WO2015037397A1

WO2015037397A1 - Hard coat film, and film mirror

Info

Publication number: WO2015037397A1
Application number: PCT/JP2014/071583
Authority: WO
Inventors: 威史濱; 克行温井; 祐也山本
Original assignee: 富士フイルム株式会社
Priority date: 2013-09-12
Filing date: 2014-08-18
Publication date: 2015-03-19
Also published as: JP2015054461A

Abstract

Provided are a hard coat film and a film mirror which each comprise a hard coat layer that satisfies a dust adhesion resistance property, an oil adhesion resistance property, a scratch resistance property, and a stain resistance property. The hard coat film has a support body and the hard coat layer which is disposed on the support body. The hard coat layer contains poly(meth)acrylate and at least one kind of metal oxide. The metal oxide is contained in an amount of 1-50 mass% relative to the total mass of the poly(meth)acrylate. The surface free energy of the hard coat layer surface is 30 mN/m or less, the surface resistance value of the hard coat layer surface is less than 1×10¹³Ω/□, and the pencil hardness of the hard coat layer surface is 2H or more.

Description

Hard coat film and film mirror

The present invention relates to a hard coat film and a film mirror, and more particularly to a hard coat film and a film mirror having a hard coat layer exhibiting predetermined characteristics (surface free energy, surface resistance value, hardness).

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.

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, Patent Document 1 discloses a film mirror having a resin base material and an outermost layer showing a predetermined electric resistance value, pencil hardness, and the like.

International Publication No. 2011/096320

On the other hand, the use of the film mirror is not limited to solar power generation, but is also used for applications such as a hot water condensing mirror and a lighting mirror.
At that time, it is required to suppress adhesion of sand and dust in the atmosphere, and resistance to oil generated in daily life is also required. In addition, when considering the installation in the field, scratch resistance against sand dust, contamination resistance against contamination due to rainfall or drying after dew, etc. are also required. That is, it is required to have all adhesion resistance to dust, adhesion resistance to oil, scratch resistance, and contamination resistance.
The inventors of the present invention have evaluated the above-mentioned performance with respect to the outermost layer in the film mirror described in Patent Document 1, and found that a material satisfying all the above-mentioned performances cannot be obtained, and further improvement is necessary.

In view of the above circumstances, an object of the present invention is to provide a hard coat film including a hard coat layer excellent in adhesion resistance to dust, adhesion resistance to oil, scratch resistance, and contamination resistance.

As a result of earnest research to achieve the above-mentioned problems, the present inventor has found that the above-mentioned problems can be solved if the hard coat layer satisfies predetermined requirements, and has completed the present invention.
That is, the present inventors have found that the above problem can be solved by the following configuration.

(1) A hard coat film having a support and a hard coat layer disposed on the support,
The hard coat layer contains poly (meth) acrylate and a metal oxide, and the metal oxide is contained in an amount of 1 to 50% by mass relative to the total mass of the hard coat layer,
The surface free energy of the hard coat layer surface is 30 mN / m or less,
The surface resistance value of the hard coat layer surface is less than 1 × 10 ¹³ Ω / □,
A hard coat film having a pencil hardness of 2H or more on the surface of the hard coat layer.
(2) The hard coat film according to (1), wherein a water contact angle on the surface of the hard coat layer is 90 ° or more.
(3) The hard coat film according to (1) or (2), wherein the surface resistance value of the surface of the hard coat layer is 1 × 10 ¹¹ Ω / □ or less.
(4) The hard coat layer is a layer obtained by curing a composition for forming a hard coat layer containing at least a polymerizable compound having a (meth) acryloyl group and a metal oxide. The hard coat film according to any one of 3).
(5) The hard coat film according to (4), wherein the composition for forming a hard coat layer further contains a fluorine compound having no polymerizable group.
(6) The hard coat film according to (4) or (5), wherein the polymerizable compound having a (meth) acryloyl group contains at least a polymerizable compound having a (meth) acryloyl group and a fluorine atom.
(7) The hard coat film according to any one of (1) to (6), wherein the metal oxide includes at least one selected from the group consisting of tin oxide, phosphorus-doped tin oxide, and fluorine-doped tin oxide.
(8) The hard coat film according to any one of (1) to (7), which has a metal reflective layer between the support and the hard coat layer, and is used as a film mirror.
(9) The hard coat film according to (8), which is used as a solar light collecting film mirror.
(10) a metal reflective layer that reflects light;
A hard coat layer disposed on the metal reflective layer to form a light incident surface and containing poly (meth) acrylate and a metal oxide;
With
The content of the metal oxide is 1 to 50% by mass with respect to the total mass of the hard coat layer,
The surface is
The surface free energy is 30 mN / m or less,
The surface resistance value is less than 1 × 10 ¹³ Ω / □,
A film mirror having a pencil hardness of 2H or more.

According to the present invention, it is possible to provide a hard coat film including a hard coat layer having excellent resistance to dust, adhesion to oil, scratch resistance, and contamination resistance.

It is sectional drawing which shows 1st Embodiment of the hard coat film of this invention. It is sectional drawing which shows 2nd Embodiment of the hard coat film of this invention. It is sectional drawing which shows 3rd Embodiment of the hard coat film of this invention. It is sectional drawing which shows 4th Embodiment of the hard coat film of this invention.

Below, suitable embodiment of the hard coat film of this invention is described.
First, as a feature point compared with the prior art of this invention, the point which uses the hard-coat layer which contains a predetermined component and shows a predetermined surface free energy, a surface resistance value, and pencil hardness is mentioned.

<First Embodiment>
Below, 1st Embodiment of the hard coat film of this invention is described with reference to drawings. In FIG. 1, sectional drawing of one Embodiment of the hard coat film of this invention is shown.
The hard coat film 10 has a support 12 and a hard coat layer 14.
Below, each layer which comprises the hard coat film 10 is explained in full detail.

[Support]
A support body is a base material which supports the hard-coat layer mentioned later. The type of the support is not particularly limited, and a resin film, a glass film, paper, or the like can be used from the viewpoint of flexibility and weight reduction. Among these, a resin film (resin support) is preferable in terms of excellent handleability. The resin film is formed by molding glass epoxy, polyester, polyimide, thermosetting polyphenylene ether, polyamide, polyaramid, liquid crystal polymer, or the like into a film shape.
As the resin material in the resin film, any resin that can be formed into a film can be used. 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, Polyacetylene and the like are suitable, and particularly suitable supports include polyester resins and polyimide resins.
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. If it is in the said range, it will be excellent in the handling at the time of production and will be easy to shape | mold. More preferably, it is 20 μm to 1 mm, and still more preferably 25 μm to 500 μm.

Moreover, in order to make it easy to form the below-mentioned resin layer on a support body, you may perform a surface treatment for a support body previously.
Surface treatment includes UV irradiation, ozone treatment, plasma treatment, corona treatment, flame treatment and other surface activation treatments, hydrazine, N-methylpyrrolidone, sodium hydroxide solution, alkaline solution such as potassium hydroxide solution And treatment with an acidic solution such as sulfuric acid, hydrochloric acid and nitric acid. Examples of the treatment for removing and cleaning the surface of the support include treatment with an organic solvent such as methanol, ethanol, toluene, ethyl acetate, and acetone, and washing with water to remove attached dust.
These surface treatments may be performed in combination of a plurality of types.

The hard coat film may include a metal reflective layer as in the second embodiment described later. When the metal coating layer is included in the hard coat film, the surface roughness (Ra) of the support is preferably 50 nm or less, more preferably 20 nm or less, and more preferably 5 nm or less for the purpose of improving reflectivity. More preferably it is.

The support may contain an ultraviolet absorber. Moreover, you may contain the plasticizer for maintaining a softness | flexibility, the antioxidant which prevents deterioration of the film itself, a radical scavenger, etc. The types of these additives will be described later.
When the support contains an ultraviolet absorber, the content of the ultraviolet absorber is in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin in the support when the support is a resin film. It is preferable.
When the support contains an antioxidant, the content of the antioxidant is in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin in the support when the support is a resin film. It is preferable.

