JP2017094638A - Laminate, decorative film, manufacturing method of decorative film, decorative molded body and manufacturing method of decorative molded body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate, a decorative film, a decorative film, a decorative molded body and a manufacturing method of the decorative molded body achieving both of color tone with depth and glossiness.SOLUTION: There are provided a laminate having a first coloring agent containing a coloring material and a resin, a second coloring layer containing a coloring agent and a resin, a bright layer arranged between the first coloring layer and the second coloring layer and a metal-containing refractive layer arranged in an opposite side to the side where the bright layer of the first coloring layer and having a metal, a decorative film, a manufacturing method of the decorative film, a decorative molded body and a manufacturing method of the decorative molded body.SELECTED DRAWING: None

Description

  The present invention relates to a laminate, a decorative film, a method for manufacturing a decorative film, a decorative molded body, and a method for manufacturing a decorative molded body.

In recent years, electronic devices such as mobile phones, car navigation systems, personal computers, ticket vending machines, and bank terminals have been equipped with a tablet-type input device on the surface of a liquid crystal device, etc., and instructions displayed in the image display area of the liquid crystal device There is a type in which information corresponding to an instruction image can be input by touching a part where the instruction image is displayed with a finger or a touch pen while referring to the image.
In such an input device, a frame-shaped decorative material that surrounds an information display unit that is touched with a finger, a touch pen, or the like in order to prevent a user from seeing a routing circuit or the like of the display device and to improve the appearance. Is decorated. As such a decorative material (for example, a decorative film), in recent years, a high degree of design is required in order to cope with a variety of consumer preferences.

  As a decorating material, a base sheet made of a thermoplastic resin, a first transparent colored ink layer printed on one surface of the base sheet, and a side opposite to the base sheet side of the first transparent colored ink layer A glittering ink layer containing a glittering pigment printed on the surface, and a second transparent colored ink layer printed on the surface opposite to the first transparent colored ink layer side of the glittering ink layer, A decorative sheet provided has been proposed (see, for example, Patent Document 1).

  In addition, as other decorative material, a pearl pigment produced by multilayer coating of titanium oxide on a pattern layer, mica or glass fine powder on the surface of a base film formed of a polyethylene terephthalate film or an acrylic film There has been proposed a decorative film formed by laminating a glitter layer containing a light shielding layer and a concealing layer in this order (see, for example, Patent Document 2).

JP 2014-200787 A JP 2012-201006 A

In order to achieve a high degree of design in a decorative material (for example, a decorative film), it is required to reproduce various colors. As a characteristic for reproducing various colors in a decorative film, the decorative film is required to have both a deep color and gloss.
The decorative sheet described in Patent Document 1 and the decorative film described in Patent Document 2 cannot be compatible with deep color and glossiness, and the demand for a decorative film that satisfies these two characteristics is as follows. It is growing.
A deep color is one in which a change in color is seen depending on the viewing angle, and the coating film has a depth.

  The present invention has been made in view of the above, and a laminated body, a decorative film, a method for producing a decorative film, a decorative molded body, and a decorative molded body that have both a deep color and gloss. It is an object to provide a manufacturing method.

Specific embodiments of the present invention for solving the above problems include the following embodiments.
<1> A first colored layer containing a color material and a resin, a second colored layer containing a color material and a resin, and a bright layer disposed between the first colored layer and the second colored layer A laminate having a metal-containing reflective layer containing a metal disposed on the side opposite to the side on which the bright layer of the first colored layer is disposed.

<2> The laminated body according to <1>, wherein the metal-containing reflective layer includes metal particles.
<3> The laminated body according to <1> or <2>, wherein the metal-containing reflective layer contains aluminum metal particles.
<4> The laminated body according to <2> or <3>, wherein the metal-containing reflective layer includes a graft-type silicone polymer represented by the following formula (1).

In formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ are each independently a hydrogen atom, a hydroxy group, or an aryl group Or an alkyl group having 1 to 3 carbon atoms, R ¹¹ and R ¹² each independently represents an arylene group or an alkylene group having 1 to 3 carbon atoms, and R ¹³ and R ¹⁴ are each independently A single bond or a divalent organic linking group is represented, A represents a group having a particle adsorption site, B represents a group having a structure represented by the following formula (2), and l and n are each independently 1 represents an integer of 1 or more, and m represents an integer of 0 or more.

In Formula (2), R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, a hydroxy group, an aryl group, or an alkyl group having 1 to 3 carbon atoms, and k represents an integer of 1 or more.

<5> The layered product according to any one of <1> to <4>, wherein the glitter layer includes a pigment having light transmittance and light reflectivity.
<6> The laminate according to <5>, wherein the pigment having light transmittance and light reflectivity is mica, glass, titanium oxide-coated mica, or titanium oxide-coated glass.
<7> The glitter layer is a laminate according to any one of <1> to <6>, including at least one resin selected from an acrylic resin, an ester resin, and a silicone resin.
<8> Any one of <1> to <7>, wherein the resin contained in the first colored layer and the second colored layer is at least one resin selected from an acrylic resin, an ester resin, and a silicone resin. The laminated body as described in one.

<9> A decorative film in which the laminate according to any one of <1> to <8> is disposed on a base film.
<10> The decorative film according to <9>, wherein the base film is a polyethylene terephthalate film, an acrylic film, or a polycarbonate film.

<11> A decorative molded body comprising the decorative film according to <9> or <10> and a resin molded body.
<12> A decorative molded body comprising the laminate according to any one of <1> to <8> and a resin molded body.

<13> A second colored layer forming step of applying a second colored layer coating solution on the base film to form the second colored layer, and a bright layer coating solution on the second colored layer. A bright layer forming step of forming a bright layer, a first colored layer forming step of applying a first colored layer coating liquid on the bright layer, and forming a first colored layer; And a metal-containing reflective layer forming step of forming a metal-containing reflective layer on the colored layer.
<14> A method for producing a decorative molded body including a step of fixing a resin molded body to the decorative film according to <9> or <10>.
<15> The method for producing a decorative molded body according to <14>, further including a step of peeling the base film of the decorative film.

  According to the present invention, there are provided a laminate, a decorative film, a method for manufacturing a decorative film, a decorative molded body, and a method for manufacturing a decorative molded body that have both a deep color and gloss.

It is a cross-sectional schematic diagram which shows an example of the laminated constitution of the laminated body of this invention. It is a cross-sectional schematic diagram which shows an example of the laminated constitution of the decorating film of this invention.

Hereinafter, the laminated body of the present invention, a decorative film, a method for manufacturing a decorative film, a decorative molded body, and a method for manufacturing a decorative molded body will be described in detail.
In this specification, the numerical range indicated using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.

<Laminated body>
The laminated body includes a first colored layer containing a color material and a resin, a second colored layer containing the color material and a resin, and a glittering layer disposed between the first colored layer and the second colored layer. And a metal-containing reflective layer containing a metal disposed on the side opposite to the side on which the glitter layer of the first colored layer is disposed.

The reason why the effect of the present invention appears is not clear, but is estimated as follows.
As a layer structure of a conventional decorative film, for example, a laminate in which a colored layer, a glitter layer, and a reflective layer are laminated in this order on a substrate is known. Since reflection from the origin is suppressed, glossiness is not sufficient. In addition, for example, a configuration having a laminate in which a glitter layer, a colored layer, and a reflective layer are laminated in this order on a substrate is also included, and since a strong gloss derived from the glitter layer is seen on the entire surface of the coating film, A certain color cannot be obtained.
In order to meet the demand for advanced design properties in recent years, it is required to achieve both deep color and gloss.
The decorative sheet described in Patent Document 1 does not have a reflective layer, and a white base sheet is assumed although the base sheet also serves as the function of the reflective layer, so that a deep color is not obtained. . Moreover, since the decorating film of patent document 2 does not have a reflection layer, it does not have a deep color. Thus, the decorative sheet described in Patent Document 1 and the decorative film described in Patent Document 2 cannot achieve both deep color and gloss.
The laminate of the present invention has a bright layer between the first colored layer and the second colored layer, and the metal-containing reflection on the surface side of the first colored layer opposite to the side having the bright layer. Having a layer.
In this way, the bright layer is sandwiched between the two colored layers, and the metal-containing reflective layer is disposed on the outer side of the one colored layer (the side not having the bright layer), so that the light enters from the second colored layer side. Light passes through the second colored layer, part of the light is reflected by the glitter layer, and part of light passes through the glitter layer and the first colored layer and is reflected by the metal-containing reflective layer. Therefore, it is considered that the laminate can achieve both deep color and gloss.
In addition to the deep color and gloss, the laminate of the present invention is considered to have excellent shielding properties against the color of the material behind the metal-containing reflective layer by having a metal-containing layer.
The shielding property means a property that the color of the material arranged behind the decorative film is not visually recognized from the front side of the decorative film.

[First colored layer]
The first colored layer includes a color material and a resin.
A laminated body has a 1st colored layer and has a deep color by having the below-mentioned 2nd colored layer through the below-mentioned bright layer.

(Color material)
The first colored layer includes at least one color material. The color material is not particularly limited, and can be selected from color materials having a desired color. The color material may be a pigment or a dye.
As the pigment, various conventionally known inorganic pigments and organic pigments can be used.
Examples of the inorganic pigment include white pigments described in paragraphs 0015 and 0114 of JP-A-2005-7765.
Specific examples of inorganic pigments include white pigments such as titanium dioxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, and barium sulfate, and carbon black, titanium black, and titanium carbon. And black pigments such as iron oxide, titanium oxide, and graphite.
As an organic pigment, the organic pigment of Paragraph 0093 of Unexamined-Japanese-Patent No. 2009-256572 is mentioned, for example.
Specific examples of the organic pigment include C.I. I. Pigment Red 177, 224, 242, 254, 255, 264 and the like, C.I. I. Pigment Yellow 138, 139, 150, 180, 185 and the like, C.I. I. Pigment Orange 36, 38, 71 and other orange pigments, C.I. I. Pigment Green 7, 36, 58 and the like, C.I. I. Pigment Blue 15: 6 and other blue pigments, C.I. I. And purple pigments such as Pigment Violet 23.
These inorganic pigments and organic pigments may be used alone or in combination of two or more. Moreover, you may use together an inorganic pigment and an organic pigment.

