WO2016010049A1 - Film laminé et procédé de production associé - Google Patents

Film laminé et procédé de production associé Download PDF

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Publication number
WO2016010049A1
WO2016010049A1 PCT/JP2015/070199 JP2015070199W WO2016010049A1 WO 2016010049 A1 WO2016010049 A1 WO 2016010049A1 JP 2015070199 W JP2015070199 W JP 2015070199W WO 2016010049 A1 WO2016010049 A1 WO 2016010049A1
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WIPO (PCT)
Prior art keywords
layer
infrared
mass
refractive index
laminated film
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PCT/JP2015/070199
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English (en)
Japanese (ja)
Inventor
小沼　太朗
聡史 久光
翔太 畠沢
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コニカミノルタ株式会社
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Application filed by コニカミノルタ株式会社 filed Critical コニカミノルタ株式会社
Priority to JP2016534457A priority Critical patent/JPWO2016010049A1/ja
Publication of WO2016010049A1 publication Critical patent/WO2016010049A1/fr

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Classifications

    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/28—Interference filters

Definitions

  • the present invention relates to a laminated film and a method for producing the same.
  • a laminated film in which a high refractive index layer and a low refractive index layer are alternately laminated by adjusting the respective optical film thicknesses is theoretically supported by selectively reflecting light of a specific wavelength, It is used as a laminated film that transmits visible light and selectively reflects near infrared rays.
  • Such a laminated film is used as a reflective film for heat ray shielding used for windows of buildings, members for vehicles, and the like.
  • an infrared reflective multilayer film comprising an outer reflective layer and an infrared light absorbing nanoparticle layer laminated adjacently on the infrared reflective layer.
  • the infrared light absorbing nanoparticle layer is an antimony-doped tin oxide (also referred to as antimony-doped tin oxide; hereinafter referred to as ATO) or indium tin oxide (also referred to as indium-doped tin oxide) which is an infrared absorber. ) Etc.
  • a multilayer film having a high effect of shielding infrared rays by providing an infrared light-absorbing nanoparticle layer containing an infrared absorber as disclosed in JP-T-2008-528313 (corresponding to US Patent Application Publication No. 2006/154049) Is provided.
  • an object of the present invention is made in view of the above circumstances, and in a laminated film having a layer containing an infrared absorber, even if it is exposed to sunlight for a long period of time, it is a laminated film with less occurrence of cracks.
  • Another object of the present invention is to provide a laminated film that has a layer containing an infrared absorber and that does not easily discolor even when exposed to sunlight for a long period of time.
  • Still another object of the present invention is to provide a laminated film having a layer containing an infrared absorber and capable of reducing haze even when exposed to sunlight for a long period of time.
  • the present inventors have found that the object of the present invention can be achieved by adopting the following configuration.
  • the infrared absorption layer further includes a surfactant, and the total concentration of the iron, copper, and chromium with respect to the surfactant in the infrared absorption layer is more than 0.3% by mass and less than 160% by mass. 1.
  • the infrared absorber is antimony-doped tin oxide, indium-doped tin oxide, cesium-doped tungsten oxide, lanthanum hexaboride, antimony-doped zinc oxide, indium-doped zinc oxide, conductive polymer, conductive carbon material 1. At least one selected from the group consisting of ⁇ 3.
  • a method for producing a laminated film having an infrared absorbing layer containing an infrared absorbent and a resin on one surface of a substrate comprising a step of preparing a coating solution so that a total concentration of iron, copper and chromium contained in the infrared absorbing layer is 1 to 500 ppm.
  • the laminated film according to the present invention has an infrared absorption layer containing an infrared absorber and a resin.
  • a laminated film having an infrared absorption layer containing an infrared absorber as in the technique of JP-T-2008-528313 (corresponding to US Patent Application Publication No. 2006/154049), It has been found that when the laminated film is exposed to sunlight for a long period of time, discoloration and cracking occur and a haze problem occurs.
  • the inventors examined the suppression of cracks in the laminated film.
  • the total concentration of the specific metal is particularly 500 ppm. It has been found that the tendency to become prominent is exceeded.
  • the crack in the infrared absorbing layer is explained by the following mechanism.
  • the thermal conductivity of the metal and the resin is greatly different, so the degree of thermal expansion and contraction of the metal and the degree of thermal expansion and contraction of the resin Are very different.
  • the infrared absorbing agent absorbs infrared rays and the infrared absorbing layer generates heat. If it does so, the interface of a metal and resin will become the starting point of the crack in the infrared rays absorption layer containing these by a temperature difference, and it will be thought that it becomes easy to generate
  • the specific metal promotes the photo-oxidation of the resin by sunlight, heat, and water, so that the haze of the film is deteriorated. Accordingly, when the total concentration of the specific metals exceeds 500 ppm, haze deterioration becomes a problem, but by setting it to 500 ppm or less, haze deterioration is effectively suppressed. Furthermore, if the total concentration of the specific metals is more than 500 ppm, the resin is salted out by the metals, so that the film is likely to be clouded. Therefore, also for the purpose of suppressing such salting out, the total concentration of the specific metal is preferably 500 ppm or less.
  • iron, copper and chromium also referred to as “specific metal” in this specification
  • iron, copper and chromium also referred to as “specific metal” in this specification
  • discoloration of the infrared absorption layer is suppressed by setting the total concentration to a certain value (specifically, 1 ppm) or more. The reason is not clear, but it is thought as follows.
  • the infrared absorbing agent contained in the infrared absorbing layer is exposed to sunlight for a long period of time, and as a result, the light absorption region is changed as a result of the change of the electronic state, and the infrared absorbing layer is colored.
  • the specific metal when a certain amount or more of the specific metal is contained in the infrared absorption layer, the specific metal interacts with the infrared absorber, and the infrared absorber is oxidized or reduced, whereby the infrared absorber. Can be maintained in a neutral state (state without charge).
  • the electronic state of the infrared absorbing agent can be kept in the initial state, so that the infrared absorbing layer can be effectively colored. It is thought that it can be suppressed.
  • X to Y indicating a range means “X or more and Y or less”. Unless otherwise specified, measurement of operation and physical properties is performed under conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50%.
  • the laminated film which concerns on this invention has a base material and the infrared rays absorption layer arrange
  • the infrared absorbing layer may be disposed adjacent to the substrate, or another layer (functional layer) may be interposed between the substrate and the infrared absorbing layer.
  • an infrared absorption layer is arrange
  • One feature of the laminated film of the present invention is that it has an infrared absorption layer, and the total concentration of iron, copper and chromium contained in the infrared absorption layer is 1 to 500 ppm.
  • ppm refers to a concentration based on mass (mass ppm).
  • the infrared absorbing layer is a layer having the ability to absorb light in the near infrared region having a wavelength of 800 to 2500 nm, and includes an infrared absorbing agent, a resin, and specific metals (iron, copper, and chromium).
  • the infrared absorbing layer may contain other additives in order to impart other functions or improve various properties.
  • specific metals contained in the infrared absorbing layer have a total concentration of 1 to 500 ppm. That is, the infrared absorbing layer contains 1 to 500 ppm of these specific metals with respect to the total mass of the total solid content of the infrared absorbing layer.
  • concentration of the specific metal refers to a value measured using an ICP-AES (inductively coupled plasma emission spectrometer), and a specific measurement method is the method described in the examples. Shall be followed.
  • the total concentration of iron, copper and chromium may be in the above range, and the infrared absorbing layer may contain only one kind of these metals, or two or more kinds thereof.
  • the aspect which an infrared rays absorption layer contains may be sufficient. That is, in the present invention, the infrared absorption layer contains at least one metal selected from the group consisting of iron, copper and chromium, and the total concentration range of the metal is 1 to 500 ppm. Therefore, for example, the infrared absorption layer may contain only iron and copper, and may contain only chromium, or may contain no iron and contain copper and chromium. Moreover, when 2 or more types of metals are included, the ratio (mass ratio) is not specifically limited.
  • the infrared absorption layer preferably contains Fe among the above-mentioned specific metals. Fe is particularly easy to interact with an infrared absorber in terms of energy, and has a high effect of suppressing coloring. In addition, since Fe has a thermal conductivity close to that of resin (resin contained in the infrared absorption layer) compared to other metals, cracking due to thermal expansion and contraction is suppressed while suppressing coloring of the infrared absorption layer. Can be suppressed.
  • the specific concentration of the specific metals (iron, copper and chromium) contained in the infrared absorption layer is preferably 50 to 500 ppm. 60 to 450 ppm, more preferably 70 to 400 ppm, even more preferably 80 to 350 ppm, and particularly preferably 100 to 300 ppm.
  • the thickness of the infrared absorbing layer is not particularly limited, but is preferably 0.1 to 20 ⁇ m, more preferably 1 ⁇ m to 20 ⁇ m, still more preferably 3 to 15 ⁇ m, and particularly preferably 3 to 10 ⁇ m. If it is 0.1 ⁇ m or more, the infrared absorption ability tends to be improved. On the other hand, if it is 20 ⁇ m or less, more preferably 15 ⁇ m or less, and further preferably 10 ⁇ m or less, the crack resistance of the coating film is improved.
