JP2014199330A - Film mirror and solar reflector using the same - Google Patents

Abstract

[PROBLEMS] To maintain the characteristics of a film mirror that is lightweight and flexible, has good adhesion between a support and a metal reflective layer, and has a weather resistance that can withstand long-term use in harsh environments. Provide an excellent film mirror. A film mirror having a metal reflective layer and an ultraviolet absorber-containing layer containing a compound represented by the following general formula (1) in this order on a resin support. In general formula (1), R1a to R1e each represent a monovalent substituent excluding a hydrogen atom or a hydroxy group, and at least one of the substituents represents a substituent having a positive Hammett's σp value. . R1g to R1p each represents a hydrogen atom or a monovalent substituent. [Selection figure] None

Description

  The present invention relates to a film mirror and a sunlight reflecting plate using the film mirror.

  In recent years, research on alternative energy alternatives to fossil fuels typified by oil, coal, and natural gas has been actively conducted. In particular, natural energy such as solar light, wind power, and geothermal heat has attracted attention as clean energy without concern about resource depletion and global warming. Among these, solar energy using sunlight is expected to be further developed as energy that can be stably supplied.

On the other hand, however, solar energy has a problem of low energy density. In order to solve this problem, in recent years, attempts have been made to collect sunlight using a huge reflector.
Until now, a reflector for condensing sunlight has been used outdoors because it is installed outdoors and exposed to ultraviolet rays, heat, wind and rain, sand dust and the like caused by sunlight. However, although the glass-made reflecting mirror is excellent in weather resistance, there is a problem that there is room for improvement in handling property because it is heavy, easily broken, and lacks flexibility.

In order to solve the above problem, it is considered to replace the glass reflector with a light and flexible resin reflector. For example, a film mirror is disclosed in which a first stretched film and a second stretched film are laminated via an adhesive layer in a form sandwiching a silver reflective layer provided on the first stretched film ( For example, see Patent Document 1). According to Patent Document 1, the main stretch direction of the first stretched film and the second stretched film is crossed at a specific intersection angle, so that even when used in a harsh environment for a long time, the mirror surface It is said that a film mirror can be provided in which no distortion occurs and the decrease in regular reflectance is suppressed.
Moreover, as a metal reflective layer in a film mirror, in order to achieve the outstanding reflectance, it is supposed that a silver reflective layer is preferable. In order to achieve higher weather resistance in film mirrors that are inferior in weather resistance compared to glass reflectors, a technology is proposed in which a protective layer is provided on the surface of the metal reflective layer and a specific UV absorber is contained in the protective layer. (For example, refer to Patent Document 2).

JP 2012-83527 A JP, 2012-173379, A

According to the study by the present inventors, the metal reflective layer achieves an excellent reflectivity, but has low reflectivity in the ultraviolet light, particularly in the UV-B region, and as disclosed in Patent Document 1, for example. When resin is used as a support, there is a concern about deterioration of the resin support due to ultraviolet rays.
In order to suppress such deterioration of the resin support, for example, when a surface protective layer as described in Patent Document 2 is applied to a film mirror having a resin support as described in Patent Document 1, a protective layer is obtained. It has been found that there arises a problem that the reflectance is lowered due to the resin material constituting the. Further, due to the difference in physical properties between the surface protective layer and the metal reflective layer, when the film mirror is used for a long time under severe conditions, peeling occurs at the interface between the surface protective layer and the metal reflective layer, and the metal reflective layer It has been found that the flatness of the film is impaired and the reflectance is lowered. For this reason, it has been found that the protective layer is excellent in adhesion to the metal reflective layer, and even when it is a thin layer, a sufficient ultraviolet blocking property is required.

The present invention has been made in view of the above circumstances, and the object of the present invention is to maintain the characteristics of a film mirror that is lightweight and flexible, and to be deteriorated due to ultraviolet rays even in a harsh environment. An object of the present invention is to provide a film mirror excellent in weather resistance that is suppressed and can maintain a high reflectance over a long period of time.
Moreover, the other subject of this invention is providing the sunlight reflecting plate excellent in the weather resistance which was produced using the film mirror of this invention.

Specific means for solving the above problems are as follows.
<1> A film mirror having a metal reflective layer and an ultraviolet absorber-containing layer containing a compound represented by the following general formula (1) in this order on a resin support.

(In the general formula (1), R ^1a , R ^1b , R ^1c , R ^1d , and R ^1e each independently represent a monovalent substituent other than a hydrogen atom or a hydroxy group, One represents a substituent having a positive Hammett's σp value: R ^1g , R ^1h , R ¹ⁱ , R ^1j , R ^1k , R ^1m , R ¹ⁿ , and R ^1p are each independently a hydrogen atom or R ^1a , R ^1b , R ^1c , R ^1d , R ^1e , R ^1g , R ^1h , R ¹ⁱ , R ^1j , R ^1k , R ^1m , R ¹ⁿ , and R ^1p are monovalent. Any two or more of them may be bonded to each other to form a ring.
Here, “having a resinous support, a metal reflective layer, and an ultraviolet absorber-containing layer in this order” means that these layers are provided in the order of description, and arbitrary layers provided between the upper and lower sides thereof. The existence of a layer, for example, a back coat layer, an intermediate layer, a surface coating layer, etc. is not denied.
<2> In the general formula (1), R ^1a , R ^1b , R ^1c , R ^1d , R ^1e , R ^1g , R ^1h , R ¹ⁱ , R ^1j , R ^1k , R ^1m , R ¹ⁿ , and R ^1p Are each independently a monovalent substituent having no hydrogen atom or acidic group, <1>.

<3> Compound group represented by the following general formula (TS-I), general formula (TS-II), general formula (TS-III), general formula (TS-VI), and general formula (TS-V) <1> or <2> The film mirror according to <1>, having a light stabilizer-containing layer containing at least one compound selected from the group consisting of:

In the general formula (TS-I), R ⁹¹ is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylcarbonyl group, an alkenylcarbonyl group, an alkyloxycarbonyl group, an alkenyloxycarbonyl group, Represents an aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, a phosphinotolyl group, a phosphinyl group, or —Si (R ⁹⁷ ) (R ⁹⁸ ) (R ⁹⁹ ), wherein R ⁹⁷ , R ⁹⁸ , and R ⁹⁹ are each independently An alkyl group, an alkenyl group, an aryl group, an alkoxy group, an alkenyloxy group, or an aryloxy group is represented. X ⁹¹ represents —O—, —S— or —N (—R ¹⁰⁰ ) —, and R ¹⁰⁰ has the same meaning as R ⁹¹ . R ⁹² , R ⁹³ , R ⁹⁴ , R ⁹⁵ , and R ⁹⁶ each independently represent a hydrogen atom or a monovalent substituent. R ⁹¹ and R ⁹² , R ¹⁰⁰ and R ⁹⁶ , and R ⁹¹ and R ¹⁰⁰ may be bonded to each other to form a 5-membered to 7-membered ring together with the adjacent carbon atoms. R ⁹² and R ⁹³ , R ^{100 93} and R ⁹⁴ may be bonded to each other to form a 5- to 7-membered ring, a spiro ring, or a bicyclo ring with adjacent carbon atoms. However, all of R ⁹¹ , R ⁹² , R ⁹³ , R ⁹⁴ , R ⁹⁵ , R ⁹⁶ , and R ¹⁰⁰ are not hydrogen atoms, and the total contained in the compound represented by the general formula (TS-I) Carbon number is 9 or more.

In the general formula (TS-II), R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , and R ¹⁰⁴ each independently represent a hydrogen atom, an alkyl group, or an alkenyl group, and R ¹⁰¹ and R ¹⁰² , R ¹⁰³ and R ¹⁰⁴ And may be bonded to each other to form a 5-membered to 7-membered ring together with adjacent carbon atoms. X ¹⁰¹ is a hydrogen atom, alkyl group, alkenyl group, alkyloxy group, alkenyloxy group, alkyloxycarbonyl group, alkenyloxycarbonyl group, aryloxycarbonyl group, acyl group, acyloxy group, alkyloxycarbonyloxy group, alkenyloxycarbonyl It represents an oxy group, an aryloxycarbonyloxy group, an alkylsulfonyl group, an alkenylsulfonyl group, an arylsulfonyl group, an alkylsulfinyl group, an alkenylsulfinyl group, an arylsulfinyl group, a sulfamoyl group, a carbamoyl group, a hydroxy group, or an oxy radical group. X ¹⁰² represents a nonmetallic atom group necessary for forming a 5-membered to 7-membered ring together with a carbon atom and a nitrogen atom.

In the general formula (TS-III), R ¹⁰⁵ and R ¹⁰⁶ are each independently a hydrogen atom, an aliphatic group, an acyl group, an aliphatic oxycarbonyl group, an aromatic oxycarbonyl group, an aliphatic sulfonyl group, or an aromatic group. Represents a sulfonyl group, and R ¹⁰⁷ represents an aliphatic group, aliphatic oxy group, aromatic oxy group, aliphatic thio group, aromatic thio group, acyloxy group, aliphatic oxycarbonyloxy group, aromatic oxycarbonyloxy group, substituted It represents an amino group, a heterocyclic group, or a hydroxy group, and R ¹⁰⁵ and R ¹⁰⁶ are not both hydrogen atoms, and the total carbon number contained in R ¹⁰⁵ and R ¹⁰⁶ is 7 or more. R ¹⁰⁵ and R ¹⁰⁶ , R ¹⁰⁶ and R ¹⁰⁷ , R ¹⁰⁵ and R ¹⁰⁷ may be bonded to each other to form a 5-membered to 7-membered ring with an adjacent nitrogen atom. It does not form a 2,2,6,6-tetraalkylpiperidine skeleton.

In the general formula (TS-IV), R ¹¹¹ and R ¹¹² each independently represents an aliphatic group, and the aliphatic group may further have a substituent, and the total carbon contained in R ¹¹¹ and R ¹¹² The number is 10 or more. R ¹¹¹ and R ¹¹² may be bonded to each other to form a 5- to 7-membered ring with an adjacent sulfur atom. n represents 0, 1, or 2.
In the general formula (TS-V), R ¹²¹ and R ¹²² each independently represents an aliphatic oxy group or an aromatic oxy group, and R ¹²³ represents an aliphatic group, an aromatic group, an aliphatic oxy group, or an aromatic group. Represents a group oxy group, and the total carbon number contained in R ¹²¹ , R ¹²² and R ¹²³ is 10 or more. m represents 0 or 1; R ¹²¹ and R ¹²² , R ¹²¹ and R ¹²³ may be bonded to each other to form a 5- to 8-membered ring together with the adjacent phosphorus atom. )

<4> The film mirror according to <3>, wherein the ultraviolet absorber-containing layer and the light stabilizer-containing layer are the same layer.
<5> The film mirror according to any one of <1> to <4>, wherein the ultraviolet absorber-containing layer has a thickness of 3 μm or more and 30 μm or less.
<6> The ultraviolet absorber-containing layer contains at least one resin selected from the group consisting of acrylic resin, polyvinyl butyral, ethylene vinyl acetate resin, and ethylene acrylate copolymer resin, <1> to <5 > The film mirror of any one of>.
<7> The film mirror according to <1> to <6>, wherein the ultraviolet absorber-containing layer is selected from the group consisting of carbodiimide, isocyanate, and epoxy, and contains at least one crosslinking agent.
<8> In the ultraviolet absorber-containing layer, when the content of the compound represented by the general formula (1) is A and the content of the crosslinking agent is B, the ratio (A / B) between them is based on mass. The film mirror according to <7>, which is 0.05 or more and 10 or less.

<9> The film mirror according to any one of <1> to <8>, further comprising a surface coating layer on the ultraviolet absorber-containing layer.
<10> The film mirror according to any one of <1> to <9>, wherein the metal reflective layer contains silver.
<11> Between any one of <1> to <10>, further comprising a plating undercoat polymer layer between the resin support and the metal reflective layer, wherein the metal reflective layer is formed by plating. The film mirror described.
<12> The film mirror according to any one of <1> to <11>, which is used for collecting sunlight.
<13> The film mirror according to any one of <1> to <12> is bonded to a substrate made of any of resin, metal, or ceramic via an adhesive layer, or A solar reflector that is attached to a frame made of resin, metal, or ceramic via a fixing jig.

In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
The description “(meth) acryl” means either or both of “acryl” and “methacryl”. Similarly, the description of (meth) acrylate means either or both of “acrylate” and “methacrylate”.

According to the present invention, while maintaining the characteristics of a film mirror that is lightweight and flexible, deterioration due to ultraviolet rays is suppressed even under harsh environments, and weather resistance that can maintain a high reflectance over a long period of time. It is possible to provide an excellent film mirror.
Moreover, according to this invention, the sunlight reflecting plate produced using the film mirror of this invention and excellent in the weather resistance can be provided.

  Hereinafter, specific embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and may be implemented with appropriate modifications within the scope of the object of the present invention. be able to.

[Film mirror]
The film mirror of this invention has a metal reflective layer and the ultraviolet absorber containing layer containing the compound represented by General formula (1) explained in full detail below in this order on a resin-made support body.
As the support for the film mirror, a resin substrate represented by a polyester film such as a polyethylene terephthalate (PET) film that is inexpensive and excellent in mechanical strength is selected. However, normally, the resin material is easily deteriorated by ultraviolet rays, and in consideration of the usage mode of a film mirror that is exposed to sunlight, solar heat, wind and rain, dust, etc. for a long period of time, an ultraviolet absorber-containing layer having excellent ultraviolet blocking properties It is important to form
Therefore, in particular, benzotriazole-based ultraviolet absorbers are used as compounds that can absorb ultraviolet rays in a wide range from long wave ultraviolet rays to short wave ultraviolet rays. However, those having a maximum absorption wavelength (λmax) in the long wave ultraviolet region have a problem that the light resistance is poor, and the ultraviolet shielding effect decreases with time. For this reason, the compound represented by the following general formula (1) used in the present invention as a compound exhibiting a broad ultraviolet shielding effect from the UV-A region to the UV-B region and having an excellent ultraviolet light absorption ability than ever before. (Hereinafter, referred to as (1) a specific compound as appropriate).
(1) By using a specific compound, even a thin layer exhibits excellent ultraviolet blocking properties, and the film mirror is exposed to sunlight, solar heat, wind and rain, dust, etc. for a long time without reducing the reflectance of the metal reflective layer. Even when used in a harsh environment, it has developed excellent weather resistance.
Hereinafter, each material which comprises the film mirror of this invention is demonstrated in detail.
First, the ultraviolet absorber-containing layer, which is an important requirement of the present invention, will be described.

<Ultraviolet absorber-containing layer>
In the film mirror of the present invention, in order to prevent the deterioration or breakage of the metal reflective layer, resin support or plating undercoat polymer layer provided by sunlight, rainwater, dust, etc., and to stabilize the mirror surface (1) An ultraviolet absorber-containing layer containing a specific compound is provided on the incident light side surface of the metal reflective layer described in detail below.
〔resin〕
The ultraviolet absorber-containing layer in the present invention contains a resin. The resin material used for forming the ultraviolet absorber-containing layer is a resin capable of forming a film or layer, and the strength or durability of the formed film or layer, air and moisture blocking properties, and further, ultraviolet rays In addition to the adhesion between the absorber-containing layer and the adjacent layer, for example, a metal reflective layer or a surface coating layer, a resin having transparency, particularly high transparency to light having a wavelength required by the film mirror is preferable.

Specifically, for example, cellulose ester resins, polyester resins, polycarbonate resins, polyarylate resins, polysulfone (including polyether sulfone) resins, polyethylene terephthalate, polyester resins such as polyethylene naphthalate, polyethylene, Polypropylene, cellulose diacetate resin, cellulose triacetate resin, cellulose acetate propionate resin, cellulose acetate butyrate resin, polyvinyl alcohol, polyvinyl butyral, ethylene vinyl alcohol resin, ethylene vinyl acetate resin, and ethylene acrylate copolymer, polycarbonate , Norbornene resin, polymethylpentene resin, polyamide, fluorine resin, polymethyl methacrylate, acrylic resin , Olefin resin, polyurethane resin, and silicone resin.
Among these, from the viewpoint of transparency, affinity with the compound represented by the following general formula (1), and adhesion between the ultraviolet absorber-containing layer and the metal reflective layer, it is contained in the ultraviolet absorber-containing layer. The resin to be used is preferably at least one resin selected from acrylic resin, polyvinyl butyral, ethylene vinyl acetate resin, and ethylene acrylate copolymer.

[Compound represented by the general formula (1)]
The ultraviolet absorber-containing layer according to the present invention contains a compound represented by the following general formula (1). (1) The specific compound has an ultraviolet absorbing ability.

In the general formula (1), R ^1a , R ^1b , R ^1c , R ^1d , and R ^1e each independently represent a monovalent substituent other than a hydrogen atom or a hydroxy group, and at least one of the substituents One represents a substituent having a positive Hammett's σp value. R ^1g , R ^1h , R ¹ⁱ , R ^1j , R ^1k , R ^1m , R ¹ⁿ , and R ^1p each independently represent a hydrogen atom or a monovalent substituent. When R ^1a , R ^1b , R ^1c , R ^1d , R ^1e , R ^1g , R ^1h , R ¹ⁱ , R ^1j , R ^1k , R ^1m , R ¹ⁿ , and R ^1p represent a monovalent substituent, optional Two or more of these may be bonded to each other to form a ring.
Among these, from the viewpoint that the decrease in reflectance due to oxidation of the metal reflective layer adjacent to the ultraviolet absorber-containing layer is suppressed and the weather resistance is further improved, in the general formula (1), R ^1a , R ^1b , R ^1c , R ^1d , R ^1e , R ^1g , R ^1h , R ¹ⁱ , R ^1j , R ^1k , R ^1m , R ¹ⁿ , and R ^1p are each independently a monovalent group having no hydrogen atom or acidic group It is preferable to represent the substituent. That is, when R ^1a , R ^1b , R ^1c , R ^1d , R ^1e , R ^1g , R ^1h , R ¹ⁱ , R ^1j , R ^1k , R ^1m , R ¹ⁿ , and R ^1p are 1 substituents Since none of them has an acidic group, the reflectance of the metal reflective layer is maintained at a high level for a long time, and there is no influence of the acidic group on the resin contained in the ultraviolet absorber-containing layer. It can be said that it is more preferable from the viewpoint of the stability of the resin.
Here, the acidic group refers to a group having a pKa of 5.0 or less, more specifically, a sulfonic acid group, a nitric acid group, a carboxylic acid group, a phosphonic acid group, or the like.

