WO2014157355A1 - Miroir en film - Google Patents

Miroir en film Download PDF

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Publication number
WO2014157355A1
WO2014157355A1 PCT/JP2014/058573 JP2014058573W WO2014157355A1 WO 2014157355 A1 WO2014157355 A1 WO 2014157355A1 JP 2014058573 W JP2014058573 W JP 2014058573W WO 2014157355 A1 WO2014157355 A1 WO 2014157355A1
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WO
WIPO (PCT)
Prior art keywords
group
resin layer
resin
layer
film mirror
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/JP2014/058573
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English (en)
Japanese (ja)
Inventor
祐也 阿形
祐也 山本
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Fujifilm Corp
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Fujifilm Corp
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Filing date
Publication date
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Publication of WO2014157355A1 publication Critical patent/WO2014157355A1/fr
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/022—Mechanical properties
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
    • F24S23/00—Arrangements for concentrating solar-rays for solar heat collectors
    • F24S23/70—Arrangements for concentrating solar-rays for solar heat collectors with reflectors
    • F24S23/82—Arrangements for concentrating solar-rays for solar heat collectors with reflectors characterised by the material or the construction of the reflector
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/08—Mirrors
    • G02B5/0808—Mirrors having a single reflecting layer
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02S—GENERATION OF ELECTRIC POWER BY CONVERSION OF INFRARED RADIATION, VISIBLE LIGHT OR ULTRAVIOLET LIGHT, e.g. USING PHOTOVOLTAIC [PV] MODULES
    • H02S40/00—Components or accessories in combination with PV modules, not provided for in groups H02S10/00 - H02S30/00
    • H02S40/20—Optical components
    • H02S40/22—Light-reflecting or light-concentrating means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2551/00—Optical elements
    • B32B2551/08—Mirrors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/40—Solar thermal energy, e.g. solar towers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/52—PV systems with concentrators

Definitions

  • the present invention relates to a film mirror that can be suitably used for collecting sunlight.
  • glass mirrors have been used for sunlight reflecting devices because they are exposed to ultraviolet rays, heat, wind and rain, and dust from sunlight.
  • a glass mirror when a glass mirror is used, there are problems that it is damaged during transportation and that a high strength is required for the mount on which the mirror is installed, resulting in an increase in construction costs.
  • film mirrors are required to have characteristics (reflectance and the like) that are not easily lowered even when used for a long time in a harsh environment. For example, it is required that the decrease in reflectance is suppressed even when exposed to dust.
  • dust or the like adheres it leads to deterioration of characteristics such as reflectance, so that it is required that the dust or the like is difficult to adhere.
  • Patent Document 1 states that “in a film mirror for solar power generation having a reflective layer on a substrate and a hard coat layer on the outermost surface, a leveling agent having fluorine atoms is formed on the outermost surface.
  • a "film mirror for solar power generation” characterized in that it is contained in the outermost hard coat layer at a ratio of 0.1 mass% or more and 10 mass% or less of the resin solid content in the hardcoat layer is disclosed. According to Patent Document 1, it is described that it is excellent in scratch resistance and the like by adopting such an aspect.
  • an object of the present invention is to provide a film mirror in which a decrease in reflectance is suppressed even when exposed to dust, and dust or the like is hardly attached.
  • the present inventors have provided two resin layers having a specific relationship in elastic recovery rate, and are less likely to be scratched even when exposed to dust, thereby suppressing a decrease in reflectance.
  • the present inventors have found that dust and the like are less likely to adhere to the present invention. That is, the present inventors have found that the above problem can be solved by the following configuration.
  • a resin base material with a metal reflective layer, a first resin layer, and a second resin layer are provided in this order, and the elastic recovery rate E2 of the second resin layer is higher than the elastic recovery rate E1 of the first resin layer. Big film mirror.
  • the ratio of the thickness of the second resin layer to the thickness of the first resin layer is greater than 0.20, (1) or ( The film mirror as described in 2).
  • the difference (E2 ⁇ E1) between the elastic recovery rate E2 of the second resin layer and the elastic recovery rate E1 of the first resin layer is 10% or more and less than 40%.
  • the film mirror in any one of.
  • (6) The film mirror according to any one of (1) to (5), which is used for collecting sunlight.
  • the film mirror of this invention is equipped with the resin base material with a metal reflective layer, the 1st resin layer, and the 2nd resin layer in this order.
  • the elastic recovery rate E2 of the second resin layer is larger than the elastic recovery rate E1 of the first resin layer. That is, the film mirror of the present invention first includes a first resin layer on a resin base with a metal reflective layer, and further has an elastic recovery rate larger than that of the first resin layer. Two resin layers are provided.
  • the film mirror of the present invention is considered to exhibit excellent dust resistance and adhesion resistance by taking such a configuration.
  • the film mirror includes a first resin layer and a second resin layer having an elastic recovery rate larger than the elastic recovery rate of the first resin layer, so that the film mirror is exposed even when exposed to dust. This is considered to be because the deformation of the surface is suppressed (or the deformation returns to its original state even if it is deformed), and the embedding of dust on the surface of the film mirror when the dust collides with the film mirror is reduced.
  • the film mirror of the present invention is characterized in that the elastic recovery rate of the second resin layer (surface side) is larger than the elastic recovery rate of the first resin layer (resin substrate side with a metal reflection layer). .
  • FIG. 1 is a cross-sectional view of one embodiment of the film mirror of the present invention.
  • the film mirror 100 includes a resin base material 20 with a metal reflection layer having a resin base material 10 and a metal reflection layer 12, a first resin layer 30, and a second resin layer 40 in this order.
  • light such as sunlight is incident from the second resin layer 40 side and reflected on the surface of the metal reflection layer 12.
  • the 1st resin layer 30 and the 2nd resin layer 40 are provided on the metal reflective layer 12 of the resin base material 20 with a metal reflective layer, as shown in FIG.
  • the first resin layer 30 and the second resin layer 40 may be provided on the resin base material 10.
  • FIG. 1 is a cross-sectional view of one embodiment of the film mirror of the present invention.
  • the film mirror 100 includes a resin base material 20 with a metal reflection layer having a resin base material 10 and a metal reflection layer 12, a first resin layer 30, and a second resin layer 40 in this order.
  • light such as sunlight is incident from the second resin layer 40 side
  • a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • the resin base material with a metal reflection layer is not particularly limited as long as the metal reflection layer is laminated on at least one main surface of the resin base material.
  • the resin substrate is not particularly limited as long as it is a resin substrate on which a metal reflective layer can be laminated.
  • the material constituting the resin substrate include polyolefin resins such as polyethylene and polypropylene; polyester resins such as polyethylene terephthalate and polyethylene naphthalate; polycarbonate resins; acrylic resins such as polymethyl methacrylate; polyamide resins; Polyimide resin; polyvinyl chloride resin; polyphenylene sulfide resin; polyether sulfone resin; polyethylene sulfide resin; polyphenylene ether resin; styrene resin; cellulose resin such as cellulose acetate; Among these, from the viewpoint of the weather resistance of the film mirror, a polyester resin or an acrylic resin is preferable.
  • the shape of the resin base material is not limited to a planar shape, and may be any of a concave shape, a convex shape, and the like, for example.
  • the thickness of the resin substrate is not particularly limited because it depends on the shape of the resin substrate. However, when the resin substrate is planar, it is usually preferably 25 to 300 ⁇ m.
  • the metal constituting the metal reflection layer is not particularly limited, and specific examples thereof include Au, Ag, Cu, Pt, Pd, In, Ga, Sn, Ge, Sb, Pb, Zn, Bi, Fe, Ni, Co. , Mn, Tl, Cr, V, Ru, Rh, Ir, Al and the like. Especially, it is preferable that it is Ag, Ni, or Cu from a viewpoint of the initial stage reflectance of a film mirror, and it is more preferable that it is Ag.
  • the metal constituting the metal reflective layer is Ag (silver)
  • the silver content in the metal reflective layer is preferably 30 mol% or more, and 50 mol% with respect to the total metal constituting the metal reflective layer.
  • the shape of the metal reflection layer is not particularly limited, and may be a layer that covers the entire main surface of the resin base material or a layer that partially covers the main surface.
  • the thickness of the metal reflective layer is not particularly limited, but is preferably 50 to 500 nm, more preferably 80 to 300 nm from the viewpoint of the reflectance of the film mirror and the like.