  • the thickness is set to 0.1 ⁇ m to 20 ⁇ m, more preferably 0.1 to 10 ⁇ m, a haze reduction effect can be obtained, and the discoloration suppression effect can be further improved while suppressing the occurrence of cracks. Can do.
  • an infrared rays absorption layer is a coating liquid (usually containing the infrared absorber and resin which are explained in full detail below with a specific metal (iron, copper, and chromium). Any of a coating film coated with an aqueous solvent such as water), a coating film coated with a coating solution containing an organic solvent-soluble resin (usually including an organic solvent), and a coating film of a solventless resin composition But you can.
  • the infrared absorption layer contains an infrared absorber.
  • the “infrared absorber” is not particularly limited as long as it is more excellent in infrared absorbing ability than the resin material constituting the laminated film, and is generally used by adding to a transparent resin. Can be used.
  • an infrared absorber a light transmittance of a wavelength of 550 nm is obtained in a part or all of a near infrared wavelength region of 800 to 2500 nm in a solution in which 1 part by mass of a compound is dissolved / dispersed in 100 parts by mass of a good solvent. Compounds that are 50% or less, more preferably 30% or less, are preferred.
  • the infrared absorbing layer When the infrared absorbing layer contains an infrared absorbing agent, the infrared absorbing layer absorbs infrared rays. At this time, since the infrared absorbing agent absorbs infrared rays and generates heat (heat storage), the infrared absorbing layer is particularly likely to have a high temperature. . Therefore, when metals other than infrared absorbers (especially iron, copper and chromium) are contained in the infrared absorbing layer, the influence of the difference in the degree of thermal expansion and contraction between these metals and the resin constituting the infrared absorbing layer. Is particularly large, and cracks are likely to occur. However, according to the present invention, the occurrence of such cracks can be effectively suppressed by setting the total concentration of the specific metals (iron, copper and chromium) to 1 to 500 ppm.
  • infrared absorbers are exposed to excessive energy when exposed to sunlight for a long period of time. As a result, the electronic state changes, the light absorption characteristics change, and the film is colored. It becomes.
  • the specific metals iron, copper, and chromium
  • these metals contribute to the redox of the infrared absorber, and the electronic state of the infrared absorber is easily maintained in the initial state. Therefore, coloring is also suppressed.
  • the infrared absorbent contained in the infrared absorbing layer is not particularly limited, and may be an inorganic infrared absorbent or an organic infrared absorbent.
  • inorganic infrared absorbers that can be contained in the infrared absorbing layer include tin oxide, antimony-doped tin oxide (ATO), indium-doped tin oxide (ITO), cesium-doped tungsten oxide (CWO), and lanthanum hexaboride (LaB). 6 ), zinc oxide, antimony-doped zinc oxide (AZO), indium-doped zinc oxide (IZO), gallium-doped zinc oxide (GZO), aluminum-doped zinc oxide, and nickel complex compounds.
  • ATO antimony-doped tin oxide
  • ITO indium-doped tin oxide
  • CWO cesium-doped tungsten oxide
  • LaB lanthanum hexaboride
  • ZO antimony-doped zinc oxide
  • IZO indium-doped zinc oxide
  • GZO gallium-doped zinc oxide
  • aluminum-doped zinc oxide and nickel complex compounds.
  • Cd / Se, GaN, Y 2 O 3, Au may also be used those made of Ag.
  • the average particle size of the inorganic infrared absorber is preferably 5 to 150 nm, more preferably 10 to 120 nm. By setting it to 5 nm or more, the dispersibility in the resin and the infrared absorptivity are satisfactorily maintained, and by setting the thickness to 150 nm or less, a decrease in visible light transmittance can be suppressed.
  • the measurement of an average particle diameter is image
  • Organic infrared absorbers that can be contained in the infrared absorbing layer include conductive polymers such as polyacetylene compounds, polyparaphenylene compounds, polyphenylene vinylene compounds, polypyrrole, polythiophene compounds, PEDOT-PSS; imonium compounds; phthalocyanine compounds (however, the center Metals other than iron, copper, and chromium are preferred); and conductive carbon materials such as carbon nanotubes, acetylene black, ketjen black (registered trademark), and carbon black.
  • conductive polymers such as polyacetylene compounds, polyparaphenylene compounds, polyphenylene vinylene compounds, polypyrrole, polythiophene compounds, PEDOT-PSS; imonium compounds; phthalocyanine compounds (however, the center Metals other than iron, copper, and chromium are preferred); and conductive carbon materials such as carbon nanotubes, acetylene black, ketjen black (registered trademark), and carbon black.
  • the infrared absorbing agent is antimony-doped tin oxide, indium-doped tin oxide, cesium-doped tungsten oxide, hexaboronated lanthanum, antimony-doped. It is preferable that it is 1 type, or 2 or more types selected from the group which consists of zinc trioxide, indium dope zinc oxide, a conductive polymer, and a conductive carbon material.
  • the said infrared absorber can be used individually or in combination of 2 or more types.
  • a polythiophene compound and PEDOT-PSS are preferable from the viewpoint of high visible light transmittance.
  • the content of the infrared absorbent in the infrared absorbing layer is not particularly limited, but from the viewpoint of adjusting the physical properties such as film strength and film elastic modulus and optical properties such as transmittance to the desired value, the total mass of the infrared absorbing layer (In terms of solid content when the total mass of the infrared absorbing layer is 100% by mass), preferably 0.1 to 80% by mass, more preferably 1 to 80% by mass, It is especially preferable that it is 70 mass%. If the content is 0.1% or more, a sufficient infrared absorption effect can be obtained, and if it is 80% by mass or less, a sufficient amount of visible light can be transmitted.
  • the coloring suppression effect can be further improved by appropriately adjusting the content of the infrared absorbing agent in the infrared absorbing layer and the content of the specific metal.
  • the content of the infrared absorbing agent in the infrared absorbing layer and the content of the specific metal are preferably in the following relationship. That is, the total concentration of iron, copper and chromium with respect to the infrared absorber in the infrared absorbing layer is preferably 100 to 26000 ppm. If it is 100 ppm or more, it is preferable because the coloration suppressing effect can be improved, and if it is 26000 ppm or less, it is preferable in terms of suppressing discoloration.
  • the total concentration is more preferably 200 to 10000 ppm, and particularly preferably 200 to 1000 ppm.
  • an infrared rays absorption layer contains resin with the said infrared absorber.
  • resin either a water-soluble resin or an organic solvent-soluble resin can be used.
  • water-soluble resin is not particularly limited, and examples thereof include polyvinyl alcohol resins, gelatin, celluloses, thickening polysaccharides, and polymers having reactive functional groups.
  • water-soluble means a G2 glass filter (maximum pores 40 to 50 ⁇ m) when dissolved in water so as to have a concentration of 0.5% by mass at the temperature at which the substance is most dissolved. This means that the mass of insoluble matter to be filtered out is within 50% by mass of the added polymer.
  • organic solvent-soluble resin is not particularly limited, but acrylic resin, urethane-modified acrylic resin, polyurethane resin, polyester resin, melamine resin, polyvinyl acetate, cellulose acetate, polycarbonate, polyacetal, polybutyral, polyamide (nylon) resin, polystyrene Examples thereof include resins, polyimide resins, ABS resins, polyvinylidene fluoride, and ultraviolet curable resins.
  • ultraviolet curable resin examples include (meth) acrylate, urethane acrylate, polyester acrylate, epoxy acrylate, epoxy resin, and oxetane resin, and these can also be used as a solvent-free resin composition.
  • the ultraviolet curable resin it is preferable to add a photopolymerization initiator to accelerate curing.
  • Photoinitiators include acetophenones, benzophenones, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds, thiuram compounds, fluoroamine compounds Etc. are used.
  • the photopolymerization initiator examples include 2,2′-diethoxyacetophenone, 2,4-dimethylacetophenone, p-methylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 1-hydroxydimethylphenyl ketone, 2-methyl-4 Acetophenones such as' -methylthio-2-morpholinopropiophenone and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl Benzoins such as ether and benzyldimethylletal, benzophenone, 2,4'-dichlorobenzophenone, benzophenones such as 4,4'-dichlorobenzophenone and p-chlorobenzophenone, 2,4,6-trimethylbenzoyldiph Cycloalkenyl phosphine oxide, anthraquinod
  • photopolymerization initiator Commercially available products may be used as such a photopolymerization initiator, and preferred examples include Irgacure (registered trademark) 819, 184, 907, 651 manufactured by BASF Japan.
  • Irgacure registered trademark 819, 184, 907, 651 manufactured by BASF Japan.
  • the infrared absorbing layer can be provided with scratch resistance (hard coat property). Therefore, the infrared absorbing layer also serves as a hard coat layer described later. May be.
  • hard coat properties can be imparted to the infrared absorbing layer.
  • the hard coat property means that the pencil hardness according to JIS K 5600-5-4: 1999 is H or more, preferably 2H or more.
  • the hardness of the hard coat is preferably in terms of scratch resistance as long as the layer is not damaged or peeled off when an external stress such as bending is applied.
