WO2014148366A1 - Film réflecteur de lumière et son procédé de fabrication - Google Patents

Film réflecteur de lumière et son procédé de fabrication Download PDF

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Publication number
WO2014148366A1
WO2014148366A1 PCT/JP2014/056789 JP2014056789W WO2014148366A1 WO 2014148366 A1 WO2014148366 A1 WO 2014148366A1 JP 2014056789 W JP2014056789 W JP 2014056789W WO 2014148366 A1 WO2014148366 A1 WO 2014148366A1
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Prior art keywords
refractive index
index layer
layer
high refractive
light reflecting
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English (en)
Japanese (ja)
Inventor
晃純 木村
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Konica Minolta Inc
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Konica Minolta Inc
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Priority to JP2015506735A priority Critical patent/JPWO2014148366A1/ja
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/26—Reflecting filters
    • 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
    • B32B7/023—Optical properties
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/08—Mirrors
    • G02B5/0816—Multilayer mirrors, i.e. having two or more reflecting layers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/28—Interference filters
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/418—Refractive

Definitions

  • the present invention relates to a light reflecting film and a method for producing the same. More specifically, the present invention relates to a light reflecting film having improved reflection characteristics and a method for producing the same.
  • a laminated film consisting of a structure in which a high refractive index layer and a low refractive index layer are alternately laminated is used by using a dry film forming method such as a vapor deposition method or a sputtering method.
  • a method of forming has been proposed.
  • the wavelength range of the light beam to be reflected can be selected by appropriately selecting the refractive index, the film thickness, the laminated structure, and the like of the high refractive index layer and the low refractive index layer.
  • the dry imitation method has a problem that the vacuum device used for formation becomes large, the manufacturing cost is high, and it is difficult to increase the area, and the base material is limited to a heat-resistant material. .
  • Patent Document 1 a high refractive index layer coating liquid in which a thermosetting silicone resin containing a metal compound fine particle such as a metal oxide or an ultraviolet curable acrylic resin is dispersed in an organic solvent, a bar coater is used.
  • a method of forming a transparent laminate by applying onto a substrate by a conventional wet coating method is disclosed.
  • Patent Document 2 a coating composition for a high refractive index containing rutile-type titanium oxide, a heterocyclic nitrogen compound, a binder precursor and an organic solvent is formed by a wet coating method using a bar coater.
  • a method of forming a transparent laminate by coating on it is disclosed.
  • the light reflection film for example, in application to be attached to a window glass, for example, when shielding heat rays, not only an excellent infrared light shielding effect, but also transparency and weather resistance, etc. Performance is also required.
  • Patent Document 3 a heat ray blocking material (infrared shielding film) is applied by a method in which a slurry of spherical rutile-type titanium oxide particles and a slurry of spherical colloidal silica sol are dissolved and applied alternately, that is, by a coating method. A method of manufacturing is described. According to Patent Document 3, it is described that the obtained heat ray blocking material has sufficient heat ray blocking performance and has transparency.
  • a high refractive index layer and a low refractive index layer made of a water-soluble polymer and inorganic oxide particles.
  • the refractive index particles are filled in a high amount, the refractive index does not increase, and the improvement of the reflectance reaches its peak.
  • An object of the present invention is to provide a light reflecting film that eliminates these problems, further increases the difference in refractive index between the high refractive index layer and the low refractive index layer, and improves the reflection characteristics.
  • the high refractive index layer is a) a water-soluble polymer having a refractive index of 1.4 to 1.6, b) an inorganic oxide of 40% by volume or more in the high refractive index layer, and c) a chelate compound having a refractive index of 10% by volume or more in the high refractive index layer, which is higher than the refractive index of the water-soluble polymer, At least one selected from acylate compounds and salts thereof, A light reflecting film containing
  • a light reflection film has at least one unit, usually a plurality of units, in which high refractive index layers and low refractive index layers are alternately laminated on a transparent substrate.
  • the inventors of the present invention have studied the phenomenon in which the refractive index reaches a peak even when a large amount of high-refractive-index inorganic oxide particles are filled in the high-refractive-index layer in the above-described conventional light reflecting film. As a result, it was found that when high refractive index inorganic oxide particles were filled in the resin constituting the high refractive index layer, voids were generated in the resin. In particular, when the high refractive index inorganic oxide particles are 40% by volume or more in the high refractive index layer, voids start to be generated in the high refractive index layer, and when the amount is 50% by volume or more, the generation tends to be remarkable.
  • the present inventor can reduce the voids in the high refractive index layer and expand the refractive index difference between the high refractive index layer and the low refractive index layer with the following configuration. It has been found that a light reflecting film having excellent characteristics can be realized.
  • the present invention provides: a) a water-soluble polymer having a refractive index of 1.4 to 1.6 in the high refractive index layer, b) an inorganic oxide of 40% by volume or more in the high refractive index layer, and c).
  • the high refractive index layer contains at least one selected from a chelate compound, an acylate compound, and a salt thereof having a refractive index equal to or higher than 10% by volume of the water-soluble polymer.
  • Chelate compounds acylate compounds having a refractive index higher than that of the water-soluble polymer, wherein 40% by volume or more of the high refractive index inorganic oxide particles are contained in the water-soluble polymer having a refractive index of 1.4 to 1.6, and these It has been found that by containing at least 10% by volume of at least one selected from these salts, the refractive index can be further improved with less voids. Further, when the high refractive index layer and the low refractive index layer are formed using an aqueous simultaneous multilayer coating (aqueous simultaneous multilayer coating), at least one low refractive index layer selected from a chelate compound, an acylate compound, and a salt thereof is used.
  • aqueous simultaneous multilayer coating aqueous simultaneous multilayer coating
  • the light-reflecting film targeted by the wood invention usually uses respective coating liquids that can form a high refractive index layer and a low refractive index layer, and each coating liquid is applied with a high refractive index by sequential coating or simultaneous multilayer coating. It is manufactured by laminating a layer and a low refractive index layer.
  • the high refractive layer contains a water-soluble polymer having a refractive index of 1.4 to 1.6 and high refractive index inorganic oxide particles of 40% by volume or more, and has a refractive index higher than that of the water-soluble polymer.
  • the chelate compound which is generally a low molecule, At least one selected from an acylate compound and a salt thereof diffuses into multiple layers, but there is almost no diffusion in the above configuration. Further, mixing of the high refractive index layer and the low refractive index layer is also suppressed.
  • the refractive index of the high refractive index layer remains high, and the light reflecting film has a high reflectance.
  • at least one selected from a chelate compound, an acylate compound, and a salt thereof specifically and strongly interacts with the surface of the inorganic oxide particles, and also has a strong interaction with a water-soluble polymer.
  • Conceivable therefore, when 40% by volume or more inorganic oxide particles and a water-soluble polymer are contained, at least one selected from a chelate compound, an acylate compound, and a salt thereof is suppressed from being diffused into multiple layers. Conceivable. Furthermore, it is considered that these compounds are adsorbed on the surface of the high refractive index inorganic oxide, so that the physical properties of the surface are modified and voids are hardly generated.