[Hard coat layer]
The hard coat layer is a layer disposed on the outermost surface of the hard coat film, and is a layer that suppresses external influences such as dust and oil on the hard coat film. The hard coat layer forms the outermost surface of the hard coat film.
The hard coat layer includes poly (meth) acrylate and at least one metal oxide. Hereinafter, these components will be described in detail.

(Poly (meth) acrylate)
The poly (meth) acrylate is a polymer obtained by polymerizing a polymerizable compound having a (meth) acryloyl group, and preferably has a crosslinked structure from the viewpoint of hardness. In other words, as will be described later, the hard coat layer is a layer obtained by curing a composition containing a polymerizable compound having a (meth) acryloyl group.
In this specification, (meth) acrylate includes acrylate and methacrylate. More specifically, poly (meth) acrylate is meant to include polyacrylate and polymethacrylate (polymethacrylate). Further, the (meth) acrylate monomer is meant to include a methacrylate monomer (a monomer having a methacryloyl group) and an acrylate monomer (a monomer having an acryloyl group). Further, the (meth) acryloyl group includes an acryloyl group and a methacryloyl group.

The polymerizable compound having a (meth) acryloyl group is not particularly limited as long as it is a compound having a (meth) acryloyl group, and may be a so-called (meth) acrylate monomer (monomer) or oligomer. Among them, a polymerizable compound (polyfunctional (meth) acrylate) having two or more (meth) acryloyl groups is preferable in that the hardness of the obtained hard coat layer is more excellent, for example, ethylene glycol diacrylate, diethylene glycol. Diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, tetramethylolmethane triacrylate, tetramethylolmethane tetraacrylate, pentaglycerol triacrylate, pentaerythritol diacrylate Acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, glycerin triacrylate, dipentaerythritol Triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tris (acryloyloxyethyl) isocyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl Glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, tetramethylol methane trimethacrylate, tetramethylol methane tetramethacrylate, pentaglycerol trimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate Acrylate, glycerol trimethacrylate, dipentaerythritol trimethacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol penta methacrylate, dipentaerythritol hexa methacrylate, isobornyl acrylate, multifunctional urethane (meth) acrylate preferably. These compounds are used alone or in admixture of two or more. It may be an oligomer such as a dimer or trimer of the above monomer.

(Metal oxide)
The metal oxide has a function of increasing the hardness of the hard coat layer and a function of decreasing the surface resistance value.
The type of metal oxide is not particularly limited. For example, tin oxide, antimony pentoxide, zinc antimonate, antimony doped tin oxide, tin doped indium oxide, titanium dioxide, zirconia, zinc oxide, phosphorus doped tin oxide, fluorine doped Examples thereof include tin oxide (FTO), niobium-doped tin oxide, and tantalum-doped tin oxide. Among these, tin oxide, phosphorus-doped tin oxide, and fluorine-doped tin oxide are preferable, and phosphorus-doped tin oxide is particularly preferable in that the surface resistance value of the hard coat layer is further reduced and infrared light is transmitted.

The average particle diameter of the metal oxide is not particularly limited, but the dispersibility of the metal oxide in the hard coat layer is superior, and various performances (adhesion resistance to dust, adhesion to oil, or scratch resistance and contamination resistance) ) Is preferably 1 to 100 nm, and from the viewpoint of increasing the transparency and reducing the haze of the coating film, 1 to 50 nm is more preferable. preferable.
The average particle diameter is calculated as follows. An image obtained by TEM observation of the metal oxide dispersion was taken into image processing software ImageJ and subjected to image processing. The image processing was performed on 500 particles arbitrarily extracted from TEM images of several fields of view. The diameter of a circle having the same area as the particle area calculated from the TEM image was taken as the particle diameter. The same processing is performed on 500 particles, and the average value is defined as the average particle diameter.

The content of the metal oxide in the hard coat layer is 1 to 50% by mass with respect to the total mass of the hard coat layer in that the effect of the present invention is more excellent, and the effect of the present invention is more excellent. 10 mass% or more is preferable, 15 mass% or more is more preferable, 20 mass% or more is further more preferable, 40 mass% or less is preferable, and 35 mass% or less is more preferable.
When the content is 1% by mass or more, the surface resistance value is sufficiently lowered, so that the adhesion to sand dust and scratch resistance are excellent. In the case of 50% by mass or less, the surface resistance value is sufficiently reduced, and the metal oxide occupying the hard coat layer is suppressed from being excessively increased, so that it is difficult to become brittle and scratch resistance is excellent.

The surface free energy on the surface of the hard coat layer is 30 mN / m or less, and 26 mN / m or less is preferable and 24 mN / m or less is more preferable in that the effect of the present invention is more excellent. The lower limit is not particularly limited, but is often 15 mN / m or more.
The surface free energy is calculated according to a predetermined formula (Young's formula, Owens' formula) from the obtained values by measuring the two-component static contact angle of water and methylene iodide.

The surface resistance of the hard coat layer surface is less than ^{1 × 10 13 Ω / □ (} ohms per square), in that the effect of the present invention is more excellent, preferably 1 × 10 ¹² Ω / □ or less, 1 × 10 ¹¹ Ω / □ or less is more preferable, 1 × 10 ¹⁰ Ω / □ or less is more preferable, and 1 × 10 ⁹ Ω / □ or less is more preferable.
The surface resistance value is measured using Hiresta MCP-HT450 type (manufactured by Mitsubishi Chemical Analytech Co., Ltd.) and URS probe.

The pencil hardness on the surface of the hard coat layer is 2H or higher, 3H or higher is preferable from the viewpoint that the effects of the present invention are more excellent, and 4H or higher is more preferable from the viewpoint that it is superior to dust scratch resistance.
The pencil hardness is measured according to JIS K 5600-5-4.

Although the water contact angle on the surface of the hard coat layer is not particularly limited, it is preferably 90 ° or more, more preferably 95 ° or more, and further preferably 100 ° or more from the viewpoint that the effect of the present invention is more excellent.
In the method for measuring the water contact angle, the contact angle (static contact angle) of the hard coat layer surface is measured using Drop Master 700 (Kyowa Interface Science Co., Ltd.). Specifically, the syringe part is connected to the AUTO DISPENSER AD-31, and a certain amount of pure water is pushed out of the syringe and deposited on the surface of the hard coat layer.
Further, the contact angle of methylene iodide with respect to the hard coat layer surface is not particularly limited, but is preferably 60 ° or more, more preferably 63 ° or more, still more preferably 67 ° or more, in view of more excellent effects of the present invention, 70 It is particularly preferable that the angle is at least.
As a method for measuring the contact angle of methylene iodide, the contact angle (static contact angle) of the hard coat layer surface is measured using Drop Master 700 (Kyowa Interface Science Co., Ltd.). Specifically, the syringe part is connected to the AUTO DISPENSER AD-31, and a certain amount of methylene iodide is pushed out of the syringe and deposited on the surface of the hard coat layer.

The method for forming the hard coat layer is not particularly limited, but a composition for forming a hard coat layer containing at least a polymerizable compound having a (meth) acryloyl group and a metal oxide from the viewpoint of easy control of the thickness of the hard coat layer. The method of apply | coating an object on a support body and making it harden | cure is mentioned.
The coating method is not particularly limited, and examples include known coating methods (for example, gravure coating method, reverse coating method, die coating method, blade coater, roll coater, air knife coater, screen coater, bar coater, curtain coater, etc.).
As the curing method, an optimal method is appropriately selected depending on the type of the polymerizable compound having a (meth) acryloyl group to be used, but usually a heat treatment or a light irradiation treatment is performed.

The definitions of “polymerizable compound having (meth) acryloyl group” and “metal oxide” contained in the composition for forming a hard coat layer are as described above. The ratio of the content of the polymerizable compound having a (meth) acryloyl group and the metal oxide is appropriately set so that the content of the metal oxide in the hard coat layer falls within the above range.
In addition, the hard coat layer forming composition may contain other components other than “polymerizable compound having (meth) acryloyl group” and “metal oxide”.
For example, it is preferable that the composition for forming a hard coat layer further contains “a fluorine compound having no polymerizable group” in that the effect of the present invention is more excellent.
In addition, as another preferred embodiment, the polymerizable compound having a (meth) acryloyl group is a polymerizable compound having a fluorine atom together with a (meth) acryloyl group (hereinafter referred to as “fluorine”). Containing at least (containing (meth) acrylate).
Most preferably, the composition for forming a hard coat layer further contains a “fluorine compound having no polymerizable group”, and the “polymerizable compound having a (meth) acryloyl group” is a fluorine-containing (meth) acrylate. The aspect (henceforth "the aspect X") which contains at least is mentioned.
The reason why a more excellent effect can be obtained in the aspect X is that the fluorine-containing (meth) acrylate remains inside the hard coat layer through a chemical bond, and the fluorine compound having no polymerizable group moves to the surface. This is presumably because the fluorine compound is present uniformly throughout the coat layer.

