JP2015049472A - Film mirror - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide film mirrors that are excellent in an adhesion property between a protection layer and a metallic reflection layer even after exposed under a high temperature and high humidity or even after cleaned, and enable high reflectance to be maintained.SOLUTION: A film mirror has: a metallic reflection layer; and a protection layer that is adjacently provided on the metallic reflection layer, and the protection layer contains resin that has at least a part of a repeating unit expressed by a following expression (1) (where Rdenotes a hydrogen atom or a methyl group, Rdenotes the hydrogen atom or an optionally branched C1-C6 alkyl group, Rdenotes the hydrogen atom or the optionally branched C1-C6 alkyl group, and L denotes a divalent connection group.)

Description

  The present invention relates to a film mirror that can be suitably used for a solar reflective film mirror.

Conventionally, glass mirrors have been used for sunlight reflecting devices because they are exposed to ultraviolet rays, heat, wind and rain, and dust from sunlight.
However, when a glass mirror is used, there are problems that it is damaged during transportation and that a high strength is required for the mount on which the mirror is installed, resulting in an increase in construction costs.
In order to solve such problems, in recent years, it has been proposed to replace a glass mirror with a resin reflection sheet (film mirror).

  For example, Patent Document 1 states that “a plastic layer has a structure in which an anchor layer, a metal reflection layer, and a protective resin layer are laminated on one side, and the protective resin layer contains an acrylic resin and hexamethylene diisocyanate. (Refer to claim 1) ”, and the above configuration ensures sufficient adhesion between the protective resin layer and the metal reflective layer. It is described that the protective resin layer does not peel off and corrosion of the metal reflective layer can be prevented ([0012]).

JP 2011-173365 A

  When the present inventors examined the reflective film described in Patent Document 1, when the reflective film was exposed to high temperature and high humidity, it was between the protective resin layer (protective layer) and the metal reflective layer. It became clear that the protective layer might fall off the metal reflective layer when the surface of the reflective film was washed (especially by rubbing) after exposure to high temperature and high humidity. . In addition, when exposed to high temperature and high humidity, the reflectance tends to decrease with time, and it has been clarified that the anticorrosive property of the metal reflective layer is not sufficient.

  Therefore, the present invention has an object to provide a film mirror that has excellent adhesion between the protective layer and the metal reflective layer even after being exposed to high temperature and high humidity and after cleaning, and can maintain a high reflectance. And

As a result of earnest research to achieve the above-mentioned problems, the present inventors have found that a film mirror in which a protective layer containing a resin having a specific repeating unit having a nitrogen atom in the side chain is provided adjacent to the metal reflective layer. The present invention was completed by finding that the film was excellent in adhesion between the protective layer and the metal reflective layer even after being exposed to high temperature and high humidity and after cleaning, and that high reflectance could be maintained.
That is, it has been found that the above-described problem can be achieved by the following configuration.

[1] A film mirror having a metal reflective layer and a protective layer provided adjacent to the metal reflective layer,
The film mirror in which a protective layer contains resin which has a repeating unit represented by following formula (1) at least in part.

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or an optionally branched alkyl group having 1 to 6 carbon atoms, and R ³ represents a hydrogen atom or 1 to 6 carbon atoms. Represents an alkyl group which may be branched, and L represents a divalent linking group.)
[2] The film mirror according to [1], wherein the protective layer contains 1 to 50% by mass of the repeating unit represented by the formula (1) with respect to the resin solid content of the protective layer.
[3] The film mirror according to [1] or [2], wherein the surface of the metal reflective layer has an arithmetic average roughness Ra of 5 nm or less.
[4] The film mirror according to any one of [1] to [3], which is used for sunlight reflection.

As will be described below, according to the present invention, the film having excellent adhesion between the protective layer and the metal reflective layer even after being exposed to high temperature and high humidity and after cleaning, and capable of maintaining a high reflectance. A mirror can be provided.
Moreover, since the film mirror of this invention has such a characteristic, it can be used suitably as a film mirror for sunlight reflection exposed to a heat | fever, a wind and rain, sand dust, etc. for a long time.

It is sectional drawing which shows typically an example of the embodiment of the film mirror of this invention. It is sectional drawing which shows typically another example of the embodiment of the film mirror of this invention. It is sectional drawing which shows typically another example of the embodiment of the film mirror of this invention.

  The film mirror of the present invention is a film mirror having a metal reflective layer and a protective layer provided adjacent to the metal reflective layer, wherein the protective layer has at least one repeating unit represented by the above formula (1). It is the film mirror containing resin which has in a part.

The film mirror of the present invention having such a configuration is excellent in the adhesion between the protective layer and the metal reflective layer even after being exposed to high temperature and high humidity and after cleaning, and can maintain a high reflectance.
Although this is not clear in detail, the present inventors presume as follows.
That is, the resin having at least a part of the repeating unit represented by the formula (1) is a metal due to the interaction between the nitrogen atom contained in the formula (1) in the protective layer and the metal atom in the metal reflective layer. This is thought to be due to strong adsorption to the reflective layer. In addition, it is considered that corrosion of the metal reflective layer is usually caused by the effects of oxidation of metal atoms, migration of metal atoms (migration), etc. due to aging with wet heat, but nitrogen atoms and metals included in the above formula (1) This is considered to be because the above-described corrosion of the metal reflection layer was suppressed by the action of stabilization and fixation of the metal atoms due to the interaction with the metal atoms of the reflection layer.
This indicates that, as shown in a comparative example described later, in the case where the protective layer is composed only of a resin not having the repeating unit represented by the above formula (1), the adhesion after the wet heat resistance test or after the cleaning is performed. It can also be inferred from the inferior nature.

1-3 is sectional drawing which shows typically an example of the embodiment of the film mirror of this invention.
A film mirror 10 shown in FIG. 1 has a metal reflective layer 1 and a protective layer 2.
Moreover, as shown in FIG. 2, it is preferable that the film mirror of this invention provides the support body 3 in the surface on the opposite side to the surface in which the protective layer 2 of the metal reflective layer 1 was provided.
Furthermore, as shown in FIG. 3, the film mirror of the present invention preferably has a surface coating layer 4 on the surface of the protective layer 2 opposite to the surface on which the metal reflective layer 1 is provided.
The layer configuration of the film mirror is not particularly limited to these drawings. For example, if necessary, a resin layer described later may be provided between the support and the metal reflective layer. A back coat layer may be provided on the body side.
Below, each layer which comprises the film mirror of this invention is explained in full detail.

<Metal reflective layer>
The metal reflective layer included in the film mirror of the present invention is a layer having a function of reflecting light incident from the protective layer side described later.
The material for forming the metal reflective 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 increases the reflectance in the visible light region of the film mirror, and can reduce the dependency of the reflectance on the incident angle. The visible light region means a wavelength region of 400 to 700 nm. Here, the incident angle means an angle with respect to a line perpendicular to the layer surface.
As a silver alloy, from the point that the durability of the metal reflective layer is improved, other metals such as gold, palladium, copper, nickel, iron, gallium, indium, etc. One or more metals selected from the group consisting of titanium and bismuth may be included. 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 viewpoint of heat and humidity resistance, reflectance, and the like.