  • the manufacturing method in particular of the resin base material with a metal reflective layer is not restrict
  • the method of forming a metal reflective layer with respect to the resin base material by a well-known method is mentioned.
  • the method for forming the metal reflective layer include a plating method (electroless plating and electroplating), a method in which a solution containing a metal complex compound is applied and heated, a vacuum deposition method, a sputtering method, an ion plating method, and the like. Is mentioned.
  • the plating method is preferred from the viewpoint of adhesion between the resin base material and the metal reflective layer.
  • the resin base material with a metal reflective layer As a suitable aspect of the manufacturing method of the resin base material with a metal reflective layer, for example, (i) a primer layer is formed on the resin base material, (ii) a plating catalyst or a precursor thereof is imparted to the formed primer layer, (Iii) The method of plating with respect to the primer layer to which the plating catalyst or its precursor was provided, etc. are mentioned.
  • the resin base material with a metal reflective layer which has a resin base material, a metal reflective layer, and the primer layer arrange
  • each step (i) to (iii) will be described in detail.
  • Step (i) is a step of forming a primer layer on the resin base material.
  • a primer layer is a layer arrange
  • the primer layer is obtained by subjecting a layer containing a polymer having a functional group and a polymerizable group that interacts with the plating catalyst or its precursor to at least one of heat treatment and light irradiation treatment (hereinafter also referred to as energy application). .
  • energy application hereinafter also referred to as energy application.
  • the polymer used for the primer layer includes a functional group that interacts with the plating catalyst or its precursor (hereinafter also referred to as an interactive group) and a polymerizable group.
  • the interactive group is a group that interacts with the plating catalyst or a precursor thereof, and plays a role of improving the adhesion between the metal reflective layer and the primer layer.
  • the polymerizable group is subjected to at least one of a heat treatment and a light irradiation treatment, which will be described later, so that a crosslinking reaction proceeds and increases the strength of the primer layer, and a part of the polymerizable group reacts with the resin substrate. It plays the role which improves adhesiveness with a primer layer.
  • the polymerizable group may be a functional group that can form a chemical bond between polymers or between a polymer and a resin substrate by applying energy.
  • 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.
  • the radical polymerizable group include a methacryloyl group, an acryloyl group, an itaconic acid ester group, a crotonic acid ester group, an isocrotonic acid ester group, a maleic acid ester group, a styryl group, a vinyl group, an acrylamide group, and a methacrylamide group. It is done.
  • methacryloyl group, acryloyl group, vinyl group, styryl group, acrylamide group, and methacrylamide group are preferable, and methacryloyl group, acryloyl group, acrylamide group, methacrylamide from the viewpoint of radical polymerization reactivity and synthesis versatility.
  • Group is more preferable, and from the viewpoint of alkali resistance, an acrylamide group and a methacrylamide group are more preferable.
  • the type of the interactive group is not particularly limited as long as it is a group that forms an interaction with the plating catalyst or its precursor.
  • ionic polar groups such as carboxyl group, sulfonic acid group, phosphoric acid group, and boronic acid group, and ether group or cyano group.
  • a functional group is more preferable.
  • the polymer is represented by a unit (repeating unit) represented by the following formula (1) and the following formula (2).
  • the unit represented is included.
  • R 10 represents a hydrogen atom or an alkyl group (for example, a methyl group, an ethyl group, etc.).
  • L 2 represents a single bond or a divalent linking group.
  • the divalent linking group a substituted or unsubstituted divalent aliphatic hydrocarbon group (preferably having 1 to 8 carbon atoms, for example, an alkylene group such as a methylene group, an ethylene group, or a propylene group), substituted or unsubstituted A divalent aromatic hydrocarbon group (preferably having 6 to 12 carbon atoms, such as a phenylene group), —O—, —S—, —SO 2 —, —N (R) — (R: alkyl group), And —CO—, —NH—, —COO—, —CONH—, or a combination thereof (for example, an alkyleneoxy group, an alkyleneoxycarbonyl group, an alkylenecarbonyloxy group,
  • R 11 represents an interactive group.
  • the definition, specific examples and preferred embodiments of the interactive group are as described above.
  • the polymer may contain units kinds of interactive group represented by R 11 is represented by two or more expressions that different (1).
  • a unit represented by the formula (1) in which R 11 is an ionic polar group and a unit represented by the formula (1) in which R 11 is a non-dissociable functional group are contained in the polymer. May be.
  • R 12 to R 15 each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group.
  • R 12 to R 15 are a substituted or unsubstituted alkyl group
  • an alkyl group having 1 to 6 carbon atoms is preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable.
  • examples of the unsubstituted alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group
  • examples of the substituted alkyl group include a methoxy group, a hydroxy group, and a halogen atom (for example, a chlorine atom).
  • a bromine atom, a fluorine atom) and the like and a methyl group, an ethyl group, a propyl group, and a butyl group.
  • R 12 is preferably a hydrogen atom, a methyl group, or a methyl group substituted with a hydroxy group or a bromine atom.
  • R 13 is preferably a hydrogen atom, a methyl group, or a methyl group substituted with a hydroxy group or a bromine atom.
  • R 14 is preferably a hydrogen atom.
  • R 15 is preferably a hydrogen atom.
  • L 3 represents a single bond or a divalent linking group. Specific examples and preferred embodiments of the divalent linking group are the same as L 2 in the above formula (1).
  • a copolymer comprising a unit represented by the following formula (A), a unit represented by the following formula (B), and a unit represented by the following formula (C)
  • a copolymer comprising a unit represented by the following formula (A) and a unit represented by the following formula (B), a unit represented by the following formula (A) and a unit represented by the following formula (C); And the like, and the like.
  • R 21 to R 26 each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms.
  • X, Y, Z, and U each independently represent a single bond or a divalent linking group.
  • L 4 , L 5 and L 6 each independently represents a single bond or a divalent linking group.
  • W represents an interactive group composed of a non-dissociable functional group.
  • V represents an interactive group composed of an ionic polar group. Specific examples and preferred embodiments of the divalent linking group are the same as L 2 in the above formula (1).
  • Y and Z are preferably each independently an ester group, an amide group, or a phenylene group (—C 6 H 4 —).
  • L 4 is preferably a substituted or unsubstituted divalent organic group (particularly a hydrocarbon group) having 1 to 10 carbon atoms.
  • W is preferably a cyano group or an ether group.
  • X and L 5 is preferably either a single bond.
  • V is preferably a carboxylic acid group
  • V is a carboxylic acid group
  • L 6 is a 4-membered to 8-membered ring at the portion where V is connected to V.
  • V is a carboxylic acid group and the chain length of L 6 is 6 to 18 atoms is also preferable.
  • V is a carboxylic acid group and U and L 6 are single bonds.
  • an embodiment in which V is a carboxylic acid group and both U and L 6 are single bonds is most preferable.
  • the content of the units represented by the formulas (A) to (C) is preferably in the following range. That is, in the case of a copolymer including a unit represented by the formula (A), a unit represented by the formula (B), and a unit represented by the formula (C), the copolymer is represented by the formula (A).
  • Unit: Unit represented by formula (B): Unit represented by formula (C) 5-50 mol%: 5-40 mol%: 20-70 mol% is preferable, 10-40 mol%: 10-35 mol %: More preferably 20 to 60 mol%.
  • a unit represented by the formula (A): a unit represented by the formula (C) 5 to 50 mol%: 50 to 95 mol% is preferable, and 10 to 40 mol%: 60 to 90 mol% is more preferable.
  • a unit represented by the formula (A): a unit represented by the formula (C) 5 to 50 mol%: 50 to 95 mol% is preferable, and 10 to 40 mol%: 60 to 90 mol% is more preferable.
  • the method for forming the layer containing the polymer is not particularly limited, and a known method can be adopted.
  • the layer forming composition containing the said polymer is apply
  • the layer containing the polymer is subjected to at least one of heat treatment and light irradiation treatment.
  • the treatment carried out on the layer containing the polymer may be carried out either by heat treatment or light irradiation treatment, or by both. Moreover, when performing both processing, you may implement by a separate process and may implement simultaneously.
  • the polymerizable group is activated, the reaction proceeds between the polymerizable groups and between the polymerizable group and the resin base material, and a primer layer adhered to the resin base material is formed.
  • the optimum conditions for the heat treatment are selected according to the type of polymer used. Among them, the crosslinking density of the primer layer is increased, and the weather resistance and flexibility of the film mirror are enhanced.
  • the treatment is preferably performed at (preferably 80 to 120 ° C.) for 0.1 to 3 hours (preferably 0.5 to 2 hours).
