JP7151182B2 - Metallic decorative member and metallic decorative molding using the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a metallic decorative member and a metallic decorative molding using the same.

2. Description of the Related Art As a technique for improving the design of materials such as vehicles such as automobiles, interior materials and exterior materials of buildings, and furniture, painting by spraying or the like is performed. However, painting has a high environmental load due to solvents and a high _CO2 emission load due to the electricity required in the drying and cooling processes. In addition, since painting is performed multiple times (for example, in the case of pearl-like paint, it may be painted six times: primer, undercoat, intermediate coat, topcoat color base, pearl base, and clear topcoat). And the series of steps of drying is repeated, which tends to exacerbate the above-mentioned problems and further increases the cost. 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 during the cooling process.
However, when the resin member has a three-dimensional structure, uneven coating occurs, and it is difficult to apply a clean coating.

As a film capable of solving 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 the problems of painting (environmental load due to solvent, CO ₂ emission load based on electricity required in drying and cooling processes).
By the way, a dark plate such as a black plate is often arranged on the inner layer side of the metallic decorative member. The reason for this is, for example, to suppress the reflection of light on the inner layer side and stabilize the accuracy of quality control.
Since the bright layer of Patent Document 1 has a weak hiding power, it is not possible to sufficiently suppress the influence of the dark color of the dark plate on the design of the outer layer side of the metallic decorative member. In other words, although the decorative sheet having the bright layer can solve the problem of coating, it poses a new problem that it is not possible to sufficiently suppress the influence of the dark color of the dark plate on the design.

In order to solve the above problems, the present inventors have studied forming a masking layer between the glitter printed layer and the dark plate. However, a metallic decorative member in which a masking layer is formed between a glittering printed layer and a dark plate may cause cracks during molding, or the base of the dark plate may show through after molding, resulting in color unevenness. could not be granted frequently.
The present inventors have further studied and found that by making a specific layer structure between the bright printed layer and the dark plate, while hiding the dark color of the dark plate on the inner layer side, cracks during molding and after molding This led to the completion of a metallic decorative member capable of suppressing color unevenness.

The present invention provides the following [1] to [2].
[1] In order from the outer layer side, it has a transparent substrate, a glitter printed layer, a colored layer, a colored film and a dark plate, the colored film contains an ABS resin as a binder resin, and the total light reflection SCI of the colored film ^{A metal} _- ^{tone decorative member} [ ₂ ^] above [ 1].

According to the present invention, the problem of coating (environmental load due to solvent, _CO2 emission load based on electricity required in the drying and cooling process) can be solved, and the dark color of the dark plate on the inner layer side can be hidden. In addition, it is possible to provide a metallic decorative member capable of suppressing cracks during molding and color unevenness after molding, and a metallic decorative molding using the same.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view showing an embodiment of a metallic decorative member of the present invention; FIG. 4 is a cross-sectional view showing another embodiment of the metallic decorative member of the present invention;

[Metallic decorative materials]
The metallic decorative member of the present invention comprises, in order from the outer layer side, a transparent base material, a glittering printed layer, a colored layer, a colored film and a dark plate, the colored film containing an ABS resin as a binder resin, and the L ₁ ^* SCI is 70 or more when the L ^* value of the L ^* a ^* b ^* color system calculated from the spectral spectrum of the total light reflection SCI of the colored film is L ₁ ^* SCI. .

1 and 2 are sectional views showing an embodiment of the metallic decorative member of the present invention.
A metallic decorative member 100 shown in FIGS. 1 and 2 has a transparent substrate 10, a glitter printed layer 20, a colored layer 30, a colored film 40 and a dark plate 50 in order from the outer layer side. Moreover, the metallic decorative member 100 of FIG. 2 has an adhesive layer 60 between the colored layer 30 and the colored film 40 .

<Transparent substrate>
Examples of transparent substrates include polyolefin resins such as polyethylene and polypropylene; vinyl resins such as polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene/vinyl acetate copolymer, and ethylene/vinyl alcohol copolymer; polyethylene terephthalate; Polyester resins such as polyethylene naphthalate and polybutylene terephthalate; acrylic resins such as polymethyl (meth)acrylate and poly(ethyl meth)acrylate; styrene resins such as polystyrene; Examples include plastic films made of resins such as polyamide resins.
Among these transparent substrates, an acrylic resin film is preferable because it has excellent light resistance and moldability, has excellent transparency due to its low refractive index, and has less conspicuous scratches. Among acrylic resin films, an acrylic resin film containing rubber particles is preferable because it can improve moldability.

The haze of the transparent base material is preferably 5% or less, more preferably 3% or less, even more preferably 1% or less according to JIS K7136:2000.
The transparent substrate preferably has a total light transmittance of 85% or more, more preferably 90% or more, according to JIS K7361-1:1997.

The transparent base material may be subjected to adhesion-facilitating treatment such as physical treatment and chemical treatment in order to improve adhesion to the glitter print layer and optionally formed surface protective layer. In order to improve adhesion, the transparent substrate may have an easy-adhesion layer on the plastic film.
Moreover, the transparent base material may contain additives such as ultraviolet absorbers and light stabilizers.

The thickness of the transparent substrate is preferably from 50 to 250 μm, more preferably from 60 to 200 μm, even more preferably from 70 to 150 μm, from the viewpoint of the balance between moldability and protection of the glitter 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 this specification, AA to BB means from AA to BB.

