclined in a certain direction with respect to the coated surface of the material to be coated. (See Fig. 6). Then, when the bright pigment is arranged at an angle in a certain direction in the bright print layer, the anisotropy of the bright property is exhibited, and the formulas (1) to (3) can be easily satisfied. Further, the anisotropy of brilliance developed in this way is substantially maintained even after a subsequent step (for example, a step of laminating resin plates, a molding step, etc.).
In the method of forming a coating film by spraying the ink for a glittering printing layer (Comparative Example 1 described later) and the method of forming a coating film by screen printing (Comparative Example 2 described later), the glittering printing is performed. The bright pigments are randomly arranged in the layer, and it is difficult to satisfy the formulas (1) to (3).

<< Bright Pigment >>
Glittering pigments include pearl pigments and metal scales. Among these, pearl pigments, which change the color depending on the observation angle and can improve the design, are preferable.

The pearl pigment is a thin plate-like pigment having a coating layer made of a high refractive index material such as titanium dioxide on the surface of a scaly base material such as mica, alumina and glass, and has light transmittance. .. Therefore, by arranging the thin plate-like pigments in layers, light can be multiplely reflected to give a metallic luster.
As described above, the pearl pigment is not a metal itself but mainly composed of a metal oxide, but is a material capable of producing a metallic luster.
The pearl pigment preferably has an alumina base from the viewpoint of increasing the brightness and further enhancing the metallic luster.

Examples of the pearl pigment include white pearl pigment, interfering pearl pigment, colored pearl pigment and the like.
The white pearl pigment is obtained by covering a scaly base material such as mica, alumina, and glass with a coating layer made of a colorless high refractive index material such as titanium dioxide, and the thickness of the coating layer is 0.1 to 0. It is relatively small, about 15 μm, and reflects almost all wavelengths of light, so it looks white or silver.
In the interference pearl pigment, the coating layer is a colorless high refractive index material such as titanium dioxide, and the thickness of the coating layer is larger than that of the white pearl pigment, which is more than 0.15 μm. Depending on this thickness, the reflected light and the transmitted light change, and various interference colors are generated. Sometimes called iridescent pearls.
The colored pearl pigment is chromatic and the coating layer is a colored high refractive index material such as ferric oxide, and the periphery of the white pearl pigment is further colored high refractive index material such as ferric oxide or other colored material. There are those coated with a pigment, or those in which a pigment or other colorant is added to the coating layer.

The average length of the pearl pigment is preferably 5 to 70 μm, more preferably 10 to 40 μm.
The average length of the pearl pigment and the average length of the metal scales described later are the average lengths of any 20 particles (pearl pigment or metal scales) observed with an optical microscope or an electron microscope from the plane direction of the metal decoration member. It is calculated as the average value of the length. The length of one pearl pigment and metal scale means the maximum length of one pearl pigment and metal scale in the plane direction.

Examples of the metal scale include metals and alloys such as aluminum, gold, silver, brass, titanium, chromium, nickel, nickel chromium, and stainless steel.
The metal scale is obtained, for example, obtained by peeling a metal thin film formed by vacuum-depositing the metal or alloy on a plastic film from the plastic film, crushing and stirring the peeled metal thin film, or a powder of the metal or alloy. And a solvent are mixed, and the powder obtained by spreading and / or pulverizing the powder with a medium stirring mill, a ball mill, an attritor, or the like, or a resin-coated surface thereof can be used. it can.

The metal scales preferably have an average length of 1 to 50 μm, more preferably 2 to 30 μm, and even more preferably 5 to 20 μm.

The average thickness of the metal scale and the pearl pigment is determined as the average value of any 20 particles (pearl pigment or metal scale) obtained by observing the cross section of the metal-like decorative member with an optical microscope or an electron microscope. The thickness of one pearl pigment or metal scale is obtained by dividing a cross-sectional image of one pearl pigment or metal scale into five regions having equal lengths in the length direction, and the thickness of the central portion of each region ( _{t 1, t 2, t 3} , t 4, t 5) were _measured, it means an average of the t 1 ~t _5.

Bright pigments such as pearl pigments and metal scales are flaky and _{preferably have a thickness T 1} of 0.01 to 5.00 μm, more preferably 0.02 to 3.00 μm, and even more preferably 0. It is 05 to 1.00 μm.
By setting the thickness of the glitter pigment to 0.01 μm or more, the metallic luster can be easily increased, and by setting the thickness of the glitter pigment to 5 μm or less, the glitter pigment is randomly tilted in the glitter print layer. Can be easily suppressed.

The thickness T ₂ of the brilliant print layer is preferably 3 to 30 μm, more preferably 5 to 20 μm, still more preferably 7 to 7, from the viewpoint of suppressing cracks during molding while imparting a sufficient metallic luster. It is 15 μm.

The thickness _{T 1} of the bright pigment and the thickness _{T 2} of the photoluminescent printing layer preferably satisfies the relationship _{0.01 ≦ T 1 / T 2 ≦} 0.20, the relationship 0.02-0.10 It is more preferable to satisfy.
By _{setting T 1} / T ₂ to 0.01 or more, it is possible to easily suppress the deterioration of the flatness of the bright pigment when the bright print layer is dried and shrunk or cured and shrunk. Further, by _{setting T 1} / T ₂ to 0.20 or less, it is possible to facilitate the arrangement of the bright pigment in the bright printing layer so as to be tilted in a predetermined direction.