  • Optimum conditions are selected for the light irradiation treatment depending on the type of polymer used.
  • the exposure density is increased in that the crosslinking density of the primer layer increases and the weather resistance and flexibility of the film mirror increases. preferably 10 ⁇ 8000mJ / cm 2 is more preferably 100 ⁇ 3000mJ / cm 2.
  • the exposure wavelength is preferably 200 to 300 nm.
  • the light source used for exposure is not particularly limited, and examples thereof include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, and a carbon arc lamp.
  • Examples of radiation include electron beams, X-rays, ion beams, and far infrared rays.
  • the unreacted polymer may be appropriately removed from the composition after the heat treatment or light irradiation treatment.
  • the removal method include a method using a solvent.
  • a solvent that dissolves a polymer or an alkali-soluble polymer an alkaline developer (sodium carbonate, sodium bicarbonate, aqueous ammonia, aqueous sodium hydroxide) Etc. can be removed.
  • the thickness of the primer layer is not particularly limited, but is preferably 0.05 to 10 ⁇ m, more preferably 0.3 to 5 ⁇ m, in terms of excellent weather resistance and flexibility of the film mirror.
  • a catalyst provision process is a process of providing a plating catalyst or its precursor to a primer layer.
  • the plating catalyst or its precursor is adsorbed on the interactive group in the primer layer.
  • the plating catalyst or a precursor thereof include those that function as a plating catalyst or an electrode in “step (iii): plating step” described later. Therefore, the plating catalyst or its precursor is determined by the type of plating in the plating process.
  • the plating catalyst for example, electroless plating catalyst used or its precursor is explained in full detail.
  • the electroless plating catalyst is preferably one that can be an active nucleus during electroless plating.
  • Examples thereof include metals having catalytic ability for autocatalytic reduction reaction (known as metals capable of electroless plating having a lower ionization tendency than Ni), and specifically include Pd, Ag, Cu, Ni, Al, Fe, and the like. , Co and the like. Of these, Pd or Ag is preferable because of its high catalytic ability.
  • the electroless plating catalyst precursor those capable of becoming an electroless plating catalyst by a chemical reaction are preferable.
  • the metal ions of the metals mentioned as the electroless plating catalyst are used.
  • the metal ion that is an electroless plating catalyst precursor becomes a zero-valent metal that is an electroless plating catalyst by a reduction reaction.
  • the electroless plating catalyst may be converted into a zero-valent metal by a separate reduction reaction.
  • the plating catalyst precursor may be immersed in an electroless plating bath and changed to a metal (electroless plating catalyst) by a reducing agent in the electroless plating bath.
  • the metal ion which is an electroless-plating catalyst precursor is provided to a primer layer using a metal salt.
  • the metal salt used is not particularly limited as long as it is dissolved in a suitable solvent and dissociated into a metal ion and a base (anion), and M (NO 3 ) n , MCl n , M 2 / n (SO 4 ), M 3 / n (PO 4 ) Pd (OAc) n (M represents an n-valent metal atom), and the like.
  • a metal ion the thing which said metal salt dissociated can be used suitably. Specific examples include Ag ions, Cu ions, Al ions, Ni ions, Co ions, Fe ions, and Pd ions. Among them, those capable of multidentate coordination are preferable, and Ag ions, Cu ions, and Pd ions are particularly preferable in terms of the number of types of functional groups capable of coordination and catalytic ability.
  • the catalyst activation liquid often contains a reducing agent capable of reducing the electroless plating catalyst precursor (mainly metal ions) to a zero-valent metal and a pH adjusting agent for activating the reducing agent.
  • the concentration of the reducing agent with respect to the entire liquid is preferably 0.1 to 10% by mass.
  • the reducing agent it is possible to use a boron-based reducing agent such as sodium borohydride or dimethylamine borane, or a reducing agent such as formaldehyde or hypophosphorous acid. In particular, reduction with an aqueous alkaline solution containing formaldehyde is preferred.
  • the catalyst used in order to perform electroplating directly, without performing electroless plating as a plating catalyst.
  • a catalyst include zero-valent metals, and more specifically, Pd, Ag, Cu, Ni, Al, Fe, Co, and the like.
  • Pd, Ag, and Cu are particularly preferable from the viewpoints of the adsorptive (adhesive) property to interactive groups and the high catalytic ability.
  • a solution containing these for example, a dispersion in which a metal is dispersed in an appropriate dispersion medium, or a metal that has been dissociated by dissolving a metal salt in an appropriate solvent.
  • a solution containing ions is prepared, and the dispersion or solution is applied onto the primer layer, or the resin substrate on which the primer layer is formed is immersed in the dispersion or solution.
  • a plating process is a process of forming a metal reflective layer by performing a plating process with respect to the primer layer to which the plating catalyst or its precursor was provided.
  • the resin base material with a metal reflective layer which has a resin base material, a primer layer, and a metal reflective layer is obtained.
  • the type of plating performed in this step includes electroless plating and electroplating, and can be appropriately selected depending on the function of the plating catalyst applied to the primer layer or the precursor thereof in the catalyst application step. That is, in this step, electroplating may be performed on the primer layer provided with the plating catalyst or its precursor, or electroless plating may be performed.
  • the plating process suitably performed in this process will be described.
  • Electroless plating refers to an operation of depositing a metal by a chemical reaction using a solution in which metal ions to be deposited as a plating are dissolved. Electroless plating is performed, for example, by immersing a resin base material provided with a primer layer provided with an electroless plating catalyst in water after removing excess electroless plating catalyst (metal) and then immersing it in an electroless plating bath. .
  • a known electroless plating bath can be used as the electroless plating bath used.
  • the substrate is It is preferable to immerse in an electroless plating bath after washing to remove excess precursors (such as metal salts). In this case, reduction of the plating catalyst precursor and subsequent electroless plating are performed in the electroless plating bath.
  • a known electroless plating bath can be used as described above.
  • electroplating can be performed on the primer layer provided with the plating catalyst or its precursor.
  • a conventionally known method can be used as the electroplating method in the present invention.
  • a metal used for the electroplating of this process copper, chromium, lead, nickel, gold
  • the formed plating film may be used as an electrode, and electroplating may be further performed.
  • the silver compounds used for plating include silver nitrate, silver acetate, silver sulfate, silver carbonate, silver methanesulfonate, ammonia silver, silver cyanide, silver thiocyanate, silver chloride, silver bromide, silver chromate, and chloranilic acid.
  • Examples thereof include silver, silver salicylate, silver diethyldithiocarbamate, silver diethyldithiocarbamate, and silver p-toluenesulfonate.
  • silver methanesulfonate is preferable because the initial reflectance of the film mirror is further improved.
  • the first resin layer is not particularly limited as long as it is a resin layer.
  • the elastic recovery rate E1 of the first resin layer is preferably 60% or more from the reason that haze increase after the dust test is suppressed, and among them, 80% from the reason that the dust resistance of the film mirror is more excellent. Is less than 75%, more preferably 75% or less, and particularly preferably 70% or less.
  • the elastic recovery rate E1 of the first resin layer is an elastic recovery rate in a direction perpendicular to the main surface of the first resin layer.
  • the elastic recovery rate is determined by measuring “maximum indentation depth (hmax)” and “indentation depth after load removal (hf)” by a nanoindentation method in accordance with an international standard (ISO14577). -Hf) / hmax.
  • the measurement conditions are as follows. ⁇ Indenter: Belkovic triangular pyramid indenter (115 ° opposite angle) ⁇ Maximum load: 1mN ⁇ Maximum load holding time: 1 second ⁇ Temperature: 23 °C The load is set to the maximum load over 10 seconds, held at the maximum load for 1 second, and then the load is completely removed over 10 seconds.
  • the maximum indentation depth (hmax) is the indentation depth when the maximum load is held.
  • the indentation depth (hf) after removing the load is the indentation depth (indentation depth) 10 seconds after the load is completely removed.
  • it can be measured using an ultra micro hardness meter (DUH-201S, manufactured by Shimadzu Corporation).
  • the material for forming the first resin layer is not particularly limited.
  • the material for forming the first resin 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 thermosetting resins such as phenol resin, urea resin (urea resin), phenoxy resin, silicone resin, polyimide resin, diallyl phthalate resin, furan resin, bismaleimide resin, cyanate resin, etc. You may use, and may use 2 or more types together.
  • the expression “(meth) acrylate” in the present application is an expression representing acrylate or methacrylate.
