JP2013208746A - Functional film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a functional film which hardly warps by suppressing a difference in stress between front and back sides.SOLUTION: A functional film (10) has a reflection layer 1, at least one protective layer (a polyester layer 3, an acrylic layer 5) disposed on the light incidence side of the reflection layer 1, and at least one supporting layer (the polyester layer 3, the acrylic layer 5) disposed on the side opposite the light incidence side of the reflection layer 1. The protective layer and the supporting layer are mainly formed of the same material, and have ≥10 μm thickness, respectively.

Description

  The present invention relates to a functional film, and more particularly to a functional film provided with a reflective layer.

In recent years, functional films have been used for various applications. For example, functional films such as antifouling films, protective films, heat shield films, and reflective films (film mirrors) are known.
These functional films are formed by laminating various functional layers according to the application on a substrate such as a resin film.

  For example, a film mirror is known in which an acrylic film, an adhesive layer, a polyester film, a silver layer (reflective layer), and a pressure-sensitive adhesive layer are sequentially laminated (see, for example, Patent Document 1).

Special table 2009-520174

However, in the case of the above-mentioned Patent Document 1, since a plurality of layers having different materials and different thicknesses are laminated, the stress difference between the front and back surfaces of the film mirror generated when the layers are bonded, and the expansion coefficient of each layer at the time of temperature change. Due to differences and stress differences, warping and curling may occur.
In particular, if the thermal barrier film or film mirror provided with a reflective layer for reflecting heat or light is warped or distorted, the reflectivity of the reflective layer decreases, and the functional film functions sufficiently. There was a problem that it could not be made. Further, when the warp is in the direction opposite to the adhesive layer, there is also a problem that the adhesive fixing the film mirror is also peeled off.

  This invention is made | formed in view of the said subject, It is providing the functional film which suppresses the stress difference of the front and back, and is hard to produce a curvature.

In order to solve the above problems, the invention described in claim 1
A reflective layer;
At least one protective layer disposed on the light incident side of the reflective layer;
At least one support layer disposed on the side opposite to the light incident side of the reflective layer;
A functional film having
The protective layer and the support layer are made of the same material and both have a thickness of 10 μm or more.

The invention according to claim 2 is the functional film according to claim 1,
The protective layer and the support layer are polyester materials.

The invention according to claim 3 is the functional film according to claim 1 or 2,
The protective layer and the support layer are polyethylene terephthalate.

The invention according to claim 4 is the functional film according to claim 1,
The protective layer and the support layer are made of an acrylic material.

The invention according to claim 5 is the functional film according to any one of claims 1 to 4,
The protective layer contains an ultraviolet absorber.

Invention of Claim 6 in the functional film as described in any one of Claims 1-5,
At least the protective layer of the protective layer and the support layer includes at least one ultraviolet absorber (A) having a maximum absorption wavelength of 360 to 400 nm and at least one ultraviolet absorber having a maximum absorption wavelength of less than 360 nm. (B) is contained, The ratio of the ultraviolet absorber (A) and an ultraviolet absorber (B) is the range of 1: 1-1: 100, It is characterized by the above-mentioned.

The invention according to claim 7 is the functional film according to any one of claims 1 to 6,
The protective layer is the thickest layer among the plurality of layers disposed on the light incident side of the reflective layer, and the support layer is disposed on the opposite side of the light incident side of the reflective layer. It is characterized by being the thickest layer among the plurality of layers.

The invention according to claim 8 is the functional film according to any one of claims 1 to 7,
The thickness of all the layers including the protective layer laminated on the light incident side of the reflective layer is U (μm), and all the layers including the support layer laminated on the opposite side of the light incident side of the reflective layer The following formula (1) is satisfied, where D is a thickness of D (μm).
| U−D | / U ≦ 2 (1)

The invention according to claim 9 is the functional film according to any one of claims 1 to 8,
When the thickness of the support layer is X (μm) and the thickness of the protective layer is Y (μm), the following formula (2) is satisfied.
| X−Y | / X ≦ 1 (2)

The invention according to claim 10 is the functional film according to any one of claims 1 to 9,
The thickness obtained by subtracting the protective layer from the thickness of all layers on the light incident side of the reflective layer is α (μm), and the thickness of all layers on the side opposite to the light incident side of the reflective layer is β (μm). The following expression (3) is satisfied.
| α−β | / α ≦ 20 (3)

Invention of Claim 11 is a functional film as described in any one of Claims 1-10,
The functional film is a heat shielding film.

Invention of Claim 12 in the functional film as described in any one of Claims 1-10,
The functional film is a film mirror for solar power generation.

  ADVANTAGE OF THE INVENTION According to this invention, the functional film which suppresses the stress difference of front and back, and cannot produce a curvature can be provided.

It is explanatory drawing which shows an example of a structure of the functional film of this invention. It is explanatory drawing which shows an example of a structure of the functional film of this invention. It is explanatory drawing which shows an example of a structure of the functional film of this invention. It is explanatory drawing which shows an example of a structure of the functional film of this invention. It is explanatory drawing which shows an example of a structure of the functional film of this invention. It is explanatory drawing which shows an example of a structure of the functional film of this invention. It is explanatory drawing which shows an example of a structure of the functional film of a comparative example. It is explanatory drawing which shows an example of a structure of the functional film of a comparative example. It is explanatory drawing which shows an example of a structure of the functional film of a comparative example.

  Hereinafter, preferred embodiments for carrying out the present invention will be described with reference to the drawings. However, although various technically preferable limitations for implementing the present invention are given to the embodiments described below, the scope of the invention is not limited to the following embodiments and illustrated examples.

In the functional film of the present invention, both the protective layer and the support layer have a thickness of 10 μm or more. Therefore, the protective layer and the support layer have a certain thickness with respect to the front and back directions of the functional film. Become. Then, the warp generated in the functional film depends on the warp of the protective layer and the support layer.
Under such circumstances, the present invention uses the same material for the protective layer and the support layer, so that both layers have uniform strength against warpage, and a difference in stress during adhesion between the protective layer and the support layer is unlikely to occur. Since the thermal expansion at the time of temperature change can be made the same on both sides, the stress difference at the time of temperature change can be suppressed. If it does so, warp will not arise by the difference of the stress of a protective layer and a support layer, the stress difference of the front and back of a functional film can be suppressed, and the functional film which cannot produce a curvature easily can be provided.
Below, the functional film which concerns on this invention is demonstrated concretely.

(1) Outline of Configuration of Functional Film The functional film of the present invention includes a reflective layer. At least one protective layer is disposed on the light incident side of the reflective layer, and at least one support layer is disposed on the opposite side of the reflective layer from the light incident side. The layers are made of the same material.

Specifically, an example of the functional film 10 is shown in FIG. The example of FIG. 1 includes a reflective layer 1, and four layers of layers are stacked on the light incident side of the reflective layer 1, and four layers are formed on the side opposite to the light incident side of the reflective layer 1. Layers are stacked.
On the light incident side of the functional film 10, a resin layer 2, a polyester layer 3 as a protective layer, an adhesive layer 4, and an acrylic layer 5 as a protective layer are arranged in order from the reflective layer 1 side. Further, on the side opposite to the light incident side of the functional film 10, a resin layer 2, a polyester layer 3 as a support layer, an adhesive layer 4, and an acrylic layer 5 as a support layer are arranged in this order from the reflective layer 1 side. ing.
The functional film 10 includes a polyester layer 3 and an acrylic layer 5 as protective layers, but the thickest acrylic layer 5 among the constituent layers on the light incident side of the reflective layer 1 functions as a protective layer. That's fine. The functional film 10 includes a polyester layer 3 and an acrylic layer 5 as a support layer, but the acrylic layer 5 which is the thickest layer among the constituent layers opposite to the light incident side of the reflective layer 1 supports the functional film 10. It only needs to function as a layer.
For example, the acrylic layer 5 as a protective layer is a layer made of an acrylic film. The acrylic layer 5 as a support layer is a layer made of an acrylic film.

An example of the functional film 20 is shown in FIG. The functional film 20 includes a reflective layer 1, two constituent layers are laminated on the light incident side of the reflective layer 1, and three layers are formed on the opposite side of the reflective layer 1 from the light incident side. The constituent layers are stacked.
On the light incident side of the functional film 20, a resin layer 2 and an acrylic layer 5 as a protective layer are disposed in order from the reflective layer 1 side. Further, on the side opposite to the light incident side of the functional film 20, a resin layer 2, an acrylic layer 5 made of an acrylic film, and an acrylic layer 5 made of an acrylic adhesive are arranged in this order from the reflective layer 1 side. The acrylic layer 5 made of this acrylic film and the acrylic layer 5 made of an acrylic pressure-sensitive adhesive function as a support layer.
For example, the acrylic layer 5 as a protective layer is a layer made of an acrylic film. The acrylic layer 5 as a support layer made of an acrylic pressure-sensitive adhesive is preferably covered with a release sheet 6.

An example of the functional film 30 is shown in FIG. The functional film 30 includes a reflective layer 1, two constituent layers are laminated on the light incident side of the reflective layer 1, and three layers are formed on the opposite side of the reflective layer 1 from the light incident side. The constituent layers are stacked.
On the light incident side of the functional film 30, a resin layer 2 and a polyester layer 3 as a protective layer are disposed in order from the reflective layer 1 side. Further, on the side opposite to the light incident side of the functional film 30, a resin layer 2, a polyester layer 3 as a support layer, and an acrylic layer 5 made of an acrylic pressure-sensitive adhesive are arranged in this order from the reflective layer 1 side.
For example, the polyester layer 3 as the protective layer is a layer made of a polyester film. Moreover, the polyester layer 3 as a support layer is a layer which consists of a polyester film. The acrylic layer 5 made of an acrylic pressure-sensitive adhesive is preferably covered with a release sheet 6.

An example of the functional film 40 is shown in FIG. The functional film 40 includes the reflective layer 1, and three layers are laminated on the light incident side of the reflective layer 1, and two layers are formed on the opposite side of the light incident side of the reflective layer 1. The constituent layers are stacked.
On the light incident side of the functional film 40, a resin layer 2, an adhesive layer 4, and an acrylic layer 5 as a protective layer are disposed in order from the reflective layer 1 side. Further, on the side opposite to the light incident side of the functional film 40, a resin layer 2 and an acrylic layer 5 as a support layer are arranged in order from the reflective layer 1 side.
For example, the acrylic layer 5 as a protective layer is a layer made of an acrylic film. The acrylic layer 5 as a support layer is a layer made of an acrylic film.

An example of the functional film 50 is shown in FIG. The functional film 50 includes the reflective layer 1, and three layers are laminated on the light incident side of the reflective layer 1, and three layers are formed on the side opposite to the light incident side of the reflective layer 1. The constituent layers are stacked.
On the light incident side of the functional film 50, a resin layer 2, an adhesive layer 4, and a polyester layer 3 as a protective layer are arranged in this order from the reflective layer 1 side. Further, on the side opposite to the light incident side of the functional film 50, a resin layer 2, a polyester layer 3 as a support layer, and an acrylic layer 5 made of an acrylic adhesive are disposed in this order from the reflective layer 1 side.
For example, the polyester layer 3 as a protective layer is a layer made of a highly durable polyester film. Moreover, the polyester layer 3 as a support layer is a layer which consists of a polyester film. The acrylic layer 5 made of an acrylic pressure-sensitive adhesive is preferably covered with a release sheet 6.

