JP6264798B2 - Wavelength selective reflection film for transfer, transfer method using the same, and transfer molding - Google Patents

Description

  The present invention relates to a wavelength-selective reflection film for transfer, a transfer method using the same, and a transfer molded product.

  Wavelength-selective reflective articles are used in various applications. For example, sunlight entering a room or in a car through a window includes ultraviolet rays and infrared rays in addition to visible rays. However, by using articles that selectively reflect ultraviolet rays and infrared rays, It is possible to prevent the deterioration of the resin and the resin, and to prevent the temperature rise in the room and the interior of the vehicle due to infrared rays (Patent Document 1).

  However, in patent document 1, visible light is permeate | transmitted and infrared rays are selectively reflected by providing the selective reflection layer containing the rod-shaped compound which has a cholesteric structure on a transparent base material. Here, since the rod-like compound having a cholesteric structure is contained in the selective reflection layer, the wavelength of light that can be selectively reflected by a change in temperature changes, and there is a problem that the wavelength selectivity is weak.

  On the other hand, as a reflective article that does not cause such a problem, an optical system used in an optical device such as a camera, a copying machine, or a printer, or an optical communication device reflects light in a specific wavelength region to another wavelength region. A dichroic mirror that transmits a certain amount of light is used, and this type of dichroic mirror uses a dielectric material having a high refractive index and a low refractive index as an optical film thickness (refractive index n ×) of a design center wavelength λ. It is composed of dielectric multilayer films alternately stacked as the film thickness d) (Patent Document 2).

  In Patent Document 2, by providing a dielectric multilayer film in which high refractive index films and low refractive index films having an optical film thickness of ¼ of the design center wavelength λ are alternately stacked on the surface of a transparent substrate, The wavelength of light that can be selectively reflected is unlikely to change due to temperature changes. However, the method for manufacturing a dielectric multilayer film disclosed in Patent Document 2 is quite difficult to industrialize because interference layers are sequentially laminated in several tens of layers and accurate film thickness control is required for each layer. Met.

JP 2012-32759 A JP 2000-171625 A

  Accordingly, the present invention provides a reflective film for transfer having a multilayer structure in which a high refractive index layer and a low refractive index layer having selectivity with respect to a reflection target wavelength are alternately laminated. Thus, it is possible to easily produce a transfer molding having a wavelength-selective multilayer structure using the same, and to provide a transfer molding having a wavelength-selective function obtained by the method.

In the first invention, a reflective layer is provided on a support film having releasability, and the reflective layer includes a low refractive index layer (TL1) having a first heat adhesion property and a laminated high refractive index layer. (H1), 1 to 4 units of a laminate including the low refractive index layer (L) and the high refractive index layer (H) as one unit, and a low refractive index layer (TL2) having a second heat adhesion property In this order, and in each laminate, the low refractive index layer (L) is located closer to the laminated high refractive index layer (H1) than the high refractive index layer (H),
The refractive index of the low refractive index layer (TL1) and the low refractive index layer (L) having the first heat adhesion and the low refractive index layer (TL2) having the second heat adhesion is the stacked high refractive index. Lower than the refractive index of the layer (H1) and the high refractive index layer (H),
The reflection target wavelength is λa, the refractive index of the low refractive index layer (TL1) having the first heat adhesion property (TL1) is nTL1, the film thickness is dTL1, the refractive index of the stacked high refractive index layer (H1) is nH1, and the film thickness. DH1, the refractive index of the low-refractive index layer (L) is nL, the film thickness is dL, the refractive index of the high-refractive index layer (H) is nH, the film thickness is dH, and the second heat adhesion property is provided. When the refractive index of the low refractive index layer (TL2) is nTL2 and the film thickness is dTL2, the transfer satisfies the following expressions (1), (2), (5), and (6): It is a wavelength selective reflection film for use.
λa = 4nTL1 × dTL1 + 4nTL2 × dTL2 (1)
dH1 = λa / 4nH1 (2)
dH = λa / 4nH (5)
dL = λa / 4nL (6)

In the second invention, a reflective layer is provided on a support film having releasability, and the reflective layer includes a high refractive index layer (TH1) having a first heat adhesion property and a laminated low refractive index layer. (L1), 1 to 4 units of a laminate including the high refractive index layer (H) and the low refractive index layer (L) as one unit, a high refractive index layer (TH2) having a second heat-adhesive property, and In this order, the high refractive index layer (H) is positioned closer to the laminated low refractive index layer (L1) than the low refractive index layer (L) in each laminated body, The refractive index of the high refractive index layer (TH1) and high refractive index layer (H) having heat adhesion and the second refractive index layer (TH2) having heat adhesion is the same as that of the laminated low refractive index layer (L1). And higher than the refractive index of the low refractive index layer (L),
The reflection target wavelength is λa, the refractive index of the first high-refractive-index layer (TH1) having the heat-adhesive property (TH1) is nTH1, the film thickness is dTH1, and the refractive index of the laminated low-refractive index layer (L1) is nL1. DL1, the refractive index of the high-refractive index layer (H) is nH, the film thickness is dH, the refractive index of the low-refractive index layer (L) is nL, the film thickness is dL, and the second heat adhesion property is provided. When the refractive index of the high refractive index layer (TH2) is nTH2 and the film thickness is dTH2, the transfer satisfies the following formulas (3), (4), (5), and (6): It is a wavelength selective reflection film for use.
λa = 4nTH1 × dTH1 + 4nTH2 × dTH2 (3)
dL1 = λa / 4nL1 (4)
dH = λa / 4nH (5)
dL = λa / 4nL (6)

The third invention comprises (a) a step of heat-treating a layer located on the outermost layer of the wavelength-selective reflective film for transfer according to any one of the inventions 1 and 2 in close contact with the transfer object; 1) a step of peeling a support film having releasability; and (c) one or a plurality of the steps (a) and (b) using the reflective layer transferred in the steps (a) and (b) as a transfer object. A transfer method characterized in that the method has a step of repeating a number of times.

According to a fourth aspect of the present invention , a reflective layer is provided on a support film having releasability, and the reflective layer includes a high refractive index layer (TH1) having a first heat adhesion property and a laminated low refractive index layer. (L1) and the high refractive index layer (TH2) having the second heat adhesive property in this order, the high refractive index layer (TH1) having the first heat adhesive property and the second heat adhesive property. The high refractive index layer (TH2) having a refractive index higher than the refractive index of the laminated low refractive index layer (L1),
The reflection target wavelength is λa, the refractive index of the first high-refractive-index layer (TH1) having the heat-adhesive property (TH1) is nTH1, the film thickness is dTH1, and the refractive index of the laminated low-refractive-index layer (L1) is nL1. Where dL1 is the refractive index of the second high-refractive-index layer (TH2) having the heat adhesion property and the film thickness is dTH2, the following formulas (3) to (4) are satisfied. A step of heat-treating a layer located on the outermost layer of the wavelength-selective reflective film for transfer to be in close contact with the transfer object, (b) a step of peeling the support film having releasability, and (c) Repeating the steps (a) and (b) one or more times using the reflective layer transferred in the steps (a) and (b) as a transfer object,
The transfer method is characterized in that the high refractive index layers adhere to each other.
λa = 4nTH1 × dTH1 + 4nTH2 × dTH2 (3)
dL1 = λa / 4nL1 (4)
A fifth invention is a transfer molded product formed by the transfer method of the third or fourth invention.

  According to the present invention, a wavelength-selective reflective film for transfer that has selectivity for a reflective target wavelength and can easily produce a molded product having a multilayer structure in which high refractive index layers and low refractive index layers are alternately laminated. As well as a transfer method and a transfer molding using the same.

1 is a cross-sectional view of a transfer wavelength selective reflection film according to Embodiment 1. FIG. 3 is a graph showing reflection selectivity of a transfer molded product obtained using the transfer wavelength selective reflection film of Embodiment 1. FIG. 6 is a cross-sectional view of a wavelength selective reflection film for transfer according to Embodiment 2. FIG. It is sectional drawing of the wavelength-selective reflective film for transfer which concerns on Embodiment 3. FIG. It is sectional drawing of the wavelength-selective reflective film for transcription | transfer which concerns on Embodiment 4.

<< First Embodiment >>
≪Transfer wavelength selective reflection film≫
As shown in FIG. 1, in the first embodiment, the transfer wavelength-selective reflective film 2 is formed on a support film 4 having releasability and a low refractive index layer (TL1) having a first heat adhesion property. ), A laminated high refractive index layer (H1), and a low refractive index layer (TL2) having a second heat adhesion property in this order. The refractive index of the low refractive index layer (TL1) having the first heat adhesion and the low refractive index layer (TL2) having the second heat adhesion is lower than the refractive index of the stacked high refractive index layer (H1). , The reflection target wavelength is λa, the refractive index of the first refractive index layer (TL1) having heat adhesion is TL1, the film thickness is dTL1, the refractive index of the stacked high refractive index layer (H1) is nH1, and the film When the thickness is dH1, the refractive index of the second low-refractive-index layer (TL2) having heat adhesiveness is nTL2, and the film thickness is dTL2, the following formulas (1) and (2) are satisfied. Is done. Further, the refractive index and film thickness of the low refractive index layer having the first heat adhesive property may be the same as or different from the refractive index and film thickness of the low refractive index layer having the second heat adhesive property. May be. In addition, all the layers provided on the support film and transferred are referred to as a reflective layer 6.
λa = 4nTL1 × dTL1 + 4nTL2 × dTL2 (1)
dH1 = λa / 4nH1 (2)
Here, λa corresponds to the wavelength of light at which the reflectance becomes maximum in a transfer molding with a wavelength-selective reflection function described later. That is, for example, by setting λa to 800 nm, the reflectance of light can be maximized at a wavelength of 800 nm in a transfer molding described later.

≪Support film with releasability≫
The support film is for supporting the reflective layer, and the kind thereof is not particularly limited. For example, polyester film such as polyethylene terephthalate (PET) film, polyolefin film such as polyethylene or polypropylene, polycarbonate film, acrylic resin film, triacetyl Examples thereof include resin films such as cellulose and norbornene films [manufactured by JSR Corporation, Arton, etc.], cloth, paper, and the like. In these, the resin film is preferable from the point of light weight or ease of handling.

  In the support film of the present invention, it is preferable that release properties are imparted by forming a release layer on the support film so that the reflective layer provided thereon can be easily peeled off. This release layer has a property of peeling at the interface between the release layer and the reflective layer when the reflective layer is thermally transferred from the transfer film to the transfer target, and remains on the support film side after transfer. . Examples of the resin constituting the release layer include epoxy-melamine resin, acrylic-melamine resin, melamine resin, urea resin, urea-melamine resin, silicone resin, acrylic-silicone resin, and fluorine resin. A coating agent such as an organic solvent solution or emulsion of one or more of these resins is applied onto a support film by a normal coating method such as a roll coating method or a gravure coating method, and the solvent is dried (thermosetting resin). In the case of an electron beam curable resin, an ultraviolet curable resin or the like, it is cured).