Examples of the “fluorine compound having no polymerizable group” include so-called fluorine surfactants. Examples of the polymerizable group include a (meth) acryloyl group, a radical polymerizable group such as a vinyl group, and a cationic polymerizable group.
Commercially available fluorine-based surfactants are trade names manufactured by Dainippon Ink and Chemicals, Inc .: MegaFuck F-443, F-444, F-445, F-446, F-475, F-142D, F-144D, F-171, F-172, F-173, F-177, F-178A, F-178K, F-179, F-179A, F-183, F-184, F-191, F-812, F- 815, F-1405, F410, F-443, F-445, F-450, F-471, F-472SF, F-475, F-479, F-482, R-30, MCF-350, TF1025, Trade name: EFTOP EF-101, EF-121, EF-122B, EF-122C, EF-122A3, EF-121, EF-123A, EF-123B, EF-126 F-127, EF-301, EF-302, EF-351, EF-352, EF-601, EF-801, EF-802, manufactured by Neos Co., Ltd. Trade name: Footage 250, 251, 222F, FTX- 218, 212M, 245M, 290M, FTX-207S, FTX-211S, FTX-220S, FTS-230S, FTX-209F, FTX-213F, FTX-233F, FTX-245F, FTX-208G, FTX-218G, FTX- 230G, FTS-240G, FTX-204D, FTX-208D, FTX-212D, FTX-216D, FTX-218D, FTX-220D, FTX-222D, FTX-720C, FTX-740C, manufactured by Seimi Chemical Co., Ltd. : Surflon S-111, S-112, S- 113, S-121, S-131, S-132, S-141, S-145, S-381, S-383, S-393, S-101, KH-40, SA-100, and the like.

The fluorine-containing (meth) acrylate is a polymerizable compound containing a (meth) acryloyl group and a fluorine atom, and its structure is not particularly limited. The fluorine-containing (meth) acrylate may be a so-called (meth) acrylate monomer (monomer) or oligomer containing a fluorine atom. Further, the number of (meth) acryloyl groups is not particularly limited, and may be one or two or more.
As the fluorine-containing (meth) acrylate, commercially available products can be used. For example, Beam Set 1402 (Arakawa Chemical Industry Co., Ltd.), Beam Set 1461 (Arakawa Chemical Industries Co., Ltd.), FH-700 (Manufactured by DIC Corporation), MegaFac RS-75 (manufactured by DIC Corporation) (perfluoropolyether (meth) acrylate), and the like.
The “polymerizable compound having a (meth) acryloyl group” in the composition for forming a hard coat layer is a polymerization having a “(meth) acryloyl group not having a fluorine atom” together with the fluorine-containing (meth) acrylate. (Hereinafter also referred to as “fluorine-free (meth) acrylate”).
That is, the composition for forming a hard coat layer may be an embodiment A containing “fluorine-containing (meth) acrylate” and “fluorine-free (meth) acrylate”, “fluorine-containing (meth) acrylate”, It may be an embodiment B containing "fluorine-free (meth) acrylate" and "fluorine atom compound having no polymerizable group".
In the case of aspect B, the fluorine-containing (meth) acrylate is preferably contained in an amount of 0.1 to 10% by mass with respect to the total solid content in the composition for forming a hard coat layer. In addition, solid content intends the component which comprises a hard-coat layer, and a solvent is not contained.

Moreover, the hard coat layer forming composition may contain a solvent. Specific examples of the solvent include water, monohydric alcohols having 1 to 6 carbon atoms, dihydric alcohols having 1 to 6 carbon atoms, and alcohols such as glycerin; formamide, N-methylformamide, N-ethylformamide Amides such as N, N-dimethylformamide, N, N-diethylformamide, N-methylacetamide, N-ethylacetamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methylpyrrolidone; Diethyl ether, di (n-propyl) ether, diisopropyl ether, diglyme, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether, pro Ethers such as lenglycol dimethyl ether; esters such as ethyl formate, methyl acetate, ethyl acetate, ethyl lactate, ethylene glycol monomethyl ether acetate, ethylene glycol diacetate, propylene glycol monomethyl ether acetate, diethyl carbonate, ethylene carbonate, propylene carbonate; Ketones such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl (n-butyl) ketone, methyl isobutyl ketone, methyl amyl ketone, cyclopentanone, cyclohexanone; acetonitrile, propionitrile, n-butyronitrile, isobutyronitrile, etc. Nitriles; dimethyl sulfoxide, dimethyl sulfone, sulfolane and the like are preferably used.

The hard coat layer forming composition may contain a polymerization initiator. Examples of the polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator, and an optimal polymerization initiator is selected according to the curing conditions.

[Hard coat film]
The average transmittance of the hard coat film having the support and the hard coat layer described above in the near-infrared light (wavelength 780 nm to 1700 nm) is not particularly limited. % Or more is preferable, 90% or more is more preferable, and 95% or more is particularly preferable. The average transmittance can be measured using, for example, an ultraviolet-visible near-infrared spectrophotometer UV-3100 (manufactured by Shimadzu Corporation).

<Second Embodiment>
Below, 2nd Embodiment of the hard coat film of this invention is described with reference to drawings. In FIG. 2, sectional drawing of one Embodiment of the hard coat film of this invention is shown.
The hard coat film 110 has the support body 12, the metal reflective layer 16, and the hard coat layer 14 in this order. The hard coat film 110 can be used as a film mirror that reflects light as described later. In the film mirror, the hard coat layer 14 forms a surface on which light is incident. In the present embodiment, the surface on which light is incident is the surface on the side opposite to the support 12 and means the surface on the side on which light is incident on the metal reflection layer 16.
Since the hard coat film 110 shown in FIG. 2 has the same configuration as the hard coat film 10 shown in FIG. 1 except that the metal reflective layer 16 is provided, the same reference numerals denote the same components. The description is omitted, and the metal reflective layer 16 will be mainly described in detail below.

[Metal reflective layer]
The metal reflection layer is a layer provided on the support and has a function of reflecting light incident from the hard coat layer 14 side.
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 can increase the reflectance of the hard coat film in the visible light region, 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 silver content is preferably 90 to 99.8 atomic% in the total (100 atomic%) of silver and other metals in the metallic reflective layer. The content of other metals is preferably 0.2 to 10 atomic% from the viewpoint of durability.

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

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. As shown in the fourth embodiment to be described later, when the plating undercoat polymer layer is formed on the support, the metal particles contained in the plating undercoat polymer layer have a function as an electrode. By performing electroplating, it is possible to form a metal reflective layer having excellent adhesion to the support. 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 film 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 not forming irregularities that scatter light on the surface of the metal reflection layer. It is more preferably 0.08 to 0.5 μm.

Further, the metal reflective layer may be formed by performing dry plating such as vacuum deposition using a plating undercoat polymer layer containing reduced metal particles. 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 the electroplating, the metal reflective layer may be treated with strong acid or strong alkali 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 hard coat film of the second embodiment can be suitably used as a film mirror (reflecting mirror). Among these, it can be suitably used for collecting sunlight. As the application mode, for example, application to a sunlight reflecting plate can be mentioned. More specifically, a hard coat film including a metal reflection layer is fixed to a substrate or frame made of any of resin, metal, and ceramic, thereby creating a mirror surface by the metal reflection layer and reflecting sunlight. A plate can be made. 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.
Further, the hard coat film of the second embodiment may be used as a daylighting mirror. Since the hard coat film of the second embodiment has flexibility, it has good followability to a surface having a curvature, so that it is also preferable to install it on such a surface.