An example of the functional film 60 is shown in FIG. The functional film 60 includes the reflective layer 1, and three layers are laminated on the light incident side of the reflective layer 1, and three layers are formed on the side opposite to the light incident side of the reflective layer 1. The constituent layers are stacked.
On the light incident side of the functional film 60, a resin layer 2, an adhesive layer 4, and an acrylic layer 5 as a protective layer are disposed in order from the reflective layer 1 side. Further, on the side opposite to the light incident side of the functional film 30, a resin layer 2, a polyester layer 3 as a support layer, and an acrylic layer 5 as a support layer are arranged in order from the reflective layer 1 side.
For example, the acrylic layer 5 as a protective layer is a layer made of an acrylic film. Moreover, the polyester layer 3 as a support layer is a layer which consists of a polyester film.

  In addition, it is possible to substitute the adhesive layer 4 for the resin layer 2 in the functional films 10 to 60 described above, and it is possible to substitute the resin layer 2 for the adhesive layer 4, depending on the material of the protective layer and the support layer. What is necessary is just to use properly.

These functional films include all layers including a protective layer laminated on the light incident side of the reflective layer 1 and all layers including a support layer laminated on the side opposite to the light incident side of the reflective layer 1. It is desirable that the thickness of each be substantially the same. In such a case, the thickness of all layers including the protective layer stacked on the light incident side of the reflective layer is U (μm), and all the layers including the support layer stacked on the opposite side of the light incident side of the reflective layer are included. When the thickness of the layer is D (μm), it is desirable to satisfy the following formula (1).
| U−D | / U ≦ 2 (1)
In addition, if the thicknesses of all layers on the light incident side of the reflective layer 1 and the thicknesses of all layers on the opposite side of the light incident side of the reflective layer 1 are made substantially the same, other than the above constituent layers Other layers (for example, an anchor layer, a corrosion prevention layer, a hard coat layer, etc.) may be provided.
And the functional film provided with the reflection layer can be used as a heat shield film or a film mirror for solar power generation, for example. The thickness of the entire functional film is desirably 75 to 250 μm, and more preferably 100 to 220 μm.

(2) Reflective layer The reflective layer 1 formed in the functional film according to the present invention is a layer made of a metal or the like having a function of reflecting sunlight or heat.
The surface reflectance of the reflective layer 1 is 70% or more, preferably 80% or more in the wavelength range of 2500 nm to 800 nm. Preferably it is 80% or more in the wavelength range of 800 nm-400 nm, More preferably, it is 90% or more. The reflective layer 1 is preferably formed of a material containing any element selected from the element group consisting of Al, Ag, Cr, Cu, Ni, Ti, Mg, Rh, Pt, and Au. Among these, it is preferable that Al or Ag is a main component from the viewpoint of reflectance and corrosion resistance, and two or more such metal thin films may be formed. In the present invention, a silver reflecting layer mainly containing silver is particularly preferable.
Moreover, a layer made of a metal oxide such as SiO ₂ or TiO ₂ may be provided on the reflective layer 1 to further improve the reflectance.
As a method for forming the reflective layer 1 (for example, a silver reflective layer) in the present invention, for example, either a wet method or a dry method can be used.
The wet method is a general term for a plating method or a metal complex solution coating method, and is a method of forming a film by depositing a metal from a solution. Specific examples include silver mirror reaction and silver layer formation by firing of silver complex ink.
On the other hand, the dry method is a general term for a vacuum film forming method, and specifically includes a resistance heating vacuum deposition method, an electron beam heating vacuum deposition method, an ion plating method, an ion beam assisted vacuum deposition method, and a sputtering method. Etc. In particular, a vapor deposition method capable of a roll-to-roll method for continuously forming a film is preferably used in the present invention. That is, the reflective layer 1 in the present invention is preferably formed by silver vapor deposition.
The thickness of the reflective layer 1 is preferably 30 μm or more and 200 μm or less when used as a film mirror for solar power generation, and is preferably 0.1 nm or more and 50 nm or less when used as a heat shielding film.

(3) Resin layer The resin material used for the resin layer 2 is, for example, a material containing any of silicone, acrylic, polyolefin (particularly cycloolefin resin), cellulose, and vinyl chloride from the viewpoint of preventing yellowing due to ultraviolet rays. It is preferable that
Among these, as a material particularly excellent in weather resistance, a silicone resin having a siloxane bond or an acrylic copolymer obtained by copolymerizing at least two or more acrylic monomers can be suitably used.

As the silicone resin, for example, trimethoxysilane (Kanto Chemical), Solgard NP-730 (Nippon Dacro Shamrock), Tosgard 510 (Toshiba Silicone), KP-64 (Shin-Etsu Chemical Co., Ltd.) can be employed.
The main component of such a silicone resin is represented by R _X Si (OR ′) _{4 -X,} where R and R ′ are organic groups such as methyl and ethyl groups, and X is 0 and a natural number.

Specific examples of the acrylic copolymer include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, The main component is one or more monomers selected from monomers having no functional group in the side chain (hereinafter referred to as non-functional monomers) such as alkyl (meth) acrylates such as cyclohexyl methacrylate and 2-ethylhexyl methacrylate. And one or more monomers selected from monomers such as 2-hydroxyethyl methacrylate, glycidyl methacrylate, acrylic acid, methacrylic acid, and itaconic acid. A monomer having a functional group such as OH or COOH (hereinafter referred to as a functional monomer) or a combination of two or more thereof is used for heavy polymerization such as solution polymerization, suspension polymerization, emulsion polymerization, and bulk polymerization. Examples thereof include acrylic copolymers having a weight average molecular weight of 40,000 to 1,000,000, preferably 100,000 to 400,000, obtained by copolymerization by a legal method.
Among them, a non-functional monomer that gives a relatively low Tg polymer such as ethyl acrylate, methyl acrylate, 2-ethylhexyl methacrylate, etc., and a polymer having a relatively high Tg such as methyl methacrylate, isobutyl methacrylate, cyclohexyl methacrylate, etc. An acrylic polymer containing 10 to 50% by mass of the non-functional monomer to be provided and 0 to 10% by mass of a functional monomer such as 2-hydroxyethyl methacrylate, acrylic acid or itaconic acid is most preferable.

Moreover, the cycloolefin resin which can be used suitably for the resin layer 2 in this invention consists of polymer resin containing an alicyclic structure.
A preferred cycloolefin resin is a resin obtained by polymerizing or copolymerizing a cyclic olefin.
Examples of the cyclic olefin include norbornene, dicyclopentadiene, tetracyclododecene, ethyltetracyclododecene, ethylidenetetracyclododecene, tetracyclo [7.4.0.110, 13.02,7] trideca-2,4. Unsaturated hydrocarbons having a polycyclic structure such as 6,11-tetraene and derivatives thereof, cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexene, cyclo Examples thereof include monocyclic unsaturated hydrocarbons such as octene, 3a, 5,6,7a-tetrahydro-4,7-methano-1H-indene, cycloheptene, cyclopentadiene, cyclohexadiene, and derivatives thereof.
Preferred cycloolefin resins may be those obtained by addition copolymerization of monomers other than cyclic olefins. Examples of addition copolymerizable monomers include ethylene, α-olefin such as ethylene, propylene, 1-butene and 1-pentene, 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl- Examples include dienes such as 1,4-hexadiene and 1,7-octadiene.
Examples of the cycloolefin resin include the following norbornene resins. The norbornene-based resin preferably has a norbornene skeleton as a repeating unit. Specific examples thereof include, for example, JP-A Nos. 2003-139950, 2003-14901, and 2003-161832. JP-A 2003-195268, JP-A 2003-111588, JP-A 2003-211589, JP-A 2003-268187, JP-A 2004-133209, JP-A 2004-3091979, JP 2005-121813, JP 2005-164632, JP 2006-72309, JP 2006-178191, JP 2006-215333, JP 2006-268065, JP 2006. -299199 and the like Including without being limited thereto. Moreover, these may be used individually by 1 type and may use 2 or more types together. Specifically, ZEONEX, ZEONOR manufactured by Nippon Zeon Co., Ltd., Arton manufactured by JSR Corporation, APPEL manufactured by Mitsui Chemicals, Inc. (APL8008T, APL6509T, APL6013T, APL5014DP, APL6015T) and the like are preferably used.

In the present invention, the resin layer 2 preferably contains a thermosetting resin or an ultraviolet curable resin.
As the thermosetting resin, acrylate resins such as various epoxy resins, epoxy group-containing (meth) acrylates and urethane-modified (meth) acrylates can be used. Here, examples of the epoxy resin include bisphenol A (BPA) type epoxy resin, bisphenol F (BPF) epoxy resin, and novolac type epoxy resin. Among these thermosetting resins, bisphenol A (BPA) type epoxy resins and bisphenol F (BPF) epoxy resins are suitable.
UV curable resins include methyl acrylate, ethyl acrylate, isopropyl acrylate, isobutyl acrylate, epoxy acrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, trimethylol propane triacrylate, dimethylol tricyclodecane diacrylate, tetramethylene glycol tetraacrylate 2-hydroxy-1,3-diacryloxypropane, 2,2-bis [4- (acryloxymethoxy) phenyl] propane, 2,2-bis [4- (acryloxyethoxy) phenyl] propane, dicyclo Various acrylate resins such as pentenyl acrylate, tricyclodecanyl acrylate, tris (acryloxyethyl) isocyanurate, and the aforementioned thermosetting resins Available epoxy group-containing (meth) acrylate, acrylate resins such as urethane-modified (meth) acrylate. Moreover, these may be used individually by 1 type and may use 2 or more types together. Further, methacrylate may be used instead of such acrylate.
When an ultraviolet curable resin is used, it is necessary to add a photopolymerization initiator. Examples thereof include benzoin ethers such as benzoin ethyl ether and isopropyl benzoin ether, benzyl ketals such as benzylhydroxycyclohexyl phenyl ketone, ketones such as benzophenone and acetophenone and derivatives thereof, thioxanthones, and bisimidazoles. These may be used alone or in combination of two or more. Moreover, you may add sensitizers, such as amines, a sulfur compound, a phosphorus compound, to these photoinitiators in arbitrary ratios as needed.

The thickness of the resin layer 2 is preferably 1 to 50 μm, more preferably 1 to 20 μm.
The resin layer 2 preferably contains at least one of a corrosion inhibitor and an ultraviolet absorber, and may contain an antioxidant.
In particular, the resin layer 2 adjacent to the reflective layer 1 preferably contains a corrosion inhibitor.
The resin layer 2 disposed on the outermost surface of the functional film functions as a hard coat layer that prevents the surface of the functional film from being scratched or soiled, and preferably contains an ultraviolet absorber. .
If the thickness of the resin layer 2 is 1 μm or more, a corrosion inhibitor for preventing bleeding out and protecting the reflective layer 1 from corrosion can be satisfactorily contained. Further, for the purpose of protecting the resin layer 2 itself from ultraviolet rays, an ultraviolet absorber, an antioxidant and the like can be favorably contained.
If the resin layer 2 is 50 μm or less, particularly 20 μm or less, the light absorption and light scattering of the resin layer 2 can be minimized, and the influence of the decrease in reflectance can be kept light.

  This resin layer 2 is formed by a known coating method or coating method. In the present invention, conventionally known coating methods such as gravure coating, reverse coating, and die coating can be applied. Thereby, the resin layer 2 with a uniform film thickness can be easily formed.