Here, as the monovalent substituent having a positive Hammett's σp value, —COORr, —CONRs ₂ , a cyano group, a trifluoromethyl group, a halogen atom, a nitro group, and —SO ₃ M [Rr and Rs are Each independently represents a hydrogen atom or a monovalent substituent, and M represents a hydrogen atom or an alkali metal atom. ] And -COORr [Rr represents a hydrogen atom or a monovalent substituent. ] Is preferable.
R ^1a , R ^1b , R ^1c , R ^1d , and R ^1e , or R ^1g , R ^1h , R ¹ⁱ , R ^1j , R ^1k , R ^1m , R ¹ⁿ , and R ^1p are each monovalent substitutions Examples of the monovalent substituent in the case of representing a group include substituents described in paragraphs [0019] to [0032] of JP2012-126882A, and among them, a substituted or unsubstituted alkyl group, alkylene An oxy group, a nitro group, an amide group and the like are preferable.
As the compound represented by the general formula (1), at least one of R ^1a , R ^1b , R ^1c , R ^1d , and R ^1e , more preferably R or R ^1d has a Hammett's σp value. A preferred embodiment is a monovalent substituent that is positive and each of R ^1g , R ^1h , R ¹ⁱ , R ^1j , R ^1k , R ^1m , R ¹ⁿ , and R ^1p is a hydrogen atom.

The compound represented by the general formula (1) is described in detail in JP 2012-126882 A.
Among these, examples of the compound represented by the above general formula (1) that are particularly preferably used in the present invention include exemplified compounds (UVA-1) to (UVA-6) below. The compound is not limited to the exemplified compounds. Among these, (UVA-1) to (UVA-5) having no acidic group in R ^{1a to} R ^1e are more preferable.

The compound represented by the general formula (1) has a substituent having a positive Hammett's σp value in at least one of R ^1a , R ^1b , R ^1c , R ^1d , and R ^1e. LUMO is stabilized by the attractive group. For this reason, the excitation life is shortened, and (1) the specific compound has excellent light resistance and the ultraviolet absorbing ability lasts for a long time. For example, when a known triazine-based compound is used as the ultraviolet absorber, the ultraviolet absorber-containing layer is adversely affected, such as decomposition and yellowing when used for a long time. Since the compound represented by 1) has excellent light resistance, it has an advantage that it does not decompose and does not yellow even when used for a long time.
The maximum absorption wavelength of the compound represented by the general formula (1) is not particularly limited, but is preferably 250 nm to 400 nm, and more preferably 280 nm to 380 nm. The full width at half maximum is preferably 20 nm to 100 nm, more preferably 40 nm to 80 nm.
The (1) specific compound according to the present invention preferably has no absorption in the visible range from the viewpoint of suppressing a decrease in reflectance of the film mirror.
Those skilled in the art can easily measure the maximum absorption wavelength and the half-value width defined in the present invention. The measurement method is described in, for example, “The Fourth Edition Experimental Chemistry Course 7 Spectroscopy II” (Maruzen, 1992), pages 180-186, edited by the Chemical Society of Japan. Specifically, the sample is dissolved in a suitable solvent, and measurement is performed by a spectrophotometer using a cell made of quartz or glass and using two cells for sample and control. The solvent to be used is required to have no absorption in the measurement wavelength region, have a small interaction with the solute molecule, and have a very low volatility in addition to the solubility of the sample. Any solvent satisfying the above conditions can be selected and used. From the viewpoint of the solubility of the compound represented by the general formula (1), amide solvents, sulfone solvents, sulfoxide solvents. Ureido solvents, ether solvents, ketone solvents, halogen solvents, hydrocarbon solvents, alcohol solvents, ester solvents, or nitrile solvents are preferred.

The compound represented by the general formula (1) can take a tautomer depending on the structure and the environment in which the compound is placed. In the present invention, one of the representative forms is described, but tautomers different from the description of the present invention are also included in the compound of the present invention.
The compound represented by the general formula (1) may contain an isotope (for example, 2H, 3H, 13C, 15N, 17O, 18O, etc.).

The compound represented by the general formula (1) can be synthesized by any method.
Known patent documents and non-patent documents, for example, JP-A-7-188190, JP-A-11-315072, JP-A-2001-220385, “Dyes and Drugs”, Vol. 40 No. 12 (1995), p325-p339. It can be synthesized with reference to the above.

  In the composition for forming an ultraviolet absorber-containing layer according to the present invention, the compound represented by the general formula (1) can contain any amount necessary for imparting desired performance. As content of the compound represented by General formula (1), it is preferable that it is more than 0 mass% and 30 mass% or less in a composition for ultraviolet absorber content layer formation, and is more than 0 mass% and 10 mass% or less. More preferably, it is more preferably 0.05% by mass or more and 5% by mass or less. If the content is in the above range, a sufficient ultraviolet shielding effect by the ultraviolet absorber-containing layer is obtained, and bleeding out of the ultraviolet absorber with time is suppressed.

[Crosslinking agent]
The ultraviolet absorber-containing layer according to the present invention preferably further contains a crosslinking agent. By including a cross-linking agent, the cross-linking structure is formed in the ultraviolet absorber-containing layer, so that the strength is further improved, and further, the adhesion with the adjacent metal reflective layer is further improved. It will be.
As the crosslinking agent, it can be selected depending on the correlation with the resin constituting the ultraviolet absorber-containing layer, and examples thereof include carbodiimide compounds, isocyanate compounds, epoxy compounds, oxetane compounds, melamine compounds, bisvinylsulfone compounds, and the like. From the viewpoint of effects, at least one crosslinking agent selected from the group consisting of carbodiimide compounds, isocyanate compounds, and epoxy compounds is preferred.
Commercially available products may be used as the crosslinking agent. For example, Nisshinbo Chemical Co., Ltd., Carbodilite V-05 (trade name), Mitsui Chemicals, Takenate D110N (trade name), Nagase ChemteX Corporation ) Manufactured by Denacor EX-614B (trade name).
When the crosslinking agent is contained in the ultraviolet absorber-containing layer, the content of the compound represented by the general formula (1) is A, and the content of the crosslinking agent is B. The ratio (A / B) is preferably from 0.05 to 10 and more preferably from 0.5 to 2 on a mass basis.
By using the crosslinking agent in the above ratio, the adhesion with the metal reflective layer is further improved, and an interaction is formed between the crosslinking agent and the ultraviolet absorber represented by the general formula (1). ) It also has the effect of improving the bleed-out suppression effect of the specific compound.
The formation of a crosslinked structure in the ultraviolet absorber-containing layer is confirmed by the disappearance of the peak corresponding to the reactive group of the crosslinking agent by infrared absorption spectrum. In addition, as a simple confirmation method, there is a confirmation method by improving the solvent resistance of the formed ultraviolet absorber-containing layer (dry film). Specifically, the dry film is immersed in a solvent for a predetermined time. It can be confirmed by comparing the weight change after the treatment or by dropping a solvent on the surface of the ultraviolet absorber-containing layer and visually comparing the swelling and dissolution state of the dropped portion.
In addition to the above components, the ultraviolet absorber-containing layer may contain additives such as a photopolymerization initiator, an antistatic agent, a coating aid (leveling agent), an antioxidant, and an antifoaming agent. Good.

[Method for forming ultraviolet absorber-containing layer]
There is no restriction | limiting in particular as a formation method of the ultraviolet absorber containing layer in this invention, For example, the ultraviolet absorber containing layer formation containing each component used together with the compound represented by General formula (1), resin, and if desired. A method for forming a UV absorber-containing layer by reducing the solvent after dissolving the composition for solvent in a solvent and coating the metal reflective layer, a temperature at which the resin contained in the UV absorber-containing layer forming composition melts To form a UV absorber-containing layer by casting on a metal reflective layer, the above-mentioned composition for forming an UV absorber-containing layer is formed into a film in advance, and the resulting film is bonded. Examples include a method of forming an ultraviolet absorber-containing layer by a method such as pasting to a metal reflective layer via an agent, or fusing to a metal reflective layer by a method such as thermal lamination.

Hereinafter, as an example of a method for forming the ultraviolet absorber-containing layer in the present invention, at least (1) a composition containing a specific compound and a resin is dissolved in a solvent and applied onto the metal reflective layer, and then the ultraviolet absorber is applied. A method for forming the containing layer will be described.
In this method, (1) a specific compound and a resin contained in the ultraviolet absorber-containing layer are dissolved in a solvent to prepare a coating solution composition for forming an ultraviolet absorber-containing layer, and then applied onto the surface of the metal reflective layer. And drying to form a coating composition composition for forming an ultraviolet absorber-containing layer on the surface of the metal reflective layer. Thereafter, the ultraviolet absorbent-containing layer is formed by curing the coating liquid composition layer for forming the ultraviolet absorbent-containing layer. When using the coating liquid composition for forming an ultraviolet absorber-containing layer containing a crosslinking agent, a method of forming a crosslinked structure by heating may be employed.
The solvent used for dissolving the resin material for forming the ultraviolet absorber-containing layer is not particularly limited as long as it is suitable for the resin. For example, acetone, ethyl acetate, butyl acetate, methyl ethyl ketone (MEK), N, N-dimethylformamide (DMF), cyclohexane, cyclohexanol, cyclohexanone, ethylbenzene and the like can be mentioned. Only 1 type may be used for a solvent and it may combine 2 or more types.
From the viewpoint of good solubility of the ultraviolet absorber represented by the general formula (1), amide solvents (for example, N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl- 2-pyrrolidone), sulfone solvents (eg, sulfolane), sulfoxide solvents (eg, dimethyl sulfoxide), ureido solvents (eg, tetramethylurea), ether solvents (eg, dioxane, tetrahydrofuran, cyclopentyl methyl ether), ketone solvents ( For example, acetone, cyclohexanone), hydrocarbon solvents (for example, toluene, xylene, n-decane), halogen solvents (for example, tetrachloroethane, chlorobenzene, chloronaphthalene), alcohol solvents (for example, methanol, ethanol, isopropyl alcohol, ethanol) Renglycol, cyclohexanol, phenol), pyridine solvents (eg, pyridine, γ-picoline, 2,6-lutidine), ester solvents (eg, ethyl acetate, butyl acetate), nitrile solvents (eg, acetonitrile) are preferably used. It is done.

From the viewpoint of uniformly forming an ultraviolet absorber-containing layer having excellent adhesion, the solid content concentration of the coating composition for forming an ultraviolet absorber-containing layer may be in the range of 1% by mass to 30% by mass. preferable.
The method of curing the resin film applied to the surface of the metal reflective layer is not particularly limited, and a method according to the resin material used for forming the ultraviolet absorber-containing layer, such as heating or ultraviolet irradiation, can be appropriately selected. That's fine.
Conventionally known methods such as gravure coating, reverse coating, die coating, blade coating, roll coating, air knife coating, screen coating, bar coating, curtain coating, etc. The coating method can be used.
The method of curing the resin film applied to the surface of the metal reflective layer is not particularly limited, and a method according to the resin material used for forming the ultraviolet absorber-containing layer, such as heating or ultraviolet irradiation, can be appropriately selected. That's fine.

  The film thickness of the ultraviolet absorber-containing layer may be 2 μm or more, and is preferably 50 μm or less in consideration of the balance between light reflectivity and protective function. From the viewpoint of achieving the necessary protective function and durability and suppressing reduction in light reflectivity, the range is preferably 3 μm to 30 μm, and more preferably 5 μm to 10 μm.

<Light stabilizer containing layer>
In the film mirror of the present invention, in order to prevent the deterioration or breakage of the metal reflective layer, resin support or plating undercoat polymer layer provided by sunlight, rainwater, dust, etc., and to stabilize the mirror surface In addition, a light stabilizer-containing layer containing a light stabilizer selected from (TS-I) to (TS-VI) and a resin may be provided on the incident light side of the metal reflective layer described in detail below. .

[Compounds Represented by General Formulas (TS-I) to (TS-VI)]
The light stabilizer-containing layer is an arbitrary layer provided to further improve the weather resistance of the film mirror, and includes the following general formula (TS-I), general formula (TS-II), and general formula (TS-III). ), General formula (TS-VI), general formula (TS-V), and at least one compound selected from the compound group represented by general formula (TS-VI). By further providing a light stabilizer-containing layer containing at least one compound selected from these compounds, the weather resistance of the film mirror is further improved. In the present specification, hereinafter, those belonging to these compound groups are sometimes referred to as “light stabilizers”.

In the general formula (TS-I), R ⁹¹ is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylcarbonyl group, an alkenylcarbonyl group, an alkyloxycarbonyl group, an alkenyloxycarbonyl group, Represents an aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, a phosphinotolyl group, a phosphinyl group, or —Si (R ⁹⁷ ) (R ⁹⁸ ) (R ⁹⁹ ), wherein R ⁹⁷ , R ⁹⁸ , and R ⁹⁹ are each independently An alkyl group, an alkenyl group, an aryl group, an alkoxy group, an alkenyloxy group, or an aryloxy group is represented. X ⁹¹ represents —O—, —S— or —N (—R ¹⁰⁰ ) —, and R ¹⁰⁰ has the same meaning as R ⁹¹ . R ⁹² , R ⁹³ , R ⁹⁴ , R ⁹⁵ , and R ⁹⁶ each independently represent a hydrogen atom or a monovalent substituent. R ⁹¹ and R ⁹² , R ¹⁰⁰ and R ⁹⁶ , and R ⁹¹ and R ¹⁰⁰ may be bonded to each other to form a 5-membered to 7-membered ring together with the adjacent carbon atoms. R ⁹² and R ⁹³ , R ^{100 93} and R ⁹⁴ may be bonded to each other to form a 5- to 7-membered ring, a spiro ring, or a bicyclo ring with adjacent carbon atoms. However, all of R ⁹¹ , R ⁹² , R ⁹³ , R ⁹⁴ , R ⁹⁵ , R ⁹⁶ , and R ¹⁰⁰ are not hydrogen atoms, and the total contained in the compound represented by the general formula (TS-I) Carbon number is 9 or more.

In the general formula (TS-II), R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , and R ¹⁰⁴ each independently represent a hydrogen atom, an alkyl group, or an alkenyl group, and R ¹⁰¹ and R ¹⁰² , R ¹⁰³ and R ¹⁰⁴ And may be bonded to each other to form a 5-membered to 7-membered ring together with adjacent carbon atoms. X ¹⁰¹ is a hydrogen atom, alkyl group, alkenyl group, alkyloxy group, alkenyloxy group, alkyloxycarbonyl group, alkenyloxycarbonyl group, aryloxycarbonyl group, acyl group, acyloxy group, alkyloxycarbonyloxy group, alkenyloxycarbonyl It represents an oxy group, an aryloxycarbonyloxy group, an alkylsulfonyl group, an alkenylsulfonyl group, an arylsulfonyl group, an alkylsulfinyl group, an alkenylsulfinyl group, an arylsulfinyl group, a sulfamoyl group, a carbamoyl group, a hydroxy group, or an oxy radical group. X ¹⁰² represents a nonmetallic atom group necessary for forming a 5-membered to 7-membered ring together with a carbon atom and a nitrogen atom.

In the general formula (TS-III), R ¹⁰⁵ and R ¹⁰⁶ are each independently a hydrogen atom, an aliphatic group, an acyl group, an aliphatic oxycarbonyl group, an aromatic oxycarbonyl group, an aliphatic sulfonyl group, or an aromatic group. Represents a sulfonyl group, and R ¹⁰⁷ represents an aliphatic group, aliphatic oxy group, aromatic oxy group, aliphatic thio group, aromatic thio group, acyloxy group, aliphatic oxycarbonyloxy group, aromatic oxycarbonyloxy group, substituted It represents an amino group, a heterocyclic group, or a hydroxy group, and R ¹⁰⁵ and R ¹⁰⁶ are not both hydrogen atoms, and the total carbon number contained in R ¹⁰⁵ and R ¹⁰⁶ is 7 or more. R ¹⁰⁵ and R ¹⁰⁶ , R ¹⁰⁶ and R ¹⁰⁷ , R ¹⁰⁵ and R ¹⁰⁷ may be bonded to each other to form a 5-membered to 7-membered ring with an adjacent nitrogen atom. It does not form a 2,2,6,6-tetraalkylpiperidine skeleton.

In the general formula (TS-IV), R ¹¹¹ and R ¹¹² each independently represents an aliphatic group, and the aliphatic group may further have a substituent, and the total carbon contained in R ¹¹¹ and R ¹¹² The number is 10 or more. R ¹¹¹ and R ¹¹² may be bonded to each other to form a 5- to 7-membered ring with an adjacent sulfur atom. n represents 0, 1, or 2.
In the general formula (TS-V), R ¹²¹ and R ¹²² each independently represents an aliphatic oxy group or an aromatic oxy group, and R ¹²³ represents an aliphatic group, an aromatic group, an aliphatic oxy group, or an aromatic group. Represents a group oxy group, and the total carbon number contained in R ¹²¹ , R ¹²² and R ¹²³ is 10 or more. m represents 0 or 1; R ¹²¹ and R ¹²² , R ¹²¹ and R ¹²³ may be bonded to each other to form a 5- to 8-membered ring together with the adjacent phosphorus atom. )
The light stabilizer that can be used in the present invention is described in detail in JP 2012-126882 A, and the exemplified compounds described in paragraphs [0095] to [0166] of the same publication are also preferably used in the present invention. Is done. Especially, the compound represented by general formula (TS-II) is preferable at the point that an effect can be maintained for a long period of time. Examples of the light stabilizer that can be used in the present invention are listed below, but the present invention is not limited thereto.

〔resin〕
The light stabilizer-containing layer in the present invention contains a resin.
The resin material used for forming the light stabilizer-containing layer is a resin that can form a film or layer, and the strength or durability of the formed film or layer, air and moisture blocking properties, In addition to adhesion to light stabilizer-containing layers, for example, metal reflective layers, UV absorber layers, surface coating layers, etc., transparency, especially high transparency to light of the wavelength required by film mirrors A resin having is preferred.

Specifically, for example, cellulose ester resins, polyester resins, polycarbonate resins, polyarylate resins, polysulfone (including polyether sulfone) resins, polyethylene terephthalate, polyester resins such as polyethylene naphthalate, polyethylene, Polypropylene, cellulose diacetate resin, cellulose triacetate resin, cellulose acetate propionate resin, cellulose acetate butyrate resin, polyvinyl alcohol, polyvinyl butyral, ethylene vinyl alcohol resin, ethylene vinyl acetate resin, and ethylene acrylate copolymer, polycarbonate , Norbornene resin, polymethylpentene resin, polyamide, fluorine resin, polymethyl methacrylate, acrylic resin , Olefin resin, polyurethane resin, and silicone resin.
Among these, transparency, affinity with compounds represented by the following general formulas (TS-I) to (TS-VI), and adjacent layers, for example, an ultraviolet absorber-containing layer and a metal reflective layer From the viewpoint of adhesion, the resin contained in the light stabilizer-containing layer is preferably one or more resins selected from acrylic resins, polyvinyl butyral, ethylene vinyl acetate resins, and ethylene acrylate copolymer. .

[Method for forming light stabilizer-containing layer]
There is no restriction | limiting in particular as a formation method of the light stabilizer content layer in this invention, For example, each represented by general formula (TS-I)-(TS-VI), resin, and each used together depending on necessity. A method for forming a light stabilizer-containing layer by dissolving a composition for forming a light stabilizer-containing layer containing a component in a solvent and applying the composition on a metal reflective layer and then reducing the solvent, the light stabilizer-containing layer A method of forming a light stabilizer-containing layer by heating to a temperature at which the resin contained in the composition for composition is melted and casting on the metal reflective layer, using the above-mentioned composition for forming a light stabilizer-containing layer Pre-molded into a film, and the resulting film is bonded to the metal reflective layer via an adhesive, or it is fused to the metal reflective layer by a method such as thermal lamination. Examples include a method of forming a layer.