<Third Embodiment>
Below, 3rd Embodiment of the hard coat film of this invention is described with reference to drawings. In FIG. 3, sectional drawing of one Embodiment of the hard coat film of this invention is shown.
The hard coat film 210 includes the support 12, the metal reflective layer 16, the protective layer 18, and the hard coat layer 14 in this order. The hard coat film 210 can be used as a film mirror that reflects light as described later.
The hard coat film 210 shown in FIG. 3 has the same configuration as that of the hard coat film 110 shown in FIG. 2 except that the hard coat film 210 includes the protective layer 18. The description thereof will be omitted, and the protective layer 18 will be mainly described in detail below.

[Protective layer]
The protective layer is a layer provided to improve the adhesion between the hard coat layer and the metal reflective layer and to stabilize the specularity of the metal reflective layer, and is provided on the incident light side surface of the metal reflective layer. Is a layer.
The resin material used for forming the protective layer is a resin that can form a film or a layer, and the strength or durability of the formed film or layer, air and moisture blocking properties, and further, a hard coat layer and In addition to the adhesiveness, a resin having transparency, particularly high transparency to light having a wavelength required by the film mirror is preferable.
Examples of the material for forming the protective layer 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 phenol resins. And thermosetting resins such as urea resin (urea resin), phenoxy resin, silicone resin, polyimide resin, diallyl phthalate resin, furan resin, bismaleimide resin, cyanate resin, etc., and these can be used alone. Or two or more of them may be used in combination.

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 more preferable because the hardness of the hard coat film is easily adjusted. As the urethane (meth) acrylate resin, for example, a polyester polyol (A) and a polyisocyanate (B) are reacted to synthesize an isocyanate group-terminated urethane prepolymer, and then a hydroxyl group-containing (meth) acrylate compound (C) is used. Preferable examples include products obtained by reaction.
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 tri (meth) acrylate.
As 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. Are UV curable urethane acrylate resins manufactured by Nippon Gosei Co., Ltd., such as UV1700B, UV6300B, UV7600B, and polymer acrylates manufactured by DIC, such as Unidic V-6840, Unidic V-6841, Unidic WHV-649. Unidic EKS-675 or the like can be used.

Other resins that can be used for the protective layer include, for example, cellulose ester resins, polycarbonate resins, polyarylate resins, polysulfone (including polyether sulfone) resins, polyesters such as polyethylene terephthalate and polyethylene naphthalate. Resins, olefinic resins such as 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 resins, polyurethane resins, and silicone resins.
Among these, from the viewpoint of adhesion between the protective layer and the metal reflective layer, the resin contained in the protective layer is selected from acrylic resin, polyvinyl butyral, ethylene vinyl acetate resin, and ethylene acrylate copolymer. One or more resins are preferred.

Although the thickness of the protective layer is not particularly limited, it is preferably 0.1 μm or more, more preferably 1 μm or more, and further preferably 5 μm or more, for the reason that dust scratch resistance and sand adhesion are more excellent. Preferably, it is 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.

The method for forming the protective layer is not particularly limited. For example, the protective layer-forming composition containing a photocurable resin or a thermosetting resin is applied to the surface of the metal reflective layer, and then the solvent is removed as necessary. And a method of curing by ultraviolet irradiation or heating.
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 protective layer forming composition, conventionally known coating methods such as gravure coating method, reverse coating method, die coating method, blade coater, roll coater, air knife coater, screen coater, bar coater, curtain coater and the like can be used.
The method for curing the protective layer-forming composition 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 protective layer, such as heating or UV irradiation, can be selected as appropriate. That's fine.

The composition for forming a protective layer may contain a solvent and various additives in addition to the components described above.
The solvent is not particularly limited, and examples thereof include alcohol solvents such as water, methanol, ethanol, propanol, ethylene glycol, glycerin, propylene glycol monomethyl ether, acids such as acetic acid, ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone, formamide, Amide solvents such as dimethylacetamide and N-methylpyrrolidone, nitrile solvents such as acetonitrile and propionitrile, ester solvents such as methyl acetate and ethyl acetate, carbonate solvents such as dimethyl carbonate and diethyl carbonate, benzene, toluene, In addition to aromatic hydrocarbon solvents such as xylene, other than these, ether solvents, glycol solvents, amine solvents, thiol solvents, halogen solvents, and the like can be given. 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.

The film thickness of the protective layer is preferably in the range of 3 to 30 μm, preferably in the range of 5 to 10 μm, from the viewpoints of achieving the necessary protective function and durability and suppressing the reduction in light reflectivity. It is more preferable.

<Fourth Embodiment>
Below, 4th Embodiment of the hard coat film of this invention is described with reference to drawings. In FIG. 4, sectional drawing of one Embodiment of the hard coat film of this invention is shown.
The hard coat film 310 includes the support 12, the resin layer 20, the metal reflective layer 16, the protective layer 18, and the hard coat layer 14 in this order. The hard coat film 310 can be used as a film mirror that reflects light, as will be described later.
Since the hard coat film 310 shown in FIG. 4 has the same configuration as the hard coat film 210 shown in FIG. 3 except that the resin layer 20 is provided, the same reference numerals are assigned to the same components. The description will be omitted, and the resin layer 20 will be mainly described in detail below.

[Resin layer]
A resin layer is a layer arrange | positioned between a support body and a metal reflective layer, and has a function which mainly improves both adhesiveness. Examples of the resin layer include an adhesive layer for facilitating adhesion of metal and a plating undercoat polymer layer useful when a metal reflective layer is formed by a plating method. It may be composed of the above plural layers.

(Adhesive layer)
The adhesive layer is a layer that improves the adhesion between the support and the 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 is a structural unit other than “structural unit containing a polymerizable group” and “structural unit containing an interactive group” depending on the purpose (hereinafter, referred to as “other structural unit” as appropriate). May be included. By including other structural units, when a composition for forming a plating undercoat polymer is used, a uniform plating undercoat polymer layer having excellent solubility in water or an organic solvent can be formed.

As a preferred embodiment of the plating undercoat polymer, an acrylic polymer having a polymerizable group and an acidic 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 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 groups-
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, Nitrogen-containing functional groups such as pyrazole group, group containing alkylamine structure, cyano group, cyanate group (R—O—CN); ether group, hydroxyl group, phenolic hydroxyl group, carboxyl group, carbonate group, carbonyl group, ester group, Oxygen-containing functional groups such as groups containing N-oxide structures, groups containing S-oxide structures, groups containing N-hydroxy structures; thiophene groups, thiol groups, thiourea groups, sulfoxide groups, sulfonic acid groups, sulfonic acid ester structures Sulfur-containing functional group such as a group containing phosphine group: phosphor group, phosphoramide group, phosphine group, 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 is preferable, and in particular, 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 less concern, excellent 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 a suitable constitution of the plating undercoat polymer, paragraphs [0106] to [0112] of JP-A-2009-007540 are referred to as “polymer having a radical polymerizable group and an interactive group composed of a non-dissociable functional group”. Can be used. As the “polymer having a radically polymerizable group and an interactive group comprising an ionic polar group”, the polymers described in paragraphs [0065] to [0070] of JP-A-2006-135271 can be used. . As the “polymer having a radical polymerizable group, an interactive group composed of a non-dissociable functional group, and an interactive group composed of an ionic polar group”, paragraph [0010] of JP2010-248464A. To [0128], JP 2010-84196 A, and US Patent Application Publication No. 2010-080964, paragraphs [0030] to [0108] can be used.

The metal precursor described later may be applied after the formation of the plating undercoat polymer layer, or may be contained from the beginning in the composition for forming the plating undercoat polymer layer.

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, 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, particularly 0, from the viewpoint of sufficient interaction formation with the metal precursor described later. 3 to 5 g / m ² is more preferable. The coating solution for the plating undercoat polymer layer forming composition containing the plating undercoat polymer applied to the 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. More 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. Also, g-line, i-line, deep-UV light, and high-density energy beam (laser beam) are 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. A range of 100 to 3000 mJ / cm ² is more preferable. 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 preferably in the range of 40 to 120 ° C. More preferably, it is the range.

After the application of energy, a step of removing unreacted polymer may be provided as appropriate. The film thickness of the plating undercoat polymer layer is not particularly limited, but is preferably 0.05 to 10 μm, more preferably 0.3 to 5 μm from the viewpoint of adhesion to a support or the like. 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, diethyldithio 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.