(4) Adhesive layer The adhesive layer 4 formed in the functional film according to the present invention is not particularly limited as long as it has a function of improving the adhesion between the polyester layer 3 and the acrylic layer 5. Therefore, the adhesive layer 4 needs to have adhesiveness and smoothness for closely attaching the polyester layer 3 and the acrylic layer 5.
The thickness of the adhesive layer 4 is preferably 0.01 to 20 μm, more preferably 0.1 to 10 μm, from the viewpoints of adhesion, smoothness, the reflectance of the reflective layer 1 and the like.
When the adhesive layer 4 is a resin, there is no particular limitation as long as it satisfies the above conditions of adhesion and smoothness, polyester resin, acrylic resin, melamine resin, epoxy resin, polyamide resin, Single or mixed resins such as vinyl chloride resins and vinyl chloride vinyl acetate copolymer resins can be used. From the viewpoint of weather resistance, a mixed resin of a polyester resin and a melamine resin is preferable, and a thermosetting resin in which a curing agent such as isocyanate is further mixed is more preferable. As a method for forming the adhesive layer 4, a conventionally known coating method such as a gravure coating method, a reverse coating method, a die coating method or the like can be used.
When the adhesive layer 4 is a metal oxide, for example, silicon oxide, aluminum oxide, silicon nitride, aluminum nitride, lanthanum oxide, lanthanum nitride, or the like formed by various vacuum film forming methods can be used. For example, a resistance heating vacuum deposition method, an electron beam heating vacuum deposition method, an ion plating method, an ion beam assisted vacuum deposition method, or a sputtering method can be used as a method for forming the adhesive layer 7 (film formation method).

(5) Support layer, protective layer The support layer of the present invention is disposed at least one layer on the side opposite to the light incident side of the reflective layer, and has a role of supporting the reflective layer of the functional film, and is 10 μm or more. It has the thickness of. For example, among the plurality of layers disposed on the side opposite to the light incident side of the reflective layer, the thickest layer among the plurality of layers disposed on the side opposite to the light incident side of the reflective layer is A support layer is desirable. The material is preferably polyester or acrylic.
The protective layer of the present invention is disposed at least one layer on the light incident side of the reflective layer, has a role of protecting the reflective layer of the functional film from the outside, and has a thickness of 10 μm or more. For example, among the plurality of layers arranged on the light incident side of the reflective layer, the thickest layer is preferably the protective layer, and the material is preferably polyester or acrylic.
Furthermore, it is desirable that the protective layer and the support layer are formed of the same material. Further, it is desirable that the protective layer and the support layer have substantially the same thickness. In this case, when the thickness of the support layer is X (μm) and the thickness of the protective layer is Y (μm), it is desirable to satisfy the following formula (2).
| X−Y | / X ≦ 1 (2)
In addition, at least the protective layer of the protective layer and the support layer includes at least one ultraviolet absorber (A) having a maximum absorption wavelength of 360 to 400 nm and at least one ultraviolet absorber having a maximum absorption wavelength of less than 360 nm ( It is desirable to contain the ultraviolet absorber composition which consists of B).

(5-1) Polyester layer As an example of a preferable material for the protective layer and the support layer, a polyester layer will be described below.
The polyester layer 3 disposed on the light incident side of the reflective layer 1 can function as a protective layer, and the polyester layer 3 disposed on the side opposite to the light incident side of the reflective layer 1 functions as a support layer. Can do. This is because when the polyester layer 3 is applied to the protective layer, the polyester layer 3 is also applied to the support layer when the protective layer and the support layer are mainly composed of the same material.

The polyester layer 3 is made of a polyester material and preferably contains an ultraviolet absorber.
Polyester materials that can be used for the polyester layer 3 include polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polytetramethylene terephthalate, polyhexamethylene. There are terephthalates, among which polyethylene terephthalate (PET) is preferred.
Among polyethylene terephthalate (PET), it is particularly preferable to use highly durable PET. The highly durable PET referred to in the present invention is polyethylene terephthalate (PET) with enhanced light resistance as compared with ordinary polyethylene terephthalate (PET). Desirable is PET containing a specific ultraviolet absorber. It is excellent in manufacturing suitability when kneading a UV absorber into a polymer or dissolved in a solvent, and does not cause precipitation of the UV absorber or bleed out due to long-term use. There is an effect that it is maintained for a long period and is excellent in light resistance (fastness to ultraviolet light). Moreover, since highly durable PET has the outstanding light resistance, it can be used as a protective material of the building material used outdoors, a solar reflective mirror, and the panel for photovoltaic power generation. In addition, since it has excellent long-wave ultraviolet absorption ability, it can be used as a filter, packaging material, container, paint, coating film, building material, etc., which protects the contents that are sensitive to ultraviolet rays, and is a compound that is unstable to light. Decomposition can also be suppressed. Particularly useful ultraviolet absorbers used for high durability PET will be described later. It is desirable that at least the protective layer is made of high durability PET, such as PET as a support layer and high durability PET as a protective layer.

  Hereinafter, the polyester will be described. Polyesters used in the present invention include, as monomer components, the following dicarboxylic acids and their acid halides or dicarboxylic acids composed of polyvalent carboxylic acids and diols or their acid halides: adipic acid, speric acid, azelaic acid, sebacin Acid, dodecanedioic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, ethyl succinic acid, pimelic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, 2-methylsuccinic acid, 2-methyladipic acid, 3-methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid, dimer acid, hydrogenated dimer acid, 1,2- And 1,3-cyclopentanedicarboxylic acid, 1,2-, 1,3-, 1,4-cyclohexanedicar Aliphatic acids such as acid, cycloaliphatic, phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyl Dicarboxylic acid, 2-methylisophthalic acid, 3-methylphthalic acid, 2-methylterephthalic acid, 2,4,5,6-tetramethylisophthalic acid, 3,4,5,6-tetramethylphthalic acid, 2-chloroterephthalic acid Acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, 2,6-naphthalenedicarboxylic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, 3-chloroisophthalic acid, 3-methoxyisophthalic acid 2-fluoroisophthalic acid, 3-fluorophthalic acid, 2-fluoroterephthalic acid, , 4,5,6-tetrafluoroisophthalic acid, 3,4,5,6-tetrafluorophthalic acid, 4,4'-oxybisbenzoic acid, 3,3'-oxybisbenzoic acid, 3,4'-oxybisbenzoic acid Acid, 2,3′-oxybisbenzoic acid, 4,4′-oxybisoctafluorobenzoic acid, 3,3′-oxybisoctafluorobenzoic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid 4,4′-biphenyldicarboxylic acid, 4,4′-diphenylethercarboxylic acid, and the like.

Examples of polycarboxylic acids other than dicarboxylic acids include ethanetricarboxylic acid, propanetricarboxylic acid, butanetetracarboxylic acid, pyromellitic acid, trimellitic acid, trimesic acid, 3,4,3 ′, 4′-biphenyltetracarboxylic acid Examples include acids. Regarding the polyester used in the present invention, among these dicarboxylic acid and polycarboxylic acid components, adipic acid, malonic acid, succinic acid, terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 2, 5-Naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and trimellitic acid are preferably used. Terephthalic acid, isophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalene It is particularly preferred to use a dicarboxylic acid. Examples of diols include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol, triethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 1,4-butylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2- Cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediethanol, 1,10-decamethylene glycol, 1,12-dodecanediol, polyethylene glycol, poly Aliphatic glycols exemplified by rimethylene glycol and polytetramethylene glycol, hydroquinone, 4,4′-dihydroxybisphenol, 1,4-bis (β-hydroxyethoxy) benzene, 1,4-bis (β-hydroxyethoxy) Phenyl) sulfone, bis (p-hydroxyphenyl) ether, bis (p-hydroxyphenyl) sulfone, bis (p-hydroxyphenyl) methane, 1,2-bis (p-hydroxyphenyl) ethane, bisphenol A, bisphenol C, Aromatic glycols exemplified by 2,5-naphthalenediol, glycols obtained by adding ethylene oxide to these glycols, and the like can be mentioned. For the polyester used in the present invention, among these diol components, it is preferable to use ethylene glycol, 1,3-propylene glycol, diethylene glycol, neopentyl glycol, hydroquinone, 4,4′-dihydroxybisphenol, bisphenol A, and ethylene. It is particularly preferred to use glycol, 4,4′-dihydroxybisphenol.
That is, a preferable monomer combination and polymer in the polyester used in the present invention are terephthalic acid as the dicarboxylic acid component, polyethylene terephthalate using ethylene glycol as the diol component, terephthalic acid as the dicarboxylic acid component, and 1,4-butylene glycol as the diol component. And poly (butylene terephthalate) using 2,6-naphthalenedicarboxylic acid as the dicarboxylic acid component and polyethylene naphthalate using ethylene glycol as the diol component.

  The polyester material used for the polyester layer 3 may be a polyester film previously formed into a film shape or a sheet shape, and a liquid containing a high molecular weight saturated copolyester resin or an unsaturated polyester resin is predetermined. You may use what is coated on the layer of this and solidified in the sheet form.

  In the present invention, the support layer and the protective layer are made of the same material. For example, if the support layer and the protective layer are polyester materials, for example, the support layer is polyethylene terephthalate (PET) and the protective layer is also polyethylene terephthalate. The case where it is (PET) or the case where the support layer is polytrimethylene terephthalate (PTT) and the protective layer is polytrimethylene terephthalate (PTT). Therefore, the support layer is polyethylene terephthalate (PET) and the protective layer is not included such as polytrimethylene terephthalate (PTT). However, when polyethylene terephthalate (PET) and the protective layer are high durability polyethylene terephthalate (PET) and the difference is an additive such as an ultraviolet absorber, they are regarded as the same material.

(5-2) Acrylic layer As an example of this preferable material for the protective layer and the support layer, an acrylic layer is described below. The acrylic layer 5 disposed on the light incident side of the reflective layer 1 can function as a protective layer, and the acrylic layer 5 disposed on the side opposite to the light incident side of the reflective layer 1 functions as a support layer. Can do. This is because the protective layer and the support layer are mainly composed of the same material, and therefore when the acrylic layer 5 is applied to the protective layer, the acrylic layer 5 is also applied to the support layer.

The acrylic layer 5 is mainly composed of an acrylic material and preferably contains an ultraviolet absorber.
The acrylic material that can be used for the acrylic layer 5 is preferably a material mainly composed of a methacrylic resin. The methacrylic resin is a polymer mainly composed of a methacrylic acid ester, and may be a homopolymer of the methacrylic acid ester. A copolymer may also be used. Here, as the methacrylic acid ester, an alkyl ester of methacrylic acid is usually used. A particularly preferred methacrylic resin is polymethyl methacrylate resin (PMMA).

  The preferred monomer composition of the methacrylic resin is 50 to 100% by weight of methacrylic acid ester, 0 to 50% by weight of acrylic acid ester, and 0 to 49% by weight of other monomers based on all monomers. More preferably, the methacrylic acid ester is 50 to 99.9% by weight, the acrylic acid ester is 0.1 to 50% by weight, and other monomers are 0 to 49% by weight.

Here, examples of the alkyl methacrylate include methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and the like. The alkyl group usually has 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. It is. Of these, methyl methacrylate is preferably used.
Examples of alkyl acrylates include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and the like. The alkyl group usually has 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. is there.

