WO2015037514A1 - Procédé de fabrication d'un film diélectrique multicouche - Google Patents

Procédé de fabrication d'un film diélectrique multicouche Download PDF

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Publication number
WO2015037514A1
WO2015037514A1 PCT/JP2014/073386 JP2014073386W WO2015037514A1 WO 2015037514 A1 WO2015037514 A1 WO 2015037514A1 JP 2014073386 W JP2014073386 W JP 2014073386W WO 2015037514 A1 WO2015037514 A1 WO 2015037514A1
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Prior art keywords
layer
refractive index
multilayer film
dielectric multilayer
water
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PCT/JP2014/073386
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English (en)
Japanese (ja)
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丈範 熊谷
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コニカミノルタ株式会社
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Priority to JP2015536551A priority Critical patent/JPWO2015037514A1/ja
Publication of WO2015037514A1 publication Critical patent/WO2015037514A1/fr

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    • 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
    • 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
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/102—Oxide or hydroxide
    • 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
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/204—Di-electric
    • 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
    • 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
    • B32B2307/70—Other properties
    • B32B2307/712—Weather resistant
    • 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
    • B32B2605/00—Vehicles
    • B32B2605/006—Transparent parts other than made from inorganic glass, e.g. polycarbonate glazings

Definitions

  • the present invention relates to a method for producing a dielectric multilayer film.
  • a dielectric multilayer film in which a high refractive index layer and a low refractive index layer are laminated by adjusting the optical film thickness selectively reflects light of a specific wavelength theoretically. It has been.
  • a film having such a dielectric multilayer film is used as, for example, a heat ray shielding film installed on a building window or a vehicle member.
  • Such a heat ray shielding film transmits visible light and selectively shields near infrared rays, but the reflection wavelength can be controlled only by adjusting the film thickness and refractive index of each layer. Can be reflected.
  • a method of forming a dielectric multilayer film there is generally a method of laminating by a dry film forming method, but formation of a dielectric multilayer film by a dry film forming method is not practical because it requires a lot of manufacturing costs.
  • a coating solution containing a mixture of a water-soluble polymer and metal oxide fine particles is applied and laminated by a wet coating method (for example, International Publication No. 2012/014607 (US Patent Application Publication No. 2013/107355)) and a method of laminating a resin film (see, for example, JP-T-2008-528313 (US Pat. No. 7,632,568)).
  • a wet coating method for example, International Publication No. 2012/014607 (US Patent Application Publication No. 2013/107355)
  • a method of laminating a resin film see, for example, JP-T-2008-528313 (US Pat. No. 7,632,568).
  • the wet coating method requires a small number of
  • the present invention has been made in view of the above problems, and an object thereof is to provide means for improving the weather resistance of a dielectric multilayer film.
  • a dielectric multilayer having a hard coat layer on one side of a dielectric multilayer film having a substrate and a layer containing a water-soluble polymer and metal oxide particles, and an adhesive layer on the other side In the method for producing a film film, the above-described problem is achieved by a production method including forming the adhesive layer on the dielectric multilayer film prior to forming the hard coat layer on the dielectric multilayer film. Has been found to solve the problem, and the present invention has been completed.
  • a dielectric multilayer film having a base material and a layer containing a water-soluble polymer and metal oxide particles has a hard coat layer on one surface and is adhered to the other surface.
  • a method for producing a dielectric multilayer film having a layer, wherein the adhesive layer is formed on the dielectric multilayer film before the hard coat layer is formed on the dielectric multilayer film It is achieved by the manufacturing method of a dielectric multilayer film containing.
  • FIG. 1A is a base material
  • 2A is a low refractive index layer
  • 3A is a high refractive index layer
  • 4A is a multilayer film
  • 5A is an intermediate layer
  • 6A is a hard coat layer
  • 7A is an adhesive layer
  • 8A is a separator.
  • FIG. 1B is a base material
  • 2B is a low refractive index layer
  • 3B is a high refractive index layer
  • 4B-1 and 4B-2 are multilayer films
  • 5B is an intermediate layer
  • 6B is a hard coat layer
  • 7B is an adhesive layer
  • 8B is a separator
  • 10 is the sun.
  • the present invention provides a dielectric having a hard coat layer on one side of a dielectric multilayer film having a substrate and a layer containing a water-soluble polymer and metal oxide particles, and an adhesive layer on the other side
  • a method for producing a multilayer film comprising: forming the adhesive layer on the dielectric multilayer film prior to forming the hard coat layer on the dielectric multilayer film. It is a manufacturing method of a multilayer film.
  • the dielectric multilayer film according to the present invention obtained by such a manufacturing method can have improved durability.
  • a near-infrared reflective film having a dielectric multilayer film having a layer containing a water-soluble polymer and metal oxide fine particles such as International Publication No. 2012/014607 (US Patent Application Publication No. 2013/107355). It was found that a phenomenon occurs in which cracking occurs in the dielectric multilayer film when left in a dry state for a long time. The details of the cause are unknown, but the dielectric multilayer film is composed of water-soluble polymer and metal oxide fine particles. It is considered that the moisture in the dielectric multilayer film was lost, the film contracted, and cracks occurred. In particular, it is considered that the dielectric multilayer film on the adhesive layer side is easily cracked because it is fixed to glass.
  • the adhesive layer is formed on the dielectric multilayer film before the hard coat layer is formed on the dielectric multilayer film.
  • FIG. 1 is a schematic sectional view showing an example of a layer structure of a dielectric multilayer film according to the present invention.
  • the dielectric multilayer film shown in FIG. 1 includes a multilayer film 4A and an adhesive layer 7A in which a plurality of low refractive index layers 2A and high refractive index layers 3A are alternately laminated on a base material 1A, for example, a transparent resin base material. And a separator 8A. On the opposite side, an intermediate layer 5A and a hard coat layer 6A are provided. The separator 8A is removed when the dielectric multilayer film is attached to a window glass or the like.
  • FIG. 2 is a schematic sectional view showing another example of the layer structure of the dielectric multilayer film according to the present invention.
  • a multilayer film 4B-1, an intermediate layer 5B, and a hard coat layer 6B in which a plurality of low-refractive index layers 2B and high-refractive index layers 3B are alternately stacked are provided on one surface of the substrate 1B.
  • the opposite surface has a multilayer film 4B-2 in which a plurality of low refractive index layers 2B and high refractive index layers 3B are alternately laminated, an adhesive layer 7B, and a separator 8B.
  • the adhesive layer 7B is disposed on the sun 10 side when disposed on a window glass or the like.
  • the separator 8B is removed when the dielectric multilayer film is attached to a window glass or the like.
  • the total thickness of the dielectric multilayer film according to the present invention is preferably 40 to 315 ⁇ m, more preferably 50 to 200 ⁇ m, and still more preferably 60 to 100 ⁇ m.
  • the dielectric multilayer film of the present invention has a conductive layer, an antistatic layer, a gas barrier layer, and an easy adhesion layer for the purpose of adding further functions under the base material or on the outermost surface layer opposite to the base material.
  • Adhesive layer antifouling layer, deodorant layer, droplet layer, slippery layer, wear-resistant layer, antireflection layer, electromagnetic wave shielding layer, ultraviolet absorbing layer, infrared absorbing layer, printed layer, fluorescent light emitting layer, hologram Layer, release layer, adhesive layer, infrared cut layer (metal layer, liquid crystal layer) other than the high refractive index layer and low refractive index layer of the present invention, a colored layer (visible light absorbing layer), an intermediate film used for laminated glass One or more other functional layers such as layers may be included.
  • the dielectric multilayer film of the present invention is used as various films such as an infrared shielding film, an ultraviolet shielding film, an antifogging film, a gas barrier film, and a liquid crystal film.
  • the dielectric multilayer film according to the present invention is an infrared shielding film or an ultraviolet shielding film
  • a layer containing a water-soluble polymer and metal oxide particles is alternately composed of a high refractive index layer and a low refractive index layer. It has a laminated structure.
  • the layer containing the water-soluble polymer and the metal oxide particles is an infrared shielding layer that exhibits a function of reflecting infrared rays, or an ultraviolet shielding layer that exhibits a function of reflecting ultraviolet rays.
  • the dielectric multilayer film according to the present invention has a layer containing a water-soluble polymer having a single layer structure and metal oxide particles.
  • the dielectric multilayer film of the present invention is also used as an ultraviolet shielding film.
  • the contents of the constituent elements described below are applied as they are except for the thicknesses of the high refractive index layer and the low refractive index layer. sell.
  • the thickness of the high refractive index layer is preferably in the range of 10 to 500 nm
  • the thickness of the low refractive index layer is preferably in the range of 10 to 500 nm.
  • the dielectric multilayer film according to the present invention includes a substrate.
  • the substrate according to the present invention is preferably a transparent resin film and serves as a support for the dielectric multilayer film.
  • the material, thickness, and the like are set so that the value obtained by dividing the heat shrinkage rate of the dielectric multilayer film by the heat shrinkage rate of the base material is in the range of 1 to 3. Those are preferred.
  • the thickness of the substrate according to the present invention is preferably 30 to 200 ⁇ m, more preferably 30 to 150 ⁇ m, and further preferably 35 to 125 ⁇ m.
  • the thickness is 30 ⁇ m or more, wrinkles during handling are less likely to occur, and when the thickness is 200 ⁇ m or less, for example, when pasting to a transparent substrate, for example, following a curved transparent substrate Improves wrinkle resistance.
  • the base material according to the present invention is preferably a biaxially stretched polyester film, but an unstretched or at least one stretched polyester film can also be used.
  • a stretched film is preferable from the viewpoint of strength improvement and thermal expansion suppression. In particular, when used as a windshield of an automobile, a stretched film is more preferable.
  • polyesters terephthalic acid, 2,6-naphthalenedicarboxylic acid, diol component, ethylene glycol and 1,4-cyclohexanedimethanol are used as dicarboxylic acid components in terms of transparency, mechanical strength, dimensional stability, etc.
  • Polyester 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 layer containing the water-soluble polymer and the metal oxide particles only needs to be formed on at least one surface of the substrate, and is formed on both surfaces of the substrate. Also good.
