JP2019209549A - Member for metallic decoration and metallic decorative molded body using the same - Google Patents

Abstract

To provide a member for metallic decoration in which occurrence of cracks after molding is suppressed, and a metallic decorative molded body using the same.SOLUTION: A member for metallic decoration contains a transparent acrylic base material, a brilliant print layer and a coloring layer in order from an outer layer side, in which the coloring layer contains a pigment and a binder resin, and the binder resin contains an acrylic resin A and an acrylic resin B having mutually different mass average molecular weights.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a member for metallic decoration and a metallic decorative molded body using the same.

As a technique for enhancing the design of materials such as vehicles such as automobiles, interior and exterior materials of buildings, and furniture, painting by spraying or the like is performed. However, the 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. For this reason, in recent years, in automobile painting, switching to painting of resin members that can reduce CO ₂ emissions in the cooling process has been performed.
However, the coating of the resin member causes uneven coating when the resin member has a three-dimensional structure, and it has been difficult to apply a beautiful coating.

  As a means for solving the above problem, a means for completing the production of the decorative member by a roll-to-roll method is conceivable. Since the roll-to-roll method manufactures a decorative member by vapor deposition or coating on a film, the problem of uneven coating can be solved. For example, as an alternative to metal plating, a means for decorating the surface of an adherend such as a resin molded body using a decorative sheet having a metal vapor deposition film has been proposed (Patent Document 1).

Japanese Patent No. 5809768

However, the metal vapor-deposited film cannot be produced in-line with other layers constituting the decorative sheet. For this reason, the decorative sheet having a metal vapor deposition film as in Patent Document 1 can solve the problem of coating (uneven coating) on the resin member, but has a problem in that the production efficiency is low and the cost cannot be reduced sufficiently. is there.
In order to solve the problem, a means for forming a layer having a metallic luster (brilliant print layer) by printing using a pearl pigment, a metal scale, or the like can be considered.

  By the way, a colored layer may be arrange | positioned from viewpoints of the designability including color provision, concealment property, etc. in the inner layer of the glittering printing layer of the member for metallic decorations. However, the colored layer may contain a large amount of pigment from the viewpoint of design, for example. Moreover, from the viewpoint of concealment, the thickness of the colored layer may be further increased. As a result, fine cracks (hereinafter sometimes referred to as “microcracks”) may occur in the colored layer during molding. And when the microcrack which arose in the colored layer propagates to a glitter printing layer and a transparent acrylic base material, it may become a molding defect.

  This invention is made | formed in view of such a situation, and it is a subject to provide the member for metal decorations in which generation | occurrence | production of the crack after shaping | molding was suppressed, and the metal decoration decoration molded object using the same And

The present invention provides the following [1] to [2].
[1] A metallic decoration member including a transparent acrylic base material, a glitter printing layer, and a colored layer in order from the outer layer side, wherein the colored layer includes a pigment and a binder resin, and the binder resin is a mass average A metallic decorative member comprising an acrylic resin A and an acrylic resin B having different molecular weights.
[2] A metallic decorative molded body formed from the metallic decorative member according to (1) above.

  ADVANTAGE OF THE INVENTION According to this invention, the member for metal decorations in which generation | occurrence | production of the crack after shaping | molding was suppressed and the metal decoration decoration molded object using the same can be provided.

It is sectional drawing which shows 1st embodiment of the member for metallic decorations of this invention. It is sectional drawing which shows 2nd embodiment of the member for metallic decorations of this invention.

[Metallic decoration members]
The metallic decoration member of the present invention is a metallic decoration member including a transparent acrylic substrate, a glitter printing layer, and a colored layer in order from the outer layer side, and the colored layer includes a pigment and a binder resin. The binder resin contains an acrylic resin A and an acrylic resin B having different mass average molecular weights.

FIG.1 and FIG.2 is sectional drawing which shows embodiment of the member for metallic decorations of this invention.
1A has a transparent acrylic base material 2, a glossy printed layer 3, an adhesive colored layer 4a, and a resin plate 6 in order from the outer layer side. Moreover, the member 1B for metallic decorations of FIG. 2 has the resin board 6 via the adhesive layer 5 on the colored layer 4b.

<Transparent acrylic substrate>
A transparent acrylic base material is used as the base material for the metallic decoration member of the present invention from the viewpoint of protecting the glitter printing layer and maintaining the transparency. The acrylic base material is not particularly limited. For example, poly (meth) methyl acrylate base material, poly (meth) ethyl acrylate base material, (meth) methyl acrylate- (meth) butyl acrylate copolymer group An acrylic resin film made of a material or the like is used. The acrylic resin film is excellent in light resistance and moldability, and has a small difference in refractive index from air, so that the surface reflectance is low, the transparency is excellent, and scratches are not noticeable. Among acrylic resin films, an acrylic resin film containing rubber particles is preferable in that the moldability can be improved.