In the following, as an example of a method for forming a light stabilizer-containing layer in the present invention, at least (1) a composition containing a specific compound and a resin is dissolved in a solvent and applied on a metal reflective layer, and then light stable. A method for forming the agent-containing layer will be described.
In this method, the light stabilizer and the resin represented by (TS-I) to (TS-VI) contained in the light stabilizer-containing layer are dissolved in a solvent, and the light stabilizer-containing layer-forming coating is applied. After preparing a liquid composition, it is apply | coated on the surface of a metal reflective layer, it is made to dry, and the coating liquid composition layer for light stabilizer containing layer formation is formed on the surface of a metal reflective layer. Thereafter, the light stabilizer-containing layer is formed by curing the coating solution composition layer for forming the light stabilizer-containing layer. When using the coating solution composition for light stabilizer containing layer formation containing a crosslinking agent, you may take the method of forming a crosslinked structure by heating.
The solvent used for dissolving the resin material for forming the light stabilizer-containing layer is not particularly limited as long as it is suitable for the resin. For example, acetone, ethyl acetate, butyl acetate, methyl ethyl ketone (MEK) N, N-dimethylformamide (DMF), cyclohexane, cyclohexanol, cyclohexanone, ethylbenzene and the like. Only 1 type may be used for a solvent and it may combine 2 or more types.
Further, from the viewpoint of good solubility of the light stabilizers represented by the general formulas (TS-I) to (TS-VI), amide solvents (for example, N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone), sulfone solvents (eg sulfolane), sulfoxide solvents (eg dimethyl sulfoxide), ureido solvents (eg tetramethylurea), ether solvents (eg dioxane, tetrahydrofuran, Cyclopentyl methyl ether), ketone solvents (eg acetone, cyclohexanone), hydrocarbon solvents (eg toluene, xylene, n-decane), halogen solvents (eg tetrachloroethane, chlorobenzene, chloronaphthalene), alcohol solvents (eg methanol) , Ethanol, isop (Pyr alcohol, ethylene glycol, cyclohexanol, phenol), pyridine solvents (eg pyridine, γ-picoline, 2,6-lutidine), ester solvents (eg ethyl acetate, butyl acetate), nitrile solvents (eg acetonitrile), etc. Is preferably used.

From the viewpoint of uniformly forming a light stabilizer-containing layer having excellent adhesion, the solid content concentration of the coating composition for forming a light stabilizer-containing layer is in the range of 1% by mass to 30% by mass. It is preferable.
Conventionally known methods such as gravure coating, reverse coating, die coating, blade coating, roll coating, air knife coating, screen coating, bar coating, curtain coating, etc. The coating method can be used.
The method of curing the resin film applied to the surface of the metal reflective layer is not particularly limited, and a method according to the resin material used to form the light stabilizer-containing layer, such as heating or ultraviolet irradiation, is appropriately selected. do it.

The film thickness of the light stabilizer-containing layer is preferably in the range of 3 μm to 30 μm from the viewpoint of achieving necessary protective functions and durability and suppressing light reflectivity reduction. More preferably, it is the range.
When the light stabilizer-containing layer is provided alone, the position may be between the metal reflective layer and the ultraviolet absorber-containing layer, or the surface on the incident light side of the ultraviolet absorber-containing layer.

The ultraviolet absorber-containing layer and the light stabilizer-containing layer may be provided separately as described above, or these may be provided as the same layer. That is, by including the ultraviolet absorber and the light stabilizer in the same layer, the ultraviolet absorber-containing layer also has a function as a light stabilizer-containing layer. In this case, high light resistance and weather resistance can be expected due to the synergistic effect of the ultraviolet absorber and the light stabilizer, which is preferable.
By containing at least one light stabilizer in the ultraviolet absorber-containing layer, the stability of the resin used in the ultraviolet absorber-containing layer containing the compound represented by the general formula (1) is further improved. The weather resistance becomes more excellent.

Mixing in the case where the compound represented by the general formula (1) used in the present invention and at least one compound selected from the general formulas (TS-I) to (TS-V) are contained in the same layer The mass ratio is not particularly limited, but is preferably 1: 0 from the viewpoint of the balance between the light resistance that is further improved by containing these components and the effect of suppressing the bleed out from the resin of the specific compound (1). 0.05 to 1: 5, more preferably 1: 0.5 to 1: 2, more preferably 1: 1.
Moreover, the total content of at least one compound selected from the compound group represented by the general formulas (TS-I) to (TS-V) is based on the entire composition constituting the ultraviolet absorber-containing layer. Preferably, it is greater than 0% by mass and 30% by mass or less, more preferably 0% by mass to 10% by mass, and particularly preferably 0.05% by mass to 5% by mass. If the content is in the above range, it is preferable because further improvement in light resistance and weather resistance and suppression of bleed out can be achieved at the same time.

The film mirror of the present invention has a resin support such as a polyester film as described below. The resin constituting the support also has a tendency to improve the weather resistance, such as having a crosslinked structure, but in order to further improve the weather resistance, as described above, a specific layer is added to the ultraviolet absorber-containing layer. Contains an ultraviolet absorber. In the present invention, from the viewpoint of reflectivity, it is said that the metal of the metal reflective layer preferably contains silver, but the silver-containing metal reflective layer tends to transmit UV-B. (1) It is important for the weather resistance of the resin support to improve that the specific compound is contained in the ultraviolet absorber-containing layer.
The content of the specific compound (1) in the ultraviolet absorber-containing layer is 0.1% by mass to 20% by mass, preferably 1% by mass to 15% by mass, and more preferably based on the total mass of the ultraviolet absorber-containing layer. 3% by mass to 10% by mass. When it is more than 20% by mass, the adhesion is deteriorated, and when it is less than 0.1% by mass, the effect of improving weather resistance is small.

<Resin support>
The film mirror of the present invention uses a resin support as a support. Resin which comprises a support body is not specifically limited, According to the objective, it selects suitably.
Examples of the resin constituting the support include polyolefin resins such as polyethylene and polypropylene; polyester resins such as polyethylene terephthalate and polyethylene naphthalate; polycarbonate resins; acrylic resins such as polymethyl methacrylate; polyamide resins; polyimides Polyvinyl chloride resin; Polyphenylene sulfide resin; Polyethersulfone resin; Polyethylene sulfide resin; Polyphenylene ether resin; Styrene resin; Cellulose resin such as cellulose acetate;
Of these, polyester resins and acrylic resins are preferred from the viewpoint of good transparency and weather resistance of the film mirror.

In the present invention, the shape of the support is not particularly limited, and is appropriately selected depending on the intended use mode. The shape may be any one having a surface shape such as a sheet shape (planar shape), a diffusion surface, a concave surface, or a convex surface.
The thickness of the support is appropriately selected depending on the shape of the resin substrate and the location where the film mirror is installed. More preferably, ~ 250 μm. The support in the present invention tends to improve the mechanical strength when the thickness is 25 μm or more, and is advantageous in terms of cost when the thickness is 400 μm or less.

<Resin intermediate layer>
The film mirror of the present invention has a resin intermediate layer on a support. In the present invention, the resin intermediate layer is provided from the viewpoint of adhesion between the support and the metal reflective layer. The resin intermediate layer is composed of one or two layers selected from an easy adhesion layer and a plating undercoat polymer layer. In addition, when a resin intermediate | middle layer is comprised from 2 layers of an easily bonding layer and a plating undercoat polymer layer, it forms in order of an easily bonding layer and a plating undercoat polymer layer on a support body.

[Easily adhesive layer]
In the present invention, an easy adhesion layer may be provided in order to improve the adhesion between the support and the metal reflective layer. In addition, when a plating undercoat polymer layer is provided on the easy adhesion layer, the easy adhesion layer improves the adhesion between the support and the plating undercoat polymer layer, resulting in adhesion between the support and the metal reflective layer. More improved.

In the present invention, the easy-adhesion layer contains the same resin as the resin constituting the support or a resin having an affinity for the resin constituting the support from the viewpoint of adhesion to the adjacent support. Is preferred. Examples of the resin having affinity with the resin constituting the support include resins having similar thermal properties such as glass transition point, elastic modulus, and linear expansion coefficient. Moreover, when providing a metal reflective layer directly on an easily bonding layer, the resin which has a functional group with affinity with the metal contained in the metal reflective layer formed, or the surface of the formed layer is adhesive, It is preferable to use a resin capable of forming an adhesive layer from the viewpoint that it becomes easier to accept a metal by having adhesiveness.
The resin contained in the easy adhesion layer may be, for example, a thermosetting resin, a thermoplastic resin, or a mixture thereof. Examples of the thermosetting resin include epoxy resin, phenol resin, polyimide resin, polyester resin, bismaleimide resin, polyolefin resin, isocyanate resin, and the like. Examples of the thermoplastic resin include phenoxy resin, polyether sulfone, polysulfone, polyphenylene sulfone, polyphenylene sulfide, polyphenyl ether, polyether imide, and the like.
The thermoplastic resin and the thermosetting resin may be used alone or in combination of two or more. The combined use of two or more kinds of resins is performed for the purpose of expressing a more excellent effect by compensating for each defect.

When the easy adhesion layer is provided between the plating undercoat polymer layer and the support, the functional group and polymerizable group interacting with the plating catalyst or precursor thereof contained in the plating undercoat polymer layer described in detail below. It is preferable to contain an active species that generates an active site capable of interacting with a polymer compound having a. Such an easy-adhesion layer is preferably, for example, a polymerization initiation layer containing a radical polymerization initiator or a polymerization initiation layer made of a resin having a functional group capable of initiating polymerization. More specifically, the easy adhesion layer is composed of a layer containing a polymer compound and a radical polymerization initiator, a layer containing a polymerizable compound and a radical polymerization initiator, or a resin having a functional group capable of initiating polymerization. A layer is preferred.
Examples of the layer made of a resin having a functional group capable of initiating polymerization include polyimide having a polymerization initiation site described in paragraphs [0018] to [0078] of JP-A-2005-307140 in the skeleton.

  Furthermore, when forming an easy-adhesion layer, a compound having a polymerizable double bond, specifically an acrylate compound or a methacrylate compound, may be used in order to promote crosslinking in the layer. It is preferable to use those. In addition, as a compound having a polymerizable double bond, a part of a thermosetting resin or a thermoplastic resin such as an epoxy resin, a phenol resin, a polyimide resin, a polyolefin resin, a fluorine resin, etc. Alternatively, a (meth) acrylated resin using acrylic acid or the like may be used.

As long as the effects of the present invention are not impaired, the easy-adhesion layer in the present invention contains one or more various additives such as an adhesion-imparting agent, a silane coupling agent, an antioxidant, and an ultraviolet absorber as necessary. Two or more kinds may be added.
In the case of adding these materials, it is preferable to add them in the range of more than 0% by mass and not more than 200% by mass, more preferably more than 0% by mass, with respect to the resin as the main component. It is added in the range of mass% or less.

  In order to generate an active site (active species) capable of interacting with a polymer compound having a functional group and a polymerizable group that interacts with the plating catalyst or its precursor, an easy adhesion layer should be given some energy. Well, as energy that can be applied, light (ultraviolet rays, visible light, X-rays, etc.), plasma (oxygen, nitrogen, carbon dioxide, argon, etc.), heat, electricity, etc. are used. Further, active sites may be generated by chemically decomposing the surface with an oxidizing liquid (potassium permanganate solution) or the like.

  Examples of materials that generate active sites include thermal polymerization initiators and photopolymerization initiators. Specifically, a functional group having a polymerization initiating ability described in paragraph [0044] of JP-A-2007-154306 or paragraphs [0011] to [0158] of JP-A-2004-161995. Is a polymer in which a side chain is pendant, and a known polymerization initiator represented by this can be appropriately selected and used according to the purpose. Among these, use of photopolymerization is preferable from the viewpoint of production suitability, and therefore, it is preferable to use a photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it is active against irradiated actinic rays and can express active sites. For example, radical polymerization initiator, anionic polymerization initiator, cationic polymerization initiator From the viewpoint of reactivity, a radical polymerization initiator is preferable.

  The content of the polymerization initiator in the case of using a polymerization initiator for the easy-adhesion layer is preferably 0.1% by mass to 50% by mass in terms of solid content, and preferably 1.0% by mass to 30% by mass. More preferred.

[Method of forming easy-adhesion layer]
The easy-adhesion layer in the present invention is formed by dissolving each of the above-described components in a solvent that can be dissolved and then applying it to the support by a method such as coating, and hardening it by heating or light irradiation. Can do.
The easy adhesion layer is preferably formed by a hard film by heating and / or light irradiation. In particular, after drying by heating, when preliminarily cured by light irradiation, when a polymerizable compound is contained, a certain degree of curing is performed in advance, so that a plating undercoat polymer layer is formed on the easily adhesive layer. This is preferable because it can effectively suppress the situation where the easy-adhesion layer falls off after fixing.
The heating temperature and time may be selected under conditions that allow the coating solvent to sufficiently dry. However, from the viewpoint of production suitability, the temperature is preferably 100 ° C. or less, and the drying time is preferably within 30 minutes, and the drying temperature is 40 ° C. to 80 ° C. It is more preferable to select heating conditions within a drying time of 10 minutes.

The easy adhesion layer is preferably formed on the surface of the support by applying a known layer forming method such as a coating method, a transfer method, or a printing method.
The solvent used when forming the easy-adhesion layer by coating is not particularly limited as long as it can dissolve the above components. From the viewpoint of easy drying and workability, a solvent having a boiling point that is not too high is preferable. Specifically, a solvent having a boiling point of about 40 ° C to 150 ° C may be selected.
Specifically, cyclohexanone, methyl ethyl ketone and the like described in paragraph [0045] of JP-A-2007-154306 can be used. The above exemplified solvents can be used alone or in combination. The concentration of the solid content in the coating solution is suitably 2% by mass to 50% by mass.

  In general, the thickness of the easy-adhesion layer in the present invention is preferably in the range of 0.1 μm to 10 μm, and more preferably in the range of 0.2 μm to 5 μm.

[Plating undercoat polymer layer]
The plating undercoat polymer layer in the present invention has at least reduced metal particles and a plating undercoat polymer described later.
In the present invention, using a composition containing a metal precursor and a plating undercoat polymer to be described later, a plating undercoat polymer layer containing the metal precursor is formed on the support by a method such as coating or the like. A metal precursor is formed by forming a layer on a support using a composition containing a plating undercoat polymer, and then bringing the composition containing a metal precursor into contact with the layer provided on the support by a method such as immersion. It is preferable to form a polymer layer containing, and then reduce the metal precursor of the plating undercoat polymer layer containing the metal precursor to form a plating undercoat polymer layer containing the reduced metal particles.

(Plating undercoat polymer)
First, the plating undercoat polymer used for forming the plating undercoat polymer layer will be described.
The plating undercoat polymer used for forming the plating undercoat polymer layer in the present invention has at least a polymerizable group and a functional group that interacts with the metal precursor (hereinafter referred to as “interactive group” as appropriate). .
The main skeleton of the plating undercoat polymer is preferably an acrylic polymer, polyether, acrylamide, polyamide, polyimide, acrylic polymer, polyester, or the like, and more preferably an acrylic polymer.

The plating undercoat polymer only needs to have a polymerizable group and an interactive group in the molecule, and the polymerizable group only needs to be at least one of the main chain terminal and the side chain of the polymer. For example, a polymer composed of a structural unit having a polymerizable group and a structural unit having an interactive group can be mentioned, and the same structural unit includes a polymerizable group and an interactive group. Also good. Moreover, 2 or more types of polymeric groups may be included, and 2 or more types of interactive groups may be included. The polymerizable group may be introduced by polymer reaction after the production of the polymer.
The plating undercoat polymer may contain a constitutional unit other than a constitutional unit containing a polymerizable group and an interaction group depending on the purpose. When a plating undercoat composition is formed by including a structural unit other than the structural unit containing a polymerizable group and a structural unit containing an interactive group (hereinafter referred to as other structural unit as appropriate), water or It is excellent in solubility in an organic solvent, and a uniform plating undercoat layer can be formed.

As a preferable embodiment of the plating undercoat polymer, an acrylic polymer having an acidic group and a polymerizable group as an interactive group in the side chain can be mentioned.
Hereinafter, a polymerizable group, an interactive group, and characteristics of the plating undercoat polymer will be described in detail.

-Polymerizable group-
The polymerizable group of the plating undercoat polymer forms a chemical bond between the polymers or between the polymer and the base layer (a support or an easy-adhesion layer or an undercoat layer provided on the support) by applying energy. Any functional group can be used. Examples of the polymerizable group include a radical polymerizable group and a cationic polymerizable group. Of these, a radical polymerizable group is preferable from the viewpoint of reactivity.
Examples of the radical polymerizable group include methacryloyl group, acryloyl group, itaconic acid ester group, crotonic acid ester group, isocrotonic acid ester group, maleic acid ester group, styryl group, vinyl group, acrylamide group and methacrylamide group. It is done. Among these, a methacryloyl group, an acryloyl group, a vinyl group, a styryl group, an acrylamide group, and a methacrylamide group are preferable, and from the viewpoint of radical polymerization reactivity and synthesis versatility, a methacryloyl group, an acryloyl group, an acrylamide group, and A methacrylamide group is preferable, and an acrylamide group and a methacrylamide group are more preferable from the viewpoint of alkali resistance.
Among them, various polymerizable groups introduced into the acrylic polymer include (meth) acryl groups such as (meth) acrylate groups or (meth) acrylamide groups, vinyl ester groups of carboxylic acids, vinyl ether groups, and allyl ether groups. A polymerizable group is preferred.

-Interactive group-
The interaction group of the plating undercoat polymer is a functional group that interacts with the metal precursor (for example, a coordination group, a metal ion adsorbing group, etc.), and can form an electrostatic interaction with the metal precursor. A functional group, or a nitrogen-containing functional group, a sulfur-containing functional group, an oxygen-containing functional group or the like that can form a coordination with a metal precursor can be used.
More specifically, as an interactive group, amino group, amide group, imide group, urea group, tertiary amino group, ammonium group, triazine ring, triazole ring, benzotriazole group, imidazole group, pyridine group, pyrimidine group A nitrogen-containing functional group such as a pyrazine group, a triazine group, a piperidine group, a piperazine group, a pyrrolidine group, a pyrazole group, a group containing an alkylamine structure, a cyano group, a cyanate group (R—O—CN); an ether group, a hydroxyl group, Oxygen-containing functional groups such as phenolic hydroxyl group, carboxyl group, carbonate group, carbonyl group, ester group, group containing N-oxide structure, group containing S-oxide structure, group containing N-hydroxy structure; thiophene group, thiol Group, thiourea group, sulfoxide group, sulfone group, sulfite group, sulfonic acid group, sulfone Sulfur-containing functional groups such as groups containing an ester structure; Phosphorus-containing functional groups such as phosphate groups, phosphoramide groups, phosphine groups, groups containing phosphate ester structures; groups containing halogen atoms such as chlorine and bromine In the functional group capable of taking a salt structure, those salts can also be used.
The interactive group may be a non-dissociative functional group or an ionic polar group, and these may be contained at the same time, but an ionic polar group is preferred.