  • the layer containing the water-soluble polymer and the metal oxide particles is preferably formed on both surfaces of the substrate from the viewpoint of light reflectance.
  • the layer containing the water-soluble polymer and metal oxide particles is: It has a structure in which high refractive index layers and low refractive index layers are alternately stacked.
  • the thickness per layer of the high refractive index layer is preferably 20 to 800 nm, and more preferably 50 to 500 nm.
  • the thickness per layer of the low refractive index layer is preferably 20 to 800 nm, and more preferably 50 to 500 nm.
  • the high refractive index layer and the low refractive index layer may have a clear interface between them, or may have a structure in which the composition changes continuously.
  • the maximum refractive index minus the minimum refractive index ⁇ n in the region where the respective layers are mixed and the refractive index continuously changes.
  • a point of refractive index + ⁇ n / 2 is regarded as a layer interface. The same applies to the layer thickness of the low refractive index layer described later.
  • the profile of the metal oxide particles in the dielectric multilayer film formed by laminating the high refractive index layer and the low refractive index layer is etched from the surface to the depth direction using a sputtering method, and the XPS surface Using an analyzer, the outermost surface can be set to 0 nm, sputtered at a rate of 0.5 nm / min, and the atomic composition ratio can be measured. It is also possible to confirm the cut surface by cutting the laminated film and measuring the atomic composition ratio with an XPS surface analyzer. In the mixed region, when the concentration of the metal oxide particles changes discontinuously, the boundary can be confirmed by a tomographic photograph using an electron microscope (TEM).
  • TEM electron microscope
  • the XPS surface analyzer is not particularly limited and any model can be used.
  • ESCALAB-200R manufactured by VG Scientific, Inc. can be used.
  • Mg is used for the X-ray anode, and measurement is performed at an output of 600 W (acceleration voltage: 15 kV, emission current: 40 mA).
  • the range of the total number of layers is preferably 6 to 50 layers, more preferably 8 to 40 layers, and further preferably 9 to 35 layers. Further, from the viewpoint of infrared reflectance and translucency, and suppression of film peeling and cracking due to heating, the total number of high refractive index layers and low refractive index layers is preferably 11 to 31 layers.
  • the difference in refractive index between the adjacent high refractive index layer and low refractive index layer is preferably 0.1 or more, more preferably 0.3 or more, still more preferably 0.35 or more, particularly preferably. Is 0.4 or more.
  • the outermost layer and the lowermost layer a configuration outside the above preferred range may be used.
  • the reflectance in a specific wavelength region is determined by the difference in refractive index between two adjacent layers and the number of layers, and the larger the difference in refractive index, the same reflectance can be obtained with a smaller number of layers.
  • the 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 reduces productivity, but also at the lamination interface. Scattering increases, transparency decreases, and it becomes very difficult to manufacture without failure. From the standpoint of improving reflectivity and reducing the number of layers, there is no upper limit to the difference in refractive index, but practically about 1.4 is the limit.
  • the dielectric multilayer film according to the present invention preferably has a layer structure in which the lowermost layer adjacent to the base material is a low refractive index layer from the viewpoint of adhesion to the base material.
  • the constitution of the high refractive index layer according to the present invention contains a water-soluble polymer and metal oxide particles, and further, if necessary, a curing agent, other binder resins, and a surfactant. It is preferable that the composition contains various additives.
  • the refractive index of the high refractive index layer according to the present invention is preferably 1.80 to 2.50, more preferably 1.90 to 2.20.
  • the water-soluble polymer used in the high refractive index layer preferably has a weight average molecular weight of 1,000 to 200,000, preferably 3,000 to 40,000. It is more preferable that
  • the weight average molecular weight as used in the present invention can be measured by a known method, for example, static light scattering, gel permeation chromatography (GPC), time-of-flight mass spectrometry (TOF-MASS), etc.
  • the measurement is performed by gel permeation chromatography which is a generally known method.
  • the content of the water-soluble polymer in the high refractive index layer is preferably 5 to 50% by mass and more preferably 10 to 40% by mass with respect to 100% by mass of the solid content of the high refractive index layer. .
  • the water-soluble polymer applied to the high refractive index layer is preferably polyvinyl alcohol.
  • the water-soluble polymer applied to the low refractive index layer described later is also preferably polyvinyl alcohol.
  • polyvinyl alcohol (A) is used as the water-soluble polymer used in the high refractive index layer, and polyvinyl alcohol (B) is used as the water-soluble polymer used in the low refractive index layer. Called.
  • each refractive index layer contains a plurality of polyvinyl alcohols having different saponification degrees and polymerization degrees
  • the polyvinyl alcohol having the highest content in each refractive index layer is changed to polyvinyl alcohol (A ), And polyvinyl alcohol (B) in the low refractive index layer.
  • the “degree of saponification” is the ratio of hydroxy groups to the total number of acetyloxy groups (derived from the starting vinyl acetate) and hydroxy groups in polyvinyl alcohol.
  • the degree of polymerization is calculated assuming that the polyvinyl alcohol having a saponification degree difference of 3 mol% or less is the same polyvinyl alcohol. .
  • a low polymerization degree polyvinyl alcohol having a polymerization degree of 1000 or less is a different polyvinyl alcohol (even if there is a polyvinyl alcohol having a saponification degree difference of 3 mol% or less, it is not regarded as the same polyvinyl alcohol).
  • polyvinyl alcohol having a saponification degree of 90 mol%, a saponification degree of 91 mol%, and a saponification degree of 93 mol% is contained in the same layer by 10 mass%, 40 mass%, and 50 mass%, respectively.
  • These three polyvinyl alcohols are the same polyvinyl alcohol, and these three mixtures are polyvinyl alcohol (A) or (B).
  • the above-mentioned “polyvinyl alcohol having a saponification degree difference of 3 mol% or less” suffices to be within 3 mol% when attention is paid to any polyvinyl alcohol.
  • polyvinyl alcohol having a saponification degree different by 3 mol% or more is contained in the same layer, it is regarded as a mixture of different polyvinyl alcohols, and the polymerization degree and the saponification degree are calculated for each.
  • PVA203 5% by mass
  • PVA117 25% by mass
  • PVA217 10% by mass
  • PVA220 10% by mass
  • PVA224 10% by mass
  • PVA235 20% by mass
  • PVA245 20% by mass
  • most contained A large amount of PVA (polyvinyl alcohol) is a mixture of PVA 217 to 245 (the difference in the degree of saponification of PVA 217 to 245 is within 3 mol%, and is the same polyvinyl alcohol), and this mixture is polyvinyl alcohol (A) or ( B).
  • the difference in the absolute value of the saponification degree between the polyvinyl alcohol (A) and the polyvinyl alcohol (B) is preferably 3 mol% or more, and more preferably 5 mol% or more. If it is such a range, since the interlayer mixing state of a high refractive index layer and a low refractive index layer will become a preferable level, it is preferable. Moreover, although the difference of the saponification degree of polyvinyl alcohol (A) and polyvinyl alcohol (B) is so preferable that it is separated, it is 20 mol% or less from the viewpoint of the solubility to water of polyvinyl alcohol. It is preferable.
  • the saponification degree of polyvinyl alcohol (A) and polyvinyl alcohol (B) is preferably 75 mol% or more from the viewpoint of solubility in water. Furthermore, between polyvinyl alcohol (A) and polyvinyl alcohol (B), one of them has a saponification degree of 90 mol% or more and the other is 90 mol% or less. Is preferable for achieving a preferable level. It is more preferable that one of the polyvinyl alcohol (A) and the polyvinyl alcohol (B) has a saponification degree of 95 mol% or more and the other is 90 mol% or less. In addition, although the upper limit of the saponification degree of polyvinyl alcohol is not specifically limited, Usually, it is less than 100 mol% and is about 99.9 mol% or less.
  • the polymerization degree of the two types of polyvinyl alcohols having different saponification degrees is preferably 1000 or more, particularly preferably those having a polymerization degree in the range of 1500 to 5000, more preferably in the range of 2000 to 5000. Those are more preferably used. This is because when the polymerization degree of polyvinyl alcohol is 1000 or more, there is no cracking of the coating film, and when it is 5000 or less, the coating solution is stabilized. In the present specification, “the coating solution is stable” means that the coating solution is stable over time.
  • the degree of polymerization of at least one of polyvinyl alcohol (A) and polyvinyl alcohol (B) is in the range of 2000 to 5000, it is preferable because cracks in the coating film are reduced and the reflectance at a specific wavelength is improved. It is preferable that both the polyvinyl alcohol (A) and the polyvinyl alcohol (B) are 2000 to 5000 because the above effects can be more remarkably exhibited.
  • the “degree of polymerization” as used in the present invention refers to the viscosity average degree of polymerization, and is measured according to JIS K6726 (1994). PVA is completely re-saponified and purified, and then measured in water at 30 ° C. From [ ⁇ ] (dl / g), it is obtained by the following mathematical formula (1).
  • the polyvinyl alcohol (B) contained in the low refractive index layer preferably has a saponification degree in the range of 75 to 90 mol% and a polymerization degree in the range of 2000 to 5000.
  • polyvinyl alcohol having such characteristics is contained in the low refractive index layer, it is preferable in that interfacial mixing is further suppressed. This is considered to be because there are few cracks of a coating film and set property improves.
  • the polyvinyl alcohol (A) and (B) used in the present invention may be a synthetic product or a commercially available product.
  • Examples of commercially available products used as polyvinyl alcohol (A) and (B) include, for example, PVA-102, PVA-103, PVA-105, PVA-110, PVA-117, PVA-120, PVA-124, PVA -203, PVA-205, PVA-210, PVA-217, PVA-220, PVA-224, PVA-235 (manufactured by Kuraray Co., Ltd.), JC-25, JC-33, JF-03, JF-04 , JPF-05, JP-03, JP-04, JP-05, JP-45 (above, manufactured by Nippon Vinegar Poval Co., Ltd.) and the like.
  • the water-soluble polymer according to the present invention may contain modified polyvinyl alcohol partially modified in addition to normal polyvinyl alcohol obtained by hydrolysis of polyvinyl acetate. Good.