  • the infrared absorbing layer contains the specific metal (iron, copper and chromium), and the total concentration of iron, copper and chromium with respect to the resin is preferably 1 to 1000 ppm. More preferably, it is ⁇ 300 ppm.
  • a surfactant In addition to the specific metals (iron, copper and chromium), the infrared absorber and the resin, it is preferable to add a surfactant to the infrared absorbing layer for the purpose of exerting a function as a leveling agent or a slipping agent. .
  • the surfactant is not particularly limited, and examples include zwitterionic surfactants, cationic surfactants, anionic surfactants, nonionic surfactants, fluorosurfactants and silicon surfactants. . Of these, acrylic surfactants, silicon surfactants, or fluorosurfactants are preferred, and fluorosurfactants are particularly preferred from the viewpoint of the uniformity and appearance of the coating film surface.
  • a surfactant containing a long-chain alkyl group is preferable, and a surfactant having an alkyl group having 6 to 20 carbon atoms is more preferable.
  • Zwitterionic surfactants include alkylbetaines, alkylamine oxides, cocamidopropyl betaines, lauramidopropyl betaines, palm kernel fatty acid amidopropyl betaines, cocoamphoacetic acid N, lauroamphoacetic acid Na, lauramidopropyl hydroxysultains, lauramide
  • Examples include propylamine oxide, myristamidopropylamine oxide, hydroxyalkyl (C12-14) hydroxyethyl sarcosine.
  • Examples of the cationic surfactant include alkylamine salts and quaternary ammonium salts.
  • anionic surfactant examples include alkyl sulfate ester salt, polyoxyethylene alkyl ether sulfate ester salt, alkylbenzene sulfonate, fatty acid salt, polyoxyethylene alkyl ether phosphate, and dipotassium alkenyl succinate.
  • nonionic surfactant examples include polyoxyethylene alkyl ether (for example, Emulgen manufactured by Kao), polyoxyethylene sorbitan fatty acid ester (for example, Leodol TW series manufactured by Kao), glycerin fatty acid ester, polyoxyethylene fatty acid ester, poly Examples thereof include oxyethylene alkylamine and alkyl alkanolamide.
  • Fluorosurfactants include Surflon S-211, S-221, S-231, S-241, S-242, S-243, S-420 (manufactured by AGC Seimi Chemical Co., Ltd.), Megafac F-114, Examples thereof include F-410, F-477, F-552, F-553 (manufactured by DIC), FC-430, FC-4430, and FC-4432 (manufactured by 3M).
  • silicon-based surfactants examples include BYK-345, BYK-347, BYK-348, and BYK-349 (manufactured by Big Chemie Japan).
  • the said surfactant can be used individually or in combination of 2 or more types.
  • the content of the surfactant in the infrared absorbing layer is not particularly limited, but for the purpose of sufficiently obtaining the function as a leveling agent or a slipping agent, when the total mass of the infrared absorbing layer coating liquid is 100% by mass,
  • the range is preferably 0.001 to 0.30% by mass, and more preferably 0.005 to 0.10% by mass.
  • the content of the surfactant is preferably in the range of 0.005 to 5% by mass with respect to the total mass of the infrared absorption layer (when the total mass of the infrared absorption layer is 100% by mass). More preferably, the content is 0.01 to 3% by mass.
  • the infrared absorption layer preferably further contains a surfactant.
  • the total concentration of iron, copper and chromium with respect to the surfactant is more than 0.3% by mass and less than 160% by mass.
  • the concentration exceeds 0.3% by mass, cracks are less likely to occur, and when it is less than 160% by mass, it is preferable from the viewpoint of suppressing discoloration.
  • the concentration is preferably 4% by mass to less than 160% by mass, more preferably 10% by mass to 150% by mass, still more preferably 20% by mass to 145% by mass, and even more preferably 30% by mass to 100% by mass. Is particularly preferred.
  • the infrared absorption layer preferably contains a surfactant in addition to the specific metal (iron, copper and chromium), the infrared absorber and the resin, but unless the effects of the present invention are impaired. Further, other additives may be included.
  • the infrared absorption layer may contain inorganic nanoparticles as other additives.
  • the inorganic nanoparticles mean particles made of an inorganic compound (preferably inorganic oxide) having an average particle diameter measured by a dynamic scattering method of 200 nm or less.
  • SiO 2 is a metal oxide which can be used in the dielectric multilayer film to be described below, Al 2 O 3, ZrO 2 , TiO 2, CeO 2 , etc. Can be used.
  • the content of the inorganic nanoparticles in the infrared absorbing layer is not particularly limited, but is preferably 10 to 80 mass from the viewpoint of adjusting physical properties such as surface hardness and film elastic modulus and optical properties such as transmittance to desired values. %, More preferably 20 to 65% by mass.
  • the method for forming the infrared absorbing layer is not particularly limited as long as the infrared absorbing layer having a total concentration of iron, copper, and chromium contained in the layer of 1 to 500 ppm can be formed. It is preferable to use a method (wet method) in which an infrared absorbing layer coating solution for forming the infrared absorbing layer is prepared in advance and applied.
  • the 2nd form of this invention is a manufacturing method of the laminated
  • a method for producing a laminated film including a step of preparing a coating solution so that the total concentration of iron, copper and chromium is 1 to 500 ppm.
  • the infrared absorbing layer coating solution so that the total concentration of the specific metal (iron, copper and chromium) is 1 to 500 ppm with respect to the total solid mass of the infrared absorbing layer, It becomes easy to disperse the specific metals (iron, copper and chromium) contained in the infrared absorbing layer and the infrared absorbing agent uniformly in advance.
  • the formed infrared absorption layer not only has a high discoloration suppressing effect, but also has a high haze reduction effect.
  • the method for preparing the infrared absorbing layer coating solution is not particularly limited as long as the total concentration of the specific metal can be 1 to 500 ppm with respect to the total solid content in the coating solution.
  • the infrared absorbing layer coating liquid can be prepared, for example, by adding an infrared absorbent, a resin, and other additives such as a surfactant used as necessary to a solvent, and stirring and mixing.
  • the order of addition of the respective components is not particularly limited, and the respective components may be sequentially added and mixed while stirring, or may be added and mixed at one time while stirring.
  • an infrared absorption layer coating solution is prepared by mixing a solvent, an infrared absorber, a resin, and various additives that are added as necessary, and then the total solid mass contained in the coating solution It is preferable that the step of measuring the total concentration of the specific metal is performed. And when the total density
  • equipment that contacts the coating solution may contain iron, chromium, etc. contained in the SUS due to contact between the coating liquid and SUS.
  • the total concentration of the specific metals tends to exceed 500 ppm. Therefore, when preparing the infrared absorbing layer coating solution, it is preferable to measure the total concentration of the specific metal immediately before coating.
  • the infrared absorbing layer coating liquid when the infrared absorbing layer coating liquid is transported via a pipe containing SUS, the total concentration of the specific metal tends to increase as the transport time (coating liquid circulation time) increases. is there. Therefore, in order to reduce the total concentration of the specific metal, a method of shortening the circulation time of the infrared absorbing layer coating solution, or a method of covering the surface in the pipe with a material not containing the specific metal, etc. The method is taken.
  • the covering material for covering the surface in the pipe is not particularly limited, and any material can be suitably used as long as the material does not include the specific metal. Specifically, a fluororesin coat such as a glass coat, a silicon coat, and Teflon (registered trademark, hereinafter the same) can be used.
  • the circulation time of the infrared absorbing layer coating solution In order to set the specific metal concentration to 1 to 500 ppm relative to the mass of the total solid content contained in the infrared absorbing layer coating liquid, for example, when a SUS pipe with no surface coating is used, the circulation time of the coating liquid Is preferably 0.5 to 15 hours, more preferably 1 to 10 hours, and particularly preferably 2 to 10 hours.
  • the metal concentration in the infrared absorbing layer can be 1 to 500 ppm by applying the infrared absorbing layer coating liquid as it is without further adding / removing the specific metal. It can be. Further, the concentration of the specific metal in the infrared absorbing layer coating solution can be controlled by the flow rate of the coating solution, the piping material, the coating solution concentration, and the like.
  • the method for producing a laminated film according to the present invention includes a step of measuring the total concentration of iron, copper and chromium with respect to the total solid mass in the infrared absorbing layer coating solution (concentration measuring step). It is preferable that And in the said density
  • coating a coating liquid is performed after the total density
  • the result obtained in the concentration measurement step is The process of adding or removing a specific metal is performed in consideration of the amount of the metal mixed in.
  • the solvent used in the infrared absorbing layer coating solution is not particularly limited as long as it can sufficiently disperse the resin and the infrared absorbing agent, and various organic solvents and aqueous solvents can be used.
  • the organic solvent is not particularly limited, and examples thereof include alcohols such as methanol, ethanol, n-propanol and i-propanol, esters such as ethyl acetate, butyl acetate and propylene glycol monomethyl ether acetate, diethyl ether and propylene glycol.
  • esters such as ethyl acetate, butyl acetate and propylene glycol monomethyl ether acetate, diethyl ether and propylene glycol.