  As the interactive group comprising an ionic polar group, among the above interactive groups, the plating undercoat polymer support (in the case where the easy adhesion layer is formed on the support, the easy adhesion layer) From the viewpoint of adhesion, carboxylic acid groups, sulfonic acid groups, phosphoric acid groups, and boronic acid groups can be mentioned. Among them, it has moderate acidity (does not decompose other functional groups), and affects other functional groups. Carboxylic acid groups are particularly preferred from the viewpoint of less concern, excellent compatibility with the plating layer, and easy availability of raw materials.

An ionic polar group such as a carboxylic acid group can be introduced into the plating undercoat polymer by copolymerizing a radical polymerizable compound having an acidic group.
Hereinafter, the suitable structure of the plating undercoat polymer used in the present invention will be described in detail.

The acrylic polymer suitably used as the plating undercoat polymer in the present invention described above will be described more specifically. An acrylic resin containing a carboxylic acid group as an acidic group, a cyclic ether group-containing polymerizable compound such as glycidyl acrylate, Epoxy group-containing compounds such as glycidyl esters of unsaturated fatty acids such as glycidyl methacrylate and cinnamic acid, and compounds having alicyclic epoxy groups (for example, epoxy groups such as cyclohexene oxide in the same molecule) and (meth) acryloyl groups Examples include compounds obtained by adding a polymerizable compound. In addition, a compound obtained by adding an isocyanate group-containing polymerizable compound such as isocyanate ethyl (meth) acrylate to an acrylic resin containing an acidic group and a hydroxyl group, an acrylic resin containing an anhydride group, a hydroxyalkyl ( Examples thereof include compounds obtained by adding a polymerizable compound containing a hydroxyl group such as (meth) acrylate. In addition, a compound obtained by copolymerizing a cyclic ether group-containing polymerizable compound such as glycidyl methacrylate and a vinyl monomer such as (meth) acryloylalkyl ester and adding (meth) acrylic acid to the side chain epoxy group is also available. Can be mentioned.
Specific examples of these polymers are described in Japanese Patent Publication Nos. 2763775, 3-172301, 2000-232264, and the like, and the polymers described herein can be suitably used in the present invention. .

  Among these, the above acrylic polymer is obtained by adding a polymerizable compound containing a cyclic ether group (for example, a group having an epoxy group or an oxetane group in a partial structure) to a part of the acidic group of the polymer compound. It is more preferable that the polymer compound is selected from any of those obtained by adding a carboxyl group-containing polymerizable compound to part or all of the cyclic ether group of the molecular compound. In this case, the addition reaction between the acidic group and the compound having a cyclic ether group is preferably carried out in the presence of a catalyst. In particular, the catalyst is preferably selected from an acidic compound and a neutral compound.

The acidic group represented by the carboxylic acid group can be imparted to the plating undercoat polymer by copolymerizing a radically polymerizable compound having an acidic group.
The radical polymerizable compound having a carboxylic acid group is not particularly limited and may be appropriately selected depending on the purpose. For example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, p- Examples thereof include carboxyl styrene, and among these, acrylic acid, methacrylic acid, and p-carboxy styrene are preferable. These may be used individually by 1 type and may use 2 or more types together.

  The content of the acidic group such as a carboxylic acid group in the plating undercoat polymer is 1.0 meq / g to 10.0 meq / g, preferably 2.0 meq / g to 9.0 meq / g, 2.5 meq / g to 8.0 meq / g is more preferable. By setting the content of the carboxylic acid group within this range, the affinity with the plating layer is sufficient, and damage on the plating surface due to post-treatment using alkaline water or the like can be further reduced.

  In this invention, a plating undercoat polymer may be used individually by 1 type, and 2 or more types may be mixed and used for it. Moreover, you may mix and use the other high molecular compound from which a structure differs from a plating undercoat polymer. In this case, the content of the other polymer compound in the plating undercoat polymer is preferably 50% by mass or less, and more preferably 30% by mass or less.

1000 to 700,000 are preferable, as for the weight average molecular weight of the plating undercoat polymer in this invention, More preferably, it is 2000 to 200,000, More preferably, it is 10,000 to 100,000. By setting the weight average molecular weight within this range, higher adhesion strength can be obtained, resistance to a treatment solution such as alkaline water can be obtained, and storage stability with time can be further improved. In particular, from the viewpoint of polymerization sensitivity, the weight average molecular weight of the plating undercoat polymer in the present invention is preferably 20000 or more. From the viewpoint of suppressing gelation during synthesis, the upper limit of the molecular weight is preferably 150,000, more preferably 100,000 or less.
In addition, the weight average molecular weight described here is a polystyrene conversion value measured using GPC (used solvent: N-methylpyrrolidone), and can be measured, for example, under the following conditions.
Column: guard column; TOSOH TSK guard column Super AW
-H
Separation column; TOSOH TSKgelSuper AWM-H
(3 size 6.0 mm x 15 cm connected)
Eluent: N-methylpyrrolidone (containing LiBr 10 mM)
・ Flow rate: 0.35 mL / min
・ Detection method: RI
-Temperature: Column 40 ° C, inlet 40 ° C, RI 40 ° C
Sample concentration: 0.1 wt%
・ Injection volume: 60 μL
Moreover, as a polymerization degree of the plating undercoat polymer in this invention, it is preferable to use a 10-mer or more thing, More preferably, it is a 20-mer or more thing. Moreover, 1500-mer or less is preferable and 1000-mer or less is more preferable.

  Specific examples of the plating undercoat polymer include polymers described in paragraphs [0106] to [0112] of JP-A-2009-007540 as a polymer having an interactive group composed of a radical polymerizable group and a non-dissociable functional group. Etc. can be used. As the polymer having a radical polymerizable group and an interactive group composed of an ionic polar group, polymers described in paragraphs [0065] to [0070] of JP-A-2006-135271 can be used. Examples of the polymer having a radical polymerizable group, an interactive group composed of a non-dissociative functional group, and an interactive group composed of an ionic polar group include paragraphs [0010] to [0010] of [2010] -248464. [0128], polymers described in paragraphs [0030] to [0108] of JP 2010-84196 A and US Patent Application Publication No. 2010-080964 may be used.

  The content of the plating undercoat polymer in the composition for forming the plating undercoat polymer layer (hereinafter referred to as the composition for forming the plating undercoat polymer layer) is not particularly limited, but is 2 mass with respect to the total amount of the composition. % To 50% by mass is preferable, and 5% to 30% by mass is more preferable. Within this range, the composition is easy to handle and the thickness of the polymer layer can be easily controlled.

  When the plating undercoat polymer is an acrylic polymer, the content of the plating undercoat polymer with respect to the solid content of the composition for forming a plating undercoat polymer layer is preferably 1% by mass to 80% by mass, and more preferably 2% by mass to 70% by mass. preferable. By setting the content of the plating undercoat polymer in the above range, the surface state of the coating film becomes better, and the coating liquid does not become highly viscous, and it becomes easier to obtain a desired coating film thickness.

  In addition, the metal precursor mentioned later may be provided after the plating undercoat polymer layer is formed, or may be contained in the composition for the plating undercoat polymer layer from the beginning. When the metal precursor is contained in the plating undercoat polymer layer forming composition, the content of the metal precursor is preferably 0.5% by mass to 100% by mass with respect to the total amount of the composition, and 1% by mass to 50%. The mass% is more preferable.

The plating undercoat polymer layer preferably contains a radical polymerization initiator such as a photopolymerization initiator or a thermal polymerization initiator in order to increase sensitivity to energy application. The radical polymerization initiator is not particularly limited, and generally known ones are used.
However, if the plating undercoat polymer can generate an active site that interacts with the support or the easy-adhesion layer by applying energy, that is, when using a polymer having a polymerization initiation site in the polymer skeleton described above, It is not necessary to add these radical polymerization initiators.

  The amount of the radical polymerization initiator to be contained in the plating undercoat polymer layer forming composition is selected according to the configuration of the plating undercoat polymer layer forming composition, but in general, the plating undercoat polymer layer forming composition. It is preferable that it is about 0.05 mass%-30 mass% in it, and it is more preferable that it is about 0.1 mass%-10.0 mass%.

[Method of forming plating undercoat polymer layer]
(Formation of polymer layer)
-Application of polymer layer forming composition containing plating undercoat polymer-
A polymer layer containing a plating undercoat polymer (hereinafter, appropriately referred to as a polymer layer) is, for example, a polymer containing a plating undercoat polymer on the surface of the support or the easy-adhesion layer provided on the support. After applying the coating liquid of the layer forming composition, it can be formed by applying energy.
When the polymer layer is directly provided on the support, it is preferable to perform an easy adhesion treatment such as applying energy to the surface of the support in advance.
The method for providing the polymer layer on the support is not particularly limited, and a method of immersing the support in a polymer layer forming composition containing a plating undercoat polymer or a polymer layer forming composition containing a plating undercoat polymer is used as a support. The method of apply | coating on the top etc. is mentioned. From the viewpoint of easily controlling the thickness of the resulting polymer layer, a method of applying a polymer layer forming composition containing a plating undercoat polymer on a support is preferred. The coating method is not particularly limited, and a known method can be used.

Plating coating amount of the polymer layer forming composition containing undercoat polymer, from the viewpoint of sufficient interaction formed with the later-described metal precursor, preferably from 0.05g ^/ m ² ~10g / m 2 in terms of solid content In particular, 0.3 g / m ^{2 to} 5 g / m ² are preferable.
The coating solution of the composition for forming a polymer layer containing a plating undercoat polymer applied to a support or the like is dried at 20 ° C. to 60 ° C. for 1 second to 2 hours, and then dried at a temperature exceeding 60 ° C. for 1 second to 2 hours. More preferably, after drying at 20 ° C. to 60 ° C. for 1 second to 20 minutes, it is more preferable to dry at a temperature exceeding 60 ° C. for 1 second to 20 minutes.

  The composition for forming a polymer layer containing a plating undercoat polymer has a polymer in an energy application region by applying energy after contacting the support or the easy adhesion layer provided on the support. An interaction is formed between the polymerizable groups or the polymerizable group of the polymer and the support or the easy-adhesion layer provided on the support. A fixed polymer layer is formed on the support via the adhesive layer. Thereby, a support body and a polymer layer adhere | attach firmly.

-Granting energy-
Examples of the energy application method include heating and exposure.
As an energy application method by exposure, specifically, light irradiation by a UV lamp, visible light, or the like is possible. Examples of the light source used for exposure include a mercury lamp, a metal halide lamp, a xenon lamp, and a chemical lamp. Examples of radiation include electron beams, X-rays, ion beams, and far infrared rays. Further, g-line, i-line, deep-UV light, and high-density energy beam (laser beam) are also used.
Exposure power, in order to easily proceed polymerization, also for suppressing the degradation of the polymer, or, because the polymer forms a good interaction in the range from the viewpoint of 10mJ ^/ cm ² ~8000mJ ^/ cm 2, such as preferably ^there, and more preferably in the range of ^{100mJ / cm 2 ~3000mJ / cm 2} .
Note that exposure may be performed in an atmosphere in which substitution with an inert gas such as nitrogen, helium, or carbon dioxide is performed, and the oxygen concentration is suppressed to 600 ppm or less, preferably 400 ppm or less.

Energy application by heating can be performed by, for example, a general heat heat roller, laminator, hot stamp, electric heating plate, thermal head, laser, blower dryer, oven, hot plate, infrared dryer, heating drum, or the like.
In addition, when energy is applied by heating, the temperature is preferably in the range of 20 ° C. to 200 ° C. in order to facilitate the polymerization and to suppress thermal denaturation of the support, A range of 120 ° C. is more preferable.

-Removal of unreacted undercoating polymer-
After energy application, a step of removing unreacted polymer may be provided as appropriate. Examples of the removal method include a method using a solvent. For example, in the case of a solvent that dissolves a polymer or an alkali-soluble polymer, an alkaline developer (sodium carbonate, sodium bicarbonate, aqueous ammonia, aqueous sodium hydroxide) Etc. can be contacted with the support on which the polymer layer is formed to remove the unreacted polymer.

The film thickness of the polymer layer obtained by the above method is not particularly limited, but is preferably 0.05 μm to 10 μm and more preferably 0.3 μm to 5 μm from the viewpoint of adhesion with the support and the like. preferable.
Further, the surface roughness (Ra) of the polymer layer obtained by the above method is preferably 20 nm or less, more preferably 10 nm or less, from the viewpoint of reflection performance.

-Reduced metal particles-
The plating undercoat polymer layer in the present invention contains reduced metal particles. The reduced metal particles contained in the plating undercoat polymer layer provide a metal precursor to the support or the plating undercoat polymer layer formed on the easy-adhesion layer provided on the support, By reducing the metal precursor, the metal precursor is obtained as reduced metal particles. When the metal precursor is applied to the plating undercoat polymer layer, the metal precursor adheres to the interactive group by interaction.
The metal precursor contained in the plating undercoat polymer layer will be described below.

-Metal precursor-
The metal precursor used in the present invention is not particularly limited as long as it functions as an electrode by changing to a metal by a reduction reaction. Moreover, as a metal precursor, what functions as an electrode of plating in formation of a metal reflective layer is mentioned preferably. Therefore, what functions as an electrode by reducing a metal precursor to a metal is preferable.
Specifically, metal ions such as Au, Pt, Pd, Ag, Cu, Ni, Al, Fe, and Co are used. Metal ions that are metal precursors are contained in a composition containing a plating undercoat polymer (a composition for forming a plating undercoat polymer layer). After forming a layer on the support, zero-valent metal particles are formed by a reduction reaction. It becomes.
It is preferable that the metal ion which is a metal precursor is contained in the composition for forming a plating undercoat polymer layer as a metal salt.
The metal salt used is not particularly limited as long as it is dissolved in a suitable solvent and dissociated into a metal ion and a base (anion), but the type, number, and number of functional groups capable of coordination. From the viewpoint of catalytic ability, Ag ion, Cu ion, and Pd ion are preferable.

One preferred example of the metal precursor used in the present invention is silver ion.
When silver ions are used, those obtained by dissociating silver compounds as shown below can be suitably used. Specific examples of the silver compound include silver nitrate, silver acetate, silver sulfate, silver carbonate, silver cyanide, silver thiocyanate, silver chloride, silver bromide, silver chromate, silver chloranilate, silver salicylate, silver diethyldithiocarbamate, Examples thereof include silver diethyldithiocarbamate and silver p-toluenesulfonate. Among these, silver nitrate is preferable from the viewpoint of water solubility.
Moreover, as a metal precursor, a copper ion is mentioned as another preferable example. When using copper ion, the thing which the copper compound as shown below dissociated can be used suitably. Specific examples of copper compounds include copper nitrate, copper acetate, copper sulfate, copper cyanide, copper thiocyanate, copper chloride, copper bromide, copper chromate, copper chloranilate, copper salicylate, copper diethyldithiocarbamate, diethyldithiol. Examples thereof include copper carbamate and copper p-toluenesulfonate. Among these, copper sulfate is preferable from the viewpoint of water solubility.

The metal precursor is preferably applied to the plating undercoat polymer layer as a dispersion or solution (metal precursor liquid).
As an application method, for example, a polymer layer is formed on a support using a composition containing a plating undercoat polymer, and then a composition (dispersion or solution) containing a metal precursor is applied onto the polymer layer. Examples thereof include a method or a method of immersing the support on which the polymer layer is formed in a composition (dispersion or solution) containing a metal precursor.
As described above, by bringing a dispersion or solution containing a metal precursor into contact with the polymer layer, an interaction group in the plating undercoat polymer can interact with an intermolecular force such as van der Waals force, or The metal precursor can be adsorbed by utilizing the interaction due to the coordinate bond by the lone electron pair.

From the viewpoint of sufficiently adsorbing the metal precursor, the concentration of the metal precursor in the dispersion or solution containing the metal precursor is preferably 0.001% by mass to 50% by mass, It is more preferable that it is mass%-30 mass%.
Water or an organic solvent is used as a solvent for the metal precursor dispersion and solution. By containing water or an organic solvent, the permeability of the metal precursor to the polymer layer is improved, and the metal precursor can be efficiently adsorbed to the interactive group.

When the dispersion is used for applying the metal precursor to the plating undercoat polymer layer, the particle diameter of the metal precursor is preferably 1 nm to 200 nm, more preferably 1 nm to 100 nm, and still more preferably 1 nm to 60 nm. By setting this particle size, the particle size of the reduced metal particles can be controlled to a desired size.
In addition, a particle diameter is an average primary particle diameter (volume conversion) here, and is read from the image of SEM (S-5200, Hitachi High-Tech Manufacturing & Service Co., Ltd.).

It is preferable that the water used for the metal precursor liquid does not contain impurities. From such a viewpoint, it is preferable to use RO water, deionized water, distilled water, purified water, etc., and it is particularly preferable to use deionized water or distilled water. The organic solvent used in the metal precursor liquid is not particularly limited as long as it is a solvent that can penetrate into the polymer layer. However, from the viewpoint of compatibility with the metal precursor and permeability into the polymer layer, water or water-soluble The organic solvent is preferably acetone, dimethyl carbonate, dimethyl cellosolve, triethylene glycol monomethyl ether, diethylene glycol dimethyl ether, or diethylene glycol diethyl ether.
Furthermore, you may make a dispersion liquid and a solution contain another additive according to the objective. Examples of other additives include swelling agents and surfactants.

Metal ions, which are metal precursors applied to the plating undercoat polymer layer, are reduced by a metal activation liquid (reducing liquid). The metal activation liquid is composed of a reducing agent that can reduce a metal precursor (mainly metal ions) to a zero-valent metal and a pH adjuster for activating the reducing agent.
The concentration of the reducing agent with respect to the entire metal activation liquid is preferably 0.05% by mass to 50% by mass, and more preferably 0.1% by mass to 30% by mass.
As the reducing agent, boron-based reducing agents such as sodium borohydride and dimethylamine borane, and reducing agents such as formaldehyde and hypophosphorous acid can be used. In particular, reduction with an aqueous alkaline solution containing formaldehyde is preferred.

The concentration of the pH adjuster with respect to the entire metal activation liquid is preferably 0.05% by mass to 10% by mass, and more preferably 0.1 to 5% by mass.
As the pH adjuster, acetic acid, hydrochloric acid, sulfuric acid, nitric acid, sodium hydrogen carbonate, aqueous ammonia, sodium hydroxide, potassium hydroxide and the like can be used.
The temperature during the reduction is preferably 10 ° C to 100 ° C, more preferably 20 ° C to 70 ° C.
These concentrations and temperature ranges are preferably within this range from the viewpoint of the particle diameter of the metal precursor, the surface roughness of the polymer layer, the conductivity (surface resistance value), and the deterioration of the reducing solution during reduction.

The particle diameter of the reduced metal particles contained in the plating undercoat polymer layer is preferably 1 nm to 200 nm, more preferably 1 nm to 100 nm, and still more preferably 1 nm to 60 nm from the viewpoint of reflection performance. By being in this range, the reflectance after plating becomes good.
Here, the particle diameter is read from an SEM (S-5200 manufactured by Hitachi High-Tech Manufacturing & Service) image.