The content of the brilliant pigment in the brilliant print layer is 0.05 to 50% by mass of the total solid content of the brilliant print layer from the viewpoint of suppressing cracks during molding while imparting a sufficient metallic luster. It is preferable to have.
When the brilliant pigment is a pearl pigment, it is more preferably 5 to 40% by mass, still more preferably 10 to 30% by mass.
When the bright pigment is a metal scale, it is more preferably 0.07 to 10% by mass, and further preferably 0.10 to 5% by mass.

Examples of the binder resin for the glittering printing layer include acrylic resins such as methyl poly (meth) acrylate and ethyl poly (meth) acrylate, polyolefin resins such as polyethylene resins and chlorinated polypropylene resins, and nitrocellulose. , Fibrous resins such as ethyl cellulose, acetylbutyl cellulose and ethyloxyethyl cellulose, rubber resins such as rubber chloride and cyclized rubber, petroleum resins, natural resins such as rosin and casein, polyvinyl chloride resins, polyvinyl acetate. Based resin, vinyl chloride-vinyl acetate copolymer, polystyrene resin, styrene-butadiene copolymer, vinylidene fluoride resin, polyvinyl alcohol resin, polyvinyl acetal resin, polyvinyl butyral resin, polybutadiene resin, polyester Examples thereof include resins, polyamide-based resins, alkyd-based resins, epoxy-based resins, unsaturated polyester-based resins, melamine-based resins, urea-based resins, polyurethane-based resins, phenol-based resins, xylene-based resins, and maleic acid resins. These may be used alone or in combination of two or more.
Among these binder resins, acrylic resins are preferable from the viewpoint of transparency.

Further, the binder resin of the glittering printing layer preferably contains two types of resins having different mass average molecular weights (a resin having a small mass average molecular weight (A1) and a resin having a large mass average molecular weight (B1)).
The mass average molecular weight of the resin (A1) is preferably 100,000 or less, more preferably 30,000 to 100,000, and even more preferably 50,000 to 90,000. The mass average molecular weight of the resin (B1) is preferably more than 100,000, more preferably 120,000 to 800,000, and even more preferably 150,000 to 500,000.
The difference between the mass average molecular weight of the resin (B1) and the mass average molecular weight of the resin (A1) is preferably 50,000 or more, more preferably 100,000 or more, and further preferably 150,000 or more. preferable.
The mass ratio of the resin (A1) to the resin (B1) is preferably 1: 3 to 3: 1, more preferably 1: 2 to 2: 1.
By using the resin (A1) and the resin (B1) in combination as described above, it is possible to easily improve the cohesive force of the brilliant print layer while suppressing cracks during molding. Further, by using the resin (A1) and the resin (B1) in combination, the viscosity of the glitter printing layer ink is adjusted within an appropriate range, and the glitter pigment excessively flows in the glitter printing layer ink. This can be suppressed and the coating film satisfying the formulas (1) to (3) can be easily controlled.
The resin (A1) and the resin (B1) are preferably resins of the same type, and more preferably acrylic resins.
In the present specification, the mass average molecular weight is a polystyrene-equivalent mass average molecular weight measured by the GPC method.

The glitter printing layer preferably contains a plasticizer in order to suppress cracks during molding.
Examples of the plasticizer include phthalates, adipates, trimellitic acids and the like. The content of the plasticizer in the brilliant printing layer is preferably 1 to 20% by mass, more preferably 3 to 15% by mass, and further preferably 5 to 10% by mass of the total solid content of the brilliant printing layer. Is. By setting the content of the plasticizer to 1% by mass or more, cracks during molding can be easily suppressed, and by setting the content of the plasticizer to 20% by mass or less, deterioration of heat resistance and light resistance is suppressed. At the same time, it is possible to suppress deformation of the coating film due to excessive flexibility.

It is preferable to contain an aligning agent in the brilliant printing layer. Examples of the orienting agent include layered silicates such as mica.
The content of the aligning agent in the brilliant printing layer is preferably 1 to 20% by mass, more preferably 3 to 15% by mass, and further preferably 5 to 10% by mass of the total solid content of the brilliant printing layer. Is. By setting the content of the orienting agent to 1% by mass or more, it is possible to easily arrange the bright pigment uniformly in the layer, and it is possible to easily suppress an extreme variation in metallic luster. Further, by setting the content of the orienting agent to 20% by mass or less, the ratio of other components such as a bright pigment can be secured, and cracks can be easily suppressed during molding.

The bright printing layer may contain, for example, a light stabilizer such as an ultraviolet absorber, a pigment other than the bright pigment, a viscosity modifier, a filler, a stabilizer, an antioxidant, a dispersant, and a desiccant. Any additive such as a lubricant, an antistatic agent, and a cross-linking agent can be added.