  • Examples include ethers such as monomethyl ether, amides such as dimethylformamide, and ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone.
  • These organic solvents may be used alone or in combination of two or more.
  • the organic solvents in view of the dispersibility of the resin and the infrared absorber, it is preferable to use esters, ethers, and ketones, and it is more prefer
  • the aqueous solvent is not particularly limited, and includes water or a mixed solvent of water and methanol, ethanol, n-propanol, i-propanol, or ethyl acetate.
  • a mixed solvent of water and methanol, ethanol, n-propanol, or i-propanol is particularly preferable in consideration of the dispersibility of the resin and the infrared absorber.
  • the content of water in the mixed solvent is preferably 10 to 60% by mass, based on 100% by mass of the entire mixed solvent, and 20 to 50% by mass. It is more preferable that
  • the concentration of the resin in the infrared absorbing layer coating solution (when using a plurality of types of resins, the total concentration) is preferably 0.1 to 80% by mass, more preferably 0.3 to 50% by mass. 0.5 to 30% by mass is particularly preferable.
  • the concentration of the infrared absorber in the infrared absorbing layer coating solution is preferably 0.1 to 50% by mass, and more preferably 0.15 to 30% by mass.
  • the infrared absorbing layer contains a surfactant.
  • the surfactant is preferably added to the infrared absorbing layer coating solution, and the concentration of the surfactant in the infrared absorbing layer coating solution is preferably 0.005 to 0.30% by mass.
  • the infrared absorbing layer can be formed by applying the infrared absorbing layer coating solution prepared as described above.
  • the application method is not particularly limited, and for example, it can be formed by a wet method such as coating with a wire bar, spin coating, or dip coating.
  • a continuous coating apparatus such as a die coater, a gravure coater, or a comma coater.
  • the application and drying conditions of the infrared absorbing layer are not particularly limited, and an appropriate temperature and drying time can be employed to promote curing and crosslinking.
  • an ultraviolet curable resin is used as the resin, the irradiation wavelength, the illuminance, and the light amount of the ultraviolet light are also appropriately adjusted.
  • the laminated film according to the present invention includes a base material for supporting the infrared absorbing layer and other optionally provided layers (for example, a dielectric multilayer film).
  • a base material of the laminated film various resin films can be used.
  • Polyolefin film polyethylene, polypropylene, etc.
  • polyester film polyethylene terephthalate (PET), polyethylene naphthalate, etc.
  • polyvinyl chloride cellulose acetate, etc.
  • a polyester film is preferable.
  • it does not specifically limit as a polyester film (henceforth polyester) It is preferable that it is polyester which has the film formation property which has a dicarboxylic acid component and a diol component as main structural components.
  • the main constituent dicarboxylic acid components include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenylsulfone dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenylethanedicarboxylic acid, Examples thereof include cyclohexane dicarboxylic acid, diphenyl dicarboxylic acid, diphenyl thioether dicarboxylic acid, diphenyl ketone dicarboxylic acid, and phenylindane dicarboxylic acid.
  • diol component examples include ethylene glycol, propylene glycol, tetramethylene glycol, cyclohexanedimethanol, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyethoxyphenyl) propane, bis ( 4-Hydroxyphenyl) sulfone, bisphenol fluorene hydroxyethyl ether, diethylene glycol, neopentyl glycol, hydroquinone, cyclohexanediol and the like.
  • polyesters having these as main components from the viewpoints of transparency, mechanical strength, dimensional stability, etc., dicarboxylic acid components such as terephthalic acid, 2,6-naphthalenedicarboxylic acid, diol components such as ethylene glycol and 1 Polyester having 1,4-cyclohexanedimethanol as the main constituent is preferred.
  • polyesters mainly composed of polyethylene terephthalate and polyethylene naphthalate, copolymerized polyesters composed of terephthalic acid, 2,6-naphthalenedicarboxylic acid and ethylene glycol, and mixtures of two or more of these polyesters are mainly used. Polyester as a constituent component is preferable.
  • the thickness of the substrate used in the present invention is preferably 10 to 300 ⁇ m, particularly 20 to 150 ⁇ m.
  • two substrates may be stacked, and in this case, the type may be the same or different.
  • the base material preferably has a visible light region transmittance of 85% or more shown in JIS R3106-1998, and particularly preferably 90% or more.
  • the base material has the above transmittance or more, it is advantageous in that the transmittance in the visible light region shown in JIS R3106-1998 is 50% or more (upper limit: 100%) when a laminated film is formed. preferable.
  • the base material using the resin or the like may be an unstretched film or a stretched film.
  • a stretched film is preferable from the viewpoint of strength improvement and thermal expansion suppression.
  • the base material can be manufactured by a conventionally known general method.
  • an unstretched substrate that is substantially amorphous and not oriented can be produced by melting a resin as a material with an extruder, extruding it with an annular die or a T-die, and quenching.
  • the unstretched base material is subjected to a known method such as uniaxial stretching, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular-type simultaneous biaxial stretching, or the flow direction of the base material (vertical axis), or A stretched substrate can be produced by stretching in the direction perpendicular to the flow direction of the substrate (horizontal axis).
  • the draw ratio in this case can be appropriately selected according to the resin as the raw material of the base material, but is preferably 2 to 10 times in each of the vertical axis direction and the horizontal axis direction.
  • the laminated film of the present invention reflects and shields at least a part of light when light having a specific wavelength (for example, infrared light) is incident (and thus heat shielding effect in the case of infrared light). ), It is preferable to further include a dielectric multilayer film in which low refractive index layers and high refractive index layers are alternately laminated.
  • the dielectric multilayer film may be provided on the opposite side of the infrared absorption layer via the base material, or may be provided on the same side as the infrared absorption layer on the base material.
  • whether the refractive index layer constituting the dielectric multilayer film is a low refractive index layer or a high refractive index layer is determined by comparing the refractive index with the adjacent refractive index layer. Specifically, when a refractive index layer is used as a reference layer, if the refractive index layer adjacent to the reference layer has a lower refractive index than the reference layer, the reference layer is a high refractive index layer (the adjacent layer is a low refractive index layer). It is judged to be a rate layer.
  • the refractive index of the adjacent layer is higher than that of the reference layer, it is determined that the reference layer is a low refractive index layer (the adjacent layer is a high refractive index layer). Therefore, whether the refractive index layer is a high refractive index layer or a low refractive index layer is a relative one determined by the relationship with the refractive index of the adjacent layer. Depending on the relationship, it can be a high refractive index layer or a low refractive index layer.
  • refractive index layer used in the said technical field.
  • a refractive index layer formed using a dry film forming method a refractive index layer formed by extrusion molding of a resin, and a refractive index layer formed using a wet film forming method Is mentioned.
  • the wet film forming method is preferably used from the viewpoint of production efficiency.
  • the layer is a low refractive index layer or a high refractive index layer is a relative one that is determined by the relationship with the adjacent refractive index layer.
  • the structure of a typical high refractive index layer and low refractive index layer among refractive index layers that can be formed by a wet film forming method will be described below.
  • the refractive index layer can be formed by a method of sequentially applying and drying the coating solution, a method of applying and drying the coating solution in multiple layers, and the like.
  • the refractive index layer of the laminated film according to the present embodiment is preferably formed by this wet film forming method, and more preferably formed by a method of applying and drying a coating solution in multiple layers.
  • the high refractive index layer preferably contains metal oxide particles from the viewpoint of easy control of the refractive index, and further contains a water-soluble resin, a curing agent, a surfactant, and other additives as necessary. You may go out.
  • the metal oxide particles and the water-soluble resin contained in the high refractive index layer are hereinafter referred to as “first metal oxide particles” and “first water-soluble resin” for convenience.
  • the first metal oxide particles are not particularly limited, but are preferably metal oxide particles having a refractive index of 2.0 to 3.0. Specifically, titanium oxide, zirconium oxide, zinc oxide, alumina, colloidal alumina, lead titanate, red lead, yellow lead, zinc yellow, chromium oxide, ferric oxide, iron black, copper oxide, magnesium oxide, water Examples thereof include magnesium oxide, strontium titanate, yttrium oxide, niobium oxide, europium oxide, lanthanum oxide, zircon, and tin oxide.
  • the first metal oxide particles are preferably titanium oxide or zirconium oxide from the viewpoint of forming a transparent and high refractive index layer having a high refractive index. From the viewpoint of improving weather resistance, the first metal oxide particles are preferably a rutile type (tetragonal type). ) Titanium oxide is more preferable.
  • the titanium oxide may be in the form of core / shell particles coated with a silicon-containing hydrated oxide.
  • the core / shell particles have a structure in which the surface of the titanium oxide particles is coated with a shell made of a silicon-containing hydrated oxide on titanium oxide serving as a core.
  • the first metal oxide particles described above may be used alone or in combination of two or more.
  • the content of the first metal oxide particles is 15 to 85% by mass with respect to 100% by mass of the solid content of the high refractive index layer from the viewpoint of increasing the refractive index difference from the low refractive index layer. It is preferably 20 to 80% by mass, more preferably 30 to 77% by mass.
