WO2020008960A1

WO2020008960A1 - Decorative film, decoration method, method for producing decorative molded body, and decorative molded film

Info

Publication number: WO2020008960A1
Application number: PCT/JP2019/025212
Authority: WO
Inventors: 威史濱; 隆志有冨; 漢那　慎一
Original assignee: 富士フイルム株式会社
Priority date: 2018-07-02
Filing date: 2019-06-25
Publication date: 2020-01-09
Also published as: JP7039701B2; JPWO2020008960A1

Abstract

The present invention addresses the problem of providing a decorative film having exceptional color change properties, a decoration method and a method for producing a decorative molded body in which the decorative film is used, and a decorative molded film having exceptional color change properties. This decorative film (10) has, in the stated order, a temporary support body (22), a coloration layer (24), a color change layer A (28) that includes at least one compound selected from the group consisting of resins and polymeric compounds, and a color change layer B (30). The color change layer B (30) is such that the refractive index thereof is at least 0.1 less than that of the color change layer A (28). This decorative molded film (40) has, in the stated order, a substrate (16), a coloration layer (24), a color change layer A (28) that includes at least one compound selected from the group consisting of resins and polymeric compounds, and a color change layer B (30). The color change layer B (30) is such that the refractive index thereof is at least 0.1 less than that of the color change layer A (28).

Description

Decorative film, decoration method, method for manufacturing decorative molded body, and decorative molded film

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

2. Description of the Related Art A decorative molded body in which a decorative film is arranged on the surface of a resin molded body to color the surface into a desired hue or a desired pattern is provided on the surface is known.
The decorative molded body is obtained, for example, by placing a decorative molded film in a mold in advance and injecting a base resin into the mold, and the decorative film is integrally formed on the surface of the resin molded body. It has a generalized structure.
In the present disclosure, the decorative molded film refers to a film obtained by attaching a decorative film to a molding substrate.
Here, performing the injection molding of the base resin after disposing the decorative molding film in the mold in advance may be generally referred to as film insert molding or simply insert molding.
Moreover, you may manufacture a decorative molded object by sticking a decorative film to the molded object after shaping | molding.

Further, as a conventional in-mold hard coat transfer foil, Patent Document 1, in the in-mold transfer foil having a transfer layer on the release surface of the release substrate sheet, at least the transfer layer, A first transparent cross-linked cured resin layer, a printed picture layer, a second transparent cross-linked cured resin layer, a metallic gloss layer or a metallic print layer, and an adhesive layer, which are sequentially laminated, and the second transparent cross-linked type There is described an in-mold hard coat transfer foil, wherein the cured resin layer has a thickness of 20 μm to 100 μm.
Further, as a conventional decorative laminate, Patent Document 2 discloses a decorative sheet in which at least a first base material layer, a release layer, a color changing layer B, and a second base material layer are sequentially stacked. Then, based on JIS B0601: 2001, the cut-off value is set to 0.8 mm, and the average interval Sm of irregularities when measuring the surface of the transfer layer when the decorative sheet is transferred to the transfer target is A decorative sheet having a thickness of 0.05 mm or more and 0.20 mm or less in at least a part of the surface of the transfer layer is described.

Patent Document 1: JP-A-2011-11376 Patent Document 2: JP-A-2017-47597

The problem to be solved by one embodiment of the present invention is to provide a decorative film having excellent color change.
A problem to be solved by another embodiment of the present invention is to provide a decorating method using the decorating film and a method for manufacturing a decorating molded article.
A problem to be solved by yet another embodiment of the present invention is to provide a decorative molded film having excellent color change.

Means for solving the above problems include the following aspects.
<1> The color change layer having a temporary support, a color layer, a color change layer A containing at least one compound selected from the group consisting of a resin and a polymerizable compound, and a color change layer B in this order. A decorative film in which B is a layer having a refractive index lower than that of the color change layer A by 0.1 or more.
<2> The decorative film according to <1>, wherein the colored layer contains at least one compound selected from the group consisting of a resin and a polymerizable compound.
<3> The decorative film according to <1> or <2>, wherein the thickness of the coloring layer is 3 μm or more.
<4> The decorative film according to any one of <1> to <3>, wherein the coloring layer contains a pigment as a coloring agent.
<5> The colored layer is obtained by curing at least a bifunctional or trifunctional polymerizable compound having a urethane bond and at least one partial structure selected from the group consisting of alkyleneoxy groups having 2 or 3 carbon atoms. The decorative film according to any one of <1> to <4>, which is a layer.
<6> The decorative film according to any one of <1> to <5>, wherein the color change layer B is a layer having a refractive index lower than that of the color change layer A by 0.25 or more.
<7> The decorative film according to any one of <1> to <6>, wherein the refractive index of the color change layer A is 1.6 or more.
<8> The decorative film according to any one of <1> to <7>, wherein the color changing layer A further contains zirconium oxide or titanium oxide.
<9> The decorative film according to any one of <1> to <8>, wherein the refractive index of the color change layer B is 1.4 or less.
<10> The color changing layer B according to any one of <1> to <9>, wherein the color change layer B includes at least one selected from the group consisting of a siloxane resin having a void, a fluororesin, and hollow silica particles. Decorative film.
<11> The decorative film according to any one of <1> to <10>, wherein the color change layer A has a thickness of 5 μm or more, or the color change layer B has a thickness of 5 μm or more.
<12> The decorative film according to any one of <1> to <11>, wherein the thickness of the color change layer A is 5 μm or more, and the thickness of the color change layer B is 1 μm or less.
<13> The decorative film according to any one of <1> to <11>, wherein the thickness of the color changing layer A is 1 μm or less, and the thickness of the color changing layer B is 5 μm or more.
<14> The decorative film according to any one of <1> to <13>, which is a decorative film for molding.
<15> The step of peeling the temporary support from the decorative film according to any one of <1> to <14>, and the step of peeling off the decorative film from which the temporary support is peeled from the colored layer side. A decorating method including a step of attaching to a material.
<16> The decorating method according to <15>, further comprising a step of forming an adhesive layer on a surface of the decorative film from which the temporary support has been peeled off, from which the temporary support has been peeled off.
<17> The decorating method according to <15> or <16>, wherein the substrate is a molding substrate.
<18> a step of peeling the temporary support from the decorative film according to any one of <1> to <14>, and molding the decorative film from which the temporary support is peeled from the colored layer side A method for producing a decorative molded body, comprising: a step of attaching to a substrate for molding; and a step of molding the substrate for molding to which the decorative film is attached.
<19> The color change layer B having a color change layer A containing at least one compound selected from the group consisting of a substrate, a color layer, a resin and a polymerizable compound, and a color change layer B in this order. Is a layer having a refractive index lower than that of the color change layer A by 0.1 or more.

According to one embodiment of the present invention, it is possible to provide a decorative film having excellent color changeability.
Further, according to another embodiment of the present invention, it is possible to provide a decorating method using the decorating film and a method of manufacturing a decorative molded body.
According to still another embodiment of the present invention, it is possible to provide a decorative molded film having excellent color changeability.

1 is a schematic cross-sectional view illustrating an example of a decorative film according to the present disclosure. It is an outline sectional view showing other examples of the decoration film concerning this indication. 1 is a schematic cross-sectional view illustrating an example of a decorative molded film according to the present disclosure.

Hereinafter, one embodiment of a method for manufacturing a decorative film according to the present disclosure will be described. However, the present invention is not limited to the following embodiments at all, and can be implemented with appropriate changes within the scope of the present disclosure.

Regarding the notation of a group (atomic group) in the present disclosure, the notation that does not indicate substituted or unsubstituted includes those having a substituent as well as those having no substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). Further, the “organic group” in the present specification refers to a group containing at least one carbon atom.
The term “actinic ray” or “radiation” in the present disclosure refers to, for example, an emission line spectrum of a mercury lamp, far ultraviolet represented by an excimer laser, extreme ultraviolet (EUV light: Extreme Ultraviolet), X-ray, and electron beam (EB: Electron). Beam) or the like. As used herein, “light” means actinic rays or radiation.
The term “exposure” in the present disclosure means, unless otherwise specified, the emission line spectrum of a mercury lamp, far-ultraviolet rays represented by excimer lasers, extreme ultraviolet rays, X-rays, and EUV light, as well as electron beams and ion beams. Exposure with particle beams such as
In the present disclosure, “to” is used to mean that the numerical values described before and after it are included as the lower limit and the upper limit.

In the present disclosure, (meth) acrylate represents acrylate and methacrylate, and (meth) acryl represents acryl and methacryl.
In the present disclosure, the weight average molecular weight (Mw), the number average molecular weight (Mn), and the degree of dispersion (also referred to as molecular weight distribution) (Mw / Mn) of the resin component are determined by a GPC (Gel Permeation Chromatography) apparatus (manufactured by Tosoh Corporation). GPC measurement by HLC-8120GPC (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 μL, column: TSK gel Multipore HXL-M manufactured by Tosoh Corporation, column temperature: 40 ° C., flow rate: 1.0 mL / min, detection) Detector: Defined as a polystyrene-equivalent value obtained by a differential refractive index detector (Refractive Index Detector).

In the present specification, the amount of each component in the composition, when there are a plurality of substances corresponding to each component in the composition, unless otherwise specified, the total amount of the plurality of corresponding substances present in the composition. means.
In the present specification, the term “step” is included in the term as well as an independent step as long as the intended purpose of the step is achieved even if it cannot be clearly distinguished from other steps.
As used herein, “total solids” refers to the total mass of components excluding the solvent from the total composition of the composition. As described above, the “solid content” is a component excluding the solvent, and may be a solid or a liquid at 25 ° C., for example.
In the present specification, “% by mass” and “% by weight” have the same meaning, and “parts by mass” and “parts by weight” have the same meaning.
In this specification, a combination of two or more preferred embodiments is a more preferred embodiment.

(Decorative film)
The decorative film according to the present disclosure includes a temporary support, a colored layer, a color change layer A containing at least one compound selected from the group consisting of a resin and a polymerizable compound, and a color change layer B in this order. The color change layer B is a layer having a refractive index lower than that of the color change layer A by 0.1 or more.
The application of the decorative film according to the present disclosure is not particularly limited, and specifically includes, for example, automobiles, home appliances, audio products, computers, displays, in-vehicle products, watches, accessories, optical components, doors, and window glasses. It can be used for decoration of building materials.
Above all, the decorative film according to the present disclosure can be suitably used as a decorative film used for decoration of an automobile exterior.
Further, the decorative film according to the present disclosure is excellent in three-dimensional moldability, so that it is suitable as a decorative film for molding, which is used for molding such as three-dimensional molding and insert molding. It is suitable.
For example, the decorative film according to the present disclosure may be used as a decorative molded film by peeling off the temporary support, providing an adhesive layer described below, and attaching to a molding substrate described later, or forming the adhesive layer into a molded body. It is suitably used for applications in which a decorative molded article is formed by sticking to a molded article.

Conventionally, printing, painting, vapor deposition, plating, and the like have been used for surface decoration used in home appliances, electronic devices, mobile phones, and the like.
However, a decoration technique using a decoration film has come to be used in many cases from the viewpoints of imparting functionality and environmental load, and from any removable side.
On the other hand, new design properties are required from the spread of user preferences.
The present inventors have newly found a design in which a change in color (for example, tint, fine hue) (also referred to as “color changeability”) has been made, and have studied the introduction thereof as a decoration technique.
Further, in the present disclosure, the color change may be not only a simple color change, but also a color change according to the viewing direction, and the larger the degree of the color change, the better the color change. .

As a result of intensive studies, the present inventors have found that the decorative film having the above-described structure has excellent color changeability.
Although the detailed mechanism of the manifestation of the above effects is unknown, it is estimated as follows. A temporary support, a colored layer, a color-changing layer A containing at least one compound selected from the group consisting of a resin and a polymerizable compound, and a color-changing layer B in this order; When the refractive index difference between the color changing layer B and the color changing layer B is 0.1 or more, light reflection at the interface between the color changing layer A and the color changing layer B, light reflection at the surface of the color changing layer B, When the color layer is visually recognized through the color change layer A and the color change layer B due to optical interference due to reflection of light at the interface between the color change layer A and the color layer, the color change It is presumed that a special design such as a structural color is exhibited as an example.

Hereinafter, the decorative film according to the present disclosure will be described in detail.

[Refractive index of color change layer A and color change layer B]
In the decorative film according to the present disclosure, the color change layer B is a layer having a refractive index lower than that of the color change layer A by 0.1 or more.
In the present disclosure, the refractive index is a refractive index for light having a wavelength of 550 nm at 25 ° C.
In addition, the refractive index of each layer in the present disclosure is determined by transmitting a single film of the color change layer A and the color change layer B formed on the alkali-free glass OA-10G (manufactured by Nippon Electric Glass Co., Ltd.) with a spectrophotometer. Measure the spectrum, and the transmittance obtained by the measurement, and the transmittance calculated by the light interference method, using a fitting analysis, to determine the thickness and refractive index of each layer, or The measurement is performed using a Karnew precision refractometer (KPR-3000, manufactured by Shimadzu Corporation).

The refractive index of the color change layer A is 1.5 or more from the viewpoints of color change property and black tightness (reflection suppression effect by reflected light from the outside, for example, suppression of reflection of a fluorescent lamp). Is preferably 1.6 or more, more preferably 1.65 or more, and particularly preferably 1.70 or more. Further, the upper limit is preferably 2.3 or less, more preferably 1.9 or less.
The refractive index of the color change layer B is preferably 1.5 or less, more preferably less than 1.5, and more preferably 1.4 or less, from the viewpoints of color change and blackness. More preferably, it is particularly preferably 1.35 or less, most preferably 1.32 or less. Further, the lower limit is preferably 1.1 or more, more preferably 1.2 or more, and particularly preferably 1.28 or more.

The color changing layer B is a layer having a refractive index lower than that of the color changing layer A by 0.1 or more, and is a layer having a refractive index lower by 0.15 or more from the viewpoint of color changeability and blackness. It is preferable that the layer has a refractive index of at least 0.2 or lower, more preferably a layer having a refractive index of at least 0.25 or lower, more preferably a layer having a refractive index of at least 0.25 or lower at 0.60 or lower. Is particularly preferred.
Further, from the viewpoints of color change property, black tightness, and scratch resistance, the refractive index of the color change layer A is 1.6 or more, and the refractive index of the color change layer B is 1.5 or less. More preferably, the refractive index of the color changing layer A is 1.65 or more, and the refractive index of the color changing layer B is more preferably 1.4 or less.
Further, from the viewpoint of color change property and blackness, the color change layer A has a refractive index of 1.5 or more, and the color change layer B has a refractive index of 1.4 or less. preferable.

[Preferable thickness of each layer]
The decorative film according to the present disclosure is the decorative film according to the present disclosure having a temporary support, a coloring layer, a color changing layer A, and a color changing layer B in this order.
The thickness of the temporary support is not particularly limited, but is preferably from 10 μm to 500 μm, more preferably from 20 μm to 300 μm, and particularly preferably from 50 μm to 150 μm, from the viewpoint of releasability.
The thickness of the colored layer is not particularly limited, but is preferably 0.5 μm or more, more preferably 3 μm or more, and more preferably 3 μm to 50 μm from the viewpoint of color change and three-dimensional moldability. More preferably, it is particularly preferably 3 μm to 20 μm.
The thicknesses of the color change layer A and the color change layer B are each independently preferably from 50 nm to 50 μm, more preferably from 80 nm to 30 μm, and more preferably from 100 nm to 20 μm, from the viewpoint of color change. Is particularly preferred.