The colorant preferably has a primary particle number average particle size of 10 nm to 300 nm, more preferably 30 nm to 270 nm, more preferably 50 nm to 250 nm, from the viewpoint of achieving both deep color and gloss. Further preferred.
When the number average particle diameter of the color material is 10 nm or more, it is easy to reproduce a deep color due to the concealment property derived from the color material. On the other hand, when the number average particle diameter is 300 nm or less, the glossiness is further improved.
The number average particle diameter of the primary particles is obtained by obtaining the diameter (equivalent circle diameter) of 100 particles by setting the diameter (equivalent circle diameter) when the electron micrograph image of the colorant particles is a circle of the same area. It means a value obtained by arithmetic averaging.

The content of the coloring material in the first colored layer is preferably 1% by mass or more and 60% by mass or less, more preferably 5% by mass or more and 55% by mass or less, with respect to the total mass of the first colored layer. % To 50% by mass is more preferable.
When the content of the color material in the first colored layer is 1% by mass or more, it is easy to reproduce a deep color due to the concealability derived from the color material. On the other hand, if the content of the color material in the first colored layer is 60% by mass or less, the glossiness is further improved.

(resin)
The first colored layer contains at least one resin. The resin in the first colored layer functions as a binder for fixing the color material.
It does not restrict | limit especially as resin, A well-known resin can be selected suitably. The resin is preferably a transparent resin from the viewpoint of achieving both deep color and gloss, and specifically, a resin having a total light transmittance of 80% or more is preferable.
The total light transmittance can be measured with a spectrophotometer (for example, UV-2100 manufactured by Shimadzu Corporation).

Examples of the resin include acrylic resin, silicone resin, ester resin, urethane resin, and olefin resin.
Further, the resin may be a compound obtained by polymerizing (curing) a polymerizable compound (monomer) described later to be a polymer. When using a resin obtained by curing a polymerizable compound, the strength of the laminate is improved.
Among these, from the viewpoint of transparency, an acrylic resin, a silicone resin, and an ester resin are preferable, and an acrylic resin and a silicone resin are more preferable. Furthermore, a silicone resin is preferable from the viewpoint of heat resistance.

In this specification, “acrylic resin” refers to a resin including a structural unit derived from an acrylic monomer having a (meth) acryloyl group. The (meth) acryloyl group is a concept including a methacryloyl group and an acryloyl group.
Examples of acrylic resins include acrylic acid homopolymers, methacrylic acid homopolymers, acrylic ester homopolymers, methacrylic ester homopolymers, copolymers of acrylic acid and other monomers, methacrylic acid, A copolymer of an acid and another monomer, a copolymer of an acrylate ester and another monomer, a copolymer of a methacrylic acid ester and another monomer, and the like are included.
Acrylic resins include cyclohexyl methacrylate / methyl methacrylate / methacrylic acid copolymer glycidyl methacrylate adduct, benzyl methacrylate / methacrylic acid random copolymer, allyl methacrylate / methacrylic acid copolymer, and benzyl methacrylate / methacrylic acid / Examples thereof include a copolymer of hydroxyethyl methacrylate.

The silicone resin can be selected from known silicone resins, such as methyl straight silicone resin, methylphenyl straight silicone resin, acrylic resin modified silicone resin, ester resin modified silicone resin, epoxy resin modified silicone resin, alkyd resin modified silicone. Examples thereof include resins and rubber-based silicone resins.
Among them, methyl-based straight silicone resins, methylphenyl-based straight silicone resins, acrylic resin-modified silicone resins, and rubber-based silicone resins are preferable, and methyl-based straight silicone resins, methylphenyl-based straight silicone resins, and rubber-based silicone resins are more preferable. .

  Commercially available products may be used as the silicone resin, and examples of commercially available products include KR-300, KR-311, KR-251, X-40-2406M, and KR-282 from Shin-Etsu Chemical Co., Ltd.

Examples of the ester resin include linear saturated polyesters synthesized from an aromatic dibasic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof.
Specific examples of the linear saturated polyester include polyethylene terephthalate, polyethylene isophthalate, polybutylene terephthalate, poly (1,4-cyclohexylenedimethylene terephthalate), polyethylene-2,6-naphthalate, and the like.

The content of the resin in the first colored layer is preferably 20% by mass to 90% by mass, more preferably 30% by mass to 85% by mass, and more preferably 35% by mass with respect to the total mass of the first colored layer. More preferably, it is 80 mass% or less.
When the content of the resin in the first colored layer is 20% by mass or more, it functions easily as a binder. On the other hand, if the content of the resin in the first colored layer is 90% by mass or less, it is easy to reproduce a deep color and glossiness is further improved.

(Polymerizable compound)
The first colored layer may contain a resin obtained by curing a polymerizable compound, or may contain a polymerizable compound that does not contribute to curing.
There is no restriction | limiting in particular as a polymeric compound, For example, the compound which has an unsaturated group is mentioned. Examples of the unsaturated group include an ethylenically unsaturated group and an epoxy group.
The polymerizable compound is preferably an ethylenically unsaturated bond-containing compound, and more preferably includes a compound having a (meth) acryloyl group.
Examples of the ethylenically unsaturated bond-containing compound include bifunctional polymerizable compounds such as a polymerizable compound described in paragraphs 0023 to 0024 of Japanese Patent No. 4098550 and tricyclodecanediol dimethanol diacrylate.

  Examples of the polymerizable compound include a polymerizable compound having at least five ethylenically unsaturated groups such as DPHA (dipentaerythritol hexaacrylate), dipentaerythritol (penta / hexa) acrylate, and tripentaerythritol octaacrylate; urethane (meta ) Urethane monomers such as acrylate compounds; bifunctional polymerizable compounds such as ethoxylated bisphenol A diacrylate and tricyclodecanediol dimethanol diacrylate can be preferably used.

A polymeric compound may be used individually by 1 type, and may be used in combination of 2 or more type, It is preferable from a viewpoint of a curing sensitivity to use combining 2 or more types.
The polymerizable compound is preferably a combination of a polymerizable compound having at least five ethylenically unsaturated groups and a bifunctional polymerizable compound.

  The average molecular weight of the polymerizable compound is preferably 200 to 3,000, more preferably 250 to 2,600, and particularly preferably 280 to 2,200.

  The content of the polymerizable compound in the first colored layer is preferably 1% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 45% by mass or less, with respect to the total mass of the first colored layer. % To 40% by mass is more preferable.

When a bifunctional polymerizable compound is included as the polymerizable compound, the bifunctional polymerizable compound is preferably included in the range of 10% by mass to 90% by mass with respect to all the polymerizable compounds, and is 20% by mass or more. More preferably, it is contained in the range of 85% by mass or less, and more preferably in the range of 30% by mass or more and 80% by mass or less.
When the polymerizable compound includes a polymerizable compound having at least 5 ethylenically unsaturated groups, the polymerizable compound having at least 5 ethylenically unsaturated groups is 10% by mass or more and 90% by mass with respect to all polymerizable compounds. % Is preferably included in the range of 15% by mass to 80% by mass, and more preferably in the range of 20% by mass to 70% by mass.

(Polymerization initiator)
When the first colored layer contains a resin obtained by curing a polymerizable compound, it is preferable to use a polymerization initiator for curing the polymerizable compound. As the polymerization initiator, a photopolymerization initiator is preferable.
As the photopolymerization initiator, the polymerization initiator described in paragraphs 0031 to 0042 of JP2011-95716A and the oxime polymerization initiator described in paragraphs 0064 to 0081 of JP2015-014783A may be used. it can.

  As the polymerization initiator, for example, 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)] (for example, IRGACURE (registered trademark) OXE-01, manufactured by BASF), Ethan-1-one, [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (0-acetyloxime) (eg IRGACURE® OXE-02, BASF 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (for example, IRGACURE (registered trademark) 379EG, BASF) 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (for example, IRGACURE®) 907, manufactured by BASF), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one (for example, IRGACURE ( (Registered trademark) 127, manufactured by BASF), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (for example, IRGACURE (registered trademark) 369, manufactured by BASF), 2-hydroxy 2-methyl-1-phenyl-propan-1-one (eg IRGACURE® 1173, manufactured by BASF), 1-hydroxy-cyclohexyl-phenyl-ketone (eg IRGACURE® 184, BASF) 2,2-dimethoxy-1,2-diphenylethane-1-one (for example, IRGA) URE (registered trademark) 651, manufactured by BASF), trade names of oxime ester polymerization initiators: Lunar 6 (manufactured by DKSH Japan), 2,4-diethylthioxanthone (for example, Kayacure DETX-S, Nippon Kayaku) Yakuhin Co., Ltd.), DFI-091 and DFI-020 (both manufactured by Daito Chemix Co., Ltd.), which are fluorene oxime polymerization initiators.

  Among them, it is preferable to use an initiator other than a halogen-containing polymerization initiator such as a trichloromethyltriazine compound from the viewpoint of increasing the curing sensitivity, and an α-aminoalkylphenone compound, an α-hydroxyalkylphenone compound, and an oxime ester. An oxime polymerization initiator such as a compound is more preferable.

  As for the usage-amount of a polymerization initiator, it is preferable that mass ratio with respect to a polymeric compound is 0.05-0.125, and it is more preferable that it is 0.070-0.100.