  The thickness of the release layer is appropriately selected from the range of usually 0.1 to 10 μm, preferably 0.2 to 5 μm. If the thickness of the non-transferable release layer is less than 0.1 μm, it is not preferable because it is difficult to peel off and the desired peelability cannot be obtained. On the other hand, if it is thicker than 10 μm, it is easy to peel off, so that the layers to be sequentially formed may fall off during the processing step.

  The release layer can also be formed by the following method. Water-soluble organic substances having at least one hydroxyl group, ether group, carboxyl group, amino group, and the like, for example, vinyl-based water-soluble resins such as polyvinyl alcohol and polyvinylpyrrolidone, and fibrous materials such as methyl cellulose, carboxyl methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose Ether-based resins, acrylic acid-based water-soluble substances such as sodium acrylate and ammonium acrylate, natural water-soluble substances such as starch, dextrin, glue and gelatin, and protein-based water-soluble substances such as casein, sodium caseinate and ammonium caseinate In addition, one or more substances such as polyethylene oxide, carrageenan, glucomanganese, etc., can be used as usual coating methods such as roll coating and gravure coating. Ri is coated on a support film is formed by drying.

<< Laminated high refractive index layer H1 >>
Next, the high refractive index layer H1 will be described. The laminated high refractive index layer H1 is a layer for exhibiting a reflection effect due to a significant refractive index difference from the low refractive index layer having the first and second heat adhesion properties. The refractive index of the laminated high refractive index layer is set higher than that of the low refractive index layer having the first and second heat adhesion properties. The refractive index of the laminated high refractive index layer is preferably 1.56 or more. When the refractive index of the laminated high refractive index layer is less than 1.56, when the refractive index difference with the low refractive index layer having heat adhesion becomes small, the reflection at the interface becomes weak, and the reflection performance is not sufficiently exhibited. There is. Although the upper limit of the refractive index of the laminated high refractive index layer is not particularly limited, the upper limit is substantially about 2.50 due to limitations of existing film forming materials.

  The composition for forming the laminated high refractive index layer is not particularly limited, and a composition containing metal oxide fine particles and a binder resin or a product obtained by curing a composition containing metal oxide fine particles and a binder resin is applied. can do.

  Examples of the metal oxide fine particles in the composition containing the metal oxide fine particles and the binder resin include zinc antimonate, zinc oxide, titanium oxide, cerium oxide, aluminum oxide, tantalum oxide, yttrium oxide, ytterbium oxide, zirconium oxide, and oxide. Fine particles such as indium tin and antimony-containing tin oxide can be mentioned.

  As the binder resin, an active energy ray curable resin or a thermosetting resin can be applied. As the active energy ray-curable resin, a resin that undergoes a curing reaction when irradiated with active energy rays such as ultraviolet rays or electron beams can be used, and the type thereof is not particularly limited. As the active energy ray curable resin, (meth) acrylate is preferable, and as (meth) acrylate, for example, dipentaerythritol hexa (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, tetramethylolmethanetri (meth) acrylate, Multifunctional alcohols (meth) such as trimethylolpropane tri (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,6-bis (3- (meth) acryloyloxy-2-hydroxypropyloxy) hexane Examples thereof include acrylic derivatives, polyethylene glycol di (meth) acrylate, polyurethane (meth) acrylate, and those commercially available as ultraviolet curable hard coat materials. In the present specification, (meth) acrylate refers to both acrylate and methacrylate. The same applies to (meth) acryloyl groups.

  In general, the active energy ray-curable resin is applied with a photopolymerization initiator. Any photopolymerization initiator may be used as long as it has a polymerization initiating ability by ultraviolet irradiation. For example, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1 -One, acetophenone polymerization initiators such as 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, benzoin, 2,2-dimethoxy 1,2 -Benzoin polymerization initiators such as diphenylethane-1-one, benzophenone, [4- (methylphenylthio) phenyl] phenylmethanone, 4-hydroxybenzophenone, 4-phenylbenzophenone, 3,3 ', 4,4' -Benzophenone polymerization initiators such as tetra (t-butylperoxycarbonyl) benzophenone, 2-chlorothio Xanthone, such thioxanthone type polymerization initiators such as 2,4-diethyl thioxanthone, and the like. These photopolymerization initiators can be used alone or as a mixture.

  There is no restriction | limiting in particular as a thermosetting resin, From the conventionally well-known thing, it can select suitably and can be used. Examples of the thermosetting resin include an acrylate polymer having a carbon-carbon double bond and a glycidyl group, an unsaturated polyester, an isoprene polymer, a butadiene polymer, an epoxy resin, a phenol resin, a urea resin, and a melamine resin. Can be mentioned. These may be used alone or in combination of two or more. Examples of other resins include vinyl resin, urethane resin, polyester, polyamide, polycarbonate, polyimide, nitrile resin, and silicone resin. These resins are used for adjusting the viscosity of the coating liquid or imparting desired physical properties to the hard coat layer, and may be used alone or in combination of two or more.

  In general, the thermosetting resin is applied with a curing agent or the like. Examples of the curing agent include organic peroxides such as dibenzoyl peroxide, dilauroyl peroxide, t-butyl peroxybenzoate, di-2-ethylhexyl peroxydicarbonate, 2,2′-azobisisobutyronitrile, 2 Azo compounds such as 2,2′-azobis-2-methylbutyronitrile, 2,2′-azobisdimethylvaleronitrile, polyisocyanate compounds such as tolylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, phenylenediamine, Polyamines such as hexamethylenetetramine, isophoronediamine, diaminodiphenylmethane, acid anhydrides such as dodecenyl succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, 2-methylimidazole , 2-ethylimidazole, 2-imidazoles and dicyandiamide, such as phenylimidazole, p- toluenesulfonic acid, Lewis acids such as trifluoromethanesulfonic acid, formaldehyde. These curing agents are appropriately selected according to the type of thermosetting resin to be used.

Specific materials for the metal oxide thin film include titanium oxide (TiO ₂ ) layer, ITO (indium / tin oxide) layer, Y ₂ O ₃ layer, In ₂ O ₃ layer, Si ₃ N ₄ layer, SnO _2. Examples include a layer, a ZrO ₂ layer, an HfO ₂ layer, an Sb ₂ O ₃ layer, a Ta ₂ O ₅ layer, a ZnO layer, and a WO ₃ layer.

(Formation of laminated high refractive index layer)
As a method for forming a laminated high refractive index layer using a metal oxide thin film, it can be formed by plasma CVD, vapor deposition, sputtering, or the like.

  On the other hand, as a method of forming a laminated high refractive index layer using a composition containing metal oxide fine particles and a binder resin, a method of applying a coating solution by a coating method such as a wet coating method, drying and then curing is adopted. can do. The wet coating method may be a known method, and typical examples include a roll coating method, a die coating method, a spin coating method, and a dip coating method.

<< Low Refractive Index Layer TL1 Having First Heat Adhesiveness and Second Refractive Index Layer TL2 Having Second Heat Adhesive >>
Next, the low refractive index layers TL1 and TL2 having heat adhesion will be described. The low-refractive index layers TL1 and TL2 having heat adhesiveness exhibit a reflection effect due to a significant refractive index difference from the adjacent stacked high-refractive index layer H1, and are heated at the time of adhesion to the object. Is a layer that exhibits adhesiveness. The refractive index of the low refractive index layers TL1 and TL2 having heat adhesion is required to be set lower than the refractive index of the laminated high refractive index layer H1, and the refractive index is in the range of 1.20 to 1.55. is there. When the refractive index is less than 1.20, the film becomes brittle, and it becomes difficult to handle the formed film. On the other hand, when the refractive index exceeds 1.55, the refractive index difference from the laminated high refractive index layer H1 becomes small, and it is difficult to obtain a sufficient reflection effect. In addition, heat adhesiveness means the property which expresses adhesiveness by heating (for example, 80 to 300 degreeC).

  As the composition for forming the low refractive index layers TL1 and TL2 having heat adhesion, a composition containing conventionally known hollow silicon oxide fine particles and a binder resin in the field of articles having antireflection or reflection functions, or A cured film formed by curing it may be mentioned, but in order to have heat adhesiveness, the binder resin needs to contain a thermoplastic resin.

  Examples of the hollow silicon oxide fine particles include those having cavities inside the outer shell and porous silica fine particles. The average particle diameter of the fine particles preferably does not greatly exceed the film thickness of the low refractive index layers TL1 and TL2 having heat adhesiveness, and is particularly preferably 0.1 μm or less. When the average particle size is increased, light scattering occurs and the haze value increases, so that it is not suitable as a material for a wavelength selective reflection film for transfer. Further, the surface of the fine particles can be modified with various coupling agents as required. Examples of the various coupling agents include organically substituted silicon compounds, metal alkoxides such as aluminum, titanium, zirconium, and antimony, and organic acid salts. In particular, a film having high hardness can be formed by modifying the surface with a reactive group such as a (meth) acryloyl group.

  As the binder resin, a composition containing a polymer of a fluorine-containing organic compound can be suitably used because it has a low refractive index, but a monomer not containing fluorine or a polymer thereof can also be used. Although the fluorine-containing organic compound is not particularly limited, for example, a monomer such as fluorine-containing monofunctional (meth) acrylate, fluorine-containing polyfunctional (meth) acrylate, fluorine-containing itaconic acid ester, fluorine-containing maleic acid ester, These polymers and fluorine-containing reactive polymers having a polymerizable double bond can be mentioned.

  Examples of the fluorine-containing monofunctional (meth) acrylate include 1- (meth) acryloyloxy-1-perfluoroalkylmethane, 1- (meth) acryloyloxy-2-perfluoroalkylethane, and the like. Examples of the perfluoroalkyl group include linear, branched or cyclic groups having 1 to 8 carbon atoms.

  As the fluorine-containing polyfunctional (meth) acrylate, fluorine-containing bifunctional (meth) acrylate, fluorine-containing trifunctional (meth) acrylate and fluorine-containing tetrafunctional (meth) acrylate are preferable. Examples of the fluorine-containing bifunctional (meth) acrylate include 1,2-di (meth) acryloyloxy-3-perfluoroalkylbutane, 2-hydroxy-1H, 1H, 2H, 3H, 3H-perfluoroalkyl-2 ′. , 2′-bis {(meth) acryloyloxymethyl} propionate, α, ω-di (meth) acryloyloxymethyl perfluoroalkane and the like. The perfluoroalkyl group is preferably a linear, branched or cyclic group having 1 to 11 carbon atoms, and the perfluoroalkane group is preferably a linear group. These fluorine-containing bifunctional (meth) acrylates can be used alone or as a mixture when used.

