JP7039701B2 - Decorative film, decoration method, manufacturing method of decorative molded body, and decorative molded film - Google Patents

Description

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

There is known a decorative molded body in which a decorative film is arranged on the surface of the resin molded body to color the surface to a desired hue or to provide a desired pattern on the surface.
The decorative molded body is obtained, for example, by arranging a decorative molded film in a mold in advance and injecting a base resin into the mold, and the decorative film is integrated on the surface of the resin molded body. It has a modified structure.
In the present disclosure, the decorative molded film means a film in which a decorative film is attached to a base material for molding.
Here, performing injection molding of the base resin after arranging the decorative molding film in the mold in advance may be generally referred to as film insert molding or simply insert molding.
Further, the decorative molded body may be manufactured by attaching a decorative film to the molded body after molding.

Further, as a conventional hard coat transfer foil for in-mold, Patent Document 1 states that in an in-mold transfer foil having a transfer layer on the release surface of a releasable substrate sheet, the transfer layer is at least. The first transparent cross-linked cured resin layer, the printed pattern layer, the second transparent cross-linked cured resin layer, the metallic glossy layer or the metallic printing layer, and the adhesive layer are sequentially laminated, and the second transparent cross-linked type is described above. Described is an in-mold hard coat transfer foil characterized in that the cured resin layer has a thickness of 20 μm to 100 μm.
Further, as a conventional decorative laminated body, a decorative sheet in which at least a first base material layer, a release layer, a color change layer B, and a second base material layer are laminated in order in Patent Document 2. Therefore, based on JIS B0601: 2001, the cutoff value is set to 0.8 mm, and the average spacing Sm of the unevenness when the surface of the transfer layer is measured when the decorative sheet is transferred to the transferred body is determined. A decorative sheet having a size 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: Japanese Patent Application Laid-Open No. 2011-11376 Patent Document 2: Japanese Patent Application Laid-Open No. 2017-47597

An object to be solved by one embodiment of the present invention is to provide a decorative film having excellent color changeability.
Further, an object to be solved by another embodiment of the present invention is to provide a decoration method using the decorative film and a method for manufacturing a decorative molded body.
Further, a problem to be solved by yet another embodiment of the present invention is to provide a decorative molded film having excellent color changeability.

The means for solving the above problems include the following aspects.
<1> The color changing layer A containing at least one compound selected from the group consisting of a temporary support, a colored layer, a resin and a polymerizable compound, and a color changing layer B are provided in this order, and the color changing layer is described above. A decorative film in which B is a layer having a refractive index lower than that of the color changing 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 colored layer has a thickness of 3 μm or more.
<4> The decorative film according to any one of <1> to <3>, wherein the colored layer contains a pigment as a colorant.
<5> The colored layer is formed 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 an alkyleneoxy group 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 changing layer B is a layer having a refractive index lower than that of the color changing layer A by 0.25 or more.
<7> The decorative film according to any one of <1> to <6>, wherein the color changing layer A has a refractive index of 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 color changing layer B has a refractive index of 1.4 or less.
<10> Described in any one of <1> to <9>, wherein the color changing layer B contains at least one selected from the group consisting of a siloxane resin having voids, 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 color change layer A has a thickness of 5 μm or more and the color change layer B has a thickness of 1 μm or less.
<13> The decorative film according to any one of <1> to <11>, wherein the color change layer A has a thickness of 1 μm or less and the color change layer B has a thickness of 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 decorative film from which the temporary support has been peeled off are based on the colored layer side. A decoration method including the process of pasting on the material.
<16> The decoration method according to <15>, further comprising a step of forming an adhesive layer on the surface from which the temporary support has been peeled off in the decorative film from which the temporary support has been peeled off.
<17> The decoration method according to <15> or <16>, wherein the base material is a base material for molding.
<18> The step of peeling the temporary support from the decorative film according to any one of <1> to <14>, and the decorative film from which the temporary support has been peeled off is molded from the colored layer side. A method for manufacturing a decorative molded body, which comprises a step of attaching to a base material for use and a step of molding the base material for molding to which the decorative film is attached.
<19> A color changing layer A containing at least one compound selected from the group consisting of a base material, a colored layer, a resin and a polymerizable compound, and a color changing layer B are provided in this order, and the color changing layer B is described above. However, the decorative molded film is a layer having a refractive index lower than that of the color changing 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 decoration method using the above-mentioned decorative film and a method for manufacturing a decorative molded body.
Further, according to still another embodiment of the present invention, it is possible to provide a decorative molded film having excellent color changeability.

It is a schematic sectional drawing which shows an example of the decorative film which concerns on this disclosure. It is the schematic sectional drawing which shows the other example of the decorative film which concerns on this disclosure. It is a schematic sectional drawing which shows an example of the decorative molded film which concerns on this disclosure.

Hereinafter, an 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, and can be carried out with appropriate modifications within the scope of the object of the present disclosure.

Regarding the notation of a group (atomic group) in the present disclosure, the notation that does not describe substitution or non-substitution includes those having no substituent as well as those having a 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 means a group containing at least one carbon atom.
The "active light" or "radiation" in the present disclosure means, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light: Extreme Ultraviolet), X-rays, and electron beams (EB: Electron). It means Beam) and the like. As used herein, "light" means active light or radiation.
Unless otherwise specified, "exposure" in the present disclosure means not only exposure with emission line spectrum of mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays, X-rays, EUV light, etc., but also electron beam and ion beam. Also includes exposure with particle beams such as.
In the present disclosure, "-" is used to mean that the numerical values described before and after it are included as the lower limit value and the upper limit value.

In the present disclosure, (meth) acrylate represents acrylate and methacrylate, and (meth) acrylic represents acrylic and methacrylic.
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 referred to as GPC (Gel Permeation).
GPC measurement (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 μL, column: TSK gel Multipore HXL-M manufactured by Tosoh Co., Ltd., column temperature: 40 ° C., by Chromatography) device (HLC-8120 GPC manufactured by Tosoh Co., Ltd.), Flow velocity: 1.0 mL / min, detector: defined as a polystyrene equivalent by a differential index detector.

In the present specification, the amount of each component in the composition is the total amount of the plurality of applicable substances present in the composition unless otherwise specified, when a plurality of the substances corresponding to each component are present in the composition. means.
In the present specification, the term "process" is included in this term not only as an independent process but also as long as the intended purpose of the process is achieved even if it cannot be clearly distinguished from other processes.
As used herein, the term "total solid content" refers to the total mass of the components excluding the solvent from the total composition of the composition. Further, the "solid content" is a component excluding the solvent as described above, and may be, for example, a solid or a liquid at 25 ° C.
In the present specification, "% by mass" and "% by weight" are synonymous, and "parts by mass" and "parts by weight" are synonymous.
Further, in the present 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 color change layer A containing at least one compound selected from the group consisting of a temporary support, a colored layer, 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 use of the decorative film according to the present disclosure is not particularly limited, and specifically, for example, automobiles, home appliances, audio products, computers, displays, in-vehicle products, watches, accessories, optical parts, doors, windowpanes. , Can be used for decoration of building materials, etc.
Above all, the decorative film according to the present disclosure can be suitably used as a decorative film used for decorating the exterior of an automobile.
Further, since the decorative film according to the present disclosure is also excellent in three-dimensional moldability, it is suitable as a decorative film for molding used for molding such as three-dimensional molding and insert molding, and is more suitable as a decorative film for three-dimensional molding. Suitable.
For example, in the decorative film according to the present disclosure, the temporary support is peeled off, an adhesive layer described later is provided, and the film is attached to a molding base material described later to be used as a decorative molded film, or the adhesive layer is a molded body. It is suitably used for applications where it is attached to a decorative molded body.

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, the decoration technique by using the decoration film has come to be widely used from the viewpoint of imparting functionality, environmental load, and any aspect of being replaceable.
On the other hand, new design is required due to the widespread taste of users.
This time, the present inventors have newly found a design in which a change in color (for example, a tint or a fine hue) occurs (also referred to as "color changeability"), and examined its introduction as a decoration technique.
Further, in the present disclosure, the color changeability 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 is, the better the color changeability is. ..

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

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 the refractive index for light having a wavelength of 550 nm at 25 ° C.
Further, the refractive index of each layer in the present disclosure is transmitted by a spectrophotometer to a single film of the color change layer A and the color change layer B formed on the non-alkali glass OA-10G (manufactured by Nippon Denki Glass Co., Ltd.). By measuring the spectrum and performing a fitting analysis using the transmittance obtained by the above measurement and the transmittance calculated by the optical interference method, the film thickness and the refractive index of each layer can be obtained, or It shall be measured using a Carnew precision refractometer (KPR-3000, manufactured by Shimadzu Corporation).

The refractive index of the color change layer A is 1.5 or more from the viewpoint of color changeability and blackness (suppression of reflection by reflected light from the outside, for example, suppression of reflection of fluorescent lamp). It is preferably 1.6 or more, more preferably 1.65 or more, and particularly preferably 1.70 or more. The upper limit is preferably 2.3 or less, and more preferably 1.9 or less.
The refractive index of the color changing layer B is preferably 1.5 or less, more preferably less than 1.5, and 1.4 or less from the viewpoint of color changing property and blackening property. It is more preferably 1.35 or less, particularly preferably 1.32 or less, and most preferably 1.32 or less. The lower limit is preferably 1.1 or more, more preferably 1.2 or more, and particularly preferably 1.28 or more.

The color change layer B is a layer having a refractive index lower than that of the color change layer A by 0.15 or more, and is a layer having a refractive index lower than 0.15 or more from the viewpoint of color changeability and blackening property. A layer having a refractive index as low as 0.2 or more is more preferable, a layer having a refractive index as low as 0.25 or more is further preferable, and a layer having a refractive index as low as 0.25 or more and 0.60 or less. Is particularly preferable.
Further, from the viewpoint of color changeability, blackening property, 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. It is preferable that 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 1.4 or less.
Further, from the viewpoint of color changeability and blackening property, the refractive index of the color change layer A is 1.5 or more, and the refractive index of the color change layer B is 1.4 or less. preferable.

[Preferable thickness of each layer]
The decorative film according to the present disclosure has a temporary support, a colored 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 10 μm to 500 μm, more preferably 20 μm to 300 μm, and particularly preferably 50 μm to 150 μm from the viewpoint of peelability.
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 3 μm to 50 μm from the viewpoint of color changeability and three-dimensional moldability. It is more preferably 3 μm to 20 μm, and particularly preferably 3 μm to 20 μm.
The thicknesses of the color change layer A and the color change layer B are independently, preferably 50 nm to 50 μm, more preferably 80 nm to 30 μm, and 100 nm to 20 μm from the viewpoint of color changeability. Is particularly preferable.