From the viewpoint of color changeability, it is preferable that the thickness of the color change layer A and the thickness of the color change layer B are different.
In addition, from the viewpoint of color change property and black tightness, the thickness of the color change layer A is preferably 5 μm or more, or the thickness of the color change layer B is preferably 5 μm or more. The thickness of the layer A is 5 μm or more, and the thickness of the color change layer B is 1 μm or less, or the thickness of the color change layer A is 1 μm or less, and the thickness of the color change layer B is 5 μm. More preferably, the thickness of the color change layer A is 7 μm or more, and the thickness of the color change layer B is 0.8 μm or less, or the thickness of the color change layer A is 0.1 μm or less. It is particularly preferred that the thickness be 8 μm or less, and the thickness of the color change layer B be 7 μm or more. The upper limit is preferably 100 μm or less.
From the viewpoint of color changeability, the following combinations of the thickness and the refractive index of the color change layer A, the thickness and the refractive index of the color change layer B, and the thickness of the coloring layer are preferable.

As a first preferred embodiment of the decorative film according to the present disclosure according to the present disclosure, the refractive index of the color change layer B is 1.5 or less (more preferably 1.45 or less, still more preferably 1.4 or less). .35 or less, and the refractive index of the color-changing layer A is 1.6 or more (more preferably 1.65 or more, still more preferably 1.7 or more).
Further, as a first aspect, from the viewpoint of color changeability, the thickness of the color change layer B is 5 μm or more (more preferably, 10 μm or more), the thickness of the color change layer A is 1 μm or less, and It is preferable that the color layer has a thickness of 3 μm or more.
In the first embodiment, the thickness of the color change layer A is preferably 120 nm to 150 nm, 240 nm to 280 nm, 390 nm to 430 nm, or 530 nm to 560 nm in order to enhance blue reflection. Is preferably 180 nm to 200 nm, 320 nm to 340 nm, 470 nm to 490 nm, or 600 nm to 620 nm, and to enhance red reflection, 200 nm to 220 nm, 340 nm to 370 nm, 490 nm to 510 nm, Alternatively, it is preferably from 620 nm to 640 nm, and in order to enhance the reflection of purple, it is preferably from 90 nm to 120 nm, from 220 nm to 240 nm, from 370 nm to 390 nm, or from 510 nm to 530 nm. Is 150 nm 180nm, 280nm ~ 320nm, 430nm ~ 470nm, or preferably a 560 nm ~ 600 nm.

As a preferable second aspect in the decorative film according to the present disclosure according to the present disclosure, the refractive index of the color changing layer B is 1.4 or less, and the refractive index of the color changing layer A is 1.5 or more. An embodiment is preferably mentioned.
Further, as a second aspect, from the viewpoint of color changeability, the thickness of the color change layer B is 1 μm or less, the thickness of the color change layer A is 5 μm or more, and the color layer is 3 μm or more. Is preferred.
In the second embodiment, the film thickness of the color change layer B is preferably from 120 nm to 160 nm or from 320 nm to 370 nm to enhance blue reflection, and from 210 nm to 370 nm to enhance yellow reflection. It is preferably 260 nm or 420 to 450 nm, and it is preferably 260 nm to 290 nm to enhance red reflection, and 90 nm to 120 nm or 290 nm to 320 nm to enhance violet reflection. Preferably, the thickness is 160 nm to 210 nm or 370 nm to 420 nm to enhance green reflection.

The thickness of each layer is measured by cutting the decorative film in a direction perpendicular to the film surface, observing the cut surface with a scanning electron microscope (SEM) or an optical microscope, and measuring the thickness of the layer in that range. Alternatively, the decorative film or, if it can be peeled, the peeled layer can be measured by a method of directly measuring with a vernier caliper, a film thickness meter or the like.

(Temporary support)
As the temporary support, a known resin film is used without any particular limitation, and a film that has flexibility and does not cause significant deformation, shrinkage, or elongation under pressure or under pressure and heat is preferable. Can be used for
As the temporary support, a resin film such as a cycloolefin copolymer film, a polyethylene terephthalate (PET) film, a cellulose triacetate film, a polystyrene film, a polycarbonate film, and a polymethyl methacrylate film is preferable, and a polyethylene terephthalate film is more preferable.
Further, an organic film with a release layer is more preferable in that the release property of the temporary support from the colored layer is excellent.
Commercially available temporary supports include, for example, PET with a release layer such as "Unipeel (registered trademark)" series (manufactured by Unitika Ltd.) and "Therapyel (registered trademark)" series (manufactured by Toray Film Processing Co., Ltd.). Films and the like.

-Total light transmittance-
The temporary support used in the present disclosure has a total light transmittance of preferably 80% or more, and more preferably 90% or more, when exposure is performed from the temporary support side in an exposure step described later.
The total light transmittance can be measured by a spectrophotometer (for example, spectrophotometer UV-2100, manufactured by Shimadzu Corporation).

(Release layer)
The temporary support preferably has a release layer for improving the releasability from the colored layer.
Further, the decorative film according to the present disclosure preferably has a release layer between the temporary support and the colored layer in order to improve the releasability between the temporary support and the colored layer.
Further, when the decorative film according to the present disclosure has the release layer, it is preferable that when the temporary support is peeled off, the release layer is peeled off from the colored layer together with the temporary support.
The release layer is not particularly limited, and a release layer known in the field of a transfer film or the like can be used.
Examples of the release layer include a layer containing a thermoplastic resin, and a thermoplastic resin layer described in paragraph 0026 of Japanese Patent No. 4502784 is preferably used as the release layer.
When the temporary support has a release layer, the colored layer is preferably formed on the release layer in the step of forming the colored layer.

(Coloring layer)
The decorative film according to the present disclosure has a colored layer.
The color of the colored layer is not particularly limited, and may be a colored (not colorless and transparent) layer, but is preferably an opaque colored layer (preferably a colored layer having a total light transmittance of 10% or less). .
Further, the coloring layer may be of various colors such as black, gray, white, red, orange, yellow, green, blue, and purple, but if it is a black coloring layer, the intensity of reflected light is small, and This is preferable because the change is more emphasized.

The colored layer preferably contains at least one compound selected from the group consisting of a resin and a polymerizable compound from the viewpoints of strength and scratch resistance.
Preferable examples of the resin include a binder resin described below.
Further, the colored layer may be a layer obtained by curing a polymerizable compound, may be a layer containing a polymerizable compound and a polymerization initiator, but storage stability, and, the colored layer and other layers From the viewpoint of adhesion, it is preferably a layer formed by curing a polymerizable compound, and has a urethane bond and at least one kind of partial structure selected from the group consisting of alkyleneoxy groups having 2 or 3 carbon atoms. It is more preferable that the layer is obtained by curing at least a bifunctional or trifunctional polymerizable compound.

-Colorant-
The coloring layer preferably contains a coloring agent from the viewpoint of visibility, and more preferably contains a pigment as a coloring agent from the viewpoint of durability.
The colorant is not particularly limited, and a colorant having a desired hue can be appropriately selected and used.
Examples of the colorant include a pigment and a dye, and a pigment is preferable.
Further, the pigment is preferably a particle-shaped pigment.
As the pigment, various conventionally known inorganic pigments and organic pigments can be used.
Examples of the inorganic pigment include the inorganic pigments described in paragraphs 0015 and 0114 of JP-A-2005-7765.
Specific inorganic pigments include, for example, 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. , Iron oxide, and black pigments such as graphite.
For example, known chromatic pigments such as iron oxide, barium yellow, cadmium red, and chrome yellow can be used.

Examples of the organic pigment include the organic pigments described in paragraph 0093 of JP-A-2009-256572.
Specific examples of the organic pigment include C.I. I. Red pigments such as C.I. Pigment Red 177, 179, 224, 242, 254, 255, 264; I. Pigment Yellow 138, 139, 150, 180, 185, etc .; I. Orange pigments such as C.I. Pigment Orange 36, 38 and 71; I. Green pigments such as CI Pigment Green 7, 36, 58; I. A blue pigment such as C.I. Pigment Blue 15: 6; I. Pigment Violet 23 and the like.
In addition, the pigment may include particles of a pigment having a light transmitting property and a light reflecting property (a so-called brilliant pigment).
In the case where the glitter pigment includes a step of exposing to light described below, it is preferable to use the glitter pigment within a range that does not hinder curing by exposure.

Each of the coloring agents may be used alone or in combination of two or more. Further, particles of an inorganic pigment and particles of an organic pigment may be used in combination.
The content of the coloring agent in the coloring layer is, with respect to the total mass of the coloring layer, from the viewpoint of the development of the desired hue (for example, suppression of whitening) and the maintenance of the shape following property of the coloring layer to the mold. It is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 50% by mass, and still more preferably 10% by mass to 40% by mass.
Here, “whitening” in the present disclosure indicates that the colored layer changes so as to exhibit a whitish color like a matte feeling.

-Polymerizable compound-
The colored layer used in the present disclosure preferably contains a polymerizable compound.
Examples of the polymerizable group include an ethylenically unsaturated group and an epoxy group. From the viewpoint of curability and the like, an ethylenically unsaturated group is preferable, and a (meth) acryloxy group is more preferable.
As the polymerizable group, a radical polymerizable group is preferable.
Examples of the polymerizable compound include bifunctional compounds having at least one partial structure selected from the group consisting of a urethane bond, a urea bond, an alkyleneoxy group having 2 or 3 carbon atoms, and a hydrocarbon group having 6 to 12 carbon atoms. Alternatively, a trifunctional polymerizable compound (hereinafter, also referred to as “specific polymerizable compound”) is preferable, and a urethane bond and at least one partial structure selected from the group consisting of alkylene oxide groups having 2 or 3 carbon atoms are preferable. A bifunctional or trifunctional polymerizable compound having the same is more preferable.
The specific polymerizable compound may have a linking group between the partial structure and the polymerizable group, if necessary. The specific polymerizable compound has at least two partial structures selected from the group consisting of a urethane bond, a urea bond, an alkyleneoxy group having 2 or 3 carbon atoms, and a hydrocarbon group having 6 to 12 carbon atoms. You may have.

<Bifunctional or trifunctional polymerizable compound having urethane bond>
As the bifunctional or trifunctional polymerizable compound having a urethane bond (hereinafter, also referred to as “specific polymerizable compound 1”), a urethane oligomer is preferable.
The nitrogen atom in the urethane bond may be disubstituted (one of the groups on the nitrogen atom is a hydrogen atom) or trisubstituted.
Further, the specific polymerizable compound 1 preferably has a urethane resin chain.
As the urethane oligomer, a urethane (meth) acrylate oligomer is preferable, and examples thereof include an aliphatic urethane (meth) acrylate and an aromatic urethane (meth) acrylate.
For details, reference can be made to an oligomer handbook (supervised by Junji Furukawa, Chemical Daily Co., Ltd.). The urethane oligomer described herein is appropriately selected according to the purpose and used for forming a colored layer in this step. be able to.
The molecular weight of the urethane oligomer as the specific polymerizable compound 1 is preferably from 800 to 2,000, and more preferably from 1,000 to 2,000.

As the urethane (meth) acrylate oligomer which is the specific polymerizable compound 1, a commercially available product may be used.
Commercially available urethane (meth) acrylate oligomers include, for example, U-2PPA and UA-122P manufactured by Shin-Nakamura Chemical Co., Ltd .; CN964A85, CN964, CN959, CN962, CN963J85 manufactured by Sartomer Japan K.K. , CN965, CN982B88, CN981, CN983, CN991, CN991NS, CN996, CN996NS, CN9002, CN9007, CN9178, CN9893; Etc. (above, trade names). Note that “EBECRYL” is a registered trademark.

<Bifunctional or trifunctional polymerizable compound having a urea bond>
Examples of the bifunctional or trifunctional polymerizable compound having a urea bond (hereinafter, also referred to as “specific polymerizable compound 2”) include a bifunctional or trifunctional ethylenically unsaturated compound having a urea bond.
The nitrogen atom in the urea bond may be disubstituted (one of the groups on the nitrogen atom is a hydrogen atom) or trisubstituted.
Further, the specific polymerizable compound 2 preferably has a urea resin chain.

Specific examples of the bifunctional or trifunctional ethylenically unsaturated compound having a urea bond include, for example, a synthetic product obtained by reacting an isocyanate compound having an ethylenically unsaturated group with an amine compound.
Examples of the isocyanate compound having an ethylenically unsaturated group include 2-methacryloyloxyethyl isocyanate (a commercially available product, Karenz MOI (registered trademark) manufactured by Showa Denko KK), and isocyanate of 2-methacryloyloxyethyl isocyanate. Having a group blocked with methyl ethyl ketone oxime (2- (O- [1′-methylpropylideneamino] carboxyamino) ethyl methacrylate; commercially available product, Karenz MOI-BM (registered trademark) manufactured by Showa Denko KK )), 2-methacryloyloxyethyl isocyanate in which the isocyanate group is blocked with pyrazole (2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate; if it is a commercial product, Karenz manufactured by Showa Denko KK MOI-BP (registered merchant Mark)) can be used.
In addition, as the amine compound, for example, an amine compound having two or more active hydrogen atoms, specifically, dimethylamine, trimethylamine, triethylamine, diisopropylamine, diethylenetriamine, triethylenetetramine, or the like can be used.
In addition, the specific polymerizable compound 2 is not limited to a compound obtained by this method.

Specific examples of the specific polymerizable compound 2 include ethoxylated isocyanuric acid diacrylate, ethoxylated isocyanuric acid triacrylate, and ε-caprolactone-modified tris (2-acryloxyethyl) isocyanurate.
Here, ethoxylated isocyanuric acid diacrylate, ethoxylated isocyanuric acid triacrylate, and ε-caprolactone-modified tris (2-acryloxyethyl) isocyanurate are also compounds having an ethyleneoxy group.

The specific polymerizable compound 2 is available as a commercial product.
Specific examples of commercially available products include, for example, NK esters A-9300 and A-9300-1CL manufactured by Shin-Nakamura Chemical Industry Co., Ltd .; (The above is a trade name).

<Bifunctional or trifunctional polymerizable compound having an alkyleneoxy group having 2 or 3 carbon atoms>
A bifunctional or trifunctional polymerizable compound having an alkyleneoxy group having 2 or 3 carbon atoms (also referred to as “alkylene oxide group”) (hereinafter, also referred to as “specific polymerizable compound 3”) has one molecule. For example, it has one or more ethyleneoxy groups or propyleneoxy groups, and has two or three polymerizable groups at the molecular terminals.
The propyleneoxy group includes —CH ₂ —CH ₂ —CH ₂ —O—, —CH ₂ —CH (CH ₃ ) O— or —CH (CH ₃ ) —CH ₂ O—, and —CH ₂ —CH It is preferably (CH ₃ ) O— or —CH (CH ₃ ) —CH ₂ O—.
Here, examples of the polymerizable group in the specific polymerizable compound 3 include at least one ethylenically unsaturated group selected from the group consisting of an acryloyloxy group, an acryloyl group, a methacryloyloxy group, and a methacryloyl group.

Specific examples of the specific polymerizable compound 3 include ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate, and ethoxylated trimethylolpropane. Examples include triacrylate, ethoxylated trimethylolpropane trimethacrylate, ethoxylated glycerin triacrylate, and ethoxylated glycerin trimethacrylate.
The number of ethyleneoxy groups or propyleneoxy groups contained in these compounds is preferably 3 or more, more preferably 9 to 40, and particularly preferably 15 to 30, from the viewpoint that the shape following property with respect to the mold becomes better.