<< Other layers >>
The metallic decorative member may have a layer other than the protective layer and the brilliant printing layer.
For example, the metal-like decorative member may have one or more layers selected from a coloring layer, a backer layer, an adhesive layer, and a resin plate on the inner layer side of the brilliant printing layer. In particular, it is preferable to have a resin plate on the inner layer side of the brilliant printing layer of the metal-like decorative member.

<Colored layer>
The colored layer is a layer formed on the inner layer side of the brilliant printing layer as needed.
The colored layer has, for example, a role of imparting a color to the metal-like decorative member and, when a resin plate is provided on the inner layer side of the colored layer, to conceal the color of the resin plate.

The colored layer is obtained by applying an ink for a colored layer containing a component constituting the colored layer and drying it to form a coating-type colored layer, and forming a film of the components constituting the colored layer by melt extrusion or the like. A film-type colored layer can be mentioned. The film-type colored layer can also be used as a backer layer, which will be described later.
As shown in FIG. 2, a plurality of colored layers may be provided. When a plurality of colored layers are formed, a plurality of coating film type colored layers may be formed, a plurality of film type colored layers may be formed, and a coating film type colored layer and a film type colored layer may be formed. They may be formed together.

The colored layer preferably contains a pigment and a binder resin.
Pigments include white pigments such as titanium dioxide, barium sulfate, magnesium oxide, calcium carbonate, zinc oxide and lead white, black pigments such as carbon black, yellow lead, titanium yellow, petals, cadmium red, ultramarine and cobalt blue. Examples include chromatic inorganic pigments, chromatic organic pigments such as quinacridone red, isoindolinone yellow and phthalocyanine blue.

The average particle size of the pigment is preferably 0.1 to 10 μm, more preferably 0.5 to 5 μm, and even more preferably 0.5 to 3 μm.
In the present specification, the average particle size of the pigment is 50% particle size (d50: median size) when the particles dispersed in the solution are measured by a dynamic light scattering method and the particle size distribution is expressed by a volume cumulative distribution. Is. The 50% particle size can be measured using, for example, a Microtrac particle size analyzer (manufactured by Nikkiso Co., Ltd.).

The content of the pigment in the colored layer is 20 to 250 parts by mass with respect to 100 parts by mass of the binder resin from the viewpoint of the balance between the purpose of the colored layer (imparting or hiding the color) and suppressing cracks during molding. It is preferably 30 to 220 parts by mass, and even more preferably 50 to 200 parts by mass.

As the binder resin of the coating film type colored layer, the same binder resin as those exemplified as the binder resin of the glittering printing layer can be used.
Among various binder resins, it is preferable to include an acrylic resin and a vinyl chloride-vinyl acetate copolymer resin from the viewpoint of suppressing cracks during molding. The mass ratio of the acrylic resin to the vinyl chloride-vinyl acetate copolymer resin is preferably 10: 2 to 10:20, more preferably 10: 3 to 10:15, and 10: It is more preferably 4 to 10: 8. By setting the mass ratio of the acrylic resin and the vinyl chloride-vinyl acetate resin to the above numerical range, it is possible to more easily suppress cracks during molding of the metal-like decorative member.

Further, the binder resin of the coating type colored layer preferably contains two types of resins having different mass average molecular weights (a resin having a small mass average molecular weight (A2) and a resin having a large mass average molecular weight (B2)).
The mass average molecular weight of the resin (A2) is preferably 100,000 or less, more preferably 30,000 to 100,000, and even more preferably 50,000 to 90,000. The mass average molecular weight of the resin (B2) is preferably more than 100,000, more preferably 120,000 to 800,000, and even more preferably 150,000 to 500,000.
The difference between the mass average molecular weight of the resin (B2) and the mass average molecular weight of the resin (A2) is preferably 50,000 or more, more preferably 100,000 or more, and further preferably 150,000 or more. preferable.
The mass ratio of the resin (A2) to the resin (B2) is preferably 4: 1 to 1: 1 and more preferably 3: 1 to 3: 2.
By using the resin (A2) and the resin (B2) in combination as described above, it is possible to easily improve the cohesive force of the colored layer while suppressing cracks during molding. Since the content of the white pigment in the colored layer tends to be higher than the content of the bright pigment in the bright printed layer, the colored layer is more likely to crack than the bright printed layer. Therefore, when two types of resins having different mass average molecular weights are used as the binder resin of the colored layer, the content of the resin having a small mass average molecular weight should be equal to or higher than the content of the resin having a large mass average molecular weight as described above. Is preferable.
The resin (A2) and the resin (B2) are preferably resins of the same type, and more preferably acrylic resins.

The binder resin of the film-type colored layer preferably contains an ABS resin (acrylonitrile-butadiene-styrene copolymer) from the viewpoint of suppressing cracks during molding.
The film-type colored layer may contain a binder resin other than the ABS resin. The ratio of the ABS resin to the total binder resin of the film-type colored layer is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 90% by mass or more, and 99% by mass. It is more preferably% or more, and most preferably 100% by mass.

The thickness of the coating film type colored layer is preferably 5 to 50 μm, preferably 7 to 40 μm, from the viewpoint of the balance between the purpose of the colored layer (imparting or concealing color) and suppressing cracks during molding. More preferably, it is more preferably 10 to 30 μm.