Metal ions that 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 adjusting agent 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. The temperature during the reduction is preferably 10 to 100 ° C, more preferably 20 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 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 above-described metal reflective layer 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.

In the above description, the first to fourth embodiments have been described. In each of the above embodiments, in addition to the layer configuration described above, an ultraviolet absorbing layer, an ultraviolet reflecting layer, a gas barrier are used in accordance with a desired application. You may install a layer, an adhesive layer, a support back surface protective layer, other functional layers of a white layer, and the like.

<Additives>
In the present invention, the above-mentioned support (especially resin support), hard coat layer, protective layer, resin layer, and other functional layers (hereinafter, these layers and support are collectively abbreviated as “functional layer”). .), Or the composition used for forming the functional layer, if necessary, for example, a photopolymerization initiator, a thermal polymerization initiator, a cationic polymerization initiator, an anionic polymerization initiator, an antistatic agent, a surface conditioning. Agents (eg leveling agents, fluorine antifouling additives), UV absorbers, light stabilizers, antioxidants, plasticizers, radical scavengers, antifoaming agents, thickeners, antisettling agents, pigments, dispersants And additives such as silane coupling agents 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 Flour "8035", "8036" (Both Schwegman), "BM1000", "BM1100" (BBM Himmy), MegaFuck "F-171" , “F-470”, “F-780-F”, “RS-75”, “RS-72-K” (all manufactured by DIC), 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)
As the ultraviolet absorber, for example, at least among ultraviolet absorbers such as benzotriazole, benzophenone, triazine, phenyl salicylate, hindered amine, cyanoacrylate, and inorganic particle type ultraviolet absorbers such as titanium oxide Preferably one is included.
Examples of the benzophenone ultraviolet absorber include 2,4-dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-n-octoxy-benzophenone, 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'-tetra And hydroxy-benzophenone.
Examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-5-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, 2 -(2'-hydroxy-3'-t-butyl-5'-methylphenyl) benzotriazole and the like.
Examples of the phenyl salicylate ultraviolet absorber include phenylsulcylate, 2-4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, and the like.
Examples of the hindered amine ultraviolet absorber include bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate.

Examples of triazine ultraviolet absorbers 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) -1,3,5-tria 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. Furthermore, those that exhibit an effect when used in combination with an antioxidant or a colorant, or light stabilizers that act as light energy conversion agents, called quenchers, can be used in combination.

(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 ( This 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} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}] as a light stabilizer “TINUVIN 944 (Made by 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 which is bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate ); A reaction product of bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester (1,1-dimethylethyl hydroperoxide) decane and octane “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 which is 4-hydroxyphenyl] methyl] butyl malonate; Of N-butyl-2,2,6,6-tetramethyl-4-piperidinamine-2,4,6-trichloro-1,3,5-triazine with 2-aminoethanol TINUVIN 152 (manufactured by Ciba Japan); bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl-1,2,2,6,6 As a light stabilizer which is a mixture with -pentamethyl-4-piperidyl sebacate, “TINUVIN 292” (manufactured by Ciba Japan);

(Antioxidant)
As the antioxidant, for example, a phenol-based antioxidant, a thiol-based antioxidant, or a phosphite-based antioxidant is preferably used.
Examples of phenolic antioxidants include 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 2,2′-methylenebis (4-ethyl-6-t- Butylphenol), tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, 2,6-di-t-butyl-p-cresol, 4,4 '-Thiobis (3-methyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-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-hydroxyphenyl) propionate ,bird Tylene 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. In particular, the phenolic antioxidant preferably has a molecular weight of 550 or more.

Examples of the thiol 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 described more specifically with reference to examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded.

<Example 1>
(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 mass), and a photopolymerization initiator (Esacure KTO-46, manufactured by Lamberdy) (0.35 parts by mass) are added and stirred. Thus, a coating solution for forming a plating undercoat polymer layer was prepared.

On the PET film (A4300, manufactured by Toyobo Co., Ltd.), the above-described coating solution for forming the undercoat polymer layer is applied by a bar coating method, dried at 25 ° C. for 5 minutes, and then dried at 80 ° C. for 5 minutes. A 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 at 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 to obtain a PET film with a plating undercoat polymer layer. The PET film with the plating undercoat polymer layer was immersed in a 1 wt% sodium hydrogen carbonate aqueous solution for 5 minutes to remove unreacted polymer from the plating undercoat polymer layer. Thereafter, the PET film with the plating undercoat polymer layer was washed with pure water and further air-dried.

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 imparted with silver ions.
By immersing the PET film with a plating undercoat polymer layer to which silver ions are added in an alkaline aqueous solution containing 0.14 wt% NaOH and 0.25 wt% formalin for 1 minute, and then washing with pure water and air drying. A reduced silver layer (film thickness of about 20 nm) was formed in the vicinity of the surface of the plating undercoat polymer layer. Thereby, a PET film with a reduced silver layer was obtained.

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. The PET film with a silver layer was immersed in an electroplating solution, plated at 0.33 A / dm ^{2 for} 15 seconds, then washed by pouring with pure water for 1 minute, and air-dried.
The obtained PET film with a silver layer was immersed in a thiourea aqueous solution (thiourea: 100 mass ppm) for 60 seconds to perform surface treatment of the silver layer. 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 Co., Ltd.) 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 mean roughness Ra of the surface of the formed silver layer was measured using an atomic force microscope (AFM), it was 3.4 nm.

(Preparation of protective layer)
The composition 1 for protective layer formation mentioned later was apply | coated on the surface of the silver reflection layer so that a dry film thickness might be 8 micrometers using a wire bar. Thereafter, the film was dried at 130 ° C. and cured by irradiation with ultraviolet rays (300 mJ / cm ^{2 in} terms of wavelength 365 nm) to form a protective layer.

-Composition of protective layer forming composition 1-
Acrylate monomer: Unidic EKS-675 (manufactured by DIC Corporation, solid content 55% by mass) 47.90 parts by mass Surfactant: Megafac F-780F (manufactured by DIC Corporation, solid content 3% by mass, diluted by MEK) ) 0.29 parts by mass Initiator: IRGACURE127 (manufactured by BASF Japan) 0.57 parts by mass UV absorber: TINUVIN405 (manufactured by BASF Japan) 1.43 parts by mass Light stabilizer: TINUVIN292 (BASF Japan ( 0.29 parts by mass Solvent 1: methyl isobutyl ketone 44.52 parts by mass Solvent 2: cyclohexanone 5.00 parts by mass

(Preparation of hard coat layer)
Using a wire bar, the hard coat layer forming composition 1 described later was applied onto the protective layer so that the dry film thickness was 8 μm. Thereafter, it was dried at 130 ° C. and cured by irradiation with ultraviolet rays (300 mJ / cm ^{2 in} terms of 365 nm) to form a hard coat layer. In this way, a hard coat film (hereinafter also referred to as a film mirror) having a metal reflective layer and a hard coat layer was produced.

-Composition of hard coat layer forming composition 1-
Initiator-containing acrylate monomer: FH-700 (manufactured by DIC Corporation, solid content: 91% by mass) 41.79 parts by mass Surfactant: Megafac F-780F (manufactured by DIC Corporation, solid content: 3% by mass, MEK) Dilution) 0.40 parts by mass Metal oxide: Celnax CX-S204IP (manufactured by Nissan Chemical Industries, Ltd., solid content 20% by mass) 10.01 parts by mass Solvent 1: methyl isobutyl ketone 42.80 parts by mass Solvent 2: 5.00 parts by mass of cyclohexanone

<Evaluation method: physical property evaluation of hard coat layer>
Contact angle (water), surface energy, pencil hardness, sheet resistance, steel wool scratch resistance, dust scratch resistance, sand adhesion resistance, and stain resistance, magic repellency of the hard coat layer in the obtained hard coat film The optical properties were evaluated. Hereinafter, it describes about each evaluation. The results are summarized in Table 1.