The surface resistance value of the plating undercoat polymer layer containing the reduced metal particles is preferably 0.001Ω / □ or more and 100Ω / □ or less, and more preferably 0.03Ω / □ or more and 50Ω / □ or less. Within this range, the plated surface is formed uniformly and smoothly and the reflectance is good.
Further, the surface roughness (Ra) of the plating undercoat polymer layer containing the reduced metal particles is preferably 20 nm or less, and more preferably 10 nm or less, from the viewpoint of reflection performance.
The plating undercoat polymer layer containing the metal particles thus obtained is suitably used when a metal reflective layer described in detail below is formed by a plating method that is a wet method, and plating is performed using the plating undercoat polymer layer. The metal reflective layer formed by the method is excellent in adhesion to the resin substrate and surface smoothness.

<Metal reflective layer>
The metal reflective layer in the present invention is provided directly on the resin support, or is provided via the above-described resin intermediate layer provided as desired.
The material for forming the metal reflection layer is not particularly limited as long as it is a metal material that reflects visible light and infrared light, and examples thereof include silver and aluminum. From the viewpoint of light reflection performance, silver or an alloy containing silver is preferable. Silver or an alloy containing silver can increase the reflectance in the visible light region of the film mirror and reduce the dependency of the reflectance on the incident angle. The visible light region means a wavelength region of 400 nm to 700 nm. Here, the incident angle means an angle with respect to a line perpendicular to the film surface. As a silver alloy, other metals such as gold, palladium, copper, nickel, iron, gallium, and indium are used to the extent that the durability of the silver-containing metal layer is improved and the reflective properties of the metal reflective layer are not affected. One or more metals selected from the group consisting of titanium, and bismuth may be included, and it is also a preferred embodiment to use an alloy made of silver and other metals. As the silver alloy, an alloy of silver and one or more metals selected from gold, copper, nickel, iron, and palladium is particularly preferable from the viewpoints of moist heat resistance, reflectance, and the like.

  For example, when the metal reflective layer is a film made of a silver alloy, the silver content is 90 atomic% to 99.8 atomic% in the total (100 atomic%) of silver and other metals in the metallic reflective layer. preferable. Further, the content of other metals is preferably 0.2 atomic% to 10 atomic% from the viewpoint of durability.

  The surface roughness (Ra) of the metal reflective layer in the present invention is preferably 20 nm or less, more preferably 10 nm or less, and still more preferably 5 nm or less. By setting it within this range, the reflectance of the obtained film mirror is improved, and sunlight can be collected efficiently.

[Method of forming metal reflective layer]
The method for forming the metal reflective layer in the present invention is not particularly limited, and either a wet method or a dry method may be employed.
Examples of the wet method include an electroplating method.
Examples of the dry method include a vacuum deposition method, a sputtering method, and an ion plating method.
As described above, the resin support in the present invention is not easily affected by ultraviolet rays due to the ultraviolet absorber-containing layer provided on the surface. Therefore, even when the metal reflective layer is produced by a plating method, Since the occurrence of fine damage that allows the plating solution to permeate is suppressed in the manufactured support, there is also an advantage that the support is hardly deteriorated.

Hereinafter, a case where the metal reflective layer is formed by electroplating will be described.
A conventionally known method can be used as the electroplating method.
In the present invention, since the metal particles contained in the plating undercoat polymer layer have a function as an electrode, by performing electroplating on the plating undercoat polymer layer, metal reflection excellent in adhesion to the resin support is achieved. A layer can be formed.
Examples of metal compounds used for plating include silver nitrate, silver acetate, silver sulfate, silver carbonate, silver methanesulfonate, silver ammonia, silver cyanide, silver thiocyanate, silver chloride, silver bromide, silver chromate, and chloranil. Examples thereof include silver compounds such as silver oxide, silver salicylate, silver diethyldithiocarbamate, silver diethyldithiocarbamate, and silver p-toluenesulfonate. Among these, silver methanesulfonate is preferable from the viewpoint of environmental impact and smoothness.

In addition, between the plating undercoat polymer layer and the metal reflective layer, for example, a metal layer containing another metal such as copper, nickel, chromium, iron, or the like may be provided as a base metal layer.
Moreover, the film thickness of the metal reflective layer obtained by electroplating can be controlled by adjusting the metal concentration or current density contained in the plating bath. By adding a base metal layer having an appropriate thickness, it is possible to improve reflectance and reduce pinholes by smoothing the surface.
The film thickness of the metal reflective layer is 0.05 μm to 2.0 μm from the viewpoint of forming a reflective film without pinholes and not forming irregularities that scatter light on the surface of the metal reflective layer. Preferably, it is 0.08 to 0.5 μm.

  Moreover, in this invention, you may form a metal reflective layer by performing dry plating, such as vacuum evaporation, using the plating undercoat polymer layer containing the reduced metal particle. According to this method, since the surface of the plating undercoat polymer layer is covered with metal, it is possible to form a metal reflective layer that has better adhesion than normal vapor deposition and is strong against heat.

After electroplating, the metal reflective layer may be treated with a strong acid, strong alkali, or the like in order to improve the reflection performance and durability of the metal reflective layer. Further, an inorganic film or a metal oxide film may be formed on the metal surface. Moreover, you may provide the discoloration prevention agent layer containing a discoloration prevention agent.
The anti-discoloring agent layer functions to prevent discoloration of the metal reflective layer. Examples of the discoloration preventing agent include thioether-based, thiol-based, Ni-based organic compound-based, benzotriazole-based, imidazole-based, oxazole-based, tetrazaindene-based, pyrimidine-based, and thiadiazole-based discoloration preventing agents.
The anti-discoloring agent layer is broadly classified, and those having an adsorbing group that adsorbs metals and antioxidants are preferably used.

<Surface coating layer>
The film mirror of the present invention may further have a surface coating layer on the ultraviolet absorber-containing layer. By having the surface coating layer, the weather resistance and scratch resistance of the film mirror are further improved. As long as the surface coating layer exists on the surface of the ultraviolet absorber-containing layer and can prevent physical or chemical damage to the surface of the film mirror, a known resin layer or the like can be arbitrarily used.
That is, the surface coating layer may be a soft layer having a hardness of 100 N / mm ² or less and an elastic recovery rate of 60% or more, and is a so-called hard coat layer having a hard surface. Also good.

(Soft surface coating layer)
First, the soft layer will be described. In the case of a soft layer, the hardness of the surface coating layer (hereinafter referred to as “surface hardness” as appropriate) is a Martens hardness measured according to ISO 14577-1 (instrumentation indentation hardness) of 100 N / mm ^2. Refers to the following layers. The surface hardness can be measured, for example, using an ultra micro hardness meter (DUH-201S, manufactured by Shimadzu Corporation).
The elastic recovery rate of the surface coating layer was determined by measuring the maximum indentation depth (hmax) and the indentation depth after load unloading (hf) in ISO 14577-1 (instrumentation indentation hardness). The amount of elastic recovery (hmax-hf) can be calculated as the difference between the values of, and the elastic recovery rate can be calculated from (hmax-hf) / hmax. For example, it can be measured using an ultra micro hardness meter (DUH-201S, manufactured by Shimadzu Corporation).

By providing the film mirror of the present invention with a surface coating layer having flexible properties, scratch resistance is improved, a decrease in haze value is suppressed, and a high reflectance is maintained for a longer period.
Although this effect is not clear, by setting the hardness of the surface coating layer to 100 N / mm ² or less, the impact resistance against sand dust and the like is improved, and the elastic recovery rate of the surface coating layer is 60% or more. This is thought to be due to the self-healing of scratches in microscopic areas such as dust.

In the present invention, the scratch resistance of the film mirror becomes better, the haze value is prevented from being lowered, and the reflectance is maintained at a high level for a longer period. Therefore, the hardness of the soft surface coating layer is 1 N / it is preferably mm ² ~70N / mm ^2, more preferably ^{1N / mm 2 ~50N / mm 2} .
For the same reason, the elastic recovery rate of the surface coating layer is preferably 70% to 100%, and more preferably 80% to 100%.

  Further, in the present invention, the thickness in the case of forming a soft surface coating layer is not particularly limited, for the reason that the scratch resistance of the film mirror becomes better, the haze value and the maintenance ratio of the reflectance is also higher, It is preferably 1 μm to 50 μm, and more preferably 3 μm to 30 μm.

The soft surface coating layer is not particularly limited as long as it is a layer having a hardness of 100 N / mm ² or less and an elastic recovery rate of 60% or more.
Specific examples of the forming material include photocurable resins such as urethane (meth) acrylate resins, polyester (meth) acrylate resins, silicone (meth) acrylate resins, and epoxy (meth) acrylate resins; urethane resins, And thermosetting resins such as phenol resin, urea resin (urea resin), phenoxy resin, silicone resin, polyimide resin, diallyl phthalate resin, furan resin, bismaleimide resin, cyanate resin, etc. You may use, and may use 2 or more types together.

Of these, a resin having a urethane bond is preferable. Specifically, it is more preferable to use a photocurable resin, and a urethane (meth) acrylate resin is preferable because the hardness of the film mirror can be easily adjusted. Is more preferable.
The urethane acrylate resin is obtained, for example, by reacting a polyester polyol (A) with a polyisocyanate (B) to synthesize an isocyanate group-terminated urethane prepolymer and then reacting a hydroxyl group-containing (meth) acrylate compound (C). Suitable products include: a polymer of an acrylic resin having a hydroxyl group and an isocyanate; and the like.

Here, the polyester polyol (A) is obtained by reacting a polybasic acid and a polyhydric alcohol. Specific examples thereof include polytetramethylene glycol (PTMG) and polyoxypropylene diol (PPG). And polyoxyethylene diol.
The polyisocyanate (B) is not particularly limited as long as it has two or more isocyanate groups in the molecule. Specific examples thereof include 2,4-tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI). ), Hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), xylylene diisocyanate (XDI), and the like.
Specific examples of the hydroxyl group-containing (meth) acrylate compound (C) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, Examples thereof include glycidol di (meth) acrylate and pentaerythritol triacrylate.
As the urethane (meth) acrylate resin synthesized using the above-described polyester polyol (A), polyisocyanate (B), and hydroxyl group-containing (meth) acrylate compound (C), commercially available products can be used. May be UV curable urethane acrylate resin manufactured by Nippon Gosei Co., Ltd., for example, UV1700B, UV6300B, UV7600B, etc.

  On the other hand, as a polymer of an acrylic resin having a hydroxyl group and an isocyanate, the method described in [Claim 2] and [Claim 3] and [0142] to [0148] of JP2012-25821A is used. Can be prepared.

In the present invention, the surface coating layer preferably contains a fluorine atom for reasons such as antifouling properties on the surface and reduction in friction coefficient (slipperiness).
As a method for containing a fluorine atom, for example, a method using a fluorine-containing acrylate monomer together with the above-mentioned hydroxyl group-containing (meth) acrylate compound (C), paragraph [0124] of JP2011-158751, etc. It can be contained by the fluorination treatment.

In the present invention, the method for forming the surface coating layer is not particularly limited. For example, a curable composition containing the above-described photocurable resin or thermosetting resin is provided on the metal reflective layer. Examples thereof include a method of photocuring by ultraviolet irradiation and heat curing by heating after coating on the surface of the ultraviolet absorber-containing layer.
The coating method of the curable composition is a gravure coating method, a reverse coating method, a die coating method or the like, or a conventionally known coating means such as a blade coater, a roll coater, an air knife coater, a screen coater, a bar coater, or a curtain coater. The coating method used can be used.

Here, the said curable composition may contain the solvent and various additives other than the component mentioned above.
Examples of the solvent that can be used include solvents such as hydrocarbons, hydrogen halides, ethers, esters, and ketones. Specifically, xylene and dibutyl ether can be preferably used.
Examples of additives include photopolymerization initiators, antistatic agents, leveling agents, ultraviolet absorbers, light stabilizers, antioxidants, antifoaming agents, thickeners, antisettling agents, pigments, and dispersants. And silane coupling.

(Hard surface coating layer)
On the other hand, the surface coating layer may be a hard surface coating layer known as a so-called hard coat layer. By having a hard surface coating layer on the outermost surface, it is possible to suppress a decrease in haze value due to the outermost surface being damaged by dust or the like. In addition, since the hard coat layer is excellent in strength even when it is a thin layer, the surface coating layer can be made thin, and a decrease in reflectance due to the resin constituting the surface coating layer is suppressed.

The hard surface coating layer is preferably prepared so that the surface hardness of the surface coating layer after curing has physical properties of more than 100 N / mm ² and an elastic recovery rate of 60% or more.
Moreover, the ratio of the fluorine atom number with respect to the carbon atom number of the surface layer part of resin, and F / C shall be 0.21-1.00, and the surface coating layer excellent in antifouling property can be produced. Such physical properties can be achieved, for example, by using the following resins (1) to (3).
As the resin constituting the hard surface coating layer, (1) a polymer of a monomer containing at least one or more types of fluorine-containing acrylate monomers and at least one or more types of non-fluorinated polyfunctional acrylate monomers [hereinafter referred to as (1) (Also referred to as resin), (2) a polymer of at least one fluorine-containing epoxy and / or oxetane monomer and a monomer containing at least one non-fluorine epoxy and / or oxetane monomer [hereinafter referred to as (2) resin And (3) a polymer containing a polymerizable monomer that has a small inhibition of polymerization by oxygen (hereinafter also referred to as (3) a resin). The physical properties described above are achieved by changing the mass ratio between the various monomers of these resins and the effect conditions during curing after coating, for example, the exposure conditions.
If the polymerization shrinkage of the acrylic monomer used for the surface coating layer and the thermal shrinkage of the resin support or UV absorber-containing layer are about the same, the shrinkage of each is offset and the film mirror curl is reduced. Therefore, it is preferable.

  The resin that forms the hard surface coating layer preferably contains a polymer of a monomer containing at least one or more types of fluorine-containing monomers, such as the resin (1) and the resin (2). Examples of the fluorine-containing monomer include a fluorine-containing acrylate monomer, a fluorine-containing olefin monomer, a fluorine-containing acetylene monomer, a fluorine-containing epoxy monomer, a fluorine-containing oxetane monomer, and a fluorine-containing vinyl ether monomer.

  (1) Specific examples of the polymer of monomers containing at least one kind of fluorine-containing acrylate monomer and at least one kind of non-fluorinated polyfunctional acrylate monomer include the following compounds.

  (1) The fluorine-containing acrylate monomer that can be contained in the resin used in the hard surface coating layer in the film mirror of the present invention is not particularly limited, but specifically, paragraphs of JP-A-2006-28409 Nos. [0018] to compounds f-1 to f-10 and X-1 to X-32 described in paragraphs [0023] to [0027], the following compounds (X-33), (X- 34) and (X-35) can also be preferably used.

  Further, compounds described in paragraph numbers [0135] to [0149] of International Publication No. 2005/059601 pamphlet, and compounds described in paragraph numbers [0014] to [0028] of JP-A-2006-290107 are also preferably used. be able to.

  As the non-fluorinated polyfunctional acrylate monomer that can be contained in the (1) resin, a compound containing two or more (meth) acryloyl groups in one molecule can be used. Details of these are described in JP 2010-061044 A, and the compounds described herein can also be used in the present invention.

(2) Specific examples of the polymer of at least one fluorine-containing epoxy and / or oxetane monomer and a monomer containing at least one non-fluorine epoxy and / or oxetane monomer include the following compounds. it can.
<Non-fluorine type epoxy and / or oxetane monomer>
(2) Examples of the epoxy compound that can be used for the resin include the following aromatic epoxides, alicyclic epoxides, and aliphatic epoxides. Examples of the aromatic epoxide include di- or polyglycidyl ether of bisphenol A or its alkylene oxide adduct, di- or polyglycidyl ether of hydrogenated bisphenol A or its alkylene oxide adduct, and a novolac-type epoxy resin. . Here, examples of the alkylene oxide include ethylene oxide and propylene oxide.

  As the alicyclic epoxide, cyclohexene oxide obtained by epoxidizing a compound having at least one cycloalkane ring such as cyclohexene or cyclopentene ring with a suitable oxidizing agent such as hydrogen peroxide or peracid. Or a cyclopentene oxide containing compound is mentioned. Preferable aliphatic epoxides include dihydric or polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof. Although it does not specifically limit as an alicyclic epoxide and an aliphatic epoxide, The compound as described in Unexamined-Japanese-Patent No. 2012-163691 is mentioned, The compound as described here can be used for this invention.

  Although it does not specifically limit as an aromatic epoxy monomer, For example, the compound as described in Unexamined-Japanese-Patent No. 2009-224109 is mentioned, The compound as described here can be used for this invention. As for these epoxy monomers, only 1 type may be used and 2 or more types may be used together.

  (2) Although it does not specifically limit as an oxetane monomer which can be used for resin, For example, a monofunctional or bifunctional oxetane monomer can also be used. As the oxetane monomer, for example, any known functional or bifunctional oxetane compound described in JP-A Nos. 2001-220526, 2001-310937, and 2009-224109 can be used.

  As an aromatic oxetane monomer, the compound described in Unexamined-Japanese-Patent No. 2009-224109 and 2012-163691 is mentioned, for example, The compound described here can be used for this invention.

<Fluorine-containing oxetane monomer>
The oxetane monomer is not particularly limited as long as it is a fluorine-containing oxetane compound that can be cured by a cationic polymerization initiator, and a conventionally known oxetane monomer can be used. Moreover, the molecular structure, molecular weight, etc. are not specifically limited.

  (2) The fluorine-containing oxetane monomer that can be used in the resin is particularly preferably a compound in which some or all of the hydrogen atoms in the molecule are substituted with fluorine. These oxetane monomers may be used alone or in combination of two or more. They can be used in combination.

The fluorine-containing oxetane compound is not particularly limited, and any compound in which at least a part of hydrogen atoms of the oxetane compound described above is substituted with a fluorine atom can be used in the present invention.
A fluorine-containing oxetane compound may be used individually by 1 type, and may use 2 or more types in combination.

  (2) The fluorine-containing epoxy compound that can be used for the resin is not limited, but is a reaction product of a fluorine compound and an epoxy compound such as epichlorohydrin, and details thereof are described in JP-A-2009-224109. Any of the compounds described herein can be used in the present invention.

  (3) Specific examples of the polymer containing a polymerizable monomer that is small in inhibition of polymerization by oxygen include the following compounds. When the surface coating layer contains, as a constituent resin, a polymer containing a polymerizable monomer with little polymerization inhibition by oxygen, it is suitable for forming the surface coating layer by photocuring in the presence of oxygen or in air.

  The polymerizable monomer having a small polymerization inhibition by oxygen at the time of curing used in the present invention is not limited, but a polymerizable monomer capable of forming a structural unit represented by the following general formula (2) or the following general formula (3), specifically Specifically, an acrylic monomer represented by the general formula (4) or the general formula (5) described in detail below is preferable.