  • the first metal oxide particles preferably have a volume average particle size of 1 to 100 nm, and more preferably 3 to 50 nm.
  • a volume average particle size of 100 nm or less is preferred because it has less haze and is excellent in visible light transmittance.
  • the value measured by the following method is adopted as the value of “volume average particle diameter”. Specifically, arbitrary 1000 particles appearing on the cross section or surface of the refractive index layer are observed with an electron microscope to measure the particle size, and particles having particle sizes of d1, d2,.
  • the first water-soluble resin is not particularly limited, but polyvinyl alcohol resins, gelatin, celluloses, thickening polysaccharides, and polymers having reactive functional groups can be used. . Of these, it is preferable to use a polyvinyl alcohol-based resin.
  • Polyvinyl alcohol resin As the polyvinyl alcohol resin, ordinary polyvinyl alcohol obtained by hydrolyzing polyvinyl acetate (unmodified polyvinyl alcohol), cation-modified polyvinyl alcohol, anion-modified polyvinyl alcohol, nonion-modified polyvinyl alcohol, vinyl alcohol Examples thereof include modified polyvinyl alcohol such as a polymer.
  • the modified polyvinyl alcohol may improve the film adhesion, water resistance, and flexibility.
  • Gelatin As the gelatin, various gelatins that have been widely used in the field of silver halide photographic light-sensitive materials can be applied. For example, acid-treated gelatin, alkali-treated gelatin, enzyme-treated gelatin that undergoes enzyme treatment in the production process of gelatin, a group having an amino group, imino group, hydroxyl group, carboxyl group as a functional group in the molecule, and a group that can react with it And gelatin derivatives modified by treatment with a reagent having
  • gelatin When gelatin is used, a gelatin hardener can be added as necessary.
  • a water-soluble cellulose derivative can be preferably used.
  • water-soluble cellulose derivatives such as carboxymethyl cellulose (cellulose carboxymethyl ether), methyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose; carboxylic acid group-containing celluloses such as carboxymethyl cellulose (cellulose carboxymethyl ether) and carboxyethyl cellulose; Examples thereof include cellulose derivatives such as cellulose, cellulose acetate propionate, cellulose acetate, and cellulose sulfate.
  • Thickening polysaccharides are saccharide polymers that have many hydrogen bonding groups in the molecule.
  • the thickening polysaccharide has a characteristic that the viscosity difference at low temperature and the viscosity at high temperature are large due to the difference in hydrogen bonding force between molecules depending on temperature. Further, when metal oxide fine particles are added to the thickening polysaccharide, the viscosity is increased due to hydrogen bonding with the metal oxide fine particles at a low temperature.
  • the viscosity at 15 ° C. is usually 1.0 mPa ⁇ s or more, preferably 5.0 mPa ⁇ s or more, more preferably 10.0 mPa ⁇ s or more.
  • the thickening polysaccharide that can be used is not particularly limited, and examples include generally known natural polysaccharides, natural complex polysaccharides, synthetic simple polysaccharides, and synthetic complex polysaccharides.
  • synthetic simple polysaccharides for details of these polysaccharides, reference can be made to “Biochemical Encyclopedia (2nd edition), Tokyo Chemical Doujinshi”, “Food Industry”, Vol. 31 (1988), p.
  • Polymers having reactive functional groups include polyvinylpyrrolidones, polyacrylic acid, acrylic acid-acrylonitrile copolymers, potassium acrylate-acrylonitrile copolymers, and vinyl acetate-acrylic esters.
  • Acrylic resins such as copolymers, acrylic acid-acrylic acid ester copolymers; styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, styrene-methacrylic acid-acrylic acid ester copolymers, styrene- ⁇ -Styrene acrylic resins such as methylstyrene-acrylic acid copolymer and styrene- ⁇ -methylstyrene-acrylic acid-acrylic acid ester copolymer; styrene-sodium styrenesulfonate copolymer, styrene-2-hydroxyethyl acrylate Copolymer, styrene -2-hydroxyethyl acrylate-potassium styrene sulfonate copolymer, styrene-maleic acid copolymer, styrene-maleic anhydr
  • the above water-soluble resins may be used alone or in combination of two or more.
  • the weight average molecular weight of the first water-soluble resin is preferably 1000 to 200000, more preferably 3000 to 40000.
  • the value measured by gel permeation chromatography (GPC) is adopted as the value of “weight average molecular weight”.
  • the content of the first water-soluble resin 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 curing agent has a function of reacting with the first water-soluble resin (preferably polyvinyl alcohol resin) contained in the high refractive index layer to form a hydrogen bond network.
  • first water-soluble resin preferably polyvinyl alcohol resin
  • the curing agent is not particularly limited as long as it causes a curing reaction with the first water-soluble resin, but in general, a compound having a group capable of reacting with the water-soluble resin or a different group possessed by the water-soluble resin.
  • stimulates mutual reaction is mentioned.
  • boric acid and its salt as a curing agent.
  • curing agents other than boric acid and its salt may be used.
  • boric acid and its salt mean oxygen acid and its salt having a boron atom as a central atom.
  • Specific examples include orthoboric acid, diboric acid, metaboric acid, tetraboric acid, pentaboric acid, octaboric acid, and salts thereof.
  • the content of the curing agent 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 high refractive index layer.
  • the total amount of the curing agent used is preferably 1 to 600 mg per 1 g of polyvinyl alcohol, and more preferably 100 to 600 mg per 1 g of polyvinyl alcohol. preferable.
  • the surfactant that can be contained in the high refractive index layer is not particularly limited, but the same ones that can be added to the infrared absorbing layer can be used, and the detailed explanation thereof is as follows. Omitted.
  • the high refractive index layer may also contain other additives.
  • other additives include amino acids, emulsion resins, lithium compounds, and the like.
  • the low refractive index layer also preferably contains metal oxide particles from the viewpoint of easy control of the refractive index.
  • metal oxide particles from the viewpoint of easy control of the refractive index.
  • a water-soluble resin, a curing agent, a surfactant, and other additives may be included as necessary.
  • the metal oxide particles and the water-soluble resin contained in the low refractive index layer are hereinafter referred to as “second metal oxide particles” and “second water-soluble resin” for convenience.
  • Second water-soluble resin As the second water-soluble resin, the same one as the first water-soluble resin can be used.
  • the high refractive index layer and the low refractive index layer both use a polyvinyl alcohol-based resin as the first water-soluble resin and the second water-soluble resin
  • the polyvinyl alcohol-based resins having different degrees of saponification are used. It is preferable to use a resin. Thereby, mixing of the interface is suppressed, the infrared reflectance (infrared shielding rate) becomes better, and the haze can be lowered.
  • the “degree of saponification” means the ratio of hydroxy groups to the total number of acetyloxy groups (derived from vinyl acetate as a raw material) and hydroxy groups in polyvinyl alcohol.
  • the second metal oxide particles are not particularly limited, but it is preferable to use silica (silicon dioxide) such as synthetic amorphous silica or colloidal silica, and acidic colloidal silica sol. It is more preferable to use Further, from the viewpoint of further reducing the refractive index, hollow fine particles having pores inside the particles can be used as the second metal oxide particles, and it is particularly preferable to use hollow fine particles of silica (silicon dioxide). .
  • the surface of the colloidal silica may be cation-modified, or may be treated with Al, Ca, Mg, Ba or the like.
  • the second metal oxide particles may be surface-coated with a surface coating component.
  • the second metal oxide particles (preferably silicon dioxide) contained in the low refractive index layer of the present invention preferably have an average particle size (number average; diameter) of 3 to 100 nm, preferably 3 to 50 nm. It is more preferable.
  • the “average particle diameter (number average; diameter)” of the metal oxide fine particles is 1,000 particles observed by an electron microscope on the particles themselves or on the cross section or surface of the refractive index layer. The particle size of any of the particles is measured and determined as a simple average value (number average).
  • the particle diameter of each particle is represented by a diameter assuming a circle equal to the projected area.
  • the content of the second metal oxide particles in the low refractive index layer is preferably 0.1 to 85% by mass, and 30 to 80% by mass with respect to 100% by mass of the total solid content of the low refractive index layer. More preferred is 45 to 75% by mass.
  • the above-described second metal oxide may be used alone or in combination of two or more from the viewpoint of adjusting the refractive index.
  • curing agent the same materials as those for the high refractive index layer can be used, and thus the description thereof is omitted here.
  • At least one of the high refractive index layer and the low refractive index layer uses a wet film forming method.
  • the refractive index layer is preferably formed, and both the high refractive index layer and the low refractive index layer are more preferably refractive index layers formed using a wet film forming method.
  • at least one of the high refractive index layer and the low refractive index layer contains metal oxide particles.
  • the laminated film of the present invention further includes a dielectric multilayer film in which low refractive index layers and high refractive index layers are alternately laminated, and the low refractive index layer or the high refractive index layer contains metal oxide particles. It is preferable to include.
  • both the high refractive index layer and the low refractive index layer contain metal oxide particles.