  The monomer other than alkyl methacrylate and alkyl acrylate may be a monofunctional monomer, that is, a compound having one polymerizable carbon-carbon double bond in the molecule, or a polyfunctional monofunctional monomer. Although it may be a monomer, that is, a compound having at least two polymerizable carbon-carbon double bonds in the molecule, a monofunctional monomer is preferably used. Examples of this monofunctional monomer include aromatic alkenyl compounds such as styrene, α-methylstyrene and vinyltoluene, and alkenyl cyan compounds such as acrylonitrile and methacrylonitrile. Examples of polyfunctional monomers include polyunsaturated carboxylic acid esters of polyhydric alcohols such as ethylene glycol dimethacrylate, butanediol dimethacrylate, trimethylolpropane triacrylate, allyl acrylate, allyl methacrylate, and cinnamon. Alkenyl esters of unsaturated carboxylic acids such as allyl acids, polyalkenyl esters of polybasic acids such as diallyl phthalate, diallyl maleate, triallyl cyanurate, triallyl isocyanurate, aromatic polyalkenyl compounds such as divinylbenzene, etc. Can be mentioned.

  In addition, you may use 2 or more types of said alkyl methacrylate, alkyl acrylate, and monomers other than these as needed.

The methacrylic resin preferably has a glass transition temperature of 40 ° C. or higher, more preferably 60 ° C. or higher, from the viewpoint of heat resistance of the film. This glass transition temperature can be appropriately set by adjusting the type of monomer and the ratio thereof.
The methacrylic resin can be prepared by polymerizing the monomer component by a method such as suspension polymerization, emulsion polymerization or bulk polymerization. At that time, in order to obtain a suitable glass transition temperature or to obtain a viscosity showing a formability to a suitable film, it is preferable to use a chain transfer agent during the polymerization. The amount of the chain transfer agent may be appropriately determined according to the type of monomer and the ratio thereof.

The acrylic material used for the acrylic layer 5 may be an acrylic film previously formed into a film shape or a sheet shape, or a liquid containing an acrylic resin is coated on a predetermined layer and solidified into a sheet shape. What is formed may be used.
Moreover, what is necessary is just to coat the acrylic adhesive containing an acrylic resin on a predetermined | prescribed layer, when forming the acrylic adhesive layer which has adhesiveness which makes it possible to bond a functional film to a support base material. .

Examples of the acrylic pressure-sensitive adhesive material include a pressure-sensitive adhesive containing an acrylic polymer as a base polymer (main component). The acrylic polymer is a monomer component mainly composed of an alkyl (meth) acrylate having an alkyl group having 2 to 18 carbon atoms. An acrylic polymer is preferred. Examples of the alkyl (meth) acrylate having an alkyl group having 2 to 18 carbon atoms include ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec -Butyl (meth) acrylate, t-butyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isononyl (meth) acrylate, dodecyl (meth) acrylate, iso Examples include stearyl (meth) acrylate. 1 type (s) or 2 or more types are used for this alkyl (meth) acrylate. In the acrylic polymer, a copolymerizable monomer may be used as a monomer component together with the alkyl (meth) acrylate having an alkyl group having 2 to 18 carbon atoms. Examples of such copolymerizable monomers include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, and crotonic acid; 2-hydroxyethyl (meth) acrylate, (Meth) acrylic acid 2-hydroxypropyl, (meth) acrylic acid 4-hydroxybutyl, (meth) acrylic acid 6-hydroxyhexyl, (meth) acrylic acid 8-hydroxyoctyl, (meth) acrylic acid 10-hydroxydecyl, Hydroxyl group-containing monomers such as (meth) acrylic acid 12-hydroxylauryl and (4-hydroxymethylcyclohexyl) -methyl acrylate; acid anhydride monomers such as maleic anhydride and itaconic anhydride; 2-acrylamido-2-methylprop Sulfonic acid, sulfopropyl acrylate the acrylic polymer, as a monomer component, with an alkyl (meth) acrylates having a number 2 to 18 alkyl group carbon, copolymerizable monomers may be used. Examples of such copolymerizable monomers include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, and crotonic acid; 2-hydroxyethyl (meth) acrylate, (Meth) acrylic acid 2-hydroxypropyl, (meth) acrylic acid 4-hydroxybutyl, (meth) acrylic acid 6-hydroxyhexyl, (meth) acrylic acid 8-hydroxyoctyl, (meth) acrylic acid 10-hydroxydecyl, Hydroxyl group-containing monomers such as (meth) acrylic acid 12-hydroxylauryl and (4-hydroxymethylcyclohexyl) -methyl acrylate; acid anhydride monomers such as maleic anhydride and itaconic anhydride; 2-acrylamido-2-methylprop Sulfonic acid group-containing monomers such as sulfonic acid and sulfopropyl acrylate; Phosphoric acid group-containing monomers such as 2-hydroxyethylacryloyl phosphate; Amide monomers such as N-substituted (meth) acrylamides such as (meth) acrylamide and N-methylolacrylamide Succinimide monomers such as N- (meth) acryloyloxymethylene succinimide, N- (meth) acryloyl-6-oxyhexamethylene succinimide, N- (meth) acryloyl-8-oxyoctamethylene succinimide; vinyl acetate, N-vinyl Vinyl monomers such as pyrrolidone, N-vinylcarboxylic acid amides, styrene and N-vinylcaprolactam; Cyanoacrylate monomers such as acrylonitrile and methacrylonitrile; (meth) acrylic Acrylic acid ester monomers such as glycidyl, tetrahydrofurfuryl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, fluorine (meth) acrylate, silicone (meth) acrylate, 2-methoxyethyl acrylate; methyl Examples include alkyl (meth) acrylates having an alkyl group different from alkyl (meth) acrylates constituting the main component such as (meth) acrylate and octadecyl (meth) acrylate; alicyclic acrylates such as isobornyl (meth) acrylate, and the like. . Among these, a hydroxyl group-containing monomer and a carboxyl group-containing monomer are preferable, and acrylic acid is particularly preferable. One or two or more copolymerizable monomers can be used.
The acrylic pressure-sensitive adhesive is a monomer mixture based on an alkyl (meth) acrylate having an alkyl group having 2 to 18 carbon atoms (that is, an alkyl (meth) acrylate having an alkyl group having 2 to 18 carbon atoms, or , A mixture of an alkyl (meth) acrylate having a C 2-18 alkyl group and a copolymerizable monomer) or a partial polymer thereof, a polyfunctional (meth) acrylate and a polymerization initiator are further blended A polymer obtained by polymerizing the composition is particularly preferable.
In the production method of the present invention, the polymerization initiator is preferably a thermal polymerization initiator. Examples of the thermal polymerization initiator include 2,2′-azobisisobutyronitrile and 2,2′-azobis-2-methylbutyrate. Ronitrile, 2,2′-azobis (2-methylpropionic acid) dimethyl, 4,4′-azobis-4-cyanovaleric acid, azobisisovaleronitrile, 2,2′-azobis (2-amidinopropane) dihydro Chloride, 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis (2-methylpropionamidine) disulfate, 2,2 ′ -Azo-based thermal polymerization initiators such as azobis (N, N'-dimethyleneisobutylamidine) dihydrochloride; dibenzoyl peroxide, tert-butylpermaleate, etc. Peroxide thermal polymerization initiators; and redox thermopolymerization initiators. The amount of the thermal polymerization initiator used is not particularly limited as long as it can be conventionally used as a thermal polymerization initiator.
The adhesive strength of the acrylic adhesive layer is 5 N / 25 mm or more (preferably 10 N / 25 mm or more). If the adhesive force at the interface with the supporting substrate is smaller than 5 N / 25 mm, it is not preferable because spontaneous peeling may occur at the interface between the layers.

The laminating method for forming the acrylic pressure-sensitive adhesive layer on the support layer is not particularly limited, and for example, it is preferable to continuously perform the roll-to-roll method from the viewpoint of economy and productivity.
In particular, it is desirable that the acrylic adhesive layer contains an ultraviolet absorber.
When the acrylic pressure-sensitive adhesive layer contains an ultraviolet absorber, it is possible to prevent photodegradation at the interface with the support base material on the lower layer side of the acrylic pressure-sensitive adhesive layer.
In other words, when exposed to UV light in an outdoor environment, the deterioration of the interface with the support substrate on the lower layer side of the acrylic adhesive layer is prevented, and the light reflecting surface of the silver reflecting layer is improved by suppressing the occurrence of peeling. It is possible to increase the power generation efficiency per mirror unit area because more sunlight can be reflected.

In the present invention, the term “support layer and protective layer are made of the same material” means that, for example, an acrylic material, the support layer is a polymethyl methacrylate resin and the protective layer is also a polymethyl methacrylate resin. Further, the same applies when the support layer is a polymethyl methacrylate resin and the protective layer is a polymethyl methacrylate resin containing an additive such as an ultraviolet absorber.
As another example, the support layer is a copolymer of methyl methacrylate and methyl acrylate, and the protective layer is a copolymer of methyl methacrylate-alkyl acrylate and a copolymer of methyl methacrylate-alkyl acrylate-styrene. This is a case of a mixture.
In the case of a mixture of acrylic acid-alkyl acrylate copolymer and methacrylic acid alkyl ester-acrylic acid alkyl ester-acrylic acid copolymer, the acrylic adhesive layer can be said to be composed of the same material.
The advantage of using the same material is that the coefficients of thermal expansion are close, and if the difference in coefficient of thermal expansion (/ ° C.) in the temperature range of 25 ° C. to 100 ° C. is Δα, the following formula is preferably satisfied.
Δα ≦ 5 × 10 ^ (-6)

(5-3) Ultraviolet Absorber It is desirable that at least the protective layer (polyester layer 3, acrylic layer 5) of the protective layer and the support layer contains an ultraviolet absorber. In particular, in the present invention, ultraviolet absorption comprising at least one ultraviolet absorber (A) having a maximum absorption wavelength of 360 to 400 nm and at least one ultraviolet absorber (B) having a maximum absorption wavelength of less than 360 nm. It is desirable for the ratio of the ultraviolet absorber (A) and the ultraviolet absorber (B) to be in the range of 1: 1 to 1: 100.

Among the protective layer and the support layer, at least the protective layer (polyester layer 3, acrylic layer 5) is composed of an ultraviolet absorber (A) having a maximum absorption wavelength of 360 to 400 nm and an ultraviolet absorber (B) having a maximum absorption wavelength of less than 360 nm. It is desirable to contain the ultraviolet absorber composition which contains at least 1 or more types each. Preferably, the number of ultraviolet absorbers (A) is two or less, and the case where only one type is particularly preferred. The number of ultraviolet absorbers (B) is preferably two or less, and particularly preferably one.
The mixing ratio of the ultraviolet absorber (A) and the ultraviolet absorber (B) is not particularly limited, but is preferably 1: 1 to 1: 100, more preferably 1: 2 to 1:50. Preferably it is 1: 3 to 1:25, and an ultraviolet absorber (A) is used supplementarily. In this case, the mixing ratio is expressed as a mass ratio. Here, “auxiliary used” means that the ultraviolet absorber (B) is mainly used, and the ultraviolet absorber (A) is used in the same amount or less. is there.
Moreover, from the solubility point of the ultraviolet absorber (A) and the ultraviolet absorber (B), an amide solvent, a sulfone solvent, a sulfoxide solvent, a ureido solvent, an ether solvent, a ketone solvent, a halogen solvent, It is preferable to use a hydrocarbon solvent, an alcohol solvent, an ester solvent, or a nitrile solvent.