  • the BET method is a method in which a molecule (for example, N 2 ) whose adsorption occupying area is known is adsorbed on the particle surface at the temperature of liquid nitrogen, and the specific surface area of the sample is obtained from the amount thereof. You can see if it has occurred.
  • the high refractive index layer includes at least one selected from water-soluble polymers, high refractive index inorganic oxide particles and chelate compounds, acylate compounds, and salts thereof.
  • the refractive index of the high refractive index layer is preferably 1.80 to 2.50, more preferably 1.85 to 2.20.
  • the water-soluble polymer constitutes a matrix and has a role of supporting the high refractive index layer itself. In the present invention, those having a refractive index of 1.4 to 1.6 are used.
  • the refractive index of the water-soluble polymer is preferably 1.45 to 1.55.
  • water-soluble as used in “water-soluble polymer” means that 1% by mass or more is dissolved in an aqueous medium, preferably 3% by mass or more.
  • the aqueous medium means a medium mainly composed of water, and may contain alcohol or other impurities such as methanol, ethanol, and propanol at a concentration of about the impurity, that is, a concentration of 10% by mass or less.
  • Any water-soluble polymer can be used without particular limitation as long as it has a refractive index in the above range, is water-soluble, and can form a layer.
  • Specific examples include polyvinyl alcohols, polyvinyl pyrrolidones, acrylic resins, styrene acrylic acid resins, vinyl acetate copolymers and their salts, gelatin, and thickening polysaccharides.
  • more preferred examples include polyvinyl alcohol, gelatin, polyvinyl pyrrolidones and copolymers containing the same. Particularly preferred is polyvinyl alcohol.
  • These water-soluble polymers may be used alone or in combination of two or more.
  • the weight average molecular weight of the water-soluble polymer is preferably 1,000 or more and 200,000 or less. Furthermore, 3,000 or more and 150,000 or less are more preferable. If the weight average molecular weight is within this range, sufficient mechanical strength as a film can be maintained.
  • polyvinyl alcohol preferably used in the present invention will be described below.
  • Polyvinyl alcohol has a refractive index of 1.47 to 1.53, and not only satisfies the above refractive index range, but also has a small wavelength dependency of the refractive index, and thus is particularly suitable for constituting a light reflecting film.
  • the term “polyvinyl alcohol” includes, in addition to ordinary polyvinyl alcohol (unmodified polyvinyl alcohol) obtained by hydrolysis of polyvinyl acetate, partially modified polyvinyl alcohol. .
  • water-soluble polyvinyl alcohol is used as the polyvinyl alcohol. This is because a stable coating solution can be produced by using water-soluble polyvinyl alcohol.
  • Unmodified polyvinyl alcohol may be synthesized or a commercially available product may be used.
  • Kuraray Poval registered trademark
  • PVA series manufactured by Kuraray Co., Ltd.
  • J-Poval registered trademark
  • J series manufactured by Nippon Vinegar Poval Co., Ltd.
  • modified polyvinyl alcohol examples include cation-modified polyvinyl alcohol, anion-modified polyvinyl alcohol, nonion-modified polyvinyl alcohol, and vinyl alcohol polymers.
  • modified polyvinyl alcohol is included, the adhesion of the film may be further improved.
  • the content of the modified polyvinyl alcohol is preferably 0 to 70% by mass in the total polyvinyl alcohol of the refractive index layer.
  • Examples of the cation-modified polyvinyl alcohol include primary to tertiary amino groups and quaternary ammonium groups in the main chain or side chain of the polyvinyl alcohol as described in, for example, JP-A-61-110483. It is obtained by saponifying a copolymer of an ethylenically unsaturated monomer having a cationic group and vinyl acetate.
  • Examples of the ethylenically unsaturated monomer having a cationic group include trimethyl- (2-acrylamido-2,2-dimethylethyl) ammonium chloride and trimethyl- (3-acrylamido-3,3-dimethylpropyl) ammonium chloride.
  • the ratio of the cation-modified group-containing monomer in the cation-modified polyvinyl alcohol is 0.1 to 10 mol%, preferably 0.2 to 5 mol%, relative to vinyl acetate.
  • Anion-modified polyvinyl alcohol is described in, for example, polyvinyl alcohol having an anionic group as described in JP-A-1-206088, JP-A-61-237681 and JP-A-63-307979.
  • examples thereof include a copolymer of vinyl alcohol and a vinyl compound having a water-soluble group, and a modified polyvinyl alcohol having a water-soluble group as described in JP-A-7-285265.
  • Nonionic modified polyvinyl alcohol includes, for example, a polyvinyl alcohol derivative in which a polyalkylene oxide group is added to a part of vinyl alcohol as described in JP-A-7-9758, and JP-A-8-25795.
  • vinyl alcohol polymer examples include vinyl acetate resin (for example, “Exeval” manufactured by Kuraray Co., Ltd.) and Nichigo G polymer (trade name: manufactured by Nippon Synthetic Chemical Industry Co., Ltd.).
  • Modified polyvinyl alcohol can be used in combination of two or more, such as the degree of polymerization and the type of modification.
  • the high refractive index layer is made of inorganic oxide, that is, high refractive index inorganic oxide particles (metal oxide particles) such as titanium and zirconia.
  • the total volume of the high refractive index layer is 40% by volume or more.
  • the preferred refractive index of the high refractive index inorganic oxide particles is 2.0 to 3.0, more preferably 2.3 to 2.8.
  • titanium oxide particles used in the present invention it is preferable to use particles in which the surface of an aqueous titanium oxide sol is modified to stabilize the dispersion state.
  • any conventionally known method can be used.
  • JP-A-63-17221, JP-A-7-819, JP-A-9-165218 See the matters described in Kaihei 11-43327, JP-A-63-17221, JP-A-7-819, JP-A-9-165218, JP-A-11-43327, etc. Can do.
  • titanium oxide—physical properties and applied technology Kiyono Manabu, p. 255-258 (2000), Gihodo Publishing Co., Ltd., or paragraph of WO 2007/039953.
  • step (2) Reference can be made to the method of step (2) described in the numbers 0011 to 0023.
  • titanium dioxide hydrate is treated with at least one basic compound selected from the group consisting of alkali metal hydroxides or alkaline earth metal hydroxides.
  • the titanium dioxide dispersion obtained comprises a step (2) of treating with a carboxylic acid group-containing compound and an inorganic acid.
  • JP-A-2000-053421 comprising alkyl silicate as a dispersion stabilizer, and silicon in the alkyl silicate is changed to SiO 2.
  • a titanium oxide sol having a weight ratio (SiO 2 / TiO 2 ) of 0.7 to 10 of the amount converted to TiO 2 and the amount converted to TiO 2 in titanium oxide), JP 2000-063119 A (TiO 2 -ZrO 2 -SnO 2 composite colloidal particles as the core, and the surface thereof coated with the composite oxide colloidal particles of WO 3 -SnO 2 -SiO 2 ) can be referred to .