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.
Further, from the viewpoint of color changeability and blackening property, it is preferable that the thickness of the color change layer A is 5 μm or more, or the thickness of the color change layer B is 5 μm or more, and the color change. 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. The above is more preferable, and the thickness of the color changing layer A is 7 μm or more and the thickness of the color changing layer B is 0.8 μm or less, or the thickness of the color changing layer A is 0. It is particularly preferable that the thickness is 8 μm or less and the thickness of the color changing layer B is 7 μm or more. The upper limit is preferably 100 μm or less.
From the viewpoint of color changeability, the combination of the thickness and refractive index of the color change layer A, the thickness and refractive index of the color change layer B, and the film thickness of the colored layer is preferably as follows.

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

A preferred second aspect of the decorative film according to the present disclosure according to the present disclosure is that 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. Aspects are preferred.
In the second aspect, from the viewpoint of color changeability, the film thickness of the color change layer B is 1 μm or less, the film thickness of the color change layer A is 5 μm or more, and the colored layer is 3 μm or more. Is preferable.
In the second aspect, the film thickness of the color changing layer B is preferably 120 nm to 160 nm or 320 nm to 370 nm in order to enhance the reflection of blue, and 210 nm to 210 nm in order to enhance the reflection of yellow. It is preferably 260 nm or 420 to 450 nm, preferably 260 nm to 290 nm to enhance red reflection, and 90 nm to 120 nm or 290 nm to 320 nm to enhance purple reflection. It is preferably 160 nm to 210 nm, or 370 nm to 420 nm in order to enhance the reflection of green.

The thickness of each layer is a cross-sectional observation method in which the decorative film is cut in a direction perpendicular to the film surface, the cut surface is observed with a scanning electron microscope (SEM) or an optical microscope, and the thickness of the layers is measured in that range. Further, the decorative film and, if possible, the peeled layer can be measured by a method of directly measuring with a microscope, a film thickness meter, or the like.

[Temporary support]
As the temporary support, a known resin film is used without particular limitation, and a film having flexibility and which does not cause significant deformation, shrinkage or elongation under pressure, pressure and heating 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 polymethylmethacrylate film is preferable, and a polyethylene terephthalate film is more preferable.
Further, an organic film with a release layer is more preferable because the temporary support has excellent peelability from the colored layer.
As commercial products of the temporary support, for example, PET with a release layer such as "Unipeel (registered trademark)" series (manufactured by Unitika Ltd.) and "Therapeutic (registered trademark)" series (manufactured by Toray Film Processing Co., Ltd.). Examples include films.

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

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

[Colored 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 (non-colorless and transparent) layer, but an opaque colored layer (preferably a colored layer having a total light transmittance of 10% or less) is preferable. ..
The colored layer may be of various colors such as black, gray, white, red, orange, yellow, green, blue, and purple, but the black colored layer has a low intensity of reflected light and is colored. It is preferable because the change is emphasized more.

From the viewpoint of strength and scratch resistance, the colored layer preferably contains at least one compound selected from the group consisting of resins and polymerizable compounds.
As the resin, a pineapple resin described later is preferably mentioned.
Further, the colored layer may be a layer obtained by curing the polymerizable compound, or may be a layer containing the polymerizable compound and the polymerization initiator. From the viewpoint of adhesion, the layer is preferably a cured layer of a polymerizable compound, and has at least one partial structure 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 at least curing a bifunctional or trifunctional polymerizable compound.

-Colorant-
The colored layer preferably contains a colorant from the viewpoint of visibility, and more preferably contains a pigment as the colorant 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 pigments and dyes, and pigments are preferable.
Further, the pigment is preferably a pigment in the shape of particles.
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 examples of the inorganic pigment include white pigments such as titanium dioxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, and barium sulfate, and carbon black, titanium black, and titanium carbon. , 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 also be used.

Examples of the organic pigment include the organic pigment described in paragraph 0093 of JP-A-2009-256572.
Specific organic pigments include, for example, C.I. I. Pigment Red 177, 179, 224, 242, 254, 255, 264 and other red pigments, C.I. I. Pigment Yellow 138, 139, 150, 180, 185 and other yellow pigments, C.I. I. Pigment Orange 36, 38, 71 and other orange pigments, C.I. I. Pigment Green 7, 36, 58 and other green pigments, C.I. I. Pigment Blue 15: 6, etc. blue pigment, C.I. I. Examples include purple pigments such as Pigment Violet 23.
In addition, the pigment may contain particles of a pigment having light transmittance and light reflectivity (so-called brilliant pigment).
When the above-mentioned bright pigment includes an exposure step described later, it is preferable that the bright pigment is used within a range that does not interfere with curing by exposure.

As the colorant, one type may be used alone, or two or more types may be used in combination. Further, the particles of the inorganic pigment and the particles of the organic pigment may be used in combination.
The content of the colorant in the colored layer is based on the total mass of the colored layer in terms of the expression of the desired hue (for example, suppression of whitening) and the maintenance of shape followability of the colored layer to the mold. 1% by mass to 50% by mass is preferable, 5% by mass to 50% by mass is more preferable, and 10% by mass to 40% by mass is further preferable.
Here, "whitening" in the present disclosure means that the colored layer changes to exhibit a whitish color as if a matte feeling was imparted.

-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.
Further, as the polymerizable group, a radically polymerizable group is preferable.
The polymerizable compound is a bifunctional compound 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 at least one partial structure selected from the group consisting of a urethane bond and an alkylene oxide group having 2 or 3 carbon atoms is used. Bifunctional or trifunctional polymerizable compounds having are more preferable.
In the specific polymerizable compound, a linking group may be provided between the partial structure and the polymerizable group, if necessary. Further, the specific polymerizable compound has two or more kinds of 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 be doing it.

<Bifunctional or trifunctional polymerizable compound with 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, urethane (meth) acrylate oligomer is preferable, and examples thereof include aliphatic urethane (meth) acrylate and aromatic urethane (meth) acrylate.
For details, refer to the Oligomer Handbook (supervised by Junji Furukawa, The Chemical Daily Co., Ltd.), and the urethane oligomers described here are appropriately selected according to the purpose and used for forming the colored layer in this step. be able to.
The molecular weight of the urethane oligomer which is the specific polymerizable compound 1 is preferably 800 to 2,000, and more preferably 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.
Examples of commercially available urethane (meth) acrylate oligomers include U-2PPA and UA-122P manufactured by Shin Nakamura Chemical Industry Co., Ltd .; CN964A85, CN964, CN959, CN962 and CN963J85 manufactured by Sartmer Japan Co., Ltd. , CN965, CN982B88, CN981, CN983, CN991, CN991NS, CN996, CN996NS, CN9002, CN9007, CN9178, CN9893; Etc. (above, product name). "EBECRYL" is a registered trademark.

<Bifunctional or trifunctional polymerizable compound with 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 bi-substituted (one of the groups on the nitrogen atom is a hydrogen atom) or tri-substituted.
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 a compound 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 (if it is a commercial product, Karenz MOI (registered trademark) manufactured by Showa Denko Co., Ltd.) and 2-methacryloyloxyethyl isocyanate. The group is blocked with methyl ethyl ketone oxime (2- (O- [1'-methylpropyrideneamino] carboxyamino) ethyl, and if it is a commercial product, Karenz MOI-BM (registered trademark) manufactured by Showa Denko Co., Ltd. )), 2-[(3,5-Dimethylpyrazolyl) carbonylamino] ethyl methacrylate in which the isocyanate group of 2-methacryloyloxyethyl isocyanate is blocked with pyrazole, if it is a commercial product, Karenz manufactured by Showa Denko Co., Ltd. MOI-BP (registered trademark)) and the like can be used.
Further, as the amine compound, for example, an amine compound having two or more active hydrogen atoms, specifically, dimethylamine, trimethylamine, triethylamine, diisopropylamine, diethylenetriamine, triethylenetetramine and the like can be used.
The specific polymerizable compound 2 is not limited to that obtained by this method.

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

The specific polymerizable compound 2 is available as a commercially available 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 .; Aronix (registered trademark) M-215, 313, 315 manufactured by Toagosei Co., Ltd. (The above is the product name) and the like.

<Bifunctional or trifunctional polymerizable compound having an alkyleneoxy group having 2 or 3 carbon atoms>
A bifunctional or trifunctional polymerizable compound (hereinafter, also referred to as “specific polymerizable compound 3”) having an alkyleneoxy group having 2 or 3 carbon atoms (also referred to as “alkylene oxide group”) is contained in one molecule. For example, it has one or more ethyleneoxy groups or propyleneoxy groups, and has two or three polymerizable groups at the molecular ends.
Examples of the propyleneoxy group include -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 thereof include triacrylate, ethoxylated trimethylol propanetrimethacrylate, 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 of better shape followability to the mold.

Further, from the viewpoint of further improving the shape followability 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 repeatedly. .. The number of repetitions of the ethyleneoxy group or the propyleneoxy group in the polyethyleneoxy group or the polypropyleneoxy group is preferably 3 or more, and particularly preferably 5 or more.

The specific polymerizable compound 3 is available as a commercially available product.
Specific examples of commercially available products include NK esters A-200, A-400, A-600, A-1000, 1G, 2G, 3G, 4G, 9G, 14G, and 23G manufactured by Shin Nakamura Chemical Industry 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 .; Toagosei Aronix (registered trademark) M-220, M-350 manufactured by Synthetic Co., Ltd .; SR415, SR454, SR9035 (hereinafter, trade name) manufactured by Sartmer Japan Co., Ltd. can be mentioned.

<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 is chain-like or cyclic. 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, and may be linear or branched.
Among them, a linear hydrocarbon group is preferable as the hydrocarbon group from the viewpoint of better shape followability to the mold.
Examples of the polymerizable group 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 4 include 1,6-hexanediol di (meth) acrylate, 1,7-heptanediol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, and 1,9. -Nonandiol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate, hydrogenated bisphenol A di. Examples thereof include (meth) acrylate and di (meth) acrylate of hydrogenated bisphenol F.
Among the above compounds, tricyclodecanedimethanol 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 moiety 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 the three-dimensional moldability by increasing the flexibility at the time of heating and the like. It is preferably a bifunctional or trifunctional polymerizable compound having a structure.

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

The content of the polymerizable compound is preferably 10% by mass to 50% by mass, preferably 20% by mass, based on the total mass of the uncured colored layer, from the viewpoint of improving the interlayer adhesion and imparting flexibility to the colored layer. It is more preferably from mass% to 40% by mass.