In addition, from the viewpoint of further improving the shape following property to the mold, the specific polymerizable compound 3 preferably has a polyethyleneoxy group or a polypropyleneoxy group having two or more ethyleneoxy groups or propyleneoxy groups. . The repeating number of the ethyleneoxy group or the propyleneoxy group in the polyethyleneoxy group or the polypropyleneoxy group is preferably 3 or more, more preferably 5 or more.

Specific polymerizable compound 3 is available as a commercial product.
Specific examples of commercially available products include, for example, NK esters A-200, A-400, A-600, A-1000, 1G, 2G, 3G, 4G, 9G, 14G, 23G manufactured by Shin-Nakamura Chemical Co., Ltd. , ABE-300, A-BPE-4, A-BPE-6, A-BPE-10, A-BPE-20, A-BPE-30, BPE-80N, BPE-100N, BPE-200, BPE-500 , BPE-900, BPE-1300N, A-GLY-3E, A-GLY-9E, A-GLY-20E, A-TMPT-3EO, A-TMPT-9EO; PEG400DA manufactured by Nippon Kayaku Co., Ltd .; Aronix (registered trademark) M-220, M-350 manufactured by Gosei Co., Ltd .; SR415, SR454, SR9035 (manufactured by Sartomer Japan Co., Ltd. (trade names)) and the like. It can be.

<Bifunctional or trifunctional polymerizable compound having a hydrocarbon group having 6 to 12 carbon atoms >>
A bifunctional or trifunctional polymerizable compound having a hydrocarbon group having 6 to 12 carbon atoms (hereinafter, also referred to as “specific polymerizable compound 4”) has 6 to 12 carbon atoms and has a chain shape, a cyclic shape, It has any of the branched hydrocarbon groups and two or three polymerizable groups.
Here, the hydrocarbon group in the specific polymerizable compound 4 is specifically a hydrocarbon chain having 6 to 12 carbon atoms, which may be linear or branched.
Among them, a linear hydrocarbon group is preferable as the hydrocarbon group from the viewpoint that the shape following property with respect to the mold becomes better.
The polymerizable group includes, for example, at least one ethylenically unsaturated group selected from the group consisting of an acryloyloxy group, an acryloyl group, a methacryloyloxy group, and a methacryloyl group.

Specific examples of the specific polymerizable compound 4 include 1,6-hexanediol di (meth) acrylate, 1,7-heptanediol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, 1,9 -Nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, hydrogenated bisphenol A di- (Meth) acrylate and di (meth) acrylate of hydrogenated bisphenol F are mentioned.
Among the above compounds, tricyclodecane dimethanol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) Acrylate and neopentyl glycol di (meth) acrylate are preferably used.

As the polymerizable compound, at least one portion selected from the group consisting of a urethane bond and an alkylene oxide group having 2 or 3 carbon atoms from the viewpoint of improving three-dimensional moldability, for example, by increasing flexibility upon heating. It is preferably a bifunctional or trifunctional polymerizable compound having a structure.

The coloring layer may contain other polymerizable compounds other than the specific polymerizable compound.
As the other polymerizable compound, any compound having the same polymerizable group as the specific polymerizable compound can be used without particular limitation.

The content of the polymerizable compound is preferably from 10% by mass to 50% by mass with respect to the total mass of the uncured colored layer, from the viewpoint of improving interlayer adhesion and imparting flexibility to the colored layer. More preferably, it is from 40% by mass to 40% by mass.

As the specific polymerizable compound and the other polymerizable compound, only one kind may be used alone, or two or more kinds may be used in combination.

Each of the polymerizable compounds used in the present disclosure preferably has a molecular weight (weight average molecular weight when having a molecular weight distribution) of 200 to 3,000, more preferably 250 to 2,600, and more preferably 280 to 2,000. Particularly preferred is 2,200.

-Dispersant-
From the viewpoint of improving the dispersibility of the pigment contained in the coloring layer, the coloring layer may contain a dispersant.
By including a dispersant, the dispersibility of the pigment in the formed colored layer is improved, and the hue of the obtained decorative film can be made uniform.

The dispersant can be appropriately selected and used according to the type and shape of the pigment, and is preferably a polymer dispersant.
Examples of the polymer dispersant include a silicone polymer, an acrylic polymer, and a polyester polymer.
When it is desired to impart heat resistance to the decorative film, for example, it is preferable to use a silicone polymer such as a graft-type silicone polymer as the dispersant.

The weight average molecular weight of the dispersant is preferably from 1,000 to 5,000,000, more preferably from 2,000 to 3,000,000, and more preferably from 2,500 to 3,000,000. It is particularly preferred that there is. When the weight average molecular weight is 1,000 or more, the dispersibility of the pigment is further improved.

Commercial products may be used as the dispersant. Commercially available products include EFKA 4300 (acrylic polymer dispersant) from BASF Japan, Homogenol L-18, Homogenol L-95, and Homogenol L-100 from Kao Corporation; Solsperse 20000, Solsperse 24000, DISPERBYK-110, DISPERBYK-164, DISPERBYK-180, DISPERBYK-182, etc., manufactured by BYK Japan KK.
“Homogenol”, “Solsperse”, and “DISPERBYK” are all registered trademarks.

When the coloring layer contains a dispersant, the dispersant may contain only one kind or two or more kinds.
The content of the dispersant is preferably 1 part by mass to 30 parts by mass with respect to 100 parts by mass of the colorant.

-Polymerization initiator-
The colored layer preferably contains a polymerization initiator, and more preferably contains a polymerizable compound and a polymerization initiator, in order to increase curing sensitivity and further improve interlayer adhesion.
As the polymerization initiator, a photopolymerization initiator is preferable from the viewpoint of increasing the sensitivity to exposure.
As the photopolymerization initiator, a polymerization initiator described in paragraphs 0031 to 0042 of JP-A-2011-95716 and an oxime-based polymerization initiator described in paragraphs 0064 to 0081 of JP-A-2015-014783 may be used. it can.

Specific examples of the photopolymerization initiator include, for example, 1- [4- (phenylthio)]-1,2-octanedione-2- (O-benzoyloxime) (eg, IRGACURE (registered trademark) OXE-01, BASF [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethane-1-one-1- (O-acetyloxime) (for example, IRGACURE (registered trademark) OXE- 02, manufactured by BASF), 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (for example, IRGACURE®) 379EG, manufactured by BASF), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (for example, IRGACURE (Registered trademark) 907, manufactured by BASF), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) 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® 369, manufactured by BASF), 2-hydroxy 2-methyl-1-phenylpropan-1-one (eg, IRGACURE® 1173, manufactured by BASF), 1-hydroxycyclohexylphenyl ketone (eg, IRGACURE® 184, manufactured by BASF), 2 , 2-Dimethoxy-1,2-diphenylethan-1-one (eg, IRGACU E (registered trademark) 651, manufactured by BASF), trade names of oxime ester-based polymerization initiators: Lunar # 6 (manufactured by DKSH Japan), 2,4-diethylthioxanthone (for example, Kayacure DETX-S, Nippon Kagaku) And Fluorene oxime-based polymerization initiators DFI-091 and DFI-020 (both manufactured by Daito Chemmix).

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

(4) The content of the polymerization initiator is preferably from 0.1 to 15 parts by mass, more preferably from 0.5 to 10 parts by mass, based on 100 parts by mass of the polymerizable compound.

-Binder resin-
The colored layer preferably contains a binder resin from the viewpoint of reducing curing shrinkage of the colored layer.
The binder resin is not particularly limited, and a known resin can be appropriately selected. The binder resin is preferably a transparent resin from the viewpoint of obtaining a desired hue, and specifically, a resin having a total light transmittance of 80% or more is preferable.
The total light transmittance can be measured by a spectrophotometer (for example, spectrophotometer UV-2100, manufactured by Shimadzu Corporation).

Examples of the binder resin include an acrylic resin, a silicone resin, a polyester resin, a urethane resin, and an olefin resin.
Above all, from the viewpoint of transparency, an acrylic resin, a silicone resin, or a polyester resin is preferable, and an acrylic resin or a silicone resin is more preferable. Further, from the viewpoint of heat resistance, a silicone resin is preferable.

In the present disclosure, “acrylic resin” refers to a resin containing 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.
Acrylic resins include, for example, homopolymers of acrylic acid, homopolymers of methacrylic acid, homopolymers of acrylates, homopolymers of methacrylates, copolymers of acrylic acid with other monomers, methacrylic Copolymer of acid and other monomer, copolymer of acrylate and other monomer, copolymer of methacrylate and other monomer, urethane-modified copolymer having urethane skeleton in side chain Etc. are included.
Examples of the acrylic resin include a glycidyl methacrylate adduct of cyclohexyl methacrylate / methyl methacrylate / methacrylic acid copolymer, a random copolymer of benzyl methacrylate / methacrylic acid, a copolymer of allyl methacrylate / methacrylic acid, and benzyl methacrylate / methacrylic acid / hydroxyl. Ethyl methacrylate copolymers and the like can be mentioned.

As the silicone resin, a known silicone resin can be used. For example, a methyl straight silicone resin, a methylphenyl straight silicone resin, an acrylic resin-modified silicone resin, an ester resin-modified silicone resin, an epoxy resin-modified silicone resin, an alkyd resin Modified silicone resins and rubber-based silicone resins are mentioned.
Among them, methyl straight silicone resin, methylphenyl straight silicone resin, acrylic resin modified silicone resin, or rubber silicone resin is preferable, and methyl straight silicone resin, methylphenyl straight silicone resin, or rubber silicone is preferable. Resins are more preferred.

A commercially available silicone resin may be used. Examples of the commercially available products include KR-300, KR-311, KR-251, X-40-2406M, and KR-282 manufactured by Shin-Etsu Chemical Co., Ltd.

Examples of the polyester resin include a linear saturated polyester 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-cyclohexylene dimethylene terephthalate), and polyethylene-2,6-naphthalate.

The content of the binder resin is preferably 5% by mass to 70% by mass, more preferably 10% by mass to 60% by mass, and more preferably 20% by mass with respect to the total mass of the colored layer, from the viewpoint of reducing the curing shrinkage of the colored layer. % Or more and 60% by mass is more preferable.
Further, the ratio of the total amount of the binder resin to the total amount of the polymerizable compound containing the specific polymerizable compound, that is, the total amount of the polymerizable compound / the total amount of the binder resin is preferably from 0.3 to 1.5, more preferably from 0.5 to 1 .0 is more preferred.

-Other components-
The coloring layer may contain additives in addition to the above components, if necessary.
As the additives, known additives can be used. For example, paragraphs 0017 of Japanese Patent No. 4502784, surfactants described in paragraphs 0060 to 0071 of JP-A-2009-237362, and Japanese Patent No. 4502784. And the other additives described in paragraphs 0058 to 0071 of JP-A-2000-310706.

-Formation of colored layer-
The method for forming the colored layer is not particularly limited, but is preferably formed using a composition for forming a colored layer.
The composition for forming a colored layer contains a coloring agent, and preferably contains a coloring agent and an organic solvent.
Further, the composition for forming a colored layer may further include other components described above.
The composition for forming a colored layer can be prepared, for example, by mixing an organic solvent and a component contained in the colored layer such as a coloring agent.
The content of the components contained in the colored layer is described as the content (% by mass) based on the total mass of the colored layer. , The content (% by mass) based on the total solid content of the composition for forming a colored layer.

When the composition for forming a colored layer contains a pigment as a colorant, a pigment dispersion containing the pigment and the dispersant is prepared in advance, and the composition for forming a colored layer is prepared using the pigment dispersion. Is preferred from the viewpoint of further improving the uniform dispersibility of the pigment and the dispersion stability.

The composition for forming a colored layer may be one prepared in advance by the above method, a commercially available product, or the like, or the composition for forming a colored layer may be prepared immediately before application. .

<Organic solvent>
As the organic solvent, a commonly used organic solvent can be used without any particular limitation. Specific examples include organic solvents such as esters, ethers, ketones, and aromatic hydrocarbons.
Also, methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, cyclohexanol, methyl isobutyl ketone, ethyl lactate similar to Solvent described in paragraphs 0054 and 0055 of US Patent Application Publication No. 2005/282073. Methyl lactate and the like can also be suitably used as the organic solvent in the composition for forming a colored layer.
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 organic solvent in the composition for forming a colored layer.
These organic solvents may be used alone or in combination of two or more.
The content of the organic solvent is not particularly limited, but is preferably 5% by mass to 90% by mass, and more preferably 30% by mass to 70% by mass based on the total mass of the colored layer forming composition (coating solution). More preferred.

[Color changing layer A]
The decorative film according to the present disclosure has a color change layer A containing at least one compound selected from the group consisting of a resin and a polymerizable compound, and the color change layer A is more than the color change layer B. This is a layer having a refractive index higher than 0.1.

The color change layer A contains at least one compound selected from the group consisting of a resin and a polymerizable compound as a binder, and preferably contains a resin from the viewpoint of scratch resistance.
From the viewpoint of scratch resistance, the resin preferably contains at least one resin selected from the group consisting of a thermosetting resin and a photocurable resin.
Examples of the thermosetting resin include a siloxane resin, an epoxy resin, a phenol resin, a melamine resin, a urethane resin, an unsaturated / saturated polyester, and a polyimide. Examples of the siloxane resin include a hydrolytic condensate of a bifunctional to tetrafunctional alkoxysilane. Examples of the crosslinked epoxy resin include a resin formed by polymerizing a compound having two or more polymerizable epoxy groups and a crosslinking agent.
Examples of the photocurable resin include a crosslinked acrylic resin having a polymerizable group. The crosslinked acrylic resin refers to a resin formed by polymerizing a compound having two or more polymerizable (meth) acrylate groups.

There is no particular limitation on the polymerizable compound, and known monomers and oligomers can be used. Further, as the polymerizable compound, the above-described polymerizable compound in the colored layer can be suitably used.
Further, the polymerizable compound preferably contains at least a polyfunctional polymerizable compound from the viewpoint of scratch resistance.
The polyfunctional polymerizable compound is not particularly limited, and a known compound can be used. Preferred examples thereof include a polyfunctional acrylic monomer, a polyfunctional acrylic oligomer, and a polyfunctional urethane acrylate.
Further, as the polymerizable compound, from the viewpoint of scratch resistance, an ethylenically unsaturated compound is preferable, and a (meth) acrylate compound is more preferable.
Further, from the viewpoint of scratch resistance, the color change layer A preferably contains, as a resin, a resin obtained by polymerizing a polymerizable compound, and more preferably contains a resin obtained by polymerizing at least a polyfunctional polymerizable compound. Preferably, a resin obtained by polymerizing at least a polyfunctional ethylenically unsaturated compound is contained, and particularly preferably, a resin obtained by polymerizing at least a polyfunctional (meth) acrylate compound is contained.

When the color change layer A contains a polymerizable compound, it is preferable to contain a polymerization initiator from the viewpoint of curability and scratch resistance.
As the polymerization initiator, those described above in the colored layer can be suitably used.

The color change layer A preferably has a hard coat property from the viewpoint of scratch resistance.
Examples of the material having a hard coat property include, for example, JP-A-2013-45045, JP-A-2013-43352, JP-A-2012-232524, JP-A-2012-128157, and JP-A-2011-131409. JP-A-2011-131404, JP-A-2011-126162, JP-A-2011-75705, JP-A-2009-286981, JP-A-2009-263567, JP-A-2009-75248, JP-A-2007-164206, JP-A-2006-96811, JP-A-2004-75970, JP-A-2002-156505, JP-A-2001-272503, International Publication No. 2012/018807, International Publication No. 2012/098967, International Publication No. 2012 No. 086,659, it is possible to use a material used to make the hard coat layer described in WO 2011/105594.