  • the titanium oxide particles may be coated with a silicon-containing hydrated oxide.
  • the “coating” means a state in which a silicon-containing hydrated oxide is attached to at least a part of the surface of the titanium oxide particles. That is, the surface of the titanium oxide particles used as the metal oxide particles may be completely covered with a silicon-containing hydrated oxide, and a part of the surface of the titanium oxide particles is a silicon-containing hydrated oxide. It may be coated. From the viewpoint that the refractive index of the coated titanium oxide particles is controlled by the coating amount of the silicon-containing hydrated oxide, it is preferable that a part of the surface of the titanium oxide particles is coated with the silicon-containing hydrated oxide. .
  • the “silicon-containing hydrated oxide” in the present specification may be any of a hydrate of an inorganic silicon compound, a hydrolyzate and / or a condensate of an organosilicon compound, and preferably has a silanol group.
  • silica hydrate is preferable as the silicon-containing hydrated oxide
  • titanium oxide coated with silica hydrate is hereinafter referred to as silica-attached titanium oxide (both silica-coated titanium oxide and silica-modified titanium oxide).
  • the high refractive index layer further contains at least one selected from chelate compounds, acylate compounds, and salts thereof (hereinafter also referred to as chelate compounds).
  • the titanium oxide fine particles suitably used in the present invention have a cationic surface charge.
  • the chelate compound or the like is preferably anionic, and in that case, the chelate compound tends to precipitate in the coating solution together with the cationic titanium oxide fine particles. Therefore, in the case of using titanium oxide fine particles together with an anionic chelate compound or the like in order to form a uniform dispersion and a uniform high refractive index layer, the titanium oxide fine particles are coated with silica. It is preferable. This is because the surface of the titanium oxide fine particles coated with silica exhibits an anionic property.
  • One embodiment of the present invention provides the above light reflecting film, wherein the inorganic oxide is titanium oxide particles having silica attached to the surface.
  • the titanium oxide of the titanium oxide particles coated with the silicon-containing hydrated oxide may be a rutile type or an anatase type.
  • the titanium oxide particles coated with a silicon-containing hydrated oxide are more preferably rutile-type titanium oxide particles coated with a silicon-containing hydrated oxide. This is because the rutile type titanium oxide particles have lower photocatalytic activity than the anatase type titanium oxide particles, and therefore the weather resistance of the high refractive index layer and the adjacent low refractive index layer is increased, and the refractive index is further increased. Because.
  • the coating amount of the silicon-containing hydrated oxide is 3 to 50% by mass, preferably 5 to 30% by mass, more preferably 10 to 25% by mass. This is because when the coating amount is 30% by mass or less, the desired refractive index of the high refractive index layer can be obtained, and when the coating amount is 3% or more, particles can be stably formed.
  • titanium oxide particles with a silicon-containing hydrated oxide it can be produced by a conventionally known method.
  • JP-A-10-158015 Si / Al hydration to rutile titanium oxide) Oxide treatment
  • a method for producing a titanium oxide sol in which a hydrous oxide of silicon and / or aluminum is deposited on the surface of titanium oxide after peptization in the alkali region of the titanate cake JP 2000-204301 A (A sol in which a rutile-type titanium oxide is coated with a complex oxide of Si and Zr and / or Al.
  • JP 2007-246351 Oxidation obtained by peptizing hydrous titanium oxide
  • titanium to hydrosols of the formula R1 n SiX 4-n (wherein R1 as stabilizers C1-C8 alkyl group, glycidyl-substituted C1-C8 al Or a C2-C8 alkenyl group, X is an alkoxy group, n is 1 or 2.)
  • An organoalkoxysilane or a compound having a complexing action with respect to titanium oxide is added, sodium silicate or silica sol in an alkaline region
  • the method described in, for example, a method for producing a titanium oxide hydrosol coated with a hydrous oxide of silicon by adding, pH adjusting, and aging to the above solution can be referred to.
  • the size of the inorganic oxide particles used in the high refractive index layer can be specified by the volume average particle size or the primary average particle size.
  • the volume average particle size of the inorganic oxide particles used in the high refractive index layer is preferably 30 nm or less, more preferably 1 to 30 nm, and even more preferably 5 to 15 nm.
  • a volume average particle size of 30 nm or less is preferable from the viewpoint of low haze and excellent visible light transmittance.
  • the primary average particle size is the primary average particle size of titanium oxide particles (not coated with the silicon-containing hydrated oxide). Point to.
  • the volume average particle size refers to a method of observing the particle itself using a laser diffraction scattering method, a dynamic light scattering method, or an electron microscope, or a particle image appearing on the cross section or surface of the refractive index layer.
  • the particle diameter of 1,000 arbitrary particles is measured by a method of observing with an electron microscope, and particles having particle diameters of d1, d2,. ...
  • the volume average particle diameter mv ⁇ (vi ⁇ di) ⁇ / ⁇ (vi) ⁇ Calculate the average particle size weighted by the volume represented.
  • the metal oxide particles used in the present invention are preferably monodispersed.
  • the monodispersion here means that the monodispersity obtained by the following formula is 40% or less. This monodispersity is more preferably 30% or less, and particularly preferably 0.1 to 20%.
  • the content of the high refractive index inorganic oxide particles in the high refractive index layer is preferably 40 to 60% by volume, more preferably 45 to 55% by volume with respect to the total volume of the high refractive index layer. preferable. When the content is within this range, the difference in refractive index between the high refractive index layer and the low refractive index layer can be sufficiently increased, and a light reflecting film exhibiting excellent reflection characteristics can be obtained.
  • the high refractive index layer contains at least one selected from a chelate compound having a higher refractive index than the water-soluble polymer having a refractive index of 1.4 to 1.6, an acylate compound, and a salt thereof. It contains 10 volume% or more with respect to the whole volume of a high refractive index layer. That is, one embodiment of the present invention provides the above light reflecting film, wherein at least one refractive index selected from a chelate compound, an acylate compound, and a salt thereof is 1.6 or more.
  • Such chelate compounds, acylate compounds, and salts thereof are preferably water-soluble, and more preferably anionic, since an aqueous simultaneous multilayer coating method can be applied.
  • One embodiment provides the above light reflecting film, wherein at least one selected from a chelate compound, an acylate compound, and a salt thereof is anionic.
  • anionic chelate compounds and the like are on the market and are suitable for use in combination with high refractive index inorganic oxide particles in the present invention.
  • the surface of the high refractive index inorganic oxide particles is preferably anionic, and when the chelate compound or the like is cationic, the high refractive index inorganic oxide particles Is preferably cationic.
  • titanium oxide particles having silica attached thereto it is preferable to use titanium oxide particles having silica attached thereto. This is because the surface of titanium oxide particles is usually cationic, but the surface becomes anionic due to silica adhesion.
