WO2010137367A1 - Film mirror, method for manufacturing film mirror, and solar light reflecting mirror using film mirror - Google Patents

Abstract

Provided is a film mirror, which has a metal thin film layer that is prevented from being deteriorated, is light in weight and flexible, is capable of having an increased area and being mass-produced with suppressed manufacturing cost, and has excellent beam reflectance and light/weather resistance. A method for manufacturing the film mirror, and a solar light reflecting mirror using the film mirror are also provided. The film mirror has, on a resin base material, a light reflecting layer formed of a metal thin film, and also has an inorganic oxide layer composed of an inorganic oxide film on the side which is the same side where the light reflecting layer is formed and is further from the resin base material than the light reflecting layer. The inorganic oxide film is formed of a film containing inorganic oxide particles having an average particle diameter within a range of 1 nm to 1 μm.

Description

FILM MIRROR, METHOD FOR MANUFACTURING THE SAME, AND MIRROR FOR sunshine reflection using the

The present invention relates to a film mirror having good light reflectivity and excellent light resistance and weather resistance, a method for producing the film mirror, and a solar reflective mirror using the film mirror.

In recent years, interest in environmental issues has increased and movements to utilize sunlight have become active. When utilizing sunlight, a mirror for reflecting or condensing sunlight is often used. For example, a daylighting mirror for directing sunlight into a low-rise building that has been blocked by sunlight by a high-rise building, or a reflection mirror inside a light duct used to introduce sunlight into the building. Can be mentioned. As a mirror as described above, it is a mirror that is lightweight and difficult to break to facilitate handling during installation and installation, and from the viewpoint of securing light extraction, it is a mirror that can be enlarged and mass-produced. There must be a flexible mirror that can match the shape of the installation location and the shape of the mirror, and also a mirror that has excellent light resistance and weather resistance from the viewpoint of reflecting sunlight. Has been.

Generally, a mirror made of glass in which silver is deposited on one side of a transparent glass substrate to form a silver thin film is known as a commonly used mirror having a high light reflectance. However, glass mirrors are prone to breakage and thereby expose sharp edges, so careful handling is always necessary. Furthermore, if the glass plate is too thin, it is difficult to handle it at the time of manufacture, so a certain thickness is required. For this reason, especially in a large-sized product, mass increases remarkably and special consideration is required for its transportation and installation.

For this reason, in consideration of the risk of injury due to breakage and the difficulty of handling, a mirror using a plastic resin substrate has been considered (for example, see Patent Document 1). The mirror described in Patent Document 1 is a plastic mirror in which a silver thin film layer is formed on the surface of a plate-like or film-like transparent plastic resin. In this plastic mirror, since the substrate is made of plastic resin, it is lighter and can be manufactured at a lower cost than when the substrate is made of glass. In addition, since the plastic resin can be easily processed into a film shape, it is possible to form a very flexible mirror.

Also, from the viewpoint of obtaining a high reflectance, as disclosed in Patent Document 2, a technique for forming a metal layer with silver having a high reflectance in the visible light region is known. However, these techniques have a problem that the metal layer is inferior in weather resistance and deteriorates with oxygen, water vapor, sulfur, or the like. For this problem, it is considered that the plastic substrate functions as a protective layer for the metal layer. However, since plastic easily transmits water vapor and oxygen in the air, the metal layer deteriorates due to oxidation, which causes a problem that the reflectivity of the mirror decreases.

Furthermore, when using a mirror for the purpose of reflecting sunlight, the mirror is often used outdoors. When used outdoors, the mirror is exposed to wind and rain, and in such a severe environment, the metal layer is oxidatively deteriorated, and the problem of reduction in the reflectance of the mirror becomes a more prominent problem.

Therefore, for the purpose of protecting the metal layer from water vapor and oxygen in the air, it is conceivable to provide a barrier property by providing a barrier layer immediately above the metal layer. As such a barrier layer, a technique of forming a silica thin film by a vapor deposition method is known (see, for example, Patent Document 3).

However, when silica deposition is used for the purpose of imparting barrier properties to the present invention, due to the difference between the internal stress of the metal thin film layer and the silica layer and the linear expansion coefficient including the resin base material, There has been a problem that the mirror surface is distorted.

JP 2005-59382 A JP-A-6-38860 JP 2006-334865 A

The present invention has been considered in view of the above problems, and the problem to be solved is to prevent deterioration of the metal thin film layer and to be lightweight and flexible, and to reduce the manufacturing cost and increase the area and mass production. And providing a film mirror having good light reflectivity and excellent light resistance and weather resistance, a method for producing the film mirror, and a solar reflective mirror using the film mirror.

The above-mentioned problem according to the present invention is solved by the following means.

1. An inorganic oxide film having a light reflecting layer formed of a metal thin film on a resin substrate, on the same side as the light reflecting layer, on the side far from the resin substrate with respect to the light reflecting layer; A film mirror having an oxide layer, wherein the inorganic oxide film is formed of a coating film containing inorganic oxide particles having an average particle diameter in the range of 1 nm to 1 μm.

2. 2. The film mirror according to item 1, wherein the inorganic oxide particles contain any one compound of silicon oxide, aluminum oxide, zinc oxide, titanium oxide, and zirconium oxide.

3. The film mirror according to item 1 or 2, wherein the metal thin film is a thin film mainly composed of silver.

4. The film mirror according to any one of items 1 to 3, further comprising a stress relaxation layer adjacent to the inorganic oxide layer.

5. The film according to any one of items 1 to 4, wherein the inorganic oxide layer is provided on both sides of the resin base material in a positional relationship of sandwiching the light reflecting layer. mirror.

6. A film mirror manufacturing method for manufacturing the film mirror according to any one of items 1 to 5, wherein a coating film comprising an inorganic oxide film containing inorganic oxide particles is applied in an amount of 50 to 200. The manufacturing method of the film mirror characterized by having the process of heat-processing at the heating temperature within the range of ° C.

7. The film mirror according to any one of claims 1 to 5 or a solar reflective mirror using a film mirror obtained by the method for producing a film mirror according to claim 6, A solar light reflecting mirror, which is formed by attaching the film mirror on a base material through an adhesive layer disposed on the side opposite to the light incident side of the light reflecting layer.

By the above-mentioned means of the present invention, the metal thin film layer is prevented from being deteriorated, lightweight and flexible, and can be manufactured with a large area and mass-produced with reduced manufacturing cost, good light reflectance, and light resistance. The film mirror excellent in the property and the weather resistance, its manufacturing method, and the mirror for sunlight reflection using the said film mirror can be provided.

The general | schematic flow sheet which shows the embodiment example of the manufacturing apparatus of a film-form resin substrate.

The film mirror of the present invention has a light reflection layer formed of a metal thin film on a resin base material, on the same side as the light reflection layer, on the side far from the resin base material with respect to the light reflection layer, A film mirror having an inorganic oxide layer composed of an inorganic oxide film, wherein the inorganic oxide film is formed of a coating film containing inorganic oxide particles having an average particle diameter in the range of 1 nm to 1 μm. It is characterized by. This feature is a technical feature common to the inventions according to claims 1 to 7.

As an embodiment of the present invention, from the viewpoint of manifesting the effects of the present invention, the inorganic oxide particles may contain any compound of silicon oxide, aluminum oxide, zinc oxide, titanium oxide and zirconium oxide. preferable. Moreover, it is preferable that the said metal thin film is a thin film which has silver as a main component.

As a configuration aspect of the film mirror of the present invention, an aspect having a stress relaxation layer adjacent to the inorganic oxide layer is preferable. Moreover, it is preferable that it is an aspect which has the said inorganic oxide layer in the both sides of the resin base material in the positional relationship which pinches | interposes the said light reflection layer.

The method for producing a film mirror of the present invention is a method for producing an embodiment having a step of heat-treating a coating film comprising an inorganic oxide film containing inorganic oxide particles at a heating temperature in the range of 50 to 200 ° C. It is preferable.