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

The transparent acrylic base material may be subjected to an easy adhesion treatment such as a physical treatment and a chemical treatment in order to improve the adhesion between the glitter printing layer and the surface protective layer formed as necessary. . Moreover, in order to make adhesiveness favorable, a transparent acrylic base material may have an easily bonding layer on a resin film.
The transparent acrylic substrate may contain additives such as an ultraviolet absorber and a light stabilizer.

The thickness of the transparent acrylic substrate is preferably 50 to 250 μm, more preferably 60 to 200 μm, and further preferably 70 to 150 μm, from the viewpoint of the balance between moldability and protection of the glitter printing layer. preferable. In this specification, AA to BB means AA or more and BB or less.
The thickness of the transparent acrylic substrate can be measured, for example, by observing a vertical section with an electron microscope or the like.

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

The glitter print layer may be formed on a part of the region visible from the outer layer side of the metallic decoration member, but it is preferably formed on the entire surface.
The glitter print layer is formed, for example, by printing on the inner layer side surface of the transparent acrylic substrate with the glitter print layer ink. The ink for the glitter printing layer is usually composed of a vehicle composed of a binder resin and a solvent, and an ink in which a pigment such as a glitter pigment and, if necessary, a colorant such as a dye or a pigment is added and mixed is used. It is done. Examples of the printing method include comma coater printing, bar coater printing, gravure printing, offset printing, letterpress printing, and silk screen printing.

<< Bright pigment >>
Examples of glitter pigments include pearl pigments and metal scales. Among these, pearl pigments that change the color depending on the angle to be observed and can have a better design are preferred.

The pearl pigment is a thin plate pigment having a coating layer made of a high refractive index material such as titanium dioxide on the surface of a scaly base such as mica (mica), alumina and glass, and has light transmittance. . For this reason, by arranging the thin plate pigments in layers, light is reflected multiple times, and a glossy feeling like a metal or a pearl can be generated.
As described above, the pearl pigment is mainly composed of a metal oxide, not the metal itself, but is a material capable of producing a metallic luster.
The pearl pigment preferably has alumina as the base material from the viewpoint of increasing the luminance and further increasing the metallic luster.

Examples of pearl pigments include white pearl pigments, interference pearl pigments, and colored pearl pigments.
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. 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 and exceeds 0.15 μm. Depending on the thickness, the reflected light and the transmitted light change, and various interference colors are generated. 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 further colored with a high refractive index material such as ferric oxide or other colored materials. There are those coated with a pigment, and those obtained by adding a pigment or other colorant 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.
In addition, the average length of the pearl pigment and the average length of the metal scale described later are 20 arbitrary particles (pearl pigment or metal scale) observed with an optical microscope or an electron microscope from the plane direction of the metallic decoration member. It is obtained as an average value of the lengths. The length of one pearl pigment and metal scale means the maximum length in the plane direction of one pearl pigment and metal scale.

Examples of the metal scale include metals and alloys such as aluminum, gold, silver, brass, titanium, chromium, nickel, nickel chromium, and stainless steel.
For example, the metal scale is 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 powder of the metal or alloy. And those obtained by spreading and / or pulverizing the powder with a medium stirring mill, ball mill, attritor or the like, and those having a resin-coated surface. it can.

  From the viewpoint of uniform dispersibility in the glitter printed layer, the metal scale preferably has an average length of 1 to 50 μm, more preferably 2 to 30 μm, and further preferably 5 to 20 μm. Further, from the viewpoint of obtaining handleability and high metallic gloss, the average thickness is preferably 0.01 to 5 μm, more preferably 0.02 to 3 μm, and still more preferably 0.05 to 1 μm. Further, the aspect ratio (average length / average thickness) of the metal scale is preferably 15 to 500.

The average thickness of the metal scale and the pearl pigment is determined as an average value of any 20 particles (pearl pigment or metal scale) obtained by observing the cross section of the metallic decoration member with an optical microscope or an electron microscope. In addition, 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 with an equal length in the length direction, and the thickness of the central portion 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 printing layer is 0.05 to 50% by mass of the total solid content of the glitter printing layer from the viewpoint of suppressing cracks during molding while giving sufficient metallic luster. Preferably there is.
In addition, when a luster pigment is a pearl pigment, More preferably, it is 7-40 mass%, More preferably, it is 10-30 mass%. Moreover, when a luster pigment is a metal scale, More preferably, it is 0.07-10 mass%, More preferably, it is 0.10-5 mass%.

Examples of the binder resin for the glitter printing layer include acrylic resins such as poly (meth) methyl acrylate and poly (meth) ethyl acrylate, polyolefin resins such as polyethylene resins and chlorinated polypropylene resins, and nitrocellulose. Fiber 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 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 resin resin, Polyamide-based resins, alkyd resins, epoxy resins, unsaturated polyester resins, melamine resins, urea resins, polyurethane resins, phenol resins, xylene resins, and maleic acid resin. 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.