<Glitter printing layer>
The glitter printed layer is a layer that is positioned on the inner layer side of the transparent base material and that plays a role of imparting metallic luster to the metallic decorative member.
The glitter print layer preferably contains a glitter pigment and a binder resin.

The glitter printed layer may be formed on a part of the region visible from the outer layer side of the metallic decorative member, but is preferably formed on the entire surface.
The glitter printed layer is formed, for example, by printing on the inner layer side surface of the transparent substrate with ink for a glitter printed layer. The ink for the glitter printing layer is usually composed mainly of a vehicle consisting of a binder resin and a solvent, and is mixed with a glitter pigment and, if necessary, a colorant such as a dye or pigment. be done. Examples of printing methods include comma coater printing, bar coater printing, gravure printing, offset printing, letterpress printing, and silk screen printing.

<<Glitter Pigment>>
Luminescent pigments include pearlescent pigments and metallic flakes. Among these, pearl pigments are preferable because they change color depending on the viewing angle and can improve the design.

A 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 matrix such as mica, alumina, and glass, and has light transmittance. . Therefore, by arranging the thin plate-like pigments in a layered manner, light is reflected multiple times, and a metallic or pearl-like luster can be produced.
As described above, pearl pigments are mainly composed of metal oxides rather than metals themselves, but they are materials capable of producing a feeling of metallic luster.
The pearl pigment preferably has an alumina base from the viewpoint of enhancing brightness and enhancing metallic luster.

Pearl pigments include, for example, white pearl pigments, interference pearl pigments, colored pearl pigments, and the like.
The white pearl pigment is obtained by covering a scale-like base such as mica, alumina, glass, etc. with a coating layer made of a colorless high refractive index material such as titanium dioxide, and the thickness of the coating layer is 0.1-0. It is relatively small, on the order of 15 μm, and appears white or silver because it reflects almost all wavelengths of light.
The interference pearl pigment has a coating layer made of a colorless high refractive index material such as titanium dioxide, and the thickness of the coating layer is greater than that of the white pearl pigment, exceeding 0.15 μm. This thickness changes the reflected and transmitted light, resulting in different interference colors. It is sometimes called an iris colored pearl.
The colored pearl pigment is a chromatic color, and the coating layer is made of a colored high refractive index material such as ferric oxide, and the white pearl pigment is surrounded by a colored high refractive index material such as ferric oxide or other colored There are those that are coated with pigments, and those that have pigments or other coloring agents added to the coating layer.

The particle size of the pearl pigment is not particularly limited, and the average length is preferably 5 to 70 μm, more preferably 10 to 40 μm.
Incidentally, the average length of the pearl pigment and the average length of the metal flakes, which will be described later, are the lengths of any 20 particles (pearl pigments or metal flakes) observed with an optical microscope or an electron microscope from the plane direction of the metallic decorative member. Calculated as the average length. The length of one pearl pigment and metal scale means the maximum length of one pearl pigment and metal scale in the planar direction.

Metal flakes include metals and alloys such as aluminum, gold, silver, brass, titanium, chromium, nickel, nickel-chromium, and stainless steel.
Metal flakes are obtained, for example, by peeling a metal thin film obtained by vacuum-depositing the metal or alloy on a plastic film from the plastic film, pulverizing and stirring the peeled metal thin film, or powder of the metal or alloy. and a solvent, and spread and / or pulverize the powder with a medium agitating mill, ball mill, attritor, etc., and furthermore, those whose surfaces are coated with resin etc. can be used. can.

The metal flakes preferably have an average length of 1 to 50 μm, more preferably 2 to 30 μm, still more preferably 5 to 20 μm, from the viewpoint of uniform dispersibility in the glitter print layer. Also, from the viewpoint of obtaining ease of handling and high metallic luster, the average thickness is preferably 0.01 to 5 μm, more preferably 0.02 to 3 μm, and even more preferably 0.05 to 1 μm. Also, the aspect ratio (average length/average thickness) of the metal flakes is preferably 15-500.

The average thickness of the metal flakes and the pearl pigment is determined as the average value of 20 arbitrary particles (pearl pigments or metal flakes) obtained by observing the cross section of the metallic decorative member with an optical microscope or an electron microscope. In addition, the thickness of one pearl pigment or metal scale is obtained by dividing the cross-sectional image of one pearl pigment or metal scale into five regions with an equal length in the longitudinal direction, and measuring the thickness of the central part of each region ( t ₁ , t ₂ , t ₃ , t ₄ , t ₅ ) are measured and t ₁ to t ₅ are averaged.

The content of the glitter pigment in the glitter print layer is 0.05 to 50% by mass of the total solids of the glitter print layer from the viewpoint of suppressing cracks during molding while imparting a sufficient metallic luster. Preferably.
When the luster pigment is a pearl pigment, it is more preferably 7 to 40% by mass, still more preferably 10 to 30% by mass. When the luster pigment is metallic flakes, the content is more preferably 0.07 to 10% by mass, still more preferably 0.10 to 5% by mass.

Examples of the binder resin for the glitter printing layer include acrylic resins such as polymethyl (meth)acrylate and polyethyl (meth)acrylate, polyolefin resins such as polyethylene resins and chlorinated polypropylene resins, and nitrocellulose. , cellulose resins such as ethyl cellulose, acetylbutyl cellulose and ethyloxyethyl cellulose, rubber resins such as chlorinated rubber 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-based resin, styrene-butadiene copolymer, vinylidene fluoride-based resin, polyvinyl alcohol-based resin, polyvinyl acetal-based resin, polyvinyl butyral-based resin, polybutadiene-based resin, polyester-based 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, maleic acid resins, and the like. These may be used individually by 1 type, or may use 2 or more types together.
Among these binder resins, acrylic resins are preferable from the viewpoint of transparency.