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

The arithmetic average roughness Ra of the surface of the metal reflective layer (that is, the interface with the protective layer described later) is preferably 5 nm or less. By setting it within this range, the reflectance of the film mirror is further improved, and sunlight can be efficiently reflected in sunlight reflection applications. Moreover, when using a film mirror for sunlight condensing use, since the one where arithmetic mean roughness Ra of the surface of a metal reflective layer is low can suppress the breadth of reflected light, it is preferable. Suppressing the spread of reflected light is particularly important in applications where the reflected light is focused on a target at a distant position.
Here, the arithmetic average roughness Ra refers to “arithmetic average roughness” defined in JIS B0601: 1994. The analysis from the film mirror is performed by taking a cross section of the film mirror with an electron microscope, and performing image processing with general-purpose software (for example, WinROOF, MATLAB, etc.) to determine the interface (line segment) between the metal reflective layer and the protective layer. The arithmetic average roughness Ra can be calculated from the extracted line segment.

The formation method of a metal reflective layer is not specifically limited, Either a wet method or a dry method may be employ | adopted. 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.
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. When the plating undercoat polymer layer described later is formed on the support described later, since the metal particles contained in the plating undercoat polymer layer have a function as an electrode, the plating undercoat polymer layer is supported by electroplating. A metal reflective layer excellent in adhesion to the body 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 the electroplating method can be controlled by adjusting the metal concentration contained in the plating bath or the current density. By adding a base metal layer having an appropriate thickness, it is possible to improve reflectance and reduce pinholes by smoothing the surface.
The thickness of the metal reflection layer is preferably 0.05 to 2.0 μm from the viewpoint of forming a reflection film without pinholes and from not forming irregularities that scatter light on the surface of the metal reflection layer. 0.08 to 0.5 μm is more preferable.

  Moreover, you may form a metal reflective layer by performing dry plating, such as vacuum deposition, 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. Moreover, you may form an inorganic membrane | film | coat and a metal oxide film in the metal reflective layer surface. Moreover, you may provide the discoloration prevention agent layer containing a discoloration prevention agent in the metal reflective layer surface. 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.

The film mirror of the present invention having such a metal reflection layer can be suitably used for sunlight reflection.
As the application mode, for example, application to a sunlight reflecting plate can be mentioned. Specifically, by fixing a film mirror to a substrate or frame made of any one of resin, metal, and ceramic, a mirror surface by a metal reflection layer can be produced and a solar reflector can be produced. . It is preferable to efficiently collect sunlight by arranging a plurality of mirror units thus manufactured. In particular, more efficient sunlight collection can be realized by including a solar light tracking system that tracks the mirror unit in the diurnal motion of the sun.

<Protective layer>
The protective layer which the film mirror of this invention has is a resin layer provided adjacently on the metal reflective layer mentioned above.
In the present invention, the protective layer is a resin layer containing a resin having at least part of a repeating unit represented by the following formula (1). In addition, the repeating unit represented by the following formula (1) in the protective layer may be contained not only as a repeating unit constituting a homopolymer but also as a repeating unit constituting a block copolymer. It may be contained as a repeating unit constituting the random copolymer.
By having the protective layer having such a configuration, the film mirror has excellent adhesion between the protective layer and the metal reflective layer even after being exposed to high temperature and high humidity and after cleaning, and maintains a high reflectance. Can do.

(In the above formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or an optionally branched alkyl group having 1 to 6 carbon atoms, and R ³ represents a hydrogen atom or a carbon number. 1 to 6 alkyl groups which may be branched, and L represents a divalent linking group.

Here, in said formula (1), as R < ² >, it is a hydrogen atom or a C1-C4 alkyl group (For example, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group etc.). Among them, a hydrogen atom, a methyl group or an ethyl group is more preferable.
Similarly, in the above formula (1), R ³ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, etc.). Among them, a hydrogen atom, a methyl group or an ethyl group is more preferable.

Furthermore, in the above formula (1), L representing a divalent linking group is represented by * -L ¹ -L ² — (* represents the position of linking to the main chain. The same applies hereinafter). A divalent linking group, wherein L ¹ represents * —C (═O) —, * —CONH—, * —COO—, * —OCO—, or * —NHCO—; ² is a single bond, an alkylene group having 1 to 20 carbon atoms (for example, ethylene group, propylene group, etc.), a polyoxyalkylene group having 1 to 20 carbon atoms, or a divalent linking group in which these groups are combined. It is preferable that it is a bivalent coupling group represented.

In this invention, it is preferable that a protective layer contains 1-50 mass% of repeating units represented by the said Formula (1) with respect to resin solid content which comprises a protective layer, and contains 5-30 mass%. Is more preferable.
Here, if the content of the repeating unit represented by the above formula (1) is 50% by mass or less, although depending on the resin used in combination, the physical film strength of the protective layer itself is improved, and the adhesion test And the like, since the cohesive failure of the protective layer itself is suppressed. Further, if the content of the repeating unit represented by the above formula (1) is 1% by mass or more, it depends on the resin used together, but it is preferable because the heat and humidity resistance is improved and the adhesiveness is further improved.

  The resin having a repeating unit represented by the above formula (1) is, for example, a method of homopolymerizing and curing a monomer having a nitrogen atom (hereinafter abbreviated as “nitrogen-containing monomer”); It can be prepared by a method of copolymerizing with other monomers (block copolymerization or random copolymerization) and curing;

As said nitrogen-containing monomer, the compound represented by following formula (2) is mentioned, for example.

(In the above formula (2), R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or an optionally branched alkyl group having 1 to 6 carbon atoms, and R ³ represents a hydrogen atom or a carbon number. 1 to 6 alkyl groups which may be branched, and L represents a divalent linking group.

Here, in the above formula (2), as R ^2, as in the above formula (1), a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group). , N-butyl group, etc.), and more preferably a hydrogen atom, a methyl group or an ethyl group.
Similarly, in the above formula (2), as R ^3, as in the above formula (1), a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (for example, methyl group, ethyl group, n-propyl group, isopropyl group) , N-butyl group, etc.), and more preferably a hydrogen atom, a methyl group or an ethyl group.

Further, in the above formula (2), L representing a divalent linking group is a divalent linking group represented by -L ¹ -L ² — as in the above formula (1), and L ¹ is , -C (= O)-, -CONH-, -COO-, -OCO-, or -NHCO-, and L ² is a single bond, an alkylene group having 1 to 20 carbon atoms (for example, ethylene Group, a propylene group, etc.), a polyoxyalkylene group having 1 to 20 carbon atoms, or a divalent linking group representing a divalent linking group in which these groups are combined is preferable.