The color change layer A may be a layer obtained by curing a polymerizable compound, or may be a layer containing a polymerizable compound and a polymerization initiator. From the viewpoint of adhesion between A and another layer, it is preferably a layer formed by curing a polymerizable compound, and at least one selected from the group consisting of a urethane bond and an alkyleneoxy group having 2 or 3 carbon atoms. It is more preferable that the layer is formed by curing at least a bifunctional or trifunctional polymerizable compound having a partial structure.

In addition, the color change layer A preferably contains a filler, more preferably contains an inorganic filler, and contains high refractive index particles having a refractive index of 1.55 or more from the viewpoint of enhancing scratch resistance and a refractive index. Is particularly preferred.
Further, the color change layer A preferably contains a metal oxide, and more preferably contains zirconium oxide (zirconia) or titanium oxide (titania), from the viewpoint of increasing the scratch resistance and the refractive index.
The shape of the filler is not particularly limited, but is preferably particulate.

The high-refractive-index particles having a refractive index of 1.55 or more (hereinafter, also referred to as “high-refractive-index particles”) have a volume average particle diameter of 2 nm or more and 100 nm or less from the viewpoints of aggregation suppression and layer transparency. Is preferable, and it is more preferable that the volume average particle diameter is 5 nm or more and 80 nm or less, and it is particularly preferable that the volume average particle diameter is 10 nm or more and 60 nm or less.
The fillers can be used alone or in combination of two or more.
The volume average particle diameter of the filler and the particles is measured by a Coulter counter.

As the high refractive index particles, from the viewpoint of enhancing scratch resistance and refractive index, oxidation of at least one element selected from the group consisting of aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony, and cerium. Particles, more preferably zirconium oxide particles or titanium oxide particles. Among them, zirconium oxide particles having no photocatalytic action are preferable from the viewpoint of light resistance, but it is also preferable to use titanium oxide particles having suppressed photocatalytic action.
The refractive index of the high refractive index particles is preferably from 1.60 to 3.00, more preferably from 1.80 to 2.90, and more preferably from 1.90 to 2.80, from the viewpoint of increasing the refractive index. Is particularly preferred.

For dispersing the high refractive index particles, the following various dispersants can also be preferably used.
It is preferable that the dispersant further contains a crosslinkable or polymerizable functional group. Examples of the crosslinkable or polymerizable functional group include an ethylenically unsaturated group capable of undergoing an addition reaction and a polymerization reaction by a radical species (for example, a (meth) acryloyl group, an allyl group, a styryl group, a vinyloxy group, etc.), a cationic polymerizable group (epoxy Group, oxatanyl group, vinyloxy group, etc.), polycondensation-reactive group (hydrolyzable silyl group, N-methylol group), and the like, and is preferably a functional group having an ethylenically unsaturated group.

It is preferable to use a dispersant having an anionic group for dispersing the high refractive index particles, particularly for dispersing the inorganic particles containing TiO ₂ as a main component, and more preferably to have an anionic group and a crosslinkable or polymerizable functional group. Particularly preferred is a dispersant having the crosslinkable or polymerizable functional group in a side chain. Specific examples of the crosslinkable or polymerizable functional group include the above-described functional groups.

As the anionic group, a group having an acidic proton such as a carboxy group, a sulfonic acid group (sulfo group), a phosphoric acid group (phosphono group), a sulfonamide group, or a salt thereof is preferable, and a carboxy group, a sulfonic acid group, A phosphate group or a salt thereof is more preferred, and a carboxy group or a phosphate group is particularly preferred. The number of anionic groups contained in the dispersant per molecule may be plural in one molecule, but is preferably 2 or more on average, more preferably 5 or more, Particularly preferably, the number is 10 or more. Further, a plurality of kinds of anionic groups may be contained in one molecule of the dispersant.

In the dispersant having an anionic group in the side chain, the composition of the anionic group-containing monomer unit is preferably in the range of 10 ⁻⁴ mol% to 100 mol% of all monomer units, and more preferably 1 mol% to 50 mol%. More preferably, it is particularly preferably from 5 mol% to 20 mol%.

数 The number of crosslinkable or polymerizable functional groups contained in the dispersant per molecule is preferably 2 or more on average, more preferably 5 or more, and particularly preferably 10 or more. In addition, a plurality of types of crosslinkable or polymerizable functional groups contained in the dispersant may be contained in one molecule.

In a preferred dispersant, examples of the monomer unit having an ethylenically unsaturated group in the side chain include a poly-1,2-butadiene and poly-1,2-isoprene structure or an ester or amide of (meth) acrylic acid. A repeating unit having a specific residue (R group of —COOR or —CONHR) bonded thereto can be used. Examples of the specific residue (R group) include-(CH ₂ ) _n -CR ₂₁ = CR ₂₂ R ₂₃ ,-(CH ₂ O) n-CH ₂ CR ₂₁ = CR ₂₂ R ₂₃ ,-(CH ₂ CH ₂ O) _n -CH ₂ CR ₂₁ = CR ₂₂ R ₂₃ ,-(CH ₂ ) _n -NH-CO-O-CH ₂ CR ₂₁ = CR ₂₂ R ₂₃ ,-(CH ₂ ) n-O-CO —CR ₂₁ ＣＲCR ₂₂ R ₂₃ and — (CH ₂ CH ₂ O) ₂ —X (R ₂₁ to R ₂₃ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, Represents an alkoxy group or an aryloxy group, R ₂₁ and R ₂₂ or R ₂₃ may be bonded to each other to form a ring, n represents an integer of 1 to 10, and X represents a dicyclopentadienyl residue Represents.). Specific examples of R in the ester residue include —CH ₂ CH ＝ CH ₂ (corresponding to a polymer of allyl (meth) acrylate described in JP-A-64-17047), —CH ₂ CH ₂ O—CH ₂ CH = CH ₂ , -CH ₂ CH ₂ OCOCH = CH ₂ , -CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ , -CH ₂ C (CH ₃ ) = CH ₂ , -CH ₂ CH = CH-C ₆ H _{_{_{_{5, -CH 2 CH 2 OCOCH =}}}} CH-C 6 H 5, -CH 2 CH 2 -NHCOO-CH 2 CH = CH 2 and _{_{-CH 2 CH 2 O-X (}} X is a dicyclopentadienyl residue) Is included. Specific examples of R of the amide residue include —CH ₂ CH ＝ CH ₂ , —CH ₂ CH ₂ —Y (Y is a 1-cyclohexenyl residue), and —CH ₂ CH ₂ —OCO—CH ＝ CH ₂ , —CH ₂ CH ₂ —OCO—C (CH ₃ ) ＝ CH ₂ is included.

In the dispersant having an ethylenically unsaturated group, a free radical (a polymerization initiation radical or a growing radical in the course of polymerization of the polymerizable compound) is added to the unsaturated bond group, and directly between the molecules or the polymerizable compound. Is subjected to addition polymerization through a polymerization chain of the above, and a crosslink is formed between the molecules to be cured. Alternatively, atoms in the molecule (eg, a hydrogen atom on a carbon atom adjacent to the unsaturated bonding group) are abstracted by free radicals to form polymer radicals, which are linked together to form crosslinks between the molecules. To cure.

The weight average molecular weight (Mw) of the dispersant having an anionic group and a crosslinked or polymerizable functional group and having the crosslinked or polymerizable functional group in a side chain is not particularly limited, but is 1,000 or more. It is preferably 2,000 to 1,000,000, more preferably 5,000 to 200,000, and particularly preferably 10,000 to 100,000.

The content unit of the crosslinkable or polymerizable functional group may constitute all the monomer units other than the anionic group-containing monomer unit, but is preferably 5 mol% to 50 mol% of all the monomer units, and particularly preferably. Is 5 mol% to 30 mol%.

The dispersant may be a copolymer with a suitable monomer other than a monomer having a crosslinkable or polymerizable functional group or an anionic group. The copolymerization component is not particularly limited, but is selected from various viewpoints such as dispersion stability, compatibility with other monomer components, and strength of a formed film. Preferred examples include methyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, and styrene.

形態 The form of the dispersant is not particularly limited, but is preferably a block copolymer or a random copolymer, and particularly preferably a random copolymer from the viewpoint of cost and ease of synthesis.

The content of the dispersant in the color change layer A is preferably from 1% by mass to 50% by mass, more preferably from 5% by mass to 30% by mass, based on the total mass of the high refractive index particles, It is particularly preferred that the content is 5% by mass to 20% by mass. Further, two or more dispersants may be used in combination. JP-A-2007-293313 has a detailed description of a dispersant that is preferably used.

The method of dispersing the high refractive index particles in the dispersion medium is not particularly limited, but can be dispersed using a disperser. Examples of the dispersing machine include a sand grinder mill (eg, a bead mill with pins), a high-speed impeller mill, a pebble mill, a roller mill, an attritor, a colloid mill, and the like. Among them, a sand grinder mill or a high-speed impeller mill is particularly preferable. Further, a preliminary dispersion process may be performed. Examples of the disperser used for the preliminary dispersion treatment include a ball mill, a three-roll mill, a kneader, and an extruder.
The high refractive index particles are preferably miniaturized as much as possible in the dispersion medium, and the preferred volume average particle size is in accordance with the above-mentioned particle size.

The content of the filler in the color change layer A can be appropriately adjusted according to the desired strength and refractive index. However, from the viewpoint of increasing the color change property, scratch resistance, and the refractive index, the color change layer A It is preferably from 10% by mass to 95% by mass, more preferably from 15% by mass to 90% by mass, still more preferably from 20% by mass to 85% by mass, and more preferably from 30% by mass to 85% by mass with respect to the total mass. Particularly preferred is 80% by mass.

[Color changing layer B]
The decorative film according to the present disclosure has a color changing layer B, and the color changing layer B is a layer having a refractive index lower than that of the color changing layer A by 0.1 or more.
The color change layer B is preferably a layer having antireflection ability from the viewpoint of color change and blackness.
The color change layer B is preferably a thicker layer than the color change layer A from the viewpoint of scratch resistance.

The material of the color change layer B is not particularly limited, but preferably contains the following components.
From the viewpoint of scratch resistance, the color change layer B preferably contains, as a binder, at least one compound selected from the group consisting of a resin and a polymerizable compound, more preferably contains a resin, and more preferably contains a resin. It is more preferable to include an acidic compound.
From the viewpoint of scratch resistance, the resin preferably contains at least one resin selected from the group consisting of a thermosetting resin and a photocurable resin.
As the thermosetting resin and the photocurable resin, those described above for the color change layer A can be suitably used by appropriately selecting the refractive index.
There is no particular limitation on the polymerizable compound, and known monomers and oligomers can be used. Further, as the polymerizable compound, the above-described polymerizable compound in the colored layer can be suitably used.
In addition, as the polymerizable compound, those described above in the color change layer A can be suitably used by appropriately selecting the refractive index before or after curing.
When the color change layer B contains a polymerizable compound, it is preferable to contain a polymerization initiator from the viewpoint of curability and scratch resistance.
As the polymerization initiator, those described above in the colored layer can be suitably used.

Since the color change layer B is a layer having a refractive index lower than that of the color change layer A by 0.1 or more, it is preferable to include a material having a low refractive index.
The color change layer B preferably has a refractive index of 1.5 or less, more preferably 1.4 or less, from the viewpoint of color change. In that the refractive index is 1.5 or less, the color change layer B preferably contains at least one selected from the group consisting of a siloxane resin having a void, a fluororesin, and low refractive index particles. More preferably, it contains at least one selected from the group consisting of a siloxane resin, a fluororesin, and hollow silica particles.
The fluororesin is not particularly limited, and examples thereof include those described in paragraphs 0076 to 0106 of JP-A-2009-217258 and paragraphs 0083 to 0127 of JP-A-2007-229999.
Examples of the fluorine resin include an alkyl fluoride resin in which hydrogen in an olefin is replaced with fluorine, and include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, perfluoroalkoxyalkane, and perfluoroalkyl resin. Examples include a copolymer such as ethylene propene and ethylene tetrafluoroethylene, or a fluororesin dispersion which is copolymerized with an emulsifier or a component for enhancing affinity with water and dispersed in water. Specific examples of such a fluororesin include Lumiflon and Obrigato manufactured by Asahi Glass Co., Ltd., Zeffle and Neoflon manufactured by Daikin Industries, Ltd., Teflon manufactured by DuPont, and Kynar Kayner.
Further, a compound having at least one of a polymerizable functional group and a crosslinkable functional group and containing a fluorine atom may be used, and a perfluoroalkyl (meth) acrylate, a vinyl fluoride monomer, a vinylidene fluoride, Examples include radically polymerizable monomers such as monomers, and cationically polymerizable monomers such as perfluorooxetane. Specific examples of such a fluorine compound include LINC3A manufactured by Kyoeisha Chemical Co., Ltd., Optool manufactured by Daikin Industries, Ltd., Opstar manufactured by Arakawa Chemical Industry Co., Ltd., and tetrafluorooxetane manufactured by Daikin Industries, Ltd. .
The low refractive index particles, preferably particles having a refractive index of 1.45 or less are not particularly limited, and examples thereof include those described in paragraphs 0075 to 0103 of JP-A-2009-217258.
Examples of low refractive index particles include hollow particles using inorganic oxide particles such as silica and resin particles such as acrylic, porous particles having a porous structure on the particle surface, and fluoride particles having a low refractive index of the material itself. And the like.
Specific examples of such hollow particles include hollow silica particles such as Sluria manufactured by JGC Catalysts & Chemicals Co., Ltd., Sirinax manufactured by Nittetsu Mining Co., Ltd., Techpolymer MBX and SBX manufactured by Sekisui Plastics Co., Ltd. Examples include multi-hollow resin particles. Specific examples of the porous particles include Light Star manufactured by Nissan Chemical Industry Co., Ltd., and specific examples of the fluoride particles include magnesium fluoride nanoparticles manufactured by Rare Metal Materials Laboratory Co., Ltd.

As the siloxane resin having the voids, hollow particles or core-shell particles are used in terms of suppressing deterioration such as thermal deformation of the resin base material and in that the above-described openings are not easily formed on the surface of the color change layer B. It is preferable to use a method of forming closed voids in a matrix containing a siloxane resin using Examples of a method for forming the color-changing layer B by applying a composition containing hollow particles include, for example, the methods described in paragraphs 0028 to 0029 of JP-A-2009-103808 or the paragraphs of JP-A-2008-262187. The methods described in 0030 to 0031 can be applied. In particular, a method of forming the color change layer B using core-shell particles is preferable because the adjustment of the void diameter and the void ratio is easy.

Hereinafter, a preferred embodiment of a method for forming the color-change layer B using the core-shell particles will be described, but the color-change layer B in the present disclosure is not limited to the one formed by this method.
In the method of forming the color-change layer B using the core-shell particles, it is preferable to use a coating solution containing the core-shell particles and a siloxane compound (hereinafter, also referred to as a “color-change layer B-forming coating solution”).

－Core-shell particles－
The color change layer B forming coating liquid preferably contains core-shell particles.
The core-shell particles preferably contain an organic solvent as a core material from the viewpoint of easy formation of closed voids. In particular, 20% by mass or more of the organic solvent is a nonpolar solvent having a boiling point of 90 ° C or more and 350 ° C or less. Preferably, there is.
The “boiling point” in the present disclosure is a boiling point at 1 atm (101,325 Pa). The “non-polar solvent” in the present disclosure refers to a solvent having a solubility in water of 0.1% by mass or less at 20 ° C. and a relative dielectric constant of 10 or less.