[In General Formula (2) and General Formula (3), R ¹ represents a hydrogen atom or a hydrocarbon group, and R ² , R ³ and R ⁴ each independently represents a hydrocarbon group. R ⁵ represents an alkylene group in which an ether group may be inserted in the carbon chain, and X ¹ , X ² and X ³ each independently represent a single bond or a carbonyl group. ]

The hydrocarbon group when R ^{1 to} R ⁴ represent hydrocarbon may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, and may have a substituent.
More specifically, examples of the hydrocarbon group include an alkyl group, an alkenyl group, an araalkyl group, an aryl group, and the like. Among these, an alkyl group is preferable.
As the alkyl group, a linear alkyl group or a branched alkyl group is preferable, and a linear alkyl group is more preferable. Carbon number of a linear alkyl group becomes like this. Preferably it is 1-6, More preferably, it is 1-4.
Specific examples of the alkenyl group include those in which a part of the carbon-carbon single bond of the alkyl group is substituted with a double bond.
Specific examples of the aryl group include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. Specific examples of the aralkyl group include specific examples of the alkyl group and those substituted with any of the specific examples of the aryl group.
When the hydrocarbon group has a substituent, examples of the substituent that can be introduced include an alkoxy group and a hydroxyl group, with a hydroxyl group being preferred.
In the general formula (2), a dimer structure in which the hydrocarbon groups represented by R ¹ are bonded to each other can be taken. Even when such a mode is taken, the general formula (2) in the present invention is used. To be included in the repeating unit.
R ³ and R ⁴ in the general formula (3) may be the same or different, but it is preferable that R ³ and R ⁴ are the same. Moreover, it is more preferable that X ² and X ³ in the general formula (3) are both carbonyl groups.
R ⁵ is an alkylene group in which an ether group may be inserted in the chain, and has a structure represented by the following general formula (6).

-R < ¹¹ >-(O-R < ¹² >) n- General formula (6)

In the general formula (6), R ¹¹ and R ¹² each independently represent an alkylene group, and may have a substituent. The alkylene group may be linear, branched or cyclic.
As the alkylene group, a linear alkylene group or a branched alkylene group is preferable, and a linear alkylene group is more preferable. Carbon number of a linear alkylene group becomes like this. Preferably it is 1-6, More preferably, it is 1-4. Examples of the substituent of the alkylene group include those exemplified as the substituent of the above hydrocarbon group.
In general formula (6), n represents an integer of 0 or more. n is preferably 0 to 6, and more preferably 0 to 4. When n is 2 or more, n R ^{12 s} may be the same or different.

A plurality of types of structures represented by the general formula (2) or the general formula (3) may be included in the surface coating layer, or only one type may be included. When multiple types are included, multiple types of structures represented by the general formula (2) may be included, or multiple types of structures represented by the general formula (3) may be included. The structure represented by the general formula (2) and the structure represented by the general formula (3) may be mixed.
The polymer constituting the hard surface coating layer is preferably produced by polymerizing a monomer mixture containing at least one monomer represented by the following general formula (4) or the following general formula (5).

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , X ¹ , X ² and X ³ in general formula (4) and general formula (5) are the same in general formula (2) and general formula (3), respectively. R ¹ , R ² , R ³ , R ⁴ , R ⁵ , X ¹ , X ² and X ³ have the same meaning, and the preferred ranges are also the same.
Specific examples of the monomer represented by the general formula (4) or the general formula (5) are illustrated below, but the monomer that can be used in the present invention is not limited thereto. Details thereof are described in JP-A-2009-226718.

  The monomer polymerization method is not particularly limited, but heat polymerization, light (ultraviolet ray, visible light) polymerization, electron beam polymerization, plasma polymerization, or a combination thereof is preferably used. Of these, photopolymerization is particularly preferred. When carrying out photopolymerization, a photopolymerization initiator is used in combination. Examples of the photopolymerization initiator include Irgacure series (for example, Irgacure 651, Irgacure 754, Irgacure 184, Irgacure 2959 Irgacure 907, Irgacure 369, commercially available from Ciba Specialty Chemicals. , Irgacure 379, Irgacure 819, etc.), Darocure series (eg, Darocur TPO, Darocur 1173, etc.), Quantacure PDO, Ezacure series (eg, Sartomer) Ezacure TZM, ezacure TZT, etc.).

The light to irradiate is usually ultraviolet light from a high pressure mercury lamp or a low pressure mercury lamp. The radiation energy is preferably 95mJ / cm ² or more, 100 mJ / cm ² or more is more preferable. In general, since acrylate and methacrylate are subject to polymerization inhibition by oxygen in the air, it is preferable to lower the oxygen concentration or oxygen partial pressure during polymerization. In the case of using a monomer that is not susceptible to oxygen inhibition during polymerization, it is not particularly necessary to reduce the oxygen concentration by reducing the pressure or substituting nitrogen, but the oxygen concentration is preferably 50% or less, more preferably 30% or less, and in the air Is usually 21% or less, which is the oxygen concentration normally contained.

A filler such as silica particles may be used for the hard surface coating layer as necessary. Addition of filler can be expected to improve hardness and decrease polymerization shrinkage. Although it does not specifically limit as a filler which can be used for a hard surface coating layer, For example, an inorganic particle, an organic particle, an inorganic organic composite particle, etc. are mentioned. The average particle diameter measured by the dynamic light scattering method of the filler is preferably in the range of 5 nm to 30 nm.
The inorganic particles are not particularly limited, but silica particles, alumina particles, ZnO particles and the like are preferable, and silica particles are preferable.
Although it does not specifically limit as an organic particle, The particle | grains formed using resin, such as an acrylic resin, an acrylonitrile resin, a polyurethane, a polyvinyl chloride, a polystyrene, a polyacrylonitrile, polyamide, are mentioned, An acrylic resin particle is preferable.
Examples of the inorganic / organic composite particles include particles in which at least a part of the surface of the inorganic particles described above is coated with the resin exemplified above.

A solvent, a plasticizer, etc. can be used for a hard surface coating layer as needed.
As the solvent, for example, solvents such as hydrocarbons, hydrogen halides, ethers, esters and ketones can be used, and specifically, xylene and dibutyl ether can be preferably used.
Examples of additives include photopolymerization initiators, antistatic agents, leveling agents, ultraviolet absorbers, light stabilizers, antioxidants, antifoaming agents, thickeners, antisettling agents, pigments, and dispersants. And silane coupling.

The method for forming the hard surface coating layer is a method in which each resin capable of forming the hard surface coating layer described above is dissolved in an appropriate solvent, applied to the ultraviolet absorber-containing layer according to the present invention, and dried. Can be used.
The coating method is not particularly limited, and conventionally known coating means such as a gravure coating method, a reverse coating method, a die coating method, a blade coater, a roll coater, an air knife coater, a screen coater, a bar coater, a curtain coater or the like were used. A coating method can be applied.

  The thickness of the hard surface coating layer is preferably 0.1 μm to 50 μm, more preferably 0.1 μm to 10 μm, from the viewpoint of antifouling properties and scratch resistance.

<Physical properties of film mirror>
The film mirror of the present invention has a heat shrinkage rate of 0.6% or less, preferably 0.5% or less when heat-treated at 150 ° C. for 30 minutes. Since the film mirror of the present invention is less likely to be deformed by heat and has a stable specularity, it can function as a film mirror (such as sunlight collection) even when placed outdoors for a long time. Can fully demonstrate. In particular, it is also suitable for use in deserts where the temperature difference between day and night is large.
The thermal shrinkage rate of the film mirror of the present invention can be controlled by the drying temperature condition when forming the resin intermediate layer (easily adhesive layer and / or plating undercoat polymer layer). For example, when the resin intermediate layer is dried at a high temperature, the thermal contraction rate of the formed film mirror can be lowered.
In addition, this thermal contraction rate is a value obtained by the following method.

A film mirror having a width of 10 mm and a length of 500 mm marked with an interval of about 100 mm is heat-treated for 30 minutes under conditions of a temperature of 150 ° C. and a load of 0.5 g (conforming to JIS-C2318 (2007)). Then, the gap between the marked lines before and after the heat treatment is measured using a heat shrinkage rate measuring device (AMM-1 machine, manufactured by Technone Corp.). Based on the obtained value, the thermal contraction rate (%) is calculated by the following formula.
Thermal contraction rate (%) = {(L ₀ −L) / L ₀ } × 100
L ₀ : Gauge gap before heat treatment (mm)
L: Mark gap after heat treatment (mm)

In the film mirror of the present invention, the difference in contact shrinkage between the resin support and the surface coating layer is preferably small. Specifically, the difference between the heat shrinkage rate at 100 ° C. of the resin support and the heat shrinkage rate at 100 ° C. of the surface coating layer preferably satisfies the following conditions:
[(Heat shrinkage rate of resin support) − (polymerization shrinkage rate of surface coating layer)] ≦ 10%
This is because the difference in thermal shrinkage with the ultraviolet absorber-containing layer is measured in the same manner, and if both values are within this range, the curl resistance is excellent. Preferably it is 5% or less, more preferably 3% or less. Curling resistance refers to resistance to deformation in which a laminate, which is a composite film or a film mirror, undergoes a thermal history and deforms.

<Sunlight reflector>
The solar reflective plate of the present invention is produced using the film mirror of the present invention. Specifically, the solar reflective plate of the present invention is a substrate made of any of resin, metal, or ceramic. In addition, the film mirror of the present invention is bonded via an adhesive layer.
The film mirror according to the present invention can be used for collecting sunlight, but is preferably used as a sunlight reflecting plate by being stuck on a substrate such as a resin.
The film mirror of the present invention maintains the film mirror characteristics of being lightweight and flexible, and has good adhesion between the support and the metal reflective layer, and has excellent weather resistance. The produced solar reflector is particularly suitable for photovoltaic power generation.

  As a board | substrate which hold | maintains the film mirror of this invention, it is either resin, a metal, or a ceramic, Preferably it is a metal. Examples of the metal substrate include steel plates, copper plates, aluminum plates, copper-plated steel plates, tin-plated steel plates, aluminum-plated steel plates, stainless steel plates, chrome-plated steel plates, and the like having high thermal conductivity. From the viewpoint, a plated steel plate, a stainless steel plate, and an aluminum plate are preferable.

The formation material of the adhesion layer which bonds the film mirror of this invention and the said board | substrate is not specifically limited, For example, an adhesive, a laminating agent, a heat seal agent etc. are mentioned, Preferably it is an adhesive.
As the adhesive, for example, an acrylic resin, a urethane resin, a polyester resin, a polyvinyl acetate resin, a nitrile rubber or the like is preferable, and an acrylic adhesive having an acrylic resin as a main component is preferable. Particularly preferred.
The weight average molecular weight of the acrylic resin contained in the acrylic pressure-sensitive adhesive is 20,000 to 1,000,000 (polystyrene equivalent value using GPC) from the viewpoint of adhesion between the film mirror of the present invention and the substrate. Is preferred.

  The thickness of the adhesive layer is preferably in the range of 1.5 μm to 100 μm from the viewpoints of adhesiveness, ease of formation and the like.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof.

[Production of film mirror]
<Examples 1 to 12>
On a polyethylene terephthalate (PET) film (Cosmo Shine A-4300, thickness: 100 μm, heat shrinkage rate (catalog value): 0.4%), a silver-containing metal reflective layer was provided by electroplating according to the following steps.
(Formation of silver-containing metal reflective layer)
(Formation of easy adhesion layer)
One surface of the PET film was subjected to corona discharge treatment under the condition of 730 J / m ² , and then the following easy-adhesion layer forming coating solution was applied by a bar coating method so that the dry weight was 124 mg / m ^2. did. And this was dried at 180 degreeC for 1 minute, and the easily bonding layer was formed.

-Composition of coating solution for forming an easy adhesion layer-
-Polyester resin aqueous dispersion 48 parts by mass (Vaironal 1245, solid content: 30% by mass, manufactured by Toyobo Co., Ltd. Binder)
・ PMMA resin fine particles 0.5 parts by mass (MP-1000, solid content: 100% by mass, manufactured by Soken Chemical Co., Ltd., mat material)
・ Oxazoline compound 3 parts by mass (Epocross WS-700, solid content: 25% by mass, manufactured by Nippon Shokubai Co., Ltd., cross-linking agent)
Carbodiimide compound 17 parts by mass (Carbodilite V-02-L2, solid content: 40% by mass, manufactured by Nisshinbo Co., Ltd., crosslinker)
・ Polyoxyalkylene alkyl ether 0.15 parts by mass (Naroacty CL-95, solid content: 100% by mass, manufactured by Sanyo Chemical Industries, Ltd.)

(Formation of plating undercoat polymer layer)
The plating undercoat polymer layer coating solution prepared by the following method is applied to the easy-adhesion surface of the PET film on which the easy-adhesion layer has been formed by the bar coating method so that the film thickness after drying is about 0.55 μm. Then, after drying at 25 ° C. for 10 minutes and at 80 ° C. for 5 minutes, using an ultraviolet irradiation device (UV lamp: metal halide lamp, manufactured by GS Yuasa), ultraviolet exposure (wavelength: 254 nm, ultraviolet exposure: 1000 mJ / cm ² ). Next, the ultraviolet-exposed PET film was immersed in a 1% by mass aqueous sodium hydrogen carbonate solution for 5 minutes, and then washed by pouring with pure water for 1 minute to remove unreacted polymer.

-Preparation of coating solution for forming undercoat polymer layer-
To a mixed solution of acrylic polymer 1 (7 parts by mass), 1-methoxy-2-propanol (74 parts by mass), and water (19 parts by mass) having the following structure, a photopolymerization initiator (Esacure KTO-46, manufactured by Lamberdy) ) (0.35 parts by mass) was added and stirred to prepare a solution of a plating undercoat polymer (acrylic polymer 1).

(Acrylic polymer 1)

(Give metal precursor)
As a solution containing a metal precursor, a 1% by mass aqueous solution of silver nitrate was prepared. The PET film coated with the plating undercoat polymer obtained above was immersed in a 1% by mass aqueous silver nitrate solution adjusted to 25 ° C. for 5 minutes, and then washed by pouring with pure water for 1 minute to obtain a metal precursor. The body was given.

(Reduction of metal precursor)
As a reducing solution, a 0.25 mass% formaldehyde aqueous solution containing 0.14 mass% sodium hydroxide was prepared. The PET film provided with the metal precursor obtained above is immersed in the reducing solution adjusted to a temperature of 25 ° C. for 1 minute, and then washed by pouring with pure water for 1 minute to reduce the metal precursor. did.
When the surface resistance value after the reduction was measured using a surface resistance meter, it was about 10Ω / □. Moreover, when the surface roughness (Ra) was measured using an atomic force microscope (AFM), it was about 7 nm. Furthermore, when the particle diameter of the metal after reduction was measured using a scanning electron microscope (SEM), it was about 50 nm.

(Electroplating)
As a pre-treatment for electroplating, Dyne Cleaner AC100 (manufactured by Daiwa Kasei Co., Ltd.) obtained by controlling the temperature of the PET film having the plating undercoat polymer layer containing the reduced metal particles obtained above to 25 ° C. After being immersed in a 10% by mass aqueous solution for 30 seconds, it was washed several times. Subsequently, as a pretreatment for electroplating, it was immersed in a 10% by mass aqueous solution of Dyne Silver ACC (main component: methanesulfonic acid, manufactured by Daiwa Kasei Co., Ltd.) for 10 seconds and then washed several times.
Next, Dyne Silver Bright PL50 (main component: silver methanesulfonate, manufactured by Daiwa Kasei Co., Ltd.) adjusted to pH 9.0 with 8M potassium hydroxide was prepared as an electroplating solution. Then, a PET film having a plating undercoat polymer layer containing the reduced metal particles on the surface was immersed in this electroplating solution, and plated at 0.5 A / dm ^{2 for} 20 seconds.
As a post-treatment of electroplating, the plated PET film was immersed in a 10% by mass aqueous solution of Dyne Silver ACC (trade name: manufactured by Daiwa Kasei Co., Ltd.) for 90 seconds and then washed several times.
The surface roughness (Ra) after the post-plating treatment was measured using an atomic force microscope (AFM) and found to be about 4 nm.

[Preparation of UV absorber-containing layer]
On the plating treatment surface of the metal reflection layer obtained above, after mixing at a mass ratio of the following composition, it was heated to 40 ° C. and stirred for 1 hour to prepare a coating solution for forming an ultraviolet absorber-containing layer ( OC-1) to (OC-36) were applied so that the thickness after drying would be the film thickness described in Tables 1 and 2 below, and dried at 80 ° C. for 1 minute. The film mirror which has a ultraviolet absorber content layer of the film thickness of 2 was manufactured.