The film mirror of the present invention can be suitably used for a sunlight reflecting mirror.

Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail.

(Outline of basic structure of film mirror)
The film mirror of the present invention has a light reflecting layer made of a metal thin film on a resin substrate and an inorganic oxide layer made of an inorganic oxide film containing inorganic oxide particles. It is composed of a hard coat film, an antifogging film, a functional film such as an antireflection film or an antistatic film formed on the outer surface.

(Resin base material)
As the resin base material according to the present invention, various publicly known resin films can be used. For example, cellulose ester film, polyester film, polycarbonate film, polyarylate film, polysulfone (including polyethersulfone) film, polyethylene terephthalate, polyethylene naphthalate polyester film, polyethylene film, polypropylene film, cellophane, Cellulose diacetate film, cellulose triacetate film, cellulose acetate propionate film, cellulose acetate butyrate film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, syndiotactic polystyrene film, polycarbonate film, norbornene resin film , Polymethylpentenef Can Lum, polyether ketone film, polyether ketone imide film, a polyamide film, a fluororesin film, a nylon film, polymethyl methacrylate film, and acrylic films. Among these, a polycarbonate film, a polyester film, a norbornene resin film, and a cellulose ester film are preferable.

In particular, it is preferable to use a polyester film or a cellulose ester film, and it may be a film manufactured by melt casting or a film manufactured by solution casting.

The thickness of the resin base material is preferably an appropriate thickness depending on the type and purpose of the resin. For example, it is generally in the range of 10 to 300 μm. The thickness is preferably 20 to 200 μm, more preferably 30 to 100 μm.

In addition, the manufacturing method of a resin base material is mentioned later.

(Light reflecting layer)
The light reflecting layer according to the present invention refers to a layer made of a metal that reflects visible light and infrared light.

The light reflecting layer according to the present invention is not particularly limited, but silver or aluminum can be used, and silver can be particularly preferably used. By using silver, a reflectance higher than that of aluminum can be obtained for light having a wavelength of 380 nm or more.

When silver or aluminum is used for the light reflecting layer, basically, it is desirable to use silver alone or aluminum alone, but gold, copper, nickel, iron, cobalt, tungsten, molybdenum to the extent that they do not adversely affect their properties. Metal impurities such as tantalum, chromium, indium, manganese, titanium, and palladium may be included.

When silver or aluminum is used for the light reflecting layer, the thickness of the light reflecting layer is preferably 70 to 400 nm, more preferably 100 to 300 nm, and still more preferably 150 to 250 nm, from the viewpoints of reflectivity and effective use of resources. It is.

Both the wet method and the dry method can be used as the method for forming the light reflecting layer according to the present invention. The wet method is a general term for a plating method, and is a method of forming a film by depositing a metal from a solution. Specific examples include silver mirror reaction. On the other hand, the dry method is a general term for a vacuum film-forming method. Specific examples include a resistance heating vacuum deposition method, an electron beam heating vacuum deposition method, an ion plating method, and an ion beam assisted vacuum deposition method. And sputtering method. In particular, a vacuum film forming method capable of a roll-to-roll method for continuously forming a film is preferably used in the present invention.

Also, silver is most preferably used because high reflectance can be obtained not only in the visible light region but also in the infrared light region. Further, when the light reflecting layer is formed of silver, the weather resistance deterioration becomes more prominent, so the configuration of the present invention is effective.

In the present invention, the light reflecting layer may be on the light incident side or the opposite side with respect to the support, but since the support is a resin, for the purpose of preventing resin degradation due to light, It is preferable to be positioned on the light incident side.

(Inorganic oxide layer)
The film mirror of the present invention has a light reflecting layer formed of a metal thin film on a resin substrate, and is inorganic on the same side as the light reflecting layer and on the side far from the resin substrate with respect to the light reflecting layer. A film mirror having an inorganic oxide layer made of an oxide film, wherein the inorganic oxide film is formed of a coating film containing inorganic oxide particles having an average particle diameter in the range of 1 nm to 1 μm. Features. In addition, as an embodiment, it is preferable that the inorganic oxide layer is provided on each of both sides of the resin base material in a positional relationship of sandwiching the light reflection layer.

Hereinafter, components of the inorganic oxide layer will be described.

<Inorganic oxide particles>
The composition of the inorganic oxide particles according to the present invention is not particularly limited, but is preferably any of silicon oxide, aluminum oxide, zinc oxide, titanium oxide and zirconium oxide.

The average particle size is 1 nm to 1 μm, preferably 3 to 300 nm, more preferably 5 to 100 nm. Usually, only a heat treatment of a coating film obtained from a dispersion of inorganic oxide particles in the order of μm cannot provide a strong coating film. However, as in the present invention, the inorganic oxide particles used are in the nm order. As a result, the reactivity is improved by increasing the specific surface area, and a strong inorganic oxide can be formed by heat treatment. On the other hand, inorganic oxide particles having a particle diameter of 1 nm or less are difficult to obtain themselves, and even if obtained, aggregation of particles proceeds in a short time, and is extremely unstable. It was difficult to apply to the present invention.

<Inorganic oxide film containing inorganic oxide particles>
The “inorganic oxide film” according to the present invention refers to a film containing at least the above-described inorganic oxide particles and a compound having a polysiloxane structure for forming a silica-based film described later as its constituent elements.

The content of the inorganic oxide particles is preferably 30 to 99 vol%, more preferably 50 to 80 vol% of the inorganic oxide film.

Regarding the content of the inorganic oxide particles in the inorganic oxide film, the cross section of the film is observed with a transmission electron microscope, and the ratio of the total area of the inorganic fine particles contained in the total cross-sectional area of the inorganic oxide film Indicated. Since the original particle interface of the inorganic fine particles is observed in the film, the area where the inorganic fine particles are present can be quantified. Inorganic oxide films can be formed by vapor deposition, dry processes, and wet processes such as sol-gel methods, but they all have crystal grain interfaces, so they do not have sufficient barrier properties against gases and water vapor. However, the inclusion of inorganic oxide particles in the inorganic oxide film according to the present invention can minimize the occurrence of cracks that impair the barrier property, thereby improving the barrier property. Became possible.

<Compound having polysiloxane structure>
As the compound having a polysiloxane structure according to the present invention, various conventionally known compounds can be used, but a siloxane polymer is preferably used.

The siloxane polymer according to the present invention is not particularly limited, and is a polymer having a Si—O—Si bond. Among these siloxane polymers, a hydrolytic condensate of alkoxysilane can be suitably used. Any kind of alkoxysilane can be used as the alkoxysilane. Examples of such alkoxysilanes include compounds represented by the following general formula (a).

Formula (a): R ¹ _n —Si (OR ² ) _4-n
(Wherein R ¹ is hydrogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group, R ² is a monovalent organic group, and n is an integer of 0 to 2)
Here, examples of the monovalent organic group include an alkyl group, an aryl group, an allyl group, and a glycidyl group. In these, an alkyl group and an aryl group are preferable. The alkyl group preferably has 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group. The alkyl group may be linear or branched, and hydrogen may be substituted with fluorine. The aryl group preferably has 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.

Specific examples of the compound represented by the general formula (a) include
(A1) When n = 0, examples include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane,
(A2) When n = 1, monomethyltrimethoxysilane, monomethyltriethoxysilane, monomethyltripropoxysilane, monoethyltrimethoxysilane, monoethyltriethoxysilane, monoethyltripropoxysilane, monopropyltrimethoxysilane, monopropyl Examples include monoalkyltrialkoxysilanes such as triethoxysilane, monophenyltrialkoxysilanes such as monophenyltrimethoxysilane, and monophenyltriethoxysilane.
(A3) When n = 2, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, dipropyldidimethoxysilane, dipropyldiethoxysilane, di Examples thereof include dialkyl dialkoxysilanes such as propyldipropoxysilane, diphenyldialkoxysilanes such as diphenyldimethoxysilane and diphenyldiethoxysilane.