［Ｈｅｔ¹は、２価の５あるいは６員環の芳香族ヘテロ環残基を表す。また、該芳香族ヘテロ環残基は置換基を有していても良い。
Ｘ^a、Ｘ^b、Ｘ^c及びＸ^dは、互いに独立してヘテロ原子を表す。また、Ｘ^a〜Ｘ^dは置換基を有していても良い。
Ｙ^a、Ｙ^b、Ｙ^c、Ｙ^d、Ｙ^e及びＹ^fは、互いに独立してヘテロ原子または炭素原子を表す。また、Ｙ^a〜Ｙ^fは置換基を有していても良い。
Ｈｅｔ¹に結合している環は、任意の位置に二重結合を有していても良い。］ (5-3-1) Ultraviolet absorber (A)
The ultraviolet absorber (A) is an ultraviolet absorber having a maximum absorption wavelength of 360 to 400 nm, and is preferably an ultraviolet absorber made of a compound represented by the following general formula (1).

[Het ¹ represents a divalent 5- or 6-membered aromatic heterocyclic residue. The aromatic heterocyclic residue may have a substituent.
X ^a , X ^b , X ^c and X ^d each independently represent a hetero atom. X ^{a to} X ^d may have a substituent.
Y ^a , Y ^b , Y ^c , Y ^d , Y ^e and Y ^f each independently represent a hetero atom or a carbon atom. Y ^{a to} Y ^f may have a substituent.
The ring bonded to Het ¹ may have a double bond at any position. ]

In the above general formula (1), Het ¹ represents a divalent 5- or 6-membered aromatic heterocyclic residue having at least one hetero atom. Het ¹ may be condensed.
Examples of the hetero atom include a boron atom, a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom, a sulfur atom, a selenium atom, and a tellurium atom. A hetero atom is preferably a nitrogen atom, an oxygen atom, or a sulfur atom. More preferably, they are a nitrogen atom and a sulfur atom. Particularly preferred is a sulfur atom. When two or more hetero atoms are present, they may be the same atom or different atoms.
Examples of the aromatic heterocyclic ring in which two hydrogen atoms are added to a divalent aromatic heterocyclic residue include pyrrole, pyrazole, imidazole, 1,2,3-triazole, 1,2,4-triazole, pyridine, pyridazine, Examples include pyrimidine, pyrazine, 1,3,5-triazine, furan, thiophene, oxazole, isoxazole, thiazole, isothiazole, 1,2,3-oxadiazole, 1,3,4-thiadiazole and the like. Preferred examples of the aromatic heterocycle include pyrrole, pyridine, furan and thiophene. More preferred are pyridine and thiophene. Particularly preferred is thiophene. Any position for removing the hydrogen atom of the aromatic heterocycle may be used. For example, the bonding positions in the hetero 5-membered ring compound pyrrole include the 2,3-position, 2,4-position, 2,5-position, 3,4-position, and 3,5-position. In addition, the bonding positions in the hetero 6-membered ring compound pyridine include the 2,3 position, 2,4 position, 2,5 position, 2,6 position, 3,4 position, 3,5 position and 3,6 position. It is done.

In addition, the aromatic heterocyclic residue may have a substituent. A monovalent substituent is mentioned as a substituent. Examples of the monovalent substituent (hereinafter referred to as R) include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), an alkyl group having 1 to 20 carbon atoms (for example, methyl and ethyl), and a carbon number of 6 To 20 aryl groups (eg phenyl, naphthyl), cyano groups, carboxyl groups, alkoxycarbonyl groups (eg methoxycarbonyl), aryloxycarbonyl groups (eg phenoxycarbonyl), substituted or unsubstituted carbamoyl groups (eg carbamoyl, N- Phenylcarbamoyl, N, N-dimethylcarbamoyl), alkylcarbonyl group (eg acetyl), arylcarbonyl group (eg benzoyl), nitro group, substituted or unsubstituted amino group (eg amino, dimethylamino, anilino), acylamino group ( For example, acetamide, ethoxy Rubonylamino), sulfonamide group (eg methanesulfonamide), imide group (eg succinimide, phthalimide), imino group (eg benzylideneamino), hydroxy group, alkoxy group having 1 to 20 carbon atoms (eg methoxy), aryloxy group (Eg phenoxy), acyloxy groups (eg acetoxy), alkylsulfonyloxy groups (eg methanesulfonyloxy), arylsulfonyloxy groups (eg benzenesulfonyloxy), sulfo groups, substituted or unsubstituted sulfamoyl groups (eg sulfamoyl, N- Phenylsulfamoyl), alkylthio group (eg methylthio), arylthio group (eg phenylthio), alkylsulfonyl group (eg methanesulfonyl), arylsulfonyl group (eg benze) Sulfonyl), and the like Hajime Tamaki having 6 to 20 carbon atoms (e.g. pyridyl, morpholino). Further, the substituent may be further substituted, and when there are a plurality of substituents, they may be the same or different. In that case, the above-mentioned monovalent substituent R can be mentioned as an example of a substituent. Moreover, you may combine with substituents and may form a ring.
Preferred examples of the substituent include an alkyl group, an alkoxy group, and an aryl group. An alkyl group and an aryl group are more preferable, and an alkyl group is particularly preferable.

X ^a , X ^b , X ^c and X ^d each independently represent a hetero atom. Examples of the hetero atom include a boron atom, a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom, a sulfur atom, a selenium atom, and a tellurium atom. A hetero atom is preferably a nitrogen atom, an oxygen atom, or a sulfur atom. More preferably, they are a nitrogen atom and an oxygen atom. X ^{a to} X ^d may have a substituent. Examples of the substituent include the examples of the monovalent substituent R described above.

Y ^a , Y ^b , Y ^c , Y ^d , Y ^e and Y ^f each independently represent a hetero atom or a carbon atom. Examples of the atoms constituting Y ^{a to} Y ^f include a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom. The atoms constituting Y ^{a to} Y ^f are preferably a carbon atom, a nitrogen atom and an oxygen atom, and more preferably a carbon atom and a nitrogen atom. More preferred is a carbon atom, and particularly preferred is a case where all represent a carbon atom. In addition, the atoms may be substituted, the substituents may be bonded to each other to form a ring, or may be further condensed. Examples of the substituent include the examples of the monovalent substituent R described above.

The ring formed by X ^a , X ^b , Y ^{a to} Y ^c and a carbon atom and the ring formed by X ^c , X ^d , Y ^{d to} Y ^f and a carbon atom (represented by the above Het ¹ ) At least one of the two rings bonded to the aromatic heterocyclic residue is preferably condensed. Moreover, it is preferable that at least one of the two rings is not a perimidine ring.

(5-3-2) Ultraviolet absorber (B)
The ultraviolet absorber (B) is an ultraviolet absorber having a maximum absorption wavelength of less than 360 nm. Preferably, the maximum absorption wavelength is 355 nm or less, and more preferably 350 nm or less.

  The ultraviolet absorber (B) may have any structure as long as it satisfies the condition that the maximum absorption wavelength is less than 360 nm. For example, benzotriazole, triazine, benzophenone, merocyanine, cyanine, dibenzoylmethane, cinnamic acid, acrylate, benzoate oxalate diamide, form, known as UV absorber structure Examples include amidine-based compounds and benzoxazinone-based compounds. Of these, benzotriazole, triazine, benzophenone, dibenzoylmethane, formamidine, and benzoxazinone compounds are preferred, and benzotriazole, triazine, benzophenone, and benzoxazinone compounds are further preferred. preferable. Most preferred are benzoxazinone compounds. These UV absorbers are, for example, Fine Chemicals, May 2004, pages 28-38, published by Toray Research Center, Research and Research Department, “New Development of Functional Additives for Polymers” (Toray Research Center, 1999) 96- 140 pages, supervised by Shinichi Daikatsu, “Development of Polymer Additives and Environmental Measures” (CMC Publishing Co., Ltd., 2003), pages 54-64, published by Technical Information Association, “Polymer degradation / discoloration mechanism and its stabilization "Technology-Know-how" (Technical Information Association, 2006).

(5-3-3)
Here, an ultraviolet absorber useful particularly when used for highly durable PET will be described.

(In General Formula (2), X ¹ and X ² each independently represent an oxygen atom, a sulfur atom or —NR ¹⁶ —, and R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are Each independently represents a hydrogen atom or a monovalent substituent.)

The compound represented by the general formula (2) is a merocyanine dye having an isoxazolone skeleton as an acidic heterocycle (herein, the acidic heterocycle is, for example, “The Theory of the "Photographic Process", 4th edition, Macmillan Publishers, 1977, page 197. The merocyanine pigments used here are, for example, Nobu Okawara, Ken Matsuoka, Tsuneaki Hirashima, Kei Kitao Jiro, “Functional dyes”, Kodansha Scientific Co., 1992, p. 52.)
The compound represented by the general formula (2) is known as a sensitizing dye in a photosensitive composition such as a printing material (see, for example, JP-A-3-54566). However, the usefulness as an ultraviolet absorber has not been reported, and it has not been imagined that the compound represented by the general formula (2) exhibits particularly excellent performance as a long wave ultraviolet absorbing material.

In the general formula (2), X ¹ and X ² each independently represent an oxygen atom, a sulfur atom or —NR ¹⁶ —. R ¹⁶ represents a hydrogen atom or a monovalent substituent.
Preferably, X ¹ and X ² are each independently a sulfur atom or —NR ¹⁶ —, and it is particularly preferred that both X ¹ and X ² are sulfur atoms.

R ¹⁶ is preferably a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, more preferably a substituted or unsubstituted C 1 to 20 carbon atom. An alkyl group, particularly preferably a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms.

In the general formula (2), R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or a monovalent substituent. These substituents are not particularly limited, but typical examples include halogen atoms, aliphatic groups [saturated aliphatic groups (alkyl groups, cycloalkyl groups, bicycloalkyl groups, bridged cyclic saturated hydrocarbon groups or spiro saturated hydrocarbons. A cyclic saturated aliphatic group containing a group), an unsaturated aliphatic group (a chain unsaturated aliphatic group having a double bond or a triple bond, such as an alkenyl group or an alkenyl group, or a cycloalkenyl group, bicyclo An alkenyl group, a cyclic unsaturated aliphatic group including a bridged cyclic unsaturated hydrocarbon group or a spiro unsaturated hydrocarbon group)], an aryl group (preferably a phenyl group which may have a substituent), hetero A ring group (preferably, the ring-constituting atom is a 5- to 8-membered ring containing an oxygen atom, a sulfur atom or a nitrogen atom, and may be condensed with an alicyclic ring, an aromatic ring or a heterocyclic ring), Group, aliphatic oxy group (typically alkoxy group), aryloxy group, acyloxy group, carbamoyloxy group, aliphatic oxycarbonyloxy group (typically alkoxycarbonyloxy group), aryloxycarbonyloxy group, amino group [aliphatic An amino group (typically an alkylamino group), an anilino group and a heterocyclic amino group], an acylamino group, an aminocarbonylamino group, an aliphatic oxycarbonylamino group (typically an alkoxycarbonylamino group), an aryloxycarbonylamino group, Sulfamoylamino group, aliphatic (typically alkyl) or arylsulfonylamino group, aliphatic thio group (typically alkylthio group), arylthio group, sulfamoyl group, aliphatic (typically alkyl) or aryl Sulfinyl group, aliphatic (typically alkyl) or arylsulfonyl group, acyl group, aryloxycarbonyl group, aliphatic oxycarbonyl group (typically alkoxycarbonyl group), carbamoyl group, aryl or heterocyclic azo group, imide group, fat Group oxysulfonyl groups (typically alkoxysulfonyl groups), aryloxysulfonyl groups, hydroxyl groups, nitro groups, carboxyl groups, and sulfo groups, and each group further has a substituent (for example, the substituents mentioned here). You may have.