In addition, the binder resin of the glitter print layer preferably contains two resins having different weight average molecular weights (a resin (A1) having a small weight average molecular weight and a resin (B1) having a large weight average molecular weight).
The mass average molecular weight of the resin (A1) is preferably 100,000 or less, more preferably 30,000 to 100,000, even more preferably 50,000 to 90,000. The mass average molecular weight of the resin (B1) is preferably over 100,000, more preferably 120,000 to 800,000, and even more preferably 150,000 to 500,000.
The mass ratio of resin (A1) to 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) together as described above, it is possible to easily improve the cohesive force of the glitter print layer while suppressing cracks during molding.
The resin (A1) and the resin (B1) are preferably resins of the same family, more preferably acrylic resins.
In addition, in this specification, a mass average molecular weight is the mass average molecular weight of polystyrene conversion measured by GPC method.

A plasticizer is preferably contained in the glitter print layer in order to suppress cracks during molding.
Examples of plasticizers include phthalates, adipates, and trimellitates. The content of the plasticizer in the glitter print layer is preferably 1 to 20% by mass, more preferably 3 to 15% by mass, and still more preferably 5 to 10% by mass based on the total solid content of the glitter print layer. is. When the plasticizer content is 1% by mass or more, cracks during molding can be easily suppressed, and when the plasticizer content is 20% by mass or less, deterioration in heat resistance and light resistance is suppressed. At the same time, deformation of the coating film due to excessive flexibility can be suppressed.

It is preferable to contain an alignment agent in the glitter print layer. Alignment agents include layered silicates such as mica.
The content of the alignment agent in the glitter print layer is preferably 1 to 20% by mass, more preferably 3 to 15% by mass, and still more preferably 5 to 10% by mass based on the total solid content of the glitter print layer. is. By setting the content of the alignment agent to 1% by mass or more, the bright pigment can be easily arranged uniformly in the layer, and extreme variations in metallic luster can be easily suppressed. Moreover, by setting the content of the alignment agent to 20% by mass or less, it is possible to secure the ratio of other components such as the luster pigment and to easily suppress cracks during molding.

In the glitter printing layer, if necessary, for example, light stabilizers such as ultraviolet absorbers, pigments other than glitter pigments, viscosity modifiers, fillers, stabilizers, antioxidants, dispersants, desiccants, Optional additives such as lubricants, antistatic agents, cross-linking agents, etc. can be added.

The thickness of the glitter print layer is preferably 3 to 25 μm, more preferably 7 to 15 μm, from the viewpoint of suppressing cracks during molding while imparting a sufficient feeling of metallic luster.

<Colored layer>
The colored layer is a layer located on the inner layer side of the glitter printed layer.
In the metallic decorative member of the present invention, the two layers of the colored layer and the colored film described later suppress the influence of the dark color of the dark plate on the design of the outer layer side of the metallic decorative member. At the same time, it suppresses cracks during molding, and also prevents color unevenness after molding (mainly color unevenness due to the color of the dark plate being seen through), preventing the desired design from being obtained. . Further, even if a partial coating defect occurs in the colored layer, the presence of the colored film described later makes it difficult to recognize the difference in color within the surface. For these reasons, the two layers of the colored layer and the colored film, which will be described later, can increase the yield of the metallic decorative member and the metallic decorative molding.
In addition, when trying to hide the dark color of the dark plate with only the colored layer, it is necessary to increase the thickness of the colored layer or increase the proportion of pigment in the colored layer, and as a result, cracks occur in the colored layer during molding. It becomes easier. In addition, when only the colored layer is used, unevenness in the thickness of the colored layer (for example, uneven thickness after molding due to different elongation rates at the time of molding) causes unevenness in the degree of concealment of the dark color by the dark layer. In addition, color unevenness tends to occur in molded metallic decorative members (metallic decorative moldings) due to unevenness in the degree of concealment. Further, when the dark color of the dark plate is concealed only by the colored film, the design of the outer layer side of the metallic decorative member is affected by the tint of the colored film.

The colored layer preferably contains a pigment and a binder resin.
It is preferable that the pigment of the colored layer contains a white pigment. White pigments include titanium dioxide, barium sulfate, magnesium oxide, calcium carbonate, zinc oxide and white lead. Among these, titanium dioxide is preferred because of its excellent hiding power. Moreover, among titanium dioxide, rutile type or brookite type titanium dioxide is preferable from the viewpoint of suppressing deterioration of the binder resin over time.

As the pigment of the colored layer, it is preferable to contain a pigment other than a white pigment. By including a pigment other than the white pigment as the pigment in the colored layer, the dark color of the dark plate can be more easily concealed. On the other hand, when a large amount of a pigment other than the white pigment is contained, the design of the outer layer side of the metallic decorative member is likely to be affected by the color of the pigment other than the white pigment. Therefore, the content of the pigment other than the white pigment is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 1 part by mass, based on 100 parts by mass of the white pigment.
Pigments other than white pigments include black pigments such as carbon black, titanium black and iron black; chromatic inorganic pigments such as yellow lead, titanium yellow, red iron oxide, cadmium red, ultramarine blue and cobalt blue; quinacridone red and isoindolinone. Chromatic organic pigments such as yellow and phthalocyanine blue are included.