Examples of the compound represented by the above formula (2) include compound A (dimethylacrylamide (DMAA)), compound B (diethylacrylamide (DEAA)), and compound C (isopropylacrylamide (NIPAM)) represented by the following formula: , Compound D (dimethylaminopropylacrylamide (DMAPAA)) and the like, and these may be used alone or in combination of two or more. Among these, the following compound A is preferable.

On the other hand, other monomers include (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, chloroethyl (meth) acrylate, 2-hydroxyethyl ( Nitrogen such as (meth) acrylate, trimethylolpropane mono (meth) acrylate, benzyl (meth) acrylate, methoxybenzyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ethyl acetoacetate (meth) acrylate The (meth) acrylate monomer which does not have an atom is mentioned, These may be used individually by 1 type and may use 2 or more types together.
In this specification, the expression “(meth) acrylate” refers to an expression representing acrylate or methacrylate, and similarly, the expression “(meth) acrylic acid” also refers to an expression representing acrylic acid or methacrylic acid. Say.

  Although the thickness of the protective layer is not particularly limited, the adhesion between the protective layer and the metal reflective layer becomes better, the corrosion resistance of the metal reflective layer is improved, and a higher reflectance can be maintained. It is preferably 0.1 μm or more, more preferably 1 μm or more, further preferably 5 μm or more, and particularly preferably 10 μm or more. The upper limit is not particularly limited, but is usually preferably 100 μm or less, and more preferably 50 μm or less.

Although the formation method of a protective layer is not specifically limited, For example, the composition for protective layer formation containing the nitrogen-containing monomer mentioned above, another monomer, the solvent mentioned later, an additive, etc. was apply | coated to the surface of the metal reflective layer mentioned above. Thereafter, drying by heating, curing by ultraviolet irradiation, and the like can be mentioned.
As a method for forming the protective layer, in addition to the above, the protective layer forming composition is used to form a film in advance, and the film obtained through the adhesive is bonded to the metal reflective layer, or heat Examples thereof include a method of forming a protective layer by a method such as laminating to the metal reflective layer by a method such as laminating.
Below, the aspect using the composition for protective layer formation mentioned above is explained in full detail.

As a method for applying the composition for forming a protective layer, conventionally known coating methods 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, and a curtain coater can be used.
The method for curing the composition for forming a protective layer 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 protective layer, such as heating or UV irradiation, can be appropriately selected. That's fine.

The composition for forming a protective layer may contain other resins, solvents, and various additives in addition to the components described above.
Examples of other resins that may be contained in the protective layer forming composition include urethane (meth) acrylate resins, polyester (meth) acrylate resins, silicone (meth) acrylate resins, and epoxy (meth) acrylate resins. Photo-curing resin; Thermosetting resin such as urethane resin, phenol resin, urea resin (urea resin), phenoxy resin, silicone resin, polyimide resin, diallyl phthalate resin, furan resin, bismaleimide resin, cyanate resin; polyvinyl acetal resin , Polyvinyl alcohol resin, polyvinyl chloride resin, saturated polyester resin, polyrotaxane resin, melamine resin, and the like. These may be used alone or in combination of two or more.
In addition, when it contains such other resin, it is preferable that content of other resin is 10-99 mass% with respect to the resin solid content of a protective layer, and it is 20-50 mass%. More preferred.

The solvent that may be contained in the protective layer forming composition is not particularly limited, for example, water, methanol, ethanol, propanol, ethylene glycol, glycerin, propylene glycol monomethyl ether and other alcohol solvents, acetic acid and other acids, Ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone, amide solvents such as formamide, dimethylacetamide and N-methylpyrrolidone, nitrile solvents such as acetonitrile and propionitrile, ester solvents such as methyl acetate and ethyl acetate, dimethyl carbonate Carbonate solvents such as diethyl carbonate, aromatic hydrocarbon solvents such as benzene, toluene, xylene, and other solvents, ether solvents, glycol solvents, amine solvents, thiol solvents, halogens The solvent and the like. Of these, amide solvents, ketone solvents, nitrile solvents, carbonate solvents, and aromatic hydrocarbon solvents are preferable. Specifically, acetone, dimethylacetamide, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetonitrile, propio Nitrile, N-methylpyrrolidone, dimethyl carbonate, and toluene are preferred.
From the viewpoint of uniformly forming a protective layer having excellent adhesion, the solid content concentration of the protective layer-forming composition is preferably in the range of 1 to 30% by mass.

  The composition for forming a protective layer may further contain a crosslinking agent. By containing a cross-linking agent, the cross-linked structure is formed in the protective layer, so that the strength is further improved, and further, the adhesion with the adjacent metal reflective layer is further improved. . The crosslinking agent can be selected depending on the correlation with the resin constituting the protective layer, and examples thereof include a carbodiimide compound, an isocyanate compound, an epoxy compound, an oxetane compound, a melamine compound, and a bisvinylsulfone compound. Are preferably selected from the group consisting of carbodiimide compounds, isocyanate compounds, and epoxy compounds, and at least one crosslinking agent is preferred.

<Support>
The film mirror of the present invention is a surface opposite to the surface provided with the protective layer of the metal reflective layer, for the purpose of supporting the metal reflective layer as a smooth surface, and from the viewpoint of improving the handleability of the film mirror, An optional support is preferably provided.
The support is not particularly limited. For example, glass epoxy, polyester, polyimide, thermosetting polyphenylene ether, polyamide, polyaramid, liquid crystal polymer, etc. are formed into a film from the viewpoint of flexibility and weight reduction. Resin film; glass film; paper; and the like. Among these, a resin film (resin support) is preferable in terms of excellent handleability.
Any resin material can be used as the resin material in the resin film as long as it can be molded into a film. For example, phenol resin, epoxy resin, polyimide resin, bismaleimide triazine (BT) resin, polyphenylene ether (PPE) Resin, tetrafluoroethylene resin, liquid crystal resin, polyester resin, polyethylene naphthalate (PEN), aramid resin, polyamide resin, polyethersulfone, triacetylcellulose, polyvinyl chloride, polyvinylidene chloride, polyethylene, polypropylene, polystyrene, polybutadiene, Preferred examples include polyacetylene. Of these, polyimide resins and polyester resins are preferable.

In the present invention, the shape of the support may be any shape as long as it is a shape required for various film substrates such as a flat surface, a diffusion surface, a concave surface, and a convex surface.
The thickness of the support is preferably about 10 μm to 5 mm, more preferably 20 μm to 1 mm, and even more preferably 25 μm to 500 μm from the viewpoint of workability during production and molding.

Moreover, in this invention, in order to make it easy to form the arbitrary resin layers mentioned later on a support body, you may surface-treat a support body previously.
Surface treatment includes UV irradiation, ozone treatment, plasma treatment, corona treatment, flame treatment and other surface activation treatments; alkaline solutions such as hydrazine, N-methylpyrrolidone, sodium hydroxide solution, potassium hydroxide solution Treatment with an acidic solution such as sulfuric acid, hydrochloric acid or nitric acid; and the like.
Examples of the treatment to remove and clean the surface of the support include treatment with an organic solvent such as methanol, ethanol, toluene, ethyl acetate, and acetone; washing with water to remove the attached dust.
These surface treatments may be performed in combination of a plurality of types.