  • the refractive index of the chelate compound used in the present invention is preferably 1.6 or more.
  • the refractive index is 1.6 or more and the chelate compound itself has a high refractive index
  • the high refractive index layer has a higher refractive index.
  • the addition of a chelate compound or the like suppresses the movement of the substance to the low refractive index layer, so that the refractive index difference between the high refractive index layer and the low refractive index layer can be further expanded, and the reflection of the film Characteristics can be improved.
  • the refractive index of the chelate compound or the like is more preferably 1.65 or more, and the upper limit is not particularly limited and is preferably as high as possible. However, the available chelate compound is about 1.7.
  • chelate compound titanium lactate, titanium malate, titanium citrate, titanium glycolate, titanium diisopropoxybis (triethanolaminate) is preferable.
  • acylate compound polyhydroxytitanium stearate and zirconium chloride compound aminocarboxylic acid (Orgachix ZB-126, manufactured by Matsumoto Fine Chemical Co., Ltd.) are preferable.
  • a salt of a chelate compound or an acylate compound a titanium lactate ammonium salt is preferably commercially available. In the present invention, these can be arbitrarily used, but are not limited thereto.
  • titanium lactate since the refractive index is high and the effect of reducing voids in the high refractive index is high, titanium lactate, titanium lactate ammonium salt, zirconium chloride compound aminocarboxylic acid, titanium diisopropoxybis (triethanolaminate) is preferable, At least one of titanium lactate and titanium lactate ammonium salt can be used more preferably.
  • One embodiment of the present invention provides the above light reflecting film, wherein at least one selected from a chelate compound, an acylate compound, and a salt thereof is at least one of titanium lactate and titanium lactate ammonium salt.
  • These chelate compounds are considered to be adsorbed on the surface of the high refractive index inorganic oxide particles in the coating solution. Thereby, since it is difficult for the high refractive index inorganic oxide particles to form a structure during dry operation, it is considered that the generation of voids can be prevented.
  • the chelate compound or the like exhibits a strong interaction with Ti—OH of titanium oxide and is strongly adsorbed, and the movement between the low refractive index layer and the high refractive index layer is suppressed during multilayer coating. Therefore, in the present invention, it is desirable to use titanium oxide or silica-treated titanium oxide as the high refractive index inorganic oxide particles. Furthermore, since these particles and polyvinyl alcohol interact strongly, inter-layer mixing is suppressed and high reflectance is obtained when simultaneous multilayer coating is performed.
  • chelate compounds and the like are contained in the high refractive index layer in an amount of 10% by volume or more, preferably 10 to 50% by volume, more preferably 10 to 45% by volume, and still more preferably 1 to 25% by volume. It is preferable. Furthermore, the chelate compound or the like in the high refractive index layer interacts with polyvinyl alcohol and strongly improves the adhesion of the coating film to the substrate. If the chelate compound or the like is less than 10% by volume, interlayer mixing may occur. On the other hand, if it is 50% by volume or less, sufficient film strength can be obtained. Note that how much a chelate compound or the like is contained in the high refractive index layer can be confirmed by measuring the IR spectrum by directly extracting the chelate compound or the like from the high refractive index layer.
  • the light reflecting film of the present invention has a low refractive index layer showing a lower refractive index than the above-described high refractive index layer.
  • the low refractive index layer preferably has a refractive index of 1.6 or less, more preferably 1.10 to 1.60, and 1.30 to 1.50.
  • the low refractive index layer according to the present invention contains a water-soluble polymer.
  • PVA is preferably used as the water-soluble polymer, and the degree of saponification of the PVA contained in the high refractive index layer and the low refractive index layer is more preferably 3 mol% or more, more preferably 5 mol% or more. More preferably, there is Due to the large difference in the degree of saponification, the high refractive index layer and the low refractive index layer are separated without mixing, and high reflectance is exhibited.
  • Silica (silicon dioxide) is preferably used as the metal oxide for the low refractive index layer, and specific examples include synthetic amorphous silica and colloidal silica. Of these, acidic colloidal silica sol is more preferably used, and colloidal silica dispersed in an aqueous solvent is particularly preferably used. In order to further reduce the refractive index, hollow fine particles having pores inside the particles may be used as the metal oxide particles of the low refractive index layer, and hollow fine particles of silica (silicon dioxide) are particularly preferable. Moreover, well-known metal oxide particles other than a silica can also be used.
  • the metal oxide particles (preferably silicon dioxide) contained in the low refractive index layer preferably have an average particle size of 3 to 100 nm.
  • the average particle size of primary particles of silicon dioxide dispersed in a primary particle state is more preferably 3 to 50 nm, and further preferably 3 to 40 nm. It is particularly preferably 3 to 20 nm, and most preferably 4 to 10 nm.
  • grains it is preferable from a viewpoint with few hazes and excellent visible light transmittance
  • the primary average particle diameter can be measured from an electron micrograph taken with a transmission electron microscope (TEM) or the like. You may measure by the particle size distribution meter etc. which utilize a dynamic light scattering method, a static light scattering method, etc.
  • the primary average particle diameter of the particles is observed with an electron microscope on the particles themselves or the cross section or surface of the refractive index layer, and the particle diameter of 1000 arbitrary particles is measured. It is obtained as its simple average value (number average).
  • the particle diameter of each particle is represented by a diameter assuming a circle equal to the projected area.
  • the particle diameter of the metal oxide particles of the low refractive index layer can be determined by a volume average particle diameter in addition to the primary average particle diameter.
  • the colloidal silica used in the present invention is obtained by heating and aging a silica sol obtained by metathesis with an acid of sodium silicate or the like and passing through an ion exchange resin layer.
  • a silica sol obtained by metathesis JP-A-61-20792, JP-A-61-188183, JP-A-63-17807, JP-A-4-93284 JP-A-5-278324, JP-A-6-92011, JP-A-6-183134, JP-A-6-297830, JP-A-7-81214, JP-A-7-101142 , JP-A-7-179029, JP-A-7-137431, and International Publication No. 94/26530. It is intended.
  • Such colloidal silica may be a synthetic product or a commercially available product.
  • the surface of the colloidal silica may be cation-modified, or may be treated with Al, Ca, Mg, Ba or the like.
  • hollow particles can also be used as the metal oxide particles of the low refractive index layer.
  • the average particle pore size is preferably 3 to 70 nm, more preferably 5 to 50 nm, and even more preferably 5 to 45 nm.
  • the average particle pore size of the hollow fine particles is an average value of the inner diameters of the hollow fine particles. If the average particle pore diameter of the hollow fine particles is within the above range, the refractive index of the low refractive index layer is sufficiently lowered.
  • the average particle diameter is 50 or more at random, which can be observed as an ellipse in a circular, elliptical or substantially circular shape by electron microscope observation, and obtains the pore diameter of each particle. Is obtained.
  • the average particle hole diameter means the minimum distance among the distances between the two parallel lines that surround the outer edge of the hole diameter that can be observed as a circle, an ellipse, or a substantially circle or ellipse.