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

The polymerizable compounds used in the present disclosure preferably have 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 280 to 280 to each. 2,200 is particularly preferable.

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

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 silicone polymers, acrylic polymers, polyester polymers and the like.
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 a dispersant.

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

As the dispersant, a commercially available product may be used. Commercially available products include EFKA 4300 (acrylic polymer dispersant) manufactured by BASF Japan, Homogenol L-18 manufactured by Kao Corporation, Homogenol L-95, Homogenol L-100, and Lubrizol Japan Co., Ltd. Examples thereof include Solsperth 20000, Solsperth 24000, DISPERBYK-110, DISPERBYK-164, DISPERBYK-180, DISPERBYK-182 manufactured by Big Chemie Japan Co., Ltd.
In addition, "homogenol", "sol sparse", and "DISPERBYK" are all registered trademarks.

When the colored layer contains a dispersant, the dispersant may contain only one type or two or more types.
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.

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

Specifically, as the photopolymerization initiator, for example, 1- [4- (phenylthio)] -1,2-octanedione-2- (O-benzoyloxime) (for example, IRGACURE® OXE-01, BASF). , [9-Ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] ethane-1-on-1- (O-acetyloxime) (eg, IRGACURE® OXE- 02, manufactured by BASF), 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (eg, IRGACURE®) 379EG, manufactured by BASF), 2-Methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (eg, IRGACURE® 907, manufactured by BASF), 2-hydroxy-1- {4- [4- (2-Hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methyl-propane-1-one (eg, IRGACURE® 127, manufactured by BASF), 2-benzyl-2 -Dimethylamino-1- (4-morpholinophenyl) butanone-1 (eg, IRGACURE® 369, manufactured by BASF), 2-hydroxy-2-methyl-1-phenylpropan-1-one (eg, eg) IRGACURE (registered trademark) 1173, manufactured by BASF), 1-hydroxycyclohexylphenylketone (eg, IRGACURE (registered trademark) 184, manufactured by BASF), 2,2-dimethoxy-1,2-diphenylethan-1-one (eg, IRGACURE (registered trademark) 184, manufactured by BASF). For example, IRGACURE (registered trademark) 651, manufactured by BASF, trade name: Lunar 6 (manufactured by DKSH Japan Co., Ltd.), 2,4-diethylthioxanthone (eg, Kayacure DETX-S,) which is an oxime ester-based polymerization initiator. Examples thereof include DFI-091 and DFI-020 (both manufactured by Daito Chemix), which are fluorene oxime-based polymerization initiators (manufactured by Nippon Kayaku Co., Ltd.).

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

The content of the polymerization initiator is preferably 0.1 part by mass to 15 parts by mass, and more preferably 0.5 part by mass to 10 parts by mass with respect to 100 parts by mass of the polymerizable compound.

-Binder resin-
The colored layer preferably contains a binder resin from the viewpoint of reducing the 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, a spectrophotometer UV-2100 manufactured by Shimadzu Corporation).

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

In the present disclosure, the "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, acrylic acid homopolymers, methacrylic acid homopolymers, acrylic acid ester homopolymers, methacrylic acid ester homopolymers, copolymers of acrylic acid with other monomers, and methacryl. Polymers of acid and other monomers, copolymers of acrylic acid esters and other monomers, copolymers of methacrylic acid esters and other monomers, urethane-modified copolymers having a urethane skeleton on the side chain Etc. are included.
As the acrylic resin, glycidyl methacrylate addition of cyclohexyl methacrylate / methyl methacrylate / methacrylic acid copolymer, random copolymer of benzyl methacrylate / methacrylic acid, copolymer of allyl methacrylate / methacrylic acid, benzyl methacrylate / methacrylic acid / hydroxy Examples thereof include a copolymer of ethyl methacrylate.

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, and an alkyd resin can be used. Examples thereof include modified silicone resins and rubber-based silicone resins.
Among them, methyl-based straight silicone resin, methylphenyl-based straight silicone resin, acrylic resin-modified silicone resin, or rubber-based silicone resin is preferable, and methyl-based straight silicone resin, methylphenyl-based straight silicone resin, or rubber-based silicone is preferable. Resin is more preferred.

Commercially available products may be used as the silicone resin, and 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 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 methylene terephthalate), polyethylene-2,6-naphthalate and the like.

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 20% by mass, based on 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 are more preferable.
The ratio of the total amount of the binder resin to the total amount of the polymerizable compound including the specific polymerizable compound, that is, the total amount of the polymerizable compound / the total amount of the binder resin is preferably 0.3 to 1.5, and 0.5 to 1 .0 is more preferred.

-Other ingredients-
The colored layer may contain additives in addition to the above-mentioned components, if necessary.
As the additive, a known additive can be used. For example, the surfactant described in paragraphs 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of Japanese Patent Application Laid-Open No. 2009-237362, Japanese Patent No. 4502784. The thermal polymerization inhibitor (also referred to as a polymerization inhibitor, preferably a phenothiazine) described in paragraph 0018 of the above, and other additives described in paragraphs 0058 to 0071 of JP-A-2000-310706 can be mentioned.

-Formation of colored layer-
The method for forming the colored layer is not particularly limited, but it is preferably formed using a composition for forming a colored layer.
The composition for forming a colored layer contains a colorant, and preferably contains a colorant and an organic solvent.
Further, the composition for forming a colored layer may further contain the above-mentioned other components.
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 colorant.
The content of the components contained in the colored layer is described as the content (% by mass) with respect to the total mass of the colored layer, but when these components are contained in the composition for forming the colored layer, the content thereof is used. , The content (% by mass) of the composition for forming a colored layer with respect to the total solid content shall be read as.

When the composition for forming a colored layer contains a pigment as a colorant, a pigment dispersion liquid containing the pigment and its dispersant is prepared in advance, and the pigment dispersion liquid is used to form a composition for forming a colored layer. Is preferable from the viewpoint of further enhancing the uniform dispersibility and dispersion stability of the pigment.

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

<Organic solvent>
As the organic solvent, a commonly used organic solvent can be used without particular limitation. Specific examples thereof include organic solvents such as esters, ethers, ketones and aromatic hydrocarbons.
In addition, methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, cyclohexanone, 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 an 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 organic solvents 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, preferably 30% by mass to 70% by mass, based on the total mass of the composition for forming the colored layer (coating liquid). More preferred.

[Color change 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 larger than the color change layer B. It is a layer having a high refractive index of 0.1 or more.

The color changing 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 thermosetting resins and photocurable resins.
Examples of the thermosetting resin include siloxane resin, epoxy resin, phenol resin, melamine resin, urethane resin, unsaturated / saturated polyester, and polyimide. Examples of the siloxane resin include hydrolyzed condensates of bifunctional to tetrafunctional alkoxysilanes. 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 crosslinked acrylic resins 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.

The polymerizable compound is not particularly limited, and known monomers, oligomers and the like can be used. Further, as the polymerizable compound, the above-mentioned polymerizable compound in the colored layer can be preferably 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 known ones can be used, but polyfunctional acrylic monomers, polyfunctional acrylic oligomers, polyfunctional urethane acrylates and the like are preferable.
Further, as the polymerizable compound, an ethylenically unsaturated compound is preferable, and a (meth) acrylate compound is more preferable, from the viewpoint of scratch resistance.
Further, from the viewpoint of scratch resistance, the color changing layer A preferably contains a resin obtained by polymerizing a polymerizable compound, and more preferably contains a resin obtained by at least polymerizing a polyfunctional polymerizable compound. It is more preferable to contain a resin obtained by at least polymerizing a polyfunctional ethylenically unsaturated compound, and particularly preferably to contain a resin obtained by at least polymerizing a polyfunctional (meth) acrylate compound.

When the color changing layer A contains a polymerizable compound, it preferably contains a polymerization initiator from the viewpoint of curability and scratch resistance.
As the polymerization initiator, those described above can be preferably used in the colored layer.

Further, the color changing layer A preferably has a hard coat property from the viewpoint of scratch resistance.
Examples of the material having a hard coat property include JP-A-2013-45045, JP-A-2013-43352, JP-A-2012-223459, 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, Kai 2007-164206, JP-A-2006-96811, JP-A-2004-75970, JP-A-2002-156505, JP-A-2001-272503, International Publication No. 2012/01887, International Publication No. The materials used for the preparation of the hard coat layer described in 2012/098967, International Publication No. 2012/0866559, and International Publication No. 2011/105594 can be used.

Further, 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, but has a shelf life and the color change layer. From the viewpoint of adhesion between A and other layers, it is preferable that the layer is made 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. More preferably, it is a layer formed by at least curing a bifunctional or trifunctional polymerizable compound having a partial structure of the species.

Further, the color changing 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 refractive index. Is particularly preferred.
Further, the color changing layer A preferably contains a metal oxide, and more preferably contains zirconium oxide (zirconia) or titanium oxide (titania), from the viewpoint of enhancing scratch resistance and refractive index.
The shape of the filler is not particularly limited, but is preferably in the form of particles.

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 size of 2 nm or more and 100 nm or less from the viewpoint of aggregation inhibitory property and layer transparency. Inorganic particles having a volume average particle size of 5 nm or more and 80 nm or less are more preferable, and inorganic particles having a volume average particle size of 10 nm or more and 60 nm or less are particularly preferable.
The filler can be used alone or in combination of two or more.
The volume average particle size of the filler and the particles is measured by a Coulter counter.

The high refractive index particles include oxidation of at least one element selected from the group consisting of aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony, and cerium from the viewpoint of scratch resistance and enhancing the refractive index. It is preferably a physical particle, and more preferably a zirconium oxide particle or a titanium oxide particle. Of the two, from the viewpoint of light resistance, zirconium oxide particles having no photocatalytic action are preferable, but titanium oxide particles having suppressed photocatalytic action are also preferable.
The refractive index of the high-refractive index particles is preferably 1.60 to 3.00, more preferably 1.80 to 2.90, and 1.90 to 2.80 from the viewpoint of increasing the refractive index. Is particularly preferable.

Further, the following various dispersants can also be preferably used for the dispersion of the high refractive index particles.
The dispersant preferably further contains a crosslinked or polymerizable functional group. Examples of the crosslinked or polymerizable functional group include an ethylenically unsaturated group (for example, (meth) acryloyl group, allyl group, styryl group, vinyloxy group, etc.) capable of an addition reaction / polymerization reaction with a radical species, and a cationically polymerizable group (epoxy). Groups, oxatanyl groups, vinyloxy groups, etc.), polycondensation-reactive groups (hydrolytable silyl groups, etc., N-methylol groups) and the like are mentioned, and a functional group having an ethylenically unsaturated group is preferable.