  • a resin having a urethane bond is preferable.
  • a photocurable 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.
  • 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.
  • the polyester polyol (A) is obtained by reacting a polybasic acid and a polyhydric alcohol.
  • a polyhydric alcohol include polytetramethylene glycol (PTMG) and polyoxypropylene diol (PPG).
  • polyoxyethylene diol include polytetramethylene glycol (PTMG) and polyoxypropylene diol (PPG).
  • 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.
  • hydroxyl group-containing (meth) acrylate compound (C) examples 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.
  • the urethane (meth) acrylate resin synthesized using the above-described polyester polyol (A), polyisocyanate (B), and hydroxyl group-containing (meth) acrylate compound (C) commercially available products can be used. May be UV curable urethane acrylate resin manufactured by Nippon Gosei Co., Ltd., for example, UV1700B, UV6300B, UV7600B, etc.
  • the thickness of the first resin layer is not particularly limited, but is preferably 0.1 ⁇ m or more, more preferably 1 ⁇ m or more, and more preferably 5 ⁇ m or more, because the film mirror is more excellent in dust resistance and adhesion resistance. More preferably, it is more preferably 10 ⁇ m or more.
  • the upper limit is not particularly limited, but is usually 100 ⁇ m or less and preferably 50 ⁇ m or less.
  • the method for forming the first resin layer is not particularly limited.
  • ultraviolet irradiation or Examples include a method of curing by heating.
  • a conventionally known coating method such as a gravure coating method, a reverse coating method, a die coating method, a blade coater, a roll coater, an air knife coater, a screen coater, a bar coater, or a curtain coater can be used. .
  • the resin layer forming composition may contain a solvent and various additives in addition to the above-described components.
  • the solvent used in the resin layer forming composition is not particularly limited.
  • water, methanol, ethanol, propanol, alcohol solvents such as ethylene glycol, glycerin, propylene glycol monomethyl ether, acids such as acetic acid, acetone, methyl ethyl ketone.
  • Ketone solvents such as cyclohexanone, amide solvents such as formamide, dimethylacetamide and N-methylpyrrolidone, nitrile solvents such as acetonitrile and propionitrile, ester solvents such as methyl acetate and ethyl acetate, dimethyl carbonate and diethyl carbonate Carbonate solvents such as benzene, toluene, xylene and other aromatic hydrocarbon solvents, ether solvents, glycol solvents, amine solvents, thiol solvents, halogen solvents, etc. And the like. Of these, amide solvents, ketone solvents, nitrile solvents, carbonate solvents, and aromatic hydrocarbon solvents are preferred.
  • acetone dimethylacetamide, methyl ethyl ketone, cyclohexanone, acetonitrile, propionitrile, N- Methyl pyrrolidone, dimethyl carbonate and toluene are preferred.
  • the additive used in the resin layer forming composition examples include a photopolymerization initiator, an antistatic agent, a surface conditioner (for example, a leveling agent, a fluorine-based antifouling additive), an ultraviolet absorber, a light Stabilizers, antioxidants, antifoaming agents, thickeners, antisettling agents, pigments, dispersants, silane couplings and the like can be mentioned.
  • a photopolymerization initiator for example, a leveling agent, a fluorine-based antifouling additive
  • an ultraviolet absorber for example, a leveling agent, a fluorine-based antifouling additive
  • a light Stabilizers antioxidants, antifoaming agents, thickeners, antisettling agents, pigments, dispersants, silane couplings and the like can be mentioned.
  • the resin layer forming composition preferably contains a surface conditioner, such as a fluorine-based antifouling additive (for example, MegaFix RS-75, manufactured by DIC, More preferably, KY-1203 manufactured by Shin-Etsu Chemical Co., Ltd., ZX-049 manufactured by Fuji Kasei Kogyo Co., Ltd.) is contained.
  • a fluorine-based antifouling additive for example, MegaFix RS-75, manufactured by DIC, More preferably, KY-1203 manufactured by Shin-Etsu Chemical Co., Ltd., ZX-049 manufactured by Fuji Kasei Kogyo Co., Ltd.
  • the second resin layer is not particularly limited as long as the elastic recovery rate E2 is a resin layer larger than the elastic recovery rate E1 of the first resin layer.
  • the elastic recovery rate E2 of the second resin layer is an elastic recovery rate in a direction perpendicular to the main surface of the second resin layer.
  • the definition of the elastic recovery rate is the same as that of the first resin layer described above.
  • the elastic recovery rate E2 of the second resin layer is preferably 80% or more, more preferably 90% or more and 100% or less, because the dust resistance of the film mirror is more excellent.
  • the material forming the second resin layer is not particularly limited as long as the elastic recovery rate E2 of the formed second resin layer is larger than the elastic recovery rate E1 of the first resin layer.
  • Specific examples of the material for forming the second resin layer and the method for forming the second resin layer are the same as those of the first resin layer described above.
  • the thickness of the second resin layer is preferably 0.1 ⁇ m or more, and preferably 0.5 ⁇ m or more, from the reason that the increase in haze after the dust test is suppressed and the dust resistance of the film mirror is more excellent. Is more preferably 1.0 ⁇ m or more.
  • the upper limit is not particularly limited, but is usually 100 ⁇ m or less and preferably 50 ⁇ m or less.
  • the ratio of the thickness of the second resin layer to the thickness of the first resin layer is from 0.20 because the dust resistance of the film mirror is more excellent. Is preferably larger, more preferably 0.50 or more.
  • the upper limit is not particularly limited, but is preferably 1.00 or less.
  • the second resin layer is preferably a layer containing a polyrotaxane because the dust resistance of the film mirror is more excellent.
  • the opening of the cyclic molecule is penetrated by a linear molecule in a skewered manner, and a plurality of cyclic molecules include the linear molecule at both ends (both ends of the linear molecule).
  • the polyrotaxane in addition to the molecular complex, is a cross-linked product in which the molecular complexes are cross-linked by a cyclic molecular part, and a weight obtained by polymerizing the molecular complex and another monomer or polymer. It is a concept that includes coalescence.
  • linear molecule The linear molecule constituting the polyrotaxane is not particularly limited as long as it is a molecule or substance that is included in a cyclic molecule and can be integrated non-covalently and is linear.
  • the “linear molecule” refers to a molecule including a polymer and all other substances satisfying the above requirements.
  • linear of “linear molecule” means substantially “linear”. That is, the linear molecule may have a branched chain as long as the cyclic molecule that is the rotor can rotate or the cyclic molecule can slide on the linear molecule. Further, the length of the “straight chain” is not particularly limited as long as the cyclic molecule can slide or move on the linear molecule.
  • linear molecule examples include hydrophilic polymers such as polyvinyl alcohol and polyvinyl pyrrolidone, poly (meth) acrylic acid, cellulose resins (carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, etc.), polyacrylamide, polyalkylene oxide (for example, Polyethylene glycol), polyvinyl acetal resin, polyvinyl methyl ether, polyamine, polyethyleneimine, casein, gelatin, starch, etc.
  • hydrophilic polymers such as polyvinyl alcohol and polyvinyl pyrrolidone, poly (meth) acrylic acid, cellulose resins (carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, etc.), polyacrylamide, polyalkylene oxide (for example, Polyethylene glycol), polyvinyl acetal resin, polyvinyl methyl ether, polyamine, polyethyleneimine, casein, gelatin, starch, etc.
  • hydrophilic polymers such as
  • polystyrene resins such as polymethyl methacrylate, (meth) acrylic acid ester copolymers, acrylic resins such as acrylonitrile-methyl acrylate copolymer resins, polycarbonate resins, polyurethane resins, vinyl chloride-vinyl acetate copolymer resins, polyvinyl butyral Resin, etc .; and derivatives or modified products thereof.
  • a hydrophilic polymer is preferable because the dust resistance of the film mirror is more excellent
  • polyethylene glycol, polypropylene glycol, a copolymer of polyethylene glycol and polypropylene glycol, polyisoprene, polyisobutylene, polybutadiene, Tetrahydrofuran, polydimethylsiloxane, polyethylene, or polypropylene is more preferable
  • polyethylene glycol, polyethylene glycol, and a copolymer of polyethylene glycol and polypropylene glycol are further preferable, and polyethylene glycol is particularly preferable.
  • the above linear molecule itself should have a high breaking strength.
