WO2015060305A1 - Corps de protection contre le proche infrarouge et film de protection contre le proche infrarouge - Google Patents

Corps de protection contre le proche infrarouge et film de protection contre le proche infrarouge Download PDF

Info

Publication number
WO2015060305A1
WO2015060305A1 PCT/JP2014/077960 JP2014077960W WO2015060305A1 WO 2015060305 A1 WO2015060305 A1 WO 2015060305A1 JP 2014077960 W JP2014077960 W JP 2014077960W WO 2015060305 A1 WO2015060305 A1 WO 2015060305A1
Authority
WO
WIPO (PCT)
Prior art keywords
infrared shielding
infrared
layer
resin
titanium oxide
Prior art date
Application number
PCT/JP2014/077960
Other languages
English (en)
Japanese (ja)
Inventor
晃純 木村
Original Assignee
コニカミノルタ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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 JP2015543866A priority Critical patent/JPWO2015060305A1/ja
Publication of WO2015060305A1 publication Critical patent/WO2015060305A1/fr

Links

Images

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
    • G02B5/206—Filters comprising particles embedded in a solid matrix
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
    • 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
    • B32B2307/70—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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7244—Oxygen barrier

Definitions

  • the present invention relates to a near infrared shielding body and a near infrared shielding film.
  • the near-infrared shielding film a film having a multilayer structure in which the near-infrared reflectance is selectively improved by alternately laminating a high refractive index layer and a low refractive index layer is a mainstream, and has visible light transmittance.
  • the near-infrared impermeability which reflects or absorbs the near-infrared rays contained in sunlight etc. is common.
  • the window glass may be colored dark or iridescent, or glaring due to diffuse reflection, which may impair the design.
  • Patent Document 1 discloses a photochromic material for a transparent substrate or an adhesive resin layer in a heat ray-shielding dimming window having a transparent substrate and a heat ray shielding layer formed from a resin composition containing a heat ray shielding agent and a binder resin.
  • a technique using is disclosed. In this technique, it is said that silver halides such as silver chloride can be used as inorganic photochromic compounds, such as spiropyran compounds, diarylethene compounds, spirooxazine compounds, fulgide compounds, etc. as organic photochromic compounds.
  • a main object of the present invention is to provide a near-infrared shielding body and a near-infrared shielding film provided with weather resistance for near-infrared impermeability and visible light transmissibility.
  • a near-infrared shield characterized by:
  • near-infrared shielding body and a near-infrared shielding film provided with weather resistance for near-infrared impermeability and visible light permeability.
  • Near-infrared impermeability has ultraviolet responsiveness and exhibits near-infrared impermeability under ultraviolet irradiation such as sunlight, while visible light transmissivity appears under non-ultraviolet irradiation, and dark or rainbow Glare due to coloration and irregular reflection is reduced. Therefore, it is possible to provide a near-infrared shielding body and a near-infrared shielding film that exhibit good design properties.
  • the near-infrared impermeability, visible light transmissibility, and design properties of such a near-infrared shield or near-infrared shield film have weather resistance and are difficult to deteriorate.
  • the near-infrared shielding body includes a base and a near-infrared shielding layer formed on the base and including rutile-type titanium oxide particles.
  • the near-infrared shielding layer provided in this near-infrared shielding body is laminated directly or indirectly on the surface of a base that supports and fixes the layer, with another functional layer interposed therebetween.
  • the near-infrared shield according to this embodiment is characterized in that the rutile-type titanium oxide particles contained in the near-infrared shield layer are covered with an oxygen-impermeable resin.
  • titanium oxide titanium dioxide having a rutile-type crystal structure
  • Rutile-type titanium oxide is an inorganic substance that exhibits an extremely strong absorption with an absorption coefficient exceeding 1000 particularly in the near infrared region when reduced, and thus can be a near infrared shielding material with relatively good weather resistance.
  • reduced rutile titanium oxide is rapidly oxidized and decolorized by oxygen in the air and loses near-infrared impermeability, so it is difficult to use it by attaching it to a window glass or the like.
  • the rutile-type titanium oxide particles contained in the near-infrared shielding layer are coated with an oxygen-impermeable resin so as to be isolated from oxygen in the air.
  • an oxygen-impermeable resin so as to be isolated from oxygen in the air.
  • the near-infrared shielding body has a structure in which at least a part of the base is covered with a near-infrared shielding layer formed on the base.