It is preferable to use a dispersant having an anionic group for the dispersion of the high refractive index particles, particularly the dispersion of the inorganic particles containing TiO ₂ as a main component, and it is more preferable to have an anionic group and a crosslinked or polymerizable functional group. It is particularly preferable that the dispersant has the crosslinked or polymerizable functional group in the side chain. Specific examples of the crosslinked or polymerizable functional group include the above-mentioned 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, and the like. A phosphoric acid group or a salt thereof is more preferable, and a carboxy group or a phosphoric acid group is particularly preferable. The number of anionic groups contained in the dispersant per molecule may be a plurality of types in one molecule, but is preferably 2 or more on average, and more preferably 5 or more. Particularly preferably, the number is 10 or more. Further, a plurality of types of anionic groups contained in the dispersant may be contained in one molecule.

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 the total monomer unit, and is preferably 1 mol% to 50 mol%. It is more preferably present, and particularly preferably 5 mol% to 20 mol%.

The number of crosslinked 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. Further, a plurality of types of crosslinked or polymerizable functional groups contained in the dispersant may be contained in one molecule.

Examples of monomer units having an ethylenically unsaturated group in the side chain of a preferred dispersant include poly-1,2-butadiene and poly-1,2-isoprene structures, or esters or amides of (meth) acrylic acid. A repeating unit having a specific residue (-COOR or R group of -CONHR) attached to it can be used. As an example of the above specific residue (R group),-(CH)₂)_n-CR₂₁= CR₂₂R₂₃,-(CH₂O) n-CH₂CR ₂₁= CR₂₂R₂₃,-(CH₂CH₂O)_n-CH₂CR₂₁= CR₂₂R₂₃,-(CH₂)_n-NH-CO-O-CH₂CR₂₁= CR₂₂R₂₃,-(CH₂) N-O-CO-CR₂₁= CR₂₂R₂₃And-(CH₂CH₂O)₂-X (R₂₁~ R₂₃Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkoxy group or an aryloxy group, and R₂₁And R₂₂Or R₂₃May form a ring by binding to each other, where n represents an integer of 1 to 10 and X represents a dicyclopentadienyl residue. ) Can be mentioned. A specific example of R of an ester residue is -CH.₂CH = CH ₂(Corresponding to the polymer of allyl (meth) acrylate described in JP-A-64-17047), -CH₂CH₂O-CH₂CH = CH₂, -CH₂CH₂OCOCH = CH₂, -CH₂CH₂OCOC (CH)₃) = CH₂, -CH₂C (CH)₃) = CH₂, -CH₂CH = CH-C₆H₅, -CH₂CH₂OCOCH = CH-C₆H₅, -CH₂CH₂-NHCOO-CH₂CH = CH₂And -CH₂CH₂OX (X is a dicyclopentadienyl residue) is included. A specific example of R of the amide residue is -CH.₂CH = CH₂, -CH₂CH₂-Y (Y is a 1-cyclohexenyl residue) and -CH₂CH₂-OCO-CH = CH₂, -CH₂CH₂-OCO-C (CH)₃) = CH₂Is included.

In the above dispersant having an ethylenically unsaturated group, a free radical (a polymerization initiation radical or a growth radical in the polymerization process of a polymerizable compound) is added to the unsaturated bond group, and the polymer can be directly or polymerized between molecules. By addition polymerization via the polymerization chain of the above, crosslinks are formed between the molecules and the mixture is cured. Alternatively, an atom in the molecule (eg, a hydrogen atom on a carbon atom adjacent to an unsaturated bond group) is extracted by a free radical to generate a polymer radical, which bonds to each other to form a crosslink between the molecules. And cure.

The weight average molecular weight (Mw) of the dispersant having an anionic group and a crosslinked or polymerizable functional group in the 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 crosslinked 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 is particularly preferable. Is 5 mol% to 30 mol%.

The dispersant may be a copolymer with a suitable monomer other than the monomer having a crosslinked or polymerizable functional group or 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 the formed film. Preferred examples include methyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene and the like.

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

The content of the dispersant in the color changing layer A is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 30% by mass, based on the total mass of the high refractive index particles. It is particularly preferably 5% by mass to 20% by mass. Further, two or more kinds of dispersants may be used in combination. The dispersant preferably used is described in detail in Japanese Patent Application Laid-Open No. 2007-293313.

The method for dispersing the high-refractive index particles in the dispersion medium is not particularly limited, but the particles can be dispersed using a disperser. Examples of the disperser include a sand grinder mill (eg, a bead mill with a pin), a high speed impeller mill, a pobble mill, a roller mill, an attritor, a colloid mill and the like. Of these, a sand grinder mill or a high-speed impeller mill is particularly preferable. Further, a preliminary distributed treatment may be carried out. Examples of dispersers used in the pre-dispersion process include ball mills, triple roll mills, kneaders and extruders.
The high-refractive index particles are preferably miniaturized as much as possible in the dispersion medium, and the preferable 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, but from the viewpoint of increasing the color change resistance, scratch resistance, and refractive index, the color change layer A has a filler content. It is preferably 10% by mass to 95% by mass, more preferably 15% by mass to 90% by mass, further preferably 20% by mass to 85% by mass, and 30% by mass to the total mass. It is particularly preferably 80% by mass.

[Color change layer B]
The decorative film according to the present disclosure has a color change layer B, and 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 color changing layer B is preferably a layer having an antireflection ability from the viewpoint of color changing property and blackening property.
Further, the color changing layer B is preferably a layer thicker than the color changing layer A from the viewpoint of scratch resistance.

The material of the color changing layer B is not particularly limited, but preferably contains the following components.
From the viewpoint of scratch resistance, the color changing layer B preferably contains at least one compound selected from the group consisting of a resin and a polymerizable compound as a binder, more preferably contains a resin, and the resin and the polymerization. It is more preferable to contain a sex compound.
From the viewpoint of scratch resistance, the resin preferably contains at least one resin selected from the group consisting of thermosetting resins and photocurable resins.
As the thermosetting resin and the photocurable resin, those described above in the color changing layer A can be suitably used by appropriately selecting the refractive index.
The polymerizable compound is not particularly limited, and known monomers, oligomers and the like can be used. Further, as the polymerizable compound, the above-mentioned polymerizable compound in the colored layer can be preferably used.
Further, as the polymerizable compound, the above-mentioned compound in the color change layer A can be suitably used by appropriately selecting the refractive index before or after curing.
When the color changing layer B contains a polymerizable compound, it preferably contains a polymerization initiator from the viewpoint of curability and scratch resistance.
As the polymerization initiator, those described above can be preferably used in the colored layer.

Since 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, 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, and more preferably 1.4 or less, from the viewpoint of color changeability. In terms of having a refractive index of 1.5 or less, the color changing layer B preferably contains at least one selected from the group consisting of a siloxane resin having voids, a fluororesin, and low refractive index particles, and the voids are formed. It is more preferable to include at least one selected from the group consisting of the siloxane resin, the fluororesin, and the 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 fluororesin include a fluoroalkyl resin in which hydrogen in an olefin is replaced with fluorine, and examples thereof include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, perfluoroalkoxyalkano, and perfluoro. There are copolymers such as ethylene propene and ethylene tetrafluoroethylene, or fluororesin dispersions that are water-dispersed by copolymerizing with emulsifiers and components that enhance affinity with water. Specific examples of such a fluororesin include Lumiflon manufactured by Asahi Glass Co., Ltd., Obrigato, Zeffle manufactured by Daikin Industries, Ltd., Neoflon, Teflon manufactured by DuPont, and Kinner manufactured by Arkema.
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, and vinylidene fluoride may be used. Examples thereof include a radically polymerizable monomer such as a monomer and a cationically polymerizable monomer such as perfluorooxetane. Specific examples of such a fluorine compound include LINK3A manufactured by Kyoeisha Chemical Co., Ltd., Optool manufactured by Daikin Industries, Ltd., Opstar manufactured by Arakawa Chemical Industries, 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 so on.
Specific examples of such hollow particles include hollow silica particles manufactured by JGC Catalysts and Chemicals Co., Ltd., Sirinax manufactured by Nittetsu Mining Co., Ltd., and techpolymers 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 Research Institute Co., Ltd.

The siloxane resin having the above voids is a hollow particle or a core-shell particle because it suppresses deterioration such as thermal deformation of the resin base material and it is difficult to form an opening as described above on the surface of the color change layer B. It is preferable to use a method of forming closed voids in a matrix composed of a siloxane resin. As a method for forming the color changing layer B by applying the composition containing the hollow particles, for example, the method described in paragraphs 0028 to 0029 of JP-A-2009-103808, or paragraph of JP-A-2008-262187. The method described in 0030 to 0031 can be applied. In particular, a method of forming the color changing layer B using core-shell particles is preferable because the void diameter and porosity can be easily adjusted.

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

-Core shell particles-
The color changing layer B forming coating liquid preferably contains core-shell particles.
The core-shell particles preferably contain an organic solvent as the core material from the viewpoint of easy formation of closed voids, and in particular, 20% by mass or more of the organic solvent is a non-polar solvent having a boiling point of 90 ° C. or higher and 350 ° C. or lower. It is preferable to have.
The "boiling point" in the present disclosure is the boiling point at 1 atm (101,325 Pa). Further, the "non-polar solvent" in the present disclosure means a solvent having a solubility in water of 0.1% by mass or less at 20 ° C. and a relative permittivity value of 10 or less.

Examples of the non-polar solvent having a boiling point of 90 ° C. or higher and 350 ° C. or lower include a hydrocarbon compound, a fluorinated hydrocarbon compound, a silicone compound and the like. 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 viewpoint of the strength, light transmission and haze of the color changing layer B, and the siloxane compound represented by the formula 1 described later. It is more preferable to contain a hydrolyzed condensate, and it is further preferable to contain 50% by mass or more of the hydrolyzed condensate of the siloxane compound represented by the formula 1 described later with respect to the total mass of the shell. It is particularly preferably composed of a hydrolyzed condensate of the represented siloxane compound.

The volume average particle diameter of the core-shell particles is preferably 0.05 μm to 1.5 μm, more preferably 0.08 μm to 1.0 μm, from the viewpoint of the intensity, light transmission and haze of the color changing layer B. It is more preferably 0.1 μm to 0.6 μm, and particularly preferably 0.1 μm to 0.4 μm.