(Other ingredients)
The 1st colored layer may contain the additive other than said component as needed.
Examples of the additives include surfactants described in paragraph 0017 of Japanese Patent No. 4502784, paragraphs 0060 to 0071 of JP-A-2009-237362, and thermal polymerization inhibitors described in paragraph 0018 of Japanese Patent No. 4502784 ( Also referred to as a polymerization inhibitor, preferably phenothiazine), and other additives described in paragraphs 0058 to 0071 of JP-A No. 2000-310706.

~ Thickness of first colored layer ~
The thickness of the first colored layer is preferably 1 μm to 50 μm, more preferably 1 μm to 40 μm, and even more preferably 2 μm to 40 μm.
When the thickness of the first colored layer is 1 μm or more, it is easier to reproduce a deep color. On the other hand, the glossiness is further improved when the thickness of the first colored layer is 50 μm or less.

[Second colored layer]
The second colored layer includes a color material and a resin.
A laminated body has a deep color by having a 2nd colored layer through the below-mentioned bright layer on said 1st colored layer.

(Color material)
The second colored layer includes at least one color material. The color material is not particularly limited, and can be selected from color materials having a desired color. The color material may be a pigment or a dye.
The color material that can be used for the second colored layer is the same as the color material that can be used for the first colored layer, and the same applies to the preferred embodiment.

The content of the coloring material in the second colored layer is preferably 1% by mass or more and 60% by mass or less, more preferably 5% by mass or more and 55% by mass or less, with respect to the total mass of the second colored layer. % To 50% by mass is more preferable.
When the content of the color material in the second colored layer is 1% by mass or more, it is easy to reproduce a deep color due to the concealment property derived from the color material. On the other hand, if the content of the coloring material in the second colored layer is 60% by mass or less, the glossiness is further improved.

(resin)
The second colored layer contains at least one resin. The resin in the second colored layer functions as a binder for fixing the color material.
It does not restrict | limit especially as resin, A well-known resin can be selected suitably. The resin is preferably a transparent resin from the viewpoint of achieving both deep color and gloss, and specifically, a resin having a total light transmittance of 80% or more is preferable.
The total light transmittance can be measured by the method described above.

Examples of the resin include acrylic resin, silicone resin, ester resin, urethane resin, and olefin resin.
Further, the resin may be a compound obtained by polymerizing (curing) a polymerizable compound (monomer) described later to be a polymer. When using a resin obtained by curing a polymerizable compound, the strength of the laminate is improved.
Among these, from the viewpoint of transparency, an acrylic resin, a silicone resin, and an ester resin are preferable, and an acrylic resin and a silicone resin are more preferable. Furthermore, a silicone resin is preferable from the viewpoint of heat resistance.

  Examples of the resin that can be used for the second colored layer include the same resins as those that can be used for the first colored layer, and the same applies to preferred embodiments.

The content of the resin in the second colored layer is preferably 20% by mass or more and 90% by mass or less, more preferably 30% by mass or more and 85% by mass or less, and 35% by mass with respect to the total mass of the second colored layer. More preferably, it is 80 mass% or less.
When the content of the resin of the second colored layer is 20% by mass or more, it functions easily as a binder. On the other hand, when the content of the resin in the second colored layer is 90% by mass or less, it is easy to reproduce a deep color and glossiness is further improved.

(Polymerizable compound, polymerization initiator, other components)
The polymerizable compound, polymerization initiator, and other components that can be used for the second colored layer are the same as the polymerizable compound, polymerization initiator, and other components that can be used for the first colored layer. The same applies to preferred embodiments.

-Thickness of the second colored layer-
The thickness of the second colored layer is preferably 1 μm to 50 μm, more preferably 1 μm to 40 μm, and still more preferably 2 μm to 40 μm.
When the thickness of the second colored layer is 1 μm or more, it is easier to reproduce a deep color. On the other hand, if the thickness of the second colored layer is 50 μm or less, the glossiness is further improved.

[Bright layer]
The laminate has a bright layer, and the bright layer is disposed between the first colored layer and the second colored layer. Since the glitter layer is disposed between the first colored layer and the second colored layer, the laminate is excellent in gloss.
The glitter layer is a layer having light transmittance and light reflectivity, and preferably contains a pigment having a light transmittance and a light reflectivity, and a resin.
“Having light transmissivity and light reflectivity” means that a part of the incident light is transmitted and the other part is reflected. The glitter layer preferably has a total light transmittance of 20% to 85% for incident light and a total light reflectance of 50% to 80% for incident light.
The total light transmittance can be measured by the method described above. The total light reflectance can be measured with a spectrophotometer (for example, V-570 manufactured by JASCO Corporation).

(Pigment having light transmission and light reflection properties)
The glitter layer preferably contains at least one pigment having light transmittance and light reflectivity.

Examples of pigments having optical transparency and light reflectivity include mica, glass, titanium oxide-coated mica (titanium mica), titanium oxide-coated glass, titanium oxide-coated talc, iron oxide-coated mica, pearl pigment, and bismuth pearl. Can be mentioned. In addition, a pigment in which a plurality of titanium oxide coating layers are laminated, a pigment in which a silicon oxide coating layer is laminated on a titanium oxide coating layer, and the like are also included.
Examples of mica pigments include Twinkle Pearl Series, Ultima Series, and Pearl Glaze Series manufactured by Nippon Koken Co., Ltd., MicaBased Series, and FluorologophiteBased Series manufactured by SANDREAM. Examples of the glass pigment include a metashine series manufactured by Nippon Sheet Glass Co., Ltd., and a GlassBased series manufactured by SANDREAM.

The shape of the pigment having light transmittance and light reflectivity is not particularly limited, and may be, for example, a true spherical shape, a flat plate shape, or an elliptical shape. The pigment having light transmittance and light reflectivity is preferably in the form of a flat plate because it is preferable to arrange the particles in parallel in the layer so that high light reflectivity can be obtained.
In the case of a flat plate shape, the size of the major axis is preferably 10 μm or more, more preferably 20 μm or more, and more preferably 50 μm or more in terms of gloss. In addition, the major axis is preferably 500 μm or less from the viewpoint of handling during production such as filtration of the coating solution and layer formation. In order to arrange the particles in parallel in the layer, the major axis is preferably equal to or greater than the thickness of the layer.

The content of the light-transmitting and light-reflecting pigment in the glitter layer is preferably 0.1% by mass or more and 30% by mass or less, and more preferably 1% by mass or more and 20% by mass or less based on the total mass of the glitter layer. It is preferably 2% by mass or more and 15% by mass or less.
When the content of the pigment having light transmittance and light reflectivity of the glitter layer is 0.1% by mass or more, glossiness is further improved. On the other hand, when the content of the pigment having light transmittance and light reflectivity of the glitter layer is 30% by mass or less, glare derived from the glitter layer is suppressed, and a deep color is easily reproduced.

(resin)
The bright layer preferably contains at least one resin.
It does not restrict | limit especially as resin, A well-known resin can be selected suitably. The resin is preferably a transparent resin from the viewpoint of achieving both deep color and gloss, and specifically, a resin having a total light transmittance of 80% or more is preferable.
The total light transmittance can be measured by the method described above.

  The resin content in the glitter layer is preferably 50% by mass or more and 99.5% by mass or less, more preferably 70% by mass or more and 99% by mass or less, and more preferably 80% by mass or more and 98% by mass with respect to the total mass of the glitter layer. The following is more preferable.

Examples of the resin include acrylic resin, silicone resin, ester resin, urethane resin, and olefin resin.
Further, the resin may be a compound obtained by polymerizing (curing) a polymerizable compound (monomer) described later to be a polymer. When using a resin obtained by curing a polymerizable compound, the strength of the laminate is improved.
Among these, from the viewpoint of transparency, an acrylic resin, a silicone resin, and an ester resin are preferable, and an acrylic resin and a silicone resin are more preferable. Furthermore, a silicone resin is preferable from the viewpoint of heat resistance.

  Examples of the resin that can be used for the bright layer include the same resins as those that can be used for the first colored layer, and the same applies to preferred embodiments.

(Polymerizable compound, polymerization initiator, other components)
The bright layer may contain a polymerizable compound, a polymerization initiator, and other components, and these are the same as the polymerizable compound, the polymerization initiator, and other components that can be used for the first colored layer. The same applies to preferred embodiments.

~ Thickness of glitter layer ~
The thickness of the bright layer is preferably 10 μm to 100 μm, more preferably 15 μm to 90 μm, and still more preferably 20 μm to 80 μm.
When the thickness of the glitter layer is 10 μm or more, the glossiness is further improved. On the other hand, when the thickness of the glitter layer is 100 μm or less, a deep color can be reproduced more easily.

[Metal-containing reflective layer]
The laminate includes a metal-containing layer containing a metal that is disposed on a side opposite to the side on which the bright layer of the first colored layer is disposed. The metal-containing reflective layer is a layer that reflects light incident from the second colored layer side of the laminate.
When the laminate has the metal-containing reflective layer, the laminate can realize a deep color and high shielding properties.
The total light reflectance of the metal-containing reflective layer is preferably 60% or more, more preferably 70% or more, and still more preferably 75% or more from the viewpoint of shielding properties.
The total light reflectance can be measured by the method described above.
The metal-containing reflective layer may be a layer containing metal particles and a resin, or may be a metal film itself. When the metal-containing reflective layer includes metal particles, it is more preferable to include a dispersant.