The thickness of the film-type colored layer is preferably 70 to 700 μm, more preferably 100 to 600 μm, and even more preferably 200 to 450 μm.
By setting the thickness of the film-type colored layer to 70 μm or more, it is possible to easily conceal the color of the resin plate, and by setting it to 700 μm or less, deterioration of moldability can be suppressed.

The colored layer may contain, for example, a light stabilizer such as an ultraviolet absorber, a pigment other than a white pigment, a plasticizer, a viscosity modifier, a filler, a stabilizer, an antioxidant, a dispersant, and a desiccant. Any additive such as a lubricant, an antistatic agent, and a cross-linking agent can be added.

<Backer layer>
The backer layer may, for example, increase the strength of the metal-like decorative laminate and the metal-like decorative molded product, adjust the color of the metal-like decorative laminate and the metal-like decorative molded product, or adjust the color tones of the metal-like decorative molded product. It has a role of maintaining the shape of a metallic decorative molded body formed from a decorative member.

The backer layer is preferably a plastic film. The plastic film as the backer layer preferably contains one or more resins selected from polypropylene, ABS resin and vinyl chloride resin from the viewpoint of improving moldability, and one or more resins selected from polypropylene and ABS resin. It is more preferable to contain ABS resin, and it is further preferable to contain ABS resin.
The ratio of one or more resins selected from polypropylene, ABS resin, and vinyl chloride resin to the total resin components of the backer layer is preferably 50% by mass or more, more preferably 70% by mass or more, and 90% by mass. % Or more, more preferably 99% by mass or more, and most preferably 100% by mass. The ratio of the above-mentioned resin is more preferably filled with one or more resins selected from polypropylene and ABS resin, and even more preferably filled with ABS resin.

The backer layer may contain a pigment. As the pigment, the same pigment as those exemplified in the colored layer can be used. When the backer layer contains a pigment, the backer layer can also serve as the above-mentioned colored layer.

The thickness of the backer layer is preferably 100 μm or more and less than 1000 μm, more preferably 200 to 450 μm.

<Resin plate>
The resin plate has, for example, a role of increasing the strength of the metal-like decoration member and maintaining the shape of the metal-like decoration molded body formed from the metal-like decoration member.

The thickness of the resin plate is preferably 1 to 7 mm, more preferably 1.5 to 5 mm, and even more preferably 2 to 4 mm.

The resin plate is preferably an achromatic color (gray, black) excluding white, and more preferably black in order to suppress surface reflection of the resin plate.
Therefore, it is preferable that the resin plate contains a pigment for making it achromatic. The pigment of the resin plate may be a black pigment alone or a mixture of a black pigment and another pigment (white pigment or the like).

The binder resin of the resin plate preferably contains ABS resin. Since the resin plate contains ABS resin as the binder resin, it is possible to suppress the occurrence of cracks in the resin plate during molding.
The resin plate may contain a binder resin other than ABS resin. The ratio of the ABS resin to the total binder resin of the resin plate is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 90% by mass or more, and 99% by mass or more. It is more preferably present, and most preferably 100% by mass.

If necessary, the resin plate may contain, for example, a light stabilizer such as an ultraviolet absorber, a plasticizer, a viscosity modifier, a filler, a stabilizer, an antioxidant, a dispersant, a desiccant, a lubricant, an antistatic agent, and the like. Any additive such as a cross-linking agent can be added.

<< Adhesive layer >>
The adhesive layer is a layer formed as needed in order to enhance the adhesiveness of each layer constituting the metallic decorative member.
Examples of the adhesive layer include a heat-sensitive adhesive layer and a pressure-sensitive adhesive layer (adhesive layer). The pressure-sensitive adhesive layer (adhesive layer) is more preferable because of the simplicity of the bonding process.

Examples of the heat-sensitive or pressure-sensitive resin include general-purpose acrylic resins, urethane resins, polyester resins, silicone resins, vinyl chloride resins or vinyl acetate resins, or mixtures or copolymers of two or more of these. Can be used.
The thickness of the adhesive layer may be adjusted in the range of about 0.1 to 100 μm depending on the type of adhesive.
If each layer (for example, a brilliant printing layer and a colored layer) constituting the metal-like decorative member also has adhesiveness, it is not necessary to separately form an adhesive layer, which is a point of thinning and cost reduction. Is preferable.