The volume average particle size of the particles in the present disclosure shall be 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 size means the median diameter.
The coefficient of variation of the particle size of the core-shell particles in the present disclosure is calculated by dividing the standard deviation in the volume distribution of the particle size measured in the above measurement by the median diameter.

The core size (maximum diameter) of 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 viewpoint of the strength, light transmission, and haze of the color changing layer B. It is particularly preferably at ~ 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 of the color changing layer B described above.

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

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 R ⁴ independently represents an alkyl group, a vinyl group, respectively in the case of a plurality of carbon groups. Alternatively, a vinyl group, an epoxy group, a vinylphenyl group, a (meth) acryloxy group, a (meth) acrylamide group, an amino group, an isocyanurate group, a ureido group, a mercapto group, a sulfide group, a polyoxyalkyl group, a carboxy group and a fourth group. It represents an alkyl group having a group selected from the group consisting of primary ammonium groups, where m represents an integer of 0 to 2 and n represents an integer of 1 to 20.

The hydrolysis condensate of the siloxane compound represented by the formula 1 is obtained by hydrolyzing at least a part of the substituent on the silicon atom of the siloxane compound represented by the formula 1 and the siloxane compound represented by the formula 1. , A compound fused with a compound that is 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 has a ring structure regardless of whether it is linear or has a branch. May be 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 transmission 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, a cyclohexyl group and the like. It is preferably a methyl group or an ethyl group, and more preferably a methyl group.

From the viewpoint of the strength, light transmission and haze of the protective layer, ^R4 in the formula 1 is preferably an alkyl group independently in each case, and more preferably an alkyl group having 1 to 8 carbon atoms. preferable.
Further, the carbon number of ^R4 in the formula 1 is preferably 1 to 40, more preferably 1 to 20, and particularly preferably 1 to 8.
From the viewpoint of the strength of the protective layer, light transmission, and haze, m in the formula 1 is preferably 1 or 2, and more preferably 2.
N in the formula 1 is preferably an integer of 2 to 20 from the viewpoint of the strength of the protective layer, the light transmittance and the haze.

Examples of the specific siloxane compound are 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; Dynasylan4150 manufactured by Ebonic Japan Co., Ltd .; MKC Silicate MS51, MS56, MS57, MS56S manufactured by Mitsubishi Chemical Co., Ltd .; Ethyl silicate 28, N-propyl silicate manufactured by Corcote Co., Ltd. , N-Butyl silicate, SS-101; and the like.

-Surfactant-
The coating liquid for forming the color changing layer B preferably contains a surfactant.
Examples of the surfactant include a nonionic surfactant, an anionic surfactant which is an ionic surfactant, a cationic surfactant, an amphoteric surfactant and the like, and all of them can be suitably used in the present disclosure.
Among them, nonionic surfactants, from the viewpoints of efficient formation of core-shell particles by attractive force interacting with the above-mentioned specific siloxane compound, storage stability, and light transmission and haze of the color changing layer B. In addition, at least one surfactant selected from the group consisting of cationic surfactants is preferable, and cationic surfactants are more preferable.

-Other ingredients-
The coating liquid for forming the color changing layer B may contain other components depending on the purpose, in addition to the above-mentioned components.
As other components, known additives can be used, and examples thereof include antistatic agents, condensation catalysts of siloxane compounds, and preservatives.

-Antistatic agent The coating liquid for forming the color changing layer B may contain an antistatic agent.
The antistatic agent is used for the purpose of suppressing the adhesion of contaminants by imparting antistatic properties to the color changing layer B.
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, but since they are inorganic particles, the inclusion of the metal oxide particles improves the antifouling property of the color changing layer B. 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 the light transmittance may decrease due to scattering of transmitted light. Therefore, the average primary particle size of the metal oxide particles is preferably 100 nm or less, preferably 50 nm. It is more preferably less than or equal to, and particularly preferably 30 nm or less. The lower limit is preferably 2 nm or more.
The shape of the particles is not particularly limited, and may be spherical, plate-shaped, or needle-shaped.
The average primary particle size of the metal oxide particles can be obtained from the 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 obtained, and the diameter equivalent to the circle is obtained from the projected area, which is used as the average particle diameter (average primary particle diameter). As the average primary particle diameter in the present specification, a value calculated by measuring the projected area of 300 or more particles and obtaining the equivalent circle diameter is used.
If the shape of the metal oxide particles is not spherical, it may be obtained by using another method, for example, a dynamic light scattering method.

Only one type of antistatic agent may be contained in the coating liquid for forming the color changing layer B, or two or more types may be contained. When two or more kinds of metal oxide particles are contained, two or more kinds having different average primary particle diameters, shapes, and materials may be used.
In the coating liquid for forming the color changing layer B, the content of the antistatic agent is preferably 40% by mass or less, preferably 30% by mass or less, based on the total solid content of the coating liquid for forming the color changing layer B. Is more preferable, and 20% by mass or less is particularly preferable.
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 deteriorating the film-forming property of the coating liquid for forming the color changing layer B.
Further, when the metal oxide particles are used as the antistatic agent, the content is preferably 30% by mass or less, and preferably 20% by mass or less, based on the total mass of the coating liquid for forming the color changing layer B. It is more preferably 10% by mass or less, and 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 liquid for forming the color change layer B becomes good, the generation of aggregation is suppressed, and the necessary antistatic property is changed in color. It can be applied to the layer B.

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

-Preparation of coating liquid for forming color change layer B-
The method for preparing the coating liquid for forming the color changing 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 partially hydrolyzed and condensed to form a coating liquid for forming a color change layer B, a core-shell particle containing an organic solvent as a core material, specified. Examples thereof include a method for producing by mixing a siloxane compound, a surfactant, and water.

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

The coating liquid for forming the color changing layer B may be dried at room temperature (25 ° C.) or heated. In the case of a coating liquid that sufficiently volatilizes the organic solvent contained in the coating liquid for forming the color changing layer B to form voids, the coating liquid forms voids, and from the viewpoint of light transmission and color suppression of the color changing layer B, Further, it is preferably heated to 40 ° C. to 200 ° C. from the viewpoint of heating at a temperature equal to or lower than the decomposition temperature of the resin base material. Further, from the viewpoint of suppressing thermal deformation of the resin base material, it is more preferable to heat the resin base material to 40 ° C. to 120 ° C.
When heating is performed, the heating time is not particularly limited, but is preferably 1 minute to 30 minutes.

The formation of the color change layer B by the coating liquid for forming the color changing layer B containing the core shell particles and the coating liquid for forming the color changing layer B has been described above. However, the color changing layer B containing hollow particles instead of the core shell particles has been described. The color changing layer B may be formed by using the forming coating liquid.
Here, as the hollow particles, it is preferable to use hollow silica particles containing silica as a main component in that the refractive index is 1.5 or less.
Examples of the hollow silica particles include hollow particles described in JP2013-237593A, International Publication No. 2007/068844, and the like.
Further, the hollow silica particles may be hollow silica particles having an unmodified surface or hollow silica particles having a modified surface.
Further, the hollow particles are physically subjected to plasma discharge treatment, corona discharge treatment, etc. in order to stabilize the dispersion in the coating liquid for forming the color change layer B, or to enhance the affinity and bondability with the siloxane resin. Chemical surface treatment with a target surface treatment, a surfactant, a coupling agent, or the like may be performed.

The porosity of the color changing layer B is preferably 10% to 80%, more preferably 15% to 75%, and 20% to 55% from the viewpoint of light transmission and scratch resistance. Is particularly preferable.
The diameter of the voids in the color changing layer B (hereinafter, also referred to as “void diameter”) is preferably 25 nm or more, and more preferably 30 nm or more, from the viewpoint of strength, light transmission, 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 void diameter and the porosity of the color changing layer B is as follows.
The decorative film provided with the color changing layer B is cut in a direction orthogonal to the film surface, and the cut surface is observed with a scanning electron microscope (SEM) to measure the void diameter and the void ratio.
In the SEM image of the cut surface (magnification 50,000 times), the equivalent circle diameter is calculated for each of 200 arbitrarily selected voids, and the average value thereof is used as the void diameter.
In addition, the void ratio is an image of the void portion and the matrix portion (that is, the portion other than the void containing the siloxane resin) using image processing software (ImageJ) for the SEM image of the cut surface (magnification 50,000 times). It is treated (binarized) and separated, and the ratio of the void portion is calculated to obtain the void ratio.
When there is no anisotropy in the diameter of the void, the porosity is obtained as the volume fraction of the void in the siloxane resin.

[Resin layer]
From the viewpoint of improving the adhesion between the colored layer and the color changing layer A, the decorative film according to the present disclosure preferably further has a resin layer between the colored layer and the color changing layer A. ..
The resin layer is preferably a layer containing a resin of a different type from the color changing layer A.
The resin layer is preferably a transparent resin layer, and more preferably a layer made of a transparent film, from the viewpoint of color changeability. By forming the color change layer A on the transparent film and laminating it on the colored layer, a decorative film can be easily produced.
The transparent film is not particularly limited as long as it is a transparent film having the required strength and scratch resistance.
In the present disclosure, "transparent" in a transparent film means 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 total light transmittance of the temporary support described above.

The transparent film is preferably a film obtained by forming a transparent resin into a film, and specifically, polyethylene terephthalate (PET) resin, polyethylene naphthalate (PEN) resin, acrylic resin, polycarbonate (PC) resin, and triacetyl. Examples thereof include a resin film containing a resin such as cellulose (TAC) and cycloolefin polymer (COP).
In particular, from the viewpoint of shape followability to the mold, acrylic resin, polycarbonate resin, or polyethylene terephthalate resin is 60% by mass or more (more preferably 80% by mass or more, still more preferable) with respect to all the 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, still more preferably 100% by mass) of acrylic resin with respect to all the 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.

As the transparent film, a commercially available product may be used, and examples of the commercially available product include Acriprene (registered trademark) HBS010 (acrylic resin film, manufactured by Mitsubishi Chemical Co., Ltd.) and Technoroy (registered trademark) S001G (acrylic resin film,). Examples thereof include 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 a method of laminating a transparent film on the colored layer is preferable.
As an apparatus used for laminating a transparent film, a known laminator such as a laminator, a vacuum laminator, and an auto-cut laminator capable of further increasing productivity can be used.
It is preferable that the laminator is provided with an arbitrary heatable roller such as a rubber roller and can be pressurized and heated.
By 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 improved.