Below, the substituent of the ^{R 12, R 13, R 14} , R 15 and R ^16, a further ^{R 12, R 13, R 14} , R 15 and substituent that may be substituted in each substituent of R ¹⁶ This will be described in more detail.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Of these, a chlorine atom and a bromine atom are preferable, and a chlorine atom is particularly preferable.

  The aliphatic group is a linear, branched, or cyclic aliphatic group. As described above, the saturated aliphatic group includes an alkyl group, a cycloalkyl group, and a bicycloalkyl group, and has a substituent. May be. These carbon numbers are preferably 1-30. Examples of alkyl groups are methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, benzyl and 2-ethylhexyl. Can be mentioned. Here, the cycloalkyl group includes a substituted or unsubstituted cycloalkyl group. The substituted or unsubstituted cycloalkyl group is preferably a cycloalkyl group having 3 to 30 carbon atoms. Examples include a cyclohexyl group, a cyclopentyl group, and a 4-n-dodecylcyclohexyl group. Examples of the bicycloalkyl group include a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms. Examples include a bicyclo [1.2.2] heptan-2-yl group and a bicyclo [2.2.2] octan-3-yl group. Further, it includes a tricyclo structure having many ring structures.

  The unsaturated aliphatic group is a linear, branched or cyclic unsaturated aliphatic group, and includes an alkenyl group, a cycloalkenyl group, a bicycloalkenyl group, and an alkynyl group. Examples of the alkenyl group include linear, branched, and cyclic substituted or unsubstituted alkenyl groups. As the alkenyl group, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms is preferable. Examples include vinyl group, allyl group, prenyl group, geranyl group, and oleyl group. The cycloalkenyl group is preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms. Examples include a 2-cyclopenten-1-yl group and a 2-cyclohexen-1-yl group. The bicycloalkenyl group includes a substituted or unsubstituted bicycloalkenyl group. The bicycloalkenyl group is preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a monovalent group in which one hydrogen atom of a bicycloalkene having one double bond is removed. Examples include a bicyclo [2.2.1] hept-2-en-1-yl group and a bicyclo [2.2.2] oct-2-en-4-yl group. The alkynyl group is preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, and examples thereof include an ethynyl group and a propargyl group.

  The aryl group is preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and examples thereof include a phenyl group, a p-tolyl group, a naphthyl group, an m-chlorophenyl group, and an o-hexadecanoylaminophenyl group. The phenyl group which may have a substituent is preferable.

  The heterocyclic group is a monovalent group obtained by removing one hydrogen atom from a substituted or unsubstituted aromatic or non-aromatic heterocyclic compound, and they may be further condensed. These heterocyclic groups are preferably 5- or 6-membered heterocyclic groups, and the hetero atoms of the ring structure are preferably oxygen atoms, sulfur atoms and nitrogen atoms. More preferably, it is a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms. The heterocyclic ring in the heterocyclic group includes pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, quinazoline ring, cinnoline ring, phthalazine ring, quinoxaline ring, pyrrole ring, indole ring, furan ring Benzofuran ring, thiophene ring, benzothiophene ring, pyrazole ring, imidazole ring, benzimidazole ring, triazole ring, oxazole ring, benzoxazole ring, thiazole ring, benzothiazole ring, isothiazole ring, benzisothiazole ring, thiadiazole ring, Examples include isoxazole ring, benzisoxazole ring, pyrrolidine ring, piperidine ring, piperazine ring, imidazolidine ring and thiazoline ring.

  The aliphatic oxy group (typically an alkoxy group) includes a substituted or unsubstituted aliphatic oxy group (typically an alkoxy group), and preferably has 1 to 30 carbon atoms. Examples thereof include a methoxy group, an ethoxy group, an isopropoxy group, an n-octyloxy group, a methoxyethoxy group, a hydroxyethoxy group, and a 3-carboxypropoxy group.

  The aryloxy group is preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms. Examples of the aryloxy group include phenoxy group, 2-methylphenoxy group, 4-tert-butylphenoxy group, 3-nitrophenoxy group, 2-tetradecanoylaminophenoxy group and the like. Preferably, it is a phenyloxy group that may have a substituent.

  The acyloxy group is preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, or a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms. Examples of the acyloxy group include formyloxy group, acetyloxy group, pivaloyloxy group, stearoyloxy group, benzoyloxy group, p-methoxyphenylcarbonyloxy group and the like.

  The carbamoyloxy group is preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms. Examples of carbamoyloxy groups include N, N-dimethylcarbamoyloxy group, N, N-diethylcarbamoyloxy group, morpholinocarbonyloxy group, N, N-di-n-octylaminocarbonyloxy group, Nn-octyl A carbamoyloxy group can be exemplified.

  The aliphatic oxycarbonyloxy group (typically an alkoxycarbonyloxy group) preferably has 2 to 30 carbon atoms and may have a substituent. Examples thereof include a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a tert-butoxycarbonyloxy group, and an n-octylcarbonyloxy group.

  The aryloxycarbonyloxy group is preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms. Examples of the aryloxycarbonyloxy group include a phenoxycarbonyloxy group, a p-methoxyphenoxycarbonyloxy group, and a pn-hexadecyloxyphenoxycarbonyloxy group. Preferable is a phenoxycarbonyloxy group which may have a substituent.

  The amino group includes an amino group, an aliphatic amino group (typically an alkylamino group), an arylamino group, and a heterocyclic amino group. The amino group is preferably a substituted or unsubstituted aliphatic amino group having 1 to 30 carbon atoms (typically an alkylamino group) or a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms. Examples of amino groups include, for example, amino group, methylamino group, dimethylamino group, anilino group, N-methyl-anilino group, diphenylamino group, hydroxyethylamino group, carboxyethylamino group, sulfoethylamino group, 3,5-Dicarboxyanilino group, 4-quinolylamino group and the like can be mentioned.

  The acylamino group is preferably a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, or a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms. Examples of the acylamino group include formylamino group, acetylamino group, pivaloylamino group, lauroylamino group, benzoylamino group, 3,4,5-tri-n-octyloxyphenylcarbonylamino group, and the like.

  The aminocarbonylamino group is preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms. Examples of the aminocarbonylamino group include carbamoylamino group, N, N-dimethylaminocarbonylamino group, N, N-diethylaminocarbonylamino group, morpholinocarbonylamino group and the like. The term “amino” in this group has the same meaning as “amino” in the aforementioned amino group.

  The aliphatic oxycarbonylamino group (typically an alkoxycarbonylamino group) preferably has 2 to 30 carbon atoms and may have a substituent. Examples thereof include a methoxycarbonylamino group, an ethoxycarbonylamino group, a tert-butoxycarbonylamino group, an n-octadecyloxycarbonylamino group, and an N-methyl-methoxycarbonylamino group.

  The aryloxycarbonylamino group is preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms. Examples of the aryloxycarbonylamino group include phenoxycarbonylamino group, p-chlorophenoxycarbonylamino group, m- (n-octyloxy) phenoxycarbonylamino group, and the like. The phenyloxycarbonylamino group which may have a substituent is preferable.

  The sulfamoylamino group is preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms. Examples of the sulfamoylamino group include a sulfamoylamino group, an N, N-dimethylaminosulfonylamino group, and an Nn-octylaminosulfonylamino group.

  An aliphatic (typically alkyl) or arylsulfonylamino group is a substituted or unsubstituted aliphatic sulfonylamino group having 1 to 30 carbon atoms (typically an alkylsulfonylamino group), a substituted or unsubstituted group having 6 to 30 carbon atoms. An arylsulfonylamino group (preferably a phenylsulfonylamino group which may have a substituent) is preferable. Examples thereof include a methylsulfonylamino group, a butylsulfonylamino group, a phenylsulfonylamino group, a 2,3,5-trichlorophenylsulfonylamino group, and a p-methylphenylsulfonylamino group.

  The aliphatic thio group (typically an alkylthio group) is preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms. Examples of the alkylthio group include a methylthio group, an ethylthio group, and an n-hexadecylthio group.

  The arylthio group is preferably a substituted or unsubstituted arylthio group having 6 to 12 carbon atoms. Examples of the arylthio group include a phenylthio group, a 1-naphthylthio group, and a 2-naphthylthio group.

  The sulfamoyl group is preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms. Examples of the sulfamoyl group include N-ethylsulfamoyl group, N- (3-dodecyloxypropyl) sulfamoyl group, N, N-dimethylsulfamoyl group, N-acetylsulfamoyl group, N-benzoylsulfa group. A moyl group, an N- (N′-phenylcarbamoyl) sulfamoyl) group, and the like.

  The aliphatic (typically alkyl) or arylsulfinyl group is a substituted or unsubstituted aliphatic sulfinyl group having 1 to 30 carbon atoms (typically an alkylsulfinyl group), a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms (preferably Is preferably a phenylsulfinyl group which may have a substituent. Examples thereof include a methylsulfinyl group, an ethylsulfinyl group, a phenylsulfinyl group, and a p-methylphenylsulfinyl group.

  The aliphatic (typically alkyl) or arylsulfonyl group is a substituted or unsubstituted aliphatic sulfonyl group having 1 to 30 carbon atoms (typically an alkylsulfonyl group), a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms (preferably Is preferably a phenylsulfonyl group which may have a substituent. For example, methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-toluenesulfonyl group and the like can be mentioned.

  The acyl group is a formyl group, a substituted or unsubstituted aliphatic carbonyl group having 2 to 30 carbon atoms (typically an alkylcarbonyl group), a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms (preferably a substituent). An optionally substituted phenylcarbonyl group), and a heterocyclic carbonyl group bonded to the carbonyl group at a substituted or unsubstituted carbon atom having 4 to 30 carbon atoms is preferable. Examples thereof include acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl group and the like.

  The aryloxycarbonyl group is preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms. Examples of the aryloxycarbonyl group include phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, p- (tert-butyl) phenoxycarbonyl group and the like. A phenyloxycarbonyl group which may have a substituent is preferable.

  The aliphatic oxycarbonyl group (typically an alkoxycarbonyl group) preferably has 2 to 30 carbon atoms and may have a substituent. Examples thereof include methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, n-octadecyloxycarbonyl group and the like.

  The carbamoyl group is preferably a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms. Examples of the carbamoyl group include carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl group and the like.

  Examples of the aryl or heterocyclic azo group include phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo group, and the like.

  Examples of the imide group include an N-succinimide group and an N-phthalimide group.

  The aliphatic oxysulfonyl group (typically an alkoxysulfonyl group) preferably has 1 to 30 carbon atoms and may have a substituent. For example, methoxysulfonyl, ethoxysulfonyl, n-butoxysulfonyl group and the like can be mentioned.