  • the content of the metal oxide particles in the low refractive index layer is preferably 1 to 50% by volume, more preferably 2 to 20% by volume with respect to the total volume of the low refractive index layer. More preferably, it is 10 volume%.
  • Various resin films can be used as the substrate of the light reflecting film of the present invention.
  • a polyolefin film polyethylene, polypropylene, etc.
  • a polyester film polyethylene terephthalate, polyethylene naphthalate, etc.
  • polyvinyl chloride polyvinyl chloride
  • cellulose acetate etc.
  • polyester film is preferred.
  • it does not specifically limit as a polyester film (henceforth polyester)
  • the main constituent dicarboxylic acid components include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenylsulfone dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenylethanedicarboxylic acid, Examples thereof include cyclohexane dicarboxylic acid, diphenyl dicarboxylic acid, diphenyl thioether dicarboxylic acid, diphenyl ketone dicarboxylic acid, and phenylindane dicarboxylic acid.
  • diol component examples include ethylene glycol, propylene glycol, tetramethylene glycol, cyclohexanedimethanol, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyethoxyphenyl) propane, bis ( 4-Hydroxyphenyl) sulfone, bisphenol fluorene hydroxyethyl ether, diethylene glycol, neopentyl glycol, hydroquinone, cyclohexanediol and the like.
  • polyesters having these as main components from the viewpoints of transparency, mechanical strength, dimensional stability, etc., dicarboxylic acid components such as terephthalic acid, 2,6-naphthalenedicarboxylic acid, diol components such as ethylene glycol and 1 Polyester having 1,4-cyclohexanedimethanol as the main constituent is preferred.
  • polyesters mainly composed of polyethylene terephthalate and polyethylene naphthalate, copolymerized polyesters composed of terephthalic acid, 2,6-naphthalenedicarboxylic acid and ethylene glycol, and mixtures of two or more of these polyesters are mainly used. Polyester as a constituent component is preferable.
  • the thickness of the substrate is preferably 10 to 300 ⁇ m, more preferably 20 to 150 ⁇ m.
  • the base material in the present invention may be a laminate of two or more, and in this case, the type may be the same or different.
  • the base material preferably has a visible light region transmittance of 85% or more shown in JIS R3106-1998, and particularly preferably 90% or more. It is advantageous and preferable in that the transmittance of the visible light region shown in JIS R3106-1998 when the substrate is a light reflecting film is 50% or more when the substrate has the above transmittance.
  • the base material using the resin or the like may be an unstretched film or a stretched film. A stretched film is preferable from the viewpoint of strength improvement and thermal expansion suppression.
  • the base material can be manufactured by a conventionally known general method.
  • an unstretched substrate that is substantially amorphous and not oriented can be produced by melting a resin as a material with an extruder, extruding it with an annular die or a T-die, and quenching.
  • the unstretched base material is subjected to a known method such as uniaxial stretching, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular-type simultaneous biaxial stretching, or the flow direction of the base material (vertical axis), or A stretched substrate can be produced by stretching in the direction perpendicular to the flow direction of the substrate (horizontal axis).
  • the draw ratio in this case can be appropriately selected according to the resin as the raw material of the base material, but is preferably 2 to 10 times in each of the vertical axis direction and the horizontal axis direction.
  • the base material may be subjected to relaxation treatment or offline heat treatment in terms of dimensional stability.
  • the relaxation treatment is performed in a process from the heat setting in the stretching process of the polyester film to the winding in the transversely stretched tenter or after exiting the tenter.
  • the relaxation treatment is preferably performed at a treatment temperature of 80 to 200 ° C., more preferably a treatment temperature of 100 to 180 ° C.
  • the relaxation rate is preferably in the range of 0.1 to 10% in both the longitudinal direction and the width direction, and more preferably, the relaxation rate is 2 to 6%.
  • the relaxed base material is subjected to the following off-line heat treatment to improve heat resistance and to improve dimensional stability.
  • the substrate is coated with the undercoat layer coating solution inline on one side or both sides during the film forming process.
  • undercoating during the film forming process is referred to as in-line undercoating.
  • resins used in the undercoat layer coating solution useful in the present invention include polyester resins, acrylic-modified polyester resins, polyurethane resins, acrylic resins, vinyl resins, vinylidene chloride resins, polyethyleneimine vinylidene resins, polyethyleneimine resins, and polyvinyl alcohol resins. , Modified polyvinyl alcohol resin, gelatin and the like, and any of them can be preferably used.
  • a conventionally well-known additive can also be added to these undercoat layers.
  • the undercoat layer can be coated by a known method such as roll coating, gravure coating, knife coating, dip coating or spray coating.
  • the coating amount of the undercoat layer is preferably about 0.01 to 2 g / m 2 (dry state).
  • the light reflecting film of the present invention includes at least one unit in which a high refractive index layer and a low refractive index layer are laminated.
  • it has a multilayer optical interference film in which a high refractive index layer and a low refractive index layer are alternately laminated on one side or both sides of a substrate.
  • the preferred range of the total number of high refractive index layers and low refractive index layers per side of the substrate is 100 layers or less, more preferably 45 layers or less.
  • the lower limit of the total number of layers of the high refractive index layer and the low refractive index layer per side of the substrate is not particularly limited, but is preferably 5 layers or more.
  • the preferred range of the total number of high refractive index layers and low refractive index layers is applicable even when laminated on only one side of the substrate, and when laminated simultaneously on both sides of the substrate. Is also applicable.
  • the total number of high refractive index layers and low refractive index layers on one surface of the substrate and the other surface may be the same or different.
  • the lowermost layer (layer in contact with the substrate) and the outermost layer may be either a high refractive index layer or a low refractive index layer.
  • the light reflecting film of the present invention preferably has a layer structure in which the lowermost layer and the outermost layer are low refractive index layers.
  • the difference in refractive index between at least two adjacent layers is preferably 0.3 or more, more preferably 0.35 or more, and most preferably 0.8. 4 or more.
  • the upper limit is not particularly limited, but is usually 1.4 or less.
  • This refractive index difference and the required number of layers can be calculated using commercially available optical design software. For example, in order to obtain a near-infrared reflectance of 90% or more, if the difference in refractive index is smaller than 0.1, it is necessary to laminate 200 layers or more, which not only lowers productivity but also causes scattering at the lamination interface. Larger, less transparent, and very difficult to manufacture without failure.
  • the refractive index difference between the high refractive index layer and the low refractive index layer is within the range of the preferred refractive index difference. Is preferred. However, for example, when the outermost layer is formed as a layer for protecting the film or when the lowermost layer is formed as an adhesion improving layer with the substrate, the above-mentioned preferable refraction is performed with respect to the outermost layer and the lowermost layer. A configuration outside the range of the rate difference may be used.