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

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

As the binder resin for the colored layer, the same binder resins as those exemplified as the binder resin for the glitter print layer can be used.
Among the various binder resins, acrylic resins and vinyl chloride-vinyl acetate copolymer resins are preferred from the viewpoint of suppressing cracks during molding. The mass ratio of the acrylic resin and the vinyl chloride-vinyl acetate copolymer resin is preferably 10:2 to 10:20, more preferably 10:3 to 10:15, and 10: More preferably 4 to 10:8. By setting the mass ratio of the acrylic resin to the vinyl chloride-vinyl acetate resin within the above numerical range, cracks during molding of the metallic decorative member can be more easily suppressed.

Also, the binder resin of the colored layer preferably contains two resins having different weight average molecular weights (a resin (A2) having a small weight average molecular weight and a resin (B2) having a large weight average molecular weight).
The mass average molecular weight of the resin (A2) is preferably 100,000 or less, more preferably 30,000 to 100,000, even more preferably 50,000 to 90,000. The mass average molecular weight of the resin (B2) is preferably over 100,000, more preferably 120,000 to 800,000, even more preferably 150,000 to 500,000.
The mass ratio of resin (A2) to resin (B2) is preferably 4:1 to 1:1, more preferably 3:1 to 3:2.
By using the resin (A2) and the resin (B2) together as described above, it is possible to easily improve the cohesive force of the colored layer while suppressing cracks during molding. Also, when the binder resin contains a vinyl chloride-vinyl acetate copolymer resin, it may turn yellow due to heat. Therefore, from the viewpoint of suppressing yellowing, the means of using the resin (A2) and the resin (B2) together is preferable to the means containing the vinyl chloride-vinyl acetate copolymer resin described above.
Since the content of the pigment in the colored layer tends to be greater than the content of the bright pigment in the bright printed layer, cracks are more likely to occur in the colored layer than in the bright printed layer. Therefore, when two resins having different weight average molecular weights are used as the binder resin for the colored layer, the content of the resin with the lower weight average molecular weight should be equal to or greater than the content of the resin with the higher weight average molecular weight, as described above. is preferred.
The resin (A2) and the resin (B2) are preferably resins of the same family, and more preferably acrylic resins.

In the colored layer, if necessary, 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, Optional additives such as cross-linking agents can be added.

The thickness of the colored layer is preferably 5 to 50 μm, more preferably 7 to 40 μm, more preferably 10 to 30 μm, from the viewpoint of the balance between hiding the dark color of the dark plate and suppressing cracks during molding. It is even more preferable to have

The colored layer can be formed, for example, by applying a colored layer ink containing each component constituting the colored layer onto the glitter printing layer and drying the ink.

<Colored film>
The colored film is a layer located on the inner layer side of the colored layer and on the outer layer side of the dark plate.
By having the colored film and the colored layer between the glitter printed layer and the dark plate, the dark color of the dark plate suppresses the design of the outer layer side of the metallic decorative member from being affected, It is possible to suppress cracks during molding and color unevenness after molding.

The colored film should contain ABS resin (acrylonitrile-butadiene-styrene copolymer) as a binder resin. If the colored film does not contain the ABS resin as the binder resin, cracks in the colored film during molding cannot be suppressed.
The colored film may contain a binder resin other than the ABS resin. The ratio of the ABS resin to the total binder resin of the colored film is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, and 99% by mass or more. 100% by mass is most preferable.

The colored film is required to have an L ₁ ^* SCI of 70 or more, where the L ^* value of the L ^* a ^* b ^* color system calculated from the spectral spectrum of the total light reflection SCI is L ₁ ^* SCI. . If the L ₁ ^* SCI is less than 70, the metal-like decorative member cannot have a sufficient metallic luster.
L ₁ ^* SCI is preferably 72 or more, more preferably 74 or more.
L ₁ ^* SCI is preferably 95 or less. By setting the L ₁ ^* SCI to 95 or less, it is possible to suppress deterioration in moldability due to an excessive white pigment content in the colored film.

In the colored film, L ₁ ^* SCE/L ₁ ^* SCI is 0.00, where L ₁ ^* SCE is the L ^* value of the L ^* a ^* b ^* color system calculated from the spectral spectrum of the diffuse light reflection SCE. It is preferably 90 or more, preferably 0.93 or more, and more preferably 0.95 or more.
By setting L ₁ ^* SCE/L ₁ ^* SCI to 0.90 or more, the diffusion of the colored film approaches isotropic diffusion, making it easier to eliminate the influence of the dark color of the dark plate.
_The upper limit of L1 ^* SCE/L1 ^* SCI is _about 0.99.

^{The colored film has} _{a 1} ^{_ _} _{_} ^_ The absolute values of ^* SCI and b ₁ ^* SCI are each preferably 15 or less, more preferably 10 or less, and even more preferably 5 or less.
By setting the absolute values of a ₁ ^* SCI and b ₁ ^* SCI to 15 or less, respectively, it is possible to suppress the influence of the tint of the colored film from appearing on the outer layer side of the metallic decorative member, thereby preventing deterioration in design. It can be easily suppressed.
The lower limit of the absolute values of a ₁ ^* SCI and b ₁ ^* SCI is about 0.20.