  Furthermore, in the present invention, from the viewpoint of improving the reflectivity of the film mirror, the surface roughness (Ra) of the support is preferably 50 nm or less, more preferably 20 nm or less, and 5 nm or less. Is more preferable.

<Surface coating layer>
The film mirror of the present invention has an arbitrary surface for the reason that weather resistance, scratch resistance, sand adhesion, antifouling property, etc. are good on the surface opposite to the surface provided with the metal reflective layer of the protective layer. It is preferable to provide a coating layer.
If the surface coating layer is present on the outermost surface of the film mirror and can prevent physical or chemical damage to the surface of the film mirror, a conventionally known resin layer or the like is used in a conventionally known formation method. be able to.
The surface coating layer may be, for example, a soft layer with a Martens hardness of 100 N / mm ² or less and an elastic recovery rate of 60% or more, or a hard coat layer with a hard surface. Good.
The thickness of the surface coating layer is not particularly limited. For example, when the above-described soft layer is formed, the scratch resistance of the film mirror becomes better, and the haze value and the reflectance maintenance factor become higher. It is preferably ˜50 μm, more preferably 3 μm to 30 μm. On the other hand, when forming a hard hard-coat layer, it is preferable that it is 0.1-50 micrometers from a viewpoint of antifouling property and scratch resistance, and it is more preferable that it is 0.1-15 micrometers.

  Examples of the material for forming the surface coating layer include photocurable resins such as urethane (meth) acrylate resin, polyester (meth) acrylate resin, silicone (meth) acrylate resin, and epoxy (meth) acrylate resin; urethane resin and phenol Thermosetting resins such as resin, urea resin (urea resin), phenoxy resin, silicone resin, polyimide resin, diallyl phthalate resin, furan resin, bismaleimide resin, cyanate resin; polyvinyl acetal resin, polyvinyl alcohol resin, polyvinyl chloride resin , Saturated polyester resins, polyrotaxane resins, melamine resins, and the like. These may be used alone or in combination of two or more.

<Resin layer>
The film mirror of this invention may provide the arbitrary resin layers which have the function which mainly improves both adhesiveness between a metal reflective layer and arbitrary support bodies.
Examples of the resin layer include an adhesive layer for facilitating adhesion of metal, and a plating undercoat polymer layer useful for forming a metal reflective layer by a plating method. It may be composed of the above plural layers.

(Adhesive layer)
An adhesion layer is a layer which improves the adhesiveness of a support body and a metal reflective layer. In addition, when a plating undercoat polymer layer to be described later is provided on the adhesive layer, the adhesive 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.

  The adhesive layer preferably 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 adhesiveness with the adjacent support. The resin contained in the adhesive 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, melamine resin, and isocyanate resin. Examples of the thermoplastic resin include polyolefin resin, 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.

  In the case where the adhesive layer is provided between the plating undercoat polymer layer and the support, it is included in a polymer compound having a functional group and a polymerizable group that interact with the metal precursor contained in the plating undercoat polymer layer described later. It is preferable to contain active species that generate active sites that can interact with each other. Such an adhesive 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 adhesive 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 the adhesive 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 one. 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. A resin that has been (meth) acrylated using acid, acrylic acid, or the like may be used.
As long as the effects of the present invention are not impaired, one or more additives such as an adhesion-imparting agent, a silane coupling agent, an antioxidant, and an ultraviolet absorber are added to the adhesive layer as necessary. May be.
In general, the thickness of the adhesive layer is preferably in the range of 0.1 to 10 μm, and more preferably in the range of 0.2 to 5 μm.

(Plating undercoat polymer layer)
When the metal reflective layer is produced by metal plating, it is preferable to provide a plating undercoat polymer layer between the metal reflective layer and the support. The plating undercoat polymer layer is a layer containing a component (for example, metal particles) that acts as an electrode when performing the above-described plating (such as electroplating).
The plating undercoat polymer used to form the plating undercoat polymer layer has at least a polymerizable group and a functional group that interacts with the metal precursor (hereinafter, referred to as “interactive group” as appropriate). As the main skeleton of the plating undercoat polymer, an acrylic polymer, polyether, acrylamide, polyamide, polyimide, acrylic polymer, polyester, and the like are preferable, but an acrylic polymer is more preferable.
The plating undercoat polymer may contain a structural unit other than a structural unit containing a polymerizable group and a structural unit containing an interactive group depending on the purpose. When a composition for forming a plating undercoat polymer is formed by including a structural unit containing a polymerizable group and a structural unit other than the structural unit containing an interactive group (hereinafter referred to as other structural unit as appropriate). Furthermore, it is excellent in solubility in water or an organic solvent, and a uniform plating undercoat polymer layer can be formed.

  As a preferred embodiment of the plating undercoat polymer, an acrylic polymer having an acidic group and a polymerizable group in the side chain as interactive groups 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 undercoating polymer is chemically bonded between the polymers or between the polymer and the support (in the case where the adhesive layer is formed on the support, the adhesive layer) by applying energy. Any functional group may 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. Of these, a methacryloyl group, an acryloyl group, a vinyl group, a styryl group, an acrylamide group, or a methacrylamide group is preferable. Among them, a methacryloyl group, an acryloyl group, an acrylamide group, or a methacryl group is preferable from the viewpoint of radical polymerization reactivity and synthetic versatility. An amide group is preferable, and an acrylamide group or a methacrylamide group is more preferable from the viewpoint of alkali resistance. Among these, various polymerizable groups introduced into the acrylic polymer include (meth) acrylic 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, triazole ring, imidazole group, pyridine group, pyrimidine group, pyrazine group, triazine group, piperidine group, piperazine group, pyrrolidine group, A nitrogen-containing functional group such as a pyrazole group, a group containing an alkylamine structure, a cyano group, a cyanate group (R—O—CN); an ether group, a hydroxyl group, a phenolic hydroxyl group, a carboxyl group, a carbonate group, a carbonyl group, an ester group, Oxygen-containing functional groups such as groups containing an N-oxide structure, groups containing an S-oxide structure, groups containing an N-hydroxy structure; thiophene groups, thiol groups, thiourea groups, sulfoxide groups, sulfonic acid groups, sulfonic acid ester structures Sulfur-containing functional groups such as groups containing phosphine groups: Phosphate groups, phosphoramide groups, phosphine groups, phosphoric acid Phosphorus-containing functional groups such as those containing ester structure; chlorine, such as group containing a halogen atom such as bromine and the like, in a functional group capable of having a salt structure can also be used the salts thereof.
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 composed of an ionic polar group, among the above-mentioned interactive groups, adhesion to the support of the plating undercoat polymer (or the adhesive layer when the adhesive layer is formed on the support) From the point of view, carboxylic acid group, sulfonic acid group, phosphoric acid group, or boronic acid group 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 viewpoints of low worries, good compatibility with the metal reflective 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. As for the preferred constitution of the plating undercoat polymer, as a polymer having an interactive group composed of a radical polymerizable group and a non-dissociable functional group, it is described in paragraphs [0106] to [0112] of JP-A-2009-007540. Polymers 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 metal precursor described later may be applied after the formation of the plating undercoat polymer layer, or may be contained in the composition for forming the plating undercoat polymer layer from the beginning.