  • the terms “high refractive index layer” and “low refractive index layer” refer to the refractive index layer having a higher refractive index when the refractive index difference between two adjacent layers is compared. This means that the lower refractive index layer is the lower refractive index layer. Therefore, the terms “high refractive index layer” and “low refractive index layer” are the same when each refractive index layer constituting the light reflecting film is focused on two adjacent refractive index layers. All forms other than those having a refractive index are included.
  • the reflectance can be increased.
  • n is the refractive index
  • d is the physical film thickness of the layer
  • n ⁇ d is the optical film thickness.
  • the light reflecting film of the present invention can be shielded from visible light shielding film and infrared rays (near infrared light, mid-infrared light, far-infrared light, preferably near-infrared light) by changing a specific wavelength region for increasing the reflectance. It can be a film. In other words, when the specific wavelength region for increasing the reflectance is set to the visible light region, a visible light shielding (reflection) film is obtained, and when the specific wavelength region is set to the infrared region, an infrared light shielding (reflection) film is obtained.
  • a (near) infrared light reflecting (shielding) film may be used. Further, if the reflectance is increased in the far infrared region, it becomes a far infrared shielding film, which is useful as a heat insulating film that traps indoor heat if it is attached to a window. Further, if the reflectance is increased in the ultraviolet region, it is useful as an ultraviolet cut film, and an effect of preventing sunburn and preventing light deterioration due to ultraviolet rays can be obtained.
  • the transmittance at 550 nm in the visible light region shown in JIS R3106-1998 is 50% or more. Is preferably 70% or more, more preferably 75% or more. Further, the transmittance at 1200 nm is preferably 35% or less, more preferably 25% or less, and further preferably 20% or less. It is preferable to design the optical film thickness and unit so as to be within such a suitable range. In addition, it is preferable to have a region with a reflectance exceeding 50% in a wavelength region of 900 to 1400 nm.
  • the infrared region of the incident spectrum of direct sunlight is related to the increase in indoor temperature, and by blocking this, the increase in indoor temperature can be suppressed.
  • the cumulative energy ratio from the shortest infrared wavelength (760 nm) to the longest wavelength of 3200 nm based on the weight coefficient described in Japanese Industrial Standards JIS R3106-1998, the entire infrared region from the wavelength of 760 nm to the longest wavelength of 3200 nm
  • the total energy from 760 to 1300 nm occupies about 75% of the entire infrared region. Therefore, shielding the wavelength region up to 1300 nm is efficient in energy saving effect by heat ray shielding.
  • the sensory temperature can be lowered by sensory evaluation. For example, there was a clear difference when the temperature at the window facing the southeast method in the morning of August shielded the reflectance in the near infrared light range to about 80% at the maximum peak value.
  • the reflectance does not reach 60% when the number of stacked layers is 4. However, when there are 6 layers, a reflectance of about 80% can be obtained.
  • each refractive index layer is preferably 20 to 1000 nm, more preferably 50 to 500 nm, and more preferably 50 to 350 nm. Is more preferable.
  • the total thickness of the light reflecting film of the present invention is preferably 12 ⁇ m to 315 ⁇ m, more preferably 15 ⁇ m to 200 ⁇ m, and still more preferably 20 ⁇ m to 100 ⁇ m.
  • the light reflecting film includes at least one unit in which a high refractive index layer and a low refractive index layer are laminated on a base material.
  • the unit may be formed only on one side of the substrate, or may be formed on both sides. Since the reflectance of a specific wavelength improves, it is preferable that this unit is formed on both surfaces of a base material.
  • the light reflecting film is a conductive layer, an antistatic layer, a gas barrier layer, an easy adhesion layer (adhesion layer) for the purpose of adding further functions under the base material or on the outermost surface layer opposite to the base material.
  • One or more functional layers such as layers may be included.
  • the stacking order of the above-mentioned various functional layers in the reflective film is not particularly limited.
  • a light reflecting film is pasted (internally pasted) on the indoor side of a window glass
  • a preferred example is a form in which a hard coat layer is coated on the base material surface on the side opposite to the side on which these layers are laminated.
  • the order may be an adhesive layer, a base material, an optical reflection layer, and a hard coat layer, and may further have another functional layer, a base material, or an infrared absorber.
  • the order may be an adhesive layer, a base material, an optical reflection layer, and a hard coat layer, and may further have another functional layer base material or an infrared absorber.
  • Examples of the coating method include a roll coating method, a rod bar coating method, an air knife coating method, a spray coating method, a curtain coating method, or US Pat. Nos. 2,761,419 and 2,761,791.
  • a slide bead coating method using an hopper, an extrusion coating method, or the like is preferably used. Among these, it is particularly preferable to use the slide bead coating method in order to perform the aqueous simultaneous multilayer coating.
  • the solvent for preparing the high refractive index layer coating solution and the low refractive index layer coating solution is not particularly limited, but an aqueous solvent (aqueous medium) is preferable, and water is more preferable.
  • an aqueous solvent is preferably used in order to mainly use a water-soluble polymer, preferably polyvinyl alcohol, as the resin binder.
  • the aqueous solvent does not require a large-scale production facility, so that it is preferable in terms of productivity and also in terms of environmental conservation.
  • Examples of the organic solvent that can be used by mixing with the aqueous solvent of the present invention include alcohols such as methanol, ethanol, 2-propanol, 1-butanol, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl.
  • Esters such as ether acetate, ethers such as diethyl ether, propylene glycol monomethyl ether and ethylene glycol monoethyl ether, amides such as dimethylformamide and N-methylpyrrolidone, ketones such as acetone, methyl ethyl ketone, acetylacetone and cyclohexanone Can be mentioned.
  • the solvent of the coating solution is preferably water or a mixed solvent of water and methanol, ethanol, or ethyl acetate, and more preferably water. Moreover, you may add a small amount of surfactant as needed.
  • the content of water in the mixed solvent is preferably 80 to 99.9% by mass, based on 100% by mass of the entire mixed solvent, and preferably 90 to 99%. More preferably, it is 5 mass%.
  • volume fluctuation due to solvent volatilization can be reduced, handling is improved, and by setting it to 99.9% by mass or less, homogeneity at the time of liquid addition is increased and stable. This is because the obtained liquid properties can be obtained.
  • the method for preparing the high refractive index layer coating solution and the low refractive index layer coating solution is not particularly limited.
  • the order of addition of the respective components is not particularly limited, and the respective components may be sequentially added and mixed while stirring, or may be added and mixed at one time while stirring.
  • the concentration of each component in the coating solution is adjusted so that each component has the desired content (volume%) described above after the coating film is dried.
  • the temperature of the high refractive index layer coating solution and the low refractive index layer coating solution during simultaneous multilayer coating is preferably a temperature range of 25 to 60 ° C., and a temperature range of 30 to 45 ° C. Is more preferable.
  • a temperature range of 25 to 60 ° C. is preferable, and a temperature range of 30 to 45 ° C. is more preferable.
  • the viscosity of the high refractive index layer coating solution and the low refractive index layer coating solution during simultaneous multilayer coating is not particularly limited.