  • the breaking strength of the polyrotaxane-containing layer depends on other factors such as the bond strength between the blocking group and the linear molecule, the bond strength between the cyclic molecule and other components of the second resin layer, and the bond strength between the cyclic molecules. However, if the linear molecule itself has a high breaking strength, a higher breaking strength can be provided.
  • the linear molecule has a molecular weight of 1,000 or more, such as 1,000 to 1,000,000, preferably 5,000 or more, such as 5,000 to 1,000,000 or 5,000 to 500,000. 000, more preferably 10,000 or more, for example, 10,000 to 1,000,000, 10,000 to 500,000 or 10,000 to 300,000.
  • the linear molecule is preferably a biodegradable molecule from the viewpoint of influence on the environment.
  • the linear molecule preferably has reactive groups at both ends. By having this reactive group, it can react easily with a blocking group.
  • a reactive group is dependent on the block group to be used, a hydroxyl group, an amino group, a carboxyl group, a thiol group, an aldehyde group etc. can be mentioned, for example.
  • cyclic molecule As the cyclic molecule constituting the polyrotaxane, any cyclic molecule can be used as long as it is a cyclic molecule that can be included in the linear molecule.
  • cyclic molecule refers to various cyclic substances including cyclic molecules.
  • the “cyclic molecule” refers to a molecule or substance that is substantially cyclic. In other words, “substantially ring-shaped” means that the letter “C” is not completely closed, such as the letter “C”, and one end and the other end of the letter “C” are not joined. It is intended to include those having overlapping spiral structures.
  • Examples of the cyclic molecule include various cyclodextrins (for example, ⁇ -cyclodextrin, ⁇ -cyclodextrin, ⁇ -cyclodextrin, dimethylcyclodextrin and glucosylcyclodextrin, derivatives or modified products thereof), crown ethers, Examples thereof include benzocrowns, dibenzocrowns, dicyclohexanocrowns, and derivatives or modified products thereof.
  • cyclodextrins for example, ⁇ -cyclodextrin, ⁇ -cyclodextrin, ⁇ -cyclodextrin, dimethylcyclodextrin and glucosylcyclodextrin, derivatives or modified products thereof
  • crown ethers examples thereof include benzocrowns, dibenzocrowns, dicyclohexanocrowns, and derivatives or modified products thereof.
  • the above cyclodextrins and crown ethers differ in the size of the opening of the cyclic molecule depending on the type. Therefore, the type of linear molecule to be used, specifically, when the linear molecule to be used is assumed to be cylindrical, the cyclic molecule to be used depends on the diameter of the cross section of the cylinder, the hydrophobicity or hydrophilicity of the linear molecule, etc. Can be selected. When a cyclic molecule having a relatively large opening and a cylindrical linear molecule having a relatively small diameter are used, two or more linear molecules can be included in the opening of the cyclic molecule. . Of these, cyclodextrins (especially ⁇ -cyclodextrin) are preferable from the viewpoint of environmental impact.
  • the number of cyclic molecules included (inclusion amount) by the linear molecule is preferably 0.05 to 0.60, with the maximum inclusion amount being 1. .10 to 0.50 is more preferable, and 0.20 to 0.40 is more preferable.
  • the cyclodextrin is one in which at least one of the hydroxyl groups is substituted (modified) by a hydrophobic group because the antifouling property of the film mirror is excellent. It is preferable.
  • hydrophobic groups include, for example, alkyl groups, benzyl groups, benzene derivative-containing groups, acyl groups, silyl groups, trityl groups, nitrate ester groups, tosyl groups, fluorine atom-containing organic groups, unsaturated double bond groups, etc. Is mentioned.
  • the unsaturated double bond group is an acyl group (especially acetyl group) or a fluorine atom containing organic group from the reason which the antifouling property of a film mirror is more excellent.
  • an acyl group especially acetyl group
  • a fluorine atom containing organic group from the reason which the antifouling property of a film mirror is more excellent.
  • Specific examples of the unsaturated double bond group are the same as those of the unsaturated double bond group described later.
  • the fluorine atom-containing organic group is not particularly limited as long as it is a monovalent organic group containing a fluorine atom.
  • the fluorine atom-containing organic group may contain a hetero atom (for example, an oxygen atom) other than the fluorine atom.
  • the monovalent organic group is not particularly limited, and specific examples thereof include aliphatic hydrocarbon groups (for example, alkyl groups, alkenyl groups, alkynyl groups), aromatic hydrocarbon groups (for example, aryl groups), complex Examples thereof include a ring group (for example, an azole group and a pyridyl group).
  • the fluorine atom-containing organic group is preferably a group represented by the following formula (3) because the antifouling property of the film mirror is further excellent.
  • R 31 represents an alkyl group having a fluorine atom, and specific examples thereof include a fluoromethyl group, a difluoromethyl group, and a trifluoromethyl group.
  • R 32 represents a monovalent hydrocarbon group which may be branched, and specific examples thereof include an alkyl group having 1 to 30 carbon atoms, an alkenyl group and an alkynyl group. Of these, an alkyl group having 1 to 10 carbon atoms is preferable.
  • the definitions and specific examples of L 31 and L 32 are the same as L 2 in the above formula (1).
  • L 31 is preferably an alkylene group.
  • L 32 is preferably a group represented by the following formula (4).
  • * represents a bonding position.
  • Xa and Xb represent an oxygen atom or a sulfur atom each independently.
  • * represents a bonding position.
  • the degree of modification with the hydrophobic group is preferably 0.02 or more (1 or less), more preferably 0.04 or more, and 0 if the maximum number of cyclodextrin hydroxyl groups that can be modified is 1. More preferably, it is 0.06 or more.
  • the maximum number that the hydroxyl groups of cyclodextrin can be modified is, in other words, the total number of hydroxyl groups that cyclodextrin had before modification.
  • the degree of modification is the ratio of the number of modified hydroxyl groups to the total number of hydroxyl groups.
  • any group may be used as long as the cyclic molecule maintains a form in which the cyclic molecule is skewered with a linear molecule.
  • examples of such a group include a group having “bulkiness” and / or a group having “ionicity”.
  • the “group” means various groups including a molecular group and a polymer group.
  • the “ionicity” of the group having “ionicity” and the “ionicity” of the cyclic molecule influence each other, for example, by repulsion, the cyclic molecule is skewered by linear molecules. It is possible to retain the form.
  • the blocking group may be a polymer main chain or a side chain as long as it retains a skewered form as described above.
  • the blocking group is the polymer A
  • the polyrotaxane is included as a matrix and the polymer A is included in a part thereof. There may be.
  • a composite material having a combination of the characteristics of the polyrotaxane and the characteristics of the polymer A can be formed.
  • the blocking group include dinitrophenyl groups such as 2,4-dinitrophenyl group and 3,5-dinitrophenyl group, cyclodextrins, adamantane groups, trityl groups, fluoresceins and pyrenes, and these Or derivatives thereof.
  • the blocking group may be substituted (modified) with the hydrophobic group.
  • the method for synthesizing the polyrotaxane is not particularly limited.
  • the polyrotaxane can be synthesized by the methods described in Japanese Patent No. 2810264 and Japanese Patent No. 3475252.
  • ⁇ -cyclodextrin as a cyclic molecule polyethylene glycol as a linear molecule, 2,4-dinitrophenyl group as a blocking group, acetyl group as a hydrophobic group, and acryloyl group as an unsaturated double bond group are used.
  • it can be synthesized as follows.
  • both ends of polyethylene glycol are modified with amino groups to obtain a polyethylene glycol derivative.
  • a pseudo-polyrotaxane is prepared by mixing ⁇ -cyclodextrin and a polyethylene glycol derivative.
  • the inclusion time is 1 to 48 hours, for example, so that the inclusion amount is 0.001 to 0.6 with respect to 1, and the mixing temperature is 0 ° C. to It can be 100 degreeC.
  • ⁇ -cyclodextrin a maximum of 230 ⁇ -cyclodextrins can be packaged with respect to the average molecular weight of polyethylene glycol of 20,000. Therefore, this value is the maximum inclusion amount.
  • the above condition is that, using an average molecular weight of 20,000 of polyethylene glycol, ⁇ -cyclodextrin has an average of 60 to 65 (63), that is, a maximum inclusion amount of 0.26 to 0.29 (0.28). This is a condition for inclusion by value.
  • the inclusion amount of ⁇ -cyclodextrin can be confirmed by NMR, light absorption, elemental analysis or the like.
  • the obtained pseudo polyrotaxane is reacted with 2,4-dinitrofluorobenzene dissolved in DMF to obtain a polyrotaxane having a blocking group introduced therein.