  • modified polyvinyl alcohol include cation-modified polyvinyl alcohol, anion-modified polyvinyl alcohol, nonion-modified polyvinyl alcohol, and polyvinyl alcohol-based water-soluble polymer.
  • 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.
  • 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.
  • Block copolymer of vinyl compound having hydrophobic group and vinyl alcohol, silanol-modified polyvinyl alcohol having silanol group, reactive group modification having reactive group such as acetoacetyl group, carbonyl group and carboxy group Polyvinyl alcohol etc. are mentioned.
  • a polyvinyl alcohol-based water-soluble polymer such as EXEVAL (registered trademark, manufactured by Kuraray Co., Ltd.) or Nichigo G polymer (registered trademark, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.).
  • Two or more kinds of modified polyvinyl alcohol can be used in combination, such as the degree of polymerization and the type of modification.
  • the content of the modified polyvinyl alcohol is not particularly limited, but is preferably 1 to 30% by mass with respect to the total mass (solid content) of each refractive index layer. If it is such a range, the said effect will be exhibited more.
  • the polyvinyl alcohol (A) having a low saponification degree is used for the high refractive index layer and polyvinyl alcohol (B) having a high saponification degree is used for the low refractive index layer
  • the polyvinyl alcohol ( A) is preferably contained in the range of 40% by mass to 100% by mass with respect to the total mass of all polyvinyl alcohols in the layer, more preferably 60% by mass to 95% by mass
  • the low refractive index layer The polyvinyl alcohol (B) is preferably contained in the range of 40% by mass to 100% by mass with respect to the total mass of all the polyvinyl alcohols in the low refractive index layer, and 60% by mass to 95% by mass. Is more preferable.
  • the polyvinyl alcohol (A) having a high saponification degree is used for the high refractive index layer and polyvinyl alcohol (B) having a low saponification degree is used for the low refractive index layer
  • the polyvinyl alcohol ( A) is preferably contained in the range of 40% by mass to 100% by mass with respect to the total mass of all polyvinyl alcohols in the layer, more preferably 60% by mass to 95% by mass
  • the low refractive index layer The polyvinyl alcohol (B) is preferably contained in the range of 40% by mass to 100% by mass with respect to the total mass of all the polyvinyl alcohols in the low refractive index layer, and 60% by mass to 95% by mass. More preferred.
  • the content is 40% by mass or more, interlayer mixing is suppressed, and the effect of less disturbance of the interface appears remarkably. On the other hand, if content is 100 mass% or less, stability of a coating liquid will improve.
  • the high refractive index layer As the water-soluble polymer other than polyvinyl alcohol, the high refractive index layer containing metal oxide particles forms a coating film. Anything can be used without limitation. Moreover, also in the low refractive index layer described later, as the water-soluble polymer other than polyvinyl alcohol, if the low refractive index layer containing the metal oxide particles can form a coating film, as described above, any method can be used. Anything can be used without limitation. However, in consideration of environmental problems and the flexibility of the coating film, gelatin, thickening polysaccharides, polymers having reactive functional groups, and the like are preferable. These water-soluble polymers may be used alone or in combination of two or more.
  • the content of other binder resin used together with polyvinyl alcohol preferably used as the water-soluble polymer is in the range of 5 to 50% by mass with respect to 100% by mass of the solid content of the high refractive index layer. It can also be used within.
  • the binder resin is preferably composed of a water-soluble polymer. That is, in the present invention, a water-soluble polymer other than polyvinyl alcohol and modified polyvinyl alcohol may be used as the binder resin in addition to the polyvinyl alcohol and modified polyvinyl alcohol as long as the effect is not impaired.
  • the water-soluble polymer is when it is filtered through a G2 glass filter (maximum pores 40-50 ⁇ m) when dissolved in water at a concentration of 0.5% by mass at the temperature at which the water-soluble polymer is most dissolved.
  • the mass of the insoluble matter separated by filtration is within 50% by mass of the added water-soluble polymer.
  • water-soluble polymers gelatin, celluloses, thickening polysaccharides, or polymers having reactive functional groups are particularly preferable. These water-soluble polymers may be used alone or in combination of two or more. Specific examples of such water-soluble polymers other than polyvinyl alcohol and modified polyvinyl alcohol include compounds described in paragraphs “0033” to “0041” of JP2013-007817A.
  • the metal oxide particles applicable to the high refractive index layer according to the present invention are more preferably metal oxide particles having a refractive index of 2.0 or more and 3.0 or less.
  • examples thereof include ferric iron, iron black, copper oxide, magnesium oxide, magnesium hydroxide, strontium titanate, yttrium oxide, niobium oxide, europium oxide, lanthanum oxide, zircon, and tin oxide.
  • composite oxide particles composed of a plurality of metals, core / shell particles whose metal structure changes into a core / shell shape, and the like can also be used.
  • a thiophene compound In the organic system, a thiophene compound, a polyphenylene sulfide compound, a polyacetylene compound, a polyphenylene vinylene compound, a polypyrrole compound, or a polyaniline compound can be used.
  • the high refractive index layer according to the present invention includes metal oxide particles having a high refractive index such as titanium and zirconium, that is, titanium oxide particles and It is preferable to contain zirconia oxide particles.
  • titanium oxide particles are more preferable from the viewpoint of the stability of the coating liquid for forming the high refractive index layer.
  • the rutile type tetragonal type
  • the weather resistance of the high refractive index layer and adjacent layers is higher, and the refractive index is higher. To more preferable.
  • the high refractive index is obtained by the interaction between the silicon-containing hydrated oxide of the shell layer and the water-soluble polymer.
  • core / shell particles in which titanium oxide particles are coated (surface-treated) with a silicon-containing hydrated oxide are more preferable.
  • the aqueous solution containing titanium oxide particles used for the core of the core-shell particles according to the present invention has a surface of an aqueous titanium oxide sol having a pH of 1.0 to 3.0 and a positive zeta potential of the titanium particles. It is preferable to use a hydrophobized and dispersible state in an organic solvent.
  • the content of the metal oxide particles in the high refractive index layer according to the present invention is 15 to 80% by mass with respect to 100% by mass of the solid content of the high refractive index layer, the refractive index with the low refractive index layer This is preferable from the viewpoint of providing a difference. Furthermore, it is more preferably 20 to 77% by mass, and further preferably 30 to 75% by mass.
  • the content when the metal oxide particles other than the core / shell particles are contained in the high refractive index layer according to the present invention is particularly limited as long as the effects of the present invention can be obtained. It is not a thing.
  • the volume average particle size of the metal oxide particles contained in the high refractive index layer is preferably 50 nm or less, more preferably in the range of 1 to 40 nm.
  • a volume average particle size of 50 nm or less is preferable from the viewpoint of low visible light transmittance and low haze.
  • the volume average particle size of the metal oxide particles according to the present invention refers to a method of observing the particles themselves using a laser diffraction scattering method, a dynamic light scattering method, or an electron microscope, a cross section or a surface of a refractive index layer.
  • a curing agent can be used to cure the water-soluble polymer applied to the high refractive index layer.
  • the curing agent that can be used together with the water-soluble polymer is not particularly limited as long as it causes a curing reaction with the water-soluble polymer.
  • boric acid and its salt are preferable as the curing agent.
  • known ones can be used, and in general, a compound having a group capable of reacting with polyvinyl alcohol or a compound that promotes the reaction between different groups possessed by polyvinyl alcohol. Select and use.
  • the curing agent include, for example, an epoxy curing agent (for example, diglycidyl ethyl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-diglycidyl cyclohexane, N, N— Diglycidyl-4-glycidyloxyaniline, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, etc.), aldehyde curing agents (eg, formaldehyde, glioxal, etc.), active halogen curing agents (eg, 2,4-dichloro-4-hydroxy) -1,3,5, -s-triazine, etc.), active vinyl compounds (for example, 1,3,5-trisacryloyl-hexahydro-s-triazine, bisvinylsulfonylmethyl ether, etc.), aluminum alum, etc. .
  • Boric acid and its salts refer to oxygen acids and their salts having a boron atom as a central atom, specifically, orthoboric acid, diboric acid, metaboric acid, tetraboric acid, pentaboric acid and octabored acid. Examples include acids and their salts.
  • the low refractive index layer according to the present invention includes a water-soluble polymer and metal oxide particles, and further includes a curing agent, a surface coating component, a particle surface protective agent, other binder resins, and an interface. Various additives such as an activator may be included.
  • the refractive index of the low refractive index layer according to the present invention is preferably 1.10 to 1.60, more preferably 1.30 to 1.50.
  • (2-1) Water-soluble polymer As the water-soluble polymer applied to the low refractive index layer according to the present invention, polyvinyl alcohol is preferably used. Furthermore, it is more preferable that polyvinyl alcohol (B) different from the saponification degree of polyvinyl alcohol (A) present in the high refractive index layer is used in the low refractive index layer according to the present invention. In addition, description about polyvinyl alcohol (A) and polyvinyl alcohol (B), such as a preferable weight average molecular weight of the water-soluble polymer used for a low refractive index layer here, is the water-soluble polymer of the said high refractive index layer. The description is omitted here.
  • the content of the water-soluble polymer in the low refractive index layer is preferably 20 to 99.9% by mass and preferably 25 to 80% by mass with respect to 100% by mass of the solid content of the low refractive index layer. More preferred.
  • any low refractive index layer containing metal oxide particles can form a coating film.
  • any low refractive index layer containing metal oxide particles can form a coating film.
  • gelatin, celluloses, thickening polysaccharides, or polymers having reactive functional groups are particularly preferable.
  • These water-soluble polymers may be used alone or in combination of two or more.
  • the content of other water-soluble polymer used together with polyvinyl alcohol preferably used as the water-soluble polymer is 0.1 to 10 with respect to 100% by mass of the solid content of the low refractive index layer. It is preferable that it is mass%.
  • water-soluble polymers such as gelatin, celluloses, thickening polysaccharides and polymers having reactive functional groups are the same as the water-soluble polymers described in the section of the high refractive index layer described above, Detailed description is omitted here.