  • the near infrared shielding layer having this structure includes particles of rutile-type titanium oxide, and the particles are in a state where at least a part of the surface, preferably all of the surface is coated with an oxygen-impermeable resin. Yes.
  • that the particles are coated with the oxygen-impermeable resin means that the oxygen-impermeable resin is interposed between the particles and the outside air.
  • the form in which the rutile-type titanium oxide particles are coated with the oxygen-impermeable resin includes a form in which the near-infrared shielding layer contains an oxygen-impermeable resin and a form in which the oxygen-impermeable resin does not contain, specifically, a rutile-type titanium oxide.
  • the particles are coated with a thin oxygen-impermeable resin and dispersed in the near-infrared shielding layer, or the rutile-type titanium oxide particles are made of an oxygen-impermeable resin or contain an oxygen-impermeable resin.
  • the near-infrared shielding layer in which the form dispersed in the near-infrared shielding layer or the rutile-type titanium oxide particles are dispersed is made of an oxygen-impermeable resin or a gas barrier layer containing an oxygen-impermeable resin.
  • the coated form is exemplified.
  • the near-infrared shielding layer contains an oxygen-impermeable resin
  • a near-infrared shielding body 1 in which a single-layer structure is formed on a substrate as shown in FIG.
  • a near-infrared shielding layer 20 containing an oxygen-impermeable resin is formed on one surface of the main surface of the substrate 10.
  • a near-infrared shielding body 2 in which a multi-layer structure is formed on a substrate as shown in FIG.
  • a gas barrier layer (lower layer) 30 ⁇ / b> A is formed on one surface of the main surface of the substrate 10, and the near-infrared shielding layer 20 is formed on the upper surface (the surface opposite to the substrate) of the gas barrier layer (lower layer) 30 ⁇ / b> A. Is formed, and a gas barrier layer (upper layer) 30B is formed on the upper surface of the near-infrared shielding layer 20 (the surface opposite to the base material).
  • the gas barrier layer may be provided on both the lower surface (surface on the substrate side) and the upper surface (surface opposite to the substrate) of the near infrared shielding layer as shown in FIG. You may provide in one side of an upper surface.
  • Substrate / Near-infrared shielding layer including oxygen-impermeable resin
  • Substrate / near-infrared shielding layer including oxygen-impermeable resin
  • gas barrier layer including oxygen-impermeable resin
  • Substrate / gas barrier layer / near infrared shielding layer including oxygen-impermeable resin
  • Substrate / Near-infrared shielding layer not including oxygen-impermeable resin
  • Gas barrier layer 5)
  • Substrate / gas barrier layer / near infrared shielding layer not including oxygen-impermeable resin
  • the near-infrared shielding layer mainly has a function of shielding near-infrared rays by photochromism. That is, the near-infrared shielding layer is a layer exhibiting the property that the near-infrared transmittance decreases under ultraviolet irradiation such as sunlight, while the visible light transmittance increases under non-ultraviolet irradiation.
  • the near-infrared shielding layer includes rutile titanium oxide particles and a binder resin.
  • the rutile-type titanium oxide particles are dispersed in a monodisperse form in the binder resin, and this rutile-type titanium oxide exhibits UV-responsive photochromic properties and shields near-infrared rays. To do.
  • a near-infrared shielding layer contains only a rutile type titanium oxide as near-infrared shielding components, such as a metal oxide particle.
  • the visible light transmittance of the near-infrared shielding layer is preferably 80% or more, more preferably 85% or more, and further preferably 90% or more.
  • the visible light transmittance of the near-infrared shielding layer decreases when rutile titanium oxide is reduced by ultraviolet rays, and increases when rutile titanium is oxidized by oxygen in the air or the like.
  • This transmittance value is a value when the rutile titanium oxide contained in the near-infrared shielding layer is in an oxidized state in the air.
  • the transmittance can be measured according to the method defined in JIS R3106: 1998, and can be obtained by averaging the transmittance in the wavelength region of 380 nm to 780 nm.
  • the thickness of the near-infrared shielding layer is 0.3 ⁇ m or more and 1.0 ⁇ m or less. If thickness is 0.3 micrometer or more, there exists a tendency which is easy to form the coating film of a smooth state. Therefore, even if the rutile-type titanium oxide particles are contained in a content that can sufficiently shield near infrared rays, a near infrared shielding layer with few defects can be formed. Further, when the thickness is 1.0 ⁇ m or less, it is relatively easy to ensure the transmittance of visible light.