The plating undercoat polymer layer preferably contains a radical polymerization initiator such as a photopolymerization initiator and 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, in the case where, by applying energy, the plating undercoat polymer can generate active sites that interact with the support or the adhesive layer, that is, when a polymer having a polymerization initiation site in the polymer skeleton described above is used, these The radical polymerization initiator may not be added.
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. The content is preferably about 0.05 to 30% by mass, and more preferably about 0.1 to 10.0% by mass.

  The plating undercoat polymer layer applies energy by applying a composition for forming a polymer layer containing a plating undercoat polymer on a support (or on the adhesive layer when the adhesive layer is formed on the support). Can be formed. When the plating undercoat polymer layer is directly provided on the support, it is preferable to carry out an easy adhesion treatment such as applying energy to the surface of the support in advance. The method of providing the plating undercoat polymer layer on the support is not particularly limited, and the method of immersing the support in the composition for forming the plating undercoat polymer layer containing the plating undercoat polymer or the formation of the plating undercoat polymer layer containing the plating undercoat polymer The method of apply | coating the composition for coating on a support body etc. are mentioned. From the viewpoint of easily controlling the thickness of the resulting plating undercoat polymer layer, a method of applying a plating undercoat polymer layer-forming composition containing a plating undercoat polymer on a support is preferred.

The coating amount of the composition for forming a polymer layer containing a plating undercoat polymer is preferably 0.05 to 10 g / m ^{2 in} terms of solid content from the viewpoint of sufficient interaction with the metal precursor described later, and particularly 0. 3 to 5 g / m ² is more preferable. The coating solution of the composition for forming a plating undercoat polymer layer containing a plating undercoat polymer applied to a support or the like is dried at 20 to 60 ° C. for 1 second to 2 hours, and then dried at a temperature exceeding 60 ° C. for 1 second to 2 hours. Preferably, after drying at 20 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.

  In the energy application region, the composition for forming a plating undercoat polymer layer is applied with energy after being brought into contact with the support (adhesive layer in the case where the adhesive layer is formed on the support). An interaction is formed between the polymerizable groups of the polymer, or between the polymerizable group of the polymer and the support (the adhesive layer in the case where the adhesive layer is formed on the support), A plated undercoat polymer layer fixed on the support (on the adhesive layer when the adhesive layer is formed on the support) is formed. Thereby, a support body and a plating undercoat polymer layer adhere | attach firmly.

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. The exposure power may be in the range of 10 to 8000 mJ / cm ² from the viewpoint of facilitating the polymerization, suppressing the decomposition of the polymer, or forming a good interaction of the polymer. Preferably, it is in the range of 100 to 3000 mJ / 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 to 200 ° C. in order to facilitate the polymerization and to suppress thermal denaturation of the support, and is preferably 40 to 120 ° C. More preferably, it is the range.

  After energy application, a step of removing unreacted polymer may be provided as appropriate. Although the film thickness of a plating undercoat polymer layer is not specifically limited, From a viewpoint of adhesiveness with a support body etc., it is preferable that it is 0.05-10 micrometers, and it is more preferable that it is 0.3-5 micrometers. Moreover, the surface roughness (Ra) of the plating undercoat 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.

The plating primer polymer layer includes reduced metal particles. Reduced metal particles contained in the plating primer polymer layer are obtained by applying a metal precursor to the plating primer polymer layer and reducing the metal precursor to reduce the metal precursor to 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 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.
As a metal ion, Ag ion, Cu ion, and Pd ion are preferable in terms of the type and number of functional groups capable of coordination, and catalytic ability. As the Ag ions, those obtained by dissociating the silver compounds 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. When Cu ions are used, those obtained by dissociating copper compounds as shown below can be suitably used. 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). Examples of the application method include a method of applying a metal precursor solution on a support provided with a plating undercoat polymer layer, and a method of immersing a support provided with a plating undercoat polymer layer in the metal precursor solution.
When the metal precursor liquid is used for applying the metal precursor to the plating undercoat polymer layer, the particle diameter of the metal precursor is preferably 1 to 200 nm, more preferably 1 to 100 nm, and still more preferably 1 to 60 nm. By setting this particle size, the particle size of the reduced metal particles can be controlled to a desired size.

  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 to 50% by mass, and more preferably 0.1 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 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. 10-100 degreeC is preferable and the temperature at the time of reduction | restoration has more preferable 20-70 degreeC. 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 surface resistance value of the plating undercoat polymer layer containing the reduced metal particles is preferably 0.001 to 100Ω / □, and more preferably 0.03 to 50Ω / □. 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 the metal reflective layer described above is formed by a wet plating method, and is formed by a plating method using the plating undercoat polymer layer. The metal reflective layer made is excellent in adhesion to the support and surface smoothness.

<Other functional layers>
In addition to the layer structure described above, the film mirror of the present invention has other functions such as an ultraviolet absorbing layer, an ultraviolet reflecting layer, a gas barrier layer, an adhesive layer, a support back surface protective layer, a white layer, etc., in accordance with a desired application. Layers may be installed.

<Additives>
In the present invention, the above-described protective layer, support (particularly resin support), surface coating layer, resin layer (adhesion layer, plating undercoat polymer layer), and other functional layers (hereinafter these layers and support). Are collectively abbreviated as “functional layer”), or, if necessary, for the composition forming the functional layer, for example, a photopolymerization initiator, a thermal polymerization initiator, a cationic polymerization initiator, an anionic polymerization initiator, Antistatic agent, surface conditioner (for example, leveling agent, fluorine antifouling additive, etc.), UV absorber, light stabilizer, antioxidant, plasticizer, radical scavenger, antifoaming agent, thickener, settling prevention An additive such as an agent, a pigment, a dispersant, and a silane coupling agent may be contained.