  • silica silicon dioxide
  • metal oxide particles applied to the low refractive index layer As the metal oxide particles applied to the low refractive index layer according to the present invention, silica (silicon dioxide) is used from the viewpoint of compatibility with water-soluble polymers, liquid stability, cost, and the like. It is preferable to use, and specific examples include synthetic amorphous silica and colloidal silica. Of these, acidic colloidal silica sol is more preferably used, and colloidal silica sol dispersed in an organic solvent is more preferably used. Moreover, in order to further reduce the refractive index, hollow fine particles having pores inside the particles can be used as the metal oxide particles applied to the low refractive index layer, and in particular, hollow fine particles of silica (silicon dioxide). Is preferred.
  • the average particle diameter of the metal oxide particles used for the low refractive index layer is preferably 3 to 100 nm.
  • the average particle diameter 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 average particle size of the metal oxide particles used in the low refractive index layer is determined by observing the particles themselves or particles appearing on the cross section or surface of the refractive index layer with an electron microscope and measuring the particle size of 1000 arbitrary particles. The simple average value (number average) is obtained.
  • the particle size of each particle is represented by a diameter assuming a circle equal to the projected area.
  • Colloidal silica used for the low refractive index layer is obtained by heat decomposition of silica sol obtained by metathesis of sodium silicate with an acid or the like or passing through an ion exchange resin layer.
  • Japanese Patent Application Laid-Open No. 7-179029 Japanese Patent Application Laid-Open No. 7-137431, and International Publication No. 94/26530. Is shall.
  • 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 used for 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 diameter of the hollow particles is the average value of the inner diameters of the hollow particles.
  • the average particle diameter is 50 or more at random, which can be observed as a circle, an ellipse, or substantially a circle or an ellipse by electron microscope observation, and the number of holes is determined for each particle. Is obtained.
  • the average particle hole diameter means the minimum distance among the distances between the outer edges of the hole diameter that can be observed as a circle, ellipse, substantially circle or ellipse, between two parallel lines.
  • the metal oxide particles applied to the low refractive index layer may be surface-coated with a surface coating component.
  • the content of the metal oxide particles in the low refractive index layer is preferably 0.1 to 70% by mass and preferably 30 to 70% by mass with respect to 100% by mass of the solid content of the low refractive index layer. More preferred is 45 to 65% by mass.
  • the low refractive index layer according to the present invention can further contain a curing agent as in the case of the high refractive index layer.
  • the type of the curing agent is not particularly limited as long as it causes a curing reaction with the water-soluble polymer contained in the low refractive index layer.
  • boric acid, its salt, and borax are preferred as the curing agent when polyvinyl alcohol is used as the water-soluble polymer applied to the low refractive index layer.
  • boric acid and its salts known ones can be used.
  • the content of the curing agent in the low refractive index layer is preferably 1 to 10% by mass and more preferably 2 to 6% by mass with respect to 100% by mass of the solid content of the low refractive index layer.
  • the total amount of the curing agent used is preferably 1 to 600 mg per 1 g of polyvinyl alcohol, more preferably 100 to 600 mg per 1 g of polyvinyl alcohol. .
  • the high refractive index layer and the low refractive index layer according to the present invention can contain various additives as necessary.
  • the content of the additive in the high refractive index layer is preferably 0.005 to 20% by mass with respect to 100% by mass of the solid content of the high refractive index layer. Examples of such additives are described below.
  • At least one of the high refractive index layer and the low refractive index layer may further contain a surfactant.
  • a surfactant any of zwitterionic, cationic, anionic, and nonionic types can be used. More preferably, a betaine zwitterionic surfactant, a quaternary ammonium salt cationic surfactant, a dialkylsulfosuccinate anionic surfactant, an acetylene glycol nonionic surfactant, or a fluorine cationic interface Activators are preferred.
  • the addition amount of the surfactant according to the present invention is in the range of 0.005 to 0.3% by mass when the total mass of the coating solution for high refractive index layer or the coating solution for low refractive index layer is 100% by mass.
  • the content is 0.01 to 0.1% by mass.
  • the high refractive index layer or the low refractive index layer according to the present invention can contain an amino acid, an emulsion resin, a lithium compound and the like as appropriate as other additives.
  • Fluorescence enhancement described in JP-A-59-42993, JP-A-59-52689, JP-A-62-280069, JP-A-61-242871, and JP-A-4-219266 Whitening agent, sulfuric acid, phosphoric acid, acetic acid, citric acid, sodium hydroxide, potassium hydroxide, potassium carbonate and other pH adjusters, antifoaming agents, diethylene glycol and other lubricants, preservatives, Known additives such as additives, antistatic agents, matting agents, heat stabilizers, antioxidants, flame retardants, crystal nucleating agents, inorganic particles, organic particles, thickeners, lubricants, infrared absorbers, dyes, pigments, etc. Etc.
  • the method for forming the dielectric multilayer film according to the present invention is not particularly limited.
  • the dielectric multilayer film includes a water-soluble polymer and metal oxide particles on a substrate (transparent resin film).
  • a method of coating a refractive index layer coating solution and a low refractive index layer coating solution containing a water-soluble polymer and metal oxide particles is preferred.
  • the coating method is not particularly limited as long as it is a wet coating method.
  • examples thereof include a slide hopper coating method and an extrusion coating method described in the specification and US Pat. No. 2,761,791.
  • sequential multilayer application or simultaneous multilayer application may be used as a method of applying a plurality of layers in multiple layers.
  • the solvent for preparing the coating solution for the high refractive index layer and the coating solution for the low refractive index layer is not particularly limited, but water, an organic solvent or a mixed solvent thereof is preferable.
  • organic solvent examples include alcohols such as methanol, ethanol, 2-propanol and 1-butanol, esters such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate, diethyl ether and propylene.
  • examples include ethers such as glycol monomethyl ether and ethylene glycol monoethyl ether, amides such as dimethylformamide and N-methylpyrrolidone, and ketones such as acetone, methyl ethyl ketone, acetylacetone and cyclohexanone. These organic solvents may be used alone or in combination of two or more.
  • the solvent for the coating solution is particularly preferably water or a mixed solvent of water and methanol, ethanol, or ethyl acetate.
  • concentration of the water-soluble polymer in the coating solution for the high refractive index layer and the coating solution for the low refractive index layer is preferably in the range of 1 to 10% by mass.
  • concentration of the metal oxide particles in the coating solution for the high refractive index layer and the coating solution for the low refractive index layer is preferably in the range of 1 to 50% by mass.
  • the preparation method of the coating liquid for the high refractive index layer and the coating liquid for the low refractive index layer is not particularly limited.
  • the water-soluble polymer, the metal oxide particles, and the necessity There may be mentioned a method in which other additives added in accordance with the above are added and mixed by stirring.
  • the order of addition of the water-soluble polymer, metal oxide particles, and other additives used as necessary is not particularly limited, and each component may be added and mixed sequentially while stirring. However, they may be added and mixed at once. If necessary, it is further adjusted to an appropriate viscosity using a solvent.
  • the high refractive index layer is preferably formed using an aqueous high refractive index coating solution prepared by adding and dispersing core / shell particles.
  • the core / shell particles are prepared by adding to the coating solution for the high refractive index layer as a sol having a pH in the range of 5.0 to 7.5 and a negative zeta potential of the particles. It is preferable.
  • the viscosity at 40 to 45 ° C. of the coating solution for the high refractive index layer and the coating solution for the low refractive index layer when the simultaneous multilayer coating is performed by the slide hopper coating method is 5 to 300 mPa ⁇ s. 10 to 250 mPa ⁇ s is more preferable.
  • the viscosity at 40 to 45 ° C. of the coating solution for high refractive index layer and the coating solution for low refractive index layer when simultaneous multilayer coating is performed by the slide curtain coating method is preferably 5 to 1200 mPa ⁇ s, and preferably 25 to 500 mPa ⁇ s. -S is more preferable.
  • the viscosity at 15 ° C. of the coating solution for the high refractive index layer and the coating solution for the low refractive index layer is preferably 10 mPa ⁇ s or more, more preferably 15 to 30000 mPa ⁇ s, further preferably 20 to 20000 mPa ⁇ s, 20 ⁇ 18000 mPa ⁇ s is particularly preferred.
  • the coating and drying method is not particularly limited, but the substrate (transparent resin) is heated by heating the coating solution for the high refractive index layer and the coating solution for the low refractive index layer to 30 ° C or higher.
  • the temperature of the formed coating film is preferably cooled to 1 to 15 ° C. (set), and then It is preferable to dry 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.
  • the set means a step of increasing the viscosity of the coating composition and reducing the fluidity of the substances in each layer and in each layer by means such as applying cold air to the coating film to lower the temperature.
  • 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 application of cold air to completion of setting is within 5 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 too short, mixing of the components in the layer may be insufficient. On the other hand, if the set time is too long, the interlayer diffusion of the metal oxide particles proceeds, and the refractive index difference between the high refractive index layer and the low refractive index layer may be insufficient. In addition, if the high elasticity between the high refractive index layer and the low refractive index layer occurs quickly, the step of setting may not be provided.
  • the set time is adjusted by adjusting the concentration of the water-soluble polymer and the metal oxide particles, and adding other components such as various known gelling agents such as gelatin, pectin, agar, carrageenan, and gellan gum. Can be adjusted.
  • the temperature of the cold air is preferably 0 to 25 ° C, more preferably 5 to 10 ° C. Further, the time during which the coating film is exposed to the cold air is preferably 10 to 120 seconds, although it depends on the transport speed of the coating film.
  • the dielectric multilayer film according to the present invention has a hard coat on the surface opposite to the side on which the adhesive layer of the dielectric multilayer film is formed as a surface protective layer for enhancing the scratch resistance. It has a layer (hereinafter also simply referred to as HC layer).
  • the hard coat material constituting the hard coat layer according to the present invention a material having a small shrinkage stress after curing, such as an inorganic material typified by polysiloxane or a curable resin such as an ultraviolet curable urethane acrylate resin, is used. It is preferable to use it.
  • These hard coat materials can be used alone or in combination of two or more.