In the silica-based film forming composition according to the present invention, the weight average molecular weight of the siloxane polymer is preferably 200 or more and 50000 or less, and more preferably 1000 or more and 3000 or less. If it is this range, the applicability | paintability of the composition for silica-type film formation can be improved.

Alkoxysilane hydrolytic condensation is obtained by reacting an alkoxysilane serving as a polymerization monomer in an organic solvent in the presence of an acid catalyst or a base catalyst. The alkoxysilane used as the polymerization monomer may be used alone or may be condensed in combination of plural kinds.

Also, trialkylalkoxysilanes such as trimethylmethoxysilane, trimethylethoxysilane, trimethylpropoxysilane, triethylmethoxysilane, triethylethoxysilane, triethylpropoxysilane, tripropylmethoxysilane, tripropylethoxysilane, triphenylmethoxysilane, triphenylethoxy Triphenylalkoxysilane such as silane may be added during hydrolysis.

The degree of hydrolysis of the alkoxysilane, which is the premise of the condensation, can be adjusted by the amount of water to be added, but in general, with respect to the total number of moles of alkoxysilane represented by the general formula (a). 1.0 to 10.0 times mol, and more preferably 1.5 to 8.0 times mol. By making the addition amount of water 1.0 mol or more, the degree of hydrolysis can be sufficiently increased, and the film formation can be improved. On the other hand, gelation can be prevented and the storage stability can be improved by making it 10.0 mol or less.

In addition, in the condensation of the alkoxysilane represented by the general formula (a), it is preferable to use an acid catalyst, and the acid catalyst used is not particularly limited, and conventionally used organic acids are conventionally used. Any of inorganic acids can be used. Examples of the organic acid include organic carboxylic acids such as acetic acid, propionic acid, and butyric acid, and examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, and the like. The acid catalyst may be added directly to the mixture of alkoxysilane and water, or may be added to the alkoxysilane as an acidic aqueous solution together with water.

The hydrolysis reaction is usually completed in about 5 to 100 hours. In addition, at a heating temperature not exceeding 80 ° C. from room temperature, the reaction can be performed in a short reaction time by reacting the acid catalyst aqueous solution dropwise with an organic solvent containing one or more alkoxysilanes represented by the general formula (a). It can also be completed. The hydrolyzed alkoxysilane then undergoes a condensation reaction, resulting in the formation of a Si—O—Si network.

≪Method for forming silica-based film≫
As a method for forming a silica-based coating, first, a composition for forming a silica-based coating is applied on a substrate. As a method for applying the composition for forming a silica-based film on the substrate, for example, any method such as a spray method, a spin coating method, a dip coating method, a roll coating method can be used. Used.

Next, the silica-based film forming composition applied on the substrate is heat-treated. The means, temperature, time, etc. of the heat treatment are not particularly limited, but in general, it may be heated for about 1 to 6 minutes on a hot plate at about 80 to 300 ° C.

According to the composition for forming a silica-based film of the present invention, an acid or a base is generated by heating with a heat treatment. Since hydrolysis is promoted by the generated acid or base, the alkoxy group becomes a hydroxyl group (hydroxyl group), and alcohol is generated. Thereafter, since a hydroxyl group (hydroxyl group) is polycondensed between two molecules to form a Si—O—Si network, a dense silica-based film can be obtained by heat treatment.

In addition, the heat treatment is preferably performed in three or more steps in a stepwise manner. Specifically, after performing the first heat treatment for about 30 seconds to 2 minutes on a hot plate at about 60 to 150 ° C. in an air or an inert gas atmosphere such as nitrogen, the temperature is about 100 to 220 ° C. The second heat treatment is performed for about 30 seconds to 2 minutes, and the third heat treatment is performed at about 150 to 300 ° C. for about 30 seconds to 2 minutes. Thus, by performing stepwise heat treatment of three or more steps, preferably about 3 to 6 steps, a silica-based film can be formed at a lower temperature.

(Stress relaxation layer: Synthetic resin layer)
The purpose of the stress relaxation layer according to the present invention is to obtain a stress relaxation function that prevents the film mirror constituent layer from cracking due to bending of the film.

In the film mirror of the present invention, the stress relaxation layer can be arranged in various modes, but it is preferably a film mirror having a stress relaxation layer adjacent to the inorganic oxide layer.

As the material constituting the stress relaxation layer, conventionally known various synthetic resins can be used. For example, polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate (TAC), cellulose acetate butyrate, cellulose acetate propionate (CAP), cellulose acetate Cellulose esters such as phthalate and cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyetherketone, polyimide, polyethersulfone ( PES), polysulfones, polyether ketone imide, polyamide, fluororesin Nylon, polymethyl methacrylate, acrylic or polyarylates, and cycloolefin resins such as ARTON (trade name JSR Corp.) or APEL (trade name Mitsui Chemicals, Inc.).

Among these resins, particularly preferred resins are cycloolefin resins.

Examples of cycloolefin resins (hereinafter also referred to as “cyclic olefin resins”) include norbornene resins, monocyclic cyclo (cyclic) olefin resins, cyclo (cyclic) conjugated diene resins, and vinyl alicyclic hydrocarbon resins. Examples thereof include resins and hydrides thereof. Among these, norbornene-based resins can be suitably used because of their good transparency and moldability.

Examples of the norbornene-based resin include a ring-opening polymer of a monomer having a norbornene structure, a ring-opening copolymer of a monomer having a norbornene structure and another monomer, a hydride thereof, and a norbornene structure. An addition polymer of a monomer having a monomer, an addition copolymer of a monomer having a norbornene structure and another monomer, or a hydride thereof.

Among these, a ring-opening (co) polymer hydride of a monomer having a norbornene structure is particularly suitable from the viewpoints of transparency, moldability, heat resistance, low hygroscopicity, dimensional stability, lightness, and the like. Can be used.

Examples of the monomer having a norbornene structure include bicyclo [2.2.1] hept-2-ene (common name: norbornene), tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene. (Common name: dicyclopentadiene), 7,8-benzotricyclo [4.3.0.1 ^2,5 ] dec-3-ene (common name: methanotetrahydrofluorene), tetracyclo [4.4.0. 1 ^2,5 . 1 ^7,10 ] dodec-3-ene (common name: tetracyclododecene) and derivatives of these compounds (for example, those having a substituent in the ring). Here, examples of the substituent include an alkyl group, an alkylene group, and a polar group. In addition, these substituents may be the same or different and a plurality may be bonded to the ring. Monomers having a norbornene structure can be used singly or in combination of two or more.

Examples of the polar group include heteroatoms or atomic groups having heteroatoms. Examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, and a halogen atom. Specific examples of the polar group include a carboxyl group, a carbonyloxycarbonyl group, an epoxy group, a hydroxyl group, an oxy group, an ester group, a silanol group, a silyl group, an amino group, a nitrile group, and a sulfone group.

Other monomers capable of ring-opening copolymerization with monomers having a norbornene structure include monocyclo (cyclic) olefins such as cyclohexene, cycloheptene, and cyclooctene and derivatives thereof, and cyclo ( Cyclic) conjugated dienes and derivatives thereof.

A ring-opening polymer of a monomer having a norbornene structure and a ring-opening copolymer of a monomer having a norbornene structure and another monomer copolymerizable with the monomer have a known ring-opening polymerization catalyst. It can be obtained by (co) polymerization in the presence.

Examples of other monomers that can be addition-copolymerized with a monomer having a norbornene structure include, for example, α-olefins having 2 to 20 carbon atoms such as ethylene, propylene, and 1-butene, and derivatives thereof; cyclobutene, cyclopentene, Examples thereof include cycloolefins such as cyclohexene and derivatives thereof; non-conjugated dienes such as 1,4-hexadiene, 4-methyl-1,4-hexadiene, and 5-methyl-1,4-hexadiene. These monomers can be used alone or in combination of two or more. Among these, α-olefin is preferable, and ethylene is more preferable.