-Contact angle, surface energy-
The contact angle (static contact angle) on the surface of the hard coat layer was measured using Drop Master 700 (Kyowa Interface Science Co., Ltd.). The syringe part was connected to an AUTO DISPENSER AD-31, and a fixed amount of solution was pushed out of the syringe and deposited on the surface of the hard coat layer.
In this example, contact angles were measured for pure water and methylene iodide. Next, the surface free energy of the hard coat layer was calculated from the Owens equation and the Young equation.

-Pencil hardness-
The test was conducted according to the standard of JIS K 5600-5-4. A scratch test was conducted on the outermost surface of each hard coat layer with a pencil at a 45 degree angle and a load of 750 g. Ranking was performed by the hardness symbol of the pencil that was not damaged more than 4 times out of 5 times.

-Surface resistance (sheet resistance)-
The surface resistance value on the surface of the hard coat layer was measured using a Hiresta MCP-HT450 type (manufactured by Mitsubishi Chemical Analytech Co., Ltd.) URS probe.

-Steel wool scratch resistance (SW scratch resistance)-
A load of 500 g / cm ² was applied to # 0000 Bonster (steel wool: manufactured by Nippon Steel Wool Co., Ltd.), and the hard coat layer surface was reciprocated 10 times. Thereafter, how the hard coat layer surface was damaged was observed. The number of scratches generated in a streak shape was evaluated visually.
“A”: 0 scratches “B”: 1-5 scratches “C”: 6 scratches or more

-Dust resistance and adhesion to sand-
The dust coating scratch resistance test of the hard coat layer was conducted by the method described in IEC 60068-2-68. Flattery sand previously dried at 60 ° C. for 2 hours was sprayed onto the surface of the hard coat layer for 2 hours at a dust concentration of 1 g / m ³ and a wind speed of 20 m / sec.
Dust scratch resistance and sand adhesion resistance of the hard coat layer were evaluated by using a spectrocolorimeter CM-700D (manufactured by Konica Minolta Co., Ltd.) and the diffusivity of the film mirror (regular reflection light SCI and diffuse reflection light SCE). Ratio).
D _{F is} the degree of scratching of the hard coat layer surface due to dust, where D _{F is} the diffusion degree of the film mirror before the test, D _{S is} the diffusion degree of the film mirror after the dust test, and D _W is the diffusion degree of the film mirror after the cleaning. Defined as _W- _DF . The degree of sand adhesion on the hard coat layer surface was defined as D _S -D _W. D _W -D _F represents the deterioration of the degree of diffusion of the film mirror caused by scratches on the hard coat layer, and the smaller D _W -D _F means that there are fewer scratches on the hard coat layer in the dust test. D _S -D _W represents the deterioration of the diffusion degree of the film mirror caused by sand adhesion on the hard coat layer, and the smaller D _S -D _W means that the sand adhesion on the hard coat layer in the dust test is less. In addition, dust scratch resistance was evaluated according to the following criteria.
“S”: When D _W -D _F is 5 or less “A”: When D _W -D _F is more than 5 and 7.5 or less “B”: When D _W -D _F is more than 7.5 and 10 or less “C”: When D _W −D _F is more than 10 and less than 15, “D”: When D _W −D _F is more than 20.
Further, the degree of sand adhesion was evaluated according to the following criteria.
"A": When D _S -D _W is 10 or less "B": When D _S -D _W is greater than 10 and 20 or less "C": When D _S -D _W is greater than 20 and 30 or less "D": When D _S -D _W is greater than 30

-Pollution resistance evaluation-
Contamination resistance evaluation of the hard coat layer was performed by the pollutant suspended water flow method described in JSTM J7602. The suspended water flow pollution promotion tester DT-W (manufactured by Suga Test Instruments Co., Ltd.) was used to flow and dry the contaminated water prepared at a concentration of 1.0 g / L for 50 cycles.
The measurement was performed by measuring the diffusivity of the film mirror before and after the test. The diffusion of the film mirror before test D _F, the diffusion of the film mirror after stain test as D _o, the degree of contamination of the hard coat layer is defined as D _o -D _F. D _o -D _F represents the deterioration of the degree of diffusion of the film mirror due to contamination of the hard coat layer, and the smaller D _o -D _F means that the hard coat layer is less contaminated. The contamination resistance was evaluated according to the following criteria.
“A”: When D _o -D _F is 6 or less “B”: When D _o -D _F is greater than 6 and less than 8 “C”: When D _o -D _F is greater than 8 and less than 10 “D”: When D _o -D _F exceeds 10

-Magic repellency-
The oily marker: Mackey Care (black) (manufactured by Zebra Co., Ltd.) was applied to the hard coat layer surface, and visual confirmation was performed after 3 minutes. Next, a wiping operation was performed with Bencott M-3II (manufactured by Asahi Kasei Fibers Co., Ltd.).
“A”: The magic was repelled and wiped off within 5 round trips.
“B”: Magic was slightly repelled, but a magic mark remained after 5 round trips.
“C”: Magic was not repelled, and a magic mark remained after 5 round trips.

-optical properties-
As the optical characteristics, two points of the average reflectance of the near-infrared light and the solar energy reflectance of the produced film mirror were evaluated. The specific procedure is shown below. Using a UV-visible near-infrared spectrophotometer UV-3100 (manufactured by Shimadzu Corporation), the reflectance of the film mirror in the wavelength range of 280 nm to 1700 nm was measured every 1 nm in the wavelength range.
The average reflectance of the near-infrared light of the film mirror is defined as the average value of the reflectance of the film mirror, which is obtained by averaging the values measured at intervals of 1 nm in the wavelength range of 780 nm to 1700 nm. And calculated.
The solar energy reflectance was calculated as follows.
The reflection spectrum at a wavelength of 280 nm to 1700 nm is Rs (λ) (λ: wavelength), the reference irradiance spectrum of sunlight at a wavelength of 280 nm to 1700 nm is Si (λ) (λ: wavelength), and the solar energy reflectance (Rtotal) is It was defined by the following formula. The standard irradiance spectrum Si of sunlight was a value defined by ASTM G173-03.

Rtotal means an effective reflection efficiency of solar energy in consideration of irradiation intensity at each wavelength of sunlight. The average reflectance and solar energy reflectance of near-infrared light were evaluated according to the following criteria. From a practical viewpoint, Rtotal is preferably B or more, more preferably A or more.
<Evaluation criteria for average reflectance of near-infrared light>
A: 95% or more B: 90% or more and less than 95% C: less than 90% <Solar energy reflectance evaluation criteria>
A: 92% or more B: 90% or more and less than 92% C: 80% or more and less than 90% D: Less than 80%

<Examples 2 to 4>
A hard coat film was prepared according to the same procedure as in Example 1 except that the amount of Cellux CX-S204IP used was changed to the amount shown in Table 1, and various evaluations were performed. The results are summarized in Table 1.

<Example 5>
A hard coat film was prepared according to the same procedure as in Example 1 except that the hard coat layer forming composition 2 was used instead of the hard coat layer forming composition 1, and various evaluations were performed. The results are summarized in Table 1.
-Composition for forming a hard coat layer 2-
Initiator-containing acrylate monomer: Beam Set 575CB (Arakawa Chemical Industries, Ltd., solid content: 100% by mass) 36.41 parts by mass Surfactant: MegaFac F-780-F (DIC Corporation, solid content: 3) 0.40 parts by mass Metal oxide: CELNAX CX-S204IP (manufactured by Nissan Chemical Industries, Ltd., solid content 20% by mass) 10.01 parts by mass Polymerizable fluorine compound: Megafax RS-75 (DIC Corporation, solid content 40% by mass) 4.00 parts by mass Solvent 1: methyl ethyl ketone 44.18 parts by mass Solvent 2: cyclohexanone 5.00 parts by mass

<Examples 6 to 7>
A hard coat film was produced according to the same procedure as in Example 5 except that the amount of Cellux CX-S204IP used was changed to the amount shown in Table 1, and various evaluations were performed. The results are summarized in Table 1.