  • the near-infrared absorption rate of the near-infrared shielding layer is preferably 30% or more, more preferably 50% or more, and further preferably 70% or more.
  • the near-infrared absorptance of the near-infrared shielding layer increases when rutile-type titanium oxide is reduced by ultraviolet rays and decreases when rutile-type titanium is oxidized by oxygen in the air or the like.
  • the value of this absorptance is the maximum value when the rutile titanium oxide contained in the near-infrared shielding layer is in a reduced state.
  • the absorptance can be measured according to the method defined in JIS R3106: 1998.
  • the content of rutile-type titanium oxide in the near infrared shielding layer is preferably 20% by mass or more and 50% by mass or less, more preferably 30% by mass or more and 50% by mass or less, based on the dry mass of the near infrared shielding layer. preferable. If the content of rutile titanium oxide is 20% by mass or more, the action of absorbing near infrared rays can be exhibited significantly. Moreover, if content of a rutile type titanium oxide is 50 mass% or less, generation
  • the average particle size of rutile-type titanium oxide is preferably 3 nm to 50 nm, more preferably 5 nm to 20 nm. If the average particle diameter is 3 nm or more, handling of the dried particles is relatively easy. Moreover, the increase in the cloudiness of a near-infrared shielding body can be suppressed by making an average particle diameter 50 nm or less.
  • an average particle diameter is calculated
  • the particle diameter of the primary particles is defined as the diameter of the area equivalent circle of the particles in the electron microscope image.
  • the rutile type titanium oxide particles can be prepared using a titanium oxide sol as described in JP-A-7-819, JP-A-9-165218, and JP-A-11-43327. In addition, it is described in the method described in paragraphs 0011 to 0023 of International Publication No. 2007/039953 and “Titanium oxide—physical properties and applied technology” (Kiyono Manabu, p. 255 to 258 (2000) Gihodo Publishing Co., Ltd.). It can be prepared with reference to the method.
  • the rutile-type titanium oxide particles are preferably coated with silicon or aluminum oxide, and particularly preferably with silicon oxide (silica).
  • the amount of oxide to be coated is preferably 4% by mass or more and 13% by mass or less, and more preferably 6% by mass or more and 10% by mass or less with respect to 100% by mass of rutile type titanium oxide.
  • the amount of the oxide is 4% by mass or more, the reduced rutile-type titanium oxide is colored well, and the near-infrared absorptance can be improved as compared with the case where there is no coating. If the amount of oxide is 13% by mass or less, the rutile-type titanium oxide is coated, so that the near-infrared absorptivity is reduced and the risk of decoloration due to irregular reflection is reduced.
  • a method of coating the rutile type titanium oxide particles with silicon oxide for example, by adding a water-soluble alkali metal silicate such as sodium silicate to the rutile type titanium oxide sol, and adjusting the pH
  • a water-soluble alkali metal silicate such as sodium silicate
  • examples thereof include a method of precipitating silicon hydroxide (such as hydrated oxide) on the surface of rutile titanium oxide particles and adjusting the pH or heat treatment.
  • a chelating agent such as citric acid or oxalic acid to the rutile type titanium oxide sol.
  • methods described in JP-A-10-158015, JP-A-2000-204301, JP-A-2007-246351 and the like can be used.
  • the binder resin in the near-infrared shielding layer any species can be used as long as it is a resin excellent in mechanical strength and visible light permeability, but an oxygen-impermeable resin is preferably used.
  • an oxygen-impermeable resin is preferably used.
  • oxygen is used as the binder resin in the near infrared shielding layer. It is necessary to use an impermeable resin, and the binder resin in the near-infrared shielding layer in these cases is preferably composed of only an oxygen-impermeable resin.
  • the oxygen-impermeable resin By using the oxygen-impermeable resin, it is possible to suppress dissolution and diffusion of oxygen gas contained in the air or the like into the near-infrared shielding layer. And it can avoid that the rutile type titanium oxide currently reduced is oxidized rapidly and loses near-infrared opaqueness. Moreover, it becomes possible to suppress dissolution and diffusion of oxygen gas into the near-infrared shielding layer without providing a gas barrier layer.
  • the oxygen-impermeable resin is composed of a resin species that has a property that it is difficult for oxygen gas to pass therethrough.