(Metal particles)
Examples of the metal particles that can be included in the metal-containing reflective layer include aluminum metal particles, gold particles, silver particles, and copper particles.
Among these, aluminum metal particles are preferable from the viewpoint of weight reduction of the laminate and cost.
The shape of the metal particles is not particularly limited, and may be, for example, a true spherical shape, a flat plate shape, or an elliptical shape. Since it is preferable that the metal particles are arranged in parallel in the layer so that high light reflectivity can be obtained, the metal particles preferably have a flat plate shape.
In the case of a flat plate shape, the size of the major axis is preferably 10 μm or more, more preferably 20 μm or more, and more preferably 50 μm or more in terms of gloss. In addition, the major axis is preferably 500 μm or less from the viewpoint of handling during production such as filtration of the coating solution and layer formation. In order to arrange the particles in parallel in the layer, the major axis is preferably equal to or greater than the thickness of the layer.

  Examples of the aluminum metal particles include GX series, BS series, MH series of Asahi Kasei Chemicals Corporation, Alpaste series of Toyo Aluminum Co., Ltd., and DECOMET series.

The content of metal particles in the metal-containing reflective layer is preferably 1% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 40% by mass or less, and more preferably 10% by mass or more with respect to the total mass of the metal-containing reflective layer. 30 mass% or less is more preferable.
When the content of the metal particles in the metal-containing reflective layer is 1% by mass or more, the shielding property is further improved. On the other hand, when the content of the metal particles in the metal-containing reflective layer is 50% by mass or less, the laminate can be reduced in weight.

(Dispersant)
When the metal-containing reflective layer contains metal particles, the metal-containing reflective layer preferably contains at least one dispersant.
By including the dispersant, the dispersibility of the metal particles in the metal-containing reflective layer is improved, and the laminate is more likely to realize a deep color, and the shielding property is further improved.

  Examples of the dispersant include silicone polymers, acrylic polymers, and polyester polymers. From the viewpoint of heat resistance of the laminate, a silicone polymer (for example, a graft type silicone polymer) is preferable.

-Graft type silicone polymer-
Although it does not specifically limit as a graft type silicone polymer, It is preferable that it is a graft type silicone polymer represented by following formula (1). The graft type silicone polymer represented by the following formula (1) may be a random copolymer or a block copolymer.

In Formula (1), R ^{1 to} R ¹⁰ each independently represent a hydrogen atom, a hydroxy group, an aryl group, or an alkyl group having 1 to 3 carbon atoms, and R ¹¹ and R ¹² are each independently arylene. A group or an alkylene group having 1 to 3 carbon atoms, R ¹³ and R ¹⁴ each independently represent a single bond or a divalent organic linking group, A represents a group having a particle adsorption site, and B Represents a group having a structure represented by the following formula (2), l and n each independently represents an integer of 1 or more, and m represents an integer of 0 or more.

In formula (1), R ^{1 to} R ¹⁰ are each independently preferably an aryl group or an alkyl group having 1 to 3 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms. .
Examples of the aryl group represented by R ^{1 to} R ¹⁰ include an unsubstituted phenyl group and a substituted phenyl group.
Examples of the alkyl group having 1 to 3 carbon atoms represented by R ^{1 to} R ¹⁰ include a methyl group, an ethyl group, an n-propyl group, and an i-propyl group. As an alkyl group having 1 to 3 carbon atoms, a methyl group and an ethyl group are preferable, and a methyl group is more preferable.
R ^{1 to} R ¹⁰ may have a further substituent. For example, when the ends of R ^{1 to} R ¹⁰ are a hydroxy group, a group having a hydroxy group via any alkyl group (alkoxy group) It may be. However, it is preferable that R < ¹ > -R < ¹⁰ > does not have a further substituent.

In formula (1), l represents an integer of 1 or more, preferably 1 to 100, more preferably 1 to 60, and particularly preferably 1 to 30.
In the formula (1), when l is 2 or more, l R ⁴ and R ⁵ may be the same or different from each other.

In formula (1), m represents an integer of 0 or more, and is preferably an integer of 1 or more from the viewpoint of enhancing the dispersibility of the metal particles, more preferably 1 to 60, and 1 to 30. Is particularly preferred.
In the formula (1), when m is 2 or more, the m R ^{6 s} may be the same as or different from each other.

In formula (1), n represents an integer of 1 or more, preferably 1 to 100, more preferably 1 to 60, and particularly preferably 1 to 30.
In the formula (1), when n is 2 or more, the n R ^{7 s} may be the same as or different from each other.

  The ratio of the content of each partial structure in the graft type silicone polymer represented by the formula (1) is not particularly limited. That is, in the formula (1), the ratio of l, m, and n is not particularly limited.

In formula (1), R ¹¹ and R ¹² are preferably alkylene groups having 1 to 3 carbon atoms.
Examples of the arylene group represented by R ¹¹ and R ¹² include an unsubstituted phenylene group and a substituted phenylene group.
Examples of the alkylene group having 1 to 3 carbon atoms represented by R ¹¹ and R ¹² include a methylene group, an ethylene group, a propylene group, and a trimethylene group.
When m is 2 or more, m R ^{11 s} may be the same as or different from each other. When n is 2 or more, n R ^{12 s} may be the same as or different from each other.

In Formula (1), when m is 2 or more, m R ^{13 s} may be the same as or different from each other.
In the formula (1), when n is 2 or more, the n R ^{14 s} may be the same or different.
Examples of the divalent organic linking group represented by R ¹³ or R ¹⁴ include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, and 1 to 200 hydrogen atoms. A group formed from an atom and 0 to 20 sulfur atoms is included, which may be unsubstituted or may further have a substituent.

Specific examples of the divalent organic linking group represented by R ¹³ or R ¹⁴ include structural units selected from the following structural unit group G or groups formed by combining these structural units.

R ¹³ or R ¹⁴ may be a single bond, or 1 to 50 carbon atoms, 0 to 8 nitrogen atoms, 0 to 25 oxygen atoms, 1 to 100 hydrogen atoms, and 0 Preferred is a divalent organic linking group formed from 10 to 10 sulfur atoms, a single bond, or 1 to 30 carbon atoms, 0 to 6 nitrogen atoms, 0 to 15 oxygen atoms. More preferred is a divalent organic linking group formed from 1 to 50 hydrogen atoms and 0 to 7 sulfur atoms, a single bond, or 1 to 10 carbon atoms, 0 to 5 Divalent organic linking groups formed from 1 nitrogen atom, 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms are particularly preferred.

R ¹³ or R ¹⁴ is a single bond, a structural unit selected from the structural unit group G, or a combination of these structural units, “1 to 10 carbon atoms, 0 to 5 A divalent organic linking group (having a substituent) formed from a nitrogen atom, 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms. As this substituent, for example, an alkyl group having 1 to 20 carbon atoms such as a methyl group or an ethyl group, an aryl group having 6 to 16 carbon atoms such as a phenyl group or a naphthyl group, a hydroxyl group, an amino group, C1-C6 acyloxy groups such as carboxyl group, sulfonamide group, N-sulfonylamide group, acetoxy group, etc., C1-C6 alkoxy groups such as methoxy group, ethoxy group, and halogens such as chlorine and bromine Atom, methoxycarbo Group, an ethoxycarbonyl group, an alkoxycarbonyl group having 2 to 7 carbon atoms such as cyclohexyl oxycarbonyl group, a cyano group, it is preferred that a carbonate ester group such as t- butyl carbonate and the like).
R ¹³ is preferably a divalent organic linking group represented by — (CH ₂ ) —CH (R ^13A ) —. R ^13A represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ^13A is preferably a hydrogen atom or a methyl group. R ^13A may further have a substituent, and when it has a substituent, it preferably has a carboxy group.
R ¹⁴ is preferably a divalent organic linking group represented by — (CH ₂ ) —CH (R ^14A ) —C (═O) —O— (C _p H _2p ) —. R ^14A represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and p represents an integer of 0 or more. It is preferably a hydrogen atom or a methyl group. R ^14A may further have a substituent. p is preferably an integer of 1 or more.

In formula (1), A represents a particle adsorption site.
When m is 2 or more, the m A's may be the same or different.

  A may have one particle adsorption site or may have a plurality of particle adsorption sites. When A has a plurality of particle adsorption sites, they may be the same or different.

  A is, for example, a particle adsorption site, 1 to 200 carbon atoms, 0 to 20 nitrogen atoms, 0 to 100 oxygen atoms, 1 to 400 hydrogen atoms, and 0 to It is preferably a monovalent organic group formed by bonding an organic linking group composed of 40 sulfur atoms. When the particle adsorption site itself can constitute a monovalent organic group, the particle adsorption site itself may be an organic group represented by A.

  Particle adsorption sites include acidic groups, basic nitrogen atom groups, urea groups, urethane groups, coordinating oxygen atom groups, hydrocarbon groups having 4 or more carbon atoms, heterocyclic residues, amide groups, alkoxy groups It is preferable to include at least one portion selected from a silyl group, an epoxy group, an isocyanate group, a hydroxy group, and a thiol group, and an acidic group, a group having a basic nitrogen atom, a urea group, and a coordinating oxygen atom It is more preferable to include at least one site selected from a group having a heterocyclic residue, an amide group, an alkoxysilyl group, a hydroxy group, and a thiol group, and at least 1 site selected from an acidic group and an alkoxysilyl group. More preferably, it contains a carboxylic acid group, a phosphoric acid group and a trimethoxysilyl group.

  Examples of the acidic group represented by the particle adsorption site include a carboxylic acid group, a sulfonic acid group, a monosulfate group, a phosphoric acid group (such as a phosphono group), a phosphonooxy group, a monophosphate group, and a boric acid group. Among these, a carboxylic acid group, a sulfonic acid group, a monosulfate group, a phosphoric acid group, a phosphonooxy group, and a monophosphate group are more preferable, and a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group are particularly preferable.