Examples of the nonpolar solvent having a boiling point of 90 ° C. or more and 350 ° C. or less include a hydrocarbon compound, a fluorinated hydrocarbon compound, and a silicone compound. From the viewpoint of the light transmittance and haze of the color change layer B, hydrocarbon It is preferably a compound.

The material of the shell of the core-shell particles is not particularly limited, but preferably contains a polysiloxane compound from the viewpoints of strength, light transmittance, and haze of the color change layer B. More preferably, the composition contains a hydrolysis condensate, more preferably 50% by mass or more based on the total mass of the shell, of the siloxane compound represented by Formula 1 described below, and more preferably 50% by mass or more. It is particularly preferred to be composed of a hydrolyzed condensate of the represented siloxane compound.

The volume average particle diameter of the core-shell particles is preferably from 0.05 μm to 1.5 μm, more preferably from 0.08 μm to 1.0 μm, from the viewpoint of the strength, light transmittance and haze of the color change layer B. More preferably, it is 0.1 μm to 0.6 μm, particularly preferably 0.1 μm to 0.4 μm.

The volume average particle size of the particles in the present disclosure is measured using a laser diffraction / scattering type particle size distribution measuring device (model number: Microtrac MT3300EXII, manufactured by Microtrac Bell Co., Ltd.). In the present disclosure, the average particle diameter means a median diameter.
In addition, the coefficient of variation of the particle diameter of the core-shell particles in the present disclosure is calculated by dividing the standard deviation in the volume distribution of the particle diameter measured in the above measurement by the median diameter.

The size (maximum diameter) of the core in the core-shell particles is preferably 40 nm or more, more preferably 40 nm to 1,000 nm, and more preferably 60 nm, from the viewpoints of the strength, light transmittance and haze of the color change layer B. It is particularly preferred that the thickness be up to 600 nm.
The size (maximum diameter) of the core in the core-shell particles can be measured by the same method as the method for measuring the diameter of the void in the color change layer B described above.

-Siloxane compound-
The coating liquid for forming the color change layer B preferably contains a siloxane compound.
In particular, as the siloxane compound, at least one compound selected from the group consisting of a siloxane compound represented by the following formula 1 and a hydrolyzed condensate of the siloxane compound represented by the following formula 1 (hereinafter referred to as a specific siloxane compound) Is also referred to as a compound).

In Formula 1, R ¹ , R ^2, and R ³ each independently represent an alkyl group or an alkenyl group having 1 to 6 carbon atoms, and when a plurality of R ^{4 s} are present, an alkyl group, a vinyl group, Or vinyl, epoxy, vinylphenyl, (meth) acryloxy, (meth) acrylamide, amino, isocyanurate, ureido, mercapto, sulfide, polyoxyalkyl, carboxy and quaternary Represents an alkyl group having a group selected from the group consisting of quaternary ammonium groups, m represents an integer of 0 to 2, and n represents an integer of 1 to 20.

The hydrolysis-condensation product of the siloxane compound represented by the formula 1 means that the siloxane compound represented by the formula 1 and at least a part of the substituents on the silicon atoms in the siloxane compound represented by the formula 1 are hydrolyzed. , A compound obtained by condensation with a compound having a silanol group.

The alkyl group or alkenyl group having 1 to 6 carbon atoms in R ¹ , R ² and R ³ in the formula 1 may have a ring structure, whether it is linear or branched. Is also good. The alkyl group or alkenyl group having 1 to 6 carbon atoms is preferably an alkyl group from the viewpoint of the strength, light transmittance and haze of the protective layer.
Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, and a cyclohexyl group. And preferably a methyl group or an ethyl group, and more preferably a methyl group.

In the formula 1, R ⁴ is preferably an alkyl group independently from the viewpoint of the strength, light transmittance, and haze of the protective layer, and is more preferably an alkyl group having 1 to 8 carbon atoms. preferable.
Further, the carbon number of R ⁴ in Formula 1 is preferably 1 to 40, more preferably 1 to 20, and particularly preferably 1 to 8.
M in the formula 1 is preferably 1 or 2, and more preferably 2 from the viewpoint of the strength, light transmittance and haze of the protective layer.
N in Formula 1 is preferably an integer of 2 to 20 from the viewpoints of strength, light transmittance, and haze of the protective layer.

Examples of the specific siloxane compound include KBE-04, KBE-13, KBE-22, KBE-1003, KBM-303, KBE-403, KBM-1403, KBE-503, KBM- manufactured by Shin-Etsu Chemical Co., Ltd. 5103, KBE-903, KBE-9103P, KBE-585, KBE-803, KBE-846, KR-500, KR-515, KR-516, KR-517, KR-518, X-12-1135, X- 12-1126, X-12-1131; Dynasylan 4150 manufactured by Evonik Japan Co., Ltd .; MKC silicate MS51, MS56, MS57, MS56S manufactured by Mitsubishi Chemical Corporation; ethyl silicate 28, N-propyl silicate manufactured by Colcoat Co., Ltd. , N-butyl silicate, SS-101; .

-Surfactant-
The coating liquid for forming the color change layer B preferably contains a surfactant.
Examples of the surfactant include a nonionic surfactant, an anionic surfactant that is an ionic surfactant, a cationic surfactant, an amphoteric surfactant, and the like, and any of them can be suitably used in the present disclosure.
Among them, the point that core-shell particles are efficiently formed by the above-mentioned specific siloxane compound and interactive attractive force, storage stability, and, from the viewpoint of light transmittance and haze of the color-change layer B, a nonionic surfactant, And, at least one surfactant selected from the group consisting of cationic surfactants is preferred, and cationic surfactants are more preferred.

-Other components-
The coating solution for forming the color-change layer B may contain other components in addition to the components described above, depending on the purpose.
As other components, known additives can be used, and examples thereof include an antistatic agent, a siloxane compound condensation catalyst, and a preservative.

-Antistatic agent The coating liquid for forming the color change layer B may contain an antistatic agent.
The antistatic agent is used for imparting antistatic properties to the color change layer B, thereby suppressing the attachment of contaminants.
The antistatic agent for imparting antistatic properties is not particularly limited.
As the antistatic agent used in the present disclosure, at least one selected from the group consisting of metal oxide particles, metal nanoparticles, conductive polymers, and ionic liquids can be preferably used. Two or more antistatic agents may be used in combination.
The metal oxide particles need to be added in a relatively large amount in order to provide antistatic properties. Can be enhanced.

The metal oxide particles are not particularly limited, and examples thereof include tin oxide particles, antimony-doped tin oxide particles, tin-doped indium oxide particles, zinc oxide particles, and silica particles.
The metal oxide particles have a large refractive index, and if the particle size is large, there is a concern that light transmittance may be reduced due to scattering of transmitted light, so the average primary particle size of the metal oxide particles is preferably 100 nm or less, It is more preferably at most 30 nm, particularly preferably at most 30 nm. Further, the lower limit is preferably 2 nm or more.
The shape of the particles is not particularly limited, and may be spherical, plate-like, or needle-like.
The average primary particle diameter of the metal oxide particles can be determined from a photograph obtained by observing the dispersed particles with a transmission electron microscope. From the image of the photograph, the projected area of the particles is determined, and the equivalent circle diameter is determined therefrom, which is defined as the average particle diameter (average primary particle diameter). The average primary particle diameter in the present specification uses a value obtained by measuring the projected area of 300 or more particles and calculating the equivalent circle diameter.
When the shape of the metal oxide particles is not spherical, it may be determined by using another method, for example, a dynamic light scattering method.

The antistatic agent may be contained alone or in combination of two or more in the coating solution for forming the color change layer B. When two or more types of metal oxide particles are contained, two or more types having different average primary particle diameters, shapes, and materials may be used.
In the coating solution for forming the color changing layer B, the content of the antistatic agent is preferably 40% by mass or less, and more preferably 30% by mass or less, based on the total solid content of the coating solution for forming the color changing layer B. Is more preferable, and particularly preferably 20% by mass or less.
By setting the content of the antistatic agent in the above range, the antistatic property can be effectively imparted to the color changing layer B without lowering the film forming property of the coating solution for forming the color changing layer B.
When metal oxide particles are used as the antistatic agent, the content is preferably 30% by mass or less, and more preferably 20% by mass or less, based on the total mass of the coating solution for forming the color change layer B. More preferably, it is particularly preferably 10% by mass or less.
By setting the content of the metal oxide particles in the above range, the dispersibility of the metal oxide particles in the coating solution for forming the color change layer B becomes good, the occurrence of aggregation is suppressed, and the necessary antistatic property is changed by the color change. It can be applied to layer B.

-Condensation catalyst The coating liquid for forming the color change layer B preferably contains a condensation catalyst that promotes the condensation of the siloxane compound.
When the coating solution for forming the color-change layer B contains a condensation catalyst, the color-change layer B having more excellent durability can be formed.

-Preparation of coating solution for forming color change layer B-
The method of preparing the coating solution for forming the color-change layer B is not particularly limited. For example, an organic solvent, a surfactant, and water are mixed, the organic solvent is dispersed in water, and a specific siloxane compound is added. A method for producing a core-shell particle by forming a shell layer on the surface of an organic solvent dispersed and partially hydrolyzed and condensed to produce a coating solution for forming a color-change layer B, a core-shell particle containing an organic solvent as a core material, A method of mixing and producing a siloxane compound, a surfactant, and water is exemplified.

-Formation of color change layer B-
The coating liquid for forming the color-change layer B described above is applied on the lower layer of the color-change layer B and dried to form the color-change layer B.
The method for applying the coating solution for forming the color-change layer B is not particularly limited, and any of known coating methods such as spray coating, brush coating, roller coating, bar coating, and dip coating can be applied. .
Before applying the coating solution for forming the color-change layer B, the lower layer to which the coating solution for forming the color-change layer B is applied is subjected to corona discharge treatment, glow treatment, atmospheric pressure plasma treatment, flame treatment, and ultraviolet irradiation treatment. Etc. may be applied.

Drying of the coating solution for forming the color change layer B may be performed at room temperature (25 ° C.) or may be performed by heating. In the case of a coating liquid that sufficiently volatilizes the organic solvent contained in the coating liquid for forming the color-change layer B and forms a void, a void is formed, and the light-transmitting property of the color-change layer B and the viewpoint of suppressing coloration, Further, from the viewpoint of heating at a temperature equal to or lower than the decomposition temperature of the resin base material, it is preferable to perform the heating by heating to 40 to 200 ° C. Further, from the viewpoint of suppressing thermal deformation of the resin base material, it is more preferable that the heating is performed at 40 ° C. to 120 ° C.
When heating is performed, the heating time is not particularly limited, but is preferably 1 minute to 30 minutes.

In the above, the coating liquid for forming the color-change layer B containing the core-shell particles and the formation of the color-change layer B using the coating liquid for forming the color-change layer B have been described. The color changing layer B may be formed using a coating liquid for forming.
Here, as the hollow particles, it is preferable to use hollow silica particles containing silica as a main component, since the refractive index is 1.5 or less.
Examples of the hollow silica particles include hollow particles described in JP-A-2013-237593, WO 2007/060884, and the like.
The hollow silica particles may be unmodified hollow silica particles or hollow silica particles having a modified surface.
In addition, the hollow particles are subjected to physical discharge treatment such as plasma discharge treatment and corona discharge treatment in the coating liquid for forming the color change layer B in order to stabilize the dispersion or to increase the affinity and binding with the siloxane resin. Surface treatment, a chemical surface treatment with a surfactant, a coupling agent, or the like.

The porosity of the color change layer B is preferably from 10% to 80%, more preferably from 15% to 75%, and more preferably from 20% to 55%, from the viewpoint of light transmittance and scratch resistance. Is particularly preferred.
The diameter of the voids in the color change layer B (hereinafter, also referred to as “void diameter”) is preferably 25 nm or more, and more preferably 30 nm or more, from the viewpoints of strength, light transmittance, and haze. The upper limit of the void diameter is preferably 80 nm or less, more preferably 70 nm or less, from the viewpoint of scratch resistance.

The method for measuring the pore diameter and the porosity of the color change layer B is as follows.
The decorative film provided with the color changing layer B is cut in a direction perpendicular to the film surface, and the cut surface is observed with a scanning electron microscope (SEM) to measure the void diameter and the porosity.
In the SEM image of the cut surface (magnification: 50,000 times), the circle equivalent diameter is calculated for each of the 200 arbitrarily selected voids, and the average value is defined as the void diameter.
The porosity of the cut surface was determined by using an image processing software (ImageJ) for the SEM image of the cut surface (magnification: 50,000 times), using the image processing software (ImageJ) to determine the image of the void portion and the matrix portion (that is, the portion other than the void containing the siloxane resin). Processing (binarization) is performed and separated, and the ratio of the void portion is calculated to be the porosity.
In addition, when there is no anisotropy in the diameter of the void, the porosity is obtained as a volume fraction of the void in the siloxane resin.

(Resin layer)
The decorative film according to the present disclosure preferably further includes a resin layer between the colored layer and the color changing layer A, from the viewpoint of improving the adhesion between the colored layer and the color changing layer A. .
The resin layer is preferably a layer containing a different type of resin from the color change layer A.
The resin layer is preferably a transparent resin layer from the viewpoint of color change, and more preferably a layer made of a transparent film. By forming the color change layer A on a transparent film and laminating it on a colored layer, a decorative film can be easily produced.
The transparent film is not particularly limited as long as it has the necessary strength and scratch resistance.
In the present disclosure, “transparent” in a transparent film indicates that the total light transmittance is 85% or more. The total light transmittance of the transparent film can be measured by the same method as the above-mentioned total light transmittance of the temporary support.

The transparent film is preferably a film obtained by forming a transparent resin. Specifically, polyethylene terephthalate (PET) resin, polyethylene naphthalate (PEN) resin, acrylic resin, polycarbonate (PC) resin, triacetyl A resin film containing a resin such as cellulose (TAC) or cycloolefin polymer (COP) may be used.
In particular, from the viewpoint of shape followability to a mold, an acrylic resin, a polycarbonate resin, or a polyethylene terephthalate resin is used in an amount of 60% by mass or more (more preferably 80% by mass or more, more preferably 80% by mass or more based on all resin components contained in the transparent film). Is preferably 100% by mass). In particular, a resin film containing 60% by mass or more (more preferably 80% by mass or more, more preferably 100% by mass) of an acrylic resin with respect to all resin components contained in the transparent film is more preferable.
The thickness of the resin layer is not particularly limited, but is preferably 50 μm to 150 μm.

Commercially available products may be used as the transparent film. Examples of the commercially available products include Acryprene (registered trademark) HBS010 (acrylic resin film, manufactured by Mitsubishi Chemical Corporation) and Technoroy (registered trademark) S001G (acrylic resin film, Sumitomo Chemical Co., Ltd.), C000 (polycarbonate resin film, Sumitomo Chemical Co., Ltd.), C001 (acrylic resin / polycarbonate resin laminated film, Sumitomo Chemical Co., Ltd.) and the like.

-Formation of resin layer-
The method for forming the resin layer is not particularly limited, but preferably includes a method of laminating a transparent film on the colored layer.
As a device used for laminating the transparent film, a known laminator such as a laminator, a vacuum laminator, and an auto-cut laminator capable of further increasing the productivity can be used.
The laminator is preferably provided with an optional heatable roller such as a rubber roller, and can be pressurized and heated.
By the heating from the laminator, at least one of the transparent film and the colored layer is partially melted, and the adhesion between the colored layer and the transparent film can be further increased.

The temperature at the time of laminating the transparent film may be determined according to the material of the transparent film, the melting temperature of the colored layer, and the like, but it is preferable that the temperature of the transparent film be 60 ° C. to 150 ° C. , 65 ° C to 130 ° C, more preferably 70 ° C to 100 ° C.