  Examples of the fluorine-containing trifunctional (meth) acrylate include, for example, 2- (meth) acryloyloxy-1H, 1H, 2H, 3H, 3H-perfluoroalkyl-2 ′, 2′-bis {(meth) acryloyloxy Methyl} propionate. The perfluoroalkyl group is preferably a linear, branched or cyclic group having 1 to 11 carbon atoms.

  Examples of fluorine-containing tetrafunctional (meth) acrylates include α, β, ψ, ω-tetrakis {(meth) acryloyloxy} -αH, αH, βH, γH, γH, χH, χH, ψH, ωH, ωH- Perfluoroalkane and the like are preferable. The perfluoroalkane group is preferably a linear one having 1 to 14 carbon atoms. In use, the fluorine-containing tetrafunctional (meth) acrylate can be used alone or as a mixture.

  The fluorine-containing reactive polymer having a polymerizable double bond has a main chain derived from a fluorine-containing ethylenic monomer and has a reactive group for crosslinking and curing. Examples of the reactive group include a (meth) acryloyloxy group, an α-fluoroacryloyloxy group, and an epoxy group. Such a fluorine-containing reactive polymer that is soluble in a solvent and has a polymerizable double bond has a high molecular weight, so it has good film forming properties even though it contains fluorine. By doing so, a cured layer can be obtained.

を

の過酸化物で重合させて得られるホモポリマーに、α−フルオロアクリル酸フルオライド：ＣＨ２＝ＣＦＣＯＦを反応させて水酸基をフルオロアクリレートに置換した生成物が挙げられる。 The fluorine-containing reactive polymer having a polymerizable double bond has a group content having a polymerizable double bond of usually 1 to 20% by mass, preferably 5 to 15% by mass, and mass (weight) average. The molecular weight is usually 1,000 to 500,000, preferably 3,000 to 200,000. As a specific fluorine-containing reactive polymer, perfluoro- (1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxanonenol)

The

A product obtained by reacting a homopolymer obtained by polymerization with a peroxide of [alpha] -fluoroacrylic acid fluoride: CH2 = CFCOF and substituting the hydroxyl group with fluoroacrylate.

  Specific materials for thermoplastic resins include polymethyl methacrylate resin, MS resin (copolymer of methyl methacrylate and styrene), polycarbonate because of its high transparency and ease of dissolution in the solvent used for coating. Resins are preferred. In addition, when the low refractive index layer TL having heat adhesiveness is composed only of a thermoplastic resin, it is necessary to have a refractive index of less than 1.55. Therefore, polymethyl methacrylate resin, MS resin (methyl methacrylate and styrene) Are more preferable.

  The volume of the thermoplastic resin contained in the low refractive index layer TL1 having the first heat adhesion property (VTL1), and the volume of the thermoplastic resin contained in the second refractive index layer TL2 having the heat adhesion property (VTL2). ), The volume of the components other than the thermoplastic resin contained in the low refractive index layer TL1 having heat adhesion (VO1), the volume of the components other than the thermoplastic resin contained in the low refractive index layer TL2 having heat adhesion In the case of (VO2), the volume ratio of the thermoplastic resin {VTL1 / (VTL1 + VO1)} × 100 (%) and {VTL2 / (VTL2 + VO2)} × 100 (%) may be 20% or more. preferable. When the volume ratio of the thermoplastic resin {VTL1 / (VTL1 + VO1)} × 100 (%) and {VTL2 / (VTL2 + VO2)} × 100 (%) is less than 20%, the function of heat adhesion is lowered. Therefore, it is not preferable.

  Various additives can be added to the composition for forming a low refractive index layer having heat adhesiveness as other components within a range not impairing the effects of the present invention. Examples of such additives include additives such as a dispersant, a surfactant, an ultraviolet absorber, a light stabilizer, and a leveling agent.

[Formation of Low Refractive Index Layers TL1 and TL2 having Heat Adhesiveness]
As a method for forming the low refractive index layers TL1 and TL2 having heat adhesiveness, a composition containing metal oxide fine particles and a binder resin containing a thermoplastic resin is applied by a coating method such as a wet coating method, and then dried. A method of curing can be employed. The wet coating method may be a known method, and typical examples include a roll coating method, a die coating method, a spin coating method, and a dip coating method. In these, the method which can form a coating film continuously, such as a roll coat method, is preferable from the point of productivity. The formed coating film can form a cured film by performing a curing reaction by heating, irradiation with active energy rays such as ultraviolet rays and electron beams. Among these, the curing reaction using active energy rays can be performed in an inert gas atmosphere such as nitrogen or argon.

≪Method for producing wavelength selective reflection film for transfer≫
In this embodiment, the low refractive index layer TL1 having the first heat adhesiveness is formed on the support film 4 by the above method, and the laminated high refractive index layer H1 and the second heat adhesiveness are further formed thereon. The low refractive index layer TL2 is formed in this order. At this time, the film thicknesses of the low refractive index layer TL1, the stacked high refractive index layer H1, and the second low refractive index layer TL2 having the second heat adhesive property are the reflection target wavelength and the respective ones. Is set so as to satisfy the following formulas (1) and (2).
λa = 4nTL1 × dTL1 + 4nTL2 × dTL2 (1)
dH1 = λa / 4nH1 (2)

≪Transfer method≫
(A) A heat treatment is performed by bringing the low refractive index layer TL2 having the second heat-adhesive property located on the outermost layer of the wavelength selective reflection film 2 for transfer into close contact with the transfer object, and (b) releasability. The reflective layer 6 is transferred to the transfer object by peeling off the supporting film 4 having (c) the low refractive index layer (TL1) having the first heat adhesion property with the transferred reflective layer 6 as the transfer object. Steps (a) and (b) are repeated once or a plurality of times so that the low refractive index layer (TL2) having the second heat-adhesive property is in contact with each other, thereby forming a transfer molded product which is a multilayer structure. By transferring the wavelength selective reflection film for transfer in this way, the low refractive index layer (TL1) having the first heat adhesion property, the laminated high refractive index layer (H), and the second low heat adhesion property are obtained. The refractive index layer (TL2) can be repeatedly stacked. In step (b), the release layer of the support film is peeled off together with the support film.

<< (a) Step of heat-treating a layer having heat adhesion located on the outermost surface of the wavelength selective reflection film for transfer in close contact with the transfer object >>
In order to obtain the transfer molding, the support film 4 is in a state in which the low refractive index layer TL2 having the second heat-adhesive property located on the outermost layer of the wavelength selective reflection film 2 for transfer is in close contact with the transfer object. By applying hot pressure from the side or the transfer object side, the low refractive index layer having heat adhesion located on the outermost surface of the transfer wavelength selective reflection film 2 is melted and adhered to the transfer object.

  Specific methods for applying the heat pressure include using a thermal head and a platen roll, applying heat pressure with a heat roll, or using a heating means such as a hot stamp.

  In addition, when applying heat pressure, the transfer object can be subjected to corona treatment or atmospheric plasma treatment for the purpose of enhancing the adhesion between the transfer object and the reflective layer 6.

<< (b) Step of peeling a support film having releasability >>
After the transfer wavelength selective reflection film 2 is adhered to the transfer object in the step shown in (a), the support film 4 having releasability is peeled off. By this operation, the reflective layer 6 can be provided on the surface of the transfer object, and the transferred reflective layer 6 is in a state where the low refractive index layer TL1 having the first heat adhesion property is exposed. The outermost layer of the transfer molded product to which the layer 6 is transferred has heat adhesiveness.

<< (c) Step of repeating (a) and (b) >>
When the steps (a) and (b) are performed, the three layers can be easily transferred onto the object. Therefore, in the step (c), the transferred reflection layer 6 is used as the transfer object (a) and ( By repeating the step b), it is possible to significantly reduce the manufacturing cost and time as compared with the case where the layers are further laminated one by one.

<< Transfer molding (Transfer molding with wavelength selective reflection function) >>
Transfer molded product having a low refractive index layer TL1 having a first heat adhesion property, a laminated high refractive index layer (H1), and a second low refractive index layer TL2 having a heat adhesion property in this order by the above transfer method. Can be easily manufactured. The low refractive index layer TL1, the stacked high refractive index layer (H1) having the first heat adhesive property, and the low refractive index layer TL2 having the second heat adhesive property have λa = 4nTL1 × dTL1 + 4nTL2 × dTL2 (1) )
dH1 = λa / 4nH1 (2)
Since the film thickness is determined so as to satisfy the above condition, the molded product obtained by the transfer method can selectively reflect the light having the reflection target wavelength λa. For example, FIG. 2 is a graph showing the reflection selectivity of a certain transfer molding obtained when λa is 800 nm. From FIG. 2, it is understood that the reflectance is maximized around 800 nm which is the reflection target wavelength.

  There are no particular limitations on the transfer object that is the subject of the transfer method, and various objects can be used. Examples of the object to be transferred include a plate material on which it is difficult to form a coating layer having a uniform thickness, an object or support having poor flexibility, an object such as an acrylic plate, a polycarbonate plate, glass or ceramics. In addition, front plates of various displays such as computers, touch panels, TVs, display panels, mobile phones, sunglasses lenses made of transparent plastics, optical lenses such as prescription glasses lenses, camera finder lenses, display units of various instruments, Examples include window glass for automobiles, trains, buildings, etc., information panels, dichroic mirrors used for color separation of reflector liquid crystal projectors for incandescent light bulbs, camcorders, color faxes, and color televisions. In addition, even if these molded articles are formed of a material other than resin, for example, glass or the like, the same effect as that of resin can be exhibited.

  The transfer of the wavelength selective reflection film for transfer is provided and configured such that the reflectance at a specific wavelength is selectively increased, and can exhibit a wavelength selective reflection function. Therefore, CRT, LCD, PDP, mobile phone, portable information terminal display field, LCD front panel, display front plate, mobile phone display device, PDA screen display device, art showcase, house window, incandescent light bulb reflector It can also be applied to dichroic mirrors used for color separation, such as liquid crystal projectors, camcorders, color faxes, and color televisions.