Examples of the group having a basic nitrogen atom represented by the particle adsorption site include an amino group (—NH ₂ ), a substituted imino group (—NHR ¹⁰⁸ , —NR ¹⁰⁹ R ¹¹⁰ , where R ¹⁰⁸ , R ¹⁰⁹ , and R ¹¹⁰ each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms), a guanidyl group, or an amidinyl group.

As the urea group represented by the particle adsorption site, for example, —NR ¹¹⁵ CONR ¹¹⁶ R ¹¹⁷ (R ¹¹⁵ , R ¹¹⁶ , and R ¹¹⁷ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a carbon atom. An aryl group having a number of 6 or more, or an aralkyl group having 7 or more carbon atoms). Among them, —NR ¹¹⁵ CONHR ¹¹⁷ (R ¹¹⁵ and R ¹¹⁷ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms. -NHCONHR ¹¹⁷ (R ¹¹⁷ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms) is particularly preferable. preferable.

Examples of the urethane group represented by the particle adsorption site include -NHCOOR ¹¹⁸ , -NR ¹¹⁹ COOR ¹²⁰ , -OCONHR ¹²¹ , -OCONR ¹²² R ¹²³ (R ¹¹⁸ , R ¹¹⁹ , R ¹²⁰ , R ¹²¹ , R ^122, and R ¹²³ are And each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms). Among them, —NHCOOR ¹¹⁸ , —OCONHR ¹²¹ (wherein R ¹¹⁸ and R ¹²¹ are each independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl having 7 or more carbon atoms). more preferably a represents) ^{group, -NHCOOR 118, -OCONHR 121 (R} 118, R 121 are each independently an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 or more carbon atoms, or a number of carbon atoms Represents an aralkyl group of 7 or more).

  Examples of the group having a coordinating oxygen atom represented by the particle adsorption site include an acetylacetonate group and a crown ether.

  Examples of the hydrocarbon group having 4 or more carbon atoms represented by the particle adsorption site include an alkyl group having 4 or more carbon atoms, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms. Among them, an alkyl group having 4 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms are more preferable, and an alkyl group having 4 to 15 carbon atoms (for example, an octyl group and a dodecyl group). ), An aryl group having 6 to 15 carbon atoms (for example, phenyl group, naphthyl group) and an aralkyl group having 7 to 15 carbon atoms (for example, benzyl group) are particularly preferable.

  Examples of the heterocyclic residue represented by the particle adsorption site include thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadiazole, triazole, thiadiazole, pyran, Pyridine, piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolinone, benzimidazolone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridone And anthraquinone.

As the amide group represented by the particle adsorption site, for example, —CONHR ¹²⁴ (R ¹²⁴ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms). Is mentioned.

  Examples of the alkoxysilyl group represented by the particle adsorption site include a trimethoxysilyl group and a triethoxysilyl group.

  Examples of other possible modes of the organic group having a particle adsorption site include the organic groups described in paragraphs 0016 to 0046 of JP2013-43962A.

  In formula (1), B has a structure represented by the following formula (2).

In Formula (2), R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, a hydroxy group, an aryl group, or an alkyl group having 1 to 3 carbon atoms, and k represents an integer of 1 or more.

Examples of the aryl group represented by R ¹⁵ and R ¹⁶ include an unsubstituted phenyl group and a substituted phenyl group.
Examples of the alkyl group having 1 to 3 carbon atoms represented by R ¹⁵ and R ¹⁶ include a methyl group, an ethyl group, an n-propyl group, and an i-propyl group.
R ¹⁵ and R ¹⁶ are each independently preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
k represents an integer of 1 or more, preferably 2 to 300, and more preferably 10 to 200.

The structure represented by the formula (2) is preferably a structure derived from a silicone monomer. B may be a structure derived from a silicone monomer, or a combination of B and R ¹⁴ may be a structure derived from a silicone monomer.

The silicone monomer may be a silicone macromer.
A “macromer” (also referred to as a macromonomer) is a general term for an oligomer having a polymerizable functional group (degree of polymerization of about 2 or more and about 300 or less) or a polymer, and has both properties of a polymer and a monomer (monomer). Is. The structure represented by the above formula (2) has a weight average molecular weight of 1,000 to 50,000 (more preferably 1,000 to 10,000, and still more preferably 1,000 to 5,000). A structure derived from a certain silicone-based macromer is preferable.
The weight average molecular weight can be measured, for example, by gel permeation chromatography (GPC).
Specifically, it can be measured under the following conditions.
Column: GPC column TSKgelSuper HZM-H (manufactured by Tosoh Corporation)
・ Solvent: Tetrahydrofuran ・ Standard: Monodisperse polystyrene

  Furthermore, the polymer is preferably soluble in an organic solvent. When the affinity with the organic solvent is high, for example, when used as a dispersant, the affinity with the dispersion medium is increased, and it is easy to ensure a metal-containing reflective layer sufficient for stabilizing the dispersion.

  Examples of the group having the structure represented by the formula (2) include X-22-174ASX, X-22-174BX, KF-2012, X-22-173BXX-22-3710 manufactured by Shin-Etsu Chemical Co., Ltd. And the like groups derived from.

The graft type silicone polymer represented by the formula (1) may have other repeating units other than l, m, n, and k repeating units, but may not have other repeating units. preferable.
As another repeating unit, for example, the graft type silicone polymer represented by the formula (1) may have a repeating unit having a (unreacted) thiol group represented by the following formula (3). .

In Formula (3), R ^J6 represents a hydrogen atom, a hydroxy group, an aryl group, or an alkyl group having 1 to 3 carbon atoms, R ^J11 represents an arylene group or an alkylene group having 1 to 3 carbon atoms, j Represents an integer of 0 or more.
Examples of the aryl group represented by R ^J6 include an unsubstituted phenyl group and a substituted phenyl group.
^Examples of the alkyl group having 1 to 3 carbon atoms represented by R ^J6 include a methyl group, an ethyl group, an n-propyl group, and an i-propyl group.
Examples of the arylene group represented by R ^J11 include an unsubstituted phenylene group and a substituted phenylene group.
^Examples of the alkylene group having 1 to 3 carbon atoms represented by R ^J11 include a methylene group, an ethylene group, a propylene group, and a trimethylene group.
When j is 2 or more, j R ^J6 may be the same as or different from each other. When j is 2 or more, j R ^J11 may be the same as or different from each other.

The preferred ranges of R ^J6 and R ^J11 are the same as the preferred ranges of R ⁶ and R ¹¹ .
j is preferably 0.
Examples of the polymer containing a repeating unit having a thiol group represented by the formula (3) include KF-2001 and KF-2004 manufactured by Shin-Etsu Chemical Co., Ltd.

  Among the graft type silicone polymers represented by the formula (1), the dispersant is more preferably a graft type silicone polymer represented by the following formula (4).

In formula (4), R ¹¹ and R ¹² each independently represent an arylene group or an alkylene group having 1 to 3 carbon atoms, and R ¹³ and R ¹⁴ each independently represent a single bond or a divalent organic group. Represents a linking group, and A ¹ represents an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, a heterocyclic residue, A group having a particle adsorption site containing at least one site selected from an amide group, an alkoxysilyl group, an epoxy group, an isocyanate group, a hydroxy group and a thiol group, and B is represented by the above formula (2) Represents a group having a structure, and l, m1 and n each independently represents an integer of 1 or more.

The definitions and preferred ranges of R ^{11 to} R ¹⁴ , B, l and n in formula (4) are the same as the definitions and preferred ranges of R ^{11 to} R ¹⁴ , B, l and n in formula (1), respectively. is there.
The preferred ranges of A ¹ and m1 in formula (4) are the same as the preferred ranges of A and m in formula (1), respectively.

~ Method for producing dispersant ~
There is no restriction | limiting in particular as a manufacturing method of the above-mentioned dispersing agent.
For example, it can be synthesized by a combination of the following compound A which is a mercapto-modified silicone, compound B which is a silicone macromonomer, and compound C which is a macromonomer having a particle adsorption site.
In the following scheme 1, an example using the compound B and the compound C, which are macromonomers (specifically, radically polymerizable monomers, more specifically, (meth) acrylic monomers) is shown. The manufacturing method is not limited to such a manufacturing method.
Compound A, Compound B, in compounds C and Scheme ^{1, R 1 ~R 12, l} , m and n are the same ^R 1 ^~R 12, l in the formula (1), m, and n, p is 0 more integers, k is an integer of 1 or more, R ^B is an optional substituent, R represents a methyl group, X represents a carboxy group, V-601 is an example of a polymerization initiator Dimethyl-2,2′-azobis (2-methylpropionate).

Scheme 1

  For the manufacturing method of the dispersant, the description in paragraphs 0110 to 0134 of JP2013-43962A may be referred to.

(Weight average molecular weight of dispersant)
The weight average molecular weight of the dispersant is preferably 1,000 to 5,000,000, more preferably 2,000 to 3,000,000, and 2,500 to 3,000,000. It is particularly preferred. When the weight average molecular weight is 1,000 or more, the dispersibility of the metal particles is further improved.
The weight average molecular weight can be measured by the method described above.

(Metal film)
When the metal-containing reflective layer is a metal film, the metal film may be a metal or alloy such as silver, gold, aluminum, copper, palladium, platinum, tin, indium, zinc, titanium, cadmium, iron, cobalt, chromium, nickel, etc. And the like.

-Formation of metal-containing reflective layer-
The method for forming the metal-containing reflective layer is not particularly limited and may be appropriately selected depending on the purpose. For example, a dispersion liquid for forming a metal-containing reflective layer is formed on the first colored layer by using a dip coater or a die coater. Examples thereof include a method of coating by a coater, slit coater, bar coater, gravure coater, etc., a method of forming by a method such as an LB film (Langmuir-Blodgett film) method, a self-organization method, and a spray coating method.
When the metal-containing reflective layer is a metal film, use it from a wet method such as a coating method, a physical method such as a vacuum deposition method, a sputtering method or an ion plating method, or a chemical method such as CVD or plasma CVD method. The film can be formed according to a method appropriately selected in consideration of suitability with the material to be used.