<Example 8>
A hard coat film was prepared according to the same procedure as in Example 1 except that the hard coat layer forming composition 3 was used instead of the hard coat layer forming composition 1, and various evaluations were performed. The results are summarized in Table 1.
-Composition for forming a hard coat layer 3-
Initiator-containing acrylate monomer: Beam set 1402 (Arakawa Chemical Industries, Ltd., solid content: 87.1% by mass) 43.60 parts by mass Surfactant: Megafac F-780-F (DIC Corporation, solid) 3 mass%, MEK dilution 0.40 mass parts Metal oxide: Celnax CX-S204IP (manufactured by Nissan Chemical Industries, Ltd., solid content 20 mass%) 10.00 mass parts Solvent 1: methyl ethyl ketone 41.00 mass parts Solvent 2: 5.00 parts by mass of cyclohexanone

<Examples 9 to 10>
A hard coat film was produced according to the same procedure as in Example 8, except that the amount of Cellnax CX-S204IP used was changed to the amount shown in Table 1, and various evaluations were performed. The results are summarized in Table 1.

<Example 11>
A hard coat film was prepared according to the same procedure as in Example 1 except that the hard coat layer forming composition 4 was used instead of the hard coat layer forming composition 1, and various evaluations were performed. The results are summarized in Table 1.
-Composition for forming a hard coat layer 4-
Acrylate monomer: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., solid content concentration: 100% by mass) 33.59 parts by mass 0.40 parts by mass Metal oxide: Celnax CX-S204IP (Nissan Chemical Industry Co., Ltd., solid content 20% by mass) 20.00 parts by mass Initiator: IRGACURE 127 (manufactured by BASF Japan) 0.80 parts by mass Polymerizability Fluorine compound: Megafac RS-75 (manufactured by DIC Corporation, solid content 40% by mass) 4.00 parts by mass Solvent 1: methyl ethyl ketone 36.21 parts by mass Solvent 2: cyclohexanone 5.00 parts by mass

<Examples 12 to 13>
A hard coat film was prepared and subjected to various evaluations according to the same procedure as in Example 11 except that the amount used of Celnax CX-S204IP was changed to the amount shown in Table 1. The results are summarized in Table 1.

<Example 14>
A hard coat film was prepared according to the same procedure as in Example 1 except that the hard coat layer forming composition 5 was used instead of the hard coat layer forming composition 1, and various evaluations were performed. The results are summarized in Table 1.
-Composition for forming a hard coat layer 5-
Initiator-containing acrylate monomer: Beam set 1461 (Arakawa Chemical Industries, Ltd.) 46.26 parts by mass Surfactant: MegaFac F-780-F (DIC Corporation, solid content 3 mass%, diluted MEK) 0.40 parts by mass Metal oxide: Celnax CX-S204IP (manufactured by Nissan Chemical Industries, Ltd., solid content 20% by mass) 19.98 parts by mass Solvent 1: methyl ethyl ketone 28.36 parts by mass Solvent 2: cyclohexanone 5.00 Parts by mass

<Examples 15 to 16>
A hard coat film was prepared according to the same procedure as in Example 14 except that the amount used of Celnax CX-S204IP was changed to the amount shown in Table 1, and various evaluations were performed. The results are summarized in Table 1.

<Example 17>
A hard coat film was prepared according to the same procedure as in Example 1 except that the hard coat layer forming composition 6 was used instead of the hard coat layer forming composition 1, and various evaluations were performed. The results are summarized in Table 1.
-Composition for forming a hard coat layer 6-
Initiator-containing acrylate monomer: FH-700 (manufactured by DIC Corporation, solid content: 91% by mass) 42.83 parts by mass Surfactant: Megafac F-780-F (manufactured by DIC Corporation, solid content: 3% by mass) 0.40 parts by mass Metal oxide: Fluorine-doped tin oxide 1.00 parts by mass Solvent 1: Methyl ethyl ketone 50.77 parts by mass Solvent 2: Cyclohexanone 5.00 parts by mass Particles having an average primary particle size of 27 nm prepared according to the method described in Example 1 of 2012-193071 were used.

<Comparative Example 1>
A hard coat film was prepared according to the same procedure as in Example 1 except that the hard coat layer forming composition 9 was used instead of the hard coat layer forming composition 1, and various evaluations were performed. The results are summarized in Table 2.
-Composition for forming a hard coat layer 9-
Initiator-containing acrylate monomer: FH-700 (manufactured by DIC Corporation, solid content: 85 mass%, initiator: 3 mass%) 43.96 parts by mass Surfactant: Megafac F-780-F (manufactured by DIC Corporation) 0.40 part by mass Solvent 1: methyl ethyl ketone 50.65 parts by mass Solvent 2: cyclohexanone 5.00 parts by mass

<Comparative example 2>
A hard coat film was prepared according to the same procedure as in Example 1 except that the hard coat layer forming composition 10 was used instead of the hard coat layer forming composition 1, and various evaluations were performed. The results are summarized in Table 2.
-Composition for forming a hard coat layer 10-
Initiator-containing acrylate monomer: FH-700 (manufactured by DIC Corporation, solid content 91% by mass) 43.53 parts by mass Surfactant: Megafac F-780-F (manufactured by DIC Corporation, solid content 3% by mass) 0.40 parts by mass Antistatic agent: Aclit 1SX (manufactured by Taisei Fine Chemical Co., Ltd., solid content 10% by mass, diluted MEK) (ammonium salt acrylic polymer) 4.00 parts by mass Solvent 1: methyl ethyl ketone 47.08 Mass part solvent 2: Cyclohexanone 5.00 parts by mass

<Comparative Examples 3 to 4>
A hard coat film was produced according to the same procedure as in Comparative Example 2 except that the amount of Acryt 1SX was changed to the amount shown in Table 2, and various evaluations were performed. The results are summarized in Table 2.

<Comparative Example 5>
A hard coat film was prepared according to the same procedure as in Example 1 except that the hard coat layer forming composition 11 was used instead of the hard coat layer forming composition 1, and various evaluations were performed. The results are summarized in Table 2.
-Composition for forming a hard coat layer 11-
Initiator-containing acrylate monomer: FH-700 (manufactured by DIC Corporation, solid content 91% by mass) 43.53 parts by mass Surfactant: Megafac F-780-F (manufactured by DIC Corporation, solid content 3% by mass) 0.40 parts by mass Antistatic agent: Polyaniline (manufactured by Kaken Sangyo Co., Ltd., solid content 10% by mass, MEK dilution) 4.00 parts by mass Solvent 1: methyl ethyl ketone 47.08 parts by mass Solvent 2: cyclohexanone 5.00 parts by mass

<Comparative Examples 6-7>
A hard coat film was produced according to the same procedure as in Comparative Example 5 except that the amount of polyaniline used was changed to the amount shown in Table 2, and various evaluations were performed. The results are summarized in Table 2.

<Comparative Example 8>
A hard coat film was prepared according to the same procedure as in Example 1 except that the hard coat layer forming composition 12 was used instead of the hard coat layer forming composition 1, and various evaluations were performed. The results are summarized in Table 2.
-Composition 12 for forming a hard coat layer-
Initiator-containing acrylate monomer: FH-700 (manufactured by DIC Corporation, solid content 91% by mass) 43.53 parts by mass Surfactant: Megafac F-780-F (manufactured by DIC Corporation, solid content 3% by mass 0.40 parts by mass Antistatic agent: Organic boron polymer Hiboron KB212 (manufactured by Boron International Co., Ltd., solid content 10% by mass, diluted MEK) 4.00 parts by mass Solvent 1: methyl ethyl ketone 47.08 parts by mass solvent 2: Cyclohexanone 5.00 parts by mass

<Comparative Examples 9 to 10>
A hard coat film was prepared according to the same procedure as in Comparative Example 8 except that the amount of high boron KB212 used was changed to the amount shown in Table 2, and various evaluations were performed. The results are summarized in Table 1.

<Comparative Example 11>
A hard coat film was prepared according to the same procedure as in Example 1 except that the hard coat layer forming composition 13 was used instead of the hard coat layer forming composition 1, and various evaluations were performed. The results are summarized in Table 2.
-Composition for forming a hard coat layer 13-
Initiator-containing acrylate monomer: FH-700 (manufactured by DIC Corporation, solid content: 91% by mass) 43.70 parts by mass Surfactant: Megafac F-780-F (manufactured by DIC Corporation, solid content: 3% by mass) 0.40 parts by mass Antistatic agent: Anionic surfactant Electro stripper ME2 (manufactured by Lion Corporation, solid content 10% by mass, MEK dilution) 2.00 parts by mass Solvent 1: methyl ethyl ketone 48.91 masses Part solvent 2: 5.00 parts by mass of cyclohexanone

<Comparative Example 12>
A hard coat film was prepared according to the same procedure as in Comparative Example 11 except that the amount of the electrostripper ME2 used was changed to the amount shown in Table 2, and various evaluations were performed. The results are summarized in Table 2.