  • the preferable temperature range of the coating liquid is preferably 5 to 160 mPa ⁇ s, more preferably 60 to 140 mPa ⁇ s.
  • the preferable temperature range of the coating solution is preferably 5 to 1200 mPa ⁇ s, more preferably 25 to 500 mPa ⁇ s. If it is the range of such a viscosity, simultaneous multilayer coating can be performed efficiently.
  • the viscosity at 15 ° C. of the coating solution is preferably 100 mPa ⁇ s or more, more preferably 100 to 30,000 mPa ⁇ s, and further preferably 2,500 to 30,000 mPa ⁇ s.
  • the conditions for the coating and drying method are not particularly limited.
  • One is coated on a substrate and dried to form a layer, and then the other coating liquid is coated on this layer and dried to form a laminated film precursor (unit).
  • the number of units necessary for expressing the desired shielding performance is successively applied and dried by the above method to obtain a laminated film precursor.
  • drying it is preferable to dry the formed coating film at 30 ° C. or higher.
  • drying is preferably performed in the range of a wet bulb temperature of 5 to 50 ° C.
  • a film surface temperature of 5 to 100 ° C. preferably 10 to 50 ° C.
  • hot air of 40 to 60 ° C. is blown for 1 to 5 seconds. dry.
  • warm air drying, infrared drying, and microwave drying are used.
  • drying in a multi-stage process is preferable to drying in a single process, and it is more preferable to set the temperature of the constant rate drying section ⁇ the temperature of the rate-decreasing drying section.
  • the temperature range of the constant rate drying section is preferably 30 to 60 ° C.
  • the temperature range of the decreasing rate drying section is preferably 50 to 100 ° C.
  • the conditions of the coating and drying method when performing simultaneous multilayer coating are as follows.
  • the coating solution for the high refractive index layer and the coating solution for the low refractive index layer are heated to 25 to 60 ° C., and the high refractive index is formed on the substrate.
  • the temperature of the formed coating film is preferably cooled (set) preferably to 1 to 15 ° C., and then dried at 10 ° C. or higher.
  • More preferable drying conditions are a wet bulb temperature of 5 to 50 ° C. and a film surface temperature of 10 to 50 ° C. For example, it is dried by blowing warm air at 80 ° C. for 1 to 5 seconds.
  • coating it is preferable to carry out by a horizontal set system from a viewpoint of the uniformity improvement of the formed coating film.
  • the set means that the viscosity of the coating composition is increased by means such as lowering the temperature by applying cold air or the like to the coating film, the fluidity of the substances in each layer and in each layer is reduced, or the gel It means the process of converting.
  • a state in which the cold air is applied to the coating film from the surface and the finger is pressed against the surface of the coating film is defined as a set completion state.
  • the time (setting time) from the time of application until the setting is completed by applying cold air is preferably within 5 minutes, and more preferably within 2 minutes. Further, the lower limit time is not particularly limited, but it is preferable to take 45 seconds or more. If the set time is equal to or greater than the lower limit, it is possible to avoid insufficient mixing of the components in the layer. On the other hand, when the set time is less than or equal to the upper limit value, it is possible to avoid that the interlayer diffusion of the metal oxide particles proceeds and the difference in refractive index between the high refractive index layer and the low refractive index layer becomes insufficient. If the intermediate layer between the high-refractive index layer and the low-refractive index layer is highly elastic, the setting step may not be provided.
  • the temperature of the cold air is preferably 0 to 25 ° C, more preferably 5 to 10 ° C.
  • the time for which the coating film is exposed to cold air is preferably 10 to 360 seconds, more preferably 10 to 300 seconds, and further preferably 10 to 120 seconds, although it depends on the transport speed of the coating film.
  • the light reflecting film of the present invention can be applied to a wide range of fields. That is, a preferred embodiment of the present invention is a light reflector in which the light reflecting film is provided on at least one surface of a substrate.
  • film for window pasting such as heat ray reflecting film that gives heat ray reflection effect, film for agricultural greenhouses, etc. Etc., mainly for the purpose of improving the weather resistance.
  • it is suitable for a member in which the light reflecting film according to the present invention is bonded to glass or a glass substitute resin base material directly or through an adhesive.
  • the substrate include, for example, glass, polycarbonate resin, polysulfone resin, acrylic resin, polyolefin resin, polyether resin, polyester resin, polyamide resin, polysulfide resin, unsaturated polyester resin, epoxy resin, melamine resin, and phenol.
  • examples thereof include resins, diallyl phthalate resins, polyimide resins, urethane resins, polyvinyl acetate resins, polyvinyl alcohol resins, styrene resins, vinyl chloride resins, metal plates, and ceramics.
  • the type of resin may be any of a thermoplastic resin, a thermosetting resin, and an ionizing radiation curable resin, and two or more of these may be used in combination.
  • the substrate can be produced by a known method such as extrusion molding, calendar molding, injection molding, hollow molding, compression molding or the like.
  • the thickness of the substrate is not particularly limited, but is usually 0.1 mm to 5 cm.
  • the adhesive layer or adhesive layer that bonds the light reflecting film and the substrate is preferably disposed on the sunlight (heat ray) incident surface side.
  • an adhesive mainly composed of a photocurable or thermosetting resin can be used.
  • the adhesive preferably has durability against ultraviolet rays, and is preferably an acrylic adhesive or a silicone adhesive. Furthermore, an acrylic adhesive is preferable from the viewpoint of adhesive properties and cost. In particular, since the peel strength can be easily controlled, a solvent system is preferable among the solvent system and the emulsion system in the acrylic adhesive. When a solution polymerization polymer is used as the acrylic solvent-based pressure-sensitive adhesive, known monomers can be used as the monomer.
  • a polyvinyl butyral resin or an ethylene-vinyl acetate copolymer resin used as an intermediate layer of laminated glass may be used.
  • plastic polyvinyl butyral manufactured by Sekisui Chemical Co., Ltd., Mitsubishi Monsanto Co., Ltd.
  • ethylene-vinyl acetate copolymer manufactured by DuPont, Takeda Pharmaceutical Company Limited, duramin
  • modified ethylene-vinyl acetate copolymer Mersen G, manufactured by Tosoh Corporation.
  • an ultraviolet absorber, an antioxidant, an antistatic agent, a heat stabilizer, a lubricant, a filler, coloring, an adhesion adjusting agent, and the like can be appropriately added to the adhesive layer.
  • Example 1 Preparation of coating liquid for high refractive index layer First, a titanium oxide sol dispersion containing rutile type titanium oxide was prepared.
  • silica-attached titanium dioxide sol 15.0% by mass of titanium oxide sol (SRD-W, volume average particle size 5 nm, rutile type titanium dioxide particles, manufactured by Sakai Chemical Co., Ltd.) (4.1% by volume) 2 parts by mass of pure water was added. Then, it heated at 90 degreeC. Next, an aqueous silicic acid solution (sodium silicate 4 (manufactured by Nippon Chemical Co., Ltd.) diluted with pure water so that the SiO 2 concentration becomes 0.5 mass%) (0.25 vol%) 1.3 mass parts Then, heat treatment is performed at 175 ° C.