The thickness of the colored film is preferably 70 to 700 μm, more preferably 100 to 600 μm, even more preferably 200 to 450 μm.
By setting the thickness of the colored film to 70 μm or more, the influence of the dark color of the dark plate can be easily eliminated, and in particular, color unevenness after molding can be easily suppressed. Further, by setting the thickness of the colored film to 700 μm or less, it is possible to suppress deterioration of moldability.

The total ray reflection SCI is all reflected light, including the specular direction, measured by applying light from all directions to the surface of the display element using an integrating sphere and closing the light trap. On the other hand, the diffuse light reflection SCE is measured by applying light from all directions to the sample surface using an integrating sphere and opening the light trap corresponding to the specular reflection direction. be.
A typical SCI and SCE measurement setup uses a D65 as the light source for an integrating sphere spectrophotometer, the receiver position is +8 degrees to the sample normal, and the light trap position is to the sample normal. -8 degrees, and the viewing angle is 2 degrees or 10 degrees.
An example of a measuring device that satisfies the above conditions is a handheld spectrophotometer manufactured by Konica Minolta (trade name “CM-700d”). In this specification, the viewing angle is assumed to be 10 degrees.
In this specification, L ^* SCI, L ^* SCE, a ^* SCI and b ^* SCI are represented by the L ^* a ^* b ^* table based on the spectrum of the total light reflection SCI or the diffuse light reflection SCE obtained from the above measurement. It can be obtained by calculating the L ^* value, a ^* value, and b ^* value of the color system. For example, L ^* SCI can be obtained by calculating the L ^* value in the L ^* a ^* b ^* color system based on the spectral spectrum of the total light reflection SCI obtained from the above measurement. The L ^* a ^* b ^* color system was standardized by the International Commission on Illumination (CIE) in 1976 and adopted in JIS Z8781-4:2013.
In this specification, L ^* SCI, L ^* SCE, a ^* SCI and b ^* SCI are the average values of 10 measurement values.

The colored film preferably contains a pigment.
Pigments for colored films include white pigments such as titanium dioxide, barium sulfate, magnesium oxide, calcium carbonate, zinc oxide and white lead, black pigments such as carbon black, yellow lead, titanium yellow, red iron oxide, cadmium red, ultramarine blue and cobalt. Examples include chromatic inorganic pigments such as blue, chromatic organic pigments such as quinacridone red, isoindolinone yellow and phthalocyanine blue.
By increasing the ratio of the white pigment among these pigments, L ₁ ^* SCI, L ₁ ^* SCE/L ₁ ^* SCI, a ₁ ^* SCI, and b ₁ ^* SCI can be easily set within the above ranges.
However, when only a white pigment is used, it becomes difficult to obtain a colored film excellent in flexibility, thermal shock resistance and hiding power. Therefore, by mixing a white pigment with a pigment other than the white pigment and increasing the ratio of the white pigment, L ₁ ^* SCI, L ₁ ^* SCE/L ₁ ^* SCI, a ₁ ^* SCI and b ₁ ^* SCI are obtained. The above range is preferred.

The colored film may optionally 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, Optional additives such as cross-linking agents can be added.

<Laminate with colored layer and colored film>
Regarding a laminate having a colored layer and a colored film in this order, L ^* a ^* b ^* calculated from the total light reflection SCI spectrum measured from the colored layer side of the laminate is the L ^* value of the color system. L ₂ ^* SCI−L ₁ ^* SCI is preferably 25 or less when ₂ ^* SCI is used.
By setting L ₂ ^* SCI−L ₁ ^* SCI to 25 or less, even if cracks occur in the colored layer during molding, the locations where cracks occur can be made inconspicuous, and color unevenness after molding can be suppressed. can be done easily. L ₂ ^* SCI−L ₁ ^* SCI is preferably 20 or less, more preferably 10 or less.
L ₂ ^* SCI is preferably 90 or more.
The above-mentioned effect by setting L ₂ ^* SCI−L ₁ ^* SCI to 25 or less becomes more remarkable when L ₂ ^* SCI−L ₄ ^* SCI is 50 or more, and is even more remarkable when L 2 *SCI−L 4 *SCI is 60 or more. become something. Here, L ₄ ^* SCI means the L ^* value in the L ^* a ^* b ^* color system calculated from the spectral spectrum of the total light reflection SCI of the dark film.

<Dark plate>
The dark plate is the layer located on the inner layer side of the colored film.
The L ^* value (L4 ^* SCI) of the dark plate is preferably ₄₀ or less, more preferably 30 or less. By setting the L ₄ ^* SCI to 40 or less, the reflection of light on the inner layer side can be suppressed, and the accuracy of quality control can be stabilized.

The dark plate preferably contains a pigment and a binder resin.
The pigment of the dark plate preferably contains a black pigment such as carbon black, titanium black and iron black. Further, a pigment other than a black pigment may be contained as the pigment of the dark plate.

The binder resin of the dark plate preferably contains ABS resin. By including the ABS resin as the binder resin in the dark-colored plate, it is possible to suppress the occurrence of cracks in the dark-colored plate during molding.
The dark plate may contain a binder resin other than the ABS resin. The ratio of the ABS resin to the total binder resin of the dark plate is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, and 99% by mass or more. 100% by mass is most preferable.

For the dark plate, if necessary, 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, Optional additives such as cross-linking agents can be added.