An addition polymer of a monomer having a norbornene structure and an addition copolymer of another monomer copolymerizable with a monomer having a norbornene structure can be used in the presence of a known addition polymerization catalyst. It can be obtained by polymerization.

A hydrogenated product of a ring-opening polymer of a monomer having a norbornene structure, a hydrogenated product of a ring-opening copolymer of a monomer having a norbornene structure and another monomer capable of ring-opening copolymerization thereof, Hydrogenated products of addition polymers of monomers having a norbornene structure, and hydrogenated products of addition copolymers of monomers having a norbornene structure and other monomers capable of addition copolymerization with these A known hydrogenation catalyst containing a transition metal such as nickel or palladium is added to the polymer solution, and the carbon-carbon unsaturated bond is preferably hydrogenated by 90% or more.

Among norbornene-based resins, X: bicyclo [3.3.0] octane-2,4-diyl-ethylene structure and Y: tricyclo [4.3.0.1 ^2,5 ] decane-7 are used as repeating units. , 9-diyl-ethylene structure, the content of these repeating units is 90% by mass or more based on the entire repeating units of the norbornene resin, and the X content ratio and the Y content ratio are The ratio of X: Y is preferably 100: 0 to 40:60.

The molecular weight of the cyclo (cyclic) olefin resin used in the present invention is appropriately selected according to the purpose of use. Polyisoprene or polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography using cyclohexane (toluene if the polymer resin does not dissolve) as a solvent, usually 20,000 to 150,000. . It is preferably 25,000 to 100,000, more preferably 30,000 to 80,000. When the weight average molecular weight is in such a range, the mechanical strength and molding processability of the film are highly balanced and suitable.

The glass transition temperature of the cyclo (cyclic) olefin resin may be appropriately selected according to the purpose of use. The range is preferably from 130 to 160 ° C, more preferably from 135 to 150 ° C.

Specific examples of the cycloolefin resin used in the present invention include, for example, JSR Corporation trade name: ARTON; Nippon Zeon Corporation trade name: Zeonoa; Sekisui Chemical Co., Ltd. trade name: Essina. be able to.

In addition, it is also preferable that the synthetic resin layer used as the stress relaxation layer contains an inorganic filler.

According to the above invention, by providing an inorganic filler-containing layer (stress relaxation layer) containing an inorganic filler, the gas barrier film is protected from external stress, thereby providing a gas barrier film whose performance is not deteriorated by compression / expansion stress due to environmental changes. be able to.

As an action to buffer external stress, in the inorganic filler-containing layer into which inorganic filler is introduced, there are fine pores at the boundary between the inorganic filler and the resin that is usually contained, and these pores absorb and relax external stress. Therefore, it is conceivable to reduce the load on the deposited film, prevent cracks from being introduced into the deposited film, and maintain the barrier property.

Moreover, in the form in which the transparent primer layer is provided, the adhesion between the plastic substrate and the inorganic vapor deposition layer can be enhanced.

In the mirror film of the present invention, the filler, the antioxidant, the ultraviolet absorber, the heat stabilizer, the lubricant, the antistatic agent, and the antibacterial agent are optionally added to each layer, particularly to the base material. , Pigments and the like can be added.

(Heat treatment process)
As a film mirror manufacturing method for manufacturing the film mirror of the present invention, various methods can be employed. A coating film comprising an inorganic oxide film containing inorganic oxide particles is within a range of 50 to 200 ° C. It is preferable that it is a manufacturing method of the aspect which has the process of heat-processing at heating temperature.

In the present invention, when the heat treatment temperature of the peripheral substrate is high, it is originally preferable that the heat treatment is performed at a high temperature from the viewpoint that the treatment time can be shortened. From the viewpoint of using a synthetic resin as a material, 50 to 200 ° C. is preferable. Furthermore, 70 to 150 ° C. is preferable.

Any heating means that is generally used can be applied to the heating method, but a method of heating by intermittently repeating heating for one hour is also preferably used.

As a heating method, it is preferable to form a moisture-proof layer by locally heating a coating film (also referred to as “coating layer”) of a dispersion containing inorganic oxide particles.

Here, “local heating” of the coating film means that the coating layer is substantially heated to 10 ° C. or more, preferably 20 ° C. or more higher than the resin substrate without substantially deteriorating the resin substrate by heating. Refers to heating. As a local heating method for this purpose, various conventionally known methods can be employed. For example, heating with an infrared heater, hot air, microwave, ultrasonic heating, induction heating, or the like can be selected as appropriate. Of these, methods using intermittent electromagnetic irradiation of infrared rays, electromagnetic waves such as microwaves and ultrasonic waves are preferable.

As the infrared irradiation means, an irradiation device such as an infrared lamp or an infrared heater can be used. If the inorganic oxide layer can be formed, the irradiation by the infrared irradiation device may be performed once. However, in order to locally heat the coating layer, there is a method of intermittently repeating the infrared irradiation for one hour. Preferably used. As a method of intermittently repeating short-time infrared irradiation, for example, a method of repeatedly turning on and off the infrared irradiation device in a short time, a shielding plate is provided between the infrared irradiation device and a non-irradiated object, and the shielding plate is moved And a method of repeatedly irradiating infrared rays by providing an infrared irradiation device at a plurality of locations in the conveyance direction of the non-irradiated material (resin film) and conveying the non-irradiated material.

A microwave is a general term for a UHF to EHF band with a frequency of 1 GHz to 3 THz and a wavelength of about 0.1 to 300 mm, and a microwave generator with a frequency of 2.45 GHz is common, but a microwave with a frequency of 1 to 100 GHz is common. Can be used. For example, a 2.45 GHz microwave irradiator (μ-reactor manufactured by Shikoku Keiki Kogyo Co., Ltd.), a microwave generator (magnetron) that radiates a 2.45 GHz microwave, and the like can be given.

In the present application, “ultrasonic wave” refers to an elastic vibration wave (sound wave) having a frequency of 10 kHz or more. As the heating method using ultrasonic waves according to the present invention, it is preferable that the frequency of the horn is a frequency in the range of 50 kHz or less, and heating for a single time is repeated repeatedly as in the case of infrared irradiation.

Even when the coating layer is heated using microwaves or ultrasonic waves, only the resin coating layer is locally applied without causing deterioration of the resin base material by intermittently repeating heating for a single hour as in the case of infrared irradiation. The method of heating is preferably used.

(Method for producing resin base material)
As a method for producing a resin base material according to the present invention, the usual inflation method, T-die method, calender method, cutting method, casting method, emulsion method, hot press method and the like can be used. From the viewpoints of suppressing foreign matter defects and optical defects such as die lines, the solution casting method and the melt casting method by casting are preferred.

Hereinafter, as a typical example, a production method in the case of producing a film-like resin base material will be described in detail.

<Method for producing resin base material by solution casting method>
(Organic solvent)
When the resin substrate according to the present invention is produced by the solution casting method, an organic solvent useful for forming the dope can be used without limitation as long as it dissolves a thermoplastic resin such as a cellulose ester resin. .

For example, as a chlorinated organic solvent, methylene chloride, as a non-chlorinated organic solvent, methyl acetate, ethyl acetate, amyl acetate, acetone, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, cyclohexanone, ethyl formate, 2,2,2-trifluoroethanol, 2,2,3,3-hexafluoro-1-propanol, 1,3-difluoro-2-propanol, 1,1,1,3,3,3-hexafluoro- 2-methyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3,3-pentafluoro-1-propanol, nitroethane, ethyl lactate, lactic acid , Diacetone alcohol, etc., preferably methylene chloride, methyl acetate, ethyl acetate, acetone, ethyl lactate, etc. Get.