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

Further, 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 colored 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 an adhesive layer between the temporary support and the colored layer from the viewpoint of adhesiveness to the base material to which the decorative film is attached.
Further, as will be described later, before the temporary support is attached to the base material, the temporary support is peeled off, and the adhesive layer is placed 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 pressure-sensitive adhesive layer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a known pressure-sensitive adhesive or a layer containing an adhesive can be mentioned.

-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. As an example of the adhesive, "Characteristic evaluation of release paper / release film and adhesive tape and its control technology", Information Mechanism, 2004, Acrylic adhesive described in Chapter 2, UV (UV) curable adhesive. Agents, silicone adhesives and the like can be mentioned. The acrylic pressure-sensitive adhesive refers to a pressure-sensitive adhesive containing a polymer of (meth) acrylic monomer ((meth) acrylic polymer).
When a pressure-sensitive adhesive is contained, a pressure-sensitive adhesive may be further contained.

-glue-
Examples of the adhesive include urethane resin adhesives, polyester adhesives, acrylic resin adhesives, ethylene vinyl acetate resin adhesives, polyvinyl alcohol adhesives, polyamide adhesives, silicone adhesives and the like. Urethane resin adhesives or silicone adhesives are preferable from the viewpoint of higher adhesive strength.

-Method of forming an adhesive layer-
The method for forming the adhesive layer is not particularly limited, and a method of laminating the protective film on which the adhesive layer is formed so as to be in contact with the adhesive layer and a method of laminating the adhesive layer so as to be in contact with the colored layer alone. Examples thereof include a method, a method of applying the pressure-sensitive adhesive or a composition containing the adhesive onto a colored layer, and the like. As the laminating method or the coating method, a method similar to the above-mentioned laminating method of a transparent film or a coating method of a composition for forming a colored layer is preferably mentioned.

The thickness of the adhesive layer in the decorative film is preferably 5 μm to 100 μm in terms of both 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 layer include a reflective layer, a self-repairing layer, an antistatic layer, an antifouling layer, an electromagnetic waveproof layer, a conductive layer, and the like, which are known layers in decorative films.
Other layers in the decorative film according to the present disclosure can be formed by a known method. For example, a method of applying a composition (composition for forming a layer) containing the components contained in these layers in a layered manner and drying the composition can be mentioned.

-Cover film-
The decorative film according to the present disclosure may have a cover film as the outermost layer on the color change layer B side for the purpose of preventing stains and the like.
As the cover film, any material having flexibility and good peelability can be used without particular limitation, and examples thereof include a resin film such as a polyethylene film.
The method of attaching the cover film is not particularly limited, and examples thereof include known attachment methods, such as a method of laminating the cover film on the color change layer B.

(Decorative molded film)
The decorative molded film according to the present disclosure has a substrate, a colored layer, a color changing layer A, and a color changing layer B in this order, and the color changing layer B has a higher refractive index than the color changing layer A. It is a layer lower than 0.1.
The colored 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 colored 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 the same. Furthermore, the preferred embodiments for the other layers are the same.
The base material in the decorative molded film according to the present disclosure is preferably a film base material.
Further, it is particularly preferable that the base material in the decorative molding film according to the present disclosure is a base material for molding. The base material is the same as the base material described later, and the preferred embodiment is also the same.
Further, as the method for producing the decorative molded film according to the present disclosure, it is possible to refer to the method of attaching to the substrate in the decorative method according to the present disclosure, which will be described later.

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

-Step of peeling off the temporary support-
The decoration method according to the present disclosure preferably includes a step of peeling the temporary support from the decoration film according to the present disclosure.
The peeling method is not particularly limited and may be peeled by a known method. For example, a method of grasping a part of the temporary support with a finger or a base material such as tweezers and peeling it off can be mentioned.

-Step of forming an adhesive layer-
The decoration method according to the present disclosure is also referred to as a step of forming an adhesive layer on the surface of the decorative film from which the temporary support has been peeled off (simply, a step of forming an adhesive layer). ) Is preferably included.
The method for forming the adhesive layer and the adhesive layer is the same as the method for forming the adhesive layer and the adhesive layer described above, and the preferred embodiment is also the same.

-The process of attaching to the base material-
The decoration method according to the present disclosure includes a step of attaching the decorative film from which the temporary support has been peeled off to the base material from the colored layer side (simply referred to as "a step of attaching to the base material"). Is preferable.
In the step of attaching to the base material, the decorative film from which the temporary support has been peeled off may be attached to the outermost layer on the colored layer side and the base material. The colored layer or the adhesive layer of the decorative film and the base material may be attached.

The base material is not particularly limited, and a desired base material can be used. Specific examples thereof include automobiles, home appliances, audio products, computers, displays, in-vehicle products, watches, accessories, optical parts, doors, windowpanes, building materials and the like.
Above all, the decoration method according to the present disclosure can be suitably used as a decoration method for the exterior of an automobile.

Further, as the base material, a molding base material can be preferably used.
As the base material for molding, conventionally known base materials used for molding such as three-dimensional molding and insert molding can be used without particular limitation, and are appropriately selected according to the use of the decorative film, suitability for insert molding, and the like. It should be done.
The shape and material of the molding base material are not particularly limited and may be appropriately selected as desired, but a film base material is preferable from the viewpoint of ease of insert molding.

Specifically, as the base material for molding, for example, polyethylene terephthalate (PET) resin, polyethylene naphthalate (PEN) resin, acrylic resin, polycarbonate (PC) resin, triacetyl cellulose (TAC), cycloolefin polymer (COP), etc. Examples thereof include a resin film containing a resin such as an acrylonitrile / butadiene / styrene copolymer resin (ABS resin).

The molding base material is suitable for three-dimensional molding and insert molding, and in particular, has excellent followability to the mold. Therefore, 60% by mass or more of acrylonitrile / butadiene / styrene with respect to the total resin component contained in the molding base material. A resin film containing a copolymer resin (ABS resin) is preferable. The content of ABS resin with respect to all the resin components contained in the base material for molding is more preferably 80% by mass or more, and may be 100% by mass (that is, all of the resin components are ABS resin).

The molding base material may contain additives other than the above-mentioned resin, 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, and inorganic flame retardant agents such as magnesium hydroxide and aluminum hydroxide. Organic or inorganic fillers such as halogen-based and phosphorus-based organic flame retardants, metal powder, talc, calcium carbonate, potassium titanate, glass fiber, carbon fiber, wood powder, antioxidants, ultraviolet inhibitors, lubricants, Additives such as dispersants, coupling agents, foaming agents and colorants, polyolefin resins, polyester resins, polyacetal resins, polyamide resins, polyphenylene ether resins and the like, and engineering plastics other than the above-mentioned resins can be mentioned.

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

The thickness of the base material for molding is determined according to the intended use of the decorative molded body 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, preferably 150 μm to 600 μm. More preferred.

-Paste method-
The method of attaching to the substrate is not particularly limited, 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 can be mentioned.
The laminating method is not particularly limited, and for example, the same method as the above-mentioned transparent film laminating method is used.

-Exposure process-
In the decoration method according to the present disclosure, if 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"). ) May be included.
When the colored layer is exposed, the colored layer preferably contains a polymerizable compound and a photopolymerization initiator. A cured colored layer can be obtained by exposing the colored layer containing the polymerizable compound and the photopolymerization initiator.
When the colored layer contains a polymerizable compound and a photopolymerization initiator, the decorative film after peeling the protective film is used so that the base material and the adhesive layer are in contact with each other without exposure in the method for producing the decorative film. It may be exposed after pasting. According to the above method, the adhesion between the base material and the decorative film after the protective film is peeled off is more 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 decoration method according to the present disclosure includes an exposure step, the timing of performing the exposure step is not particularly limited, and even before the step of peeling the temporary support, before the step of forming the adhesive layer. It may be before the step of sticking to the base material or after the step of sticking to the base material, but from the viewpoint of improving the adhesion between the layers, the temporary support may be used. It is preferably performed before the peeling step.
Further, from the viewpoint of the laminating property of the adhesive layer, it is preferable that the exposure step is performed before the step of forming the adhesive layer.
Further, from the viewpoint of ease of molding when ductility during heating is required, the exposure step is preferably performed after the step of attaching to the substrate.

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

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

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

In this step, for example, it is not necessary for all the polymerizable compounds in the colored layer to react, and the unpolymerized polymerizable compound and the polymer of the polymerizable compound coexist in the colored layer after exposure. It may be in a state of
By further exposing the decorative molded body obtained after molding in a state where the specific polymerizable compound and the polymer of the specific polymerizable compound coexist in the colored layer after exposure, the interlayer adhesion (with the above-mentioned colored layer). The adhesion between the color changing layer B and the colored layer and the base material) may be further improved.
The same applies to the color changing layer A and the color changing layer B.

Here, an example of the layer structure of the decorative film will be described with reference to FIG.
FIG. 1 is a schematic cross-sectional view showing an example of the layer structure of the 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. Further, the resin layer 26 has a color changing layer A28 and a color changing layer B30 on the surface opposite to the colored layer 24. The resin layer 26 is an arbitrary layer and may not be included in the decorative film 20.
Further, although not shown, the above-mentioned peeling layer may be provided between the temporary support 22 and the colored layer 24.

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

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

(Manufacturing method of decorative molded body and decorative molded body)
The method for manufacturing the decorative molded body according to the present disclosure may be any method as long as it is a method for manufacturing the decorative molded body by performing decoration and molding using the decorative film according to the present disclosure, and the above-mentioned is described from the decorative film according to the present disclosure. A step of peeling off the temporary support, a step of attaching the decorative film from which the temporary support has been peeled off to the molding base material from the colored layer side, and a step of attaching the decorative film to the molding base material. It is preferable to include a step of molding.
The decorative molded body according to the present disclosure is a decorative molded body according to the present disclosure or a decorative molded body obtained by using the decorative molded film according to the present disclosure, and is according to the method for manufacturing the decorative molded body 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 manufacturing a decorative molded body, and for example, at least one selected from the group consisting of three-dimensional molding and insert molding. It is particularly suitable for 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 being attached to the molded body after molding.
Since the decorative molded film according to the present disclosure is also excellent in three-dimensional moldability, it can be suitably used for manufacturing a decorative molded body. For example, when the molded body is a resin, it is particularly suitable for producing a decorative molded body by, for example, 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 non-melting material such as metal, it is particularly suitable for manufacturing a decorative molded body by three-dimensional molding.
By using the decorative film according to the present disclosure in the production of the decorative molded body, it becomes possible to apply it to a mold having a more complicated shape, a smaller shape, etc., and the range of applications of the decorative molded body can be expanded. can.
Hereinafter, a method for manufacturing a decorative molded body will be described in detail by taking insert molding as an example.