Moreover, it is preferable that binder resin of a glitter printing layer contains 2 types of resin (resin (A1) with small mass average molecular weight and resin (B1) with large mass average molecular weight) from which a mass average molecular weight differs.
The mass average molecular weight of the resin (A1) is preferably 100,000 or less, more preferably 30,000 to 100,000, and further 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 further preferably 150,000 to 500,000.
The mass ratio of the resin (A1) to the resin (B1) is preferably 1: 3 to 3: 1, and 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 glitter printing layer while suppressing cracks during molding.
The resin (A1) and the resin (B1) are preferably resins of the same system, and more preferably acrylic resins.
In addition, in this specification, a mass average molecular weight is a mass average molecular weight of polystyrene conversion measured by GPC method.

The glitter print layer preferably contains a plasticizer in order to suppress cracks during molding.
Examples of the plasticizer include phthalic acid ester, adipic acid ester and trimellitic acid ester. The content of the plasticizer in the glitter printing layer is preferably 1 to 20% by mass of the total solid content of the glitter printing layer, more preferably 3 to 15% by mass, and further preferably 5 to 10% by mass. It is. By making the content of the plasticizer 1% by mass or more, cracks during molding can be easily suppressed, and by making the content of the plasticizer 20% by mass or less, a decrease in heat resistance and light resistance is suppressed. At the same time, deformation of the coating film due to excessive flexibility can be suppressed.

The glitter print layer preferably contains an aligning agent. Examples of the aligning agent include layered silicates such as mica.
The content of the aligning agent in the glitter 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 glitter printing layer. It is. By setting the content of the aligning agent to 1% by mass or more, the glitter pigment can be easily arranged uniformly in the layer, and extreme variations in metallic luster can be easily suppressed. Moreover, by making content of an orientation agent into 20 mass% or less, while ensuring the ratio of other components, such as a luster pigment, it can be easy to suppress a crack at the time of shaping | molding.

  For the glitter print layer, if necessary, for example, a light stabilizer such as an ultraviolet absorber, a pigment other than the glitter pigment, a viscosity modifier, a filler, a stabilizer, an antioxidant, a dispersant, a desiccant, Arbitrary additives such as a lubricant, an antistatic agent, and a crosslinking agent 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 giving a sufficient metallic gloss.

<Colored layer>
When the colored layer is located on the inner layer side of the glitter printing layer and imparts a color to the metallic decoration member or has a resin plate described later on the inner layer side further than the colored layer, It has the role of hiding color. The colored layer preferably has adhesiveness from the viewpoint of process simplicity and the like (hereinafter sometimes referred to as “adhesive colored layer”).

The colored layer includes a pigment and a binder resin, and the binder resin includes an acrylic resin A and an acrylic resin B having different mass average molecular weights.
In the member for metallic decoration of the present invention, the binder resin in the colored layer contains an acrylic resin A and an acrylic resin B having different mass average molecular weights, thereby suppressing cracks during molding. , It is easy to suppress the cohesive force.

The mass average molecular weight of the acrylic resin A is smaller than the mass average molecular weight of the acrylic resin B.
The acrylic resin A has a mass average molecular weight of preferably 100,000 or less, more preferably 30,000 to 100,000, and further preferably 50,000 to 90,000.
The mass average molecular weight of the acrylic resin B is preferably more than 100,000, more preferably 120,000 to 800,000, and further preferably 150,000 to 500,000.
When the mass average molecular weight of the acrylic resin A is in the above range, cracks during molding can be easily suppressed, and when the mass average molecular weight of the acrylic resin B is in the above range, cohesion can be easily suppressed. it can.
If the acrylic resin A has a mass average molecular weight of about 30,000, the combined use with the acrylic resin B makes it easy to suppress an increase in the hardness of the binder resin. On the other hand, when the acrylic resin B has a mass average molecular weight of about 800,000, the weather resistance and heat resistance as the binder resin are easily maintained by the combined use with the acrylic resin A.

The mass ratio of the acrylic resin A and the acrylic resin B is preferably 4: 1 to 1: 1, more preferably 3: 1 to 3: 2, and further preferably 5: 2 to 3. : 2. When the mass ratio of the acrylic resin A and the acrylic resin B is in the above range, the balance between suppression of cracking and suppression of cohesion during molding of the metallic decoration member is easier.
In addition, since the content of the white pigment in the colored layer tends to be larger 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. For this reason, when using two kinds of resins having different mass average molecular weights as the binder resin of the colored layer, as described above, the content of the resin having a small mass average molecular weight should be equal to or more than the content of the resin having a large mass average molecular weight. Is preferred.

The glass transition temperature Tg of the acrylic resin A is preferably 80 to 110 ° C, more preferably 90 to 110 ° C, and further preferably 95 to 110 ° C.
Similarly, the glass transition temperature Tg of the acrylic resin B is preferably 80 to 110 ° C, more preferably 90 to 110 ° C, and further preferably 95 to 110 ° C.
By setting the glass transition temperature Tg of the acrylic resin A and the glass transition temperature Tg of the acrylic resin B, which have a significant difference in mass average molecular weight, to the same range as described above, the heat resistance of the colored layer can be improved. In addition to the improvement, the thermal shock resistance can be further improved by the combined use.
Tg can be determined based on the measurement of the change in calorie (DSC method) by DSC (inspection scanning calorimetry).