<Laminated structure of metal-like decorative members>
Specific examples of the laminated structure of the metal-like decorative member include the following (1) to (7). As described above, the colored layer (film type) may also serve as a backer layer, and the backer layer may also serve as a colored layer.
In addition, "/" means the boundary of each layer. The left side means the outer layer side of the metal-like decorative member, and the right side means the inner layer side.
(1) Protective layer (transparent base material) / brilliant printing layer (2) Protective layer (transparent base material) / brilliant printing layer / colored layer (coating type) / resin plate (3) Protective layer (transparent base material) / Bright printing layer / Colored layer (coating type) / Pressure-sensitive adhesive layer (adhesive layer) / Colored layer (film type) / Resin plate (4) Protective layer 1 (transparent resin layer) / Protective layer 2 (transparent group) Material) / Bright printing layer / Colored layer (coating type) / Resin plate (5) Protective layer (transparent base material) / Bright printing layer / Colored layer (coating type) / Colored layer (film type) / Pressure-sensitive adhesion Agent layer (adhesive layer) / colored layer (film type) / resin plate (6) protective layer (transparent base material) / brilliant printing layer / colored layer (coating type) / pressure sensitive adhesive layer (adhesive layer) / backer Layer / Resin plate (7) Protective layer (transparent base material) / Bright printing layer / Colored layer (coating type) / Colored layer (film type) / Pressure-sensitive adhesive layer (adhesive layer) / Backer layer / Resin plate

<Use of metal-like decorative members>
The metal-like decorative member of the present invention is suitably used for various molded bodies (for example, communication equipment, interior / exterior of a vehicle body such as an automobile, home appliances, furniture, etc.) that require a high degree of design. Can be done.

[Metallic decorative molded body]
The metal-like decorative molded body of the present invention is formed from the above-mentioned metal-like decoration member of the present invention.

The metallic decorative molded article of the present invention preferably satisfies the following condition 1'.
<Condition 1'>
Visible light is incident on the outer layer side surface of the metallic decorative molded body from an arbitrary azimuth angle (azimuth angle a) at an elevation angle of 45 degrees. ^{The L *} a ^* b ^* color system L ^* value calculated from the spectral spectrum of the reflected light in the direction in which the elevation angle is tilted 25 degrees toward the incident light side from the specular reflection direction of the incident light is m-L ^* _1-25. And.
Visible light is incident on the outer layer side surface of the metallic decorative member from an azimuth angle (azimuth angle b) opposite to the arbitrary azimuth angle at an elevation angle of 45 degrees. ^{The L *} a ^* b ^* color system L ^* value calculated from the spectral spectrum of the reflected light in the direction in which the elevation angle is tilted 25 degrees toward the incident light side from the specular reflection direction of the incident light is m-L ^* _2-25. And.
^{Under the above premise, the relationship between m-L *} _1-25 and m-L ^* _2-25 satisfies the following equations (1') and (2') at least in some azimuth angles.
m-L ^* _1-25 > m-L ^* _2-25 (1')
1.00 <{(m-L ^* _1-25 -m-L ^* _2-25 ) / mL ^* _1-25 } x 100 (2')

Since the anisotropy of brilliance is almost the same before and after molding the metal-like decoration member, if a metal-like decoration member satisfying condition 1 is used, a metal-like decoration molded body satisfying condition 1'can be obtained. It can be easily obtained.

The metallic decorative molded article of the present invention preferably satisfies the following condition 2'.
<Condition 2'>
Visible light is incident on the outer layer side surface of the metallic decorative molded body from an arbitrary azimuth angle (azimuth angle a) at an elevation angle of 45 degrees. ^{The L *} a ^* b ^* color system L ^* value calculated from the spectral spectrum of the reflected light in the direction in which the elevation angle is tilted 45 degrees toward the incident light side from the specular reflection direction of the incident light is m-L ^* _1-45. And.
Visible light is incident on the outer layer side surface of the metallic decorative member from an azimuth angle (azimuth angle b) opposite to the arbitrary azimuth angle at an elevation angle of 45 degrees. ^{The L *} a ^* b ^* color system L ^* value calculated from the spectral spectrum of the reflected light in the direction in which the elevation angle is tilted 45 degrees toward the incident light side from the specular reflection direction of the incident light is m-L ^* _2-45. And.
Under the above premise, at least in some azimuth angles, the relationship with the ^{mL *} _1-25 , the mL ^* _2-25 , the mL ^* _1-45, and the mL ^* _2-45 , The following equations (1') and (3') are satisfied.
m-L ^* _1-25 > m-L ^* _2-25 (1')
1.00 <(m-L ^* _1-15 / m-L ^* _1-45 ) / (m-L ^* _2-15 / mL ^* _2-45 ) (3')

Since the anisotropy of brilliance is almost the same before and after molding the metal-like decoration member, if a metal-like decoration member satisfying condition 2 is used, a metal-like decoration molded body satisfying condition 2'can be obtained. It can be easily obtained.

<Manufacturing method of metallic decorative molded body>
The metallic decorative molded body can be produced, for example, by vacuum forming having the following steps (y1) to (y2).
(Y1) After the metal-like decoration member is placed on a molding die having a molding surface having a predetermined shape, the metal-like decoration member is heated and softened. When the molding mold is a male mold, the side opposite to the protective layer of the metal-like decoration member (for example, the resin plate side) is arranged so as to face the molding mold (male mold) side, and when the molding mold is a female mold. Is arranged so that the protective layer (for example, transparent base material) side of the metal-like decorative member faces the molding mold (female mold) side.
(Y2) The metal-like decoration member is molded by vacuum suctioning from the molding mold side and bringing the softened metal-like decoration member into close contact with the molding surface of the mold.

If necessary, a water removal step by heating may be performed before the step (y1).