  • the above-mentioned modification of the cyclodextrins with a hydrophobic group may be performed on the synthesized polyrotaxane or may be performed on the cyclodextrins in advance before synthesizing the polyrotaxane.
  • Examples of the method of modifying with a acetyl group as a hydrophobic group include a method of modifying a hydroxyl group of cyclodextrin with acetic anhydride.
  • the polyrotaxane preferably has at least one group selected from the group consisting of an acyl group (particularly an acetyl group) and a fluorine atom-containing organic group in the cyclic molecule because the antifouling property of the film mirror is excellent. More preferably, it has a fluorine atom-containing organic group, more preferably an acyl group (particularly an acetyl group) and a fluorine atom-containing organic group.
  • the content of the polyrotaxane in the second resin layer is preferably 5% by mass or more, more preferably 10% by mass or more, and more preferably 20% by mass or more because the dust resistance of the film mirror is more excellent. More preferably, it is more preferably 50% by mass or more, and particularly preferably 90% by mass or more.
  • the content of the polyrotaxane having a fluorine atom-containing organic group in the second resin layer is preferably 0.1 to 50% by mass because the dust resistance of the film mirror is more excellent, and 0.5% by mass. % Or more and less than 30% by mass, more preferably 1 to 20% by mass, particularly preferably 10 to 20% by mass.
  • the content of the polyrotaxane can be determined by an NMR method (solution NMR method, solid NMR method), an X-ray diffraction method described in JP 2010-261134 A, or the like.
  • NMR method solution NMR method, solid NMR method
  • X-ray diffraction method described in JP 2010-261134 A
  • the second resin layer is formed by curing a resin layer-forming composition containing a polyrotaxane having at least one of a reactive group and a polymerizable group in a cyclic molecule described later.
  • the second resin layer The content of polyrotaxane in the composition refers to the content (% by mass) of the polyrotaxane based on the total solid content in the resin layer forming composition used.
  • a second resin layer is formed by curing a resin layer forming composition containing a polyrotaxane having at least one of a reactive group and a polymerizable group in a cyclic molecule, which will be described later, the second resin
  • the content of the polyrotaxane having a fluorine atom-containing organic group in the layer refers to the content (% by mass) of the polyrotaxane having a fluorine atom-containing organic group with respect to the total solid content in the used resin layer forming composition.
  • the method for forming the second resin layer containing the polyrotaxane is not particularly limited.
  • a resin layer forming composition containing a polyrotaxane having a reactive group in a cyclic molecule and a solvent is applied on the first resin layer.
  • a method of forming the second resin layer by curing at least one of heat treatment and light irradiation treatment on the applied resin layer forming composition.
  • unreacted components may be appropriately removed from the composition after the heat treatment or light irradiation treatment using a solvent.
  • the solvent used for the resin layer forming composition is the same as that of the first resin layer described above.
  • the coating method, the heat processing method, and the light irradiation processing method it is the same as that of the primer layer mentioned above.
  • the reactive group are the same as the reactive group of the linear molecule described above. Among these, a hydroxyl group (particularly a polycaprolactone group) or a polymerizable group is preferable, and a polymerizable group is more preferable.
  • the polycaprolactone group is a group represented by * — (CO—C 5 H 10 O) n —H (*: bond position, n: integer).
  • Specific examples of the polymerizable group are the same as those of the primer layer described above. Of these, an unsaturated double bond group is preferable, and an acryloyl group and a methacryloyl group are more preferable.
  • the polyrotaxane contained in the resin layer forming composition is preferably a polyrotaxane having an unsaturated double bond group in the cyclic molecule.
  • a method for introducing an unsaturated double bond group into a cyclic molecule for example, the following methods can be used. That is, a method by carbamate bond formation with isocyanate compounds, etc .; a method by ester bond formation with carboxylic acid compounds, acid chloride compounds or acid anhydrides; a method by silyl ether bond formation with silane compounds, etc .; a carbonate bond formation with chlorocarbonic acid compounds, etc. The method by etc. can be mentioned.
  • a (meth) acryloyl group is introduced as an unsaturated double bond group via a carbamoyl bond
  • the polyrotaxane is dissolved in a dehydrating solvent such as DMSO or DMF, and a (meth) acryloylating agent having an isocyanate group is added.
  • a dehydrating solvent such as DMSO or DMF
  • a (meth) acryloylating agent having an isocyanate group is added.
  • a (meth) acrylating agent having an active group such as a glycidyl group or an acid chloride can also be used.
  • the step of substituting the hydroxyl group of the cyclic molecule with an unsaturated double bond group may be before the step of preparing the pseudopolyrotaxane, between the steps, or after the step. Further, it may be before the step of preparing the polyrotaxane by introducing a blocking group into the pseudopolyrotaxane, between the steps, or after the step. Furthermore, when the polyrotaxane is a polyrotaxane having a reactive group in the cyclic molecule, it may be before the process of reacting the polyrotaxanes with each other or between the processes. It can also be provided at these two or more times.
  • the substitution step is preferably performed after the polyrotaxane is prepared by introducing a blocking group into the pseudopolyrotaxane and before the polyrotaxane is reacted with each other.
  • the conditions used in the substitution step depend on the unsaturated double bond group to be substituted, but are not particularly limited, and various reaction methods and reaction conditions can be used.
  • composition for resin layer formation contains the monomer which has a polymeric group, it hardens
  • Specific examples of the polymerizable group are the same as those of the primer layer described above.
  • Examples of the monomer having a polymerizable group include esters of polyhydric alcohol and (meth) acrylic acid [for example, ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate 1,4-cyclohexanediacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3-cyclo Xant
  • a curing agent such as a polyisocyanate compound may be used.
  • the polyisocyanate compound include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, phenylene diisocyanate, xylene diisocyanate, diphenylmethane-4,4′-diisocyanate, naphthylene-1,5-diisocyanate, and the like.
  • Hydrogenated compounds ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 1-methyl-2,4-diisocyanate cyclohexane, 1-methyl-2,6-diisocyanate cyclohexane, dicyclohexylmethane diisocyanate, tri Examples include phenylmethane triisocyanate.
  • a polymerization initiator such as a photo radical polymerization initiator or a thermal radical polymerization initiator may be used.
  • photo radical polymerization initiators examples include acetophenones, benzoins, benzophenones (1-hydroxy-1,2,3,4,5,6-hexahydrobenzophenone, etc.), phosphine oxides, ketals, anthraquinones, thioxanthones , Azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds, fluoroamine compounds, aromatic sulfoniums, lophine dimers, onium salts, borate salts, active esters, active halogens , Inorganic complexes, and coumarins.
  • thermal radical polymerization initiator for example, organic or inorganic peroxides, organic azo or diazo compounds can be used.
  • the content of the polyrotaxane relative to the total solid content in the composition for forming a resin layer is preferably 5% by mass or more, more preferably 10% by mass or more, because the dust resistance of the film mirror is more excellent. 20% by mass or more, more preferably 50% by mass or more, and particularly preferably 90% by mass or more. Further, the content of the polyrotaxane having a fluorine atom-containing organic group with respect to the total solid content in the resin layer forming composition is excellent in the antifouling property of the film mirror and more excellent in dust resistance. It is preferably 50% by mass, more preferably 0.5% by mass or more and less than 30% by mass, further preferably 1 to 20% by mass, and particularly preferably 10 to 20% by mass.
  • the film mirror of the present invention may have an ultraviolet reflecting layer, a discoloration preventing layer, an adhesive layer and the like as long as the effects of the present invention are not impaired.
  • the ultraviolet reflecting layer include a layer formed by combining two materials having different refractive indexes such as indium tin oxide (ITO), silicon oxide (SiO 2 ), and aluminum oxide (Al 2 O 3 ). Can be mentioned.
  • Examples of the material used for the discoloration preventing layer include amines, compounds having a pyrrole ring, compounds having a triazole ring, compounds having a pyrazole ring, compounds having a thiazole ring, compounds having an imidazole ring, and compounds having an indazole ring , A copper chelate compound, thiourea, a compound having a mercapto group, a hindered phenol-based antioxidant, a hindered amine-based antioxidant, a sulfur-based antioxidant, and a phosphite-based antioxidant.