  As the acrylic resin A and the acrylic resin B in the binder resin of the colored layer, an acrylic resin, an acrylic polyol resin, or the like can be used independently. Specifically, homopolymers of (meth) acrylate monomers, copolymers of two or more different (meth) acrylate monomers, copolymers of (meth) acrylate monomers and other monomers Etc. One type of acrylic resin may be used alone, or two or more types may be used in combination. In the present specification, “(meth) acryl” means “acryl or methacryl”, and other similar ones have the same meaning.

  Examples of the (meth) acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, cyclohexyl (meth) acrylate, normal butyl (meth) acrylate, (meth ) Isobutyl acrylate, secondary butyl (meth) acrylate, tertiary butyl (meth) acrylate, isobornyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) ) Acrylate and the like are preferred, and methyl (meth) acrylate is more preferred from the viewpoints of heat resistance and weather resistance. Examples of the copolymer of two or more different (meth) acrylic acid ester monomers include a copolymer of two or more (meth) acrylic acid esters selected from those exemplified above, and these copolymers May be a random copolymer or a block copolymer.

  The other monomer that forms a copolymer with the (meth) acrylic acid ester monomer is not particularly limited as long as it is copolymerizable with the (meth) acrylic acid ester, but in the present invention, (meth) acrylic acid, Styrene, maleic anhydride, fumaric acid, divinylbenzene, vinylbiphenyl, vinylnaphthalene, diphenylethylene, vinyl acetate, vinyl chloride, vinyl fluoride, vinyl alcohol, acrylonitrile, acrylamide, butadiene, isoprene, isobutene, 1-butene, Alicyclic olefin monomers such as 2-butene, N-vinyl-2-pyrrolidone, dicyclopentadiene, ethylidene norbornene, norbornene, vinylcaprolactam, citraconic anhydride, maleimides such as N-phenylmaleimide, vinyl ethers, etc. It is preferably exemplified, in particular styrene and (anhydrous) maleic acid is preferable as a copolymerization component. That is, a binary copolymer of (meth) acrylic acid ester and styrene or (anhydrous) maleic acid, or a terpolymer of (meth) acrylic acid ester, styrene and (anhydrous) maleic acid is preferable. In addition, the copolymer of (meth) acrylic acid ester and another monomer may be a random copolymer or a block copolymer.

  In addition, the acrylic polyol resin is not particularly limited, but examples thereof include (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and octyl (meth) acrylate. ) Acrylic acid alkyl ester and (meth) acrylic acid having a hydroxyl group in the molecule such as 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate What is obtained by copolymerizing with ester is mentioned.

  As long as the properties of the colored layer are not impaired, the binder resin further includes vinyl resins such as polyvinyl alcohol resin, polyvinyl acetate resin, polyvinyl butyral resin, polyvinyl acetal resin, polyvinyl pyrrolidone, polyethylene terephthalate resin, polyethylene naphthalate. Polyester resins such as trees, urethane resins such as polyurethane acrylate, ethyl cellulose resins, hydroxyethyl cellulose resins, ethyl hydroxy cellulose resins, methyl cellulose resins, cellulose acetate resins such as cellulose acetate resins, polyamide resins, aromatic polyamide resins, polyamideimide resins Such a polyamide-based resin, an acetal-based resin, and a polycarbonate-based resin may be included.

The colored layer includes a pigment. The pigment preferably contains a white pigment, a black pigment, a chromatic inorganic pigment, or a chromatic organic pigment. Moreover, it is preferable that content of the said pigment in the said colored layer is 6-300 mass parts with respect to 100 mass parts of said binder resins, It is more preferable that it is 20-250 mass parts, It is 30-200 mass parts. More preferably it is.
When the pigment content is 6 parts by mass or more, it becomes easy to obtain coloring and color reproducibility and stability are improved. Moreover, it becomes easy to suppress the crack at the time of shaping | molding as content of a pigment is 300 masses or less.

Examples of white pigments include titanium dioxide, barium sulfate, magnesium oxide, calcium carbonate, zinc oxide and lead white. Of these, titanium dioxide is preferred because of its excellent hiding power. Of titanium dioxide, rutile type or brookite type are preferable from the viewpoint of suppressing deterioration of the binder resin over time.
When the pigment in the colored layer is titanium dioxide, the content of the titanium dioxide is preferably 10 to 200 parts by mass and more preferably 20 to 200 parts by mass with respect to 100 parts by mass of the binder resin. Preferably, it is 25 to 200 parts by mass.
Moreover, it is preferable that it is 10-200 mass parts with respect to a total of 100 mass parts of the said acrylic resin A and acrylic resin B, It is more preferable that it is 20-200 mass parts, It is 25-200 mass parts. More preferably it is.
When the content of the titanium dioxide is in the above range, desired coloring can be imparted and cracks during molding can be easily suppressed.