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. The present invention is not limited to the embodiments described in the examples.

1. 1. Fabrication of Metallic Decoration Member [Example 1]
On a transparent base material (total light transmittance: 92%, haze: 0.6%) made of an acrylic resin-based film containing rubber particles having a thickness of 125 μm, the ink 1 for a glitter printing layer having the following formulation is printed by a comma coater. A bright print layer having a thickness of 10 μm was formed by coating and drying. Next, the white layer ink of the following formulation is applied and dried on the brilliant printing layer by comma coater printing to form a white layer having a thickness of 10 μm, and a protective layer (transparent substrate), a brilliant printing layer and a white layer are formed. A laminate A1 composed of the above was obtained.
Next, a gray-like colored film having a thickness of 350 μm (binder resin component: ABS resin) and a resin plate having a thickness of 3 mm (a black plate having the binder resin component as ABS resin) were heat-laminated to obtain a laminate B1.
Next, the white layer side of the laminated body A1 and the colored film side of the laminated body B1 are heat-laminated so as to face each other, and from the outer layer side, the protective layer (transparent base material), the brilliant printing layer, and the colored layer A (white layer). (Coating type)), a colored layer B (colored film), and a resin plate (black plate) were obtained in this order to obtain a metal-like decorative member of Example 1.

<Ink for brilliant printing layer 1>
-Acrylic resin (A): 8 parts by mass (mass average molecular weight 70,000, glass transition temperature 100 ° C)
-Acrylic resin (B): 7 parts by mass (mass average molecular weight 300,000, glass transition temperature 100 ° C)
-Pearl pigment: 5 parts by mass (pearl pigment with alumina as the base and titanium dioxide as the coating layer)
(Average length: 27.5 μm, average thickness: 0.4 μm)
-Sedimentation inhibitor: 0.1 parts by mass (silica, average primary particle size: 20 nm)
・ Diisodecyl phthalate: 2 parts by mass ・ Aligning agent (mica): 2 parts by mass ・ Solvent: Appropriate amount

<Ink for white layer>
-Acrylic resin (A): 16 parts by mass (mass average molecular weight 70,000, glass transition temperature 100 ° C)
-Acrylic resin (B): 7 parts by mass (mass average molecular weight 300,000, glass transition temperature 100 ° C)
・ White pigment: 16 parts by mass (titanium dioxide)
・ Solvent: Appropriate amount

[Examples 2 to 4]
The metal-like decorative members of Examples 2 to 4 were prepared in the same manner as in Example 1 except that the content of the glitter pigment, the thickness of the glitter print layer, and the thickness of the white layer were changed as shown in Table 1. Obtained.

[Examples 5 to 6]
The content of the glitter pigment, the thickness of the glitter print layer, and the thickness of the white layer are changed as shown in Table 1, and the white layer side of the laminate A1 and the resin plate having a thickness of 3 mm (the binder resin component is ABS resin). A metal-like decorative member of Examples 5 to 6 was obtained in the same manner as in Example 1 except that the black plate was heat-laminated. The metal-like decorative members of Examples 5 to 6 include a protective layer (transparent base material), a brilliant printing layer, a colored layer (white layer (coating type)), and a resin plate (black plate) from the outer layer side. It had in order.

[Example 7]
On a transparent base material (total light transmittance: 92%, haze: 0.6%) made of an acrylic resin film containing rubber particles having a thickness of 125 μm, the ink 2 for a glitter printing layer having the following formulation is printed by a comma coater. A bright print layer having a thickness of 11 μm was formed by coating and drying. Next, the black layer ink of the following formulation is applied on the glitter printing layer by comma coater printing and dried to form a black layer having a thickness of 10 μm, and a protective layer (transparent base material), a glitter print layer and a black layer are formed. A laminated body A2 composed of the above was obtained.

<Ink for brilliant print layer 2>
-Acrylic resin (A): 11.4 parts by mass (mass average molecular weight 70,000, glass transition temperature 100 ° C)
-Acrylic resin (B): 10.2 parts by mass (mass average molecular weight 300,000, glass transition temperature 100 ° C)
-Metal scales (aluminum flakes): 0.036 parts by mass (average length: 12.5 μm, average thickness: 0.4 μm)
-Sedimentation inhibitor: 0.1 parts by mass (silica, average primary particle size: 20 nm)
・ Diisodecyl phthalate: 2 parts by mass ・ Aligning agent (mica): 2 parts by mass

Next, the black layer side of the laminated body A2 and a resin plate having a thickness of 3 mm (a black plate having a binder resin component of ABS resin) are heat-laminated, and from the outer layer side, a protective layer (transparent base material) and a brilliant printing layer are formed. , A colored layer (black layer) and a resin plate (black plate) were obtained in this order, and a metal-like decorative member of Example 7 was obtained.

<Ink for black layer>
-Acrylic resin (A): 14 parts by mass (mass average molecular weight 70,000, glass transition temperature 100 ° C)
-Acrylic resin (B): 7 parts by mass (mass average molecular weight 300,000, glass transition temperature 100 ° C)
・ Black pigment: 13 parts (carbon black)
・ Solvent: Appropriate amount

[Examples 8 to 12]
Metallic decorative members of Examples 8 to 12 were obtained in the same manner as in Example 7 except that the content of the glitter pigment and the thickness of the glitter print layer were changed as shown in Table 2.