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

Further, when 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. Specific examples thereof include an adhesive containing a vinyl chloride / vinyl acetate copolymer and an acrylic resin.
A commercially available product may be used as the adhesive, and examples of the commercially available product include IMB-003 manufactured by Teikoku Printing Co., Ltd.

Hereinafter, an 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 arranging a decorative molded film formed in a quadrilateral of a certain size in a mold for injection molding and closing the mold, and then placing a molten resin in the mold. Including the step of injecting into the injection resin and the step of taking out the injection resin when it has solidified.

The mold for injection molding (that is, the molding mold) used for manufacturing the decorative molded product is 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). A female mold) is provided, and the decorative molding film is placed on the molding surface that is the inner peripheral surface of the female mold, and then the mold is closed.

Here, before arranging the decorative molding film in the molding die, the decorative molding film is formed into a decorative molding film by molding (preforming) the decorative molding film using the molding die. It is also possible to give a three-dimensional shape in advance and supply it to the molding die.
Further, when arranging the decorative film in the molding die, it is necessary to align the decorative molding film and the molding die with the decorative molding film inserted in the molding die.

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

Further, the fixing pin is formed in advance at a position where it fits with the alignment hole in the male mold.
In addition to the method of inserting the fixing pin into the alignment hole, the following methods for aligning the decorative molding film and the molding die with the decorative molding film inserted in the molding die are as follows. It is possible to use the method.

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

After aligning the decorative molding film and the molding die and closing the molding die, the molten resin is injected into the molding die into which the decorative molding film is inserted. At the time of injection, the molten resin is injected onto the molding base material side of the decorative molding film.

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

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

In the intermediate decorative molded body, a burr and a dummy part of the decorative molded body are integrated around the decorative portion which is finally a product (decorative molded body). Here, in the dummy portion, there is an insertion hole formed by inserting the fixing pin in the above-mentioned positioning.
Therefore, the decorative molded body can be obtained by performing the finishing process of removing the burrs and the dummy portion from the decorative portion in the intermediate decorative molded body before the finishing process.

The decorative molded body 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 enhanced, and the durability against heat and the like is further improved.

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

The above vacuum forming can be performed by using a vacuum forming technique widely known in the molding field, and for example, vacuum forming may be performed using Formech 508FS manufactured by Nippon Sekki Kogyo Co., Ltd.

The use of the decorative molded body obtained as described above is not particularly limited and can be used for various articles, but the interior / exterior of automobiles, the interior / exterior of electric products, packaging containers and the like are particularly preferable. Can be mentioned.

The present disclosure will be described in more detail with reference to examples below. The scope of the present disclosure is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.

<Preparation of each composition for forming a decorative film>
[Preparation of composition for forming a colored layer]
A composition 1 for forming a colored layer 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% by mass 1-methoxy-2-propylacetate solution of a copolymer (weight average molecular weight Mw: 29,000) of benzyl methacrylate / methacrylic acid (molar ratio 70/30) -Polymerable compound: Sartomer-. Made by Japan Co., Ltd., Urethane acrylate oligomer, CN-996NS (solid content: 100% by mass)
-Initiator of polymerization: OXE-02 (1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] etanone-1- (O-acetyloxime)) manufactured by BASF, interface Activator: DIC Co., Ltd., Megafuck (registered trademark) F-551, methylisobutylketone solution of perfluoroalkyl group-containing phosphate ester-type amine neutralizer (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 the black pigment dispersion, and a black pigment dispersion was obtained using a three-roll and a bead mill. The average particle diameter (median diameter) measured using Microtrac FRA (Honeywell) was 163 nm.

-Composition of black pigment dispersion-
Resin-coated carbon black produced in accordance with paragraphs 0036 to 0042 of Japanese Patent No. 5320652: 20.0% by mass.
Dispersant 1 (structure below): 1.0% by mass
Polymer (random copolymer with benzyl methacrylate / methacrylic acid = 72/28 molar ratio, weight average molecular weight 30,000): 6.0% by mass
-Propylene glycol monomethyl ether acetate: 73.0% by mass

<Making 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 colored layer forming composition 1 is applied onto the peeling layer coated surface of the temporary support so that the thickness after drying is 8 μm, and the colored layer forming composition layer is formed. It was formed and dried at 110 ° C. for 2 minutes to form a colored layer. Then, a polyethylene film (thickness 35 μm, GF-8 manufactured by Tamapoli Co., Ltd.) was adhered as a cover film.
After that, the exposure amount was 500 mJ / cm from both sides of the formed colored layer and the laminated body of the temporary support. ²The entire surface was exposed with (i-line).

[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 the color changing layer A on the surface of the transparent film (resin layer)]
Using the composition for forming the color changing layer A described later, the color changing layer A having the refractive index and the thickness shown in Table 1 was formed on the transparent film.
Specifically, an extrusion coater is used on the transparent film, and a coating liquid, which is a composition for forming a color changing layer A, is applied to one surface of the transparent film to the thickness shown in Table 1 (after drying). The color change layer A was formed by applying the film in an amount (thickness) and drying it at 80 ° C. for 2 minutes. Then, the entire surface was exposed from the formed color change layer A side with an exposure amount of 300 mJ / cm ² (i-line).

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

[Laminate of colored layer and transparent film (resin layer)]
After peeling the cover film from the colored layer, the transparent film was laminated so that the non-coated surface was in contact with the colored layer.
The laminating conditions were a roll temperature of 90 ° C., a linear pressure of 100 N / cm, and a transport speed of 0.1 m / min.

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

The details of the composition for forming the color changing layer A and the composition for forming the color changing layer B used in the comparative examples of each example are shown below.
In the following examples, the following abbreviations represent the following compounds, respectively.
O-phenylphenol acrylate ethoxylated O-phenylphenol acrylate: SZR-M manufactured by Shin-Nakamura Chemical Industry Co., Ltd., Zirconium oxide dispersion, SZR-M manufactured by Sakai Chemical Industry Co., Ltd., 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 TAYCA CORPORATION
Irgacure2959 (1% methanol diluted): Polymerization initiator, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methylpropane-1-one, BASF, 1% by mass methanol diluted solution Irgacure2959. (Powder): Polymerization initiator, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methylpropane-1-one, manufactured by BASF, powder F-444 (1% methanol diluted). ): Fluorine-based surfactant, manufactured by DIC Co., Ltd., 1% by mass methanol diluted solution F-444 (stock solution): Fluorine-based surfactant, manufactured by DIC Co., Ltd., undiluted solution F-444 (diluted with 1% distilled water) : Fluorine-based surfactant, 1% by mass distilled water diluted solution PET-30 manufactured by DIC Co., Ltd .: Polyfunctional acrylic monomer, PET-30 manufactured by Nippon Kayaku Co., Ltd., pentaerythritol triacrylate and pentaerythritol tetraacrylate Epocross WS-700: Epocross WS-700 manufactured by Nippon Catalyst Co., Ltd., Oxazoline group-containing polymer Pluscoat Z687: Polyester resin Hydran HW-350 manufactured by Mutual Chemical Industry Co., Ltd .: Polyurethane resin M-510 manufactured by DIC Co., Ltd. : Polyfunctional acrylic oligomer, M-510 manufactured by Toa Synthetic Co., Ltd., polybasic acid-modified acrylic oligomer M-1200: M-1200 manufactured by Toa Synthetic Co., Ltd., bifunctional urethane acrylate M-270: manufactured by Toa Synthetic Co., Ltd. M-270, Bifunctional Urethane Acrylate Through Rear 4110: Hollow Silica Particles, Through Rear 4110 manufactured by Nikki Catalyst Kasei Co., Ltd., average particle diameter 60 nm
MEK: Methyl ethyl ketone (manufactured by 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-Irgacure2959 (1% methanol diluted): 3.65 parts by mass-F-444 (1% methanol diluted): 2 .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 diluted): 2.80 parts by mass

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

[Composition of composition for forming color change layer B]
-Polyfunctional acrylic oligomer (M-510): 6.26 parts by mass-Hollow silica particles (Thruria 4110): 93.06 parts by mass-Irgacure2959 (powder): 0.66 parts by mass-F-444 (stock solution): 0.02 parts by mass

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

[Preparation of composition for forming color change layer B]
-Composition of Emulsion Particle Dispersion 1-
・ Hexadecane (n-hexadecan, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.): 2.77 parts ・ Ca-1 (hexadecylpyridinium chloride 10% distilled water diluted, cationic surfactant, Fujifilm Wako Pure Chemical Industries, Ltd.) (Manufactured): 4.42 parts, distilled water: 42.81 parts The preparation of the emulsion particle dispersion 1 was carried out in detail according to the following procedure.
Hexadecane emulsion is present in water by mixing hexadecane, Ca-1 and ion-exchanged water, cooling with ice water using an ultrasonic homogenizer Sonifier450 manufactured by Nippon Emerson Co., Ltd., and treating with stirring for 30 minutes. 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 with 5% distilled water): 1.26 parts-MS-51 (compound represented by formula 1, Mitsubishi Chemical Co., Ltd.) ) 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 liquid 1, and after the addition, the mixture is further stirred at 25 ° C. for 16 hours to form a core-shell particle containing a non-polar solvent as a core material, represented by the formula 1. A core-shell particle dispersion 1 containing a compound, a surfactant and water was obtained.

-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 (1% distilled water dilution): 5.50 parts

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

(Example 4)
As the composition for forming the color changing layer A, the same composition as the composition for forming the color changing 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 (Thruria 4110): 8.95 parts by mass-Irgacure2959 (powder): 0.06 parts by mass-F-444 (1% methanol) Diluted): 4.87 parts by mass, methanol: 85.51 parts by mass

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

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

(Example 11)
[Composition of composition for forming color change layer A]
-Ethoxylated O-phenylphenol acrylate: 5.90 parts by mass-Zyrax oxide dispersion (SZR-M): 10.83 parts by mass-Irgacure2959 (1% methanol diluted): 5.90 parts by mass-F-444 (1) % Methanol dilution): 4.54 parts by mass ・ Methanol: 72.83 parts by mass

As the composition for forming the color changing layer B, the same composition as in Example 2 was used.

(Example 12)
[Composition of composition for forming color change layer A]
-Ethoxylated O-phenylphenol acrylate: 7.74 parts by mass-Zyrax oxide dispersion (SZR-M): 4.64 parts by mass-Irgacure2959 (1% methanol diluted): 7.74 parts by mass-F-444 (1) % Methanol dilution): 4.54 parts by mass ・ Methanol: 75.34 parts by mass

As the composition for forming the color changing layer B, the same composition as in Example 2 was used.