  • Specific compounds include tetramethoxy silane, tetraethoxy silane, tetra-iso-propoxy silane, tetra-n-popropoxy silane, tetra-n-butoxy silane, tetra-sec-butoxy silane, tetra-tert-butoxy silane, terror Pentaethoxysilane, tetrapenta-iso-propoxysilane, tetrapenta-n-propoxysilane, tetrapenta-n-butoxysilane, tetrapenta-sec-butoxysilane, tetrapenta-tert-butoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyl Tributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethylethoxysilane, dimethylmethoxysilane, dimethylpropoxysilane, dimethylbutoxy Orchid
  • polyorganosiloxane-based hard coat material examples include Surcoat Series, BP-16N (manufactured by Doken Co., Ltd.), SR2441 (manufactured by Dow Corning Toray), Perma-New 6000 (manufactured by California Hardcoating Company). ) Etc. can be used.
  • examples of the curable resin used in the hard coat layer according to the present invention include a thermosetting resin and an active energy ray curable resin, but an active energy ray curable resin is preferable because of easy molding. .
  • Such curable resins can be used singly or in combination of two or more.
  • the active energy ray-curable resin refers to a resin that is cured through a crosslinking reaction or the like by irradiation with active energy rays such as ultraviolet rays and electron beams.
  • the active energy ray curable resin a component containing a monomer having an ethylenically unsaturated double bond is preferably used, and cured by irradiating an active energy ray such as an ultraviolet ray or an electron beam to cure the active energy ray.
  • a functional resin layer that is, a hard coat layer is formed.
  • the active energy ray curable resin include an ultraviolet curable resin and an electron beam curable resin, and an ultraviolet curable resin that is cured by irradiation with ultraviolet rays is preferable.
  • the ultraviolet curable resin examples include an ultraviolet curable urethane acrylate resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, an ultraviolet curable acrylic acrylate resin, and an ultraviolet curable epoxy resin. Etc. are preferably used.
  • the UV curable urethane acrylate resin generally includes 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter referred to as methacrylate) in addition to a product obtained by reacting a polyester polyol with an isocyanate monomer or a prepolymer. It is easily obtained by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate.
  • An ultraviolet curable polyester acrylate resin can be easily obtained by reacting a monomer such as 2-hydroxyethyl acrylate, glycidyl acrylate or acrylic acid with a hydroxyl group or carboxyl group at the end of the polyester (see, for example, Japanese Patent Laid-Open No. 59). -151112).
  • the ultraviolet curable epoxy acrylate resin is obtained by reacting a terminal hydroxyl group of an epoxy resin with a monomer such as acrylic acid, acrylic acid chloride, or glycidyl acrylate.
  • a monomer such as acrylic acid, acrylic acid chloride, or glycidyl acrylate.
  • the ultraviolet curable polyol acrylate resin include ethylene glycol (meth) acrylate, polyethylene glycol di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and diester.
  • Examples thereof include resins obtained by curing one or more monomers such as pentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentaacrylate, and pentaerythritol ethylene oxide-modified tetraacrylate.
  • monomers such as pentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentaacrylate, and pentaerythritol ethylene oxide-modified tetraacrylate.
  • examples of commercially available products of active energy ray-curable resins used for hard coat layer formation include, for example, the Hitaroid (registered trademark) series (manufactured by Hitachi Chemical Co., Ltd.), the Shikko series (Nippon Gosei Chemical Co., Ltd.) Company), ETERMER 2382 (ETERNAL CHEMICAL) and the like.
  • the hard coat layer has a configuration that does not promote shrinkage even under sunlight exposure conditions. Therefore, the hard coat layer preferably contains an ultraviolet absorber and / or an antioxidant.
  • the content of these ultraviolet absorbers and antioxidants is preferably 0.05% by mass or more and 4% by mass or less, and preferably 0.1% by mass or more and 3% by mass or less with respect to the total mass of the hard coat layer. Preferably there is.
  • the reaction in the hard coat layer is accelerated and the shrinkage stress is increased, and the hard coat layer itself becomes brittle due to the decomposition of the resin in the hard coat layer. Can happen.
  • shrinkage and decomposition of the hard coat layer can be suppressed, and weather resistance adhesion can be improved.
  • UV absorber examples include benzophenone, benzotriazole, phenyl salicylate, and triazine. Specific examples of such an ultraviolet absorber include compounds described in paragraphs “0137” to “0141” of JP2013-245849A. In addition, you may use this ultraviolet absorber individually or in mixture of 2 or more types.
  • the ultraviolet absorber may be a synthetic product or a commercially available product.
  • antioxidants examples include phenolic antioxidants, thiol antioxidants, phosphite antioxidants, hindered amine antioxidants, and the like. Further, these antioxidants and light stabilizers can be used in combination. Specific examples of such antioxidants and light stabilizers include compounds described in paragraphs “0102” to “0108” of JP-A-2014-000697. In addition, you may use this antioxidant individually or in mixture of 2 or more types.
  • the antioxidant may be a synthetic product or a commercially available product.
  • the hard coat layer may contain an infrared absorber, and may also serve as an infrared absorbing layer. Good.
  • the infrared absorber applicable to the hard coat layer according to the present invention both inorganic infrared absorbers and organic infrared absorbers can be used, but inorganic infrared absorbers are preferable, and visible light transmittance is high. From the viewpoints of infrared absorptivity, suitability for dispersion in a resin, and the like, it is more preferable to mix a zinc oxide-based infrared absorber in the hard coat layer.
  • inorganic infrared absorbers include zinc oxide, antimony-doped zinc oxide (AZO), indium-doped zinc oxide (IZO), gallium-doped zinc oxide (GZO), aluminum-doped zinc oxide, tin oxide, antimony-doped tin oxide ( ATO), indium-doped tin oxide (ITO), zinc antimonate, lanthanum boride, nickel complex compounds can be used, among which antimony-doped zinc oxide, antimony-doped tin oxide, indium-doped tin oxide or antimonic acid Zinc is preferred.
  • AZO antimony-doped zinc oxide
  • IZO indium-doped zinc oxide
  • GZO gallium-doped zinc oxide
  • ATO antimony-doped tin oxide
  • ITO indium-doped tin oxide
  • nickel complex compounds can be used, among which antimony-doped zinc oxide, antimony-doped tin oxide, indium-
  • organic infrared absorber for example, an imonium compound, a phthalocyanine compound, or an aminium compound can be used. These infrared absorbers can be used alone or in combination of two or more.
  • the infrared absorber may be a synthetic product or a commercially available product.
  • content of the infrared absorber in a hard-coat layer is 55 to 80 mass% with respect to the total mass of a hard-coat layer. If it is this range, since the said resin component in a hard-coat layer decreases, since shrinkage stress becomes small, it is preferable. When the content of the infrared absorber is less than 55% by mass, the thickness of the hard coat layer increases, shrinkage stress increases, and weather resistance tends to deteriorate. On the other hand, when the amount is more than 80% by mass, the resin component is too small, so that there is an excess of particles, and the hardness as the hard coat layer may not be exhibited.
  • the hard coat layer may contain inorganic fine particles other than the infrared absorber.
  • Preferable inorganic fine particles include fine particles of an inorganic compound containing a metal such as titanium, silica, zirconium, aluminum, magnesium, antimony, zinc or tin.
  • the average particle size of the inorganic fine particles is preferably 1000 nm or less, and more preferably in the range of 10 to 500 nm, from the viewpoint of ensuring visible light transmittance.
  • inorganic fine particles have a higher bonding strength with the curable resin forming the hard coat layer, they can be prevented from falling out of the hard coat layer, so that a photopolymerization reactivity such as monofunctional or polyfunctional acrylate is present. Those having a functional group introduced on the surface are preferred.
  • the hue can be adjusted by adding dyes or pigments to the hard coat layer.
  • dyes or pigments for example, cadmium red, molybdenum red, chromium permillion, chromium oxide, viridian, titanium cobalt green, cobalt green, cobalt chrome green, Victoria green, ultramarine blue, ultramarine blue, bitumen, Berlin blue, miloli blue, cobalt blue, cerulean blue,
  • Colored inorganic pigments such as cobalt silica blue, cobalt zinc blue, manganese violet, mineral violet, and cobalt violet, organic pigments such as phthalocyanine pigments, and anthraquinone dyes are preferably used.
  • the layer thickness of the hard coat layer is preferably from 0.1 to 50 ⁇ m, more preferably from 1 to 20 ⁇ m. If it is 0.1 ⁇ m or more, the hard coat property tends to be improved. Conversely, if it is 50 ⁇ m or less, the transparency of the dielectric multilayer film tends to be improved.
  • a coating solution for a hard coat layer is applied by coating with a wire bar, spin coating, dip coating, etc., and a dielectric multilayer substrate or water-soluble polymer and metal are used.
  • a method of coating on a layer containing oxide particles to form a film and it can also be formed by a dry film forming method such as vapor deposition.
  • a continuous coating apparatus such as a die coater, a gravure coater, or a comma coater.
  • a heat treatment for 30 minutes to several days in a temperature range of 50 to 150 ° C. is promoted in order to promote curing and crosslinking of the hard coat material. It is preferable to carry out. In consideration of the heat resistance of the coated substrate and the stability of the substrate when it is formed into a laminated roll, it is preferable to carry out the treatment within a range of 40 to 80 ° C. for 2 days or more.
  • the reactivity varies depending on the irradiation wavelength, the illuminance, and the light amount of the active energy ray, and therefore it is necessary to select optimum conditions depending on the resin to be used.
  • the illuminance is preferably 50 to 1500 mW / cm 2 and the irradiation energy amount is preferably 50 to 1500 mJ / cm 2 .
  • Examples of the solvent used in the hard coat layer coating solution include the solvents exemplified in the above (4-1).
  • a surfactant may be added to the coating solution for forming the hard coat layer to impart leveling properties, water repellency, slipping properties, and the like.
  • An acrylic surfactant, a silicon-type surfactant, a fluorine-type surfactant, etc. can be used.
  • a fluorosurfactant is preferably used from the viewpoint of leveling properties, water repellency, and slipperiness.
  • the fluorosurfactant include, for example, Megafac (registered trademark) F series (F-430, F-477, F-552 to F-559, F-561, F-562, etc., manufactured by DIC Corporation.