  • the type of adhesive used for the adhesive layer is not particularly limited as long as it satisfies the adhesion, and specific examples thereof include silicone resins, urethane resins, polyester resins, acrylic resins, and melamine resins. Examples thereof include resins, epoxy resins, polyamide resins, vinyl chloride resins, vinyl chloride vinyl acetate copolymer resins, and the like. These may be used alone or in combination of two or more. Among these, from the viewpoint of weather resistance, an epoxy resin, an acrylic resin, a urethane resin, or a silicone resin is preferable.
  • the thickness of the adhesive layer is preferably from 0.01 to 50 ⁇ m, more preferably from 0.1 to 20 ⁇ m, from the viewpoints of adhesion, reflectance, and the like.
  • the film mirror of the present invention can be used for various applications (for example, a reflection plate for a display, a reflection member for illumination, a solar member such as a solar cell or solar power generation). Especially, it can use preferably in the objective (for sunlight condensing) which condenses sunlight.
  • the precipitate was taken out and dried in vacuum at 40 ° C. for 3 hours.
  • the resulting product was dissolved in 20 ml of methylene chloride. This solution was added dropwise to 10 ml of ethylenediamine over 3 hours, followed by stirring for 40 minutes.
  • the obtained reaction product was subjected to a rotary evaporator to remove methylene chloride, then dissolved in 50 ml of water, put into a dialysis tube (molecular weight cut off 8,000), and dialyzed in water for 3 days.
  • the obtained dialyzate was dried with a rotary evaporator, and this dried product was dissolved in 20 ml of methylene chloride and reprecipitated with 180 ml of diethyl ether.
  • the liquid having a precipitate was centrifuged at 100,000 rpm for 5 minutes and vacuum dried at 40 ° C. for 2 hours to obtain 2.83 g of polyethylene glycol bisamine (number average molecular weight 20,000).
  • the obtained polyrotaxane a1 was subjected to ultraviolet light absorption measurement and 1 H-NMR measurement to calculate the inclusion amount of ⁇ -cyclodextrin.
  • the inclusion amount was 72.
  • the inclusion amount of cyclodextrin was calculated by measuring the molar extinction coefficient at 360 nm of each of the synthesized inclusion compound and 2,4-dinitroaniline.
  • 1 H-NMR measurement it was calculated from the integral ratio of the hydrogen atom of the polyethylene glycol moiety and the hydrogen atom of the cyclodextrin moiety.
  • the polyrotaxane a1 (1 g) was dissolved in 50 g of a lithium chloride / N, N-dimethylacetamide 8% solution. Thereto were added 6.7 g of acetic anhydride, 5.2 g of pyridine, and 100 mg of N, N-dimethylaminopyridine, and the mixture was stirred overnight at room temperature. The reaction solution was poured into methanol, and the precipitated solid was separated by centrifugation. The separated solid was dried and then dissolved in acetone.
  • polyrotaxane (1.2 g) in which a part of the hydroxyl groups of cyclodextrin was modified with acetyl groups. Let the obtained polyrotaxane be polyrotaxane a2.
  • the polyrotaxane a2 was subjected to 1 H-NMR measurement, and the amount of acetyl group introduced (modification degree) was calculated to be 75%.
  • the polyrotaxane a2 (1 g) was dissolved in 50 g of a lithium chloride / N, N-dimethylacetamide 8% solution. Thereto were added 5.9 g of acrylic acid chloride, 5.2 g of pyridine, and 100 mg of N, N-dimethylaminopyridine, and the mixture was stirred at room temperature overnight. The reaction solution was poured into methanol, and the precipitated solid was separated by centrifugation. The separated solid was dried and then dissolved in acetone.
  • polyrotaxane (0.8 g) in which the hydroxyl group of cyclodextrin was modified with an acryloyl group and an acetyl group.
  • the obtained polyrotaxane is referred to as crosslinkable polyrotaxane A.
  • compositions A1 to A5 and B1 which are resin layer forming compositions.
  • compositions A1 to A5 and B1 which are resin layer forming compositions.
  • composition A4 after mixing each component and stirring for 30 minutes, it filtered with the polypropylene filter with the hole diameter of 1.0 micrometer, and prepared composition A4.
  • composition B1 the polyrotaxane content with respect to the total solid content is 98% by mass.
  • composition A6 (Resin layer forming composition: Composition A6) Add ZX-049 (Fuji Kasei Kogyo Co., Ltd.) as a fluorine-based leveling agent to Rio Duras LCH (Toyo Ink Co., Ltd.) in an amount of 0.1% by mass based on the resin solids, Prepared. Let the prepared composition for resin layer formation be the composition A6.
  • Example 1 (Formation of primer layer) On a PET support (A4300, manufactured by Toyobo Co., Ltd.), a solution containing an acrylic polymer represented by formula (5) was applied by spin coating so as to have a thickness of 500 nm, and dried at 80 ° C. for 5 minutes. To obtain a coating film.
  • the numerical value in Formula (5) represents the ratio (mol%) of each unit.
  • a method for synthesizing the acrylic polymer represented by the formula (5) is as follows. 1 L of ethyl acetate and 159 g of 2-aminoethanol were placed in a 2 L three-necked flask and cooled in an ice bath. Thereto, 150 g of 2-bromoisobutyric acid bromide was added dropwise while adjusting the internal temperature to 20 ° C. or less. Thereafter, the internal temperature was raised to room temperature (25 ° C.) and reacted for 2 hours. After completion of the reaction, 300 mL of distilled water was added to stop the reaction.
  • the ethyl acetate layer was washed four times with 300 mL of distilled water, dried over magnesium sulfate, and 80 g of raw material A was obtained by distilling off ethyl acetate.
  • 47.4 g of raw material A, 22 g of pyridine, and 150 mL of ethyl acetate were placed in a 500 mL three-necked flask and cooled in an ice bath.
  • 25 g of acrylic acid chloride was added dropwise while adjusting the internal temperature to 20 ° C. or lower. Then, it was raised to room temperature and reacted for 3 hours. After completion of the reaction, 300 mL of distilled water was added to stop the reaction.
  • the preparation method of the solution containing the acrylic polymer represented by Formula (5) is as follows.
  • the acrylic polymer represented by formula (5) (7 parts by mass), 1-methoxy-2-propanol (74 parts by mass), and water (19 parts by mass) were mixed.
  • a polymerization initiator (Esacure KTO-46, manufactured by Lamberdy) (0.35 parts by mass) was added and mixed by stirring to obtain a solution containing an acrylic polymer represented by formula (5).
  • the coating film is irradiated with a cumulative exposure amount of 1000 mJ / cm 2 at a wavelength of 254 nm, A primer layer (thickness: 500 nm) was formed. Development was performed to remove unreacted polymer from the primer layer. Specifically, the PET support with a primer layer was immersed in a 1 wt% aqueous sodium hydrogen carbonate solution for 5 minutes. Thereafter, it was washed with pure water.
  • the PET support with primer layer was immersed in a 1 wt% aqueous silver nitrate solution for 5 minutes and then washed with pure water to obtain a PET support with primer layer to which an electroless plating catalyst precursor (silver ions) was applied. Obtained. Further, the obtained resin substrate with a primer layer was immersed in an alkaline aqueous solution (pH 12.5) (corresponding to a reducing agent) containing 0.14 wt% NaOH and 0.25 wt% formalin for 1 minute, and then purified. By washing with water, a PET support with a primer layer provided with a reduced metal (silver) was obtained.
  • an electroless plating catalyst precursor silver ions
  • the following electroplating process was performed with respect to the primer layer provided with the reduced metal (silver), and a metal (silver) reflective layer having a thickness of 100 nm was formed on the primer layer.
  • a metal (silver) reflective layer having a thickness of 100 nm was formed on the primer layer.
  • Dyne Silver Bright PL50 manufactured by Daiwa Kasei Co., Ltd.
  • the pH was adjusted to 9.0 with 8M potassium hydroxide.
  • a PET support with a primer layer having a reduced metal surface was immersed in an electroplating solution, plated at 0.5 A / dm 2 for 15 seconds, and then washed by pouring with pure water for 1 minute.
  • the composition A1 was coated on the metal reflective layer with an applicator so that the thickness of the cured resin layer was 12 ⁇ m. Thereafter, the film was dried at 80 ° C. for 2 minutes, and further cured by UV irradiation under a nitrogen purge to form a first resin layer.
  • Adhesion resistance The obtained film mirror was subjected to a dust test which will be described later, and the surface of the film mirror before removing the alumina particles adhering to the surface of the film mirror was visually observed, and the adhesion resistance was evaluated according to the following criteria. The results are shown in Table 2. A: Alumina particles are not confirmed on the surface of the film mirror, or are confirmed on a part of the surface. B: Alumina particles are observed on the entire surface of the film mirror.