(Surface conditioner)
The surface conditioner is a component that can be arbitrarily added to the composition forming the functional layer from the viewpoint of imparting surface smoothness and antifouling property to the functional layer described above.
Examples of a substance generally used as a surface conditioner include polyacrylate polymers such as polyalkyl acrylate; polyvinyl ether polymers such as polyalkyl vinyl ether; dimethyl polysiloxane, methylphenyl polysiloxane, polyether, polyester, Silicone polymers such as organically modified polysiloxanes with aralkyl introduced therein; those containing fluorine atoms in these polymers; and the like. These may be used alone or in combination of two or more. Also good.
The surface conditioner having a fluorine atom can be obtained, for example, by copolymerizing a monomer having a fluorine-containing group. In particular, in a film (layer) containing a fluorine-based surface conditioner, the surface energy of the film surface is lowered to form a water- and oil-repellent surface and to impart antifouling properties to the film surface. .
Specific products include, for example, Surflon “S-381”, “S-382”, “SC-101”, “SC-102”, “SC-103”, “SC-104” (all Asahi Glass shares Company-made), FLORARD "FC-430", "FC-431", "FC-173" (all made by Fluorochemicals-Sumitomo 3M), F-top "EF352", "EF301", "EF303" (all new) (Akita Kasei Co., Ltd.), Schwego Fluer "8035", "8036" (Both Schwegman Co., Ltd.), "BM1000", "BM1100" (BM Himmy Co., Ltd.), Mega Fuck "F-171" , “F-470”, “F-780-F”, “RS-75”, “RS-72-K” (all manufactured by DIC Corporation), BYK340 (Big Chemie Ja Made emissions Co., Ltd.), "ZX-049", "ZX-001", mention may be made of the "ZX-017" (both Fuji Chemical Industry Co., Ltd.), and the like.

(UV absorber)
Examples of the ultraviolet absorber include benzotriazole-based, benzophenone-based, triazine-based, phenyl salicylate-based, hindered amine-based, cyanoacrylate-based ultraviolet absorbers, inorganic particle-type ultraviolet absorbers such as titanium oxide, and the like. These may be used alone or in combination of two or more.

Specific examples of the benzophenone ultraviolet absorber include 2,4-dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-n-octoxy-benzophenone, and 2-hydroxy-4. -Dodecyloxy-benzophenone, 2-hydroxy-4-octadecyloxy-benzophenone, 2,2'-dihydroxy-4-methoxy-benzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-benzophenone, 2,2 ' , 4,4′-tetrahydroxy-benzophenone and the like.
Specific examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-5-methylphenyl) benzotriazole and 2- (2′-hydroxy-3 ′, 5′-di-t-). Butylphenyl) benzotriazole, 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) benzotriazole, and the like.

Specific examples of the phenyl salicylate ultraviolet absorber include phenylsulcylate, 2-4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, and the like. .
Specific examples of the hindered amine ultraviolet absorber include bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate.

  Specific examples of the triazine-based ultraviolet absorber include 2,4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-ethoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-propoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-butoxyphenyl) -1,3,5-triazine, 2,4- Diphenyl-6- (2-hydroxy-4-hexyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-octyloxyphenyl)- , 3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-dodecyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-) Benzyloxyphenyl) -1,3,5-triazine and the like.

  In addition to the above, the ultraviolet absorber includes a compound having a function of converting the energy held by ultraviolet rays into vibrational energy in the molecule and releasing the vibrational energy as thermal energy or the like.

(Light stabilizer)
The light stabilizer is a component that can be arbitrarily added to the composition forming the functional layer from the viewpoint of preventing oxidative degradation due to light (mainly ultraviolet rays).
As the light stabilizer, for example, a hindered amine light stabilizer, a benzoate light stabilizer, and the like are preferable, and among them, a hindered amine light stabilizer (HALS) is preferable. The light stabilizer can be used alone or in combination of two or more.
As a commercially available hindered amine light stabilizer, for example, as a light stabilizer which is a polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, TINUVIN 622 ”(manufactured by Ciba Japan); a polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol and N, N ′, N ″, N ′ '' -Tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4,7- As a light stabilizer which is a one-to-one reaction product with diazadecane-1,10-diamine, “TINUVIN 119” (manufactured by Ciba Japan); dibutylamine, 1,3-triazine, N, N′-bis ( It is a polycondensate of 2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine “TINUVIN 2020” (manufactured by Ciba Japan) as a light stabilizer; poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {TINUVIN 944 as a light stabilizer which is {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}]. (Ciba Japan); mixture of bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate “TINUVIN 765” (manufactured by Ciba Japan) as a light stabilizer; “TINUVIN 770” (Ciba Japan) as a light stabilizer that is bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate ); Decanedioic acid bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester (1,1-dimethylethyl hydroperoxide) and octane reaction product “TINUVIN 123” (manufactured by Ciba Japan) as a light stabilizer; bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl)- “TINUVIN 144” (manufactured by Ciba Japan) as a light stabilizer that is 4-hydroxyphenyl] methyl] butyl malonate; N-butyl-2,2,6,6-tetramethyl-4-piperidinamine-2,4,6-trichloro-1,3,5-triazine reaction product and 2-aminoethanol reaction product TINUVIN 152 (manufactured by Ciba Japan); bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl-1,2,2,6,6 Examples of the light stabilizer that is a mixture with -pentamethyl-4-piperidyl sebacate include "TINUVIN 292" (manufactured by Ciba Japan).

(Antioxidant)
Examples of the antioxidant include phenolic antioxidants, thiol antioxidants, and phosphite antioxidants.

  Specific examples of the phenolic antioxidant include 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane and 2,2′-methylenebis (4-ethyl). -6-tert-butylphenol), tetrakis- [methylene-3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate] methane, 2,6-di-tert-butyl-p- Cresol, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 1,3,5-tris (3 ′, 5 '-Di-t-butyl-4'-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, stearyl-β- (3,5-di-t-butyl-4 -Hydroxypheny ) Propionate, triethylene glycol bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate, 3,9-bis [1,1-di-methyl-2- [β- (3- t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 1,3,5-trimethyl-2,4,6 -Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene and the like. In particular, the phenolic antioxidant preferably has a molecular weight of 550 or more.

  Specific examples of the thiol-based antioxidant include distearyl-3,3′-thiodipropionate, pentaerythritol-tetrakis- (β-lauryl-thiopropionate), and the like. Examples of the phosphite antioxidant include tris (2,4-di-t-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, di (2,6-di-t-butylphenyl) pentaerythritol. Diphosphite, bis- (2,6-di-t-butyl-4-methylphenyl) -pentaerythritol diphosphite, tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenedi Examples thereof include phosphonite and 2,2′-methylenebis (4,6-di-t-butylphenyl) octyl phosphite.

  Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.

<Examples 1-9>
On a polyethylene terephthalate (PET) film (Toyobo Co., Ltd., Cosmo Shine A-4300, thickness: 250 μm), a silver-containing metal reflective layer was provided by electroplating according to the following steps.

(Preparation of a PET film with a silver reflective layer)
In a mixed solution of acrylic polymer 1 (22.02 parts by mass), 1-methoxy-2-propanol (72.73 parts by mass), and cyclohexanone (4.74 parts by mass) having the following structure, a surfactant (F- 780-F, solid content 30%, manufactured by DIC) (0.16 parts by weight), and photopolymerization initiator (Esacure KTO-46, manufactured by Lamberdy) (0.35 parts by mass) were added and stirred. By doing this, a coating solution for forming a plating undercoat polymer layer was prepared.