<< Second Embodiment >>
Next, a second embodiment will be described with reference to FIG. In addition, since the wavelength-selective reflective film for transfer after this embodiment is a modification of the wavelength-selective reflective film for transfer according to the first embodiment, the description will focus on the changed parts, and duplicate explanations will be omitted. . As shown in FIG. 3, in the wavelength selective reflection film 2 for transfer in the present embodiment, a high refractive index layer TH 1 having a first heat adhesion property, a laminated low refractive index layer L 1, and a first layer on the support film 4. And a high refractive index layer TH2 having a heating adhesiveness of 2 are laminated in this order, and a high refractive index layer TH1 having a first heating adhesiveness, a laminated low refractive index layer L1, and a second heating adhesiveness are provided. The film thickness of the high refractive index layer TH2 is as follows: the reflection target wavelength is λa, the refractive index of the high refractive index layer (TH1) having the first heat adhesive property (TH1) is nTH1, the film thickness is dTH1, and the laminated low refractive index layer ( When the refractive index of L1) is nL1, the film thickness is dL1, the refractive index of the second high-refractive-index layer (TH2) having heat adhesion is THH2, and the film thickness is dTH2, the following formula (3) and formula It is set so as to satisfy (4). In addition, the refractive index and film thickness of the high refractive index layer having the first heat adhesive property may be the same as or different from the refractive index and film thickness having the second heat adhesive property.
λa = 4nTH1 × dTH1 + 4nTH2 × dTH2 (3)
dL1 = λa / 4nL1 (4)

<< High Refractive Index Layer TH1 Having First Heat Adhesive Property and Second High Refractive Index Layer TH2 Having Heat Adhesive Property >>
The high refractive index layers TH1 and TH2 having heat adhesion will be described. The high-refractive index layers TH1 and TH2 having heat adhesiveness exhibit a reflection effect due to a significant refractive index difference from the adjacent laminated low-refractive index layer L1, and are heated at the time of adhesion to the object. Is a layer that exhibits adhesiveness. The refractive indexes of the high refractive index layers TH1 and TH2 having heat adhesion are set higher than those of the laminated low refractive index layer L1. The refractive index of the high refractive index layer having heat adhesion is preferably 1.56 or more. When the refractive index of the high refractive index layer having heat adhesion is less than 1.56, when the difference in refractive index from the laminated low refractive index layer becomes small, the reflection at the interface becomes weak and the reflection performance is not sufficiently exhibited. There is. The upper limit of the refractive index of the high refractive index layer having heat adhesiveness is not particularly limited, but the upper limit is substantially about 2.50 due to limitations of existing film forming materials.

  As the composition for forming a high refractive index layer having heat adhesiveness, the same composition as that for the laminated high refractive index layer described above can be used, but in order to develop the heat adhesive function, It needs to contain a plastic resin.

  There is no restriction | limiting in particular as a thermoplastic resin, From the conventionally well-known thing, it can select suitably and can be used. Examples of the thermoplastic resin include vinylidene chloride resin, polyvinyl alcohol, vinyl acetate resin, polystyrene, ABS, polyethylene, polypropylene, polyisobutylene, nylon, acetal resin, acrylic resin (polymethyl methacrylate resin, etc.), cellulose acetate, chlorine Polyether, polycarbonate, urea resin, epoxy resin, polyester resin, or a copolymer thereof (such as MS resin). Among these, polymethyl methacrylate resin, MS resin (copolymer of methyl methacrylate and styrene), and polycarbonate resin are preferable because they are highly transparent and easily dissolved in the solvent used for coating. In the case where the high refractive index layer having heat adhesiveness is composed of only a thermoplastic resin, a polycarbonate resin is more preferable because the refractive index needs to be 1.56 or more.

  The volume of the thermoplastic resin contained in the high refractive index layer (TH1) having the first heat adhesive property is (VTH1), and the volume of the thermoplastic resin contained in the second high refractive index layer (TH2) having the heat adhesive property is The volume of the component other than the thermoplastic resin contained in the high refractive index layer (TH1) having the first heat adhesion (VTH2) is (VO1), and the second layer having a high refractive index having the second heat adhesion (VTH2). If the volume of components other than the thermoplastic resin contained in TH2) is (VO2), the volume ratio of the thermoplastic resin {VTH1 / (VTH1 + VO1)} × 100 (%) and {VTH2 / (VTH2 + VO2) } × 100 (%) is preferably 20% or more. When the volume ratio of the thermoplastic resin {VTH1 / (VTH1 + VO1)} × 100 (%) and {VTH2 / (VTH2 + VO2)} × 100 (%) is less than 20%, the heat adhesive function is lowered. Therefore, it is not preferable.

  Various additives can be added to the composition for forming a high refractive index layer having heat adhesiveness as other components within a range not impairing the effects of the present invention. Examples of such additives include additives such as a dispersant, a surfactant, an ultraviolet absorber, a light stabilizer, and a leveling agent.

[Formation of High Refractive Index Layer TH1 Having First Heat Adhesive Property and First High Refractive Index Layer TH2 Having Heat Adhesive Property]
As a method for forming the high refractive index layer TH1 having the first heat adhesive property and the high refractive index layer TH2 having the first heat adhesive property, a composition comprising metal oxide fine particles and a binder resin containing a thermoplastic resin. Can be applied by a coating method such as a wet coating method, followed by drying and curing. The wet coating method may be a known method, and typical examples include a roll coating method, a die coating method, a spin coating method, and a dip coating method. In these, the method which can form a coating film continuously, such as a roll coat method, is preferable from the point of productivity. The formed coating film can form a cured film by performing a curing reaction by heating, irradiation with active energy rays such as ultraviolet rays and electron beams. Among these, the curing reaction using active energy rays can be performed in an inert gas atmosphere such as nitrogen or argon.

<< Laminated low refractive index layer L1 >>
Next, the laminated low refractive index layer L1 will be described. The laminated low refractive index layer L1 is a layer for expressing a reflection effect due to a significant refractive index difference from the above-described high refractive index layers TH1 and TH2 having heat adhesion. The refractive index of the laminated low refractive index layer L1 is required to be set lower than the refractive indexes of the high refractive index layers TH1 and TH2 having heat adhesion, and the refractive index is in the range of 1.20 to 1.55. is there. When the refractive index is less than 1.20, the film becomes brittle, and it becomes difficult to handle the formed film. On the other hand, when the refractive index exceeds 1.55, the difference in refractive index from the high refractive index layers (TH1 and TH2) having heat adhesion becomes small, and it is difficult to obtain a sufficient reflection effect.

  The composition for forming a low refractive index layer is a composition for forming a low refractive index layer which has been conventionally known in the field of articles having an antireflection or reflecting function in addition to the composition for low refractive index layer having heat adhesion. Can be used. Examples thereof include a silica film (silica oxide film), and compounds such as magnesium fluoride and silicon oxyfluoride. Moreover, since it is not necessary to have heat adhesiveness, unlike the case of the low refractive index layer TL having heat adhesiveness, it is not necessary to include a thermoplastic resin as the binder resin.

(Formation of laminated low refractive index layer)
As a method for forming a silica film (silica oxide film) or a low refractive index layer using a compound such as magnesium fluoride or silicon oxyfluoride, it can be formed by a plasma CVD method, a vapor deposition method, a sputtering method, or the like.

  On the other hand, as a method for forming a low refractive index layer using a composition containing hollow silicon oxide fine particles and a binder resin, a method of applying a coating liquid by a coating method such as a wet coating method, drying and then curing is adopted. can do. The wet coating method may be a known method, and typical examples include a roll coating method, a die coating method, a spin coating method, and a dip coating method. In these, the method which can form a coating film continuously, such as a roll coat method, is preferable from the point of productivity. The formed coating film can form a cured film by performing a curing reaction by heating, irradiation with active energy rays such as ultraviolet rays and electron beams. Among these, the curing reaction using active energy rays can be performed in an inert gas atmosphere such as nitrogen or argon.

≪Method for producing wavelength selective reflection film for transfer≫
In this embodiment, the high refractive index layer TH1 having the first heat adhesion is formed on the support film 4 by the above method, and the laminated low refractive index layer L1 and the second heat adhesion are further formed thereon. The high refractive index layer TH2 is formed in this order. As described above, the film thicknesses of the low refractive index layer TH1 having the first heat adhesion, the laminated high refractive index layer L1, and the second refractive index layer TH2 having the second heat adhesion are determined by the reflection target wavelength and It is set so as to satisfy the following formulas (3) and (4) according to each refractive index.
λa = 4nTH1 × dTH1 + 4nTH2 × dTH2 (3)
dL1 = λa / 4nL1 (4)

<< Third Embodiment >>
In the third embodiment, as shown in FIG. 4, the wavelength selective reflection film 2 for transfer has a low refractive index layer TL1 having a first heat adhesive property on a support film 4 having a releasability, The stacked high-refractive index layer H1, the low-refractive index layer L, the high-refractive index layer H, and the low-refractive index layer TL2 having the second heating adhesiveness are provided in this order. The film thicknesses of the low refractive index layer TL1, the high refractive index layer H1, the low refractive index layer L, the high refractive index layer H, and the second refractive index layer TL2 having the second heating adhesiveness are as follows. The reflection target wavelength is λa, the refractive index of the low refractive index layer (TL1) having the first heat adhesion property is TL1, the film thickness is dTL1, the refractive index of the stacked high refractive index layer (H1) is nH1, and the film thickness. DH1, the refractive index of the low-refractive index layer (L) is nL, the film thickness is dL, the refractive index of the high-refractive index layer (H) is nH, the film thickness is dH, and the second heat adhesion property is provided. When the refractive index of the low refractive index layer (TL2) is nTL2, and the film thickness is dTL2, the following formula (1), formula (2), formula (5), and formula (6) are satisfied.
λa = 4nL1 × dTL1 + 4nTL2 × dTL2 (1)
dH1 = λa / 4nH1 (2)
dH = λa / 4nH (5)
dL = λa / 4nL (6)

  In addition, although the wavelength selective reflection film 2 for transfer of this embodiment has one unit of the laminated body 8 composed of the low refractive index layer L and the high refractive index layer H, the number of the laminated bodies 8 is particularly limited. It can be changed freely. However, from the viewpoint of manufacturability and handleability, it is preferable that the maximum is 4 units, that is, the reflective layer 6 of this embodiment has a maximum 11-layer structure. If it exceeds this, accurate film thickness control becomes difficult, and manufacturability and handleability deteriorate. In each laminate 8, the low refractive index layer L is located on the laminated high refractive index layer H1 side with respect to the high refractive index layer H. That is, when there are a plurality of stacked bodies, the low refractive index layers L and the high refractive index layers H are alternately positioned.

<Low refractive index layer>
The low refractive index layer L is a layer for exhibiting a reflection effect due to a significant refractive index difference from the above-described laminated high refractive index layer H1 or a high refractive index layer H described later. The refractive index of the low refractive index layer L is required to be set lower than the refractive index of the stacked high refractive index layer H1 and the refractive index of the high refractive index layer H, and the refractive index is 1.20 to 2020. The range is 1.55. When the refractive index is less than 1.20, the film becomes brittle, and it becomes difficult to handle the formed film. On the other hand, when the refractive index exceeds 1.55, the refractive index difference from the laminated high refractive index layer (H1) or the high refractive index layer (H) becomes small, and it is difficult to obtain a sufficient reflection effect.