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

<Other layers>
The metallic decorative member may have layers other than the transparent base material, the glitter printed layer, the colored layer, the colored film and the dark plate.

<<adhesive layer>>
An adhesive layer may be provided between the transparent substrate, the glitter print layer, the colored layer, the colored film and the dark plate in order to enhance the adhesion of each layer.
The adhesive layer includes a heat-sensitive adhesive layer and a pressure-sensitive adhesive layer (adhesive layer). A pressure-sensitive adhesive layer (adhesive layer) is more preferable because of the simplicity of the lamination process.

As heat-sensitive or pressure-sensitive resins, general-purpose acrylic resins, urethane-based resins, polyester-based resins, silicone-based resins, vinyl chloride-based resins, vinyl acetate-based resins, or mixtures or copolymers of two or more of these. can be used.
The thickness of the adhesive layer may be adjusted within the range of about 0.1 to 100 μm depending on the type of adhesive.
In addition, if each layer (for example, a colored layer) constituting the metal-like decorative member also has adhesiveness, there is no need to separately form an adhesive layer, which is preferable in terms of thinning and cost reduction.

<<Protective layer>>
A protective layer may be formed on the surface of the transparent substrate opposite to the glitter printed layer, for example, in order to improve scratch resistance.

The protective layer preferably contains a cured product of the curable resin composition. The cured product of the curable resin composition includes a cured product of a thermosetting resin composition and a cured product of an ionizing radiation-curable resin composition. Among these, a cured product of an ionizing radiation-curable resin composition is preferable.

A thermosetting resin composition is a composition containing at least a thermosetting resin, and is a resin composition that is cured by heating. Thermosetting resins include acrylic resins, urethane resins, phenol resins, urea melamine resins, epoxy resins, unsaturated polyester resins, silicone resins, and the like. If necessary, a curing agent is added to these curable resins in the thermosetting resin composition.

The ionizing radiation-curable resin composition is a composition containing a compound having an ionizing radiation-curable functional group (hereinafter also referred to as an "ionizing radiation-curable compound"). Examples of ionizing radiation-curable functional groups include ethylenically unsaturated bond groups such as (meth)acryloyl groups, vinyl groups, and allyl groups, epoxy groups, and oxetanyl groups.
A compound having an ethylenically unsaturated bond group is preferable as the ionizing radiation-curable resin. In addition, from the viewpoint of suppressing damage to the resin layer during the process of manufacturing a metallic decorative member, the ionizing radiation-curable resin is more preferably a compound having two or more ethylenically unsaturated bond groups. , polyfunctional (meth)acrylate compounds having two or more ethylenically unsaturated bond groups are more preferred. Both monomers and oligomers can be used as polyfunctional (meth)acrylate compounds.
Ionizing radiation means an electromagnetic wave or a charged particle beam that has an energy quantum capable of polymerizing or cross-linking molecules, and usually ultraviolet (UV) or electron beam (EB) is used. Electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion beams can also be used.

The thickness of the protective layer is preferably 0.5 to 30 μm, more preferably 1 to 20 μm, even more preferably 3 to 10 μm.

<Lamination structure of metallic decorative member>
Specific examples of the laminated structure of the metallic decorative member include the following (1) to (4). In addition, "/" means the boundary of each layer. The left side means the outer layer side of the metallic decorative member, and the right side means the inner layer side.
(1) Transparent base material/Glitter printed layer/Colored layer/Colored film/Dark plate (2) Transparent base material/Glitter printed layer/Colored layer/Pressure-sensitive adhesive layer (adhesive layer)/Colored film/Dark plate (3) Protective layer/Transparent substrate/Glitter printing layer/Colored layer/Colored film/Dark plate

The metal-tone decorative member having the laminated structure of (1) above can be produced, for example, by the following steps (1-1) to (1-3).
(1-1) An ink for a glittering printed layer is applied onto a transparent substrate and dried to form a glittering printed layer, and then an ink for a colored layer is applied onto the glittering printed layer and dried. A step of forming a colored layer to obtain a laminate A1 comprising a transparent substrate, a glitter printed layer and a colored layer.
(1-2) A step of obtaining a laminate B1 by thermally laminating a colored film and a dark plate.
(1-3) A step of thermally laminating the laminated body A1 and the laminated body B1 with the colored layer side of the laminated body A1 facing the colored film side of the laminated body B1.

The metal-like decorative member having the laminated structure of (2) above can be produced, for example, by the following steps (2-1) to (2-3).
(2-1) On a transparent substrate, an ink for a glitter printed layer is applied and dried to form a glitter printed layer, and then an ink for a colored layer is applied on the glitter printed layer and dried. A colored layer is formed, and then an ink for a pressure-sensitive adhesive layer is applied on the colored layer and dried to form a pressure-sensitive adhesive layer (adhesive layer). and a step of obtaining a laminate A2 comprising a pressure-sensitive adhesive layer (adhesive layer).
(2-2) A step of obtaining a laminate B2 by thermally laminating the colored film and the dark plate.
(2-3) A step of laminating the pressure-sensitive adhesive layer (adhesive layer) side of the laminate A2 and the colored film side of the laminate B2 so as to face each other.

<Overall L ^* SCI>
In the metallic decorative member of the present invention, the L ^* value of the L ^* a ^* b ^* color system calculated from the spectral spectrum of the total light reflection SCI measured from the transparent substrate side of the metallic decorative member is L ₃ ^* SCI is preferably 85 or more, more preferably 87 or more, and even more preferably 90 or more, when L ₃ ^* SCI is used.
By setting the L ₃ ^* SCI to 85 or more, the feeling of metallic luster can be improved.