  • the hard coat layer included in the dielectric multilayer film of the present invention may have only one layer or two or more layers. When it has two or more layers, the configuration of each hard coat layer may be the same or different.
  • the dielectric multilayer film of the present invention may further contain an intermediate layer (hereinafter also simply referred to as a UC layer) between the hard coat layer described above and the dielectric multilayer film. .
  • the function of the intermediate layer is formed for the purpose of enhancing the adhesion between the dielectric multilayer film and the hard coat layer and further reducing the shrinkage stress of the hard coat layer.
  • the intermediate layer is preferably composed of a resin component, and examples thereof include polyvinyl acetal resin, acrylic resin, and urethane resin. These resin components can be used alone or in admixture of two or more.
  • the polyvinyl acetal resin applicable to the intermediate layer according to the present invention is a resin obtained by acetalizing polyvinyl alcohol by reaction with at least one suitable aldehyde, and specifically, polyvinyl acetal, polyvinyl formal, polyvinyl butyral, Examples thereof include copolymer acetals such as polyvinyl butyral and polyvinyl butyral acetal containing partially formalized portions. Moreover, these polyvinyl acetal resins may contain other repeating units.
  • the degree of acetalization of these polyvinyl acetal resins is preferably from 5 to 65 mol%, more preferably from 15 to 50 mol% from the viewpoint of water solubility and adhesion effects.
  • the degree of acetalization is in the above range, the adhesion with the hard coat layer and the dielectric multilayer film is excellent.
  • acrylic monomer include, for example, acrylic acid; methacrylic acid; acrylic ester, such as alkyl acrylate (for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t -Butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, phenylethyl acrylate, etc.), hydroxy-containing alkyl acrylates (eg 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, etc.); methacryl
  • the above-mentioned acrylic monomers can be used alone or in combination of two or more. Preferred are methyl methacrylate-ethyl acrylate-ammonium acrylate-acrylamide copolymer, methacrylamide-butyl acrylate-sodium acrylate-methyl methacrylate-N-methylol acrylamide copolymer, and the like.
  • the acrylic resin can be produced and obtained as an acrylic emulsion, an acrylic aqueous solution, an acrylic dispersion, or the like.
  • the acrylic resin used for the intermediate layer according to the present invention may be a synthetic product or a commercially available product.
  • LR1730 made by Mitsubishi Rayon Co., Ltd. is mentioned, for example.
  • isocyanate can be used as a crosslinking agent
  • organic diisocyanate compounds include aromatic diesters such as xylylene diisocyanate, isophorone diisocyanate, and alicyclic diisocyanates, tolylene diisocyanate, and 4,4-diphenylmethane diisocyanate.
  • Aliphatic diisocyanates such as aromatic diisocyanates and hexamethylene diisocyanate are preferred.
  • blocked isocyanate can be used, for example, product number 214 manufactured by Baxenden.
  • Urethane resin is a general term for polymers having a urethane bond in the main chain, and is usually obtained by reaction of polyisocyanate and polyol.
  • Polyisocyanates include TDI (tolylene diisocyanate), MDI (diphenylmethane diisocyanate), NDI (naphthylene diisocyanate), TODI (toluidine diisocyanate), HDI (hexamethylene dicyanate), IPDI (isophorone diisocyanate), etc. Includes ethylene glycol, propylene glycol, glycerin, hexanetriol, and the like.
  • the isocyanate of the present invention a polymer obtained by subjecting a polyurethane polymer obtained by the reaction of polyisocyanate and polyol to chain extension treatment to increase the molecular weight can also be used.
  • the polyurethane resin described in the present invention may be one or two or more polyurethane resins, or may be a mixture with a polyvinyl acetal resin or an acrylic resin.
  • a urethane-modified acrylic polymer can also be used as the urethane resin.
  • the polyurethane resin preferably has a Tg of ⁇ 30 to 60 ° C., more preferably a Tg of ⁇ 20 to 40 ° C. If the glass transition temperature Tg of the polyurethane resin contained in the intermediate layer is 60 ° C. or less, good adhesion can be obtained. If the glass transition temperature Tg of the polyurethane resin contained in the intermediate layer is ⁇ 30 ° C. or higher, it is preferable from the viewpoint of the stability of the polyurethane resin. As the polyurethane resin, a synthetic product or a commercially available product may be used.
  • a material having a polyrotaxane structure can also be used as another intermediate layer material.
  • SeRM Super Polymer A-1000 Advanced Soft Materials Co., Ltd., hydroxy group-containing polyrotaxane
  • hydroxy group-containing polyrotaxane can be mentioned as a representative example.
  • the layer thickness of the intermediate layer is preferably 1 to 10 ⁇ m, more preferably 4 to 10 ⁇ m, and even more preferably 4 to 8 ⁇ m.
  • Young's modulus of the intermediate layer is not more than 1.0 ⁇ 10 -3 GPa or 2.0 ⁇ 10 1 GPa and preferably, 1.0 ⁇ 10 -3 GPa or 1.0 ⁇ 10 1 GPa or less Is more preferable. If the Young's modulus is in this range, the intermediate layer acts as a stress relaxation layer, relieves the shrinkage stress of the hard coat layer, and even if the difference in volume shrinkage between the hard coat layer and the dielectric multilayer film increases, the peeling occurs. It becomes difficult to do.
  • the intermediate layer contained in the dielectric multilayer film of the present invention may have only one layer or two or more layers. When it has two or more layers, the structure of each intermediate
  • the method for forming the intermediate layer is not particularly limited, and examples thereof include a method for forming a film by applying a coating solution for the intermediate layer by coating with a wire bar, spin coating, dip coating, etc., and also a die coater, gravure coater, comma coater It is possible to apply and form a film using a continuous application apparatus such as the above.
  • the solvent used in the intermediate layer coating solution include the solvents exemplified in the above (4-1).
  • the dielectric multilayer film of the present invention has an adhesive layer.
  • the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is not particularly limited, and examples thereof include acrylic pressure-sensitive adhesives, silicon pressure-sensitive adhesives, urethane pressure-sensitive adhesives, polyvinyl butyral pressure-sensitive adhesives, and ethylene-vinyl acetate pressure-sensitive adhesives. Can do.
  • the dielectric multilayer film of the present invention When the dielectric multilayer film of the present invention is attached to a window glass, water is sprayed on the window, and the adhesive method of attaching the adhesive layer of the dielectric multilayer film to the wet glass surface, the so-called water pasting method is re-stretched. It is preferably used from the viewpoint of position correction. For this reason, an acrylic pressure-sensitive adhesive that has a weak adhesive force in the presence of water is preferably used.
  • the acrylic pressure-sensitive adhesive used may be either solvent-based or emulsion-based, but is preferably a solvent-based pressure-sensitive adhesive because it is easy to increase the adhesive strength and the like, and among them, those obtained by solution polymerization are preferable.
  • raw materials for producing such a solvent-based acrylic pressure-sensitive adhesive by solution polymerization include, for example, acrylic acid esters such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and octyl acrylate, and agglomerates as the main monomer serving as a skeleton.
  • a comonomer for improving strength vinyl acetate, acrylonitrile, styrene, methyl methacrylate, etc. are further functionalized to promote cross-linking, to provide stable adhesive strength, and to maintain a certain level of adhesive strength even in the presence of water.
  • the group-containing monomer include methacrylic acid, acrylic acid, itaconic acid, hydroxyethyl methacrylate, glycidyl methacrylate, and the like. Since the adhesive layer of the laminated film requires a particularly high tack as the main polymer, those having a low glass transition temperature (Tg) such as butyl acrylate are particularly useful.
  • additives for example, stabilizers, surfactants, UV absorbers, silane coupling agents, flame retardants, antistatic agents, antioxidants, thermal stabilizers, lubricants, fillers, coloring, adhesion A regulator or the like can also be contained.
  • an ultraviolet absorber when used for window sticking, the addition of an ultraviolet absorber is effective in order to suppress deterioration of the dielectric multilayer film due to ultraviolet rays.
  • the layer thickness of the adhesive layer is preferably 1 ⁇ m to 100 ⁇ m, more preferably 3 to 50 ⁇ m. If it is 1 micrometer or more, there exists a tendency for adhesiveness to improve and sufficient adhesive force is acquired. On the contrary, if the thickness is 100 ⁇ m or less, not only the transparency of the dielectric multilayer film is improved, but also when the dielectric multilayer film is attached to the window glass and then peeled off, no cohesive failure occurs between the adhesive layers, and the glass There is a tendency for the adhesive residue on the surface to disappear.
  • the method for forming the adhesive layer on the dielectric multilayer film is not particularly limited, but separately from the dielectric multilayer film, the adhesive layer coating liquid is applied on the separator and dried to form the adhesive layer.
  • a method of bonding the layer and the dielectric multilayer film is preferable.
  • Examples of the separator used at this time include a silicone-coated release PET film and a silicone-coated PE film.
  • the method of applying the coating solution for the adhesive layer on the separator is not particularly limited, and examples thereof include a method of applying the coating solution by wire bar coating, spin coating, dip coating, etc., and forming a film. It is possible to apply and form a film using a continuous coating apparatus such as a coater or comma coater.
  • the dielectric multilayer film according to the present invention is further provided with a functional layer such as a heat insulating layer, for example, within a range not impairing the object effects of the present invention. May be.
  • an adhesive layer may be further provided on one surface of the dielectric multilayer film.
  • the constitution of the adhesive layer applicable to the present invention is not particularly limited, and for example, any of a dry laminating agent, a wet laminating agent, a heat sealing agent, a hot melt agent and the like are used.
  • the adhesive include polyester resin, urethane resin, polyvinyl acetate resin, acrylic resin, and nitrile rubber.
  • the method for providing the adhesive layer is preferably a laminating method.
  • a laminating method For example, it is preferable to carry out a roll method continuously from the viewpoint of economy and productivity.
  • the thickness of the adhesive layer is usually preferably in the range of about 1 to 100 ⁇ m from the viewpoints of adhesive effect, drying speed, and the like.