  • the oxygen permeability coefficient of the oxygen-impermeable resin is 1 ⁇ 10 ⁇ 16 (cm 3 (STP) cm / (cm 2 ⁇ sec ⁇ cmHg)) or less, preferably 1 ⁇ 10 ⁇ 19 (cm 3 (STP) cm / (cm 2 ⁇ sec ⁇ cmHg)) to 1 ⁇ 10 ⁇ 16 (cm 3 (STP) cm / (cm 2 ⁇ sec ⁇ cmHg)).
  • the oxygen permeability coefficient of the oxygen-impermeable resin is 1 ⁇ 10 ⁇ 16 (cm 3 (STP) cm / (cm 2 ⁇ sec ⁇ cmHg)) or less
  • the rutile-type titanium oxide reduced by ultraviolet rays can be used in the air. It can be avoided that it is immediately oxidized by the oxygen present in the glass and loses its near-infrared opacity.
  • the oxygen permeability coefficient of the oxygen-impermeable resin is 1 ⁇ 10 ⁇ 19 (cm 3 (STP) cm / (cm 2 ⁇ sec ⁇ cmHg)) or more, the rutile-type titanium oxide reduced by ultraviolet rays is When exposed to non-ultraviolet irradiation due to the disappearance of solar radiation or the like, it is slowly oxidized by oxygen present in the air or the like, so that the visible light transmittance can be increased again to restore the design.
  • the oxygen permeability coefficient can be measured according to the method defined in JIS K7126-1.
  • the oxygen-impermeable resin examples include polyvinyl alcohol resin, polyacrylonitrile resin, polymethacrylonitrile resin, and polyvinylidene chloride resin.
  • the oxygen impermeable resin a polyvinyl alcohol resin having a relatively small oxygen permeability coefficient is particularly preferable.
  • polyvinyl alcohol resin examples include homopolymers obtained by saponifying a polymer of vinyl carboxylate, copolymers obtained by saponifying vinyl carboxylate and other vinyl compounds, and these A modified polyvinyl alcohol resin in which the terminal of the side chain or main chain is substituted with a reactive group can be mentioned.
  • vinyl carboxylate an appropriate vinyl ester such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl benzoate or the like can be used.
  • vinyl compounds forming the copolymer include unsaturated hydrocarbons such as ethylene, propylene, 1-butene, isobutene and 1,3-butadiene, and halogens such as chloroethylene and 1,1-dichloroethylene.
  • Vinyl halides such as aryl vinyls such as styrene, ⁇ -methylstyrene, allylbenzene, divinylbenzene, vinylnaphthalene, vinyl ethers such as methyl vinyl ether and ethyl vinyl ether, and acrylamides such as 2-propenamide and 2-methylacrylamide , Acrylic esters such as methyl acrylate and ethyl acrylate, methacrylic esters such as methyl methacrylate and ethyl methacrylate, acrylic acid, methacrylic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride Acid, itaconic acid, etc.
  • aryl vinyls such as styrene, ⁇ -methylstyrene, allylbenzene, divinylbenzene, vinylnaphthalene
  • vinyl ethers such as methyl vinyl ether and ethyl vinyl ether
  • acrylamides such as 2-propenamide
  • Saturated carboxylic acids or and salts thereof acetic acid 2-propenyl, acetate 3-butenyl, allyl alcohol, N- vinyl-2-pyrrolidone, acrylonitrile, can be used one or more kinds selected from methacrylonitrile and the like.
  • ethylene is preferable from the viewpoint of improving coatability and moldability and imparting flexibility.
  • the average degree of polymerization of the polyvinyl alcohol resin is preferably 1000 or more, and more preferably 1500 or more and 5000 or less.
  • the average degree of polymerization is 1000 or more, the mechanical strength of the formed layer can be secured to a certain degree.
  • average polymerization degree is 5000 or less, the fluidity
  • the average degree of polymerization of the polyvinyl alcohol resin is preferably about 1500 or more and 3000 or less in order to obtain oxygen impermeability as long as mechanical strength and fluidity during coating are ensured. Is more preferable.
  • the polymerization ratio in the copolymer of polyvinyl alcohol resin is preferably 80 mol% or more, more preferably 90 mol% or more with respect to the vinyl carboxylate monomer.
  • the saponification degree of the polyvinyl alcohol resin is preferably 70% or more, more preferably 80% or more, and further preferably 90% or more. If the degree of saponification is 70% or more, the polyvinyl alcohol resin is relatively difficult to soften, so that the production process involving heating is less likely to be difficult. Moreover, since the number of polar groups of polyvinyl alcohol resin increases, more excellent oxygen impermeability can be obtained.