<Uses of metallic decorative materials>
The metal-like decorative member of the present invention can be suitably used for various moldings (for example, communication equipment, interior and exterior of vehicle bodies such as automobiles, household appliances, furniture members, etc.) that require high designability. can be done.

[Metallic decorative molding]
The metal-tone decorative molding of the present invention is formed from the metal-tone decorative member of the present invention described above.

<Manufacturing method of metallic decorative molding>
The metal-tone decorated molded product can be produced, for example, by vacuum forming having the following steps (y1) to (y2).
(y1) After placing a metallic decorative member on a mold having a molding surface of a predetermined shape, the metallic decorative member is heated and softened. If the mold is a male mold, place the metal-tone decorative member so that the dark plate side faces the mold (male mold) side. It is arranged so that the substrate side faces the molding die (female mold) side.
(y2) Vacuum suction is applied from the molding die side, and the softened metallic decorative member is adhered along the molding surface of the molding die to mold the metallic decorative member.

In addition, before the step (y1), a step of removing moisture by heating may be performed, if necessary.

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples. In addition, this invention is not limited to the form as described in an Example.

1. Evaluation and Measurement The metal-tone decorative members obtained in Examples and Comparative Examples were evaluated and measured as follows. The results are shown in Tables 1 and 2.

1-1. Measurement of L ^* SCI, L ^* SCE, a ^* SCI and b ^* SCI Using a handheld spectrophotometer manufactured by Konica Minolta (trade name “CM-700d”), “colored film”, “colored layer The items shown in Tables 1 and 2 were measured for the "laminate comprising (white layer) and the colored film in this order" and the "metallic decorative member". The laminate was measured from the colored layer (white layer) side, and the metallic decorative member was measured from the transparent base material side.

1-2. Feeling of Metallic Luster The metallically decorated moldings obtained in Examples and Comparative Examples were visually observed from the transparent substrate side under the illumination of a fluorescent lamp to confirm whether or not a metallic luster could be perceived. A case where a metallic luster was felt was rated as "A", and a case where a metallic luster was not felt was rated as "C".

1-3. Suppressing the influence of black plates (blackness of metal-like decorative materials)
The metallic decorative members obtained in Examples and Comparative Examples were visually observed from the transparent substrate side under the illumination of a fluorescent lamp, and the degree of influence of the dark color of the dark plate (black color of the black plate) on the design was evaluated. evaluated. Twenty people evaluated the product, with 2 points indicating no blackness and excellent design, 1 point indicating neither of them, and 0 points indicating insufficient blackness and insufficient design. Calculated. Then, each average score was ranked according to the following criteria.
AA: Average score of 1.7 or more A: Average score of 1.5 or more and less than 1.7 B: Average score of 1.3 or more and less than 1.5 C: Average score of 1.0 or more and less than 1.3 D: Average score less than 1.0

1-4. Color Unevenness The metal-tone decorative moldings obtained in Examples and Comparative Examples were visually observed from the transparent substrate side under illumination of a fluorescent lamp to confirm the presence or absence of color unevenness. 2 points for excellent design without feeling unevenness in color, 1 point for something that cannot be said either way, 0 points for feeling unevenness in color and insufficient design, 20 people evaluated, and the average score was calculated. Calculated. Then, each average score was ranked according to the following criteria.
A: Average score of 1.5 or more B: Average score of 1.0 or more and less than 1.5 C: Average score of less than 1.0

1-5. Cracks The metal-tone decorative moldings obtained in Examples and Comparative Examples were visually observed from the transparent substrate side under the illumination of a fluorescent lamp to confirm whether or not cracks had occurred. "A" indicates that no cracks were observed, and "C" indicates that cracks were observed.

2. Production of metallic decorative member [Example 1]
On a transparent substrate (total light transmittance: 92%, haze: 0.6%) made of an acrylic resin film containing rubber particles with a thickness of 125 μm, an ink for a glitter printing layer having the following formulation was applied and dried. , to form a glitter printed layer having a thickness of 11 μm. Next, on the glitter printed layer, a white layer ink 1 having the following formulation is applied and dried to form a white layer (colored layer) having a thickness of 9 μm. ) was obtained.
Next, a 350 μm-thick gray-tone colored film 1 (binder resin component: ABS resin) and a 3 mm-thick black plate 1 (L ^* SCI: 27, binder resin component: ABS resin) are thermally laminated to obtain a laminate B1. got
Next, the white layer (colored layer) side of the laminate A1 and the colored film side of the laminate B1 are opposed to each other and thermally laminated. , a colored film and a black plate (dark plate) in this order, a metallic decorative member of Example 1 was obtained.
After drying the metal-tone decorative member by heating at 75° C. for 3 days, a mold having a desired shape is used, and the black plate side of the metal-tone decorative member is placed facing the mold. The molded product was vacuum-molded (at a black plate reaching temperature of 150° C.) to obtain a metal-like decorative molding of Example 1.