  The composition for forming a low refractive index layer should be a conventionally known composition for forming a low refractive index layer in the field of an article having antireflection or reflection function, like the composition for forming a low refractive index layer. Can do. Examples thereof include a silica film (silica oxide film), and compounds such as magnesium fluoride and silicon oxyfluoride. Moreover, since it is not necessary to have heat adhesiveness, unlike the case of the low refractive index layer TL having heat adhesiveness, it is not necessary to include a thermoplastic resin as the binder resin.

《High refractive index layer》
Next, the high refractive index layer H will be described. The high refractive index layer H is a layer for expressing a reflection effect due to a significant refractive index difference from the low refractive index layer or the low refractive index layer having heat adhesion. The refractive index of the high refractive index layer is set higher than that of the low refractive index layer and the low refractive index layer having heat adhesion. The refractive index of the high refractive index layer is preferably 1.56 or more. When the refractive index of the high refractive index layer is less than 1.56, the difference in refractive index between the low refractive index layer or the low refractive index layer having heat adhesion becomes small, and the reflection at the interface becomes weak, and the reflection performance is sufficient. May not be demonstrated. Although the upper limit of the refractive index of the high refractive index layer is not particularly limited, the upper limit is substantially about 2.50 due to limitations of existing film forming materials.

  The composition for forming the high refractive index layer is not particularly limited, and the composition containing the metal oxide fine particles and the binder resin or the metal oxide fine particles and the binder resin is the same as the composition for forming the laminated high refractive index layer. The thing formed by hardening | curing the composition containing this can be applied.

≪Method for producing wavelength selective reflection film for transfer≫
In the present embodiment, the low refractive index layer TL1 and the laminated high refractive index layer H1 having the first heat adhesiveness are formed on the support film 4 having releasability, and the low refractive index layer L and the high refractive index layer L are formed thereon. The refractive index layer H is formed in this order, and the low refractive index layer TL2 having the second heat adhesiveness is further formed thereon. At this time, the low refractive index layer TL1 having the first heat adhesion, the laminated high refractive index layer H1, the low refractive index layer L, the high refractive index layer H, and the second low refractive index layer having the heat adhesion. The film thickness of TL2 is set so as to satisfy the following formulas (1), (2), (5), and (6) according to the reflection target wavelength and the respective refractive indexes.
λa = 4nTL1 × dTL1 + 4nTL2 × dTL2 (1)
dH1 = λa / 4nH1 (2)
dH = λa / 4nH (5)
dL = λa / 4nL (6)

≪Transfer method≫
As in the case of the first embodiment, (a) a heat treatment is performed by bringing the low refractive index layer TL2 having heat adhesion located on the outermost layer of the wavelength selective reflection film 2 for transfer into close contact with the transfer object ( b) The reflective layer 6 is transferred to the transfer object by peeling the support film 4 having releasability, and (c) Steps (a) and (b) are performed using the transferred reflective layer 6 as the transfer object. Alternatively, a transfer molded product that is a multilayer structure is formed by repeating a plurality of times. However, the wavelength selective reflection film 2 for transfer of Embodiment 1 has three reflective layers 6 whereas the wavelength selective reflection film for transfer of Embodiment 3 has five reflective layers 6. A transfer molded product having reflection selectivity corresponding to the transfer molded product of Embodiment 1 can be obtained with a transfer number of 5 times.

≪Transcription moldings≫
By the above transfer method, the low refractive index layer TL1 having the first heat adhesive property, the laminated high refractive index layer H1, the low refractive index layer L, the high refractive index layer H, and the second heat adhesive property are provided. A transfer molding having the low refractive index layer TL2 repeatedly in this order can be easily manufactured. In addition, since five layers can be provided in one transfer step, production of a transfer molded product having a multilayer structure of 10 layers or more is produced in comparison with the case where three layers are formed as in the first embodiment. From the viewpoint of workability and workability.

<< Fourth Embodiment >>
As shown in FIG. 5, in the fourth embodiment, the wavelength selective reflection film 2 for transfer has a high refractive index layer TH1 having a first heating adhesive property on a support film 4 having a releasability. The laminated low refractive index layer L1, the high refractive index layer H, the low refractive index layer L, and the high refractive index layer TH2 having the second heating adhesiveness are provided in this order. The film thicknesses of the high refractive index layer TH1 having the first heat adhesion, the laminated low refractive index layer L1, the high refractive index layer H, the low refractive index layer L, and the second high refractive index layer TH2 having the heat adhesion are as follows. , The reflection target wavelength is λa, the refractive index of the high refractive index layer (TH1) having the first heat adhesive property (TH1) is nTH1, the film thickness is dTH1, and the refractive index of the laminated low refractive index layer (L1) is nL1. The thickness is dL1, the refractive index of the high refractive index layer (H) is nH, the film thickness is dH, the refractive index of the low refractive index layer (L) is nL, the film thickness is dL, and the second heat adhesion property is When the refractive index of the high refractive index layer (TH2) is nTH2 and the film thickness is dTH2, it is set so as to satisfy the following formulas (3), (4), (5), and (6). .
λa = 4nTH1 × dTH1 + 4nTH2 × dTH2 (3)
dL1 = λa / 4nL1 (4)
dH = λa / 4nH (5)
dL = λa / 4nL (6)

≪Method for producing wavelength selective reflection film for transfer≫
In this embodiment, the high refractive index layer TH1 and the laminated low refractive index layer L1 having the first heat adhesion are formed on the support film 4 having releasability, and the high refractive index layer H and the low refractive index layer H1 are formed thereon. The refractive index layer L is formed in this order, and the high refractive index layer TH2 having the second heat adhesiveness is further formed thereon. At this time, the high refractive index layer TH1 having the first heat adhesion, the laminated low refractive index layer L1, the high refractive index layer H, the low refractive index layer L, and the second low refractive index layer having the heat adhesion. The film thickness of TH2 is set so as to satisfy the following formulas (3), (4), (5), and (6) according to the reflection target wavelength and the respective refractive indexes.
λa = 4nTH1 × dTH1 + 4nTH2 × dTH2 (3)
dL1 = λa / 4nL1 (4)
dH = λa / 4nH (5)
dL = λa / 4nL (6)

≪Transfer method≫
(A) Heat treatment is performed by bringing the high refractive index layer TH2 having the second heat-adhesive property located on the outermost surface of the transfer wavelength selective reflection film 2 into close contact with the transfer object, and (b) releasability. The reflective layer 6 is transferred to the transfer object by peeling off the supporting film 4 having, and (c) the steps (a) and (b) are repeated one or more times using the transferred reflective layer 6 as the transfer object. A transfer molded product that is a multilayer structure can be formed.

  In the present specification, the high refractive index layer H, the low refractive index layer L, the laminated high refractive index layer H1, the laminated low refractive index layer L1, the first high refractive index layer TH1 having heat adhesion, The high refractive index layer TH2 having a heat adhesive property of 2, the low refractive index layer TH1 having the first heat adhesive property, and the low refractive index layer TL2 having the second heat adhesive property are thin films constituting the reflective layer. It is named by distinguishing it from the difference when the refractive indexes are relatively compared. The refractive indexes of the present invention all mean the refractive index at a wavelength of 589 nm. In a transfer molding with a wavelength selective reflection function described later, the low refractive index layer L at the wavelength λa of the light whose reflectance is to be maximized. , Laminated low refractive index layer L1, low refractive index layer TL1 having first heat adhesion, second low refractive index layer TL2 having heat adhesion, high refractive index layer H, laminated high refractive index layer H1, The high refractive index layer TH1 having a heat adhesion of 1 and the high refractive index layer TH2 having a second heat adhesion can be distinguished by being relatively lower than the refractive index.

  Hereinafter, the embodiment will be described more specifically with reference to examples and comparative examples, but the invention is not limited thereto. In addition, evaluation of the following items was performed as evaluation about the wavelength-selective reflective film for transfer and the transfer molding.

Spectral reflectivity: The back of the wavelength-selective reflective film is roughened with sandpaper and painted with black paint, and the spectrophotometer ("UV-1600PC", manufactured by Shimadzu Corporation) is used to measure the spectral reflectivity (350-1100 nm) 5 ° -5 ° specular reflection spectrum) was measured.

Film thickness: laminated high refractive index layer (H1), laminated low refractive index layer (L1), high refractive index layer (H, Ha, Hb), low refractive index layer (L, La, Lb), heat adhesiveness The film thickness after drying and curing of the high refractive index layer (TH) and the low refractive index layer (TL) having heat adhesiveness was measured by observing the cross section of the optical laminate with a TEM photograph.

Refractive index: An easy-adhesion layer is not provided with a PET film having a refractive index of 1.65 (trade name: “A4100”, manufactured by Toyobo Co., Ltd.) with an easy-adhesion layer provided on one surface. The film to be measured is formed on the surface with a film thickness of about 100 nm, and the film formed on the film with a reflection spectral film thickness meter ("FE3000" manufactured by Otsuka Electronics Co., Ltd.) is absolutely reflected in the range of 270 to 1040 nm. From the measured value of the obtained absolute reflectance spectrum, the dispersion formula of n-Cauchy is cited as an approximate expression of chromatic dispersion, and the unknown parameter is a spectral nonlinear least square method of absolute reflectance. And the refractive index at a wavelength of 589 nm was calculated.

Volume ratio of thermoplastic resin contained in high refractive index layer (TH) having heat adhesion or low refractive index layer (TL) having heat adhesion: thermoplastic resin before curing contained in layer forming composition ( The volume of A) is (V _A ), the specific gravity is (d _A ), the blended mass part is (W _A ), the volume of solid content (B) other than the thermoplastic resin is (V _B ), and the average specific gravity is (d _B ), where the mass part of the blended solid content is (W _B ), the volume ratio of the thermoplastic resin contained in the composition is 100 × V _A / (V _A + V _B ) (%) = 100 × It was calculated as (W _B / d _A ) / {(W _A / d _A ) + (W _B / d _B )}.

Total light transmittance: Haze value (%) was measured using NDH2000 [Nippon Denshoku Industries Co., Ltd.].

Adhesiveness: Conforms to JISK5400, made 100 squares in a grid of 1 mm on one side, and attached the adhesive tape to the entire surface, then kept one end of the adhesive tape at a right angle to the transferred material, and instantly pulled apart, The number of squares remaining without peeling was examined.

<< Production Example >>
(Preparation of coating solution for high refractive index layer (a-1) having heat adhesion)
The high refractive index layer coating solution (a-1) is a titanium oxide (TiO ₂ ) fine particle dispersion (manufactured by C-I Kasei Co., Ltd., RTTMIBK15WT% -N24, particle size 15 nm) in terms of solid content of 78 parts by mass, It was obtained by mixing 22 parts by mass of acid methyl polymer [n≈7000-7500, PMMA, manufactured by Tokyo Chemical Industry Co., Ltd.] and mixing methyl ethyl ketone (MEK) so that the solid content concentration was 10% by mass. In addition, it confirmed that the methyl methacrylate polymer was melt | dissolving without melt | dissolving visually.