  The aryloxysulfonyl group preferably has 6 to 12 carbon atoms and may have a substituent. For example, a phenoxysulfonyl, 2-naphthoxyphenyl group, etc. can be mentioned.

  In addition to these, there are a hydroxyl group, a cyano group, a nitro group, a sulfo group, and a carboxyl group.

  Each of these groups may further have a substituent, and examples of such a substituent include the above-described substituents.

R ¹² and R ¹⁵ are each independently preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon number. A 6-30 aryloxy group, a substituted or unsubstituted acyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, a hydroxyl group, or a halogen atom, more preferably hydrogen. Atoms, substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 20 carbon atoms, substituted or unsubstituted acyloxy groups having 2 to 20 carbon atoms, or 1 to carbon atoms 20 substituted or unsubstituted carbamoyloxy groups, particularly preferably substituted or unsubstituted acyloxy groups having 2 to 18 carbon atoms or substituted groups having 1 to 18 carbon atoms. It is an unsubstituted carbamoyloxy group.

R ¹³ and R ¹⁴ are each independently preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a halogen atom, or a cyano group. More preferably a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and particularly preferably a hydrogen atom.

In the general formula (2), R ¹¹ represents a monovalent substituent, and the substituent is an aliphatic group [saturated aliphatic group (alkyl group, cycloalkyl group, bicycloalkyl group, bridged cyclic saturated hydrocarbon). A cyclic saturated aliphatic group including a group or a spiro saturated hydrocarbon group), an unsaturated aliphatic group (a chain unsaturated aliphatic group having a double bond or a triple bond, such as an alkenyl group or an alkenyl group, Or a cyclounsaturated aliphatic group including a cycloalkenyl group, a bicycloalkenyl group, a bridged cyclic unsaturated hydrocarbon group or a spiro unsaturated hydrocarbon group)], an aryl group (preferably having a substituent). A good phenyl group), a heterocyclic group (preferably a 5- to 8-membered ring containing an oxygen atom, a sulfur atom or a nitrogen atom as the ring constituent atom, which may be condensed with an alicyclic ring, an aromatic ring or a heterocyclic ring) , Fat Group oxy groups (typically alkoxy groups), aryloxy groups, amino groups [including aliphatic amino groups (typically alkylamino groups), anilino groups and heterocyclic amino groups], acylamino groups, aliphatic oxycarbonylamino groups ( Typically alkoxycarbonylamino group), aryloxycarbonylamino group, sulfamoylamino group, aliphatic (typically alkyl) or arylsulfonylamino group, acyl group, aryloxycarbonyl group, aliphatic oxycarbonyl group (typically alkoxy) Carbonyl group), carbamoyl group, hydroxyl group and carboxyl group.

R ¹¹ may further have a substituent, and examples of such a substituent include the substituent groups listed in R ^{12 to} R ¹⁶ .

R ¹¹ is preferably a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted phenyl group, more preferably a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, Preferably it is a C1-C5 branched alkyl group.

  As for the preferred combination of substituents of the compound represented by the general formula (2), a compound in which at least one of these substituents is the preferred group is preferred, and more various substituents are the preferred groups. Certain compounds are more preferred, and compounds in which all substituents are the preferred groups are most preferred.

(6) Release sheet The release sheet 6 is a member that covers the surface opposite to the light incident side of the acrylic pressure-sensitive adhesive layer (acrylic layer 5 of the support layer) in the functional film.
For example, when the functional film is shipped, the release sheet 6 is stuck to the acrylic pressure-sensitive adhesive layer, and then the release sheet 6 is peeled from the pressure-sensitive adhesive layer of the functional film, and the functional film is used as a support substrate. By bonding, for example, a solar power generation reflecting device can be formed.
The release sheet 6 may be any material that can protect the adhesiveness of the pressure-sensitive adhesive layer. For example, an acrylic film or sheet, a polycarbonate film or sheet, a polyarylate film or sheet, a polyethylene naphthalate film or sheet, polyethylene Plastic film or sheet such as terephthalate film or sheet, fluorine film, or resin film or sheet kneaded with titanium oxide, silica, aluminum powder, copper powder, etc. A resin film or sheet material subjected to surface processing such as metal vapor deposition is used.

(7) Reflector for solar thermal power generation The reflective device for solar thermal power generation is composed of, for example, a functional film as a film mirror for solar thermal power generation, and a support substrate (metal substrate). That is, the solar power generation reflecting device is formed by adhering the acrylic pressure-sensitive adhesive layer (acrylic layer 5) of the functional film to the support substrate.

(7-1) Support base material As a support base material of the solar power generation reflector, for example, a steel plate, a copper plate, an aluminum plate, an aluminum-plated steel plate, an aluminum-based alloy-plated steel plate, a copper-plated steel plate, a tin-plated steel plate, and a chromium-plated steel plate. A metal material such as a stainless steel plate can be used. In the present invention, it is particularly preferable to use a plated steel plate, a stainless steel plate, an aluminum plate, or the like having good corrosion resistance.
The thickness of these supporting base materials is preferably about 0.05 mm to 3 mm from the viewpoints of handleability, thermal conductivity, heat capacity, and the like.

Hereinafter, the present invention will be described with reference to specific examples and comparative examples. However, the present invention is not limited to these. In the following examples and comparative examples, “part” or “%” is used, and “part by mass” or “% by mass” is expressed unless otherwise specified.
In this example, a film mirror as a functional film was produced.

<< Production of film mirror for sunlight reflection >>
(Production of Film Mirror No. 1: Example 1)
A curable resin layer 2 (3 μm) is applied as an easy-adhesion layer to one side of a biaxially stretched polyester film 3 (polyethylene terephthalate film, thickness 25 μm) on the support layer side. The curable resin layer 2 is cured by heat at 110 ° C. for 2 minutes, and once wound with a roll, the curable resin layer 2 is placed in a vacuum vapor deposition pot, and the reflective layer 1 (80 nm) is vacuum deposited on the curable resin layer 2. After taking out from the vapor deposition pot, a curable resin layer 2 (3 μm) is applied on the reflective layer 1. Before the resin layer containing the curing agent is completely cured, the polyester film 3 (25 μm) on the protective layer side is laminated. An adhesive layer 4 (7 μm) is applied on the polyester film 3 and an ultraviolet absorber-containing acrylic film 5 (30 μm) as a protective layer is bonded.
Further, the adhesive layer 4 (7 μm) is applied to the lower layer of the polyester film 3 on the support layer side to increase the adhesion, and the acrylic film 5 (30 μm) is bonded.
Thus, the film mirror shown in FIG. 1 was produced.

(Production of film mirror No. 2: Example 2)
The curable resin layer 2 (3 μm) is formed on one side of the support layer side acrylic film 5 (S001G (manufactured by Sumitomo Chemical Co., Ltd., 30 μm)) by coating. A silver reflective layer 1 is deposited on the curable resin layer 2 with a thickness of 80 nm by a vacuum deposition method, and a curable resin layer 2 (3 μm) is further formed thereon by coating. Next, a liquid in which an ultraviolet absorber is contained in an acrylic resin solution (BR-85: manufactured by Mitsubishi Rayon) dissolved in methyl ethyl ketone is applied onto the curable resin layer 2 so as to have a dry film thickness of 75 μm. As an acrylic layer 5 is formed.
Also, a release film in which an acrylic adhesive (Nissetsu SZ-7103, manufactured by Nippon Carbide) was applied on the surface opposite to the silver reflective layer deposition surface of the acrylic film 5 on the support layer side to a film thickness of 15 μm after drying. 6 was laminated to form an acrylic pressure-sensitive adhesive layer 5.
The acrylic film used here was formed in advance as a film, whereas the acrylic layer was solidified after applying an acrylic resin solution.
In Example 2, the acrylic film 5 and the acrylic pressure-sensitive adhesive layer 5 are combined to form a support layer because both are the same material. Here, since the temperature dependence of the expansion coefficient of the acrylic film 5 and the acrylic adhesive layer 5 is substantially the same, it can be recognized as an integral support layer.
Thus, the film mirror shown in FIG. 2 was produced.

(Production of film mirror No. 3: Example 3)
A biaxially stretched polyester film 3 (polyethylene terephthalate film, thickness 50 μm) was used as the support layer. A curable resin layer 2 (3 μm) was formed on one side of the film 3 by coating, and a silver reflective layer 1 was formed on the curable resin layer 2 to a thickness of 80 nm by vacuum deposition. An adhesive layer 2 (7 μm) was applied on the silver reflective layer 1, and a high durability polyester film 3 (thickness 50 μm) as a protective layer was bonded thereon.
In addition, an acrylic adhesive (Nissetsu SZ-7103, manufactured by Nippon Carbide) was applied on the surface opposite to the silver reflective layer deposition surface of the polyester film 3 as the support layer so as to have a film thickness of 10 μm after drying. The release film 6 was laminated to form an acrylic pressure-sensitive adhesive layer 5.
Thus, the film mirror shown in FIG. 3 was produced.

(Production of film mirror No. 4: Example 4)
A curable resin layer 2 (3 μm) is formed on one side of an acrylic film 5 (S001G (manufactured by Sumitomo Chemical), 50 μm) on the support layer side by coating. A silver reflective layer 1 is formed to a thickness of 80 nm on the curable resin layer 2 by vacuum deposition, and a curable resin layer 2 (3 μm) is further formed thereon by coating. Further, an adhesive layer 4 (7 μm) was applied thereon, and an ultraviolet absorber-containing acrylic film 5 (S001G (manufactured by Sumitomo Chemical), 50 μm) on the protective layer side was bonded to the adhesive layer 4.
Thus, the film mirror shown in FIG. 4 was produced.

(Production of film mirror No. 5: Example 5)
A curable resin layer 2 (3 μm) is formed on one side of the polyester film 3 (75 μm) on the support layer side by coating. A silver reflective layer 1 is formed to a thickness of 80 nm on the curable resin layer 2 by vacuum deposition, and a curable resin layer 2 (3 μm) is further formed thereon by coating. Further, an adhesive layer 4 (7 μm) was applied on the curable resin layer 2, and a high durability polyester film 3 (25 μm) on the protective layer side was bonded to the adhesive layer 4.
In addition, an acrylic pressure-sensitive adhesive (Nissetsu SZ-7103, manufactured by Nippon Carbide) was applied on the surface opposite to the silver reflective layer deposition surface of the polyester film 3 as the support layer so that the film thickness was 25 μm after drying. The release film 6 was laminated to form an acrylic pressure-sensitive adhesive layer 5.
Thus, the film mirror shown in FIG. 5 was produced.

(Production of film mirror No. 6: Example 6)
Polyester film film 3 (25 μm) was used as the support layer. A curable resin layer 2 (3 μm) is formed on one surface of the film 3 by coating. On the curable resin layer 2, the silver reflective layer 1 is formed to a thickness of 80 nm by vacuum vapor deposition, and further the curable resin layer 2 (3 μm) is formed thereon by coating. Further, an adhesive layer 4 (7 μm) was applied thereon, and an ultraviolet absorber-containing acrylic film 5 (thickness 90 μm) on the protective layer side was bonded to the adhesive layer 4.
In addition, an acrylic resin solution (BR-85: manufactured by Mitsubishi Rayon) dissolved in methyl ethyl ketone is applied on the surface opposite to the silver reflective layer deposition surface of the polyester film 3 as the support layer so as to have a film thickness of 25 μm after drying. Thus, an acrylic layer 5 was formed.
Thus, the film mirror shown in FIG. 6 was produced.