<Ink for Glitter Print Layer>
・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 of 300,000, glass transition temperature of 100°C)
・ Pearl pigment: 5 parts by mass (base: alumina, average length: 30 μm)
・ Anti-settling agent: 0.1 parts by mass (silica, average primary particle size: 20 nm)
・Diisodecyl phthalate: 2 parts by mass ・Orientation agent (mica): 2 parts by mass ・Solvent: Appropriate amount

<Ink 1 for white layer (colored 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 of 300,000, glass transition temperature of 100°C)
・White pigment (titanium dioxide): 16 parts by mass ・Solvent: Appropriate amount

[Examples 2 to 14]
In the same manner as in Example 1, Metallic decorative members and metallic decorative moldings of Examples 2 to 14 were obtained.
The formulations of the ink 2 for the white layer (colored layer) and the ink 3 for the white layer (colored layer) are as follows. The colored film 2 is an ivory colored film (binder resin component: ABS resin) having a thickness of 350 μm.

<Ink 2 for white layer (colored 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 of 300,000, glass transition temperature of 100°C)
・White pigment (titanium dioxide): 16 parts by mass ・Yellow pigment: 0.078 parts by mass ・Solvent: appropriate amount

<Ink 3 for white layer (colored 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 of 300,000, glass transition temperature of 100°C)
・White pigment (titanium dioxide): 16 parts by mass ・Yellow pigment: 0.039 parts by mass ・Solvent: appropriate amount

[Comparative Example 1]
A laminate A1 was obtained in the same manner as in Example 1. Next, the white layer (colored layer) side of the laminate A1 and the black plate 1 (thickness 3 mm, L ^* SCI: 27, binder resin component: ABS resin) are thermally laminated. A metallic decorative member and a metallic decorative molding of Comparative Example 1 having a glittering printed layer, a white layer (colored layer) and a black plate (dark plate) in this order were obtained.

[Comparative Examples 2 to 9]
In the same manner as in Comparative Example 1, Metallic decorative members and metallic decorative moldings of Comparative Examples 2 to 9 were obtained.
The formulations of the ink 4 for the white layer (colored layer) and the ink 5 for the white layer (colored layer) are as follows.

<Ink 4 for white layer (colored layer)>
・Acrylic resin (A): 5.2 parts by mass (mass average molecular weight 70,000, glass transition temperature 100°C)
・Acrylic resin (B): 4.6 parts by mass (mass average molecular weight: 300,000, glass transition temperature: 100°C)
・Vinyl chloride-vinyl acetate copolymer: 5.3 parts by mass ・White pigment (titanium dioxide): 24 parts by mass ・Solvent: appropriate amount

<Ink 5 for white layer (colored layer)>
・Acrylic resin (A): 5.2 parts by mass (mass average molecular weight 70,000, glass transition temperature 100°C)
・Acrylic resin (B): 4.6 parts by mass (mass average molecular weight: 300,000, glass transition temperature: 100°C)
・Vinyl chloride-vinyl acetate copolymer: 5.3 parts by mass ・White pigment (titanium dioxide): 24 parts by mass ・Yellow pigment: 0.039 parts by mass ・Solvent: Appropriate amount

From the results in Tables 1 and 2, the metallic decorative members of Examples can suppress cracks during molding and color unevenness after molding while concealing the dark color of the dark-colored plate on the inner layer side. can be confirmed. Although not shown in the table, yellowing was observed in the metal-like decorative moldings of Comparative Examples 8 and 9, which was considered to be caused by the vinyl chloride-vinyl acetate copolymer.

10: Transparent substrate 20: Luminous print layer 30: Colored layer 40: Colored film 50: Dark plate 60: Adhesive layer 100: Metallic decorative member

Claims (5)

In order from the outer layer side, it has a transparent substrate, a glitter printed layer, a colored layer, a colored film and a dark plate, the colored film contains an ABS resin as a binder resin, and from the total light reflection SCI spectrum of the colored film L ₁ ^* SCI is 70 or more and 95 or less when the L ^* value of the calculated L ^* a ^* b ^* color system is L ₁ ^* SCI ,
When the L ^* value in the L ^* a ^* b ^* color system calculated from the spectral spectrum of the diffuse light reflection SCE of the colored film is L1 ^* SCE, L1 _* ^SCE _/ L1 ^* _SCI is 0.0. is 90 or more,
When the _a ^* value and b ^* value in the L ^* a ^* b ^* color system calculated from the spectral spectrum of the total light reflection SCI of the colored film are _a1 ^* SCI and b1 _* ^SCI , a1 ^* The absolute values of SCI and b ₁ ^* SCI are each 15 or less,
The thickness of the colored film is 70 to 700 μm,
The colored layer contains a pigment and a binder resin,
including a white pigment as the pigment,
As the binder resin, an acrylic-vinyl chloride-vinyl acetate copolymer or two resins having different weight average molecular weights are included,
For a laminate comprising the colored layer and the colored film in this order, L*a*b* L* in the color system calculated from the total light reflection SCI spectrum measured from the ^colored layer ^side of ^{the laminate} . L ₂ ^* SCI−L ₁ ^* SCI is 25 or less, where L ₂ ^* SCI is the value ;
A metallic decorative member, wherein the dark plate has an L ^* value (L4 ^* SCI) of 40 or less _. 2. The metallic decorative member according to claim 1 , further comprising a pigment other than a white pigment as said pigment. The metallic decorative member according to claim 1 or 2 , wherein the glitter printed layer contains a glitter pigment and a binder resin. The metallic decorative member according to any one of claims 1 to 3 , wherein the transparent substrate is an acrylic resin film. A metal-tone decorative molding formed from the metal-tone decorative member according to any one of claims 1 to 4 .

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