(Example 13)
The same composition as in Example 12 was used as the composition for forming the color changing layer A.
As the composition for forming the color changing layer B, the same composition as in Example 1 was used.

(Example 14)
[Composition of composition for forming color change layer A]
-Ethoxylated O-phenylphenol acrylate: 8.20 parts by mass-Titanium oxide particles (HTD-780T): 3.09 parts by mass-Irgacure2959 (1% methanol diluted): 8.20 parts by mass-F-444 (1%) Dilution with methanol): 4.54 parts by mass ・ Methanol: 75.97 parts by mass

As the composition for forming the color changing layer B, the same composition as in Example 4 was used.

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

[Composition of composition for forming color change layer B]
-Polyfunctional acrylic oligomer (M-510): 10.37 parts by mass-Hollow silica particles (Thruria 4110): 70.28 parts by mass-Irgacure2959 (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 changing layer A.

[Composition of composition for forming color change layer B]
-Polyfunctional acrylic oligomer (M-510): 14.63 parts by mass-Hollow silica particles (Thruria 4110): 46.74 parts by mass-Irgacure2959 (powder): 1.54 parts by mass-F-444 (stock solution): 0.04 parts by mass ・ Methanol: 37.05 parts by mass

(Example 17)
As the composition for forming the color changing layer A, the same composition as in Example 3 was used.

[Composition of composition for forming color change layer B]
-Polyfunctional acrylic oligomer (M-510): 2.79 parts by mass-Hollow silica particles (Thruria 4110): 8.91 parts by mass-Irgacure2959 (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-Irgacure2959 (powder): 0.20 parts by mass-F-444 (1% methanol diluted): 2.78 parts by mass Department

As the composition for forming the color changing layer B, the same composition as in Example 4 was used.

(Example 19)
In Example 1, after peeling off the protective film of the remaining adhesive sheet, an acrylonitrile-butadiene-styrene copolymer (ABS) film (also referred to as ABS backer) is laminated (thickness 250 μm, manufactured by Okamoto Co., Ltd.). The decorative molded film of Example 19 in which the ABS, the adhesive layer, the colored layer, the transparent film, and the resin layer are arranged in this order by subjecting the temperature: 30 ° C., the linear pressure to 100 N / cm, and the transport speed to 0.1 m / min). Made.

(Example 20)
[Composition of composition for forming color change layer A]
-Polyester resin (plus coat Z687): 146.24 parts by mass-Zyrax oxide dispersion (SZR-CW): 185.19 parts by mass-Fluorosurfactant (sodium = bis (3,3,4,4,5) , 5, 6, 6, 6-Nonafluorohexyl) = 2-Sulfonite oxysuccinate, manufactured by Fujifilm Fine Chemicals Co., Ltd., 1% water diluted): 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-Irgacure2959 (powder): 0.56 parts by mass-F-444 (1% methanol diluted): 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-Zyrax oxide dispersion (SZR-CW): 185.19 parts by mass-Fluorosurfactant (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: 281. 47 parts by mass, ethanol (95): 384.25 parts by mass

[Composition of composition for forming color change layer B]
As the composition for forming the color changing layer B, the same composition as in Example 20 was used.

(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 ・ Fluorosurfactant (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: 263. 17 parts by mass, ethanol (95): 384.25 parts by mass

[Composition of composition for forming color change layer B]
As the composition for forming the color changing layer B, the same composition as in Example 20 was used.

(Comparative Example 1)
As the composition for forming the color changing layer A, the same composition as the composition for forming the color changing 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 (Thruria 4110): 5.46 parts by mass-Irgacure2959 (powder): 0.36 parts by mass-F-444 (1% methanol) Diluted): 4.75 parts by mass, methanol: 85.97 parts by mass

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

(Comparative Example 3)
As the composition for forming the color changing layer A, the same composition as the composition for forming the color changing 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 diluted): 4.75 parts by mass

(Comparative Example 4)
As the composition for forming the color changing layer B, the same composition as in Comparative Example 1 was used.
Moreover, the color change layer A was not formed.

The decorative films obtained in the comparative examples of each example were used, and the following evaluations were performed. The evaluation results are summarized in Table 1.

[Evaluation of three-dimensional moldability]
Assuming an automobile emblem, a three-dimensional formability was evaluated for a columnar stainless steel member having a diameter of 10 cm and a height of 3 mm to see if cracks or the like occur during stretching. Prior to the test, in Example 19 in which the ABS was laminated, the obtained film was used as it was, and in the other Examples and Comparative Examples, the protective sheet of the adhesive sheet was peeled off, and then 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 transport speed of 0.1 m / min).
Using the columnar member, the obtained decorative film was vacuum-formed at a heating temperature of 120 ° C., and it was visually evaluated whether or not cracks were generated on the surface.
A: No cracks occurred on the surface B: Cracks occurred on the surface

[Evaluation of design (color changeability)]
The obtained decorative film is designed by measuring the normal reflectance using an ultraviolet-visible-infrared spectrophotometer V-560 manufactured by Nippon Kogaku Co., Ltd. and an absolute reflectance measuring device ARV-474. evaluated.
For the design evaluation, the 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} at a wavelength of 700 nm was used. The larger the R _des , the better the color changeability.
The evaluation criteria are as follows according to the value of R _des . It is preferably A to C.
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 blackness]
The obtained decorative film was visually recognized from an angle of 45 ° when the direction perpendicular to the film was 0 °, and the blackness of the film when the fluorescent lamp was reflected was subjected to sensory evaluation. The evaluation criteria are shown below. Moreover, A is preferable as an evaluation result.
A: The reflection of the fluorescent lamp is suppressed.
B: Fluorescent lamps are strongly reflected and appear whitish as a whole.

[Evaluation of scratch resistance]
The scratch resistance of the obtained decorative film was evaluated by a steel wool rubbing test using a surface property measuring machine Heidon Type 18S manufactured by Shinto Kagaku Co., Ltd. In the steel wool rubbing 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), a swing stroke of 50 mm, a swing speed of 1000 mm / min, and 10 reciprocations. It was evaluated by visually evaluating the appearance after the above. The evaluation criteria are shown below. As an 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 its polymer Acrylic 2: PET-30 manufactured by Nippon Kayaku Co., Ltd. or its polymer siloxane 1: MS-51 (manufactured by Mitsubishi Chemical Corporation) Hydrolyzed condensate Acrylic 4: M-510 manufactured by Toa Synthetic Co., Ltd. or its polymer Acrylic 5: M-510 manufactured by Toa Synthetic Co., Ltd. or its polymer Acrylic 6: M manufactured by Toa Synthetic Co., Ltd. -510 or its polymer Acrylic 7: M-270 manufactured by Toa Synthetic Co., Ltd. or its polymer Acrylic 8: Epocross WS-700 manufactured by Nippon Catalyst Co., Ltd.
Urethane: M-1200 or its polymer Polyester: Plus Coat Z687 manufactured by GOO CHEMICAL 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: JGC Catalysts and Chemicals Co., Ltd. Through rear 4110

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 have color changeability (compared to the decorative films of Comparative Examples 1 to 4). Excellent in design).
Further, 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, blackening property, and scratch resistance. Excellent.

The disclosure of Japanese Patent Application No. 2018-126373 filed on 2 July 2018 is incorporated herein by reference in its entirety.
All documents, patent applications, and technical standards described herein are to the same extent as if the individual documents, patent applications, and technical standards were specifically and individually stated to be incorporated by reference. Is incorporated herein by reference.

10: Decorative film, 12: Adhesive layer, 14: Protective film, 16: Molding substrate, 20: Laminated body, 22: Temporary support, 24: Colored layer, 26: Resin layer, 28: Color changing layer A , 30: Color change layer B, 40: Decorative molding film

Claims (23)

Temporary support,
Colored layer,
A color change layer A containing at least one compound selected from the group consisting of resins and polymerizable compounds, and
The color changing layer B is provided in this order.
A decorative film in which 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 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 colored layer is 3 μm or more. The decorative film according to any one of claims 1 to 3, wherein the colored layer contains a pigment as a colorant. The colored layer is a layer formed by at least curing a bifunctional or trifunctional polymerizable compound having at least one partial structure selected from the group consisting of a urethane bond and an alkyleneoxy group 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 changing layer B is a layer having a refractive index lower than that of the color changing layer A by 0.25 or more. The decorative film according to any one of claims 1 to 6, wherein the color changing layer A has a refractive index of 1.6 or more. The decorative film according to any one of claims 1 to 7, wherein the color changing layer A further contains zirconium oxide or titanium oxide. The decorative film according to any one of claims 1 to 8, wherein the color changing layer B has a refractive index of 1.4 or less. The decoration according to any one of claims 1 to 9, wherein the color changing layer B contains at least one selected from the group consisting of a siloxane resin having voids, a fluororesin, and hollow silica particles. the film. The decorative film according to any one of claims 1 to 10, wherein the color changing layer A has a thickness of 5 μm or more, or the color changing layer B has a thickness of 5 μm or more. The decorative film according to any one of claims 1 to 11, wherein the color changing layer A has a thickness of 5 μm or more and the color changing layer B has a thickness of 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.
A decoration method including a step of attaching the decorative film from which the temporary support has been peeled off to a base material from the colored layer side. The decoration method according to claim 15, further comprising a step of forming an adhesive layer on the surface from which the temporary support has been peeled off in the decorative film from which the temporary support has been peeled off. The decoration method according to claim 15, wherein the base material is a base material for molding. A step of peeling the temporary support from the decorative film according to any one of claims 1 to 14.
A step of attaching the decorative film from which the temporary support has been peeled off to the molding base material from the colored layer side,
A method for manufacturing a decorative molded body, which comprises a step of molding the molding base material to which the decorative film is attached. Base material,
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 high-refractive index particles having a refractive index of 1.55 or more , and
The color changing layer B is provided in this order.
A decorative molded film in which 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 decorative molded film according to claim 19, wherein the high-refractive index particles having a refractive index of 1.55 or more contain zirconium oxide or titanium oxide. Base material,
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 an inorganic filler, and
The color changing layer B is provided 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.
Decorative molded film. The decorative molded film according to claim 21, wherein the inorganic filler contains zirconium oxide or titanium oxide. The thickness of the color changing layer A is 7 μm or more and the thickness of the color changing layer B is 0.8 μm or less, or the thickness of the color changing layer A is 0.8 μm or less and the color is said. The decorative molded film according to any one of claims 19 to 22, wherein the changing layer B has a thickness of 7 μm or more.

Images