In addition to the organic solvent, the dope may contain 1 to 40% by mass of a linear or branched aliphatic alcohol having 1 to 4 carbon atoms. When the proportion of alcohol in the dope increases, the web gels, facilitating peeling from the metal support, and when the proportion of alcohol is small, the dissolution of the thermoplastic resin in a non-chlorine organic solvent system is promoted. There is also a role.

In particular, the thermoplastic resin should be a dope composition in which at least 10 to 45% by mass of the thermoplastic resin is dissolved in a solvent containing methylene chloride and a linear or branched aliphatic alcohol having 1 to 4 carbon atoms. preferable.

Examples of the linear or branched aliphatic alcohol having 1 to 4 carbon atoms include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, and tert-butanol. Ethanol is preferred because of the stability of these dopes, the relatively low boiling point, and good drying properties.

Hereinafter, a preferred method for forming a film-like resin substrate according to the present invention (hereinafter also simply referred to as “film”) will be described.

1) Dissolution Step In this step, a thermoplastic resin, a heat-shrinkable material, and other additives are dissolved in an organic solvent mainly composed of a good solvent for the thermoplastic resin while stirring to form a dope.

For the dissolution of the thermoplastic resin, a method carried out at normal pressure, a method carried out below the boiling point of the main solvent, a method carried out under pressure above the boiling point of the main solvent, JP-A-9-95544, JP-A-9-95557 Alternatively, various dissolution methods such as a method using a cooling dissolution method as described in JP-A-9-95538 and a method using a high pressure as described in JP-A-11-21379 can be used. The method of pressurizing at a boiling point or higher is preferred.

Recycled material is a finely pulverized film, which is generated when the film is formed, cut off on both sides of the film, or the original film that has been speculated out due to scratches, etc. Reused.

2) Casting process An endless metal belt, such as a stainless steel belt or a rotating metal drum, which supports the dope is fed to a pressure die through a liquid feed pump (for example, a pressurized metering gear pump) and supported infinitely. This is a step of casting a dope from a pressure die slit to a casting position on the body.

¡Pressure dies that can adjust the slit shape of the die base and make the film thickness uniform are preferred. Examples of the pressure die include a coat hanger die and a T die, and any of them is preferably used. The surface of the metal support is a mirror surface. In order to increase the film forming speed, two or more pressure dies may be provided on the metal support, and the dope amount may be divided and stacked. Or it is also preferable to obtain the film of a laminated structure by the co-casting method which casts several dope simultaneously.

3) Solvent evaporation step In this step, the web (the dope is cast on the casting support and the formed dope film is called a web) is heated on the casting support to evaporate the solvent.

To evaporate the solvent, there are a method of blowing air from the web side and / or a method of transferring heat from the back side of the support by a liquid, a method of transferring heat from the front and back by radiant heat, etc. High efficiency and preferable. A method of combining them is also preferably used. The web on the support after casting is preferably dried on the support in an atmosphere of 40 to 100 ° C. In order to maintain the atmosphere at 40 to 100 ° C., it is preferable to apply hot air at this temperature to the upper surface of the web or heat by means such as infrared rays.

From the viewpoint of surface quality, moisture permeability, and peelability, it is preferable to peel the web from the support within 30 to 120 seconds.

4) Peeling process It is the process of peeling the web which the solvent evaporated on the metal support body in a peeling position. The peeled web is sent to the next process.

The temperature at the peeling position on the metal support is preferably 10 to 40 ° C, more preferably 11 to 30 ° C.

The amount of residual solvent at the time of peeling of the web on the metal support at the time of peeling is preferably 50 to 120% by mass depending on the strength of drying conditions, the length of the metal support, and the like. If the web is peeled off at a time when the amount of residual solvent is larger, if the web is too soft, the flatness at the time of peeling will be lost, and slippage and vertical stripes are likely to occur due to the peeling tension. The amount of solvent is determined.

The amount of residual solvent in the web is defined by the following formula.

Residual solvent amount (%) = (mass before web heat treatment−mass after web heat treatment) / (mass after web heat treatment) × 100
Note that the heat treatment for measuring the residual solvent amount represents performing heat treatment at 115 ° C. for 1 hour.

The peeling tension at the time of peeling the metal support and the film is usually 196 to 245 N / m. However, if wrinkles easily occur at the time of peeling, it is preferable to peel with a tension of 190 N / m or less. It is preferable to peel at a minimum tension of ˜166.6 N / m, and then peel at a minimum tension of ˜137.2 N / m, and particularly preferable to peel at a minimum tension of ˜100 N / m.

In the present invention, the temperature at the peeling position on the metal support is preferably −50 to 40 ° C., more preferably 10 to 40 ° C., and most preferably 15 to 30 ° C.

5) Drying and stretching step After peeling, a drying device 35 that transports the web alternately through rolls arranged in the drying device and / or a tenter stretching device 34 that clips and transports both ends of the web with clips. And dry the web.

The drying means is generally to blow hot air on both sides of the web, but there is also a means to heat by applying microwaves instead of wind. Too rapid drying tends to impair the flatness of the finished film. Drying at a high temperature is preferably performed from about 8% by mass or less of residual solvent. Throughout, drying is generally performed at 40-250 ° C. In particular, drying at 40 to 160 ° C. is preferable.

When using a tenter stretching apparatus, it is preferable to use an apparatus that can independently control the film gripping length (distance from the start of gripping to the end of gripping) left and right by the left and right gripping means of the tenter. In the tenter process, it is also preferable to intentionally create sections having different temperatures in order to improve planarity.

It is also preferable to provide a neutral zone between different temperature zones so that each zone does not cause interference.

The stretching operation may be performed in multiple stages, and it is also preferable to perform biaxial stretching in the casting direction and the width direction. When biaxial stretching is performed, simultaneous biaxial stretching may be performed or may be performed stepwise.

In this case, stepwise means that, for example, stretching in different stretching directions can be sequentially performed, stretching in the same direction is divided into multiple stages, and stretching in different directions is added to any one of the stages. Is also possible. That is, for example, the following stretching steps are possible.

-Stretch in the casting direction-Stretch in the width direction-Stretch in the casting direction-Stretch in the casting direction-Stretch in the width direction-Stretch in the width direction-Stretch in the casting direction-Stretch in the casting direction Simultaneous biaxial stretching includes stretching in one direction and contracting the other while relaxing the tension. The preferred draw ratio for simultaneous biaxial stretching can be in the range of x1.01 to x1.5 in both the width direction and the longitudinal direction.

When the tenter is used, the amount of residual solvent in the web is preferably 20 to 100% by mass at the start of the tenter, and drying is preferably performed while the tenter is applied until the amount of residual solvent in the web is 10% by mass or less. More preferably, it is 5% by mass or less.

When performing the tenter, the drying temperature is preferably 30 to 160 ° C., more preferably 50 to 150 ° C., and most preferably 70 to 140 ° C.

In the tenter process, it is preferable that the temperature distribution in the width direction of the atmosphere is small from the viewpoint of improving the uniformity of the film. The temperature distribution in the width direction in the tenter process is preferably within ± 5 ° C, and within ± 2 ° C. Is more preferable, and within ± 1 ° C. is most preferable.

6) Winding process This is a process in which the amount of residual solvent in the web becomes 2% by mass or less, and is taken up by the winder 37 as a film, and the dimensional stability is achieved by setting the residual solvent amount to 0.4% by mass or less. Can be obtained. It is particularly preferable to wind up at 0.00 to 0.10% by mass.

As a winding method, a generally used one may be used, and there are a constant torque method, a constant tension method, a taper tension method, a program tension control method with a constant internal stress, etc., and these may be used properly.

The film according to the present invention is preferably a long film, specifically a film having a thickness of about 100 m to 5000 m, and usually in a form provided in a roll shape. The film width is preferably 1.3 to 4 m, more preferably 1.4 to 2 m.