[Layer structure of laminate]
The layer structure of the laminate will be described with reference to FIG. FIG. 1 is a schematic cross-sectional view showing the layer structure of a laminate. The laminate 10 includes a metal-containing reflective layer 11, a first colored layer 12, a bright layer 13, and a second colored layer 14 in this order.

From the viewpoint of shielding properties, the laminate preferably has an optical density of 3.5 to 6.0, more preferably 4.0 to 5.5, and 4.5 to 5.0. It is particularly preferred.
The optical density can be measured using a transmission densitometer (for example, BMT-1 manufactured by Sakata Inx Corporation).

  The thickness of the entire laminate is preferably 20 μm or more and 500 μm or less, and more preferably 50 μm or more and 400 μm or less.

<Decorative film>
In the decorative film, the above-described laminate of the present invention is disposed on a base film. As for the decorative film, the 2nd colored layer and base material film of a laminated body are arrange | positioned facing.
Since the laminated body of this invention is arrange | positioned at the decorating film, deep color and glossiness can be made compatible.

[Base film]
As the base film, various materials can be used, but it is more preferable to use a film having no optical distortion or a film having high transparency.
The base film preferably has a total light transmittance of 80% or more.
The total light transmittance can be measured by the method described above.

  Examples of the base film include a polyethylene terephthalate (PET) film, a polyethylene naphthalate film, an acrylic film, a polycarbonate (PC) film, a triacetyl cellulose (TAC) film, and a cycloolefin polymer (COP) film.

  From the viewpoint of transparency, the base film is preferably a PET film, an acrylic film, or a PC film, and more preferably an acrylic film.

  Various functions may be added to the surface of the base film. Specific examples include a scratch-resistant layer, a self-healing layer, an antistatic layer, an antifouling layer, an anti-electromagnetic wave layer, and a conductive layer.

  The thickness of the base film is preferably 35 μm to 300 μm, more preferably 50 μm to 250 μm.

[Layer structure of decorative film]
The layer structure of the decorative film will be described with reference to FIG. FIG. 2 is a schematic cross-sectional view showing the layer structure of the decorative film. The decorative film 20 has the laminated body 10 and the base film 21 in this order. In the laminate 10, a metal-containing reflective layer 11, a first colored layer 12, a bright layer 13, and a second colored layer 14 are laminated in this order.

The decorative film preferably has an optical density of 2.5 to 6.0, and more preferably 3.0 to 5.5, from the viewpoint of shielding properties.
The optical density can be measured by the method described above.

  The thickness of the whole decorative film is preferably 50 μm or more and 600 μm or less, and more preferably 100 μm or more and 500 μm or less.

<Method for producing decorative film>
The method for producing a decorative film includes a second colored layer forming step of forming a second colored layer by applying a second colored layer coating solution on the base film, and a second colored layer. A bright layer forming step of applying a bright layer coating solution to form a bright layer, and a first colored layer forming step of applying a first colored layer coating solution on the bright layer to form a first colored layer And a metal-containing reflective layer forming step of forming a metal-containing reflective layer on the first colored layer.
The method for forming the metal-containing reflective layer in the metal-containing reflective layer forming step in the method for producing a decorative film is as described above.

  As a method of applying a coating solution for forming each layer, a known method can be applied, and coating is performed by a dip coater, a die coater (for example, an extrusion coater), a slit coater, a bar coater, a gravure coater, or the like. A method is mentioned.

  The coating liquid prepared for forming each layer can be prepared by mixing a solvent, a surfactant, and the like in addition to the components contained in each layer.

As the solvent that can be contained in the coating solution, a commonly used solvent can be used without particular limitation. Specific examples include solvents such as esters, ethers, ketones, and aromatic hydrocarbons.
Further, the same methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, cyclohexanol, methyl isobutyl ketone, ethyl lactate and lactic acid as described in paragraphs 0054 and 0055 of US Patent Publication No. 2005 / 282073A1 Methyl and the like can also be suitably used in the present invention.
Among them, 1-methoxy-2-propyl acetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, diethylene glycol mono Ethyl ether acetate (ethyl carbitol acetate), diethylene glycol monobutyl ether acetate (butyl carbitol acetate), propylene glycol methyl ether acetate, methyl ethyl ketone and the like are preferably used as the solvent in the present invention. These solvents may be used alone or in combination of two or more.

  When a polymerizable compound and a polymerization initiator are included as components of each layer, the formation of each layer in the production of the decorative film may be performed by providing an exposure step. The intensity | strength of a laminated body improves more by hardening a polymeric compound by an exposure process.

For the exposure step, for example, the method described in paragraphs 0035 to 0051 of JP-A-2006-23696 can be suitably used in the present invention.
In the exposure step, when a polymerizable compound and a polymerization initiator are contained in the first colored layer, the second colored layer, the bright layer, and the metal-containing reflective layer, after applying a coating solution for forming each layer It is the process of hardening the polymeric compound contained in each coating liquid to expose.

As a light source for exposure, any light source capable of irradiating light in a wavelength region capable of curing the above-described polymerizable compound (for example, 365 nm, 405 nm) can be appropriately selected and used. Specifically, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, etc. are mentioned.
Energy of exposure generally ^5mJ / cm ^{2 ~200mJ} / cm 2 or so, preferably 10mK ^/ cm ² ~100mJ ^/ cm 2 approximately.

<Decorated molded body>
The resin molded body in the decorative molded body is preferably arranged to face the surface of the decorative film on the metal-containing reflective layer side. The decorative film and the resin molded body may be in direct contact with each other and may be interposed with an adhesive layer.
In addition, the decorative molded body is an aspect in which the base film of the decorative film is peeled off after preparing the decorative molded body including the decorative film, that is, the laminate of the present invention, the resin molded body, The aspect provided with may be sufficient.
Since the decorative molded body includes the decorative film or laminate of the present invention, it is possible to achieve both a deep color and gloss.

(Resin molding)
Examples of the resin molding include moldings obtained by molding acrylic resin, silicone resin, ester resin, urethane resin, olefin resin, and the like.

(Adhesive layer)
In the decorative molded body, an adhesive layer may be provided between the decorative film and the resin molded body.
As an adhesive for forming the adhesive layer, a known adhesive can be appropriately selected. Specifically, for example, an adhesive containing a vinyl chloride / vinyl acetate copolymer and an acrylic resin can be used.
A commercially available product may be used as the adhesive, and examples of the commercially available product include IMB-003 manufactured by Teikoku Ink.

<Method for producing decorative molded body>
The manufacturing method of a decorative molded body includes the process of adhering the resin molded body to the decorative film of the present invention.
Moreover, the manufacturing method of a decorating molded object may have the process of peeling the base film of a decorating film further as processes other than the process of fixing a resin molding to the decorating film of this invention.
Below, the manufacturing method of a decoration molded object is demonstrated concretely. Here, a case where the decorative film and the resin molded body are fixed by insert molding will be described as an example.
In the following, a decorative film formed in a rectangular shape with a certain size is placed in a mold for injection molding to close the mold, and then the molten resin is injected into the mold to solidify the injection resin. The process which manufactures the decoration molded body which the decorating film adhere | attached on the surface by taking out where it did will be demonstrated.
Since the decorative film is formed into a three-dimensional shape by the above-described process, a three-dimensional decorative molded body to which the deep color and glossiness of the decorative film are imparted is produced.

  A mold for injection molding (molding mold) used for manufacturing a decorative molded body includes a mold having a convex shape (male mold) and a mold having a concave shape corresponding to the convex shape (female mold). The mold is closed after the decorative film is arranged on the molding surface which is the inner peripheral surface of the female mold.

Here, before arranging the decorative film in the molding die, the decorative film is molded (pre-formed) using the molding die, and the decorative film is preliminarily formed into a three-dimensional shape. It is also possible to supply to a molding die.
Moreover, when arrange | positioning a decoration film in a shaping die, the alignment of a decoration film and a shaping die is needed in the state which inserted the decoration film in the shaping die.

With the decorative film inserted into the molding die, as a method of aligning the decorative film and the molding die, insert and hold the fixing pin of the male mold into the alignment hole of the female mold There is a way to do it.
Here, the alignment hole is formed in advance in the female mold at the end of the decorative film (a position where a three-dimensional shape is not imparted after molding).

Further, the fixing pin is formed in advance in a position where the male pin is fitted to the alignment hole.
In addition to the method of inserting the fixing pin into the alignment hole, the following method can be used as a method of aligning the decorative film and the molding die with the decorative film inserted into the molding die. It is possible to use.

  For example, there is a method of finely adjusting the alignment film by driving on the conveying device side of the decorative film as a target to a position alignment mark provided in advance at a position where a three-dimensional shape is not imparted after molding in the decorative film. In the case of this method, it is preferable to recognize the alignment mark at two or more diagonal points as viewed from the product portion of the injection molded product (decorative molded product).

  After positioning the decorative film and the molding die and closing the molding die, the molten resin is injected into the molding die into which the decorative film is inserted. At this time, molten resin is inject | emitted to the metal-containing reflective layer side (the adhesive layer side when the adhesive layer is provided) of the decorative film.

  The temperature of the molten resin injected into the molding die is set according to the physical properties of the resin used. For example, if the resin used is an acrylic resin, the temperature of the molten resin is preferably in the range of 240 ° C. or higher and 260 ° C. or lower.