Next, the prepared coating solution for forming a plating undercoat polymer layer is applied on a PET film (A4300, manufactured by Toyobo Co., Ltd.) by a bar coating method, dried at 25 ° C. for 5 minutes, and then at 80 ° C. for 5 minutes. It dried and the coating film was obtained.
Using a UV exposure machine (model number: UVF-502S, lamp: UXM-501MD) manufactured by Mitsunaga Electric, the coating film is irradiated with an integrated exposure amount of 600 mJ / cm ² at a wavelength of 254 nm, A plating undercoat polymer layer (thickness: 0.55 μm) was formed.
Thereafter, the PET film with the plating undercoat polymer layer was immersed in a 1 wt% aqueous sodium hydrogen carbonate solution for 5 minutes to remove the unreacted polymer from the plating undercoat polymer layer.
Subsequently, the PET film with a plating undercoat polymer layer was washed with pure water and further air-dried.

(Formation of metal reflective layer)
Next, the PET film with a plating undercoat polymer layer was immersed in a 1 wt% silver nitrate aqueous solution for 5 minutes, then washed with pure water and air-dried to obtain a PET film with a plating undercoat polymer layer to which silver ions were added.
By immersing the PET film with a plating undercoat polymer layer to which silver ions have been added in an alkaline aqueous solution containing 0.05 wt% NaOH and 0.25 wt% formalin for 1 minute, then washing with pure water and air drying. A reduced silver layer (thickness of about 20 nm) was formed in the vicinity of the surface of the plating undercoat polymer layer to obtain a PET film with a reduced silver layer.
Next, the following electroplating treatment was performed on the PET film with a reduced silver layer to obtain a PET film with a silver layer having a 50 nm thick silver layer on the reduced silver layer.
As an electroplating solution, Dyne Silver Bright PL50 (manufactured by Daiwa Kasei Co., Ltd.) was used, and the pH was adjusted to 7.8 with 8M potassium hydroxide. A PET film with a reduced silver layer was immersed in an electroplating solution, plated at 0.33 A / dm ^{2 for} 15 seconds, then washed with pure water for 1 minute, and air-dried.

  The surface of the silver layer was processed by immersing the obtained PET film with a silver layer in a thiourea aqueous solution (thiourea: 100 mass ppm) for 60 seconds. After the surface treatment, it was washed with pure water and air-dried.

Next, the following electroplating treatment was performed on the silver layer after the surface treatment, and a silver layer having a thickness of 75 nm was further formed on the silver layer after the surface treatment to obtain a silver reflection layer.
As an electroplating solution, Dyne Silver Bright PL50 (manufactured by Daiwa Kasei Co., Ltd.) was used, and the pH was adjusted to 7.8 with 8M potassium hydroxide. The surface-treated PET film with a silver layer was immersed in an electrosilver plating solution, plated at 0.5 A / dm ^{2 for} 15 seconds, and then washed by pouring with pure water for 1 minute and air-dried.
Furthermore, in order to remove the oxide film, as an electroplating post-treatment, the film was immersed in a 10% by mass aqueous solution (methanesulfonic acid: 6% by mass) of Dyne Silver ACC (manufactured by Daiwa Kasei) for 90 seconds. Then, it washed by pouring with pure water for 1 minute, and air-dried.

  In this way, a PET film on which a silver reflective layer was formed was obtained. When the arithmetic average roughness Ra of the surface of the formed silver layer was measured using an atomic force microscope (AFM), it was 7.8 nm.

(Formation of protective layer)
First, as a coating solution for forming a protective layer, an acrylate polymer (Unidic EKS-675, manufactured by DIC Corporation) (30 parts by mass as a solid content), the compounds A to D shown in Table 1 below (formula (1 ) In which the content (% by mass) of the repeating unit represented by the following formula is the value shown in Table 1 below with respect to the resin solid content of the protective layer after formation), benzotriazole-based ultraviolet absorbers (TINUVIN405, BASF) (Made by Co., Ltd.) (3 parts by mass), hindered amine light stabilizer (TINUVIN292, produced by BASF) (0.3 parts by mass), cyclohexanone (1.5 parts by mass), methyl isobutyl ketone (55 parts by mass) A mixed solution of a fluorosurfactant (Megafac F-780-F, manufactured by DIC Corporation) (0.01 parts by mass as a solid content) was prepared.
Next, the prepared coating solution for forming a protective layer is applied on the silver reflective layer by a bar coating method so that the film thickness after drying is 10 μm, dried at 130 ° C. for 2 minutes, and then irradiated with UV. A protective layer was formed by performing UV exposure with a dose of 50 mJ / cm ² at a wavelength of 254 nm using a UV lamp (metal halide lamp manufactured by GS Yuasa).

(Formation of surface coating layer)
First, as a coating solution for forming a surface coating layer, a fluorine-based UV curable resin (Defenser FH-700, manufactured by DIC Corporation) (22 parts by mass as a solid content), cyclohexanone (5 parts by mass), methyl ethyl ketone (72 parts by mass) , A mixed solution of a fluorosurfactant (Megafac F-780-F, manufactured by DIC Corporation) (0.04 parts by mass as a solid content) was prepared.
Next, the prepared coating solution for forming a surface coating layer was applied on the protective layer by a bar coating method so that the dry film thickness was 10 μm, dried at 130 ° C. for 2 minutes, and then irradiated with a UV irradiation device (GS Using a UV lamp (metal halide lamp manufactured by Yuasa Co., Ltd.), ultraviolet exposure was performed at a wavelength of 254 nm with an irradiation amount of 100 mJ / cm ² to form a surface coating layer, and a film mirror was produced.

<Comparative Example 1>
A film mirror was produced in the same manner as in Example 1 except that the compound A was not used in the protective layer-forming coating solution.

<Comparative example 2>
A film mirror was produced in the same manner as in Example 1 except that the protective layer was formed by the method described below. In Comparative Example 2, after forming a protective layer by the method described below, a surface coating layer was formed on the protective layer by the same method as in Example 1 to produce a film mirror.
(Formation of protective layer)
First, an acrylic resin (UHA12; manufactured by Alpha Chemical Co., Ltd.) and a bullet type HMDI-based isocyanate (Takenate D-165N; manufactured by Mitsui Chemicals) are mixed at a mass ratio of 10: 1 and diluted with methyl ethyl ketone to obtain a resin solid content. A resin solution having a ratio of 10% by mass was prepared.
Next, the prepared resin solution was coated by a reverse coating method to form a protective resin layer having a thickness of 3 μm.

<Evaluation>
About each produced film mirror, the adhesiveness of a protective layer and a metal reflective layer and the reflectance were evaluated. Hereinafter, it describes about each evaluation. The results are summarized in Table 1 below.