When laminating the transparent film, it is preferable to apply a linear pressure of 60 N / cm to 200 N / cm between the transparent film and the coloring layer, and more preferably to apply a linear pressure of 70 N / cm to 160 N / cm. It is particularly preferable to apply a linear pressure of 80 N / cm to 120 N / cm.

(Adhesive layer)
The decorative film according to the present disclosure may have a pressure-sensitive adhesive layer between the temporary support and the colored layer from the viewpoint of adhesiveness to a substrate to which the decorative film is to be attached.
Further, as described later, before the attachment to the base material, the temporary support is peeled off, and the adhesive layer is formed on the outermost layer on the colored layer side of the decorative film from which the temporary support has been peeled off. It may be formed and then attached to a substrate.
The material of the adhesive layer is not particularly limited and can be appropriately selected depending on the purpose. For example, a layer containing a known adhesive or adhesive can be used.

-Adhesive-
Examples of the pressure-sensitive adhesive include an acrylic pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, and a silicone-based pressure-sensitive adhesive. Examples of the pressure-sensitive adhesive include acrylic pressure-sensitive adhesives described in Chapter 2 of "Evaluation of Properties of Release Papers / Release Films and Pressure-Sensitive Tapes and Their Control Techniques", Jikken, 2004, Chapter 2, and ultraviolet (UV) curable adhesives. Agents, silicone adhesives and the like. The acrylic pressure-sensitive adhesive refers to a pressure-sensitive adhesive containing a polymer of a (meth) acrylic monomer ((meth) acrylic polymer).
When an adhesive is included, a tackifier may be further included.

-adhesive-
Examples of the adhesive include a urethane resin adhesive, a polyester adhesive, an acrylic resin adhesive, an ethylene vinyl acetate resin adhesive, a polyvinyl alcohol adhesive, a polyamide adhesive, and a silicone adhesive. From the viewpoint of higher adhesive strength, urethane resin adhesives or silicone adhesives are preferred.

-Method of forming adhesive layer-
The method for forming the pressure-sensitive adhesive layer is not particularly limited, and a method of laminating the protective film on which the pressure-sensitive adhesive layer is formed so that the pressure-sensitive adhesive layer and the colored layer are in contact with each other, and laminating the pressure-sensitive adhesive layer alone so as to be in contact with the colored layer. And a method of applying a composition containing the above-mentioned pressure-sensitive adhesive or adhesive on the colored layer. As a laminating method or a coating method, a method similar to the above-described method of laminating a transparent film or a method of applying a composition for forming a colored layer is preferably exemplified.

(4) The thickness of the adhesive layer in the decorative film is preferably 5 μm to 100 μm from the viewpoint of coexistence of adhesive strength and handleability.

[Other layers]
The decorative film according to the present disclosure may have other layers other than those described above.
Examples of the other layers include a reflective layer, a self-healing layer, an antistatic layer, an antifouling layer, an anti-electromagnetic wave layer, and a conductive layer, which are known layers in the decorative film.
Other layers in the decorative film according to the present disclosure can be formed by a known method. For example, there is a method in which a composition containing the components contained in these layers (layer-forming composition) is applied in the form of a layer and dried.

－Cover film－
The decorative film according to the present disclosure may have a cover film as an outermost layer on the color change layer B side for the purpose of preventing contamination and the like.
The cover film is not particularly limited as long as it has flexibility and good releasability, and examples thereof include resin films such as polyethylene films.
The method for attaching the cover film is not particularly limited, and includes a known attaching method, such as a method of laminating the cover film on the color changing layer B.

(Decorative molded film)
The decorative molded film according to the present disclosure has a base material, a coloring layer, a color changing layer A, and a color changing layer B in this order, and the color changing layer B has a refractive index higher than that of the color changing layer A. It is a layer lower than 0.1.
The coloring layer, the color changing layer A, and the color changing layer B in the decorative molded film according to the present disclosure are the same as the coloring layer, the color changing layer A, and the color changing layer B in the decorative film according to the present disclosure. Yes, and the preferred embodiment is also the same. Further, the preferred embodiments of the other layers are also the same.
The substrate in the decorative molded film according to the present disclosure is preferably a film substrate. Moreover, it is particularly preferable that the substrate in the decorative molded film according to the present disclosure is a molding substrate. The substrate is the same as the substrate described below, and the preferred embodiment is also the same.
In addition, for the method of manufacturing a decorative molded film according to the present disclosure, a method of attaching to a base material in a decorative method according to the present disclosure described later can be referred to.

(Decoration method and decoration)
The decorating method according to the present disclosure is not particularly limited as long as it is a decorating method using the decorative film according to the present disclosure, and a step of peeling the temporary support from the decorative film according to the present disclosure, Affixing the decorative film from which the temporary support has been peeled off to the substrate from the colored layer side, preferably the surface from which the temporary support has been peeled off in the decorative film from which the temporary support has been peeled off. It is more preferable that the method further includes a step of forming an adhesive layer.
The decorative article according to the present disclosure is a decorative article using the decorative film according to the present disclosure, and is preferably a decorative article obtained by the decorating method according to the present disclosure.

-Step of peeling off the temporary support-
The decorating method according to the present disclosure preferably includes a step of peeling the temporary support from the decorative film according to the present disclosure.
The peeling method is not particularly limited, and may be a known method. For example, there is a method in which a part of the temporary support is gripped and peeled using a base material such as a finger or tweezers.

-Step of forming an adhesive layer-
The decorating method according to the present disclosure includes a step of forming an adhesive layer on a surface of the decorative film from which the temporary support has been peeled, from which the temporary support has been peeled (hereinafter, also simply referred to as a “step of forming an adhesive layer”). ) Is preferable.
The method for forming the pressure-sensitive adhesive layer and the pressure-sensitive adhesive layer is the same as the method for forming the pressure-sensitive adhesive layer and the pressure-sensitive adhesive layer described above, and the preferable embodiments are also the same.

－Process of sticking to base material－
The decorating method according to the present disclosure includes a step of sticking the decorative film from which the temporary support has been peeled off to the substrate from the colored layer side (also simply referred to as a “step of sticking to the substrate”). Is preferred.
In the step of attaching to the base material, the decorative film from which the temporary support has been removed may be attached to the outermost layer on the colored layer side and the base material. What is necessary is just to stick the said coloring layer or the said adhesive layer of a decorative film, and a base material.

The substrate is not particularly limited, and a desired substrate can be used. Specific examples include automobiles, home appliances, audio products, computers, displays, in-vehicle products, watches, accessories, optical components, doors, window glasses, building materials, and the like.
Above all, the decorating method according to the present disclosure can be suitably used as a decorating method for an automobile exterior.

In addition, a molding substrate can be suitably used as the substrate.
As the molding substrate, a conventionally known substrate used for molding such as three-dimensional molding and insert molding can be used without any particular limitation. It should be done.
The shape and material of the molding substrate are not particularly limited and may be appropriately selected as desired. However, from the viewpoint of ease of insert molding, a film substrate is preferable.

Specific examples of the molding substrate include polyethylene terephthalate (PET) resin, polyethylene naphthalate (PEN) resin, acrylic resin, polycarbonate (PC) resin, triacetyl cellulose (TAC), cycloolefin polymer (COP), A resin film containing a resin such as an acrylonitrile / butadiene / styrene copolymer resin (ABS resin) is exemplified.

The base material for molding is acrylonitrile / butadiene / styrene in an amount of 60% by mass or more based on all resin components contained in the base material for molding because of its suitability for three-dimensional molding and insert molding, and particularly excellent followability to a mold. A resin film containing a copolymer resin (ABS resin) is preferable. The content of the ABS resin with respect to all the resin components contained in the molding base is more preferably 80% by mass or more, and may be 100% by mass (that is, all of the resin components are the ABS resin).

The molding base material may contain additives other than the above-described resins, if necessary.
Examples of such additives include mineral oils, hydrocarbons, fatty acids, alcohols, fatty acid esters, fatty acid amides, metal soaps, natural waxes, lubricants such as silicones, magnesium hydroxide, inorganic flame retardants such as aluminum hydroxide, Organic or inorganic fillers such as halogen-based, phosphorus-based organic flame retardants, metal powder, talc, calcium carbonate, potassium titanate, glass fiber, carbon fiber, and wood powder, antioxidants, UV inhibitors, lubricants, Additives such as dispersants, coupling agents, foaming agents, coloring agents, etc., polyolefin resins, polyester resins, polyacetal resins, polyamide resins, polyphenylene ether resins, and the like, and engineering plastics other than the above-mentioned resins.

A commercially available product may be used as the molding substrate.
Commercially available products include, for example, ABS film (manufactured by Okamoto Corporation), ABS sheet (manufactured by Sekisui Molding Industry Co., Ltd.), Teflex (registered trademark) series (PET film, manufactured by Teijin Film Solutions Ltd.), Lumirror (Registered trademark) easy-molding type (PET film, manufactured by Toray Industries, Inc.) and the like.

The thickness of the molding substrate is determined according to the use of the decorative molded article to be produced, suitability for insert molding, handleability of the sheet, etc., and is not particularly limited, but is preferably 100 μm to 800 μm, and more preferably 150 μm to 600 μm. More preferred.

-Pasting method-
There is no particular limitation on the method of attaching the substrate to the substrate, and a known method can be used.
For example, a method of laminating a base material on the adhesive layer after peeling off the protective film of the adhesive layer as needed is mentioned.
The laminating method is not particularly limited, and for example, the same method as the above-described method for laminating a transparent film is used.

-Exposure process-
In the decorating method according to the present disclosure, as necessary, a step of exposing the colored layer, a step of exposing the color changing layer A, or a step of exposing the color changing layer B (also referred to as an “exposure step”) ).
When the colored layer is exposed, the colored layer preferably contains a polymerizable compound and a photopolymerization initiator. By exposing the colored layer containing the polymerizable compound and the photopolymerization initiator, a cured colored layer can be obtained.
Further, when the colored layer contains a polymerizable compound and a photopolymerization initiator, in the method for producing a decorative film, without performing exposure, the decorative film after the protective film is peeled off so that the substrate and the adhesive layer are in contact with each other. Exposure may be performed after sticking. According to the above method, the adhesive strength between the base material and the decorative film after peeling off the protective film is excellent.
Although the colored layer has been described, the same applies to the color changing layer A and the color changing layer B.

-Exposure timing-
When the decorating method according to the present disclosure includes an exposure step, the timing of performing the exposure step is not particularly limited, even before the step of peeling the temporary support, before the step of forming the adhesive layer. Even if it is before the step of attaching to the substrate, it may be after the step of attaching to the substrate, from the viewpoint of improving the adhesion between the layers, the temporary support It is preferably performed before the peeling step.
Further, from the viewpoint of the laminating property of the pressure-sensitive adhesive layer, the exposure step is preferably performed before the step of forming the pressure-sensitive adhesive layer.
Further, from the viewpoint of ease of molding when ductility at the time of heating is required, it is preferable that the exposure step is performed after the step of sticking to the substrate.

-Exposure method-
The exposure in the exposure step is preferably performed from the color change layer B side from the viewpoint of improving the adhesion between the color change layer A or the resin layer and the cured colored layer.
When exposing in the state having the temporary support (before peeling of the temporary support), the exposure may be performed from the temporary support side, or may be performed from both the color change layer B side and the temporary support side. May be performed. When exposure is performed from the temporary support side, as described above, the total light transmittance of the temporary support is preferably 80% or more, more preferably 90% or more.
When exposure is performed after the step of peeling the temporary support, exposure may be performed from the side of the temporary support that has been peeled, or exposure may be performed from both sides of the color change layer B and the temporary support that has been peeled. May be performed. In this case, an adhesive layer may be formed on the separated temporary support, or a protective film may be further provided.
When exposure is performed through a protective film, as described above, the total light transmittance of the protective film is preferably 80% or more, and more preferably 90% or more.

As the exposure method, for example, the methods described in paragraphs 0035 to 0051 of JP-A-2006-23696 can be suitably used in the present disclosure.

As a light source for exposure, a light source capable of irradiating light (for example, 365 nm, 405 nm) in a wavelength range capable of curing a polymerizable compound can be appropriately selected and used.
Specifically, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp and the like can be mentioned.
The exposure amount is not particularly limited and may be appropriately ^set, is preferably 5mJ / cm 2 ~ 2,000mJ / cm 2, more preferably 10mJ / cm 2 ~ 1,000mJ / cm 2 .

In this step, for example, it is not necessary that all the polymerizable compounds in the colored layer react, and the unpolymerized polymerizable compound and the polymer of the polymerizable compound coexist in the colored layer after exposure. It may be in the state of doing.
In the colored layer after the exposure, the state in which the specific polymerizable compound and the polymer of the specific polymerizable compound coexist, and the decorative molded body obtained after the molding is further exposed, whereby the interlayer adhesiveness (with the colored layer and The adhesion between the color change layer B and the adhesion between the colored layer and the substrate may be further improved.
The same applies to the color change layer A and the color change layer B.

Here, an example of the layer configuration of the decorative film will be described with reference to FIG.
FIG. 1 is a schematic cross-sectional view illustrating an example of a layer configuration of a decorative film according to the present disclosure.
The decorative film 20 has a colored layer 24 on the temporary support 22 and a resin layer 26 on the colored layer 24. The resin layer 26 has a color change layer A28 and a color change layer B30 on the surface opposite to the color layer 24. The resin layer 26 is an arbitrary layer and does not need to be included in the decorative film 20.
Although not shown, the above-described release layer may be provided between the temporary support 22 and the colored layer 24.

FIG. 2 is a schematic cross-sectional view illustrating another example of the decorative film according to the present disclosure.
The decorative film 10 has a coloring layer 24 on the adhesive layer 12, and has a resin layer 26, a color changing layer A28, and a color changing layer B30 on the coloring layer 24 in this order.
The protective film 14 is provided on the side of the adhesive layer 12 opposite to the colored layer 24.
The adhesive layer 12, the protective film 14, and the resin layer 26 are optional layers, and need not be included in the decorative film 10.

FIG. 3 is a schematic cross-sectional view illustrating an example of the decorative molded film according to the present disclosure.
The decorative molded film 40 has an adhesive layer 12, a colored layer 24, a resin layer 26, a color change layer A28, and a color change layer B30 in this order on the base material 16 for molding.
The adhesive layer 12 and the resin layer 26 are optional layers, and need not be included in the decorative molding film 40.

(Production method of decorative molded body and decorative molded body)
The method for manufacturing a decorative molded body according to the present disclosure may be any method for manufacturing a decorative molded body by performing decoration and molding using the decorative film according to the present disclosure. A step of peeling off the temporary support, a step of sticking the decorative film from which the temporary support has been peeled off to the molding base from the colored layer side, and the molding base on which the decorative film is stuck. And a molding step.
The decorative molded body according to the present disclosure is a decorative film obtained by using the decorative film according to the present disclosure or the decorative molded film according to the present disclosure. It is preferably manufactured.
Since the decorative film according to the present disclosure is also excellent in three-dimensional moldability, it can be suitably used for the production of a decorative molded body. For example, three-dimensional molding, and at least one selected from the group consisting of insert molding It is particularly suitable when producing a decorative molded body by molding.
Further, the decorative film according to the present disclosure can be made into a decorative molded body by sticking to a molded body after molding.
The decorative molded film according to the present disclosure is also excellent in three-dimensional moldability, and thus can be suitably used for the production of a decorative molded body. For example, when the molded body is a resin, it is particularly suitable, for example, when manufacturing a decorative molded body by at least one type of molding selected from the group consisting of three-dimensional molding and insert molding. Further, when the molded body is a material that does not melt, such as metal, it is particularly suitable when a decorative molded body is manufactured by three-dimensional molding.
By using the decorative film according to the present disclosure during the production of the decorative molded body, it is possible to apply it to a mold having a more complicated shape, a smaller shape, and the like, thereby expanding the range of applications of the decorative molded body. it can.
Hereinafter, a method for producing a decorative molded body will be described in detail by taking insert molding as an example.