-Composition of UV absorbent-containing layer forming coating solution (OC-1)-
Dianal BR-102 (manufactured by Mitsubishi Rayon Co., Ltd.) 17.20 parts by mass of a triazine-based ultraviolet absorber (UVA-1: compound represented by the general formula (1))
1.20 parts by mass Megafac F-780-F (manufactured by DIC Corporation) 0.03 parts by mass methyl ethyl ketone 57.80 parts by mass propylene glycol monomethyl ether 20.00 parts by mass cyclohexanone 5.00 parts by mass

-Composition of UV absorbent containing layer forming coating solution (OC-2)-
ESREC KS-10 (manufactured by Sekisui Chemical Co., Ltd.) 17.20 parts by mass of a triazine-based ultraviolet absorber (UVA-1: compound represented by the general formula (1))
1.20 parts by mass Megafac F-780-F (manufactured by DIC Corporation) 0.03 parts by mass methyl ethyl ketone 57.80 parts by mass propylene glycol monomethyl ether 20.00 parts by mass cyclohexanone 5.00 parts by mass-containing UV absorber Composition of coating liquid for layer formation (OC-3)
Soarnol DC3212 (manufactured by Nippon Synthetic Chemical Co., Ltd.) 17.20 parts by mass of triazine-based ultraviolet absorber (UVA-1: compound represented by general formula (1))
1.20 parts by mass Megafac F-780-F (manufactured by DIC Corporation) 0.03 parts by mass water 41.40 parts by mass isopropyl alcohol (hereinafter abbreviated as IPA) 41.40 parts by mass

-Composition of UV absorbent-containing layer forming coating solution (OC-4)-
NUC-6220 (manufactured by Nippon Unicar Co., Ltd.) 17.20 parts by mass of triazine-based ultraviolet absorber (UVA-1: compound represented by the general formula (1))
1.20 parts by mass Megafac F-780-F (manufactured by DIC Corporation) 0.03 parts by mass methyl ethyl ketone 57.80 parts by mass propylene glycol monomethyl ether 20.00 parts by mass cyclohexanone 5.00 parts by mass-containing UV absorber Composition of coating liquid for layer formation (OC-5)
Dianal BR-102 (manufactured by Mitsubishi Rayon Co., Ltd.) 17.11 parts by mass of triazine-based ultraviolet absorber (UVA-1: compound represented by general formula (1))
1.20 parts by mass light stabilizer (LS-1: compound represented by the following general formula (TS-II))
0.09 parts by mass Megafax F-780-F (manufactured by DIC Corporation) 0.03 parts by mass methyl ethyl ketone 57.80 parts by mass propylene glycol monomethyl ether 20.00 parts by mass cyclohexanone 5.00 parts by mass

-Composition of UV absorbent-containing layer forming coating solution (OC-6)-
ESREC KS-10 (manufactured by Sekisui Chemical Co., Ltd.) 17.11 parts by mass of triazine-based ultraviolet absorber (UVA-1: compound represented by the general formula (1))
1.20 parts by mass light stabilizer (LS-1: compound represented by general formula (TS-II)) 0.09 parts by mass Megafac F-780-F (manufactured by DIC Corporation) 0.03 mass Parts methyl ethyl ketone 57.80 parts by mass propylene glycol monomethyl ether 20.00 parts by mass cyclohexanone 5.00 parts by mass

-Composition of UV absorbent-containing layer forming coating solution (OC-7)-
Soarnol DC3212 (manufactured by Nippon Synthetic Chemical Co., Ltd.) 17.11 parts by mass of triazine ultraviolet absorber (UVA-1: compound represented by general formula (1))
1.20 parts by mass light stabilizer (LS-1: compound represented by general formula (TS-II)) 0.09 parts by mass Megafac F-780-F (manufactured by DIC Corporation) 0.03 mass Part water 41.40 parts by weight IPA 41.40 parts by weight

-Composition of UV absorbent-containing layer forming coating solution (OC-8)-
NUC-6220 (manufactured by Nippon Unicar Co., Ltd.) 17.11 parts by mass of triazine-based ultraviolet absorber (UVA-1: compound represented by general formula (1))
1.20 parts by mass light stabilizer (LS-1: compound represented by general formula (TS-II)) 0.09 parts by mass Megafac F-780-F (manufactured by DIC Corporation) 0.03 mass Parts methyl ethyl ketone 57.80 parts by mass propylene glycol monomethyl ether 20.00 parts by mass cyclohexanone 5.00 parts by mass

-Composition of UV absorbent-containing layer forming coating solution (OC-9)-
Dianal BR-102 (manufactured by Mitsubishi Rayon Co., Ltd.) 16.25 parts by mass of triazine-based ultraviolet absorber (UVA-1: compound represented by the general formula (1))
1.20 parts by mass light stabilizer (LS-1: compound represented by formula (TS-II)) 0.09 parts by mass Carbodilite V-05 (trade name: cross-linking agent, manufactured by Nisshinbo Chemical Co., Ltd.) 0.86 parts by mass Megafac F-780-F (manufactured by DIC Corporation) 0.03 parts by mass Methyl ethyl ketone 57.80 parts by mass Propylene glycol monomethyl ether 20.00 parts by mass Cyclohexanone 5.00 parts by mass

-Composition of UV absorbent containing layer forming coating solution (OC-10)-
ESREC KS-10 (manufactured by Sekisui Chemical Co., Ltd.) 16.25 parts by mass of a triazine ultraviolet absorber (UVA-1: compound represented by the general formula (1))
1.20 parts by mass light stabilizer (LS-1: compound represented by formula (TS-II)) 0.09 parts by mass Carbodilite V-05 (crosslinking agent, manufactured by Nisshinbo Chemical Co., Ltd.) 0.86 Parts by mass Megafac F-780-F (manufactured by DIC Corporation) 0.03 parts by mass methyl ethyl ketone 57.80 parts by mass propylene glycol monomethyl ether 20.00 parts by mass cyclohexanone 5.00 parts by mass

-Composition of UV absorbent containing layer forming coating solution (OC-11)-
Soarnol DC3212 (manufactured by Nippon Synthetic Chemical Co., Ltd.) 16.25 parts by mass of triazine-based ultraviolet absorber (UVA-1: compound represented by general formula (1))
1.20 parts by mass light stabilizer (LS-1: compound represented by formula (TS-II)) 0.09 parts by mass Carbodilite V-05 (crosslinking agent, manufactured by Nisshinbo Chemical Co., Ltd.) 0.86 Mass part MegaFuck F-780-F (manufactured by DIC Corporation) 0.03 parts by mass Water 41.40 parts by mass IPA 41.40 parts by mass

-Composition of UV absorbent-containing layer forming coating solution (OC-12)-
NUC-6220 (manufactured by Nippon Unicar Co., Ltd.) 16.25 parts by mass of triazine-based ultraviolet absorber (UVA-1: compound represented by the general formula (1))
1.20 parts by mass light stabilizer (LS-1: compound represented by formula (TS-II)) 0.09 parts by mass Carbodilite V-05 (crosslinking agent, manufactured by Nisshinbo Chemical Co., Ltd.) 0.86 Parts by mass Megafac F-780-F (manufactured by DIC Corporation) 0.03 parts by mass methyl ethyl ketone 57.80 parts by mass propylene glycol monomethyl ether 20.00 parts by mass cyclohexanone 5.00 parts by mass

-Composition of UV absorbent containing layer forming coating solution (OC-13)-
Dianal BR-102 (manufactured by Mitsubishi Rayon Co., Ltd.) 16.25 parts by mass of triazine-based ultraviolet absorber (UVA-2: compound represented by general formula (1))
1.20 parts by mass light stabilizer (LS-1: compound represented by formula (TS-II)) 0.09 parts by mass Carbodilite V-05 (crosslinking agent, manufactured by Nisshinbo Chemical Co., Ltd.) 0.86 Parts by mass Megafac F-780-F (manufactured by DIC Corporation) 0.03 parts by mass methyl ethyl ketone 57.80 parts by mass propylene glycol monomethyl ether 20.00 parts by mass cyclohexanone 5.00 parts by mass

-Composition of UV absorbent-containing layer forming coating solution (OC-14)-
Dianal BR-102 (manufactured by Mitsubishi Rayon Co., Ltd.) 16.25 parts by mass of a triazine-based ultraviolet absorber (UVA-3: a compound represented by the general formula (1))
1.20 parts by mass light stabilizer (LS-1: compound represented by formula (TS-II)) 0.09 parts by mass Carbodilite V-05 (crosslinking agent, manufactured by Nisshinbo Chemical Co., Ltd.) 0.86 Parts by mass Megafac F-780-F (manufactured by DIC Corporation) 0.03 parts by mass methyl ethyl ketone 57.80 parts by mass propylene glycol monomethyl ether 20.00 parts by mass cyclohexanone 5.00 parts by mass

-Composition of UV absorbent containing layer forming coating solution (OC-15)-
Dianal BR-102 (manufactured by Mitsubishi Rayon Co., Ltd.) 16.25 parts by mass of a triazine ultraviolet absorber (UVA-4: compound represented by the general formula (1))
1.20 parts by mass light stabilizer (LS-1: compound represented by formula (TS-II)) 0.09 parts by mass Carbodilite V-05 (crosslinking agent, manufactured by Nisshinbo Chemical Co., Ltd.) 0.86 Parts by mass Megafac F-780-F (manufactured by DIC Corporation) 0.03 parts by mass methyl ethyl ketone 57.80 parts by mass propylene glycol monomethyl ether 20.00 parts by mass cyclohexanone 5.00 parts by mass

-Composition of UV absorbent-containing layer forming coating solution (OC-16)-
Dianal BR-102 (manufactured by Mitsubishi Rayon Co., Ltd.) 16.25 parts by mass of triazine-based ultraviolet absorber (UVA-5: compound represented by general formula (1))
1.20 parts by mass light stabilizer (LS-1: compound represented by formula (TS-II)) 0.09 parts by mass Carbodilite V-05 (crosslinking agent, manufactured by Nisshinbo Chemical Co., Ltd.) 0.86 Parts by mass Megafac F-780-F (manufactured by DIC Corporation) 0.03 parts by mass methyl ethyl ketone 57.80 parts by mass propylene glycol monomethyl ether 20.00 parts by mass cyclohexanone 5.00 parts by mass

-Composition of UV absorbent containing layer forming coating solution (OC-17)-
Dianal BR-102 (manufactured by Mitsubishi Rayon Co., Ltd.) 13.45 parts by mass of triazine-based ultraviolet absorber (UVA-1: compound represented by the general formula (1))
1.20 parts by mass light stabilizer (LS-1: compound represented by formula (TS-II)) 0.09 parts by mass Carbodilite V-05 (crosslinking agent, manufactured by Nisshinbo Chemical Co., Ltd.) 0.86 Parts by mass Megafac F-780-F (manufactured by DIC Corporation) 0.03 parts by mass methyl ethyl ketone 57.80 parts by mass propylene glycol monomethyl ether 20.00 parts by mass cyclohexanone 5.00 parts by mass

-Composition of UV absorbent containing layer forming coating solution (OC-18)-
Dianal BR-102 (manufactured by Mitsubishi Rayon Co., Ltd.) 15.05 parts by mass of triazine-based ultraviolet absorber (UVA-1: compound represented by the general formula (1))
1.20 parts by mass light stabilizer (LS-1: compound represented by formula (TS-II)) 0.09 parts by mass Carbodilite V-05 (crosslinking agent, manufactured by Nisshinbo Chemical Co., Ltd.) 0.86 Parts by mass Megafac F-780-F (manufactured by DIC Corporation) 0.03 parts by mass methyl ethyl ketone 57.80 parts by mass propylene glycol monomethyl ether 20.00 parts by mass cyclohexanone 5.00 parts by mass

-Composition of UV absorber containing layer forming coating solution (OC-19)-
Dianal BR-102 (manufactured by Mitsubishi Rayon Co., Ltd.) 15.74 parts by mass of a triazine-based ultraviolet absorber (UVA-1: compound represented by the general formula (1))
1.20 parts by mass light stabilizer (LS-1: compound represented by formula (TS-II)) 0.09 parts by mass Carbodilite V-05 (crosslinking agent, manufactured by Nisshinbo Chemical Co., Ltd.) 0.86 Parts by mass Megafac F-780-F (manufactured by DIC Corporation) 0.03 parts by mass methyl ethyl ketone 57.80 parts by mass propylene glycol monomethyl ether 20.00 parts by mass cyclohexanone 5.00 parts by mass

-Composition of UV absorbent-containing layer forming coating solution (OC-20)-
Dianal BR-102 (manufactured by Mitsubishi Rayon Co., Ltd.) 16.65 parts by mass of triazine-based ultraviolet absorber (UVA-1: compound represented by general formula (1))
1.20 parts by mass light stabilizer (LS-1: compound represented by formula (TS-II)) 0.09 parts by mass Carbodilite V-05 (crosslinking agent, manufactured by Nisshinbo Chemical Co., Ltd.) 0.86 Parts by mass Megafac F-780-F (manufactured by DIC Corporation) 0.03 parts by mass methyl ethyl ketone 57.80 parts by mass propylene glycol monomethyl ether 20.00 parts by mass cyclohexanone 5.00 parts by mass

-Composition of UV absorbent containing layer forming coating solution (OC-21)-
Dianal BR-102 (manufactured by Mitsubishi Rayon Co., Ltd.) 16.85 parts by mass of triazine-based ultraviolet absorber (UVA-1: compound represented by general formula (1))
1.20 parts by mass light stabilizer (LS-1: compound represented by formula (TS-II)) 0.09 parts by mass Carbodilite V-05 (crosslinking agent, manufactured by Nisshinbo Chemical Co., Ltd.) 0.86 Parts by mass Megafac F-780-F (manufactured by DIC Corporation) 0.03 parts by mass methyl ethyl ketone 57.80 parts by mass propylene glycol monomethyl ether 20.00 parts by mass cyclohexanone 5.00 parts by mass

-Composition of UV absorbent containing layer forming coating solution (OC-22)-
Dianal BR-102 (manufactured by Mitsubishi Rayon Co., Ltd.) 17.05 parts by mass of triazine-based ultraviolet absorber (UVA-1: compound represented by general formula (1))
1.20 parts by mass light stabilizer (LS-1: compound represented by formula (TS-II)) 0.09 parts by mass Carbodilite V-05 (crosslinking agent, manufactured by Nisshinbo Chemical Co., Ltd.) 0.86 Parts by mass Megafac F-780-F (manufactured by DIC Corporation) 0.03 parts by mass methyl ethyl ketone 57.80 parts by mass propylene glycol monomethyl ether 20.00 parts by mass cyclohexanone 5.00 parts by mass

-Composition of UV absorbent containing layer forming coating solution (OC-23)-
Dianal BR-102 (manufactured by Mitsubishi Rayon Co., Ltd.) 16.36 parts by mass of triazine-based ultraviolet absorber (UVA-1: compound represented by general formula (1))
1.20 parts by mass light stabilizer (LS-1: compound represented by formula (TS-II)) 0.09 parts by mass Carbodilite V-05 (crosslinking agent, manufactured by Nisshinbo Chemical Co., Ltd.) 0.34 Parts by mass Megafac F-780-F (manufactured by DIC Corporation) 0.03 parts by mass methyl ethyl ketone 57.80 parts by mass propylene glycol monomethyl ether 20.00 parts by mass cyclohexanone 5.00 parts by mass

-Composition of UV absorbent-containing layer forming coating solution (OC-24)-
Dianal BR-102 (manufactured by Mitsubishi Rayon Co., Ltd.) 14.65 parts by mass of triazine-based ultraviolet absorber (UVA-1: compound represented by general formula (1))
1.20 parts by mass light stabilizer (LS-1: compound represented by formula (TS-II)) 0.09 parts by mass Carbodilite V-05 (crosslinking agent, manufactured by Nisshinbo Chemical Co., Ltd.) 0.34 Parts by mass Megafac F-780-F (manufactured by DIC Corporation) 0.03 parts by mass methyl ethyl ketone 57.80 parts by mass propylene glycol monomethyl ether 20.00 parts by mass cyclohexanone 5.00 parts by mass

-Composition of UV absorbent containing layer forming coating solution (OC-25)-
Dianal BR-102 (manufactured by Mitsubishi Rayon Co., Ltd.) 16.25 parts by mass of triazine-based ultraviolet absorber (UVA-6: compound represented by general formula (1))
1.20 parts by mass light stabilizer (LS-1: compound represented by formula (TS-II)) 0.09 parts by mass Carbodilite V-05 (crosslinking agent, manufactured by Nisshinbo Chemical Co., Ltd.) 0.86 Parts by mass Megafac F-780-F (manufactured by DIC Corporation) 0.03 parts by mass methyl ethyl ketone 57.80 parts by mass propylene glycol monomethyl ether 20.00 parts by mass cyclohexanone 5.00 parts by mass

-Composition of UV absorbent-containing layer forming coating solution (OC-26)-
ESREC KS-10 (manufactured by Sekisui Chemical Co., Ltd.) 16.25 parts by mass of triazine-based ultraviolet absorber (UVA-6: compound represented by the general formula (1))
1.20 parts by mass light stabilizer (LS-1: compound represented by formula (TS-II)) 0.09 parts by mass Carbodilite V-05 (crosslinking agent, manufactured by Nisshinbo Chemical Co., Ltd.) 0.86 Parts by mass Megafac F-780-F (manufactured by DIC Corporation) 0.03 parts by mass methyl ethyl ketone 57.80 parts by mass propylene glycol monomethyl ether 20.00 parts by mass cyclohexanone 5.00 parts by mass

-Composition of UV absorbent containing layer forming coating solution (OC-27)-
Soarnol DC3212 (manufactured by Nippon Synthetic Chemical Co., Ltd.) 16.25 parts by mass Triazine-based ultraviolet absorber (UVA-6: compound represented by general formula (1))
1.20 parts by mass light stabilizer (LS-1: compound represented by formula (TS-II)) 0.09 parts by mass Carbodilite V-05 (crosslinking agent, manufactured by Nisshinbo Chemical Co., Ltd.) 0.86 Mass part MegaFuck F-780-F (manufactured by DIC Corporation) 0.03 parts by mass Water 41.40 parts by mass IPA 41.40 parts by mass

-Composition of UV absorbent-containing layer forming coating solution (OC-28)-
NUC-6220 (manufactured by Nippon Unicar Co., Ltd.) 16.25 parts by mass of triazine-based ultraviolet absorber (UVA-6: compound represented by the general formula (1))
1.20 parts by mass light stabilizer (LS-1: compound represented by formula (TS-II)) 0.09 parts by mass Carbodilite V-05 (crosslinking agent, manufactured by Nisshinbo Chemical Co., Ltd.) 0.86 Parts by mass Megafac F-780-F (manufactured by DIC Corporation) 0.03 parts by mass methyl ethyl ketone 57.80 parts by mass propylene glycol monomethyl ether 20.00 parts by mass cyclohexanone 5.00 parts by mass

-Composition of UV absorbent containing layer forming coating solution (OC-29)-
Dianal BR-102 (manufactured by Mitsubishi Rayon Co., Ltd.) 11.45 parts by mass of triazine-based ultraviolet absorber (UVA-1: compound represented by general formula (1))
6.00 parts by mass light stabilizer (LS-1: compound represented by formula (TS-II)) 0.09 parts by mass Carbodilite V-05 (crosslinking agent, manufactured by Nisshinbo Chemical Co., Ltd.) 0.86 Parts by mass Megafac F-780-F (manufactured by DIC Corporation) 0.03 parts by mass methyl ethyl ketone 57.80 parts by mass propylene glycol monomethyl ether 20.00 parts by mass cyclohexanone 5.00 parts by mass

-Composition of UV absorbent containing layer forming coating solution (OC-30)-
Dianal BR-102 (Mitsubishi Rayon Co., Ltd.) 17.15 parts by mass Triazine UV absorber (UVA-1) 0.30 parts by mass Light stabilizer (LS-1: General formula (TS-II)) Compound represented) 0.09 parts by mass Carbodilite V-05 (cross-linking agent, manufactured by Nisshinbo Chemical Co., Ltd.) 0.86 parts by mass MegaFac F-780-F (manufactured by DIC Corporation) 0.03 parts by mass methyl ethyl ketone 57.80 parts by mass Propylene glycol monomethyl ether 20.00 parts by mass Cyclohexanone 5.00 parts by mass

-Composition of comparative UV absorber-containing layer forming coating solution (OC-31)-
Dianar BR-102 (Mitsubishi Rayon Co., Ltd.) 14.82 parts by mass Triazine UV absorber (UVA-1) 3.42 parts by mass light stabilizer (LS-1: General formula (TS-II)) Compound represented) 0.09 parts by mass Carbodilite V-05 (cross-linking agent, manufactured by Nisshinbo Chemical Co., Ltd.) 0.86 parts by mass MegaFac F-780-F (manufactured by DIC Corporation) 0.03 parts by mass methyl ethyl ketone 57.80 parts by mass Propylene glycol monomethyl ether 20.00 parts by mass Cyclohexanone 5.00 parts by mass

The following ultraviolet absorbent-containing layer forming coating solutions OC-32 to OC-36 are comparative protective layer-forming coating solutions containing an ultraviolet absorbent outside the scope of the present invention.
-Composition of comparative UV absorber-containing layer forming coating solution (OC-32)-
Dianar BR-102 (manufactured by Mitsubishi Rayon Co., Ltd.) 17.20 parts by mass TINUVIN 1577 (manufactured by BASF Co., Ltd.) (the following structure) 1.20 parts by mass MegaFuck F-780-F (manufactured by DIC Corporation) 0 0.03 parts by mass Methyl ethyl ketone 57.80 parts by mass Propylene glycol monomethyl ether 20.00 parts by mass Cyclohexanone 5.00 parts by mass

-Composition of comparative UV absorber-containing layer forming coating solution (OC-33)-
Dianar BR-102 (manufactured by Mitsubishi Rayon Co., Ltd.) 17.20 parts by mass TINUVIN 460 (manufactured by BASF Co., Ltd.) (structure shown below) 1.20 parts by mass MegaFuck F-780-F (manufactured by DIC Corporation) 0 0.03 parts by mass Methyl ethyl ketone 57.80 parts by mass Propylene glycol monomethyl ether 20.00 parts by mass Cyclohexanone 5.00 parts by mass

-Composition of comparative UV absorber-containing layer forming coating solution (OC-34)-
Dianar BR-102 (manufactured by Mitsubishi Rayon Co., Ltd.) 17.20 parts by mass TINUVIN 326 (manufactured by BASF Corp.) 1.20 parts by mass Megafac F-780-F (manufactured by DIC Co., Ltd.) 0.03 parts by mass Methyl ethyl ketone 57.80 parts by mass Propylene glycol monomethyl ether 20.00 parts by mass Cyclohexanone 5.00 parts by mass

-Composition of comparative UV absorber-containing layer forming coating solution (OC-35)-
Dianar BR-102 (manufactured by Mitsubishi Rayon Co., Ltd.) 17.20 parts by mass UVINAL3050 (manufactured by BASF Corp.) 1.20 parts by mass Megafax F-780-F (manufactured by DIC Corporation) 0.03 parts by mass Methyl ethyl ketone 57.80 parts by mass Propylene glycol monomethyl ether 20.00 parts by mass Cyclohexanone 5.00 parts by mass

-Composition of comparative UV absorber-containing layer forming coating solution (OC-36)-
AC-SQ SI-20 (manufactured by Toagosei Co., Ltd.) 17.20 parts by mass TINUVIN 460 (manufactured by BASF Corp.) 1.20 parts by mass Megafax F-780-F (manufactured by DIC Corp.) 0.03 mass Part methyl ethyl ketone 57.80 parts by mass propylene glycol monomethyl ether 20.00 parts by mass cyclohexanone 5.00 parts by mass In the film mirrors of Examples 13 to 38 and Examples 45 to 47, on the ultraviolet absorber-containing layer, Furthermore, the coating liquid for surface coating layer formation of the following prescription was apply | coated, and it dried at 80 degreeC for 2 minute (s), and formed the surface coating layer.