  • the laminated film according to the present invention it is preferable to design a large difference in refractive index between the low refractive index layer and the high refractive index layer from the viewpoint that the infrared reflectance can be increased with a small number of layers.
  • the difference in refractive index between the adjacent low refractive index layer and high refractive index layer may be 0.1 or more. Preferably, it is 0.3 or more.
  • the refractive index difference between the high refractive index layer and the low refractive index layer in all the laminated bodies is within the above-mentioned preferable range.
  • the refractive index layers constituting the uppermost layer and the lowermost layer of the dielectric multilayer film may have a configuration outside the above preferred range.
  • the transmittance in the visible light region shown in JIS R3106-1998 is preferably 50% or more, preferably 75% or more, more preferably 85% or more, and the wavelength is 900 nm. It is preferable to have a region where the reflectance exceeds 50% in a region of ⁇ 1400 nm.
  • the number of refractive index layers of the dielectric multilayer film (total number of high refractive index layers and low refractive index layers) is preferably 6 to 50 layers, and preferably 8 to 40 layers from the above viewpoint. More preferably, it is more preferably 11 to 31 layers, and particularly preferably 9 to 30 layers. It is preferable that the number of refractive index layers of the dielectric multilayer film is in the above range because excellent heat shielding performance and transparency, suppression of film peeling and cracking, and the like can be realized.
  • each high refractive index layer and / or each low refractive index layer is the same, but different. It may be a thing.
  • the thickness per layer of the high refractive index layer is preferably 20 to 800 nm, and more preferably 50 to 500 nm. Further, the thickness per layer of the low refractive index layer is preferably 20 to 800 nm, and more preferably 50 to 500 nm.
  • the composition when measuring the thickness per layer, the composition may change continuously without having a clear interface at the boundary between the high refractive index layer and the low refractive index layer.
  • the above composition can be observed from the concentration profile of the metal oxide particles.
  • the metal oxide concentration profile is formed by etching from the surface to the depth direction using a sputtering method, and using an XPS surface analyzer, sputtering is performed at a rate of 0.5 nm / min, with the outermost surface being 0 nm. It can be seen by measuring the ratio. Further, the laminated film may be cut and the cut surface may be confirmed by measuring the atomic composition ratio with an XPS surface analyzer.
  • the XPS surface analyzer is not particularly limited, and any model can be used.
  • the XPS surface analyzer for example, 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 laminated film according to the present invention may further have an adhesive layer.
  • This pressure-sensitive adhesive layer is usually provided on the surface opposite to the infrared absorption layer via a substrate, and further known release paper (separator) may be further provided.
  • the configuration of the adhesive layer is not particularly limited, and for example, any of a dry laminating agent, a wet laminating agent, an adhesive, a heat seal agent, a hot melt agent, and the like is used.
  • the adhesive for example, a polyester resin, a urethane resin, a polyvinyl acetate resin, an acrylic resin, a nitrile rubber, or the like is used.
  • 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. Conversely, if it is 100 ⁇ m or less, not only the transparency of the laminated film is improved, but also after the laminated film is attached to the window glass, it does not cause cohesive failure between the adhesive layers when peeled off, and the adhesive remains on the glass surface Tend to disappear.
  • the coating liquid for adhesion layers was apply
  • the laminated film of the present invention has a hard coat layer containing a resin curable by heat, ultraviolet rays or the like on the uppermost layer on the side opposite to the side having the adhesive layer as a surface protective layer for enhancing the scratch resistance. You may laminate. In particular, when the infrared absorption layer does not function as a hard coat layer, it is preferable to further have a hard coat layer.
  • curable resin used in the hard coat layer examples include a thermosetting resin and an ultraviolet curable resin.
  • an ultraviolet curable resin is preferable because it is easy to mold, and among them, those having a pencil hardness of at least 2H. More preferred.
  • curable resins can be used alone or in combination of two or more.
  • the same ultraviolet curable resin that can be used as the resin described in the above [Infrared absorbing layer] section can be used, and therefore detailed description thereof is omitted. To do.
  • the thickness of the hard coat layer is preferably from 0.1 ⁇ m to 50 ⁇ m, more preferably from 1 to 20 ⁇ m, from the viewpoints of improving the hard coat properties and improving the transparency of the laminated film.
  • the method for forming the hard coat layer is not particularly limited. For example, after preparing a coating liquid for hard coat layer containing the above components, the coating liquid is applied with a wire bar or the like, and the coating liquid is cured with heat and / or UV. And a method of forming a hard coat layer.
  • the laminated film according to the present invention may have a layer (other functional layer) other than the layers described above.
  • an intermediate layer can be provided as the other layer.
  • the “intermediate layer” means a layer between the base material and the infrared absorption layer or a layer between the base material and the dielectric multilayer film.
  • constituent material of the intermediate layer examples include polyester resin, polyvinyl alcohol resin, polyvinyl acetate resin, polyvinyl acetal resin, acrylic resin, urethane resin, and the like, and those having low compatibility and Tg of additives are preferably used.
  • the production method of the laminated film is not particularly limited, and any method can be used as long as the infrared absorption layer having a total concentration of iron, copper and chromium contained in the infrared absorption layer of 1 to 500 ppm can be formed.
  • the method for forming the infrared absorbing layer, the dielectric multilayer film, the adhesive layer, and the hard coat layer itself has already been described above, a detailed description of the method for manufacturing each layer (multilayer film) is omitted here.
  • Examples of a method for producing a laminated film include the following. (1) forming a dielectric multilayer film on one surface of the substrate (the surface opposite to the surface on which the separator and the adhesive layer are disposed), forming an infrared absorption layer on the dielectric multilayer film, Thereafter, if necessary, a method of forming a hard coat layer on the infrared absorbing layer; (2) forming a dielectric multilayer film on one surface of the substrate (surface on which the separator and the adhesive layer are disposed); Thereafter, an infrared absorbing layer is formed on the other surface of the substrate, and a hard coat layer is further formed on the infrared absorbing layer as necessary.
  • the step of forming the hard coat layer can be omitted when the infrared absorption layer also serves as the hard coat layer.
  • the laminated film according to the present invention can be applied to a wide range of fields.
  • a film for window pasting such as heat ray reflective film that gives heat ray reflection effect, film for agricultural greenhouses, etc. It is mainly used for the purpose of improving weather resistance.
  • it can be suitably used as a laminated film for automobiles sandwiched between glass and glass such as laminated glass for automobiles.
  • Example 1 ⁇ Production of laminated film ⁇ (Example 1) -Preparation of infrared absorbing layer coating solution 1- The constituent materials described below were sequentially added to prepare an infrared absorption layer coating solution 1. The solid content was 30% by mass.
  • the infrared-absorbing coating solution 1 prepared above is liquid for 2 hours using a stainless steel pipe. It was circulated, applied with a gravure coater, and dried at 100 ° C. for 2 minutes to obtain a layer with a dry weight of 3 g / m 2 (thickness: 10 ⁇ m). Then, the obtained laminated body was wound up in a roll shape so that the coated and dried layer was inside.
  • PET polyethylene terephthalate
  • the pressure-sensitive adhesive coating solution 1 was applied to a release surface of a separator film (NS-23MA: manufactured by Nakamoto Packs Co., Ltd.) made of polyester resin using a die coater and dried at 90 ° C. for 1 minute. I let you. Then, the said separator film provided with the adhesion layer was laminated
  • Example 2 (Example 2) -Production of laminated film 2-
  • the laminated film was made in the same manner as in Example 1 except that the solution was circulated for 6 hours using a stainless steel pipe before applying the infrared absorbing layer coating liquid 1. 2 was produced.
  • Example 1 Comparative Example 1 -Production of comparative laminated film 1-
  • Example 1 comparative lamination was carried out in the same manner as in Example 1 except that the solution was circulated for 18 hours using a stainless steel pipe before applying the infrared absorbing layer coating liquid 1. Film 1 was produced.
  • Example 2 (Comparative Example 2) -Production of comparative laminated film 2-
  • Example 1 preparation of laminated film 1
  • Example 1 preparation of laminated film 1
  • an operation of removing iron, copper and chromium by ultrafiltration was performed before applying the infrared absorbing layer coating solution 1.
  • a comparative laminated film 2 was produced.
  • Example 3 Preparation of infrared absorbing layer coating solution 2-
  • the constituent materials described below were sequentially added to prepare an infrared absorption layer coating solution 2.
  • the solid content was 15% by mass.
  • Example 1 Production of the laminated film 1
  • the infrared absorbing layer coating solution 1 is changed to the infrared absorbing layer coating solution 2 prepared as described above, and before the infrared absorbing layer coating solution 2 is applied, it is made of stainless steel.
  • a laminated film 3 was produced in the same manner as in Example 1 except that the liquid was circulated for 6 hours using piping.
  • Example 1 (preparation of laminated film 1), the infrared absorbing layer coating solution 1 is changed to the infrared absorbing layer coating solution 3 prepared as described above, and before the infrared absorbing layer coating solution 3 is applied, it is made of stainless steel.
  • a comparative laminated film 3 was produced in the same manner as in Example 1 except that the liquid was circulated for 6 hours using piping.