<Adhesion>
(1) After moist heat Each film mirror was placed in a thermo-hygrostat (manufactured by Espec Corp., PR-3J) and left for 2000 hours under environmental conditions of a temperature of 65 ° C. and a humidity of 85% RH.
Then, according to the procedure of JIS K5600-5-6, the surface of the film mirror was cut at 1 mm intervals using a cutter, and 25 grids were created. Next, an adhesive tape (manufactured by Nichiban) was firmly attached to the surface of the film mirror, and after the tape was peeled off vigorously, the film peeling on the surface of the film mirror was observed, and 0 based on JIS K5600-5-6 A score of ~ 5 was made. For practical use, it is necessary to be 2 points or less. The evaluation of adhesion of the film mirror produced in Comparative Example 2 (score 5) is a state in which the surface coating layer and the protective layer are stuck on the tape side, and the metal reflective layer remains on the support side. It was found that the adhesion between the metal and the metal reflective layer was poor.
(2) Wet heat and after washing Each film mirror was placed in a thermo-hygrostat (manufactured by Espec Corp., PR-3J) and left for 2000 hours under environmental conditions of a temperature of 65 ° C. and a humidity of 85% RH.
Then, according to the procedure of JIS K5600-5-6, the surface of the film mirror was cut at 1 mm intervals using a cutter, and 25 grids were created. Next, after pouring water for 1 minute or longer, the surface of the film mirror was rubbed with a urethane sponge in a state where water was continuously applied. In the scrubbing, after reciprocating 20 times with a width of 10 cm, the sponge rubbing is stopped, and water is poured for 1 minute or more to complete the test.
Then, how to peel off the film on the surface of the film mirror was observed, and scored from 0 to 5 based on JIS K5600-5-6. For practical use, it is necessary to be 2 points or less. In addition, since evaluation of the adhesiveness (score 5) of the film mirror produced in Comparative Examples 1 and 2 was in a state where the protective layer and the surface coating layer were dropped over the entire surface by scrubbing, the protective layer and the metal reflective layer It was found that the adhesion with was poor.

<Reflectance (maintenance)>
About each produced film mirror, using the ultraviolet visible near-infrared spectrophotometer UV-3100 (made by Shimadzu Corporation), the range reflectance from wavelength 280nm to wavelength 1700nm was measured at 1nm intervals, and the obtained reflectance was measured. The spectrum was expressed as Rs (λ) (λ: wavelength). The standard irradiance spectrum Si of sunlight on the ground surface (air mass 1.5) is defined by ASTM M173-03. When Si every 1 nm from a wavelength of 280 nm to a wavelength of 1700 nm is expressed as Si (λ), sunlight The energy reflectance (Rtotal) was calculated by the following formula.
Rtotal means the effective reflection efficiency of solar energy, taking into account the irradiation intensity at each wavelength of sunlight.

Next, each film mirror is placed in a thermo-hygrostat (manufactured by Espec Corp., PR-3J) and allowed to stand for 2000 hours under environmental conditions of a temperature of 65 ° C. and a humidity of 85% RH. The reflectance was measured, and the reflectance before and after wet heat aging was evaluated according to the following evaluation criteria. In practice, A and B are required.
(Evaluation criteria)
A: The decrease in reflectance is less than 1%.
B: Decrease in reflectance is 1% or more and less than 3%.
C: The decrease in reflectance is 3% or more.

From the results shown in Table 1, when a resin having no repeating unit represented by the above formula (1) is used as a protective layer, the adhesion between the protective layer and the metal reflective layer is poor after washing, Moreover, it turned out that a reflectance also falls after wet heat aging (comparative example 1).
Similarly to Patent Document 1 (Japanese Patent Application Laid-Open No. 2011-173365), when a bullet type HMDI-based isocyanate (Takenate D-165N; manufactured by Mitsui Chemicals) is used for the protective layer, the protective layer and the metal reflective layer It was found that the adhesion was inferior after wet heat and after washing (Comparative Example 2).
On the other hand, when the resin having the repeating unit represented by the above formula (1) is used for the protective layer, the adhesion between the protective layer and the metal reflective layer becomes good even after wet heat or after washing. Moreover, it turned out that a reflectance can also be maintained (Examples 1-9).
Moreover, from the comparison with Examples 5-9, when 10-50 mass% of repeating units represented by the said Formula (1) are contained with respect to the resin solid content of a protective layer, the adhesiveness of a protective layer and a metal reflective layer Were found to be better (Examples 5 to 7).

<Example 10>
In the step of forming the metal reflective layer of Example 1, the content of NaOH in the alkaline aqueous solution in the step of immersing the PET film with the plating undercoat polymer layer to which ions were added in an alkaline aqueous solution containing formalin was 0.14 wt%. A metal reflecting layer was formed by the same method as in Example 1 except that the PET film was formed with a silver reflecting layer.
When the arithmetic mean roughness Ra of the surface of the formed silver layer was measured using an atomic force microscope (AFM), it was 3.4 nm.
Subsequent operations were carried out in the same manner as in Example 1 to produce a film mirror.

<Comparative Example 3>
In the formation process of the metal reflection layer of Comparative Example 1, the content of NaOH in the alkaline aqueous solution in the step of immersing the PET film with the plating undercoat polymer layer provided with ions in an alkaline aqueous solution containing formalin is 0.14 wt%. A metal reflective layer was formed by the same method as in Comparative Example 1 except that the PET film was formed with a silver reflective layer.
When the arithmetic mean roughness Ra of the surface of the formed silver layer was measured using an atomic force microscope (AFM), it was 3.4 nm.
Subsequent operations were carried out in the same manner as in Comparative Example 1 to produce a film mirror.

  About the film mirror produced in Example 10 and Comparative Example 3, the adhesiveness of a protective layer and a metal reflective layer, and the reflectance were evaluated by the method mentioned above. The results are shown in Table 2 below together with the results of Example 1 and Comparative Example 1.

From the results shown in Table 2, it is difficult to maintain the adhesiveness of the protective layer from the comparison between Comparative Example 1 and Comparative Example 3 when the arithmetic average roughness Ra of the metal reflective layer is 5 nm or less. I understand. This is considered to be the deterioration of the adhesion due to the loss of the anchor effect due to the surface roughness.
On the other hand, from the comparison between Example 6 and Example 10, when the resin having the repeating unit represented by the above formula (1) is used for the protective layer, the arithmetic average roughness Ra of the metal reflective layer is 5 nm or less. Even so, it can be seen that the adhesion of the protective layer can be maintained.

DESCRIPTION OF SYMBOLS 1 Metal reflective layer 2 Protective layer 3 Support body 4 Surface coating layer 10 Film mirror

Claims (4)

A film mirror having a metal reflective layer and a protective layer provided adjacent to the metal reflective layer,
The film mirror in which the said protective layer contains resin which has at least one part the repeating unit represented by following formula (1).

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or an optionally branched alkyl group having 1 to 6 carbon atoms, and R ³ represents a hydrogen atom or 1 to 6 carbon atoms. Represents an alkyl group which may be branched, and L represents a divalent linking group.)   The film mirror of Claim 1 in which the said protective layer contains 1-50 mass% of repeating units represented by the said Formula (1) with respect to the resin solid content of the said protective layer.   The film mirror of Claim 1 or 2 whose arithmetic mean roughness Ra of the surface of the said metal reflective layer is 5 nm or less.   The film mirror according to any one of claims 1 to 3, which is used for sunlight reflection.