[Comparative Example 1]
As the metal-like decoration member of Comparative Example 1, a commercially available metal-like decoration member in which an ink for a glittering printing layer containing a pearl pigment was spray-painted on a steel sheet was prepared.

[Comparative Example 2]
A metallic decorative member of Comparative Example 2 was obtained in the same manner as in Example 1 except that the printing method of the glitter printing layer was changed to screen printing (using 200 mesh).

[Reference example 1]
A metal-like decorative member of Reference Example 1 was obtained in the same manner as in Example 7 except that the printing method of the glitter printing layer was changed to screen printing (using 200 mesh).

2. Evaluation and measurement The following evaluation and measurement were performed on the metal-like decorative members. The results are shown in Table 1.

2-1. Measurement of L ^* _1-25 , L ^* _2-25 , L ^* _1-45 and L ^* _2-45 Examples and comparisons using the part number "MA-96" of the multi-angle spectrophotometer manufactured by X-Rite. ^{L *} _1-25 , L ^* _2-25 , L ^* _1-45 and L ^* _2-45 of the metal-like decorative members obtained in the example were measured. The light source was D65 and the field of view was a 10-degree field of view. The measurement wavelength range of the measuring instrument is 400 to 700 nm, and the spectral interval is 10 nm.
In Examples 1 to 12, the azimuth angle a and the azimuth angle b at the time of measurement were parallel to the flow direction of the metal-like decoration member. The direction of the incident light when measuring L ^* _1-25 and L ^* _1-45 corresponds to the flow direction of the machine when manufacturing the metal-like decoration member.
Since there is no flow direction in Comparative Example 1, the azimuth angle a is set to an arbitrary direction.
Further, in Comparative Example 2, the azimuth angle a and the azimuth angle b at the time of measurement were set to be parallel to the moving direction of the squeegee. The direction of the incident light when measuring L ^* _1-25 and L ^* _1-45 corresponds to the direction in which the squeegee moves.

2-2. Design 1 (Comparison between white metal-like decorative members)
In a room under fluorescent lighting, the metal-like decorative members obtained in Examples 1 to 6 and Comparative Examples 1 and 2 were observed from the protective layer side from various angles while moving their heads. Using the metal-like decorative member of Comparative Example 2 as a reference, 20 people were given 2 points that were superior in design to the reference, 1 point that could not be said to be either, and 0 points that were inferior in design to the reference. Evaluated and calculated the average score. Then, each average score was ranked according to the following criteria. Since Comparative Example 2 is a reference, it cannot be compared, but it was ranked as "C" including one point.
AA: Average score is 1.7 or more A: Average score is 1.5 or more and less than 1.7 B: Average score is 1.3 or more and less than 1.5 C: Average score is 1.0 or more and less than 1.3 D: Average score is less than 1.0

2-3. Designability 2 (Comparison between black metal-like decorative members)
In a room under fluorescent lighting, the metal-like decorative members obtained in Examples 7 to 12 and Reference Example 1 were observed from the protective layer side from various angles while moving their heads. Using the metal-like decorative material of Reference Example 1 as a reference, 20 people, with 2 points having a better design than the reference, 1 point that cannot be said to be either, and 0 points having a design that is inferior to the reference. Evaluated and calculated the average score. Then, each average score was ranked according to the following criteria. As for the design, the points of evaluation were the metallic luster and the change in appearance depending on the viewing direction.
AA: Average score is 1.7 or more A: Average score is 1.5 or more and less than 1.7 B: Average score is 1.3 or more and less than 1.5 C: Average score is 1.0 or more and less than 1.3 D: Average score is less than 1.0

From the results of Tables 1 and 2, the metal-like decorative member of the example can be obtained inexpensively by the roll-to-roll method, has anisotropy in brilliance, and has a high level of designability. Can be confirmed.
On the other hand, the metal-like decoration members of Comparative Examples 1 and 2 were inferior in design to the metal-like decoration members of Examples because they had no anisotropy in brilliance.

3. 3. Fabrication and Evaluation of Metal-like Decorative Mold The metal-like decoration members of Examples 1 to 12 are heat-dried at 75 ° C. for 3 days, and then the metal-like decoration member is used using a mold having a desired molding shape. The surface on the resin plate (black plate) side of the above was arranged toward the mold and vacuum formed (black plate reaching temperature 150 ° C.) to obtain metal-like decorative molded articles of Examples 1 to 12.
When the obtained metallic decorative molded product was visually observed from the protective layer side in a room under fluorescent lighting, no cracks could be confirmed. Further, when the obtained metallic decorative molded body was visually observed from the protective layer side in a room under fluorescent lighting from various angles while moving the head, all of them were excellent in design.