(Production of Film Mirror No. 7: Comparative Example 1)
A biaxially stretched polyester film 3 (polyethylene terephthalate film, thickness 50 μm) was used as the support layer. On one side of the film 3, the silver reflective layer 1 was formed to a thickness of 80 nm by vacuum deposition. An adhesive layer 4 (7 μm) was applied on the silver reflective layer 1, and an acrylic film 5 (thickness 90 μm) on the protective layer side was bonded to the adhesive layer 4.
In addition, a release film 6 having an acrylic adhesive (Nisset SZ-7103, manufactured by Nippon Carbide) coated on the surface opposite to the silver reflective layer deposition surface of the polyester film 3 so as to have a film thickness of 9 μm after drying. The acrylic pressure-sensitive adhesive layer 5 was formed by laminating.
Thus, the film mirror shown in FIG. 7 was produced.

(Production of Film Mirror No. 8: Comparative Example 2)
On one side of a biaxially stretched polyester film 3 (polyethylene terephthalate film, thickness 25 μm), the silver reflective layer 1 was formed to a thickness of 80 nm by vacuum deposition.
An adhesive layer 4 (7 μm) was applied to the opposite surface of the polyester film 3, and an acrylic film 5 (thickness 90 μm) as a protective layer was bonded to the adhesive layer 4.
Also, an acrylic adhesive layer 5 is laminated on the lower surface of the silver reflective layer 1 by laminating a release film 6 coated with an acrylic adhesive (Nisset SZ-7103, manufactured by Nippon Carbide) to a thickness of 9 μm after drying. Formed.
Thus, the film mirror shown in FIG. 8 was produced.

(Production of film mirror No .: Comparative Example 3)
An acrylic film 5 (S001G (manufactured by Sumitomo Chemical Co., Ltd., thickness: 100 μm)) was used as the support layer. On one surface of the film 5, the silver reflective layer 1 was formed to a thickness of 80 nm by vacuum deposition. An ultraviolet curable resin 2 (NK ester M-90G (manufactured by Shin-Nakamura Chemical Co., Ltd.)) was applied as a protective layer on the silver reflective layer 1 so as to have a thickness of 5 μm after drying.
In addition, an acrylic adhesive layer 5 is laminated on the lower surface of the acrylic film 5 by laminating a release film 6 coated with an acrylic adhesive (Nisset SZ-7103, manufactured by Nippon Carbide) to a thickness of 9 μm after drying. Formed.
Thus, the film mirror shown in FIG. 9 was produced.

<Evaluation of mirror>
[Measurement of initial spot diameter]
About the produced film mirror, the spot diameter of the reflective spot was measured using the small working autocollimator WV-60 by Nikon Engineering. When the spot has a circular shape with an effective observation area of 28 mm in diameter and the mirror surface has flatness and high reflection efficiency, the same spot diameter as the diameter of the light beam incident on the mirror is obtained on the monitor through the CCD sensor. Therefore, the closer the initial spot diameter is to 28 mm, the better the reflection efficiency.
When the spot diameter was 28 mm or more and less than 35 mm, it was judged as ◯, when 20 or more and less than 28 mm or 35 mm or more and less than 45 mm, Δ, and when the spot diameter was less than 20 mm or more than 45 mm, it was judged as x.

[Initial 5 degree specular reflectance measurement]
The 5 degree regular reflectance in the sunlight incident surface side of the produced film mirror was measured. Using Hitachi spectrophotometer U-4100 (solid sample measurement system), relative reflectance measurement with respect to a reference sample having an incident angle of 5 degrees was performed. The wavelength range was measured at 250 to 2500 nm, and it was confirmed whether there was any wavelength range in which the reflectance dropped partially. The reflectance in the visible light region (400 to 800 nm) was averaged, and this was defined as the 5-degree average regular reflectance.
When the 5 degree average regular reflectance was 90% or more, it was judged as ◯, when it was 80% or more but less than 90%, Δ, and when it was less than 80%, it was judged as ×.

[Evaluation of weather resistance]
The film mirror thus prepared was allowed to stand for 30 days in an environment at a temperature of 85 ° C. and a relative humidity of 85%, and then irradiated with a xenon lamp on the light incident surface side of the mirror (using a Suga test machine SX75, the radiation intensity of 180 W / m ² , 500 hours). Next, after irradiation with a xenon lamp, the spot diameter and 5 degree regular reflectance were measured by the same method as described above. With respect to the initial spot diameter and the initial 5 degree regular reflectance, the smaller the fluctuation range, the better the weather resistance.
When the difference from the initial spot diameter was less than 5 mm, it was judged as ◯, when the difference from the initial was 5 mm or more and less than 10 mm, Δ, and when the difference from the initial was 10 mm or more, it was judged as x.
In the case of 5 degree regular reflectance, when the difference from the initial value was less than 5%, it was judged as ◯, when the difference from the initial value was 5% or more and less than 10%, Δ, and when the difference from the initial value was 10% or more, ×.

  The evaluation results are shown in Table 1. In addition, Table 2 shows characteristics regarding the thickness of each film mirror.

As is clear from the results in Table 1, all of the initial evaluations of Examples 1 to 6 are ◯. Even when the weather resistance is evaluated after that, it is within the range of ○ or Δ. This is for the following reason.
The protective layers of Examples 1 to 6, which are the present invention, are the thickest layers among the plurality of layers disposed on the light incident side of the reflective layer, and the support layer is on the opposite side of the light incident side of the reflective layer. The thickest layer among the plurality of layers disposed in the two layers, and both layers have a thickness of 10 μm or more. Therefore, the protective layer and the support layer have a certain amount or more with respect to the front and back directions of the functional film. It will have a thickness. Further, the protective layer and the support layer of Examples 1 to 6 of the present invention are made of the same material, and the strength against warping is almost uniform between the two layers, and the difference in stress between the protective layer and the support layer hardly occurs. If it does so, warp will not generate | occur | produce by the difference of a protective layer and a support layer, the stress difference of the front and back of a functional film can be suppressed, and the functional film which cannot produce a curvature will be provided.

On the other hand, in Comparative Examples 1 to 3, since the protective layer and the support layer are made of different materials, warpage is likely to occur, and the difference from the initial evaluation is large.
In Comparative Example 1, since the support layer and the protective layer have the same thickness, the initial characteristics are good in two measurements. However, since the ultraviolet absorber is not contained in the protective layer, the support layer is deteriorated by the ultraviolet rays near 320 nm that have passed through the silver reflective layer. Furthermore, since the acrylic film itself deteriorates, it was evaluated as x in two measurements after the weather resistance test. Further, in Comparative Examples 2 and 3, since the support layer and the protective layer are thick and warpage occurs from the initial stage, the initial spot diameter is evaluated as NG, and the weather resistance is evaluated as NG.

Furthermore, as shown in Table 2, in the film mirrors of Examples 1 to 6, the thickness of all layers including the protective layer laminated on the light incident side of the reflective layer is U μm, which is opposite to the light incident side of the reflective layer. When the thickness of all the layers including the support layer laminated on the side is D μm, the following formula (1) is satisfied.
| U-D | ≦ 2 (1)
Thus, in the film mirrors of Examples 1 to 6, the thicknesses of all the layers disposed on the light incident side of the reflective layer and all the layers disposed on the side opposite to the light incident side of the reflective layer. Therefore, the difference in stress between the front and back surfaces can be further suppressed, and a film mirror (functional film) that hardly warps can be manufactured.
Furthermore, the film mirrors of Examples 1 to 5 satisfy the following formula (2) when the thickness of the support layer is X (μm) and the thickness of the protective layer is Y (μm).
| X−Y | / X ≦ 1 (2)
By this, since the difference of the thickness of the protective layer of a film mirror of Examples 1-5 and a support layer becomes small, the stress difference of a front and back is further suppressed and the film mirror (functional film) which cannot produce a curvature easily can be manufactured.
Further, in the film mirrors of Examples 1 to 6, the thickness obtained by subtracting the protective layer from the thickness of all layers on the light incident side of the reflective layer is α (μm), and the thickness of all layers on the side opposite to the light incident side of the reflective layer is When the thickness is β (μm), the following formula (3) is satisfied.
| α−β | / α ≦ 20 (3)
As a result, the difference between the thickness of the reflective layer of the film mirrors of Examples 1 to 6 other than the protective layer on the light incident side and the thickness of the reflective layer other than the support layer opposite to the light incident side becomes small. Furthermore, it is possible to produce a film mirror (functional film) that suppresses the stress difference between the front and back surfaces and hardly warps.

  The application of the present invention is not limited to the above-described embodiment, and can be appropriately changed without departing from the spirit of the present invention.

1 reflective layer 2 resin layer 3 polyester layer (protective layer, support layer)
4 Adhesive layer 5 Acrylic layer (protective layer, support layer)
6 Release sheet 10, 20, 30, 40, 50, 60 Functional film

Claims (12)

A reflective layer;
At least one protective layer disposed on the light incident side of the reflective layer;
At least one support layer disposed on the side opposite to the light incident side of the reflective layer;
A functional film having
The functional film, wherein the protective layer and the support layer are made of the same material and both have a thickness of 10 μm or more.   The functional film according to claim 1, wherein the protective layer and the support layer are made of a polyester material.   The functional film according to claim 1, wherein the protective layer and the support layer are polyethylene terephthalate.   The functional film according to claim 1, wherein the protective layer and the support layer are acrylic materials.   The functional film according to claim 1, wherein the protective layer contains an ultraviolet absorber.   At least the protective layer of the protective layer and the support layer includes at least one ultraviolet absorber (A) having a maximum absorption wavelength of 360 to 400 nm and at least one ultraviolet absorber having a maximum absorption wavelength of less than 360 nm. An ultraviolet absorber composition comprising (B) is contained, and the ratio of the ultraviolet absorber (A) to the ultraviolet absorber (B) is in the range of 1: 1 to 1: 100. The functional film as described in any one of 1-5.   The protective layer is the thickest layer among the plurality of layers disposed on the light incident side of the reflective layer, and the support layer is disposed on the opposite side of the light incident side of the reflective layer. The functional film according to any one of claims 1 to 6, wherein the functional film is the thickest layer among the plurality of layers. The thickness of all the layers including the protective layer laminated on the light incident side of the reflective layer is U (μm), and all the layers including the support layer laminated on the opposite side of the light incident side of the reflective layer The functional film according to claim 1, wherein when the thickness of the functional film is D (μm), the following formula (1) is satisfied.
| U−D | / U ≦ 2 (1) The following formula (2) is satisfied, where the thickness of the support layer is X (μm) and the thickness of the protective layer is Y (μm). Functional film.
| X−Y | / X ≦ 1 (2) The thickness obtained by subtracting the protective layer from the thickness of all layers on the light incident side of the reflective layer is α (μm), and the thickness of all layers on the side opposite to the light incident side of the reflective layer is β (μm). The functional film according to any one of claims 1 to 9, wherein the following formula (3) is satisfied.
| α−β | / α ≦ 20 (3)   The functional film according to claim 1, wherein the functional film is a heat shield film.   The functional film according to any one of claims 1 to 10, wherein the functional film is a film mirror for solar power generation.

Images