Examples of black pigments include carbon black, titanium black, and iron black.
When the pigment in the colored layer is carbon black, the content of the carbon black is preferably 6 to 60 parts by mass and more preferably 15 to 55 parts by mass with respect to 100 parts by mass of the binder resin. Preferably, it is 25-50 mass parts.
Moreover, it is preferable that it is 6-60 mass parts with respect to a total of 100 mass parts of the said acrylic resin A and acrylic resin B, It is more preferable that it is 15-55 mass parts, It is 25-50 mass parts. More preferably it is.
When the content of the carbon black is within the above range, desired coloring can be imparted and cracks during molding can be easily suppressed.

Examples of the chromatic inorganic pigment include chrome-lead, titanium-yellow, petiole, cadmium red, ultramarine blue, and cobalt blue.
Examples of chromatic organic pigments include quinacridone red, isoindolinone yellow, and phthalocyanine blue.

  The average particle size of the pigment used in the colored layer is preferably from 0.1 to 10 μm, more preferably from 0.5 to 5 μm, still more preferably from 0.5 to 3 μm.

  In this specification, the average particle size of the pigment is determined by measuring the particles dispersed in the solution by a dynamic light scattering method, and the particle size distribution is represented by a cumulative volume distribution (50% particle size (d50: median size)). It is. The 50% particle diameter can be measured using, for example, a Microtrac particle size analyzer (manufactured by Nikkiso Co., Ltd.).

  The thickness of the colored layer is not particularly limited, but is appropriately adjusted according to the type and use of the pigment. From the viewpoint of suppressing cracks during molding, the thickness is preferably 5 to 50 μm, more preferably 7 to 40 μm, and even more preferably 10 to 30 μm.

  For the colored layer, if necessary, 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, a drying agent, Arbitrary additives such as a lubricant, an antistatic agent, and a crosslinking agent can be added.

  Examples of the colored layer include a coating-type colored layer obtained by applying and drying an ink for a colored layer containing components constituting the colored layer. When a plurality of colored layers are formed, a plurality of coating-type colored layers may be formed.

<Other layers>
The member for metallic decoration may have layers other than a transparent acrylic base material, a glitter printing layer, and a colored layer.

<< Colored film >>
It is preferable that a colored film is further provided on the opposite side of the colored layer from the glitter print layer side.
The colored film preferably contains, for example, a pigment and a binder resin, like the colored layer. Examples of the pigment used in the colored film include the same pigments as those used in the above-described colored layer.
The thickness of the colored layer is not particularly limited, but is appropriately adjusted according to the type and use of the pigment. From the viewpoint of suppressing cracks during molding, the thickness is preferably 0.1 to 0.5 mm, and more preferably 0.2 to 0.4 mm.

<< Resin plate >>
It is preferable that a resin plate is further provided on the opposite side of the colored layer from the glitter print layer side.
A resin board has a role which raises the intensity | strength of the member for metal decoration, for example, or maintains the shape of the metal decoration molding formed from the member for metal decoration.

A known pigment may be used for the resin plate as long as it does not affect the quality, moldability, etc. of the member for metallic decoration.
For example, when suppressing the surface reflection of the resin plate, it is preferably an achromatic color (gray, black) excluding white, and more preferably black. In this case, the pigment of the resin plate may be a black pigment alone or a mixture of a black pigment and another pigment (such as a white pigment).

The binder resin of the resin plate preferably contains an ABS resin. When the resin plate contains an ABS resin as a binder resin, it is possible to suppress the occurrence of cracks in the colored plate during molding.
The resin plate may contain a binder resin other than the 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. More preferably, it is most preferably 100% by mass.

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

  For the resin 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 drying agent, a lubricant, an antistatic agent, Arbitrary additives, such as a crosslinking agent, can be added.

<< Adhesive layer >>
An adhesive layer may be provided between the transparent acrylic substrate, the glitter printing layer, the colored layer, the colored film, and the resin plate in order to improve the adhesion of each layer.
Examples of the adhesive layer include 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 bonding process.

Examples of heat-sensitive or pressure-sensitive resins include general-purpose acrylic resins, urethane resins, polyester resins, silicone resins, vinyl chloride resins or vinyl acetate resins, or a mixture or copolymer of two or more of these. Can be used.
What is necessary is just to adjust the thickness of an adhesive bond layer in the range of about 0.1-100 micrometers according to the kind of adhesive agent.
In addition, if each layer (for example, glitter printing layer, colored layer) constituting the metallic decoration member has adhesiveness, it is not necessary to separately form an adhesive layer, and thinning and cost reduction are possible. Is preferable.

<< Protective layer >>
For example, a protective layer may be formed on the surface of the transparent acrylic substrate opposite to the glitter printing layer in order to improve the scratch resistance.

  The protective layer preferably contains a cured product of the curable resin composition. 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, a 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 necessary.