The position of the injection port (injection port) of the male mold is adjusted so that the decorative film does not deform abnormally due to heat or gas generated when the molten resin is injected into the molding mold. You may set according to a shape and the kind of molten resin.
After the molten resin injected into the molding die into which the decorative film is inserted is solidified, the molding die is opened and an intermediate decorative molded body made of the solidified molten resin and the decorative film is formed from the molding die. Take out.

In the intermediate decorative molded body, a burr and a dummy portion of the decorative molded body are integrated around a decorative portion that finally becomes a product (decorated molded body). Here, the dummy portion has an insertion hole formed by inserting the fixing pin in the above-described alignment.
And a decoration molded object is manufactured by removing said burr | flash and a dummy part from a decoration part.
The obtained decorative molded body may be a decorative molded body provided with a laminate and a resin molded body by peeling the base film of the decorative film as necessary.

  The present invention will be described more specifically with reference to the following examples. The scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, “part” is based on mass.

<Preparation of coating liquid for decorative film>
[Preparation of coating solution for colored layer]
Each colored layer coating solution described in Table 1 below was prepared to have the composition shown in Table 1. The numerical value in Table 1 shows the mass part of each component with respect to the total mass of each coating liquid, and "-" shows that the said component is not contained.

The detail of each component described in Table 1 is as follows.
-Red pigment dispersion 1: prepared by the following method-Red pigment dispersion 2: prepared by the following method-Blue pigment dispersion: prepared by the following method-Black pigment dispersion: prepared by the following method-Acrylic resin: The following structure / silicone resin 1: xylene solution of silicone resin (solid content 50% by mass), manufactured by Shin-Etsu Chemical Co., Ltd., KR-300
Silicone resin 2: Silicone resin xylene solution (solid content 60% by mass), Shin-Etsu Chemical Co., Ltd., KR-311
Monomer 1: Tricyclodecane dimethanol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd., A-DCP
Monomer 2: urethane acrylate, manufactured by Taisei Fine Chemical Co., Ltd., 8UX-015A
Monomer 3: Carboxylic acid-containing monomer, manufactured by Toagosei Co., Ltd., Aronix (registered trademark) TO-2349
Polymerization initiator 1: Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime), manufactured by BASF, OXE-02
Polymerization initiator 2: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, manufactured by BASF, IRGACURE (registered trademark) 907
Surfactant: Methyl isobutyl ketone solution (solid content 30% by mass) of a perfluoroalkyl group-containing phosphate ester type amine neutralized product, manufactured by DIC Corporation, MegaFac (registered trademark) F-551
・ MEK: Methyl ethyl ketone

(Preparation of red pigment dispersion 1)
-Preparation of red color material composition 1-
Commercially available C.I. I. 100 parts of Pigment Red 254 (red pigment), 400 parts of sodium chloride, and 140 parts of diethylene glycol as a solvent were charged into a table kneader (manufactured by Irie Shokai Co., Ltd.) and kneaded for 10 hours. Next, the obtained kneaded product was stirred and mixed with water using a dissolver (manufactured by Nippon Seiki Seisakusho), and then filtered and washed repeatedly to remove sodium chloride and the solvent to obtain a red pigment water cake. The obtained water cake was dried in an oven at 80 ° C. for 6 hours to obtain a red color material composition 1.

-Coarse dispersion-
Using the red color material composition 1 obtained above, each component having the following composition was mixed to obtain a mixture, and the mixture was then combined with Eiger Mill (registered trademark) (manufactured by Eiger Japan Co., Ltd.) and a diameter of 0. A coarse dispersion was obtained by dispersing using .8 mm zirconia beads.

-Composition-
-Red color material composition: 100 parts-Dispersing aid: 10 parts (manufactured by Nippon Lubrizol Co., Ltd., SOLPERSE (registered trademark) 22000)
・ Dispersant: 40 parts (manufactured by Nippon Lubrizol Co., Ltd., SOLPERSE (registered trademark) 24000)
Propylene glycol monomethyl ether acetate: 150 parts

-Precision dispersion-
The coarse dispersion after the coarse dispersion was taken out, and 75 parts of propylene glycol monomethyl ether acetate was added to and mixed with 300 parts of the coarse dispersion. Then, it disperse | distributed using the Eiger mill (trademark) (made by Eiger Japan Co., Ltd.) and the zirconia bead of diameter 0.1mm, and obtained the precision dispersion.

-Density adjustment-
The fine dispersion after the fine dispersion was taken out, diluted with propylene glycol monomethyl ether acetate so that the pigment concentration was 20% by mass, and red pigment dispersion 1 was obtained.
C. in red pigment dispersion 1 I. The number average particle size of Pigment Red 254 was 60 nm.
For the number average particle diameter, the diameter (equivalent circle diameter) when the electron micrograph image of the pigment particle is made into a circle of the same area is obtained for 100 particles, and the equivalent circle diameter of 100 particles is arithmetically averaged. I asked for it.
The number average particle diameter of pigments in other pigment dispersions described below was also measured in the same manner.

(Preparation of red pigment dispersion 2)
In the preparation of the red color material composition 1, C.I. I. 100 parts of Pigment Red 254 (red pigment) I. A red pigment dispersion 2 was prepared in the same manner except that it was changed to 100 parts of Pigment Red 177 (red pigment, number average particle size: 100 nm).

(Preparation of blue pigment dispersion)
In the preparation of the red color material composition 1, C.I. I. 100 parts of Pigment Red 254 (red pigment) I. A blue pigment dispersion was prepared in the same manner except that it was changed to 100 parts of Pigment Blue 15: 6 (blue pigment, number average particle size: 75 nm).

(Preparation of black pigment dispersion)
After mixing each component so that it may become the following composition, a mixture is obtained, it disperse | distributes for 3 hours with a bead mill using the zirconia bead of diameter 0.5mm, and a black pigment dispersion (number average particle diameter: 210 nm).

-Composition-
・ Carbon black: 15.0 parts (Mitsubishi Chemical Corporation)
-Acrylic polymer dispersant: 15.0 parts (BASF Japan, EFKA 4300)
Propylene glycol monomethyl ether acetate: 30.0 parts

[Preparation of brightening layer coating solution]
Each bright layer coating solution described in Table 2 below was prepared to have the composition shown in Table 2. The numerical value in Table 2 shows the mass part of each component with respect to the total mass of each coating liquid, and "-" shows that the said component is not contained.

The details of each component described in Table 2 are as follows. The acrylic resin, silicone resin 1, silicone resin 2, surfactant, and MEK are as described above.
・ Pearl pigment (titanium oxide coated mica, Nippon Koken Kogyo Co., Ltd., Twinkle Pearl SX)

[Preparation of coating solution for metal-containing reflective layer]
Each coating solution for a metal-containing reflective layer described in Table 3 below was prepared to have the composition shown in Table 3. The numerical value in Table 3 shows the mass part of each component with respect to the total mass of each coating liquid, and "-" shows that the said component is not contained.
In Table 3, coating solution 8 to coating solution 10 are coating solutions for metal-containing reflective layers, and coating solution 11 to coating solution 13 are comparative coating solutions.

The details of each component described in Table 3 are as follows. The black pigment dispersion, acrylic resin, silicone resin 1, silicone resin 2, monomer 1, monomer 2, monomer 3, polymerization initiator 1, polymerization initiator 2, surfactant, and MEK are as described above. is there.
Silver pigment dispersion liquid 1: prepared by the following method Silver pigment dispersion liquid 2: prepared by the following method White pigment dispersion liquid: Sanyo Dye Co., Ltd., FP White B422, composition (white pigment (titanium oxide): 70.0% by mass, dispersion aid: 3.5% by mass, dispersion solvent (methyl ethyl ketone): 26.5% by mass)
Silicone resin 3: Silicone resin toluene solution (solid content 20% by mass), manufactured by Shin-Etsu Chemical Co., Ltd., KR-251
Silicone resin 4: Silicone oligomer (solid content: 100% by mass), manufactured by Shin-Etsu Chemical Co., Ltd., X-40-9246
Condensation catalyst: xylene solution of zinc-containing catalyst (solid content 25% by mass), manufactured by Shin-Etsu Chemical Co., Ltd., D-15

(Preparation of silver pigment dispersion 1)
After mixing each component so that it might become the following composition, the mixture was obtained and it disperse | distributed with the bead mill for 8 hours using the zirconia bead of diameter 0.5mm, and the silver pigment dispersion liquid 1 was obtained.

-Composition-
Aluminum paste: 20.0 parts (aluminum metal particles, manufactured by Asahi Kasei Chemicals Corporation, GX-4100)
-Acrylic polymer dispersant: 2.0 parts (BASF Japan, EFKA 4300)
Propylene glycol monomethyl ether acetate: 78.0 parts

(Preparation of silver pigment dispersion 2)
After mixing each component so that it might become the following composition, the mixture was obtained and it disperse | distributed with the bead mill for 8 hours using the zirconia bead of diameter 0.5mm, and the silver pigment dispersion liquid 2 was obtained.