  • the dielectric multilayer film according to the present invention has a layer containing a water-soluble polymer having a single-layer structure and metal oxide particles
  • examples of the water-soluble polymer include carboxymethyl cellulose, polyvinyl pyrrolidone, and polyvinyl pyrrolidone. Copolymers with vinyl acetate and modified products thereof, polyvinyl alcohol, modified products thereof and the like are used.
  • a metal oxide particle a silica, titanium, a zinc oxide, a zirconia, a cerium oxide etc. are used, for example. These water-soluble polymers and metal oxide particles can be used alone or in combination of two or more.
  • the thickness of the layer containing the water-soluble polymer and metal oxide particles having a single layer structure is preferably 10 nm to 30 ⁇ m, and more preferably 10 nm to 10 ⁇ m.
  • the content of the water-soluble polymer in the layer containing the water-soluble polymer and the metal oxide particles is 10 with respect to 100% by mass of the solid content of the layer containing the water-soluble polymer and the metal oxide particles. It is preferably ⁇ 99.9% by mass, more preferably 30 to 99% by mass.
  • the content of the metal oxide particles is preferably 0.1 to 90% by mass with respect to 100% by mass of the solid content of the layer containing the water-soluble polymer and the metal oxide particles, and 1 to 80% by mass. % Is more preferable.
  • the method for forming the layer containing the water-soluble polymer and metal oxide particles is not particularly limited, and examples thereof include a method of applying a coating solution by wire bar coating, spin coating, dip coating, and the like, and forming a film. It is also possible to apply and form a film using a continuous coating apparatus such as a gravure coater or a comma coater.
  • the layer containing a water-soluble polymer having a single-layer structure and metal oxide particles may be formed on at least one surface of the base material, and may be formed on both surfaces of the base material. From the viewpoint of light reflectance and gas permeability, it is preferably formed on both surfaces of the substrate.
  • the method for producing a dielectric multilayer film of the present invention includes forming an adhesive layer on the dielectric multilayer film prior to forming the hard coat layer on the dielectric multilayer film. Thereby, the evaporation of moisture from the dielectric multilayer film on the adhesive layer side attached to the glass is suppressed, and moisture in the layer is retained. Thereby, the weather resistance of a dielectric multilayer film improves, and the dielectric multilayer film excellent in weather resistance can be obtained. Further, as described above, effects such as suppression of curling of the dielectric multilayer film, suppression of blocking at the time of manufacturing the dielectric multilayer film, or suppression of coating unevenness at the time of applying the coating liquid for the hard coat layer can be obtained. .
  • the order in which the other layers are formed is not particularly limited.
  • preferred forms include (1) formation of a layer containing a water-soluble polymer and a metal oxide on a substrate (formation of a dielectric multilayer film), and (2) formation of an adhesive layer on the dielectric multilayer film.
  • the order is (3) formation of an intermediate layer and a hard coat layer on the dielectric multilayer film, and (4) formation of other layers.
  • the dielectric multilayer film according to the present invention exhibits a function of reflecting (shielding) sunlight, infrared rays, visible rays, or ultraviolet rays.
  • the dielectric multilayer film of the present invention is suitably used as an infrared shielding film or an ultraviolet shielding film.
  • the structure can be constituted by being attached to, for example, glass through an adhesive layer. That is, this invention also provides the structure which bonded the dielectric multilayer film obtained by the said manufacturing method to glass through the said adhesion layer.
  • the boundary portion between the outdoors and the room, for example, the indoor side surface of the window glass and the surface provided with the adhesive layer of the dielectric multilayer film can be bonded to install the dielectric multilayer film.
  • a dielectric multilayer film constituting laminated glass it can be used as a dielectric multilayer film constituting laminated glass.
  • an adhesive layer is provided on the hard coat layer 6B of the dielectric multilayer film shown in FIG. 2, and a glass substrate is bonded to both surfaces of the dielectric multilayer film via the adhesive layer and the adhesive layer. Laminated glass can be produced.
  • the coating liquid L1 for low refractive index layer was prepared by finishing to 1000 parts by mass with pure water.
  • the base-treated titanium compound was suspended in pure water so as to have a TiO 2 concentration of 20 g / L, and 0.4 mol% of citric acid was added to the amount of TiO 2 with stirring to raise the temperature.
  • concentrated hydrochloric acid was added to a hydrochloric acid concentration of 30 g / L, and the mixture was stirred for 3 hours while maintaining the liquid temperature.
  • the pH and zeta potential of the obtained titanium oxide sol aqueous dispersion were measured, the pH was 1.4 and the zeta potential was +40 mV. Furthermore, when the particle size was measured by Zetasizer Nano manufactured by Malvern, the volume average particle size was 35 nm, and the monodispersity was 16%.
  • the silica-modified titanium oxide particles are a compound having a photocatalytic action.
  • AZO trade name: Celnax (registered trademark) CX-Z410K, antimony-doped zinc oxide, manufactured by Nissan Chemical Industries, Ltd.
  • Hitaroid (registered trademark) 7975 Hitachi Chemical Co., Ltd.
  • UV curable acrylic acrylate resin methyl ethyl ketone was added as a solvent.
  • the coating liquid A for hard coat layer was prepared by adjusting the amount to 55% by mass.
  • ATO (trade name: SR35M, manufactured by ANP) is used as an infrared absorber instead of AZO, and Beamset 577 (Arakawa Chemical Industries, Ltd.) is used as an ultraviolet curable resin instead of Hitaroid (registered trademark) 7975.
  • a coating liquid B for hard coat layer was prepared in the same manner as the coating liquid A for hard coat layer except for the above.
  • the coating liquid for hard coat layer was the same as the coating liquid B for hard coating layer except that 3% by mass of Coronate L (manufactured by Nippon Polyurethane Industry Co., Ltd.) was added to the coating liquid B for hard coat layer. C was produced.
  • Coronate L manufactured by Nippon Polyurethane Industry Co., Ltd.
  • Example 1 Distilling carboxymethyl cellulose (CMC, manufactured by Daicel Corporation) on a polyethylene terephthalate film (A4300 manufactured by Toyobo Co., Ltd .: double-sided easy-adhesive layer, length 200 m ⁇ width 210 mm, refractive index: 1.58, PET) having a thickness of 50 ⁇ m. Dilute to 10% by mass with water and colloidal silica (10% by mass, manufactured by Nissan Chemical Co., Ltd .; Snowtex (registered trademark) OXS) is 30% by mass with respect to the resin content of CMC. The solution was prepared to prepare a coating solution.
  • the prepared coating solution is applied using a comma coater so as to have a dry film thickness of 5 ⁇ m and dried (drying temperature 80 ° C., drying time 120 seconds), and is a layer containing a water-soluble polymer and metal oxide particles.
  • a layer having a single layer structure (hereinafter also simply referred to as a CMC layer) was formed. Thereafter, a single CMC layer was formed on the back surface of the PET film in the same manner as described above.
  • Nissetsu KP-981 manufactured by Nippon Carbide Industries Co., Ltd.
  • Tinuvin registered trademark 477 as a UV absorber. It added so that it might become the density
  • the separator SP-PET brand: PET-O2-BU
  • a comma coater Mitsubishi Chemicals Tosero Co., Ltd.
  • the film on which the CMC layer was formed was fed from the second paper feed, and laminated with the CMC layer to form an adhesive layer on the CMC layer.
  • the intermediate layer coating solution was applied onto the surface of the CMC layer opposite to the CMC layer on which the adhesive layer was formed using a gravure coater so that the dry layer thickness was 6.0 ⁇ m. Dried for a minute to form an intermediate layer. Thereafter, on the intermediate layer, the above-prepared coating solution A for hard coat layer was applied with a gravure coater under the condition that the dry layer thickness was 7.5 ⁇ m, and then dried at a drying zone temperature of 90 ° C.
  • the hard coat layer was cured by using an ultraviolet lamp and the illuminance of the irradiated part was 100 mW / cm 2 and the irradiation amount was 0.5 J / cm 2 to form a hard coat layer, thereby producing a dielectric multilayer film.
  • Example 2 A dielectric multilayer film was produced in the same manner as in Example 1 except that CMC was replaced with polyvinylpyrrolidone (manufactured by Nippon Shokubai Co., Ltd., PVP), and the coating was made with a solid content of 20% by mass.
  • CMC was replaced with polyvinylpyrrolidone (manufactured by Nippon Shokubai Co., Ltd., PVP), and the coating was made with a solid content of 20% by mass.
  • Example 3 ⁇ Formation of dielectric multilayer film (infrared shielding layer)> A slide hopper coating apparatus capable of coating 16 layers was used. A 50 ⁇ m thick polyethylene terephthalate film (manufactured by Toyobo Co., Ltd.) heated to 45 ° C. as a substrate while keeping the coating solution L1 for low refractive index layer and the coating solution H1 for high refractive index layer prepared above at 45 ° C.
  • A4300 double-sided easy-adhesion layer, length 200 m ⁇ width 210 mm, refractive index: 1.58), the lowermost layer and the uppermost layer are low-refractive index layers, and other than that, a high-refractive index layer and a low-refractive index layer
  • a total of 16 layers were simultaneously coated so that the layer thickness during drying was 150 nm for each low refractive index layer and 130 nm for each high refractive index layer.
  • Confirmation of the mixed region (mixed layer) between layers and measurement (confirmation) of the layer thickness were performed by cutting the dielectric multilayer film (dielectric multilayer film sample) and cutting the cut surface with an XPS surface analyzer. By measuring the abundance of the material (TiO 2 ) and the low refractive index layer material (SiO 2 ), it was confirmed that the layer thickness of each layer described above was ensured.
  • dielectric multilayer film A After completion of the setting, hot air of 70 ° C. was blown and dried to form a dielectric multilayer film having 16 layers of infrared reflection characteristics. This configuration is referred to as a dielectric multilayer film A.
  • a dielectric multilayer film B composed of 16 layers was formed on the surface of the base material opposite to the surface on which the dielectric multilayer film A of the polyethylene terephthalate film was formed, in the same manner as described above.
  • Nisset KP-981 manufactured by Nippon Carbide Industries Co., Ltd.
  • Tinuvin (registered trademark) 477 was added as a UV absorber so as to be 5% by mass.