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 bond group such as a (meth) acryloyl group, a vinyl group, and an allyl group, an epoxy group, and an oxetanyl group.
As the ionizing radiation curable resin, a compound having an ethylenically unsaturated bond group is preferable. In addition, from the viewpoint of suppressing damage to the resin layer in the process of producing a metallic decorative member, the ionizing radiation curable resin is more preferably a compound having two or more ethylenically unsaturated bond groups. More preferred are polyfunctional (meth) acrylate compounds having two or more ethylenically unsaturated bond groups. As the polyfunctional (meth) acrylate compound, any of a monomer and an oligomer can be used.
The ionizing radiation means an electromagnetic wave or a charged particle beam having 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, and further preferably 3 to 10 μm.

<Laminated structure of metallic decoration members>
Specific examples of the laminated structure of the metallic decoration member include the following (1) to (10). Note that “/” means the boundary of each layer. Moreover, the left side means the outer layer side of the member for metallic decoration, and the right side means the inner layer side.
(1) transparent acrylic substrate / brilliant printed layer / adhesive colored layer / resin plate (2) transparent acrylic substrate / brilliant printed layer / colored layer / adhesive layer / resin plate (3) transparent acrylic substrate / Glossy printed layer / adhesive colored layer / colored film (4) transparent acrylic substrate / glossy printed layer / adhesive colored layer / colored film / resin plate (5) transparent acrylic substrate / glossy printed layer / colored layer / Adhesive layer / Colored film / Resin plate (6) Protective layer / Transparent acrylic substrate / Bright printed layer / Adhesive colored layer / Resin plate (7) Protective layer / Transparent acrylic substrate / Bright printed layer / Colored Layer / adhesive layer / resin plate (8) protective layer / transparent acrylic substrate / brilliant printed layer / adhesive colored layer / colored film (9) protective layer / transparent acrylic substrate / brilliant printed layer / adhesive coloring Layer / colored film / resin plate (10) protective layer / transparent acrylic substrate / bright printed layer Colored layer / adhesive layer / colored film / resin plate

The metal decoration member having the laminated structure (1) can be manufactured, for example, by the following step (1-1).
(1-1) On the transparent acrylic base material, the ink for the glitter printing layer is applied and dried to form the glitter printing layer, and then the ink for the adhesive coloring layer is coated on the glitter printing layer. Drying to form an adhesive colored layer, and then bonding the adhesive colored layer side and the resin plate facing each other and bonding them by heat lamination, transparent acrylic base material, glitter printing layer, adhesive colored layer And a step of obtaining a laminate A1 made of a resin plate.

The metal decoration member having the laminated structure (5) can be manufactured, for example, by the following steps (5-1) to (5-2).
(5-1) A glittering printing layer ink is applied onto a transparent acrylic substrate and dried to form a glittering printing layer. Then, a colored layer ink is applied onto the glittering printing layer and dried. After forming the colored layer, apply the ink for the adhesive layer on the colored layer and dry to form the adhesive layer, and then paste the colored film, transparent acrylic base material, glitter printing layer, coloring The process of obtaining laminated body A5 which consists of a layer, an adhesive bond layer, and a colored film.
(5-2) The process of laminating | stacking the colored film side of laminated body A5, and a resin board facing each other, and carrying out heat lamination.

  The metallic decorative member of the present invention has good moldability and is preferably used for the exterior of a vehicle body. Here, the vehicle body is not particularly limited, and examples thereof include automobiles, bicycles, trains, trucks, buses, airplanes, and the like that accompany movement on roads, airways, and the like.

[Metallic decorative molded body]
The metal-tone decorative molded body of the present invention is formed from the above-described member for metal-style decorating of the present invention.

<Method for producing metal-like decorative molded body>
The metallic decorative molded body can be manufactured by, for example, vacuum forming having the following steps (y1) to (y2).
(Y1) After installing the metallic decoration member on a mold having a predetermined shaped molding surface, the metallic decoration member is heated and softened. If the mold is a male mold, place the metallic decoration member so that the black plate side faces the mold (male) side. If the mold is a female mold, the metallic decoration member is transparent It arrange | positions so that a base material side may face a shaping | molding die (female type | mold) side.
(Y2) Vacuum the metal from the mold side, and attach the softened metal decoration member along the molding surface of the mold to form the metal decoration member.

  In addition, you may perform the moisture removal process by heating before a process (y1) as needed.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. In addition, this invention is not limited to the form as described in an Example.

1. Evaluation, measurement The following evaluation was performed about the member for metallic decorations obtained by the Example and the comparative example. The results are shown in Tables 1 and 2.

1-1. Cracks The metallic decorative molded bodies obtained in Examples and Comparative Examples were visually observed from the transparent acrylic substrate side under the illumination of a fluorescent lamp, and it was confirmed whether or not cracks occurred. The case where no crack was confirmed was designated as “A”, and the case where a crack was confirmed was designated as “C”.

1-2. Metallic luster feeling The metallic decorative molded bodies obtained in Examples and Comparative Examples were visually observed from the transparent acrylic substrate side under illumination of a fluorescent lamp, and it was confirmed whether or not metallic luster was felt. The case where metallic luster was felt was "A", and the case where metallic luster was not felt was "C".