-Composition-
Aluminum paste: 20.0 parts (aluminum metal particles, manufactured by Asahi Kasei Chemicals Corporation, GX-4100)
Dispersant A: 4.0 parts (described in the synthesis method below)
Xylene: 78.0 parts

-Synthesis of Dispersant A-
A solution prepared by dissolving 45.8 parts of KF-2001 (manufactured by Shin-Etsu Chemical Co., Ltd.), 53.3 parts of KF-2012 (manufactured by Shin-Etsu Chemical Co., Ltd.), and 0.9 part of methacrylic acid in 100 parts of xylene. Was prepared. A polymerization initiator (dimethyl-2,2′-azobis (2-methylpropionate), manufactured by Wako Pure Chemical Industries, Ltd., V-601) was added to the prepared solution in an amount of 0.3 mol% based on the total polymerization components. The polymer was dissolved at a ratio and polymerized at 80 ° C. in a nitrogen atmosphere. Two hours after the start of the polymerization, 0.3 mol% of the polymerization initiator (V-601) was added in a ratio to the total polymerization components, and after the addition of the polymerization initiator, the polymerization was further performed for 2 hours (4 hours in total). After the polymerization, purification treatment and drying were performed to obtain Dispersant A (weight average molecular weight 40,000).
Dispersant A has a structure in which the methacryloyl group or methacrylic acid of KF-2012 is substituted by -SH of KF-2001. In the dispersant A, the part added with KF-2012 corresponds to the part of “—R ¹⁴ -B” in the formula (1), and the part added with methacrylic acid is “—R ¹³ -A in the formula (1)”. It corresponds to the part of "". In the dispersant A, R ^{1 to} R ¹⁰ in the formula (1) are methyl, R ¹¹ and R ¹² are R ^A , 1 is a1, and m + n is a2.

The weight average molecular weight was measured by gel permeation chromatography (GPC) under the following conditions.
Column: GPC column TSKgelSuper HZM-H (manufactured by Tosoh Corporation)
・ Solvent: Tetrahydrofuran ・ Standard: Monodisperse polystyrene

Said KF-2001 is a structure represented by the following structural formulas, and has a functional group equivalent of 1,900 (g / mol). In the structural formula, R ^A represents a linking group, and a1 and a2 represent natural numbers.

  Said KF-2012 is a structure represented by the following structural formulas, and has a functional group equivalent of 4,600 (g / mol). In the structural formula, R represents a substituent or a linking group, and n represents a natural number.

<Production of decorative film>
-Preparation of substrate-
As a substrate, acryloprene HBS010 (125 μm thick acrylic resin, manufactured by Mitsubishi Rayon Co., Ltd.) was prepared.

-Preparation of protective film-
Next, GF-8 (35 μm-thick polyethylene film, manufactured by Tamapoly Co., Ltd.) was prepared as a protective film.

[Production of first colored layer, bright layer, second colored layer and metal-containing reflective layer on substrate]
Using an extrusion coater, each coating solution described in Tables 1 to 3 above was applied onto the substrate so as to have the combinations and thicknesses (thickness after drying) described in Table 4 below. The liquid was dried. On the substrate, the second colored layer, the bright layer, the first colored layer, and the metal-containing reflective layer are laminated in this order, and the above-mentioned protection is provided on the uppermost layer (on the metal-containing reflective layer). The film was crimped.
Thus, the laminated body which has a 2nd colored layer, a brightness layer, a 1st colored layer, and a metal containing reflection layer was formed on the base film Example 1- Example 13 and Comparative Example 1- A decorative film of Comparative Example 7 was produced.

<Evaluation>
The following evaluation was performed about the decorative film of each Example and comparative example obtained above. Each evaluation result is shown in Table 4.

[Evaluation of deep color and gloss]
Sensory evaluation was performed according to the following reference | standard about the color (depth) and glossiness (gloss) of each Example and the comparative example. The depth is a level where only A is allowed, and the gloss is a level where A and B are allowed.
(depth)
A: The color has a depth, and the depth is felt.
B: The depth is not felt.
C: The background color appears to be transparent.
(Glossy)
A: The gloss is strong and strong reflection is observed when light is applied.
B: It is glossy, and reflection is seen when exposed to light.
C: Gloss is not seen.

[Evaluation of heat resistance (coloring)]
In order to simply evaluate the resistance to heat applied when the decorative film is formed into a decorative molded body, heat resistance evaluation was performed on the decorative films of the examples and comparative examples.
For heat resistance, the decorative film of each Example and Comparative Example was fixed to glass (thickness 0.7 mm) using a heat-resistant tape, and the colors before and after heating at 150 ° C. for 30 minutes were observed. The color change ΔE before and after heating was evaluated according to the following criteria.
The color was measured with a spectrocolorimeter CM-700d (manufactured by Konica Minolta Co., Ltd.). In addition, as a color level, it is practically necessary that it is A and B evaluation, and it is preferable that it is A.
A: Color change ΔE before and after heating is less than 0.5.
B: Color change ΔE before and after heating is 0.5 or more and less than 1.0.
C: Color change ΔE before and after heating is 1.0 or more.

(Shielding evaluation)
About the decorative film of each Example and a comparative example, optical density (OD) was measured using Sakata Inx Co., Ltd. BMT-1, and shielding property was evaluated.
When the optical density (OD) is 3 or more, the shielding property is excellent, and when it is 3.5, the shielding property is more excellent, and when it is 4.0 or more, the shielding property is further excellent.

From Table 4, it can be seen that the decorative films of the examples are both compatible with deep color and gloss.
It can be seen that Comparative Example 1 is inferior in glossiness because it does not have a glitter layer. Since Comparative Example 2 does not have the first colored layer and Comparative Example 3 does not have the second colored layer, it can be seen that neither of them has a deep color. Since Comparative Example 4 and Comparative Example 5 did not contain metal in the metal-containing layer, none of them had a deep color, and the depth was greatly reduced particularly when white was used. In Comparative Example 6, since the metal-containing layer contains neither metal nor color material, it has no deep color and is inferior in light shielding property. Since the comparative example 7 does not have a metal content layer, it turns out that it does not have a deep color and is inferior to light-shielding property.

<Production of decorative molded body>
The protective film was peeled off from the decorative film of each example, and an adhesive layer was provided on the exposed surface of the metal-containing reflective layer by silk screen printing. Here, as an adhesive for silk screen printing for providing an adhesive layer, an adhesive mainly composed of vinyl chloride / vinyl acetate copolymer and acrylic resin (IMB-003, manufactured by Teikoku Inc.) is used. The thickness of the adhesive layer was 4 μm.
The alignment hole was provided in the edge part (position where a three-dimensional shape is not provided after shaping | molding) of the decorating film which provided the contact bonding layer.
Then, the alignment hole and the fixing pin of the molding die were aligned to perform alignment, and the decorative film provided with the adhesive layer was fixed in the molding die so that the adhesive layer faced inward.

After the decorative film was fixed to the molding die, the decorative film was molded (preform) using the molding die.
The preformed decorative film is closed in a state where it is fixed to the molding die, and a melted acrylic resin (at a temperature of 240 ° C. and an injection speed of 100 mm / second) is applied to the adhesive layer side of the decorative film ( Acrypet (Mitsubishi Rayon Co., Ltd.) was injected.
Next, trim the remaining burrs of the intermediate decorative molded body obtained by solidifying the injected molten resin, and further trim and remove the dummy parts, finish the deburring and decorate A molded body was obtained.
The decorative molded body provided with the decorative film of each example had a deep color and gloss.

DESCRIPTION OF SYMBOLS 10 Laminated body 11 Metal containing reflection layer 12 1st colored layer 13 Bright layer 14 2nd colored layer 20 Decorating film 21 Base film

Claims (15)

A first colored layer containing a color material and a resin;
A second colored layer containing a color material and a resin;
A bright layer disposed between the first colored layer and the second colored layer;
A metal-containing reflective layer containing a metal, disposed on the opposite side of the first colored layer from the side on which the glitter layer is disposed;
A laminate having   The laminate according to claim 1, wherein the metal-containing reflective layer includes metal particles.   The laminate according to claim 1 or 2, wherein the metal-containing reflective layer includes aluminum metal particles. The said metal containing reflection layer is a laminated body of Claim 2 or Claim 3 containing the graft type silicone polymer represented by following formula (1).

In formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ are each independently a hydrogen atom, a hydroxy group, or an aryl group Or an alkyl group having 1 to 3 carbon atoms, R ¹¹ and R ¹² each independently represents an arylene group or an alkylene group having 1 to 3 carbon atoms, and R ¹³ and R ¹⁴ are each independently A single bond or a divalent organic linking group is represented, A represents a group having a particle adsorption site, B represents a group having a structure represented by the following formula (2), and l and n are each independently 1 represents an integer of 1 or more, and m represents an integer of 0 or more.

In Formula (2), R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, a hydroxy group, an aryl group, or an alkyl group having 1 to 3 carbon atoms, and k represents an integer of 1 or more.   The said bright layer is a laminated body of any one of Claims 1-4 containing the pigment which has a light transmittance and light reflectivity.   The laminate according to claim 5, wherein the pigment having light transmittance and light reflectivity is mica, glass, titanium oxide-coated mica, or titanium oxide-coated glass.   The said bright layer is a laminated body of any one of Claims 1-6 containing at least 1 sort (s) of resin chosen from an acrylic resin, ester resin, and a silicone resin.   The resin contained in the first colored layer and the second colored layer is at least one resin selected from an acrylic resin, an ester resin, and a silicone resin. The laminated body as described in.   The decorating film by which the laminated body of any one of Claims 1-8 was arrange | positioned on a base film.   The decorative film according to claim 9, wherein the base film is a polyethylene terephthalate film, an acrylic film, or a polycarbonate film.   A decorative molded body comprising the decorative film according to claim 9 or 10 and a resin molded body.   A decorative molded body comprising the laminate according to any one of claims 1 to 8 and a resin molded body. A second colored layer forming step of applying a second colored layer coating solution on the base film to form a second colored layer;
A glitter layer forming step of applying a glitter layer coating liquid on the second colored layer to form a glitter layer;
A first colored layer forming step of applying a first colored layer coating solution on the bright layer to form a first colored layer;
A metal-containing reflective layer forming step of forming a metal-containing reflective layer on the first colored layer;
The manufacturing method of the decorating film which has.   The manufacturing method of the decorative molded body including the process of adhering a resin molded body to the decorative film of Claim 9 or Claim 10.   Furthermore, the manufacturing method of the decorating molded object of Claim 14 which has the process of peeling the base film of the said decorating film.