  • SRD-W volume average particle size 5 nm, rutile type titanium dioxide particles, manufactured by Sakai Chemical Co., Ltd.
  • Titanium dioxide sol (hereinafter, silica-attached titanium dioxide sol) (6.2% by volume) was obtained. A part of the sample was withdrawn and the specific gravity of the particles was measured and found to be 3.8.
  • a coating solution for a high refractive index layer was prepared using the silica-modified titanium oxide sol aqueous dispersion prepared above.
  • silica-modified titanium oxide sol aqueous dispersion was heated to 40 ° C., and 120 parts of an aqueous citric acid solution (1.92%) (1.16% by volume) was further added to this solution. Further, 11 parts of titanium lactate (Orgatechs TC-315, manufactured by Matsumoto Fine Chemical, 44%) (32.9% by volume) was added and stirred for 30 minutes. Furthermore, 20 parts of polyvinyl alcohol (Poval PVA103, manufactured by Kuraray Co., Ltd., degree of saponification 98.0 to 99.0%, degree of polymerization 300) (8.16% by volume) (10%) was added and stirred for 10 minutes.
  • a coating solution 1 for high refractive index layer was prepared by adding 1 part of a diluted aqueous solution (5%) of a surfactant (SOFTAZOLINE LSB-R, manufactured by Kawaken Fine Chemicals).
  • the coating solution for low refractive index layer was prepared as follows. Specifically, 38 parts of a 10% by mass aqueous solution of acidic colloidal silica (Snowtex OXS, primary particle size: 5.4 nm, manufactured by Nissan Chemical Industries, Ltd.) (5.2% by volume) and a 3% aqueous solution of boric acid 3 parts by weight (2.1% by volume) was added, and 39 parts by weight of a 6% by weight aqueous solution of polyvinyl alcohol, which is a water-soluble polymer (JP-45, polymerization degree 4500, saponification degree 88 mol%, manufactured by Nihon Vineyard Poval) ) (4.86% by volume) and 1 part of a 5% by weight aqueous solution of a surfactant (SOFTAZOLINE LSB-R, manufactured by Kawaken Fine Chemical Co., Ltd.) in this order at 45 ° C., and coating for a low refractive index layer A liquid
  • the specific gravity of each material used in this example is as follows. Polyvinyl alcohol: 1.25, titanium lactate (TC-315): 1.6, silica: 2.1, boric acid: 1.44, pure water: 1, citric acid: 1.67.
  • Example preparation Using a slide hopper coating apparatus capable of coating 9 layers, a polyethylene terephthalate film having a thickness of 50 ⁇ m heated to 40 ° C. while keeping the coating solution for the low refractive index layer and the coating solution for the high refractive index layer at 40 ° C.
  • Example 2 to 8 and Comparative Examples 1 to 5 high refractive index layer coating solutions were prepared in the same manner as in Example 1 except that the following changes were made. That is, at least one of the chelate compound, acylate compound and salt thereof in the high refractive index layer is the material shown in Table 1-1 and Table 1-2, and the volume ratio after drying is shown in Table 1-1 and Table 1-2.
  • Each of the coating liquids for high refractive index layer was prepared by adjusting the content to be as shown in FIG.
  • a light reflecting film was prepared in the same manner as in Example 1 except that these coating solutions for high refractive index layers were used.
  • the back side on the measurement side of each sample is roughened, and then light absorption treatment is performed with a black spray to reflect light on the back side.
  • the refractive index was obtained from the measurement result of the reflectance in the visible light region (400 nm to 700 nm) under the condition of regular reflection at 5 degrees.
  • n1 / n ⁇ 100 (%) is calculated, where n is the number of cross-cut cells and n1 is the number of cells remaining on the support after the tape is peeled off. did.
  • Examples 1 to 8 all exhibited a high maximum reflectance and excellent adhesion as compared with the Comparative Example.
  • Examples 1, 2, 5, and 8 in which the content of the chelate compound and the like was 10 to 20% by volume showed better adhesion.
  • Example 5 having a higher content of high refractive index inorganic oxide particles also showed a more excellent maximum reflectance.
  • the adhesiveness of a base material, a high refractive index layer, and a low refractive index layer improved by reducing the space
  • Comparative Examples 3 to 5 it can be seen that the single layer refractive index does not increase even if it is added by 40% by volume or more simply by increasing the addition amount of the high refractive index inorganic fine particles. This is presumably because voids were generated in the high refractive index layer by adding a large amount of high refractive index inorganic oxide particles. Moreover, from the result of Comparative Example 2, it can be seen that when the content of the chelate compound or the like is less than 10% by volume, the improvement of the reflectance as the light reflecting film is not realized even if the single layer refractive index is increased. This is considered because the high refractive index layer and the low refractive index layer were mixed by the multilayer coating.

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Abstract

[Problème] L'invention a pour objet de mettre en oeuvre un film réflecteur de lumière qui réduit l'apparition de vides dans une couche à indice de réfraction élevé et qui a d'excellentes propriétés de réflexion. [Solution] La présente invention met en oeuvre un film réflecteur de lumière qui comprend, sur un matériau de base, au moins une unité stratifiée comportant une couche à indice de réfraction faible et une couche à indice de réfraction élevé, et dans lequel la couche à indice de réfraction élevé contient a) un polymère soluble dans l'eau ayant un indice de réfraction allant de 1,4 à 1,6, b) un oxyde inorganique qui représente au moins 40 % en volume de la couche à indice de réfraction élevé and c) et au moins un type sélectionné parmi un composé chelaté, un composé acylé, et des sels de ceux-ci, qui représente au moins 10 % en volume de la couche à indice de réfraction élevé et qui a un indice de réfraction qui est au moins celui du polymère soluble dans l'eau.
PCT/JP2014/056789 2013-03-19 2014-03-13 Film réflecteur de lumière et son procédé de fabrication Ceased WO2014148366A1 (fr)

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JP2017219694A (ja) * 2016-06-07 2017-12-14 コニカミノルタ株式会社 光学反射フィルム、光学反射フィルムの製造方法、及び、光学反射体
JPWO2017110651A1 (ja) * 2015-12-25 2018-10-11 コニカミノルタ株式会社 光学反射フィルム
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JP2017194563A (ja) * 2016-04-20 2017-10-26 コニカミノルタ株式会社 光学反射フィルム、光学反射フィルムの製造方法、及び、光学反射体
JP2017219694A (ja) * 2016-06-07 2017-12-14 コニカミノルタ株式会社 光学反射フィルム、光学反射フィルムの製造方法、及び、光学反射体
JP2023138941A (ja) * 2018-04-16 2023-10-03 ロミー エム． ファイン， 受動放射冷却のための製作方法、構造体、および使用
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