In the insert molding, the decorative molded body is obtained by, for example, disposing a decorative molded film in a mold in advance and injection molding a base resin in the mold. By this insert molding, a decorative molded body in which the decorative film is integrated with the surface of the resin molded body is obtained.

Further, at the time of producing the decorative molded body, an adhesive layer may be provided between the decorative molded film and the resin molded body.
As the 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 may be used.
A commercially available adhesive may be used, and examples of the commercially available adhesive include IMB-003 manufactured by Teikoku Ink.

Hereinafter, one embodiment of a method for producing a decorative molded body by insert molding will be described.
The method for producing a decorative molded body is a step of placing a decorative molded film formed into a quadrilateral of a certain dimension in a mold for injection molding and closing the mold, and then putting the molten resin in the mold. And a step of taking out when the injected resin is solidified.

A mold for injection molding (that is, a molding die) used for manufacturing a decorative molded body includes a mold having a convex shape (that is, a male mold) and a mold having a concave shape corresponding to the convex shape (that is, a mold). After the decorative molding film is disposed on the molding surface that is the inner peripheral surface of the female mold, the mold is closed.

Here, before placing the decorative molding film in the molding die, the decorative molding film is molded (preformed) using a molding die to form a decorative molding film. It is also possible to provide a three-dimensional shape in advance and supply it to a molding die.
In addition, when the decorative film is placed in the molding die, it is necessary to position the decorative molding film and the molding die while the decorative molding film is inserted into the molding die.

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

Further, the fixing pin is formed in advance at a position where the fixing pin fits with the positioning hole in the male mold.
In addition, as a method of performing positioning between the decorative molding film and the molding die in a state where the decorative molding film is inserted into the molding die, in addition to the method of inserting the fixing pin into the positioning hole, the following method is also used. A method can be used.

For example, there is a method of finely adjusting and aligning the decorative molding film by driving the conveying device side of the decorative molding film as a target to a positioning mark previously attached to a position where a three-dimensional shape is not provided after molding in the decorative molding film. In this method, it is preferable that the alignment mark is recognized at two or more diagonal points when viewed from the product part of the injection molded product (decorative molded product).

(4) Align the decorative molding film with the molding die, close the molding die, and then inject the molten resin into the molding die into which the decorative molding film is inserted. At the time of injection, molten resin is injected into the decorative molding film on the molding substrate side.

温度 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 to be used is an acrylic resin, the temperature of the molten resin is preferably in the range from 240 ° C. to 260 ° C.

The position of the injection port (injection port) of the male mold is set to prevent the decorative molded film from being abnormally deformed by heat or gas generated when the molten resin is injected into the molding die. It may be set according to the shape of the molding die or the type of the molten resin.
After the molten resin injected into the molding die into which the decorative molding film is inserted is solidified, the molding die is opened, and the decorative molding film is transferred from the molding die to the molding base, which is the solidified molten resin. Take out the fixed intermediate decorative molded body.

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 (decorative molded body). Here, the dummy portion has an insertion hole formed by inserting the fixing pin in the above-described alignment.
For this reason, the decorative molded body can be obtained by performing the finishing process of removing the burrs and the dummy portions from the decorative portion of the intermediate decorative molded body before the finishing processing.

The decorative molded article obtained as described above may be exposed to increase the degree of curing of the colored layer in the decorative film.
By performing this exposure, the adhesion between the colored layer and the transparent film and between the colored layer and the decorative molded body is further increased, and the durability against heat and the like is further improved.

The decorative film and the decorative molded film according to the present disclosure also preferably include three-dimensional molding.
As the three-dimensional molding, heat molding, vacuum molding, air pressure molding, vacuum pressure molding, and the like are preferably exemplified.
The method of vacuum molding is not particularly limited, but a method of performing three-dimensional molding in a heated state under vacuum is preferable.
The vacuum means a state in which the interior of the room is evacuated to a degree of vacuum of 100 Pa or less.
The temperature during the three-dimensional molding may be appropriately set according to the molding substrate to be used, but is preferably a temperature range of 60 ° C. or higher, more preferably a temperature range of 80 ° C. or higher, and further preferably a temperature range of 100 ° C. or higher. . The upper limit of the temperature during three-dimensional molding is preferably 200 ° C.
The temperature at the time of performing three-dimensional molding refers to the temperature of the molding substrate used for three-dimensional molding, and is measured by attaching a thermocouple to the surface of the molding substrate.

真空 The above-mentioned vacuum molding can be performed using a vacuum molding technique widely known in the molding field. For example, vacuum molding may be performed using Formech 508FS manufactured by Nippon Zokeki Kogyo Co., Ltd.

The application of the decorative molded body obtained as described above is not particularly limited and can be used for various articles, but the interior and exterior of automobiles, the interior and exterior of electric products, packaging containers and the like are particularly preferable. No.

本 Hereinafter, the present disclosure will be described more specifically with reference to examples. The scope of the present disclosure is not limited to the specific examples described below. Unless otherwise specified, “parts” and “%” are based on mass.

<Preparation of each composition for decorative film formation>
(Preparation of colored layer forming composition)
A colored layer forming composition 1 having the following composition was prepared.
Black pigment dispersion: 302.9 parts by mass Binder resin: 253.9 parts by mass Polymerizable compound: 74.4 parts by mass Polymerization initiator: 0.9 parts by mass Surfactant: 0.4 parts by mass Organic solvent: 367. 5 parts by mass

Details of each of the above compounds are shown below.
Binder resin: 40 mass% 1-methoxy-2-propyl acetate solution of benzyl methacrylate / methacrylic acid (molar ratio 70/30) copolymer (weight average molecular weight Mw: 29,000) Polymerizable compound: Sartomer Japan Co., Ltd., urethane acrylate oligomer, CN-996NS (solid content: 100% by mass)
Polymerization initiator: OXE-02 (1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone-1- (O-acetyloxime) manufactured by BASF)
Surfactant: Megafac (registered trademark) F-551, manufactured by DIC Corporation, a solution of a phosphate-type amine-neutralized product containing a perfluoroalkyl group in methyl isobutyl ketone (solid content: 30% by mass)
・ Organic solvent: methyl ethyl ketone

(Preparation of black pigment dispersion)
Carbon black, a dispersant, a polymer, and a solvent were mixed so as to have the following composition of a black pigment dispersion, and a black pigment dispersion was obtained using a three-roll mill and a bead mill. The average particle size (median size) measured using Microtrack FRA (Honeywell) was 163 nm.

-Composition of black pigment dispersion-
-Resin-coated carbon black produced according to the description of paragraphs 0036 to 0042 of Japanese Patent No. 5320652: 20.0% by mass
Dispersant 1 (the following structure): 1.0% by mass
-Polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio random copolymer, weight average molecular weight 300000): 6.0% by mass
-Propylene glycol monomethyl ether acetate: 73.0% by mass

<Preparation of decorative film>
(Preparation of temporary support)
As a temporary support, a PET film with a release layer (Unipeel TR-6, thickness 75 μm, manufactured by Unitika Ltd.) was prepared.

[Formation of Colored Layer (Step of Forming Colored Layer)]
Using an extrusion coater, the composition 1 for forming a colored layer is applied on the surface of the temporary support on which the release layer is to be applied so that the thickness after drying is 8 μm. This was dried at 110 ° C. for 2 minutes to form a colored layer. Thereafter, a polyethylene film (35 μm thick, GF-8 manufactured by Tamapoly Corporation) was adhered as a cover film.
Thereafter, the entire surface was exposed at an exposure amount of 500 mJ / cm ² (i-line) from both sides of the laminated body of the formed colored layer and the temporary support.

[Preparation of transparent film]
As a transparent film, Technoroy S001G (100 μm thick acrylic resin film, manufactured by Sumika Acrylic Sales Co., Ltd.) was prepared.

<Preparation of resin layer and color change layer A>
[Formation of color change layer A on the surface of a transparent film (resin layer)]
A color-changing layer A having a refractive index and a thickness shown in Table 1 was formed on the transparent film using a composition for forming a color-changing layer A described later.
Specifically, using an extrusion coater on a transparent film, a coating solution as a composition for forming a color-changing layer A was coated on one surface of the transparent film with a thickness shown in Table 1 (after drying). (Color thickness) was formed, and dried at 80 ° C. for 2 minutes to form a color change layer A. Thereafter, the entire surface was exposed from the side of the formed color changing layer A at an exposure amount of 300 mJ / cm ² (i-line).

[Formation of color change layer B]
Next, a color change layer B having a refractive index and a thickness shown in Table 1 was formed on the color change layer A.
Specifically, using an extrusion coater, a coating solution, which is a composition for forming a color-changing layer B, is applied on the color-changing layer A in an amount of the thickness (thickness after drying) shown in Table 1. This was dried at 80 ° C. for 2 minutes to form a color change layer B. Thereafter, the entire surface was exposed from the formed color changing layer B side at an exposure amount of 300 mJ / cm ² (i-line). However, Example 3 was not exposed.

[Lamination of colored layer and transparent film (resin layer)]
After peeling off the cover film from the coloring layer, lamination was performed so that the non-coated surface of the transparent film was in contact with the coloring layer.
Laminating conditions were as follows: roll temperature: 90 ° C., linear pressure: 100 N / cm, conveyance speed: 0.1 m / min.

(Preparation of adhesive layer)
After peeling off the temporary support from the laminated body after exposure, after peeling off one side of the protective film of the pressure-sensitive adhesive sheet (G25, manufactured by Niei Kako Co., Ltd.) having protective films on both sides, the temporary support is peeled off. An adhesive sheet was laminated (temperature: 30 ° C., linear pressure: 100 N / cm, conveyance speed: 0.1 m / min). The protective film on one side was not peeled off.
Thus, the decorative films of Examples 1 to 18 each including the protective film, the adhesive layer, the coloring layer, the resin layer, the color changing layer A, and the color changing layer B were formed.

The details of the composition for forming the color-change layer A and the composition for forming the color-change layer B used in the comparative examples are shown below.
In the following examples, the following abbreviations represent the following compounds, respectively.
Ethoxylated O-phenylphenol acrylate: Shin-Nakamura Chemical Co., Ltd. SZR-M: Zirconium oxide dispersion, Sakai Chemical Industry Co., Ltd., SZR-M, 30% by mass methanol solution, median diameter: 3 nm
SZR-CW: zirconium oxide dispersion, SZR-CW manufactured by Sakai Chemical Industry Co., Ltd., 30% by mass aqueous solution, median diameter: 6 nm
HTD-780T: titanium oxide particles, HTD-780T manufactured by Teica Corporation
Irgacure 2959 (1% methanol dilution): polymerization initiator, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methylpropan-1-one, manufactured by BASF, 1% by mass methanol dilution Irgacure 2959 (Powder): polymerization initiator, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methylpropan-1-one, manufactured by BASF, powder F-444 (1% methanol dilution) ): Fluorosurfactant, manufactured by DIC Corporation, 1% by mass methanol diluted solution F-444 (stock solution): Fluorosurfactant, manufactured by DIC Co., stock solution F-444 (1% diluted with distilled water) : Fluorinated surfactant, manufactured by DIC Corporation, 1% by mass diluted with distilled water PET-30: polyfunctional acrylic monomer, Nippon Kayaku Co., Ltd. PET-30, pen Mixture of erythritol triacrylate and pentaerythritol tetraacrylate Epocros WS-700: manufactured by Nippon Shokubai Co., Ltd. Epocross WS-700, an oxazoline group-containing polymer Pluscoat Z687: polyester resin Hydran HW-350: manufactured by Ryogo Chemical Industry Co., Ltd. Polyurethane resin M-510: polyfunctional acrylic oligomer manufactured by Toagosei Co., Ltd. M-510: polybasic acid-modified acrylic oligomer M-1200: Toagosei Co., Ltd. M-1200: bifunctional urethane acrylate M -270: M-270, manufactured by Toagosei Co., Ltd., bifunctional urethane acrylate, sluria 4110: hollow silica particles, sluria 4110, manufactured by Nikki Shokubai Kasei Co., Ltd., average particle diameter 60 nm
MEK: methyl ethyl ketone (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

(Example 1)
[Composition of composition for forming color change layer A]
Ethoxylated O-phenylphenol acrylate: 3.65 parts by mass SZR-M: 18.41 parts by mass Irgacure 2959 (1% methanol dilution): 3.65 parts by mass F-444 (1% methanol dilution): 2 0.72 parts by mass. Methanol: 71.56 parts by mass.

[Composition of composition for forming color change layer B]
・ Polyfunctional acrylic monomer PET-30: 67.28 parts by mass ・ MEK: 29.92 parts by mass ・ F-444 (1% methanol dilution): 2.80 parts by mass

(Example 2)
The same composition as in Example 1 was used as the composition for forming the color-change layer A.

[Composition of composition for forming color change layer B]
-Polyfunctional acrylic oligomer (M-510): 6.26 parts by mass-Hollow silica particles (Thrulia 4110): 93.06 parts by mass-Irgacure 2959 (powder): 0.66 parts by mass-F-444 (stock solution): 0.02 parts by mass

(Example 3)
As the composition for forming the color-change layer A, the same composition as the composition for forming the color-change layer B of Example 1 was used.

[Preparation of composition for forming color-change layer B]
-Composition of emulsion particle dispersion 1-
Hexadecane (n-hexadecane, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.): 2.77 partsCa-1 (hexadecylpyridinium chloride 10% diluted in distilled water, cationic surfactant, Fujifilm Wako Pure Chemical Industries, Ltd.) Preparation: 4.42 parts / Distilled water: 42.81 parts The emulsion particle dispersion 1 was prepared in detail by the following procedure.
Hexadecane, Ca-1, and ion-exchanged water are mixed, and cooled with ice water using an ultrasonic homogenizer Sonifier 450 manufactured by Nippon Emerson Co., Ltd., and treated with stirring for 30 minutes, whereby an emulsion of hexadecane is present in water. A dispersion was obtained.

-Composition of core-shell particle dispersion 1-
-Emulsion particle dispersion 1: 35.94 parts-Distilled water: 2.84 parts-Acetic acid (diluted in 5% distilled water): 1.26 parts-MS-51 (compound represented by formula 1, Mitsubishi Chemical Corporation) 9.96 parts) MS-51 is a compound in which R ¹ , R ² and R ³ in the above formula 1 are methyl groups, m is 2, and n is 5 on average.

Next, MS-51, acetic acid, and distilled water are added to the emulsion particle dispersion 1, and the mixture is further stirred at 25 ° C. for 16 hours to obtain core-shell particles containing a nonpolar solvent as a core material, represented by Formula 1. And a core-shell particle dispersion 1 containing a compound, a surfactant and water.

-Composition of composition for forming color change layer B-
・ Core-shell particle dispersion 1: 15.04 parts ・ Ion-exchanged water: 79.46 parts ・ F-444 (diluted with 1% distilled water): 5.50 parts

Next, ion-exchanged water and F-444 were added to the core-shell particle dispersion 1, and the mixture was stirred at 25 ° C. for 2 days to obtain a composition for forming a color-change layer B of Example 3.

(Example 4)
As the composition for forming the color-change layer A, the same composition as the composition for forming the color-change layer B of Example 1 was used.