The film thickness of the film according to the present invention is not particularly limited, but is preferably 20 to 200 μm, more preferably 25 to 150 μm, and particularly preferably 30 to 120 μm.

<Manufacturing method of substrate by melt casting film forming method>
The method in the case of manufacturing the resin base material which concerns on this invention as a film-form resin base material by the melt casting film forming method is demonstrated.

<Melted pellet manufacturing process>
The composition constituting a film made of a thermoplastic resin and a heat shrinkable material used for melt extrusion is usually preferably kneaded in advance and pelletized.

The pelletization may be performed by a known method. For example, an additive comprising a dried thermoplastic resin and a heat-shrinkable material is supplied to an extruder with a feeder and kneaded using a single-screw or twin-screw extruder. It is possible to extrude into a strand, cool with water or air, and cut.

It is important to dry the raw material before extruding to prevent the raw material from being decomposed. In particular, since cellulose ester easily absorbs moisture, it is preferable to dry it at 70 to 140 ° C. for 3 hours or more with a dehumidifying hot air dryer or a vacuum dryer so that the moisture content is 200 ppm or less, and further 100 ppm or less.

Additives may be fed into the extruder and fed into the extruder, or may be fed through individual feeders. In order to mix a small amount of additives such as an antioxidant uniformly, it is preferable to mix them in advance.

The antioxidant may be mixed with each other, and if necessary, the antioxidant may be dissolved in a solvent, impregnated with a thermoplastic resin and mixed, or mixed by spraying. May be.

A vacuum nauter mixer or the like is preferable because drying and mixing can be performed simultaneously. Further, if the contact with air, such as the exit from the feeder unit or die, it is preferable that the atmosphere such as dehumidified air and dehumidified N ₂ gas.

The extruder is preferably processed at as low a temperature as possible so as to be able to be pelletized so that the shear force is suppressed and the resin does not deteriorate (molecular weight reduction, coloring, gel formation, etc.). For example, in the case of a twin screw extruder, it is preferable to rotate in the same direction using a deep groove type screw. From the uniformity of kneading, the meshing type is preferable.

Film formation is performed using the pellets obtained as described above. It is also possible to feed the raw material powder directly to the extruder with a feeder and form a film as it is without pelletization.

<Process for extruding molten mixture from die to cooling roll>
First, the pellets produced are extruded using a single-screw or twin-screw extruder, the melting temperature Tm during extrusion is set to about 200 to 300 ° C., filtered through a leaf disk type filter or the like to remove foreign matter, and then the T-die The film is coextruded into a film, solidified on a cooling roll, and cast while pressing with an elastic touch roll.

When introducing from the supply hopper to the extruder, it is preferable to prevent oxidative decomposition or the like under vacuum or reduced pressure or in an inert gas atmosphere. Tm is the temperature of the die exit portion of the extruder.

∙ If foreign matter such as scratches or plasticizer aggregates adheres to the die, streaky defects may occur. Such defects are also referred to as die lines, but in order to reduce surface defects such as die lines, it is preferable to have a structure in which the resin retention portion is minimized in the piping from the extruder to the die. . It is preferable to use a die that has as few scratches as possible inside the lip.

The inner surface that comes into contact with the molten resin, such as an extruder or a die, is preferably subjected to surface treatment that makes it difficult for the molten resin to adhere to the surface by reducing the surface roughness or using a material with low surface energy. Specifically, a hard chrome plated or ceramic sprayed material is polished so that the surface roughness is 0.2 S or less.

In the present invention, the cooling roll is not particularly limited, but it is a roll having a structure in which a heat medium or a coolant that can be controlled in temperature flows with a highly rigid metal roll, and the size is not limited. The size of the cooling roll is usually about 100 mm to 1 m.

The surface material of the cooling roll includes carbon steel, stainless steel, aluminum, titanium and the like. Further, in order to increase the hardness of the surface or improve the releasability from the resin, it is preferable to perform a surface treatment such as hard chrome plating, nickel plating, amorphous chrome plating, or ceramic spraying.

The surface roughness of the cooling roll surface is preferably 0.1 μm or less in terms of Ra, and more preferably 0.05 μm or less. The smoother the roll surface, the smoother the surface of the resulting film. Of course, it is preferable that the surface processed is further polished to have the above-described surface roughness.

In the present invention, as an elastic touch roll, JP-A Nos. 03-124425, 08-224772, JP-A-07-1000096, JP-A-10-272676, WO97 / 028950, JP-A-11-235747, As described in JP-A-2002-36332, JP-A-2005-172940 and JP-A-2005-280217, a thin-film metal sleeve-covered silicon rubber roll can be used.

When peeling the film from the cooling roll, it is preferable to control the tension to prevent deformation of the film.

<Extension process>
In the present invention, the film obtained as described above can be further stretched 1.01 to 3.0 times in at least one direction after passing through the step of contacting the cooling roll.

Preferably, the film is stretched 1.1 to 2.0 times in both the longitudinal (film transport direction) and lateral (width direction) directions.

As the stretching method, a known roll stretching machine or tenter can be preferably used.

The slow axis of the optical film becomes the width direction by stretching in the width direction.

Usually, the draw ratio is 1.1 to 3.0 times, preferably 1.2 to 1.5 times, and the drawing temperature is usually Tg to Tg + 50 ° C. of the resin constituting the film, preferably Tg to Tg + 50 ° C. In the temperature range.

The stretching is preferably performed under a uniform temperature distribution controlled in the longitudinal direction or the width direction. The temperature is preferably within ± 2 ° C, more preferably within ± 1 ° C, and particularly preferably within ± 0.5 ° C.

When the film-like resin substrate produced by the above method is used as an optical film, the film may be contracted in the longitudinal direction or the width direction for the purpose of adjusting the retardation of the optical film and reducing the dimensional change rate.

In order to shrink in the longitudinal direction, for example, there is a method in which the film is shrunk by temporarily clipping out the width stretching and relaxing in the longitudinal direction, or by gradually narrowing the interval between adjacent clips of the transverse stretching machine.

Uniformity in the slow axis direction is also important, and the angle is preferably −5 to + 5 ° with respect to the film width direction, more preferably in the range of −1 to + 1 °, particularly −0. A range of 5 to + 0.5 ° is preferable, and a range of −0.1 to + 0.1 ° is particularly preferable. These variations can be achieved by optimizing the stretching conditions.

The film-like resin base material of the present invention is preferably a long film, specifically, a film having a thickness of about 100 m to 5000 m, and usually in a form provided in a roll shape. The film width is preferably 1.3 to 4 m, more preferably 1.4 to 2 m.

The film thickness of the film-like resin substrate according to the present invention is not particularly limited, and is preferably changed according to the purpose.

<Flexible resin substrate manufacturing equipment>
FIG. 1 is a schematic flow sheet showing an overall configuration of an example of a resin base material manufacturing apparatus according to the present invention. In FIG. 1, a flexible resin substrate is manufactured by mixing and extruding a film material such as a thermoplastic resin and then extruding from a casting die 4 onto a first cooling roll 5 using an extruder 1. In addition to circumscribing the cooling roll 5, the film 10 is further circumscribed by the total of three cooling rolls, the second cooling roll 7 and the third cooling roll 8, and cooled and solidified to form the film 10. Next, the film 10 peeled off by the peeling roll 9 is then stretched in the width direction by holding both ends of the film by the stretching device 12 and then wound by the winding device 16. In addition, a touch roll 6 is provided that clamps the molten film on the surface of the first cooling roll 5 in order to correct the flatness. The touch roll 6 has an elastic surface and forms a nip with the first cooling roll 5.

In the present invention, it is preferable to add a device for automatically cleaning the belt and the roll to the manufacturing apparatus. There is no particular limitation on the cleaning device, but for example, a method of niping a brush roll, a water absorbing roll, an adhesive roll, a wiping roll, etc., an air blowing method for spraying clean air, a laser incinerator, or a combination thereof. is there.