10: Protective layer 11: Transparent base material 20: Bright printing layer 21: Bright pigments 30, 30A, 30B: Colored layer 40: Resin plate 50: Adhesive layer 100: Metallic decorative member 201: Commalol 202 : Coating roll 203: Liquid pool of ink for brilliant printing layer 204: Liquid level 205: Material to be coated

Claims (10)

A metallic decorative member having a protective layer and a bright printing layer containing a bright pigment and a binder resin in this order from the outer layer side, and satisfying the following condition 1.
<Condition 1>
Visible light is incident on the outer layer side surface of the metallic decorative member from an arbitrary azimuth angle (azimuth angle a) at an elevation angle of 45 degrees. Let ^{L * a *} b ^{* L *} value of the color system be ^{L *} _1-25 calculated from the spectral spectrum of the reflected light in the direction in which the elevation angle is tilted 25 degrees toward the incident light side from the specular reflection direction of the incident light. ..
Visible light is incident on the outer layer side surface of the metallic decorative member from an azimuth angle (azimuth angle b) opposite to the arbitrary azimuth angle at an elevation angle of 45 degrees. Let ^{L * a *} b ^{* L *} value of the color system be ^{L *} _2-25 calculated from the spectral spectrum of the reflected light in the direction in which the elevation angle is tilted 25 degrees toward the incident light side from the specular reflection direction of the incident light. ..
^{Under the above premise, the relationship with L *} _1-25 and L ^* _2-25 satisfies the following equations (1) and (2) at least in some azimuth angles.
L ^* _1-25 > L ^* _2-25 (1)
1.00 <{(L ^* _1-25- L ^* _2-25 ) / L ^* _1-25 } x 100 (2) Further, the metal-like decorative member according to claim 1, which satisfies the following condition 2.
<Condition 2>
Visible light is incident on the outer layer side surface of the metallic decorative member from an arbitrary azimuth angle (azimuth angle a) at an elevation angle of 45 degrees. Let ^{L * a *} b ^{* L *} value of the color system be ^{L *} _1-45 calculated from the spectral spectrum of the reflected light in the direction in which the elevation angle is tilted 45 degrees toward the incident light side from the specular reflection direction of the incident light. ..
Visible light is incident on the outer layer side surface of the metallic decorative member from an azimuth angle (azimuth angle b) opposite to the arbitrary azimuth angle at an elevation angle of 45 degrees. Let ^{L * a *} b ^{* L *} value of the color system be ^{L *} _2-45 calculated from the spectral spectrum of the reflected light in the direction in which the elevation angle is tilted 45 degrees toward the incident light side from the specular reflection direction of the incident light. ..
^{Under the above premise, the relationship between L *} _1-25 , L ^* _2-25 , L ^* _1-45 and L ^* _2-45 is related to the following equations (1) and (1) at least in some azimuth angles. 3) is satisfied.
L ^* _1-25 > L ^* _2-25 (1)
1.00 <(L ^* _1-25 / L ^* _1-45 ) / (L ^* _2-25 / L ^* _2-45 ) (3) The metal-like decorative member according to claim 1 or 2, wherein the protective layer is a transparent base material. The metal-like decorative member according to any one of claims 1 to 3, wherein the bright pigment is flaky and has a thickness t _{1 of 0.01 to 5.00 μm.} Wherein the photoluminescent thickness _{t 1} of the pigment, and the bright printed layer thickness _{t 2} of satisfy the relationship of 0.01 ≦ _t 1 / _{t 2} ≦ 0.20, any one of claims 1 to 4 The metal-like decorative member described in. The metal-like decorative member according to any one of claims 1 to 5, wherein the content ratio of the bright pigment in the bright printing layer is 0.05 to 50% by mass. The metal-like decorative member according to any one of claims 1 to 6, which has a resin plate on the inner layer side of the brilliant printing layer. The metal-like decoration member according to any one of claims 1 to 7, wherein the azimuth angle a is parallel to the flow direction of the metal-like decoration member. A metal-like decorative molded body formed from the metal-like decoration member according to any one of claims 1 to 8. The metallic decorative molded article according to claim 9, which satisfies the following condition 1'.
<Condition 1'>
Visible light is incident on the outer layer side surface of the metallic decorative molded body from an arbitrary azimuth angle (azimuth angle a) at an elevation angle of 45 degrees. ^{The L *} a ^* b ^* color system L ^* value calculated from the spectral spectrum of the reflected light in the direction in which the elevation angle is tilted 25 degrees toward the incident light side from the specular reflection direction of the incident light is m-L ^* _1-25. And.
Visible light is incident on the outer layer side surface of the metallic decorative member from an azimuth angle (azimuth angle b) opposite to the arbitrary azimuth angle at an elevation angle of 45 degrees. ^{The L *} a ^* b ^* color system L ^* value calculated from the spectral spectrum of the reflected light in the direction in which the elevation angle is tilted 25 degrees toward the incident light side from the specular reflection direction of the incident light is m-L ^* _2-25. And.
^{Under the above premise, the relationship between m-L *} _1-25 and m-L ^* _2-25 satisfies the following equations (1') and (2') at least in some azimuth angles.
m-L ^* _1-25 > m-L ^* _2-25 (1')
1.00 <{(m-L ^* _1-25 -m-L ^* _2-25 ) / mL ^* _1-25 } x 100 (2')

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