[Composition of composition for forming color change layer B]
-Polyfunctional acrylic oligomer (M-510): 0.60 parts by mass-Hollow silica particles (Thrulia 4110): 8.95 parts by mass-Irgacure 2959 (powder): 0.06 parts by mass-F-444 (1% methanol) (Dilution): 4.87 parts by mass. Methanol: 85.51 parts by mass.

(Examples 5 to 7)
As the composition for forming the color-change layer A, the same composition as the composition for forming the color-change layer B of Example 1 was used.
The same composition as that of Example 4 was used as the composition for forming the color-change layer B.

(Examples 8 to 10)
The same composition as in Example 1 was used as the composition for forming the color-change layer A.
The same composition as that used in Example 2 was used as the composition for forming the color change layer B.

(Example 11)
[Composition of composition for forming color change layer A]
Ethoxylated O-phenylphenol acrylate: 5.90 parts by mass Zirconium oxide dispersion (SZR-M): 10.83 parts by mass Irgacure 2959 (1% methanol dilution): 5.90 parts by mass F-444 (1 % Methanol dilution): 4.54 parts by mass. Methanol: 72.83 parts by mass.

The same composition as in Example 2 was used as the composition for forming the color change layer B.

(Example 12)
[Composition of composition for forming color change layer A]
Ethoxylated O-phenylphenol acrylate: 7.74 parts by mass Zirconium oxide dispersion (SZR-M): 4.64 parts by mass Irgacure 2959 (diluted with 1% methanol): 7.74 parts by mass F-444 (1 % Methanol dilution): 4.54 parts by mass. Methanol: 75.34 parts by mass.

(Example 13)
The same composition as that of Example 12 was used as the composition for forming the color change layer A.
The same composition as in Example 1 was used as the composition for forming the color-change layer B.

(Example 14)
[Composition of composition for forming color change layer A]
Ethoxy O-phenylphenol acrylate: 8.20 parts by mass Titanium oxide particles (HTD-780T): 3.09 parts by mass Irgacure 2959 (1% methanol dilution): 8.20 parts by mass F-444 (1% (Methanol dilution): 4.54 parts by mass. Methanol: 75.97 parts by mass.

The same composition as that of Example 4 was used for the composition for forming the color change layer B.

(Example 15)
The same composition as in Example 1 was used as the composition for forming the color-change layer A.

[Composition of composition for forming color change layer B]
・ Polyfunctional acrylic oligomer (M-510): 10.37 parts by mass ・ Hollow silica particles (Thrulia 4110): 70.28 parts by mass ・ Irgacure 2959 (powder): 1.09 parts by mass ・ F-444 (stock solution): 0.04 parts by mass / methanol: 18.22 parts by mass

(Example 16)
The same composition as in Example 1 was used as the composition for forming the color-change layer A.

[Composition of composition for forming color change layer B]
・ Polyfunctional acrylic oligomer (M-510): 14.63 parts by mass ・ Hollow silica particles (Suria 4110): 46.74 parts by mass ・ Irgacure 2959 (powder): 1.54 parts by mass ・ F-444 (stock solution): 0.04 parts by mass / methanol: 37.05 parts by mass

(Example 17)
The same composition as in Example 3 was used as the composition for forming the color-change layer A.

[Composition of composition for forming color change layer B]
-Polyfunctional acrylic oligomer (M-510): 2.79 parts by mass-Hollow silica particles (Suria 4110): 8.91 parts by mass-Irgacure 2959 (powder): 0.29 parts by mass-F-444 (stock solution): 0.05 parts by mass / methanol: 87.96 parts by mass

(Example 18)
[Composition of composition for forming color change layer A]
-Urethane acrylate monomer (M-1200): 67.14 parts by mass-MEK: 29.86 parts by mass-Irgacure 2959 (powder): 0.20 parts by mass-F-444 (1% methanol dilution): 2.78 parts by mass Department

(Example 19)
In Example 1, after the protective film of the remaining pressure-sensitive adhesive sheet was peeled off, an acrylonitrile-butadiene-styrene copolymer (ABS) film (also referred to as ABS backer) was laminated (250 μm thick, manufactured by Okamoto Corporation). Temperature: 30 ° C., linear pressure: 100 N / cm, conveyance speed: 0.1 m / min) to give the decorative molded film of Example 19 in which the ABS, the adhesive layer, the colored layer, the transparent film, and the resin layer were arranged in this order. Produced.

(Example 20)
[Composition of composition for forming color change layer A]
Polyester resin (Plus Coat Z687): 146.24 parts by massZirconium oxide dispersion (SZR-CW): 185.19 parts by massFluorine surfactant (sodium bis (3,3,4,4,5) , 5,6,6,6-Nonafluorohexyl) = 2-sulfonite oxysuccinate, manufactured by FUJIFILM Fine Chemicals Co., Ltd., diluted with 1% water): 27.23 parts by mass, ion-exchanged water: 257.09 Parts by mass / ethanol (95): 384.25 parts by mass

[Composition of composition for forming color change layer B]
Acrylate monomer (M-270): 555.12 parts by mass MEK: 444.10 parts by mass Irgacure 2959 (powder): 0.56 parts by mass F-444 (1% methanol dilution): 0.22 parts by mass

(Example 21)
[Composition of composition for forming color change layer A]
-Polyurethane resin (Hydran HW-350): 121.86 parts by mass-Zirconium oxide dispersion (SZR-CW): 185.19 parts by mass-Fluorinated surfactant (sodium bis (3,3,4,4,4) 5,5,6,6,6-nonafluorohexyl) = 2-sulfonite oxysuccinate, manufactured by FUJIFILM Fine Chemicals Co., Ltd., diluted with 1% water): 27.23 parts by mass, ion-exchanged water: 281. 47 parts by mass / ethanol (95): 384.25 parts by mass

[Composition of composition for forming color change layer B]
The same composition as in Example 20 was used as the composition for forming a color-change layer B.

(Example 22)
[Composition of composition for forming color change layer A]
Acrylic resin (Epocross WS-700): 109.76 parts by mass Zirconium oxide dispersion (SZR-CW): 215.58 parts by mass Fluorinated surfactant (sodium = bis (3,3,4,4,4) 5,5,6,6,6-nonafluorohexyl) = 2-sulfonite oxysuccinate, manufactured by FUJIFILM Fine Chemicals Co., Ltd., diluted with 1% water): 27.23 parts by mass, ion-exchanged water: 263. 17 parts by mass / ethanol (95): 384.25 parts by mass

(Comparative Example 1)
As the composition for forming the color-change layer A, the same composition as the composition for forming the color-change layer B of Example 1 was used.

[Composition of composition for forming color change layer B]
・ Polyfunctional acrylic oligomer (M-510): 3.46 parts by mass ・ Hollow silica particles (Thrulia 4110): 5.46 parts by mass ・ Irgacure 2959 (powder): 0.36 parts by mass ・ F-444 (1% methanol) (Dilution): 4.75 parts by mass. Methanol: 85.97 parts by mass.

(Comparative Example 2)
As the composition for forming the color-change layer A, the same composition as the composition for forming the color-change layer B of Example 1 was used.
Further, the color change layer B was not formed.

(Comparative Example 3)
As the composition for forming the color-change layer A, the same composition as the composition for forming the color-change layer B of Example 1 was used.

[Composition of composition for forming color change layer B]
・ Polyfunctional acrylic monomer (PET-30): 4.91 parts by mass ・ MEK: 90.34 parts by mass ・ F-444 (1% methanol dilution): 4.75 parts by mass

(Comparative Example 4)
The same composition as that of Comparative Example 1 was used as the composition for forming the color change layer B.
Further, the color change layer A was not formed.

Each Example The following evaluation was performed using the decorative film obtained in the comparative example. Table 1 summarizes the evaluation results.

[Evaluation of three-dimensional moldability]
Assuming an automobile emblem, three-dimensional moldability of a cylindrical stainless steel member having a diameter of 10 cm and a height of 3 mm was evaluated for occurrence of cracks or the like during stretching. In Example 19 in which ABS was laminated before the test, the obtained film was used as it was, and in the other Examples and Comparative Examples, after the protective sheet of the pressure-sensitive adhesive sheet was peeled off, the ABS film was laminated (thickness 250 μm, The test was carried out after laminating Okamoto Co., Ltd. at a laminating temperature of 30 ° C., a linear pressure of 100 N / cm, and a conveying speed of 0.1 m / min.
Using a columnar member, the obtained decorative film was vacuum molded at a heating temperature of 120 ° C., and whether or not cracks occurred on the surface was visually evaluated.
A: No crack occurred on the surface B: Crack occurred on the surface

[Evaluation of design (color change)]
The decorative film obtained was measured for specular reflectance using an ultraviolet-visible infrared spectrophotometer V-560 (manufactured by JASCO Corporation) and an absolute reflectance measuring device ARV-474 to improve the design. evaluated.
For the evaluation of the design properties, a value R _des obtained by dividing the maximum value R _max of the reflectance of the obtained decorative film in visible light (wavelength 380 nm to 780 nm) by the reflectance R ₇₀₀ nm in the wavelength of 700 nm was used. The larger the R _{des, the} better the color change.
The evaluation criteria are as follows according to the value of R _des . A to C are preferred.
A: 2% or more B: 1.5% or more and less than 2% C: 1% or more and less than 1.5% D: 0.5% or more and less than 1% E: less than 0.5%

[Evaluation of black tightness]
The obtained decorative film was visually observed from an angle of 45 ° when the direction perpendicular to the film was 0 °, and the sensory evaluation was performed on the blackness of the film when reflected by a fluorescent lamp. The evaluation criteria are shown below. A is preferred as the evaluation result.
A: The reflection of the fluorescent lamp is suppressed.
B: Fluorescent light is strongly reflected and looks whitish as a whole.

[Evaluation of scratch resistance]
The evaluation of the scratch resistance of the obtained decorative film was performed by a steel wool rubbing test using a surface property measuring device Heidon Type 18S manufactured by Shinto Kagaku Co., Ltd. In the steel wool rub test, a 30 mmφ Nippon Steel Wool Co., Ltd. Bonster commercial grade # 0000 was pressed against the surface of the decorative film (load 50 g), swing stroke 50 mm, swing speed 1000 mm / min, 10 reciprocating conditions. And then visually evaluated the appearance. The evaluation criteria are shown below. As the evaluation result, A is preferable.
A: The number of scratches is 20 or less B: The number of scratches is more than 20

The details of the abbreviations in Table 1 are as follows.
Acrylic 1: Ethoxylated O-phenylphenol acrylate or a polymer thereof Acrylic 2: PET-30 manufactured by Nippon Kayaku Co., Ltd. or a polymer thereof Siloxane 1: MS-51 (manufactured by Mitsubishi Chemical Corporation) Hydrolysis condensate Acrylic 4: M-510 manufactured by Toagosei Co., Ltd. or polymer thereof Acrylic 5: M-510 manufactured by Toagosei Co., Ltd. or polymer thereof Acrylic 6: M manufactured by Toagosei Co., Ltd. -510 or its polymer Acrylic 7: M-270 manufactured by Toagosei Co., Ltd. or its polymer Acrylic 8: Epocross WS-700 manufactured by Nippon Shokubai Co., Ltd.
Urethane: M-1200 or a polymer thereof Polyester: Pluscoat Z687 manufactured by Ryogo Chemical Industry Co., Ltd.
Polyurethane: Hydran HW-350 manufactured by DIC Corporation
ZrO ₂ -A: SZR-M
ZrO ₂ -B: SZR-CW
TiO ₂ : HTD-780T
Hollow silica: Sluria 4110 manufactured by JGC Catalysts & Chemicals, Inc.

From the results shown in Table 1, the decorative films of Examples 1 to 18 and 20 to 22 and the decorative molded film of Example 19 had a color change property (comparable to the decorative films of Comparative Examples 1 to 4). Excellent design).
In addition, from the results shown in Table 1, the decorative films of Examples 1 to 18 and 20 to 22 and the decorative molded film of Example 19 also have three-dimensional moldability, black tightness, and scratch resistance. Excellent.

The disclosure of Japanese Patent Application No. 2018-126373 filed on Jul. 2, 2018 is incorporated herein by reference in its entirety.
All publications, patent applications, and technical standards referred to in this specification are to the same extent as if each individual publication, patent application, and technical standard were specifically and individually stated to be incorporated by reference. Incorporated herein by reference.

10: decorative film, 12: adhesive layer, 14: protective film, 16: base material for molding, 20: laminate, 22: temporary support, 24: colored layer, 26: resin layer, 28: color changing layer A , 30: color change layer B, 40: decorative molded film

Claims

Temporary support,
Colored layer,
A color change layer A containing at least one compound selected from the group consisting of a resin and a polymerizable compound, and
Having a color changing layer B in this order,
The decorative film, wherein the color change layer B is a layer having a refractive index lower than that of the color change layer A by 0.1 or more.
The decorative film according to claim 1, wherein the colored layer contains at least one compound selected from the group consisting of a resin and a polymerizable compound.
The decorative film according to claim 1 or 2, wherein the thickness of the coloring layer is 3 µm or more.
(4) The decorative film according to any one of (1) to (3), wherein the coloring layer contains a pigment as a coloring agent.
The colored layer is a layer obtained by at least curing a bifunctional or trifunctional polymerizable compound having a urethane bond and at least one partial structure selected from the group consisting of alkyleneoxy groups having 2 or 3 carbon atoms. The decorative film according to any one of claims 1 to 4.
The decorative film according to any one of claims 1 to 5, wherein the color change layer B is a layer having a refractive index lower than that of the color change layer A by 0.25 or more.
The decorative film according to any one of claims 1 to 6, wherein the refractive index of the color change layer A is 1.6 or more.
The decorative film according to any one of claims 1 to 7, wherein the color change layer A further contains zirconium oxide or titanium oxide.
The decorative film according to any one of claims 1 to 8, wherein the refractive index of the color change layer B is 1.4 or less.
The decoration according to any one of claims 1 to 9, wherein the color change layer B contains at least one selected from the group consisting of a siloxane resin having a void, a fluororesin, and hollow silica particles. the film.
The decorative film according to any one of claims 1 to 10, wherein the thickness of the color changing layer A is 5 μm or more, or the thickness of the color changing layer B is 5 μm or more.
The decorative film according to any one of claims 1 to 11, wherein the thickness of the color change layer A is 5 μm or more, and the thickness of the color change layer B is 1 μm or less.
The decorative film according to any one of claims 1 to 11, wherein the color-changing layer A has a thickness of 1 μm or less, and the color-changing layer B has a thickness of 5 μm or more.
The decorative film according to any one of claims 1 to 13, which is a decorative film for molding.
A step of peeling the temporary support from the decorative film according to any one of claims 1 to 14,
Attaching the decorative film from which the temporary support has been peeled to the substrate from the colored layer side.
16. The decorating method according to claim 15, further comprising: a step of forming an adhesive layer on a surface of the decorative film from which the temporary support has been peeled off, from which the temporary support has been peeled off.
The decorating method according to claim 15 or 16, wherein the substrate is a molding substrate.
A step of peeling the temporary support from the decorative film according to any one of claims 1 to 14,
Affixing the decorative film from which the temporary support has been peeled to a molding substrate from the colored layer side,
Molding the substrate for molding to which the decorative film has been adhered.
Base material,
Colored layer,
A color change layer A containing at least one compound selected from the group consisting of a resin and a polymerizable compound, and
Having a color changing layer B in this order,
The decorative molded film, wherein the color change layer B is a layer having a refractive index lower than that of the color change layer A by 0.1 or more.