<Preparation of surface coating layer coating solution>
The surface coating layer coating solution was prepared by mixing at the following composition and mass ratio, then heating to 40 ° C. and stirring for 1 hour.
-Coating liquid for surface coating layer formation (TC-1)-
NATCO UV self-healing (manufactured by NATCO) 48.04 parts by mass Mega-Fac RS-75 (manufactured by DIC) 0.40 parts by mass IRGACURE 127 (manufactured by BASF Corp.) 1.50 parts by mass Mega-Fuck F- 780-F (manufactured by DIC Corporation) 0.06 parts by mass Methyl isobutyl ketone 45.00 parts by mass Cyclohexane 5.00 parts by mass -Coating liquid for forming a surface coating layer (TC-2)-
Defender FH-700 (manufactured by DIC Corporation) 50.00 parts by mass IPA 50.00 parts by mass

  Thus, on the PET film as a support, a resin intermediate layer composed of an easy-adhesion layer and a plating undercoat polymer layer, a metal reflective layer, an ultraviolet absorber-containing layer, and a surface coating layer provided as desired are formed in this order. Film mirrors of Examples 1 to 47 and Comparative Examples 1 to 5 were prepared.

  The ultraviolet absorbers used in the examples and comparative examples are the compounds disclosed in the exemplary compounds.

[Evaluation]
The film mirrors of Examples 1 to 47 and Comparative Examples 1 to 5 produced above were evaluated according to the following criteria. These results are shown in Tables 3-4.
<Performance evaluation of film mirror>
(1) Reflection performance The reflectance was measured about the obtained film mirror. The reflectance was measured using a spectrophotometer (UV-3100PC, manufactured by Shimadzu Corporation). Evaluation was performed according to the following criteria from the reflectance immediately after the production of the film mirror.
A: Reflectance is 95% or more B: Reflectance is 90% or more and less than 95% C: Reflectance is less than 90%

(2) Durability test The obtained film mirror was placed in a xenon lamp light resistance tester (ATLAS, Ci5000, power: 180 W, Black Panel Temperature: 83 ° C), temperature 55 ° C, humidity 50%. The film mirror was allowed to stand for 6000 hours under the condition of RH, and the decrease in reflectance at 450 nm of the film mirror at that time (reflectance before leaving (%) − reflectance after leaving (%)) was evaluated. The reflectance was measured using an ultraviolet-visible near-infrared spectrophotometer UV-3100 (manufactured by Shimadzu Corporation).
(2-1) Silver Reflective Layer Durability Test A: The reflectance of the silver reflecting layer is less than 5% B: The reflectance is reduced by 5% or more and less than 10% C: The reflectance is reduced by 10% or more (2 -2) Resin base material durability test About the resin base material durability, the resin base material of the back surface was observed visually, and the following references | standards evaluated.
A: Visual change is not recognized.
B: Although yellowing, surface roughness, etc. are recognized visually, it does not break easily by pulling with a finger.
C: Yellowing, surface roughness, etc. are observed visually, and breakage is caused by pulling with a finger.
(2-3) Ultraviolet absorber-containing layer durability test About the ultraviolet absorber-containing layer durability, the surface of the ultraviolet absorber-containing layer was observed visually and with an optical microscope, and evaluated according to the following criteria.
A: No change is observed.
B: Although no change is visually recognized, minute surface roughness or the like is observed by observation with an optical microscope.
C: At least one of yellowing and surface roughness that are clearly visible is observed.

(3) Adhesiveness About the obtained film mirror, the crosscut test (JIS K5400) was done. Evaluation was made according to the following criteria from the number of peeled cells.
A: The number of peeled squares is 0 square.
B: The number of peeled squares is 1 to 5 squares.
C: The number of peeled squares is 6 squares or more.
(4) Bleed-out resistance test The UV-absorber-containing layer coated product is allowed to stand for 1 month at room temperature of 40 ° C and a humidity of 60%. (1) Precipitates of the specific compound on the UV-absorber-containing layer surface The presence or absence of was visually observed and evaluated according to the following criteria.
A: When precipitation is not recognized C: When precipitation is recognized

(5) Solvent resistance test 50 μL of ethanol was dropped on the surface of the coated product with the UV absorber-containing layer, and then naturally dried. The traces of the droplets were visually observed and evaluated according to the following criteria.
A: No traces are observed B: Traces are recognized but not clouded C: Traces are cloudy

(6) Scratch resistance test A scratch resistance test was performed according to "Sand drop abrasion test method" described in JIS H 8503 (1989). Specifically, the film mirrors of the produced examples and comparative examples were cut into 3 cm squares, fixed to a measuring device so that the SiO ₂ particles collided from an angle of 45 degrees, and then 320 g of SiO ₂ particles were added to 100 cm. Freely dropped from the height and collided. Thereafter, the sample was subjected to ultrasonic cleaning in pure water to remove the adhered particles. The difference (ΔH) in haze values before and after the dust test was measured, and the results were evaluated as follows.
AA: ΔH is 2% or less A: ΔH is 2% or more and less than 5% B: ΔH is 5% or more and less than 10% C: ΔH is 10% or more

In Examples 1 to 4, the ultraviolet absorber-containing layer contains (1) a specific compound having good stability to ultraviolet light, and high durability is obtained by maintaining the ultraviolet absorbing ability for a long period of time. .
In Examples 5 to 8, a light stabilizer (radical scavenger) was added in addition to (1) the specific compound according to the present invention, and higher durability was achieved by the synergistic effect of both.
In Examples 9 to 12, the addition of a crosslinking agent further improved the adhesion and solvent resistance with the metal reflective layer, indicating that a crosslinked structure was formed in the ultraviolet absorber-containing layer. .
In Examples 20-32, it turns out that the flaw resistance is improving by providing a surface coating layer further on a ultraviolet absorber content layer.
Examples 33 to 38 and Examples 45 and 46 show the relationship between the film thickness of the ultraviolet absorber-containing layer and various performances. In order to shield the ultraviolet rays and protect the substrate, a certain ultraviolet absorbing material is required per unit area. Therefore, it is preferable to increase the concentration of the ultraviolet absorber contained in the ultraviolet absorber-containing layer as the film thickness is reduced. In Example 33 and Example 45, the UV absorber concentration in the UV absorber-containing layer is increased, the haze is increased, the reflection performance is slightly lowered, and the low molecular weight component is increased, thereby being adhered. The sex is decreasing. However, there is no problem in practical use.
Further, when the surface coating layer is applied onto the ultraviolet absorber-containing layer, there is a concern that the ultraviolet absorber is diffused into the surface coating layer due to the influence of the coating solvent and the ultraviolet curing is inhibited. In that case, since the scratch resistance cannot obtain a desired improvement effect, it is considered that consideration such as selection of a coating solvent is necessary.
In Example 38, as the film thickness increased, the light absorption of the ultraviolet absorber-containing layer itself increased, and the reflection performance slightly decreased. In Example 46, the film thickness was further increased, and here, the reflection performance was lowered, but all were at a level causing no practical problem.

Examples 39, 40, and 47 show the effect of the ratio of UV absorber and crosslinker on various performances. As the amount of the UV absorber increases, a higher degree of crosslinking is required to suppress bleeding out of the UV absorber and extraction into the surface coating layer. Therefore, the ratio of the ultraviolet absorber and the crosslinking agent as well as their absolute amounts is important. By increasing the ratio of the UV absorber / crosslinking agent, the movement of the UV absorber cannot be suppressed in Comparative Example 1, and the bleed-out resistance and the scratch resistance of the surface coating layer do not satisfy the desired performance.
Examples 41 to 44 are cases where an acidic group-containing compound (Exemplary Compound UVA-6) is used as the ultraviolet absorber, and silver oxidation in the silver-containing metal reflective layer proceeds due to the influence of the acidic group. It can be seen that the durability of the metal reflective layer is slightly lowered.
In Comparative Examples 2 to 4, since the ultraviolet absorber itself lacks stability to ultraviolet light, it is decomposed and colored, and the resin cannot be shielded from ultraviolet light, and the deterioration of the resin is also progressing. In Comparative Example 2, bleed out occurs due to insufficient compatibility between TINUVIN 460 and the resin.
In Comparative Example 5, although the ultraviolet absorber itself is insufficiently stable with respect to ultraviolet light, it is decomposed and colored, but the ultraviolet absorber-containing layer itself has not deteriorated because it has good light resistance. Since a highly peelable silsesquioxane resin is used, adhesion is not satisfied. In addition, bleed out occurs due to insufficient compatibility between TINUVIN 460 and the resin.

[Production of solar reflector]
For each of the film mirrors (F-1 to F-4) of Examples 21 to 24, an aluminum plate having a thickness of 0.6 mm is bonded to the surface opposite to the surface on which the metal reflective layer is provided. (SK-2057, manufactured by Soken Chemical Co., Ltd.) was used to bond the solar reflectors of Example 48 to Example 51.
The produced solar reflectors of Example 48 to Example 51 all showed excellent specularity equivalent to a glass mirror. Further, the produced solar reflectors of Example 48 to Example 51 were placed in a xenon lamp light resistance tester (ATLAS, Ci5000, power: 180 W, Black Panel Temperature: 83 ° C.), and the temperature was 55. When held for 6000 hours under the conditions of ° C. and humidity of 50% RH, there was little decrease in reflectivity, no surface roughness, no peeling, etc., and good durability was exhibited.

Claims (13)

The film mirror which has a metal reflective layer and the ultraviolet absorber containing layer containing the compound represented by following General formula (1) on a resin-made support body in this order.


(In the general formula (1), R ^1a , R ^1b , R ^1c , R ^1d , and R ^1e each independently represent a monovalent substituent other than a hydrogen atom or a hydroxy group, One represents a substituent having a positive Hammett's σp value: R ^1g , R ^1h , R ¹ⁱ , R ^1j , R ^1k , R ^1m , R ¹ⁿ , and R ^1p are each independently a hydrogen atom or R ^1a , R ^1b , R ^1c , R ^1d , R ^1e , R ^1g , R ^1h , R ¹ⁱ , R ^1j , R ^1k , R ^1m , R ¹ⁿ , and R ^1p are monovalent. Any two or more of them may be bonded to each other to form a ring. In the general formula (1), R ^1a , R ^1b , R ^1c , R ^1d , R ^1e , R ^1g , R ^1h , R ¹ⁱ , R ^1j , R ^1k , R ^1m , R ¹ⁿ , and R ^1p are hydrogen. The film mirror according to claim 1, which represents a monovalent substituent having no atom or acidic group. It is selected from the group of compounds represented by the following general formula (TS-I), general formula (TS-II), general formula (TS-III), general formula (TS-VI), and general formula (TS-V). The film mirror according to claim 1, further comprising a light stabilizer-containing layer containing at least one compound.

(In the general formula (TS-I), R ⁹¹ is a hydrogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, acyl group, alkylcarbonyl group, alkenylcarbonyl group, alkyloxycarbonyl group, alkenyloxycarbonyl group. , An aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, a phosphinotolyl group, a phosphinyl group, or —Si (R ⁹⁷ ) (R ⁹⁸ ) (R ⁹⁹ ), wherein R ⁹⁷ , R ⁹⁸ , and R ⁹⁹ are each independent. Represents an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an alkenyloxy group, or an aryloxy group, X ⁹¹ represents —O—, —S—, or —N (—R ¹⁰⁰ ) —, and R ¹⁰⁰ represents the above-mentioned the same meaning as ^{R 91 .R 92, R 93,} R 94, R 95, and ^{R 96} are each To stand, the hydrogen atom or a monovalent represents a substituent ^{.R 91} and ^{R 92,} and ^{R 100} and ^{R 96, R 91} and ^{R 100,} 5-membered to 7-membered ring together with the respective carbon atom adjacent bonded to each other R ⁹² and R ⁹³ , R ⁹³ and R ⁹⁴ are bonded to each other to form a 5-membered to 7-membered ring, a spiro ring, or a bicyclo ring together with adjacent carbon atoms. However, R ⁹¹ , R ⁹² , R ⁹³ , R ⁹⁴ , R ⁹⁵ , R ⁹⁶ , and R ¹⁰⁰ are not all hydrogen atoms, and the compound represented by the general formula (TS-I) The total carbon number contained is 9 or more.
In the general formula (TS-II), R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , and R ¹⁰⁴ each independently represent a hydrogen atom, an alkyl group, or an alkenyl group, and R ¹⁰¹ and R ¹⁰² , R ¹⁰³ and R ¹⁰⁴ And may be bonded to each other to form a 5-membered to 7-membered ring together with adjacent carbon atoms. X ¹⁰¹ is a hydrogen atom, alkyl group, alkenyl group, alkyloxy group, alkenyloxy group, alkyloxycarbonyl group, alkenyloxycarbonyl group, aryloxycarbonyl group, acyl group, acyloxy group, alkyloxycarbonyloxy group, alkenyloxycarbonyl It represents an oxy group, an aryloxycarbonyloxy group, an alkylsulfonyl group, an alkenylsulfonyl group, an arylsulfonyl group, an alkylsulfinyl group, an alkenylsulfinyl group, an arylsulfinyl group, a sulfamoyl group, a carbamoyl group, a hydroxy group, or an oxy radical group. X ¹⁰² represents a nonmetallic atom group necessary for forming a 5-membered to 7-membered ring together with a carbon atom and a nitrogen atom.
In the general formula (TS-III), R ¹⁰⁵ and R ¹⁰⁶ are each independently a hydrogen atom, an aliphatic group, an acyl group, an aliphatic oxycarbonyl group, an aromatic oxycarbonyl group, an aliphatic sulfonyl group, or an aromatic group. Represents a sulfonyl group, and R ¹⁰⁷ represents an aliphatic group, aliphatic oxy group, aromatic oxy group, aliphatic thio group, aromatic thio group, acyloxy group, aliphatic oxycarbonyloxy group, aromatic oxycarbonyloxy group, substituted It represents an amino group, a heterocyclic group, or a hydroxy group, and R ¹⁰⁵ and R ¹⁰⁶ are not both hydrogen atoms, and the total carbon number contained in R ¹⁰⁵ and R ¹⁰⁶ is 7 or more. R ¹⁰⁵ and R ¹⁰⁶ , R ¹⁰⁶ and R ¹⁰⁷ , R ¹⁰⁵ and R ¹⁰⁷ may be bonded to each other to form a 5-membered to 7-membered ring with an adjacent nitrogen atom. It does not form a 2,2,6,6-tetraalkylpiperidine skeleton.
In the general formula (TS-IV), R ¹¹¹ and R ¹¹² each independently represents an aliphatic group, and the aliphatic group may further have a substituent, and the total carbon contained in R ¹¹¹ and R ¹¹² The number is 10 or more. R ¹¹¹ and R ¹¹² may be bonded to each other to form a 5- to 7-membered ring with an adjacent sulfur atom. n represents 0, 1, or 2.
In the general formula (TS-V), R ¹²¹ and R ¹²² each independently represents an aliphatic oxy group or an aromatic oxy group, and R ¹²³ represents an aliphatic group, an aromatic group, an aliphatic oxy group, or an aromatic group. Represents a group oxy group, and the total carbon number contained in R ¹²¹ , R ¹²² and R ¹²³ is 10 or more. m represents 0 or 1; R ¹²¹ and R ¹²² , R ¹²¹ and R ¹²³ may be bonded to each other to form a 5- to 8-membered ring together with the adjacent phosphorus atom. )   The film mirror according to claim 3, wherein the ultraviolet absorber-containing layer and the light stabilizer-containing layer are the same layer.   The film mirror of any one of Claims 1-4 whose thickness of the said ultraviolet absorber content layer is 3 micrometers or more and 30 micrometers or less.   The said ultraviolet absorber content layer contains at least 1 sort (s) of resin chosen from the group which consists of an acrylic resin, polyvinyl butyral, ethylene vinyl acetate resin, and ethylene acrylate ester copolymer resin. The film mirror of any one.   The film mirror according to claim 1, wherein the ultraviolet absorber-containing layer is selected from the group consisting of a carbodiimide compound, an isocyanate compound, and an epoxy compound, and contains at least one crosslinking agent.   In the ultraviolet absorber-containing layer, when the content of the compound represented by the general formula (1) is A and the content of the cross-linking agent is B, the ratio (A / B) between them is based on mass. The film mirror according to claim 7, which is 0.05 or more and 10 or less.   The film mirror according to any one of claims 1 to 8, further comprising a surface coating layer on the ultraviolet absorber-containing layer.   The film mirror according to claim 1, wherein the metal reflective layer contains silver.   11. The method according to claim 1, further comprising a plating undercoat polymer layer between the resin support and the metal reflective layer, wherein the metal reflective layer is formed by plating. The film mirror described.   The film mirror according to any one of claims 1 to 11, which is used for collecting sunlight.   The film mirror according to any one of claims 1 to 12 is bonded to a substrate made of any one of resin, metal, or ceramic via an adhesive layer, or a fixing jig. A solar reflector that is attached to a frame made of any of resin, metal, or ceramic via