  • the sand dust test was performed according to the “sand drop wear test method” described in JIS H 8503: 1989. Specifically, the obtained film mirror was cut into a 3 cm square and fixed so that the alumina particles collided with the surface of the film mirror from an angle of 45 degrees, and then 200 g of alumina particles were freely dropped from a height of 100 cm. And collided. Thereafter, alumina particles adhering to the surface of the film mirror were removed.
  • Example 2 A film mirror was produced according to the same procedure as in Example 1 except that the first resin layer was formed using the composition A2 instead of the composition A1. The obtained film mirror was subjected to various evaluations according to the same procedure as in Example 1. The results are shown in Table 2.
  • Example 3 A film mirror was produced according to the same procedure as in Example 1 except that the thickness after curing of the first resin layer was 14.5 ⁇ m and the thickness after curing of the second resin layer was 0.5 ⁇ m. The obtained film mirror was subjected to various evaluations according to the same procedure as in Example 1. The results are shown in Table 2.
  • Example 4 A film mirror was produced according to the same procedure as in Example 1 except that the thickness after curing of the first resin layer was 14.8 ⁇ m and the thickness after curing of the second resin layer was 0.2 ⁇ m. The obtained film mirror was subjected to various evaluations according to the same procedure as in Example 1. The results are shown in Table 2.
  • Example 5 A film mirror was produced according to the same procedure as in Example 1 except that the second resin layer was formed using the composition A2 instead of the composition B1. The obtained film mirror was subjected to various evaluations according to the same procedure as in Example 1. The results are shown in Table 2.
  • Example 6 A film mirror was produced according to the same procedure as in Example 1 except that the first resin layer was formed using the composition A3 instead of the composition A1. The obtained film mirror was subjected to various evaluations according to the same procedure as in Example 1. The results are shown in Table 2.
  • Example 7 Example 1 except that the first resin layer was formed using the composition A4 instead of the composition A1, and the second resin layer was formed using the composition A5 instead of the composition B1.
  • a film mirror was manufactured according to the same procedure. The obtained film mirror was subjected to various evaluations according to the same procedure as in Example 1. The results are shown in Table 2.
  • Example 1 except that the first resin layer was formed using the composition B1 instead of the composition A1, and the second resin layer was formed using the composition A1 instead of the composition B1.
  • a film mirror was manufactured according to the same procedure. The obtained film mirror was subjected to various evaluations according to the same procedure as in Example 1. The results are shown in Table 2.
  • Example 1 except that the first resin layer was formed using the composition A2 instead of the composition A1, and the second resin layer was formed using the composition A1 instead of the composition B1.
  • a film mirror was manufactured according to the same procedure. The obtained film mirror was subjected to various evaluations according to the same procedure as in Example 1. The results are shown in Table 2.
  • Example 3 According to the same procedure as in Example 1, a PET support on which a metal (silver) reflective layer was formed was obtained. Next, the composition A6 was coated on the metal reflective layer with an applicator so that the cured resin layer had a thickness of 15 ⁇ m. Thereafter, it was dried at 80 ° C. for 2 minutes, and further cured by UV irradiation under a nitrogen purge to form a resin layer. Thus, a film mirror was manufactured. In addition, the obtained film mirror is a film mirror provided only with the resin layer formed from composition A6 as a resin layer. The obtained film mirror was subjected to various evaluations according to the same procedure as in Example 1. The results are shown in Table 2.
  • ⁇ Comparative example 4> According to the same procedure as in Example 1, a PET support on which a metal (silver) reflective layer was formed was obtained. Next, the composition B1 was coated on the metal reflective layer with an applicator so that the cured resin layer had a thickness of 15 ⁇ m. Thereafter, it was dried at 80 ° C. for 2 minutes, and further cured by UV irradiation under a nitrogen purge to form a resin layer. Thus, a film mirror was manufactured. In addition, the obtained film mirror is a film mirror provided only with the resin layer formed from composition B1 as a resin layer. The obtained film mirror was subjected to various evaluations according to the same procedure as in Example 1. The results are shown in Table 2.
  • Example 1 in which E2-E1 was 25% or more showed further excellent dust resistance.
  • Example 1 in which the elastic recovery rate of the second resin layer was 90% or more showed more excellent dust resistance.
  • Comparative Examples 1 and 2 in which two resin layers having different elastic recovery rates are provided on the resin base with a metal reflective layer, but the elastic recovery rate of the second resin layer is equal to or lower than the elastic recovery rate of the first resin layer are as follows. It was inferior to the examples of the present application in terms of dust resistance.

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Abstract

La présente invention vise à proposer un miroir en film qui n'est pas sensible à l'adhésion de poussière ou analogues et dont la diminution de réflectance est réduite même si le miroir en film est exposé à la poussière. Un miroir en film selon la présente invention comprend, de manière séquentielle, une base en résine avec une couche réfléchissante métallique, une première couche de résine et une seconde couche de résine, dans cet ordre. Le rapport de restitution de module élastique (E2) de la seconde couche de résine est supérieur au rapport de restitution de module élastique (E1) de la première couche de résine.
PCT/JP2014/058573 2013-03-28 2014-03-26 Miroir en film Ceased WO2014157355A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016193611A1 (fr) * 2015-06-02 2016-12-08 Saint-Gobain Glass France Miroir á durabilité améliorée
JP2019065066A (ja) * 2017-09-28 2019-04-25 株式会社ネオス 硬化性組成物および硬化被膜の製造方法ならびに樹脂成形物品

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022025619A (ja) * 2020-07-29 2022-02-10 三菱ケミカル株式会社 硬化膜及び積層体、並びにこれらの製造方法

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JPH0313638U (fr) * 1989-06-26 1991-02-12
JP2010034513A (ja) * 2008-07-02 2010-02-12 Fujifilm Corp インプリント用硬化性組成物、これを用いた硬化物およびその製造方法、並びに、液晶表示装置用部材
JP2010144351A (ja) * 2008-12-16 2010-07-01 Aibii:Kk 浴室内汚染ガラス面再生処理方法、および再生ガラス面保守方法
JP2010237415A (ja) * 2009-03-31 2010-10-21 Konica Minolta Opto Inc 紫外反射膜を有するフィルムミラー
JP2012008166A (ja) * 2010-06-22 2012-01-12 Konica Minolta Opto Inc 太陽熱発電用フィルムミラー、太陽熱発電用フィルムミラーの製造方法及び、太陽光発電用反射装置
WO2012026312A1 (fr) * 2010-08-25 2012-03-01 コニカミノルタオプト株式会社 Film miroir pour la conversion thermodynamique, procédé pour la production d'un film miroir pour la conversion thermodynamique et dispositif réfléchissant pour la conversion thermodynamique

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0313638U (fr) * 1989-06-26 1991-02-12
JP2010034513A (ja) * 2008-07-02 2010-02-12 Fujifilm Corp インプリント用硬化性組成物、これを用いた硬化物およびその製造方法、並びに、液晶表示装置用部材
JP2010144351A (ja) * 2008-12-16 2010-07-01 Aibii:Kk 浴室内汚染ガラス面再生処理方法、および再生ガラス面保守方法
JP2010237415A (ja) * 2009-03-31 2010-10-21 Konica Minolta Opto Inc 紫外反射膜を有するフィルムミラー
JP2012008166A (ja) * 2010-06-22 2012-01-12 Konica Minolta Opto Inc 太陽熱発電用フィルムミラー、太陽熱発電用フィルムミラーの製造方法及び、太陽光発電用反射装置
WO2012026312A1 (fr) * 2010-08-25 2012-03-01 コニカミノルタオプト株式会社 Film miroir pour la conversion thermodynamique, procédé pour la production d'un film miroir pour la conversion thermodynamique et dispositif réfléchissant pour la conversion thermodynamique

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016193611A1 (fr) * 2015-06-02 2016-12-08 Saint-Gobain Glass France Miroir á durabilité améliorée
FR3037060A1 (fr) * 2015-06-02 2016-12-09 Saint Gobain Miroir a durabilite amelioree
US10746902B2 (en) 2015-06-02 2020-08-18 Saint-Gobain Glass France Mirror with improved durability
JP2019065066A (ja) * 2017-09-28 2019-04-25 株式会社ネオス 硬化性組成物および硬化被膜の製造方法ならびに樹脂成形物品

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