¡In the case of a system in which a cleaning roll is nipped, the cleaning effect is great if the belt linear velocity and roller linear velocity are changed.

(Sunlight reflection mirror)
The film mirror of the present invention can be preferably used for the purpose of collecting sunlight. The film mirror can be used alone as a sunlight collecting mirror, but more preferably, via a pressure-sensitive adhesive layer coated on the surface of the resin substrate opposite to the side having the light reflecting layer with the resin substrate interposed therebetween. The film mirror is stuck on another base material, particularly on a metal base material, and used as a solar reflective mirror.

When used as a mirror for reflecting sunlight, the shape of the reflecting device is made into a bowl shape (semi-cylindrical shape), and a cylindrical member having a fluid inside is provided at the center of the semicircle, and sunlight is condensed on the cylindrical member. The form which heats an internal fluid by this, converts the heat energy, and generates electric power is mentioned as one form. In addition, flat reflectors were installed at multiple locations, and the sunlight reflected by each reflector was collected on one reflector (central reflector) and reflected by the reflector. The form which generate | occur | produces electricity by converting a thermal energy in a power generation part is also mentioned as one form. In particular, in the latter form, the film mirror of the present invention is particularly preferably used because a high regular reflectance is required for the reflection device used.

<Adhesive layer>
The adhesive layer is not particularly limited, and for example, any of a dry laminating agent, a wet laminating agent, an adhesive, a heat seal agent, a hot melt agent, and the like is used.

For example, polyester resin, urethane resin, polyvinyl acetate resin, acrylic resin, nitrile rubber and the like are used.

The laminating method is not particularly limited, and for example, it is preferable to carry out the roll method continuously from the viewpoint of economy and productivity.

The thickness of the pressure-sensitive adhesive layer is usually preferably in the range of about 1 to 50 μm from the viewpoint of the pressure-sensitive adhesive effect, the drying speed, and the like.

The other base material to be bonded to the film mirror of the present invention that is appropriately employed in the present invention may be any substrate that can impart the protection of the light reflecting layer, for example, an acrylic film or sheet, a polycarbonate film or sheet, Polyarylate film or sheet, polyethylene naphthalate film or sheet, polyethylene terephthalate film or sheet, plastic film or sheet such as fluorine film, or resin film or sheet kneaded with titanium oxide, silica, aluminum powder, copper powder, etc. A resin film or sheet coated with a resin kneaded with a resin or subjected to surface processing such as metal deposition is used.

The thickness of the laminated film or sheet is not particularly limited but is preferably in the range of 12 to 250 μm.

In addition, these other base materials may be bonded after providing a concave portion or a convex portion before being bonded to the film mirror of the present invention, or may be formed to have a concave portion or a convex portion after being bonded. In addition, the bonding and the molding so as to have a concave portion or a convex portion may be performed at the same time.

<Metal base material>
The metal substrate of the solar reflective mirror according to the present invention includes a steel plate, a copper plate, an aluminum plate, an aluminum plated steel plate, an aluminum alloy plated steel plate, a copper plated steel plate, a tin plated steel plate, a chrome plated steel plate, a stainless steel plate, etc. A metal material having a high rate can be used. In the present invention, it is particularly preferable to use a plated steel plate, a stainless steel plate, an aluminum plate, or the like having good corrosion resistance.

Hereinafter, the present invention will be specifically described with reference to examples and comparative examples.

[Comparative Example 1]
(Formation of evaporated aluminum film by vacuum deposition)
A biaxially stretched polyester film (polyethylene terephthalate film, thickness 175 μm) was used as the substrate. Next, aluminum having a purity of 99.9% is used, and the ultimate vacuum of the chamber is 0.5 × 10 ⁻⁴ torr (6.7 × 10 ⁻³ Pa) using a take-up vacuum deposition apparatus. ), And vacuum deposition was performed until the film thickness reached 100 nm. During vacuum processing, no gas was generated, and the vapor-deposited aluminum deposited metal film had a mirror-like appearance.

[Comparative Example 2]
The sample on which the aluminum deposited film obtained in Comparative Example 1 was formed was wound using a vacuum deposition apparatus, and the ultimate vacuum in the chamber was 3.0 × 10 ⁻⁵ torr (4.0 × 10 ⁻³ Pa). Then, oxygen gas is introduced in the vicinity of the coating drum while maintaining the pressure in the chamber at 3.0 × 10 ⁻⁴ torr (4.0 × 10 ⁻² Pa), and the evaporation source is oxidized. Comparative Example 2 A silicon oxide moisture-proof layer having a thickness of 1 μm was formed while silicon was heated and vapor-deposited with a pierce-type electron gun at a power of about 10 kw and traveled on a coating drum at a speed of 120 m / min. A sample of was prepared.

[Comparative Example 3]
Silver having a purity of 99.9% was used in place of aluminum, and a silver deposited film was formed in a thickness of 100 nm by the same method as in Comparative Example 1. Further, a silicon oxide moisture-proof layer having a thickness of 1 μm was formed on the silver vapor-deposited film in the same manner as in Comparative Example 2 to produce a sample of Comparative Example 3.

[Example 1]
(Inorganic oxide particle-containing coating solution-1)
400 g of pure water was put into a 1 L stainless steel pot, and 600 g of silicon oxide (trade name: SFP-30M average particle size 700 nm, manufactured by Denki Kagaku Kogyo Co., Ltd.) was used at 6000 rpm using an Ultra Turrax T25 Digital (IKA). It was added over a period of time and then dispersed for 30 minutes. Thereafter, 1000 g of MEK was added, and the operation of removing the solvent with an evaporator until the residual mass reached 800 g under a reduced pressure of bath temperature of 40 ° C. and 2.0 × 10 ² torr (2.7 × 10 ⁴ Pa) was 3 Repeatedly, finally, 200 g of MEK was added to make the total mass 1000 g, and dispersion 1 was obtained. Next, 20 parts by mass of tetraethoxysilane (Si (C ₂ H ₅ O) ₄ ), 80 parts by mass of phenyltriethoxysilane (C ₆ H ₅ Si (OC ₂ H ₅ ) ₃ ) and 100 parts by mass of ethyl alcohol The formic acid was reacted as a catalyst to obtain an acidic solution. Next, the acidic solution was neutralized with triethylamine ((C ₂ H ₅ ) ₃ N) to obtain a neutralized solution. Then, the solvent of the neutralized solution was replaced with methyl ethyl ketone to obtain a resin solution-1 having a resin nonvolatile content concentration of 60% and a viscosity of 400 cp. 30 g of Dispersion-1 and 70 g of Resin Solution-1 were mixed to obtain 100 g of inorganic oxide particle coating solution-1.

(Preparation of coated sample of Example 1)
An aluminum vapor deposition film was formed on one side of a biaxially stretched polyester film (polyethylene terephthalate film, thickness 175 μm) by vacuum vapor deposition in the same manner as in Comparative Example 1. Subsequently, the inorganic oxide particle-containing coating solution-1 was bar-coated so that the thickness of the dried film was 1 μm, and dried by heating in a dry oven at 150 ° C. for 30 minutes. Was made.

[Example 2]
On one side of a biaxially stretched polyester film (polyethylene terephthalate film, thickness 175 μm), silver with a purity of 99.9% was used instead of aluminum, and a silver deposited film with a film thickness of 100 nm was used in the same manner as in Comparative Example 1. Formed. Subsequently, the coating solution-1 containing inorganic oxide particles was bar-coated so that the thickness of the dried film was 1 μm, and dried by heating in a dry oven at 150 ° C. for 30 minutes. Produced.