2. Production of metallic decoration member [Example 1]
On the transparent acrylic 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 for glittering printing layer having the following formulation is applied and dried. Then, a glitter printing layer having a thickness of 10 μm was formed. Next, a colored layer ink having the following formulation is applied onto the glitter printing layer and dried to form an adhesive colored layer having a thickness of 10 μm, and a laminate composed of a transparent acrylic substrate, the glitter printed layer, and the adhesive colored layer. Got the body.
Next, the adhesive colored layer side of the laminate and a 3 mm thick resin plate (binder resin component: ABS resin) are bonded and bonded together, and from the outer layer side, the transparent acrylic base material, the glitter printing layer, and the adhesive The member for metallic decoration of Example 1 which has a property colored layer and a resin board in this order was obtained.
Moreover, after heat-drying the metallic decoration member for 3 days at 75 ° C., a mold having a desired molding shape is used, and the black plate side surface of the metallic decoration member is arranged facing the mold. And vacuum forming (black plate arrival temperature of 150 ° C.) to obtain a metallic decorative molded body of Example 1.

<Ink for glitter printing layer>
Acrylic resin (A1): 8 parts by mass (mass average molecular weight 70,000, glass transition temperature 100 ° C.)
Acrylic resin (B1): 7 parts by mass (mass average molecular weight 300,000, glass transition temperature 100 ° C.)
Pearl pigment: 5 parts by mass (a pearl pigment whose base material is alumina and whose coating layer is titanium dioxide)
(Average length: 27.5 μm, average thickness: 0.4 μm)
Anti-settling agent (silica, average primary particle size: 20 nm)
・ Diisodecyl phthalate: 2 parts by mass ・ Orienting agent (mica): 2 parts by mass ・ Solvent: Appropriate amount

<Ink for colored layer>
Acrylic resin A: 12.84 parts by mass (mass average molecular weight 70,000, glass transition temperature 100 ° C.)
Acrylic resin B: 5.68 parts by mass (mass average molecular weight 300,000, glass transition temperature 100 ° C.)
White pigment (titanium dioxide): 25.84 parts by mass Solvent: appropriate amount

[Example 2]
In the same manner as in Example 1, except that the acrylic resin A was changed to 14.60 parts by mass, the acrylic resin B was changed to 6.22 parts by mass, and the titanium dioxide was changed to 22.61 parts by mass. A decorative member and a metallic decorative molded body were obtained.

[Example 3]
In the same manner as in Example 1, except that the acrylic resin A was changed to 15.28 parts by mass, the acrylic resin B was changed to 6.76 parts by mass, and titanium dioxide was changed to 19.38 parts by mass. A decorative member and a metallic decorative molded body were obtained.

[Example 4]
The metallic tone of Example 4 was the same as Example 1 except that the acrylic resin A was changed to 16.50 parts by mass, the acrylic resin B was changed to 7.30 parts by mass, and the titanium dioxide was changed to 16.15 parts by mass. A decorative member and a metallic decorative molded body were obtained.

[Example 5]
In the same manner as in Example 1, except that the acrylic resin A was changed to 17.72 parts by mass, the acrylic resin B was changed to 7.84 parts by mass, and the titanium dioxide was changed to 12.92 parts by mass. A decorative member and a metallic decorative molded body were obtained.

[Example 6]
Except for changing the acrylic resin A to 20.16 parts by mass, the acrylic resin B to 8.92 parts by mass, and titanium dioxide to 6.46 parts by mass, the metallic tone of Example 6 was changed in the same manner as Example 1. A decorative member and a metallic decorative molded body were obtained.

[Example 7]
Except having changed titanium dioxide into 35.00 mass parts, it carried out similarly to Example 1, and obtained the member for metallic decorations of Example 7, and a metallic decoration molding.

[Example 8]
Except having changed acrylic resin B into 4.28 mass parts, it carried out similarly to Example 1, and obtained the member for metallic decorations of Example 8, and a metallic decoration molding.

[Comparative Example 1]
Except having used only 18.52 mass parts of acrylic resin A as binder resin, it carried out similarly to Example 1, and obtained the member for metallic decorations and the metallic decoration molding of the comparative example 1. FIG.

[Reference Example 1]
In the same manner as in Example 1, except that the acrylic resin A was changed to 10.40 parts by mass, the acrylic resin B was changed to 4.60 parts by mass, and the titanium dioxide was changed to 32.30 parts by mass. A decorative member and a metallic decorative molded body were obtained.

[Example 9]
Example 9 was carried out in the same manner as in Example 1 except that 14.82 parts by mass of acrylic resin A, 6.84 parts by mass of acrylic resin B, and 9.76 parts by mass of titanium dioxide as carbon black were used. The metal-tone decoration member and metal-tone decoration molded body were obtained.

[Example 10]
In the same manner as in Example 9, except that the acrylic resin A was changed to 15.73 parts by mass, the acrylic resin B was changed to 7.26 parts by mass, and the carbon black was changed to 8.54 parts by mass. A decorative member and a metallic decorative molded body were obtained.

[Example 11]
The metal tone of Example 11 was the same as Example 9, except that the acrylic resin A was changed to 16.64 parts by mass, the acrylic resin B to 7.68 parts by mass, and the carbon black to 7.32 parts by mass. A decorative member and a metallic decorative molded body were obtained.