なお、表中の略称は以下の成分を示す。
TiO₂：酸化チタン（TiO₂）微粒子分散液、シーアイ化成（株）製、ＲＴＴＭＩＢＫ１５ＷＴ％−Ｎ２４、粒子径15nm
ZrO₂：酸化ジルコニウム（ZrO₂）微粒子分散液、シーアイ化成（株）製、ＺＲＭＥＫ２５％−Ｆ４７、粒子径15nm
ＵＶ７６００Ｂ：ウレタンアクリレート〔紫光（株）製、紫光ＵＶ−７６００Ｂ〕
Ｉ−９０７：紫外線重合開始剤（ＢＡＳＦジャパン株式会社製、Ｉｒｕｇａｃｕｒｅ−９０７） (Preparation of high refractive index layer coating liquids (a-2) to (a-4) having heat adhesion)
The high refractive index layer coating liquids (a-2) to (a-4) were prepared in the same manner as the high refractive index layer coating liquid (a-1) with the formulation (parts by mass and components) shown in Table 1. .

In addition, the abbreviation in a table | surface shows the following components.
TiO ₂ : Titanium oxide (TiO ₂ ) fine particle dispersion, manufactured by CI Kasei Co., Ltd., RTTMIBK15WT% -N24, particle size 15 nm
ZrO ₂ : Zirconium oxide (ZrO ₂ ) fine particle dispersion, manufactured by CI Kasei Co., Ltd., ZRMEK 25% -F47, particle size 15 nm
UV7600B: Urethane acrylate [manufactured by Shigemitsu Co., Ltd., purple light UV-7600B]
I-907: UV polymerization initiator (BASF Japan, Irugacure-907)

(Production of fluorine-containing polymer δ1 having a polymerizable double bond)
In a four-necked flask, 104 parts of perfluoro- (1,1,9,9-tetrahydro-2,5-bisfluoromethyl-3,6-dioxanonenol) and bis (2,2,3,3, 4,4,5,5,6,6,7,7-dodecafluoroheptanoyl) peroxide 11 parts by weight of 8% by weight perfluorohexane was added. The hollow portion was purged with nitrogen, and then stirred at 20 ° C. for 24 hours under a nitrogen stream to obtain a highly viscous solid. A solution obtained by dissolving the obtained solid in diethyl ether was poured into perfluorohexane, followed by separation and vacuum drying to obtain a colorless and transparent polymer.

  When this polymer was analyzed by 19F-NMR (nuclear magnetic resonance spectrum), 1H-NMR, and IR (infrared absorption spectrum), it was a fluorine-containing polymer having a hydroxyl group at the end of the side chain consisting of the structural unit of the allyl ether. The number average molecular weight measured by GPC (gel permeation chromatograph) was 72,000, and the mass average molecular weight was 118,000.

  5 parts of the obtained hydroxyl group-containing fluorine-containing allyl ether polymer, 43 parts of methyl ethyl ketone (MEK) and 1 part of pyridine were charged into a four-necked flask and cooled to 5 ° C. or lower with ice. And what melt | dissolved 1 part of (alpha) -fluoroacrylic acid fluoride in 9 parts of MEK was dripped over 10 minutes, stirring under nitrogen stream. Then, a solution of the fluorine-containing polymer δ1 having a polymerizable double bond was obtained.

(Preparation of low refractive index layer coating solution (b-1) having heat adhesion)
The coating solution for low refractive index layer (b-1) having heat adhesive properties was obtained by 55 parts by mass of hollow silica fine particles having a particle diameter of 60 nm and a solvent-soluble methyl methacrylate polymer [n≈7000-7500, Tokyo Chemical Industry Co., Ltd. )] Was mixed with 45 parts by mass in terms of solid content, and methyl isobutyl ketone (MIBK) was mixed so that the solid concentration was 5% by mass.
In addition, about the methyl methacrylate polymer [n = 7000-7500, Tokyo Chemical Industry Co., Ltd.], it confirmed that it melt | dissolved without melt | dissolving visually.

(Preparation of low refractive index layer coating liquids (b-2) to (b-6) having heat adhesion)
The low refractive index layer coating liquids (b-2) to (b-6) having heat adhesiveness were mixed with the high refractive index layer coating liquid (b-1) with the formulation (parts by mass and components) shown in Table 2. Prepared similarly. In Table 2, DPHA is an abbreviation for dipentaerythritol hexaacrylate.

(Preparation of high refractive index layer coating solution (c-1))
The high refractive index layer coating liquid (c-1) is a titanium oxide (TiO ₂ ) fine particle dispersion (manufactured by C-I Kasei Co., Ltd., RTTMIBK15WT% -N24, particle diameter 15 nm) in terms of solid content, 78 parts by mass, urethane 17 parts by mass of an acrylate [manufactured by Shimitsu Co., Ltd., purple UV-7600B], 5 parts by mass of an ultraviolet polymerization initiator Irugacure-907 (2-methyl-1- (4-methylthiophenyl) -2-morpholinepropan-1-one) And methyl isobutyl ketone (MIBK) was mixed to obtain a solid content concentration of 5% by mass.

(Preparation of high refractive index layer coating solutions (c-2) to (c-6))
The high refractive index layer coating solutions (c-2) to (c-6) were prepared in the same manner as the high refractive index layer coating solution (c-1) with the formulation (parts by mass and components) shown in Table 3. . In production examples (c-1) and (c-3), RTIMIBK15WT% -N24, a particle diameter of 15 nm, manufactured by CI Kasei Co., Ltd., was used as a titanium oxide (TiO ₂ ) fine particle dispersion. In Production Examples (c-2) and (c-4), ZRMEK25% -F47, manufactured by Sea Chemicals Co., Ltd., and a particle diameter of 15 nm were used as a zirconium oxide (ZrO ₂ ) fine particle dispersion. (C-5) and (c-6) are materials that can be formed by a vapor deposition process ((c-5) is titanium oxide (TiO ₂ ), and (c-6) is zirconium oxide (ZrO ₂ )). Solvents such as methyl isobutyl ketone (MIBK) are not included.

(Preparation of low refractive index layer coating solution (d-1))
The low refractive index layer coating solution (d-1) comprises 55 parts by mass of hollow silica fine particles having a particle size of 60 nm, 45 parts by mass of a solvent-soluble fluoropolymer (δ1) in terms of solid content, and a photopolymerization initiator [ Irugacure-907] was obtained by mixing isopropyl alcohol (IPA) to a solid content concentration of 5% by mass.

(Preparation of low refractive index layer coating solutions (d-2) to (d-3))
The low refractive index layer coating solutions (d-2) and (d-3) were prepared in the same manner as the low refractive index layer coating solution (d-1) with the formulation (parts by mass and components) shown in Table 4. In addition, (d-3) and (d-4) were prepared using methyl isobutyl ketone (MIBK) instead of isopropyl alcohol (IPA) so that the solid content concentration was 5% by mass.
Note that (d-5) and (d-6) are materials that can be formed by a vapor deposition process ((d-5) is magnesium fluoride (MgF ₂ ), and (d-6) is silicon oxide (SiO ₂ ). A single compound) and does not contain a solvent such as isopropyl alcohol (IPA) or methyl isobutyl ketone (MIBK).

(Production of wavelength selective reflection film for transfer)
(Example 1-1)
Forming a support film having releasability: As a support film, a solution of acrylic silicone resin, toluene, and methyl isobutyl ketone was applied on one side of a 38 μm-thick polyethylene terephthalate (PET) film by gravure reverse coating and dried. A release layer having a thickness of 0.7 μm was formed.

  Formation of the low refractive index layer (TL1) having the first heat adhesion property: After applying the low refractive index layer coating solution (b-1) having the heat adhesion property on the support film having the releasability, drying is performed. Then, a low refractive index layer having a thickness of 91 nm and having the first heat adhesiveness was formed.

  Formation of laminated high refractive index layer (H1): A high refractive index layer coating liquid (c-1) is applied on the first low refractive index layer having heat adhesiveness, dried, and laminated with a thickness of 100 nm. A high refractive index layer (H1) was formed.

  Formation of second refractive index layer (TL2) having heat adhesion property: Applying low refractive index layer coating liquid (b-1) having second heat adhesion property to the laminated high refractive index layer (H1). After coating, the film was dried to form a 55 nm thick second refractive index layer (TL2) having heat adhesiveness.

  A wavelength-selective reflective film for transfer was obtained as described above. The obtained wavelength-selective reflective film for transfer had no tack on the surface and was easy to handle.

(Example 1-2)
In order to form the low refractive index layer (TL1) having the first heat adhesion property, the coating liquid (b-6) is used, the film thickness after drying is set to 50 nm, and the laminated high refractive index layer is coated thereon. (C-2) was used as a liquid to form a 118 nm layer, and the film thickness of the second refractive index low-refractive index layer (TL2) having a thickness of 91 nm was changed to 91 nm in the same manner as in Example 1-1. A wavelength selective reflection film for transfer was obtained.

(Example 2-1)
Formation of support film having releasability and low refractive index layer (TL1) having first heat adhesiveness: first heat adhesiveness on support film having releasability as in Example 1-1 A low refractive index layer coating solution (b-2) having a thickness of 124 nm was applied and dried to form a low refractive index layer (TL1) having a thickness of 124 nm and having a first heat adhesion property.

  Formation of laminated high refractive index layer: A high refractive index layer coating liquid (c-1) is applied on the low refractive index layer (TL1) having the first heat adhesion property, dried, and then cured by ultraviolet irradiation. A laminated high refractive index layer (H1) having a thickness of 100 nm was formed.

  Formation of a low refractive index layer: A low refractive index layer coating solution (d-1) is applied on the laminated high refractive index layer, dried and then cured by ultraviolet irradiation, and a low refractive index layer (La) having a thickness of 153 nm. Formed.

  Formation of a high refractive index layer: A high refractive index layer coating solution (a-4) is applied on the low refractive index layer, dried, and then cured by ultraviolet irradiation to form a high refractive index layer (Ha) having a thickness of 127 nm. Formed.

  Formation of second refractive index layer (TL2) having heat adhesion property: After applying low refractive index layer coating liquid (b-2) having heat adhesion property on the high refractive index layer (Ha), and after drying Then, a low refractive index layer (TL2) having a second heat adhesion property having a thickness of 18 nm was formed by curing with ultraviolet irradiation.

A wavelength-selective reflective film for transfer was obtained as described above. The obtained wavelength-selective reflective film for transfer had no tack on the surface and was easy to handle.
(Example 2-2)
Formation of a support film having releasability and a low refractive index layer (TL1) having first heat adhesiveness: In the same manner as in Example 1-1, low heat resistance is obtained on a support film having releasability. The refractive index layer coating solution (b-3) was applied, dried, and then cured by ultraviolet irradiation to form a low refractive index layer having a heat adhesion of 72 nm in thickness.