  • Example 4 Preparation of infrared absorbing layer coating solution 4-
  • the constituent materials described below were sequentially added to prepare an infrared absorption layer coating solution 4.
  • the solid content was 30% by mass.
  • MITO dispersion of ATO particles, solid content 35.3 mass%, particle concentration 35 mass%, average particle size 80 nm, manufactured by Advanced Nano Products 497 mass parts Megafac F-552 (fluorine surfactant: manufactured by DIC Corporation) 0.1 mass parts.
  • Example 1 the infrared absorbing layer coating solution 1 was changed to the infrared absorbing layer coating solution 4 prepared as described above, and the solution was applied for 6 hours using a stainless steel pipe before applying the infrared absorbing layer coating solution 4.
  • a laminated film 4 was produced in the same manner as in Example 1 (production of the laminated film 1) except that it was circulated.
  • Example 4 Comparative Example 4 -Production of comparative laminated film 4-
  • Example 4 preparation of laminated film 4
  • comparative lamination was performed in the same manner as in Example 4 except that liquid circulation was performed for 18 hours using a stainless steel pipe before applying the infrared absorbing layer coating liquid 4.
  • Film 4 was produced.
  • Aronix M-220 Tripropylene glycol diacrylate: manufactured by Toagosei Co., Ltd. 600 parts by mass Beam set 577 (urethane acrylate UV curable resin: manufactured by Arakawa Chemical Industries) 1229 parts by mass UF-8001G (oligourethane acrylate (molecular weight ⁇ 4500): manufactured by Kyoeisha Chemical Co., Ltd.) 150 parts by mass Purple light UV-7600B (urethane acrylate UV curable resin: manufactured by Nippon Synthetic Chemical Co., Ltd.) 300 parts by mass Irgacure 184 (photopolymerization initiator: manufactured by BASF) 120 parts by mass F-552 (fluorine surfactant: manufactured by DIC Corporation) 0.9 parts by mass.
  • Beam set 577 urethane acrylate UV curable resin: manufactured by Arakawa Chemical Industries
  • UF-8001G oligourethane acrylate (molecular weight ⁇ 4500): manufactured by Kyoeisha Chemical Co.
  • the UV curable resin layer coating solution (hard coating layer coating solution) prepared as described above was applied.
  • the illuminance of the irradiated part is 100 mW / cm 2
  • the irradiation amount is 0.5 J / cm 2
  • the coating layer is cured
  • the hard coat layer (HC layer) is formed so that the dry film thickness is 4 ⁇ m.
  • the laminated film 5 was produced.
  • Example 6 Production of the laminated film 4
  • the liquid before applying the infrared absorbing layer coating liquid 4, the liquid was circulated for 18 hours using a stainless steel pipe whose inner surface was processed with Teflon (registered trademark).
  • Teflon registered trademark
  • Example 7 Preparation of Infrared Absorbing Layer Coating Solution 5-
  • the constituent materials described below were sequentially added to prepare an infrared absorption layer coating solution 5.
  • the solid content was 44% by mass.
  • Methyl isobutyl ketone 86 parts by weight Beam set 577 (urethane acrylate UV curable resin: manufactured by Arakawa Chemical Industries) 177 parts by weight SR35M (MITO dispersion of ATO particles, solid content 35.3% by weight, particle concentration 35% by weight, Average particle size 80 nm, manufactured by Advanced Nano Products) 729 parts by mass Irgacure 819 (photopolymerization initiator: manufactured by BASF) 7.4 parts by mass MegaFuck F-552 (fluorinated surfactant: manufactured by DIC) 0.1 Parts by mass.
  • Beam set 577 urethane acrylate UV curable resin: manufactured by Arakawa Chemical Industries
  • SR35M MIEO dispersion of ATO particles, solid content 35.3% by weight, particle concentration 35% by weight, Average particle size 80 nm, manufactured by Advanced Nano Products
  • Irgacure 819 photopolymerization initiator: manufactured by BASF
  • laminated film 7 On the surface of one easy-adhesion layer of a 50 ⁇ m thick polyethylene terephthalate (PET) film (with double-sided easy-adhesion layer) made of polyester resin, the inner surface of the infrared absorbing layer coating solution 5 prepared above is processed with Teflon (registered trademark). The solution was circulated for 18 hours using a stainless steel pipe, coated with a gravure coater, and dried at 100 ° C. for 2 minutes.
  • PET polyethylene terephthalate
  • an infrared ray absorbing layer (also serving as an HC layer) having a dry film thickness of 4 ⁇ m is cured by using an ultraviolet lamp to cure the coating layer with an illuminance of the irradiated portion of 100 mW / cm 2 and an irradiation amount of 0.5 J / cm 2. Formed. Then, the obtained laminated body was wound up in a roll shape so that the coated and dried layer was inside.
  • the pressure-sensitive adhesive coating solution 1 was applied to a release surface of a separator film (NS-23MA: manufactured by Nakamoto Packs Co., Ltd.) made of polyester resin using a die coater and dried at 90 ° C. for 1 minute. I let you. Then, the said separate film provided with the adhesion layer was laminated on the surface by which the infrared rays absorption layer is not formed of the laminated body wound up by roll shape, and the laminated film 7 was produced. The thickness of the adhesive layer was 15 ⁇ m.
  • Example 8 Preparation of Infrared Absorbing Layer Coating Solution 6-
  • the constituent materials described below were sequentially added to prepare an infrared absorption layer coating solution 6.
  • the solid content was 40% by mass.
  • Beam set 577 urethane acrylate UV curable resin: manufactured by Arakawa Chemical Industries
  • Celnax CX-Z400K ZnSb 2 O 6 fine particles (AZO) dispersion, solid content 40% by mass
  • Example 7 Production of the laminated film 7
  • the laminated film 8 was prepared in the same manner as in Example 7 except that the infrared absorbing layer coating solution 5 was changed to the infrared absorbing layer coating solution 6 prepared as described above. Produced.
  • Example 9 Preparation of infrared absorbing layer coating solution 7- The constituent materials described below were sequentially added to prepare an infrared absorption layer coating solution 7. The solid content was 35% by mass.
  • Methyl isobutyl ketone 78 parts by weight Beam set 577 (urethane acrylate UV curable resin: manufactured by Arakawa Chemical Industries) 101 parts by weight ITO dispersion (solid content 30% by weight, particle concentration 17% by weight, average particle diameter 80 nm: Mitsubishi Materials) 817 parts by mass Irgacure 819 (photopolymerization initiator: manufactured by BASF) 4.2 parts by mass MegaFuck F-552 (fluorine-based surfactant: manufactured by DIC) 0.1 part by mass
  • Beam set 577 urethane acrylate UV curable resin: manufactured by Arakawa Chemical Industries
  • ITO dispersion solid content 30% by weight, particle concentration 17% by weight, average particle diameter 80 nm: Mitsubishi Materials
  • Irgacure 819 photopolymerization initiator: manufactured by BASF
  • MegaFuck F-552 fluorine-based surfactant: manufactured by DIC
  • Example 7 Production of the laminated film 7
  • the laminated film 9 was prepared in the same manner as in Example 7 except that the infrared absorbing layer coating solution 5 was changed to the infrared absorbing layer coating solution 7 prepared as described above. Produced.
  • Example 10 Preparation of infrared absorbing layer coating solution 8-
  • the constituent materials described below were sequentially added to prepare an infrared absorption layer coating solution 8.
  • the solid content was 30% by mass.
  • Methyl isobutyl ketone 542 parts by mass Beam set 577 (urethane acrylate UV curable resin: manufactured by Arakawa Chemical Industries) 259 parts by mass KHF-7AH (LaB 6 , solid content 16% by mass, particle concentration 3.2% by mass, toluene dispersion Body, average particle size 50 nm: manufactured by Sumitomo Metal Mining Co., Ltd.) 187 parts by mass Irgacure 819 (photopolymerization initiator: manufactured by BASF) 10 parts by mass MegaFuck F-552 (fluorinated surfactant: manufactured by DIC) 0.1 Parts by mass.
  • Beam set 577 urethane acrylate UV curable resin: manufactured by Arakawa Chemical Industries
  • KHF-7AH LaB 6 , solid content 16% by mass, particle concentration 3.2% by mass, toluene dispersion Body, average particle size 50 nm: manufactured by Sumitomo Metal Mining Co., Ltd.
  • Example 7 Production of the laminated film 7
  • the laminated film 10 was prepared in the same manner as in Example 7 except that the infrared absorbing layer coating solution 5 was changed to the infrared absorbing layer coating solution 8 prepared as described above. Produced.
  • Example 11 Preparation of Infrared Absorbing Layer Coating Liquid 9-
  • the constituent materials described below were sequentially added to prepare an infrared absorption layer coating solution 9.
  • the solid content was 30% by mass.