  • the separator SP-PET brand: PET-O2-BU
  • a comma coater Mitsubishi Chemicals Tosero Co., Ltd.
  • the intermediate layer coating solution is applied onto the surface of the dielectric multilayer film B opposite to the substrate using a gravure coater so that the dry layer thickness is 6.0 ⁇ m. Dried for a minute to form an intermediate layer.
  • the above-prepared coating solution A for hard coat layer was applied with a gravure coater under the condition that the dry layer thickness was 7.5 ⁇ m, and then dried at a drying zone temperature of 90 ° C. for 1 minute,
  • the hard coat layer is cured by using an ultraviolet lamp and the irradiation part has an illuminance of 100 mW / cm 2 and an irradiation amount of 0.5 J / cm 2 to form a hard coat layer on the dielectric multilayer film B.
  • a film was prepared.
  • the refractive index of the high refractive index layer formed above was 1.95, and the refractive index of the low refractive index layer was 1.45.
  • Example 4 An adhesive layer is formed on the dielectric multilayer film A, the dielectric multilayer film layer B and the intermediate layer are not formed, and a hard coat layer is formed on the surface of the substrate opposite to the dielectric multilayer film A side. did. Except for this, a dielectric multilayer film was prepared in the same manner as in Example 4.
  • Example 5 A dielectric multilayer film having ultraviolet reflection characteristics is produced by coating so that the layer thickness of each layer of the low refractive index layer is 50 nm and the layer thickness of each layer of the high refractive index layer is 43 nm. did. A dielectric multilayer film was produced in the same manner as Example 3 except for the above.
  • Example 6 A dielectric multilayer film having ultraviolet reflection characteristics is produced by coating so that the layer thickness of each layer of the low refractive index layer is 50 nm and the layer thickness of each layer of the high refractive index layer is 43 nm. did. A dielectric multilayer film was produced in the same manner as in Example 4 except for the above.
  • Example 7 A dielectric multilayer film was produced in the same manner as in Example 3 except that the hard coat layer coating solution A was changed to the hard coat layer coating solution B.
  • Example 8 A dielectric multilayer film was produced in the same manner as in Example 4 except that the hard coat layer coating solution A was changed to the hard coat layer coating solution B.
  • Example 9 A dielectric multilayer film was produced in the same manner as in Example 3 except that the hard coat layer coating solution A was changed to the hard coat layer coating solution C.
  • Example 10 A dielectric multilayer film was produced in the same manner as in Example 4 except that the hard coat layer coating solution A was changed to the hard coat layer coating solution C.
  • the prepared coating solution was applied and dried (drying temperature 80 ° C., drying time 120 seconds) using a comma coater to form a dry film thickness of 5 ⁇ m. Thereafter, a PVP layer was formed in the same manner as described above on the back surface of the PET film. Next, the intermediate layer coating solution is applied to the surface of the PVP layer on one side using a gravure coater so that the dry layer thickness is 6.0 ⁇ m, and dried at 90 ° C. for 1 minute. Formed. Then, after coating the coating liquid A for hard coat layer prepared above on the intermediate layer with a gravure coater under the condition that the dry layer thickness is 7.5 ⁇ m, after drying at a drying section temperature of 90 ° C.
  • the hard coat layer was cured by setting the illuminance of the irradiated part to 100 mW / cm 2 and the irradiation amount to 0.5 J / cm 2 to form a hard coat layer.
  • Nissetsu KP-981 manufactured by Nippon Carbide Industries Co., Ltd.
  • Tinuvin registered trademark 477 as a UV absorber. It added so that it might become the density
  • the separator SP-PET (manufactured by Mitsui Chemicals, Inc.) was coated with a comma coater so that the dry film thickness was 10 ⁇ m, dried at 80 ° C. for 1 minute, A PVP layer formed on the opposite side of the PVP layer on which the hard coat layer was formed was fed, and an adhesive layer was laminated on the PVP layer to form an adhesive layer, thereby producing a dielectric multilayer film.
  • A4300 double-sided easy-adhesion layer, length 200 m ⁇ width 210 mm, refractive index: 1.58), the lowermost layer and the uppermost layer are low-refractive index layers, and other than that, a high-refractive index layer and a low-refractive index layer
  • a total of 16 layers were simultaneously applied so that the layer thickness during drying was 150 nm for each low refractive index layer and 130 nm for each high refractive index layer.
  • Confirmation of the mixed region (mixed layer) between layers and measurement (confirmation) of the layer thickness were performed by cutting the dielectric multilayer film (dielectric multilayer film sample) and cutting the cut surface with an XPS surface analyzer. By measuring the abundance of the material (TiO 2 ) and the low refractive index layer material (SiO 2 ), it was confirmed that the layer thickness of each layer described above was ensured.
  • dielectric multilayer film A After completion of the setting, hot air of 70 ° C. was blown and dried to form a dielectric multilayer film having 16 layers of infrared reflection characteristics. This configuration is referred to as a dielectric multilayer film A.
  • a dielectric multilayer film B composed of 16 layers was formed on the surface of the polyethylene terephthalate film opposite to the surface on which the dielectric multilayer film A was formed in the same manner as described above.
  • the intermediate layer coating solution is applied using a gravure coater so that the dry layer thickness is 6.0 ⁇ m, and dried at 90 ° C. for 1 minute to form the intermediate layer. Formed.
  • the above-prepared coating solution A for hard coat layer was applied with a gravure coater under the condition that the dry layer thickness was 7.5 ⁇ m, and then dried at a drying zone temperature of 90 ° C. for 1 minute,
  • the hard coat layer was cured on the dielectric multilayer film B by using an ultraviolet lamp and setting the illuminance of the irradiated portion to 100 mW / cm 2 and the irradiation amount to 0.5 J / cm 2 .
  • Nissetu KP-981 manufactured by Nippon Carbide Industries Co., Ltd.
  • Tinuvin (registered trademark) 477 is added as a UV absorber to a concentration of 5% by mass.
  • the separator SP-PET brand: PET-O2-BU
  • a comma coater Mitsubishi Chemicals Tosero Co., Ltd.
  • dry feed the film with the hard coat layer formed from the second paper feed, laminate it with the dielectric multilayer film A, and form the adhesive layer on the dielectric multilayer film A to produce the dielectric multilayer film did.
  • the refractive index of the high refractive index layer formed above was 1.95, and the refractive index of the low refractive index layer was 1.45.
  • Comparative Example 4 Sixteen dielectric multilayers were formed on one side of the PET film. Thereafter, a hard coat layer was formed on the opposite side of the dielectric multilayer film by the same method as in Comparative Example 2 to produce a dielectric multilayer film.
  • ⁇ Xenon irradiation weather resistance evaluation> The produced glass-bonded film was irradiated for 60 days in an environment of 23 ° C. and 50% RH using an Isuperxenon tester (model: XER-W75) manufactured by Iwasaki Electric Co., Ltd., and the appearance was observed. The cracks were ranked according to the same evaluation criteria as described above.
  • the weather resistance of the obtained dielectric multilayer film is greatly improved by the production method of the present invention in which the adhesive layer is formed before the hard coat layer, and an excellent dielectric multilayer film is obtained. It was shown that.

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  • Optics & Photonics (AREA)
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Abstract

L'invention permet d'améliorer la résistance aux intempéries d'un film diélectrique multicouche. Elle se réfère à un procédé de fabrication d'un film diélectrique multicouche, dans lequel une couche de revêtement dur est formée sur une surface d'un stratifié diélectrique, et une couche adhésive autocollante est prévue sur l'autre surface dudit stratifié diélectrique, lequel stratifié diélectrique comprend un substrat et une couche contenant à la fois un polymère soluble dans l'eau et des particules d'oxyde métallique. Dans le procédé, la couche adhésive autocollante est formée sur le stratifié diélectrique avant la formation de la couche de revêtement dur.
PCT/JP2014/073386 2013-09-12 2014-09-04 Procédé de fabrication d'un film diélectrique multicouche WO2015037514A1 (fr)

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JP2017066381A (ja) * 2015-09-30 2017-04-06 Ｈｏｙａ Ｃａｎｄｅｏ Ｏｐｔｒｏｎｉｃｓ株式会社 紫外線吸収塗料、紫外線吸収膜、光吸収膜、光学素子、光学ユニットおよび光照射装置
US10988624B2 (en) 2015-09-30 2021-04-27 Hoya Corporation Ultraviolet absorbing film provided on a surface of an optical element and use thereof for reducing internal reflections

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WO2013054912A1 (fr) * 2011-10-12 2013-04-18 コニカミノルタホールディングス株式会社 Film de blocage de l'infrarouge proche et corps de blocage de l'infrarouge proche
WO2013077252A1 (fr) * 2011-11-21 2013-05-30 コニカミノルタ株式会社 Film de protection contre les infrarouges et corps de protection contre les infrarouges
WO2013111735A1 (fr) * 2012-01-25 2013-08-01 コニカミノルタアドバンストレイヤー株式会社 Film optique

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JP2012220706A (ja) * 2011-04-08 2012-11-12 Konica Minolta Holdings Inc 赤外反射フィルムおよびそれを用いた赤外反射体
WO2013054912A1 (fr) * 2011-10-12 2013-04-18 コニカミノルタホールディングス株式会社 Film de blocage de l'infrarouge proche et corps de blocage de l'infrarouge proche
WO2013077252A1 (fr) * 2011-11-21 2013-05-30 コニカミノルタ株式会社 Film de protection contre les infrarouges et corps de protection contre les infrarouges
WO2013111735A1 (fr) * 2012-01-25 2013-08-01 コニカミノルタアドバンストレイヤー株式会社 Film optique

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Publication number Priority date Publication date Assignee Title
JP2017066381A (ja) * 2015-09-30 2017-04-06 Ｈｏｙａ Ｃａｎｄｅｏ Ｏｐｔｒｏｎｉｃｓ株式会社 紫外線吸収塗料、紫外線吸収膜、光吸収膜、光学素子、光学ユニットおよび光照射装置
US10988624B2 (en) 2015-09-30 2021-04-27 Hoya Corporation Ultraviolet absorbing film provided on a surface of an optical element and use thereof for reducing internal reflections

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