[Example 12]
In the same manner as in Example 9, except that the acrylic resin A was changed to 17.55 parts by mass, the acrylic resin B was changed to 8.10 parts by mass, and the carbon black was changed to 6.10 parts by mass. A decorative member and a metallic decorative molded body were obtained.

[Example 13]
Except for changing the acrylic resin A to 18.46 parts by mass, the acrylic resin B to 8.52 parts by mass, and carbon black to 4.88 parts by mass, the metal tone of Example 13 was changed in the same manner as Example 9. A decorative member and a metallic decorative molded body were obtained.

[Example 14]
Except for changing the acrylic resin A to 20.28 parts by mass, the acrylic resin B to 9.36 parts by mass, and the carbon black to 2.44 parts by mass, the metal tone of Example 14 was changed in the same manner as Example 9. A decorative member and a metallic decorative molded body were obtained.

[Example 15]
Except having changed carbon black into 11.50 mass parts, it carried out similarly to Example 9, and obtained the member for metallic decorations of Example 15, and a metallic decoration molding.

[Comparative Example 2]
A metallic decorative member and a metallic decorative molded body of Comparative Example 2 were obtained in the same manner as in Example 9, except that only 21.66 parts by mass of acrylic resin B was used as the binder resin.

[Comparative Example 3]
A metallic decorative member of Comparative Example 3 in the same manner as in Example 9, except that only 19.00 parts by mass of acrylic resin A was used as the binder resin and carbon black was changed to 12.20 parts by mass. And the metal decoration decoration molded object was obtained.

[Reference Example 2]
The member for metallic decoration and the metallic decoration of Reference Example 2 are the same as Comparative Example 3 except that the acrylic resin A is changed to 13.00 parts by mass and the acrylic resin B is changed to 6.00 parts by mass. A molded body was obtained.

From the results of Tables 1 and 2, it can be confirmed that the metallic decoration member of the example can be obtained at low cost by the roll-to-roll method.
Moreover, from the result of Table 1, Examples 1-8 which contain two types of acrylic resins in a colored layer rather than the member for metal decoration of the comparative example 1 which contains only one type of acrylic resins in a colored layer. It can be confirmed that the metallic decorative member has a larger allowable amount of white pigment (titanium dioxide particles) that can suppress cracks (particularly, the comparison between Examples 7 to 8 and Comparative Example 1).
Furthermore, from the results of Table 2, Examples 9 to 2 including two types of acrylic resins in the colored layer are included rather than the members for metallic decoration of Comparative Examples 2 to 3 including only one type of acrylic resin in the colored layer. It can be confirmed that the metal decoration member 15 has a larger allowable amount of black pigment (carbon black particles) that can suppress cracks (particularly, comparison between Example 15 and Comparative Example 2).

  The metallic decoration member of the present invention has good formability. For this reason, it can be suitably used for exteriors of vehicle bodies such as automobiles and various molded bodies (for example, interior and exterior of automobiles, home appliances, furniture, etc.) that require a high degree of design.

1: Metal decoration member 2: Transparent acrylic base material 3: Glossy printed layer 4a: Adhesive colored layer 4b: Colored layer 5: Adhesive layer 6: Resin plate

Claims (9)

  In order from the outer layer side, a metallic decorative member including a transparent acrylic substrate, a glitter printing layer, and a colored layer, wherein the colored layer includes a pigment and a binder resin, and the binder resin has a mass average molecular weight of each other. Metal decoration member including different acrylic resin A and acrylic resin B.   The mass average molecular weight of the acrylic resin A is smaller than the mass average molecular weight of the acrylic resin B, and the mass ratio of the acrylic resin A and the acrylic resin B is 4: 1 to 1: 1. The metal decoration member according to 1.   The metal decorating member according to claim 1 or 2, wherein the acrylic resin A has a mass average molecular weight of 100,000 or less, and the acrylic resin B has a mass average molecular weight of over 100,000.   The metal adjustment of any one of Claims 1-3 whose glass transition temperature of the said acrylic resin A is 80-110 degreeC, and whose glass transition temperature of the said acrylic resin B is 80-110 degreeC. Decoration member.   The said pigment is titanium dioxide, Content of the said titanium dioxide in the said colored layer is 10-200 mass parts with respect to a total of 100 mass parts of the said acrylic resin A and acrylic resin B, Claim 1 5. The member for metal decoration according to any one of 4 above.   The pigment is carbon black, and the content of the carbon black in the colored layer is 6 to 60 parts by mass with respect to 100 parts by mass in total of the acrylic resin A and the acrylic resin B. The member for metallic decoration of any one of 5.   The member for metallic decorations of any one of Claims 1-6 in which the said glitter printing layer contains a glitter pigment and binder resin.   The member for metallic decorations of any one of Claims 1-7 used for vehicle body exteriors.   The metal-like decoration molded object formed from the member for metal-tone decoration of any one of Claims 1-8.