  • Methyl isobutyl ketone 451 parts by mass Beam set 577 (urethane acrylate UV curable resin: manufactured by Arakawa Chemical Industries) 193 parts by mass YMF-02A (cesium-doped tungsten oxide (Cs 0.33 WO 3 ), solid content 28.7 Mass%, particle concentration 18.5% by mass, average particle diameter 15 nm, refractive index 1.66: manufactured by Sumitomo Metal Mining Co., Ltd.) 347 parts by mass Irgacure 819 (photopolymerization initiator: manufactured by BASF) 7 parts by mass MegaFuck F- 552 (fluorine-based surfactant: manufactured by DIC) 0.1 parts by mass.
  • Beam set 577 urethane acrylate UV curable resin: manufactured by Arakawa Chemical Industries
  • YMF-02A cesium-doped tungsten oxide (Cs 0.33 WO 3 ), solid content 28.7 Mass%, particle concentration 18.5% by mass, average particle diameter 15 nm
  • Example 7 Production of laminated film 7
  • the laminated film 11 was prepared in the same manner as in Example 7 except that the infrared absorbing layer coating solution 5 was changed to the infrared absorbing layer coating solution 9 prepared as described above. Produced.
  • Example 5 Production of the laminated film 8
  • the liquid was circulated for 18 hours using a stainless steel pipe (the inner surface of which was not processed with Teflon (registered trademark)).
  • a comparative laminated film 5 was produced in the same manner as in Example 8 except that.
  • Example 12 Preparation of coating solution L1 for low refractive index layer-
  • the constituent materials described below were sequentially added and stirred at 45 ° C. Finally, it was finished to 1000 parts by mass with pure water to prepare a coating solution L1 for a low refractive index layer.
  • the refractive index of the layer formed with the coating liquid L1 for the low refractive index layer was 1.48.
  • the measuring method of a refractive index is as follows (hereinafter the same).
  • a titanium oxide sol dispersion containing rutile-type titanium oxide was prepared as follows.
  • the base-treated titanium compound was suspended in pure water to 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.
  • citric 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%.
  • Sol dispersion of silica-modified titanium oxide particles (20.0% by mass) 320 parts by mass Citric acid aqueous solution (1.92% by mass) 120 parts by mass Polyvinyl alcohol (10% by mass, PVA103, polymerization degree 300, saponification degree 99 mol%) 20 parts by mass Boric acid aqueous solution (3% by mass) 100 parts by mass Polyvinyl alcohol (4% by mass, manufactured by Kuraray Co., Ltd., PVA124, polymerization degree 2400, saponification degree 88 mol%) 350 parts by mass Softazoline LSB-R (5 masses) %, Lauramidopropylhydroxysultain (long-chain alkyl group-containing amphoteric surfactant), manufactured by Kawaken Fine Chemical Co., Ltd. 1 part by mass.
  • the refractive index of the layer formed with the high refractive index layer coating solution H1 was 1.82.
  • a polyethylene terephthalate (PET) film having a thickness of 50 ⁇ m (Toyobo Co., Ltd. A4300: double-sided easy-adhesive layer, length 200 m ⁇ width 210 mm), the lowermost layer and the uppermost layer are low refractive index layers, and the others are alternately dried.
  • the measurement (confirmation) of the film thickness is performed by cutting the laminated film (laminated film sample) and using the XPS surface analyzer to cut the cut surface with the abundance of the high refractive index material (TiO 2 ) and the low refractive index material (SiO 2 ). It was confirmed that the film thickness of each of the above layers was secured by measuring.
  • the infrared absorbing layer coating solution 5 prepared above is applied to the surface on the side where the dielectric multilayer film is not formed (the easy adhesion layer), and the inner surface is coated with Teflon ( (Registered trademark) Liquid was circulated for 18 hours using a processed stainless steel pipe and applied by a gravure coater. Subsequent operations were performed in the same manner as in Example 7 (production of laminated film 7), and laminated film 12 was produced.
  • Example 13 Provided film 13- A laminated film 13 was produced in the same manner as in Example 12 except that the infrared absorbing layer coating solution 5 was changed to the infrared absorbing layer coating solution 9 in Example 12 (production of the laminated film 12).
  • Example 14 Preparation of infrared absorbing layer coating solution 10-
  • the constituent materials described below were sequentially added to prepare an infrared absorption layer coating solution 10.
  • the solid content was 40% by mass.
  • SR35M MITO dispersion of ATO particles, solid content 35.3% by mass, particle concentration 35% by mass, average particle size 80 nm, manufactured by Advanced Nano Products
  • Irgacure 819 photopolymerization initiator: manufactured by BASF
  • MegaFuck F-552 fluorinated surfactant: manufactured by DIC
  • Example 12 Production of the laminated film 12
  • the laminated film 14 was prepared in the same manner as in Example 12 except that the infrared absorbing layer coating solution 5 was changed to the infrared absorbing layer coating solution 10 prepared as described above. Produced.
  • the results of calculating the concentration with respect to the surfactant contained in the infrared absorption layer and the concentration with respect to the infrared absorber contained in the infrared absorption layer are also shown.
  • the measured value of the content of iron, copper and chromium in the sample obtained by collecting and drying the infrared absorbing layer coating solution immediately before coating is the infrared absorbing layer of the laminated film produced using the coating solution. It was confirmed that the value was the same as the middle value.
  • ⁇ , ⁇ , ⁇ ⁇ , and ⁇ can be used without any problem in practice.
  • the color difference ( ⁇ E) of the laminated film sample was evaluated before and after the light irradiation under the above conditions.
  • a spectrocolorimeter CM-3700d manufactured by Konica Minolta Co., Ltd.
  • ⁇ E was obtained from the CIE Lab value, and evaluated according to the following criteria. The results are shown in Table 1-2.
  • the laminated film further includes a dielectric multilayer film
  • discoloration and cracking are suppressed and the haze reduction effect is further improved.
  • This is considered to be due to the fact that, in the durability evaluation, light incident from the side of the dielectric multilayer film provides a shielding effect in the dielectric multilayer film, and thus light incident on the infrared absorption layer is reduced. .

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Optical Filters (AREA)
  • Laminated Bodies (AREA)

Abstract

　La présente invention concerne un film laminé : comprenant un substrat, et une couche d'absorption de lumière infrarouge, qui est disposée sur une surface du substrat et qui contient un agent d'absorption de lumière infrarouge et une résine; et ayant une concentration totale de fer, de cuivre et de chrome contenue dans la couche d'absorption de lumière infrarouge allant de 1 à 500 ppm. La présente invention permet de produire un film laminé ayant une couche contenant un agent d'absorption d'infrarouge, qui présente une fissuration très limitée, même après une exposition prolongée à la lumière solaire.
PCT/JP2015/070199 2014-07-16 2015-07-14 Film laminé et procédé de production associé WO2016010049A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017219774A (ja) * 2016-06-09 2017-12-14 コニカミノルタ株式会社 光学反射フィルム
KR20190070481A (ko) * 2017-12-13 2019-06-21 에스케이씨 주식회사 적외선 차단 다층 필름
JP2020111747A (ja) * 2019-01-11 2020-07-27 熊本県 熱線吸収材およびその製造方法、熱線吸収フィルム
WO2022163709A1 (fr) * 2021-01-29 2022-08-04 キヤノン株式会社 Toner et procédé de lecture d'image

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Publication number Priority date Publication date Assignee Title
JP2006039300A (ja) * 2004-07-28 2006-02-09 Mitsubishi Chemicals Corp 光学フィルター及びその製造方法
JP2008528313A (ja) * 2005-01-07 2008-07-31 スリーエム イノベイティブ プロパティズ カンパニー 太陽光制御多層フィルム
JP2010134457A (ja) * 2008-11-06 2010-06-17 Uni-Chemical Co Ltd 赤外線遮断性フィルム及び赤外線遮断性積層フィルム
WO2013077274A1 (fr) * 2011-11-24 2013-05-30 コニカミノルタ株式会社 Film de protection contre les infrarouges

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006039300A (ja) * 2004-07-28 2006-02-09 Mitsubishi Chemicals Corp 光学フィルター及びその製造方法
JP2008528313A (ja) * 2005-01-07 2008-07-31 スリーエム イノベイティブ プロパティズ カンパニー 太陽光制御多層フィルム
JP2010134457A (ja) * 2008-11-06 2010-06-17 Uni-Chemical Co Ltd 赤外線遮断性フィルム及び赤外線遮断性積層フィルム
WO2013077274A1 (fr) * 2011-11-24 2013-05-30 コニカミノルタ株式会社 Film de protection contre les infrarouges

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017219774A (ja) * 2016-06-09 2017-12-14 コニカミノルタ株式会社 光学反射フィルム
KR20190070481A (ko) * 2017-12-13 2019-06-21 에스케이씨 주식회사 적외선 차단 다층 필름
KR102001496B1 (ko) * 2017-12-13 2019-07-18 에스케이씨 주식회사 적외선 차단 다층 필름
JP2020111747A (ja) * 2019-01-11 2020-07-27 熊本県 熱線吸収材およびその製造方法、熱線吸収フィルム
JP7378066B2 (ja) 2019-01-11 2023-11-13 熊本県 熱線吸収材およびその製造方法、熱線吸収フィルム
WO2022163709A1 (fr) * 2021-01-29 2022-08-04 キヤノン株式会社 Toner et procédé de lecture d'image

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