<Comparative Example 13>
A hard coat film was prepared according to the same procedure as in Example 1 except that the hard coat layer forming composition 14 was used instead of the hard coat layer forming composition 1, and various evaluations were performed. The results are summarized in Table 2.
-Composition for forming a hard coat layer 14-
Initiator-containing acrylate monomer: FH-700 (manufactured by DIC Corporation, solid content: 91% by mass) 43.70 parts by mass Surfactant: Megafac F-780-F (manufactured by DIC Corporation, solid content: 3% by mass) 0.40 parts by mass Antistatic agent: Cationic surfactant ARCARD T-50 (manufactured by Kao Corporation, solid content 10% by mass, diluted MEK) 2.00 parts by mass Solvent 1: methyl ethyl ketone 48.91 Mass part solvent 2: Cyclohexanone 5.00 parts by mass

<Comparative example 14>
A hard coat film was prepared according to the same procedure as in Comparative Example 13 except that the amount of Arcade T-50 used was changed to the amount shown in Table 2, and various evaluations were performed. The results are summarized in Table 2.

<Comparative Example 15>
A hard coat film was prepared according to the same procedure as in Example 1 except that the hard coat layer forming composition 15 was used instead of the hard coat layer forming composition 1, and various evaluations were performed. The results are summarized in Table 2.
-Composition 15 for forming a hard coat layer-
Initiator-containing acrylate monomer: Beam Set 575CB (Arakawa Chemical Industries, Ltd.) 40.03 parts by mass Solvent 1: methyl ethyl ketone 54.97 parts by mass Solvent 2: cyclohexanone 5.00 parts by mass

<Comparative Example 16>
A hard coat film was prepared according to the same procedure as in Example 1 except that the hard coat layer forming composition 16 was used instead of the hard coat layer forming composition 1, and various evaluations were performed. The results are summarized in Table 2.
-Composition 16 for forming a hard coat layer-
Initiator-containing acrylate monomer: Beamset 575CB (Arakawa Chemical Industries, Ltd.) 39.97 parts by mass Surfactant: MegaFac F-780-F (DIC Corporation, solid content 3% by mass, diluted MEK) 0.40 parts by mass Solvent 1: methyl ethyl ketone 54.63 parts by mass Solvent 2: cyclohexanone 5.00 parts by mass

<Comparative Example 17>
A hard coat film was prepared according to the same procedure as in Example 1 except that the hard coat layer forming composition 17 was used instead of the hard coat layer forming composition 1, and various evaluations were performed. The results are summarized in Table 2.
-Composition 17 for forming a hard coat layer-
Initiator-containing acrylate monomer: Beam set 1461 (manufactured by Arakawa Chemical Co., Ltd.) 51.54 parts by mass Solvent 1: methyl ethyl ketone 43.36 parts by mass Solvent 2: cyclohexanone 5.00 parts by mass

<Comparative Example 18>
A hard coat film was prepared according to the same procedure as in Example 1 except that the hard coat layer forming composition 7 was used instead of the hard coat layer forming composition 1, and various evaluations were performed. The results are summarized in Table 2.
-Composition 7 for forming a hard coat layer-
Initiator-containing acrylate monomer: FH-700 (manufactured by DIC Corporation, solid content: 91% by mass) 43.33 parts by mass Surfactant: Megafac F-780-F (manufactured by DIC Corporation, solid content: 3% by mass) 0.40 parts by mass Metal oxide: ITO paint P1-3 (Mitsubishi Materials Electronic Chemicals, total solid content 40%, ITO concentration 28%) 1.43 parts by mass Solvent 1: methyl ethyl ketone 49.83 parts by mass Solvent 2: 5.00 parts by mass of cyclohexanone

<Comparative Example 19>
A hard coat film was prepared according to the same procedure as in Comparative Example 18 except that the amount of P1-3 used was changed to the amount shown in Table 2, and various evaluations were performed. The results are summarized in Table 2.

<Comparative Example 20>
A hard coat film was produced by the method described in Paragraph [0159] of International Publication No. 2011/096320, and various evaluations were performed. The results are summarized in Table 2.

In Table 1, “concentration” in the metal oxide column represents mass% of the metal oxide with respect to the total solid mass in the hard coat layer.
In Table 2, “Concentration” in the other antistatic agent column represents mass% of the antistatic agent relative to the total solid mass in the hard coat layer.
Since “FH-700”, “beam set 1402”, and “beam set 1461” used as initiator-containing acrylate monomers correspond to fluorine-containing (meth) acrylates, in Tables 1 and 2, “(meth)” The above compounds are described in both the “acrylate” column and the “polymerizable group” column of the “fluorine compound” column. “Megafac RS-75” used as a polymerizable fluorine compound also corresponds to a fluorine-containing (meth) acrylate.
In Tables 1 and 2, “E + 12” in the “Surface resistance value” column is intended to be “10 ¹² ”, and “10 ^A ” is also intended for other numerical values A. Note that “1E13 or more” is intended to mean “1 × 10 ¹³ ” or more.

As shown in Table 1, it was confirmed that each example, which is a hard coat film according to an embodiment of the present invention, is excellent in various performances.
Especially, it was confirmed from the comparison between Examples that when the surface resistance value on the surface of the hard coat layer is 1 × 10 ¹¹ Ω / □ or less, the dust scratch resistance and sand adhesion resistance are more excellent.
Moreover, it was confirmed from the comparison between Examples that when the surface energy of the hard coat layer is 26 mN / m or less, the magic repellent property (adhesion resistance to oil) is more excellent.
On the other hand, the aspect of the comparative example having a hard coat layer that does not exhibit the predetermined characteristics was inferior in performance.

10, 110, 210, 310 Hard coat film 12 Support 14 Hard coat layer 16 Metal reflective layer 18 Protective layer 20 Resin layer

Claims

A hard coat film having a support and a hard coat layer disposed on the support,
The hard coat layer contains poly (meth) acrylate and a metal oxide, and the metal oxide is contained in an amount of 1 to 50% by mass with respect to the total mass of the hard coat layer,
The surface free energy of the hard coat layer surface is 30 mN / m or less,
The surface resistance value of the hard coat layer surface is less than 1 × 10 13 Ω / □,
The hard coat film whose pencil hardness of the said hard-coat layer surface is 2H or more.
The hard coat film according to claim 1, wherein a water contact angle on the surface of the hard coat layer is 90 ° or more.
The hard coat film according to claim 1 or 2, wherein a surface resistance value of the hard coat layer surface is 1 × 10 11 Ω / □ or less.
4. The hard coat layer according to claim 1, wherein the hard coat layer is a layer obtained by curing a composition for forming a hard coat layer containing at least a polymerizable compound having a (meth) acryloyl group and a metal oxide. 2. The hard coat film according to item 1.
The hard coat film according to claim 4, wherein the composition for forming a hard coat layer further contains a fluorine compound having no polymerizable group.
The hard coat film according to claim 4 or 5, wherein the polymerizable compound having a (meth) acryloyl group contains at least a polymerizable compound having a (meth) acryloyl group and a fluorine atom.
The hard coat film according to any one of claims 1 to 6, wherein the metal oxide includes at least one selected from the group consisting of tin oxide, phosphorus-doped tin oxide, and fluorine-doped tin oxide.
The hard coat film according to any one of claims 1 to 7, which has a metal reflective layer between the support and the hard coat layer, and is used as a film mirror.
The hard coat film according to claim 8, which is used as a film mirror for collecting sunlight.
A metal reflective layer that reflects light;
A hard coat layer disposed on the metal reflective layer to form a surface on which light is incident and containing poly (meth) acrylate and a metal oxide;
With
The content of the metal oxide is 1 to 50% by mass with respect to the total mass of the hard coat layer,
The surface is
The surface free energy is 30 mN / m or less,
The surface resistance value is less than 1 × 10 13 Ω / □,
A film mirror having a pencil hardness of 2H or more.