  Formation of laminated high refractive index layer: A high refractive index layer coating solution (c-2) is applied on the low refractive index layer having the first heat-adhesive property, dried, and then cured by ultraviolet irradiation to a thickness of 118 nm. The high refractive index layer (H1) was formed.

  Formation of the first low-refractive index layer: The low-refractive index layer coating solution (d-2) is applied on the laminated high-refractive index layer, dried and then cured by ultraviolet irradiation, and the low-refractive index layer having a thickness of 147 nm (La) was formed.

  Formation of the first high refractive index layer: The high refractive index layer coating solution (a-4) is applied on the first low refractive index layer, dried and then cured by ultraviolet irradiation, and has a high refractive index of 127 nm. A layer (Ha) was formed.

  Formation of the second low-refractive index layer: The low-refractive index layer coating solution (d-3) is applied on the first high-refractive index layer, dried, and then cured by ultraviolet irradiation to form a second 142 nm thick second layer. The low refractive index layer (Lb) was formed.

  Formation of the second high refractive index layer: The high refractive index layer coating solution (a-4) is applied on the second low refractive index layer, dried, and then cured by ultraviolet irradiation to form a second layer having a thickness of 127 nm. A high refractive index layer (Hb) was formed.

  Formation of the low refractive index layer (TL2) having the second heat adhesion property: After applying the low refractive index layer coating liquid (b-3) having the heat adhesion property on the second high refractive index layer, and drying, A low refractive index layer (TL2) having a thickness of 72 nm and having a second heat adhesive property was formed by curing with ultraviolet irradiation. A wavelength-selective reflective film for transfer was obtained as described above.

(Example 2-3)
A transfer wavelength-selective reflective film was obtained in the same manner as in Example 2-2 except that the embodiment shown in Table 5 was used. In addition, when the coating liquid (b-4, d-4, c-3) containing active energy ray-curable resin was used, it hardened | cured by drying and ultraviolet irradiation. The coating liquids (c-5, d-5) are obtained by DC magnetron sputtering, with each material TiO ₂ or MgF ₂ (purity 99.9%) as a target and argon having a purity of 99.5% as sputtering gas. As a result, the layer was formed so that TiO ₂ or MgF ₂ had a predetermined film thickness.

(Example 3-1)
Forming a support film having releasability: As a support film, a solution of acrylic silicone resin, toluene, and methyl isobutyl ketone was applied on one side of a 38 μm-thick polyethylene terephthalate (PET) film by gravure reverse coating and dried. A release layer having a thickness of 0.7 μm was formed.

  Formation of the high refractive index layer (TH1) having the first heat adhesion property: After applying and drying the low refractive index layer coating solution (a-1) having the heat adhesion property on the support film having releasability, A low refractive index layer (TH1) having a thickness of 63 nm and having a first heat adhesion property was formed by curing with ultraviolet irradiation.

  Formation of the laminated low refractive index layer (L1): The high refractive index layer coating solution (d-1) is applied on the first high refractive index layer (TH1) having heat adhesion, dried, and then irradiated with ultraviolet rays. Cured to form a laminated low refractive index layer (L1) having a thickness of 153 nm.

  Formation of second refractive index layer (TH2) having heat adhesion property: After applying high refractive index layer coating liquid (a-1) having heat adhesion property on laminated low refractive index layer (L1), drying is performed. Then, a high refractive index layer having a thickness of 38 nm and having heat adhesiveness was formed. A wavelength-selective reflective film for transfer was obtained as described above.

(Examples 3-1, 4-1 to 4-2)
A transfer wavelength-selective reflective film was obtained in the same manner as in Example 3-1, except that the embodiment shown in Table 6 was used. In addition, the coating liquid (a-3, a-4, c-1, c-2, c-3, c-4, d-1, d-2, d-3, containing active energy ray curable resin, When d-4) is used, it is cured by drying and ultraviolet irradiation, and when a coating liquid (a-1, a-2) containing a resin other than the active energy ray curable resin is used, only drying is performed. Curing was carried out. The coating liquids (c-5, d-5) were obtained by DC magnetron sputtering, using the respective materials TiO ₂ or MgF ₂ (purity 99.9%) as a target, argon having a purity of 99.5% as a sputtering gas, and TiO _2. Alternatively, the layer was formed so that MgF ₂ had a predetermined thickness.

(Production of transfer molding using wavelength selective reflection film for transfer)
(Example 5-1)
Transfer of wavelength selective reflection layer to transfer object (planar transfer product) made of acrylic resin plate: heating adhesiveness located on outermost surface of wavelength selective reflection film for transfer obtained in Example 1-1 The surface was sandwiched between stainless steel plates having a mirror-like surface so that the low refractive index layer had contact with the transfer object. Pressurization (3923 kPa) was applied from above the stainless steel plate and heated at 130 ° C. for 5 minutes. After heating, the temperature was returned to room temperature, and the support film was peeled off. In this way, the low refractive index having the stacked high refractive index layer (H1) and the second heat adhesiveness is provided on the lower surface of the transfer object via the low refractive index layer (TL1) having the first heat adhesive property. The low refractive index layer (TL1) and the laminated high refractive index layer (H1) having the first heat adhesion and the low refractive index layer (TL2) having the second heat adhesion are transferred. A transfer product in which only one unit of a three-layer reflective layer was provided was obtained.

  Repetitive transfer of reflection layer to transfer object provided with 1 unit of reflection layer: Heat adhesion of second transfer wavelength selective reflection film on high refractive index layer having heat adhesion of transfer material Was sandwiched between stainless steel plates having a mirror-like surface so that the low refractive index layer having Pressurization (3923 kPa) was applied from above the stainless steel plate and heated at 130 ° C. for 5 minutes. After heating, the temperature was returned to room temperature, and the support film was peeled off. In this way, a transfer product in which two units of the wavelength selective reflection layer were provided was obtained.

  Hereinafter, the transfer object provided with the wavelength selective reflection layer was used as a transfer object, and a wavelength selective reflection article provided with 5 units of the wavelength selective reflection layer was obtained in the same manner. As shown in Table 7, the obtained transfer molding has the highest reflectance of 90.4% with respect to light having a wavelength of 800 nm, which is the target wavelength, is transparent, and is wavelength selective with good film adhesion. It was confirmed that it was a reflective article.

(Example 5-2)
The transfer wavelength selective reflection film prepared in Example 1-2 was used in place of the transfer wavelength selective reflection film prepared in Example 1-1, and the number of transfers to the resin plate (= wavelength to the resin plate). A transfer molded article was obtained under the same conditions as in Example 5-1, except that the stacking unit of the selective reflection layer (6) was changed from 5 times to 7 times. The obtained transfer molding has the highest reflectance with respect to the target wavelength of 800 nm wavelength light of 81.6%, is transparent, and is confirmed to be a wavelength-selective reflective article with good film adhesion. did.

(Example 5-3)
The transfer wavelength selective reflection film prepared in Example 2-1 was used in place of the transfer wavelength selective reflection film prepared in Example 1-1, and the number of transfers (= wavelength selective reflection layer on the resin plate). The transfer molded product was obtained under the same conditions as in Example 5-1, except that the stacking unit was changed from 5 times to 3 times. The obtained transfer molding has the highest reflectivity with respect to the target wavelength of 800 nm wavelength light of 78.9%, is transparent, and is confirmed to be a wavelength-selective reflective article with good film adhesion. did.

(Example 5-4)
Using the wavelength selective reflection film for transfer produced in Example 2-2 instead of the wavelength selective reflection film for transfer produced in Example 1-1, the number of times of transfer (= wavelength selective reflection on the resin plate) A transfer molding was obtained under the same conditions as in Example 5-1, except that the layer stacking unit was changed from 5 times to 3 times. The obtained transfer molding has the highest reflectivity with respect to the target wavelength of 800 nm wavelength light of 78.0%, is transparent, and is confirmed to be a wavelength-selective reflective article with good film adhesion. did.

(Example 5-5)
Using the wavelength selective reflection film for transfer prepared in Example 2-3 instead of the wavelength selective reflection film for transfer prepared in Example 1-1, the number of times of transfer (= wavelength selective reflection on the resin plate) A transfer molding was obtained under the same conditions as in Example 5-1, except that the layer stacking unit was changed from 5 times to 3 times. The obtained transfer molding has the highest reflectivity with respect to the target wavelength of 800 nm wavelength light of 99.0%, is transparent, and is confirmed to be a wavelength-selective reflective article with good film adhesion. did.

(Comparative Example 5-1)
A transfer molded product was obtained under the same conditions as in Example 5-1, except that the number of times of transfer to the resin plate (= lamination unit of the wavelength-selective reflective layer on the resin plate) was changed from 5 times to 1 time. . It was confirmed that the obtained transfer molding had a reflectance of 11.9% with respect to light having a target wavelength of 800 nm, which was lower than that of Example 5-1.

(Comparative Example 5-2)
A transfer molded product was obtained under the same conditions as in Example 5-2, except that the number of times of transfer to the resin plate (= lamination unit of the wavelength selective reflection layer on the resin plate) was changed from 7 times to 1 time. . The obtained transfer molding confirmed that the reflectance with respect to light with a wavelength of 800 nm which is a target wavelength was 11.3%, which was lower than Example 5-2.

(Comparative Example 5-3)
A transfer molded product was obtained under the same conditions as in Example 5-3, except that the number of times of transfer to the resin plate (= lamination unit of the wavelength-selective reflective layer on the resin plate) was changed from 3 times to 1 time. . The obtained transfer molding confirmed that the reflectance with respect to the wavelength light of 800 nm which is a target wavelength was 11.8%, and was lower than Example 5-3.

(Comparative Example 5-4)
A transfer molded product was obtained under the same conditions as in Example 5-4, except that the number of times of transfer to the resin plate (= lamination unit of the wavelength-selective reflective layer on the resin plate) was changed from 3 times to 1 time. . The obtained transfer molding confirmed that the reflectance with respect to light with a wavelength of 800 nm which is a target wavelength was 21.5%, which was lower than that of Example 5-4.

(Comparative Example 5-5)
A transfer molded product was obtained under the same conditions as in Example 5-5, except that the number of times of transfer to the resin plate (= lamination unit of the wavelength-selective reflective layer on the resin plate) was changed from 2 times to 1 time. . The obtained transfer molding confirmed that the reflectance with respect to the wavelength light of 800 nm which is a target wavelength was 84.3%, and was lower than Example 5-5.

And the haze, adhesiveness, and reflectance were measured about the transcription | transfer material of the obtained wavelength selective reflection layer. The results are shown in Table 7.

  As shown in Table 7, in Examples 5-1 to 5-5, the reflectance with respect to light having a wavelength of 800 nm is selectively high, and the haze value is small, so that the transparency is excellent and the adhesiveness is also good. Met.