[Example 3]
The inorganic oxide particles were the same as the coating solution-1 containing the inorganic oxide particles except that the silicon oxide was changed to trade name: SFP-20M (average particle size: 300 nm) manufactured by Denki Kagaku Kogyo Co., Ltd. Containing coating solution-2 was obtained. Further, the same operation as in Example 2 was performed to prepare a sample of Example 3.

[Example 4]
The inorganic oxide particle-containing coating solution-1 was the same as the coating solution-1 containing inorganic oxide particles except that silicon oxide was changed to Corefront Co., Ltd., trade name: sicastar (average particle size: 70 nm). -3 was obtained. Furthermore, the sample of Example 4 was produced in the same manner as in Example 2.

[Example 5]
Into a 1 L stainless steel pot, an aqueous dispersion of aluminum oxide (trade name: NANOBYK-3600, average particle diameter: 40 nm) and 1000 g of MEK were added, and the bath temperature was 40 ° C., 2.0 × 10 ² torr (2 The operation of removing the solvent with an evaporator was repeated three times under a reduced pressure of 0.7 × 10 ⁴ Pa) until the residual mass reached 800 g. Finally, 200 g of MEK was added to make the total mass 1000 g, thereby obtaining a dispersion. 30 g of this dispersion and 70 g of resin solution-1 were mixed to prepare inorganic oxide particle-containing coating solution-4. Furthermore, the sample of Example 5 was produced in the same manner as in Example 2.

[Example 6]
An inorganic oxide particle-containing coating solution-5 was prepared in the same manner as in the inorganic oxide particle-containing coating solution-1, except that silicon oxide was replaced with titanium oxide having an average particle size of 50 nm. Furthermore, the sample of Example 6 was produced in the same manner as in Example 2.

[Example 7]
(Preparation of stress relaxation layer coating solution-1)
Weigh 1000 g of cyclohexane in a 2 L stainless beaker and add 200 g of cycloolefin polymer (ZEONOR 1060R manufactured by Nippon Zeon Co., Ltd.) while stirring with a magnetic stirrer. It was set to 1.

(Sample preparation of Example 7)
The stress relaxation layer coating solution-1 was applied on the moisture-proof layer of the sample of Example 2 so that the dry film thickness was 3 μm, and then dried in a dry oven at 75 ° C. for 20 minutes. A sample was obtained.

[Example 8]
The inorganic oxide particle-containing coating solution-3 was bar-coated on the PET substrate opposite to the silver vapor-deposited film of Example 7 so that the thickness of the dried film was 1 μm. Example 8 Got a sample.

[Example 9]
The inorganic oxide particle-containing coating solution-1 was coated in the same manner except that the silicon oxide was replaced with zinc oxide having an average particle size of 20 nm (Nano Fine manufactured by Sakai Chemical Industry Co., Ltd.). Liquid-6 was prepared. After forming a moisture-proof layer on the silver vapor-deposited film using the inorganic oxide particle-containing coating solution-6 by the same operation as in Example 2, the stress relaxation layer coating solution-1 was further formed on the moisture-proof layer. Was applied to a dry film thickness of 3 μm and dried in a dry oven at 75 ° C. for 20 minutes.

Further, the inorganic oxide particle-containing coating liquid-6 was bar-coated on a PET base material opposite to the silver vapor-deposited film so that the thickness of the dried film was 1 μm. After heating and drying for 30 minutes, the above-described stress relaxation layer coating solution-1 was applied so that the dry film thickness was 3 μm, and then dried at 75 ° C. for 20 minutes in a dry oven. Obtained.

[Example 10]
Inorganic oxide particle-containing coating solution-7, except that silicon oxide was replaced with zirconium oxide having an average particle size of 40 nm (manufactured by Sumitomo Osaka Cement) with respect to inorganic oxide particle-containing coating solution-1. Was prepared. In the same manner as in Example 9, a silver deposited film was formed on one side of the substrate, a moisture-proof layer and a stress relaxation layer were formed on both sides of the substrate, and a sample of Example 10 was obtained.

(Production of solar collector mirror)
The sample was pasted on a stainless steel (SUS304) plate having a thickness of 0.1 mm and a length of 4 cm × width 5 cm through a 3 μm thick adhesive layer to produce a solar reflective mirror.

[Evaluation]
About the solar reflective mirror obtained above, the light reflectance, weather resistance, and flex resistance were measured by the following methods.

<Light reflectance measurement>
A spectrophotometer “UV265” manufactured by Shimadzu Corporation was used with an integrating sphere reflection accessory attached thereto, and a barium sulfate powder pressed and used as a reference plate. Evaluation was made with respect to the light reflectance at 555 nm, which is the wavelength with the highest human eye sensitivity.

<Weight resistance test of light reflectance>
The reflectance of the film mirror after being left for 30 days under the conditions of a temperature of 85 ° C. and a humidity of 85% RH is measured by the same method as the light reflectance measurement, and the reflectance of the film mirror before the forced deterioration and after the forced deterioration are measured. From the film mirror reflectance, the reduction rate of the reflectance before and after the xenon lamp irradiation was calculated. The evaluation criteria for the weather resistance test are described below.

5: Reflection decrease rate is less than 5% 4: Reflectance decrease rate is 5% or more and less than 10% 3: Reflection decrease rate is 10% or more and less than 15% 2: Reflection decrease rate is 15% or more Less than 20% 1: Decrease in reflectance is 20% or more <Bend resistance test>
Using a gel bow flex tester device manufactured by Rigaku Kogyo Co., Ltd., the sample is subjected to a bending test at 23 ° C. and 50% RH atmosphere, and after the bending is repeated 10 times, the same test as the light reflectance weathering test is performed. did.

The contents of the obtained film mirror are shown in Table 1 below, and the results of evaluating the characteristics are shown in Table 2 below.

As is apparent from the results shown in Table 2, it can be seen that the film mirror of the present invention has high light reflectance and excellent weather resistance and flexibility.

DESCRIPTION OF SYMBOLS 1 Extruder 2 Filter 3 Static mixer 4 Casting die 5 Rotating support body (1st cooling roll)
6 Nipping pressure rotating body (touch roll)
7 Rotating support (second cooling roll)
8 Rotating support (3rd cooling roll)
DESCRIPTION OF SYMBOLS 9 Peeling roll 10 Film 11, 13, 14 Conveyance roll 12 Stretching machine 15 Slitter 16 Winding machine F The film-form resin base material which concerns on this invention

Claims (7)

1. An inorganic oxide film having a light reflecting layer formed of a metal thin film on a resin substrate, on the same side as the light reflecting layer, on the side far from the resin substrate with respect to the light reflecting layer; A film mirror having an oxide layer, wherein the inorganic oxide film is formed of a coating film containing inorganic oxide particles having an average particle diameter in the range of 1 nm to 1 μm.
2. The film mirror according to claim 1, wherein the inorganic oxide particles contain any one compound of silicon oxide, aluminum oxide, zinc oxide, titanium oxide and zirconium oxide.
3. The film mirror according to claim 1 or 2, wherein the metal thin film is a thin film mainly composed of silver.
4. The film mirror according to claim 1, further comprising a stress relaxation layer adjacent to the inorganic oxide layer.
5. 5. The film mirror according to claim 1, wherein the inorganic oxide layer is provided on both sides of the resin base material in a positional relationship of sandwiching the light reflection layer. 6. .
6. A film mirror manufacturing method for manufacturing a film mirror according to any one of claims 1 to 5, wherein a coating film comprising an inorganic oxide film containing inorganic oxide particles is applied at 50 to 200 ° C. The manufacturing method of the film mirror characterized by having the process of heat-processing with the heating temperature within the range of this.
7. It is the mirror for sunlight reflection using the film mirror obtained by the film mirror as described in any one of Claim 1- Claim 5, or the film mirror as described in Claim 6, Comprising: A solar light reflecting mirror, which is formed by attaching the film mirror on a base material through an adhesive layer disposed on the side opposite to the light incident side of the light reflecting layer.

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