(Example 6-1)
Using the wavelength selective reflection film for transfer prepared in Example 3-1 instead of the wavelength selective reflection film for transfer prepared in Example 1-1, the number of transfers to the resin plate (= to the resin plate) A transfer molded article was obtained under the same conditions as in Example 5-1, except that the wavelength-selective reflection layer lamination unit was changed from 5 times to 6 times. However, in Example 5-1, the second heat-adhesiveness disposed on the outermost surface opposite to the support film having releasability of the transferable wavelength selective reflection film obtained in Example 1-1. The low-refractive-index layer (TL2) having thermo-compression was pressed so as to be in contact with the transfer object, but the wavelength-selective reflective film for transfer of Example 3-1 was a high-refractive-index layer having the second heat adhesion property. Since (TH2) is arranged on the outermost surface opposite to the support film having releasability, it is not the second low refractive index layer (TL2), but has a high refractive index having the second heating adhesiveness. The layer (TH2) was thermocompression bonded so as to be in contact with the transfer object. The obtained transfer molding is confirmed to be a wavelength-selective reflective article having the highest reflectivity of 98.3% with respect to light having a wavelength of 800 nm as a target wavelength, transparency, and good film adhesion. did.

(Example 6-2)
Using the wavelength selective reflection film for transfer prepared in Example 3-2 instead of the wavelength selective reflection film for transfer prepared in Example 3-1, the number of times of transfer to the resin plate (= to the resin plate) A transfer molded product was obtained under the same conditions as in Example 6-1 except that the wavelength selective reflection layer stacking unit was changed from 6 times to 7 times. The obtained transfer molding is confirmed to be a wavelength selective reflection article having the highest reflectance of 91.8% with respect to light having a wavelength of 800 nm which is a target wavelength, transparency, and good film adhesion. did.

(Example 6-3)
Using the wavelength selective reflection film for transfer prepared in Example 4-1 instead of the wavelength selective reflection film for transfer prepared in Example 3-1, the number of transfers to the resin plate (= to the resin plate) A transfer molded product was obtained under the same conditions as in Example 6-1 except that the wavelength selective reflection layer stacking unit was changed from 6 times to 4 times. The obtained transfer molding is confirmed to be a wavelength-selective reflective article having the highest reflectivity with respect to a target wavelength of 800 nm wavelength light of 99.2%, transparency, and good film adhesion. did.

(Example 6-4)
Using the wavelength selective reflection film for transfer prepared in Example 4-2 instead of the wavelength selective reflection film for transfer prepared in Example 3-1, the number of times of transfer to the resin plate (= to the resin plate) A transfer molded product was obtained under the same conditions as in Example 6-1 except that the wavelength selective reflection layer stacking unit was changed from 6 times to 3 times. The obtained transfer molding is confirmed to be a wavelength-selective reflective article having the highest reflectance of 89.6% with respect to light having a wavelength of 800 nm as a target wavelength, transparency, and good film adhesion. did.

(Comparative Example 6-1)
A transfer molded product was obtained under the same conditions as in Example 6-1 except that the number of times of transfer to the resin plate (= laminating unit of the wavelength selective reflection layer on the resin plate) was changed from 6 times to 1 time. . The obtained transfer molding confirmed that the reflectance with respect to the wavelength light of 800 nm which is a target wavelength was 26.1%, and was lower than Example 6-1.

(Comparative Example 6-2)
A transfer molded product was obtained under the same conditions as in Example 6-2, except that the number of times of transfer to the resin plate (= lamination unit of the wavelength selective reflection layer on the resin plate) was changed from 7 times to 1 time. . The obtained transfer molding confirmed that the reflectance with respect to the wavelength light of 800 nm which is a target wavelength was 7.8%, and was lower than Example 6-2.

(Comparative Example 6-3)
A transfer molded product was obtained under the same conditions as in Example 6-3 except that the number of times of transfer to the resin plate (= lamination unit of the wavelength selective reflection layer on the resin plate) was changed from 4 times to 1 time. . The obtained transfer molding confirmed that the reflectance with respect to light with a wavelength of 800 nm which is a target wavelength was 53.2%, which was lower than that of Example 5-1.

(Comparative Example 6-4)
A transfer molded product was obtained under the same conditions as in Example 6-4, except that the number of times of transfer to the resin plate (= lamination unit of the wavelength selective reflection layer on the resin plate) was changed from 3 times to 1 time. . The obtained transfer molding confirmed that the reflectance with respect to light with a wavelength of 800 nm which is a target wavelength was 31.9%, which was lower than Example 6-4.

And the haze, adhesiveness, and reflectance were measured about the transcription | transfer material of the obtained wavelength selective reflection layer. The results are shown in Table 8.

  As shown in Table 8, in Examples 6-1 to 6-4, the reflectance with respect to light having a wavelength of 800 nm is selectively high and the haze value is small, so that the transparency is excellent and the adhesiveness is also good. Met.

Furthermore, the technical idea grasped from the embodiment will be described below.
The temperature of the heat treatment is a transfer method of a wavelength selective reflection film for transfer, wherein the temperature is 80 ° C. or higher. According to this transfer method, the heat-adhesive layer disposed on the outermost surface opposite to the support film having releasability by heat treatment can be securely adhered to the transfer object. Specifically, a method of thermocompression-bonding a wavelength-selective reflective film for transfer with a roll-to-roll using a silicon rubber roll or a mirror surface metal roll heated against a thermoplastic resin sheet, or a mold called in-mold molding For example, a method of setting the transfer wavelength-selective reflection film on the cavity surface and injecting and molding a molten thermoplastic resin, and integrating the transfer wavelength-selective reflection layer at the same time as molding may be used.

  By subjecting the transfer object to corona treatment or atmospheric plasma treatment, adhesion to the transfer object can be improved, and sufficient integration of the layer having heat adhesion and the transfer object can be achieved. It can be carried out.

2 Transferable Wavelength Selective Reflective Film 4 Support Film 6 Reflective Layer 8 Laminated Body Containing Low Refractive Index Layer L and High Refractive Index Layer H

Claims (5)

A reflective layer is provided on a support film having releasability, and the reflective layer includes a low refractive index layer (TL1) having a first heat adhesion property, a laminated high refractive index layer (H1), and a low refractive index layer. 1 to 4 units of a laminate including the refractive index layer (L) and the high refractive index layer (H) as one unit, and a low refractive index layer (TL2) having a second heat-adhesive property in this order, In each laminate, the low refractive index layer (L) is located closer to the laminated high refractive index layer (H1) than the high refractive index layer (H),
The refractive index of the low refractive index layer (TL1) and the low refractive index layer (L) having the first heat adhesion and the low refractive index layer (TL2) having the second heat adhesion is the stacked high refractive index. Lower than the refractive index of the layer (H1) and the high refractive index layer (H),
The reflection target wavelength is λa, the refractive index of the low refractive index layer (TL1) having the first heat adhesion property (TL1) is nTL1, the film thickness is dTL1, the refractive index of the stacked high refractive index layer (H1) is nH1, and the film thickness. DH1, the refractive index of the low-refractive index layer (L) is nL, the film thickness is dL, the refractive index of the high-refractive index layer (H) is nH, the film thickness is dH, and the second heat adhesion property is provided. When the refractive index of the low refractive index layer (TL2) is nTL2 and the film thickness is dTL2, the transfer satisfies the following expressions (1), (2), (5), and (6): Wavelength selective reflection film.
λa = 4nTL1 × dTL1 + 4nTL2 × dTL2 (1)
dH1 = λa / 4nH1 (2)
dH = λa / 4nH (5)
dL = λa / 4nL (6) A reflective layer is provided on a support film having releasability, and the reflective layer includes a high refractive index layer (TH1) having a first heat adhesion property, a laminated low refractive index layer (L1), and a high refractive index layer (L1). 1 to 4 units of a laminate including the refractive index layer (H) and the low refractive index layer (L) as one unit, and a high refractive index layer (TH2) having a second heating adhesiveness in this order, In each laminate, the high refractive index layer (H) is located closer to the laminated low refractive index layer (L1) than the low refractive index layer (L),
The refractive index of the high refractive index layer (TH1) and the high refractive index layer (H) having the first heat adhesion and the high refractive index layer (TH2) having the second heat adhesion is the low refractive index of the laminate. Higher than the refractive index of the layer (L1) and the low refractive index layer (L),
The reflection target wavelength is λa, the refractive index of the first high-refractive-index layer (TH1) having the heat-adhesive property (TH1) is nTH1, the film thickness is dTH1, and the refractive index of the laminated low-refractive-index layer (L1) is nL1. DL1, the refractive index of the high-refractive index layer (H) is nH, the film thickness is dH, the refractive index of the low-refractive index layer (L) is nL, the film thickness is dL, and the second heat adhesion property is provided. When the refractive index of the high refractive index layer (TH2) is nTH2 and the film thickness is dTH2, the transfer satisfies the following formulas (3), (4), (5), and (6): Wavelength selective reflection film.
λa = 4nTH1 × dTH1 + 4nTH2 × dTH2 (3)
dL1 = λa / 4nL1 (4)
dH = λa / 4nH (5)
dL = λa / 4nL (6) (A) a step of heat-treating a layer located on the outermost layer of the wavelength-selective reflective film for transfer according to claim 1 or 2 in close contact with the transfer object; and (b) releasability. A step of peeling the supporting film, and a step of (c) repeating the steps (a) and (b) one or more times using the reflective layer transferred in the steps (a) and (b) as a transfer object. A transfer method comprising: A reflective layer is provided on a support film having releasability, and the reflective layer includes a high refractive index layer (TH1) having a first heat adhesion property, a laminated low refractive index layer (L1), and a first layer. 2 having a high refractive index layer (TH2) having heating adhesiveness in this order, the high refractive index layer (TH1) having first heating adhesiveness and the high refractive index layer having second heating adhesiveness. The refractive index of (TH2) is higher than the refractive index of the laminated low refractive index layer (L1),
The reflection target wavelength is λa, the refractive index of the first high-refractive-index layer (TH1) having the heat-adhesive property (TH1) is nTH1, the film thickness is dTH1, and the refractive index of the laminated low-refractive-index layer (L1) is nL1. Where dL1 is the refractive index of the second high-refractive-index layer (TH2) having the heat adhesion property and the film thickness is dTH2, the following formulas (3) to (4) are satisfied. A step of heat-treating a layer located on the outermost layer of the wavelength-selective reflective film for transfer to be in close contact with the transfer object, (b) a step of peeling the support film having releasability, and (c) Repeating the steps (a) and (b) one or more times using the reflective layer transferred in the steps (a) and (b) as a transfer object,
A transfer method comprising adhering high refractive index layers together.
λa = 4nTH1 × dTH1 + 4nTH2 × dTH2 (3)
dL1 = λa / 4nL1 (4) A transfer molded product formed by the transfer method according to claim 3 or 4 .

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