  • the degree of saponification means the fraction of the total number of hydroxy groups generated by hydrolysis with respect to the total number of ester groups derived from polymerized vinyl carboxylate and the like.
  • modified polyvinyl alcohol resin examples include a cationic modified polyvinyl alcohol resin having a cationic group, an anion modified polyvinyl alcohol resin having an anionic group, and a nonionic modified polyvinyl alcohol resin having a nonionic group.
  • Examples of the cation-modified polyvinyl alcohol resin include primary amino groups, secondary amino groups, tertiary amino groups, and quaternary ammonium bases as described in JP-A-61-110483. And a polyvinyl alcohol resin having a cationic group at the end of the side chain or main chain.
  • Such a cation-modified polyvinyl alcohol resin can be obtained, for example, by saponifying a copolymer of vinyl carboxylate and another vinyl compound having a cationic group.
  • anion-modified polyvinyl alcohol resin examples include polyvinyl alcohol resins having an anionic group as described in JP-A-1-206088 and JP-A-61-237681, and JP-A-63-330779. Examples thereof include a polyvinyl alcohol resin having a repeating unit as described in the gazette and a polyvinyl alcohol resin having a hydrophilic group as described in JP-A-7-285265.
  • Nonionic modified polyvinyl alcohol resins include, for example, polyvinyl alcohol resins having an alkylene oxide moiety as described in JP-A-7-9758, and hydrophobic properties as described in JP-A-8-25795. Examples thereof include polyvinyl alcohol resins obtained by saponifying a copolymer of a monomer and vinyl carboxylate.
  • polyvinyl alcohol resin examples include “Kuraray Poval (registered trademark)” (manufactured by Kuraray Co., Ltd.), “Exeval (registered trademark)” (manufactured by Kuraray Co., Ltd.), and “J-Poval (registered trademark)” (Japan).
  • polyacrylonitrile resin examples include homopolymers such as acrylonitrile, methacrylonitrile, 1,1-dichloroethylene, and other vinyls used in these and the above polyvinyl alcohol resins. And a copolymer with one or more compounds.
  • a curing agent that crosslinks and cures resin molecules via a reactive group can be used in combination.
  • Curing agents include, for example, orthoboric acid, metaboric acid, tetraboric acid, orthoborate, metaborate, diborate, tetraborate, pentaborate, octaborate, depending on the type of reactive group.
  • Boric acids such as borates and borax, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, m-xyl Isocyanate curing agents such as diisocyanate, 1,5-naphthylene diisocyanate, isophorone diisocyanate, norbornene methane diisocyanate, diglycidyl ethyl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl Epoxy curing agents such as ether, 1,6-diglycidylcyclohexane, N, N-diglycidyl-4-glycidyloxyaniline, sorbitol polyglycidyl ether,
  • the content of the curing agent is preferably 0.1% by mass or more and 60% by mass or less, more preferably 10% by mass or more and 60% by mass or less per mass of the oxygen-impermeable resin.
  • the binder resin in the near-infrared shielding layer when providing a gas barrier layer that covers the near-infrared shielding layer in the near-infrared shielding body, it is preferable to use another water-soluble resin instead of the oxygen-impermeable resin.
  • the water-soluble resin refers to a mixture obtained by adding the polymer constituting the water-soluble resin to water so that the concentration is 0.5% by mass and mixing at a temperature showing the maximum solubility.
  • a resin in which the mass of insoluble matter separated by filtration through a glass filter maximum pore size; 40 ⁇ m to 50 ⁇ m) is 50% by mass or less of the added polymer.
  • water-soluble resins include gelatin, celluloses, thickening polysaccharides, and polymers having reactive functional groups.
  • gelatin industrial gelatin used as a silver halide photographic light-sensitive material can be used. Specific examples include acid-treated gelatin, alkali-treated gelatin, enzyme-treated gelatin, and derivatives thereof.
  • acid-treated gelatin for example, T.W. H. James: The Theory of Photographic Process 4th. ed. Reference can be made to descriptions such as 1977 (Macmillan) p55, Science Photo Handbook (above) p72-75 (Maruzen), Fundamentals of Photographic Engineering-Silver Salt Photo Editing p119-124 (Corona). Also, Research Disclosure Magazine Vol. 176, No. The gelatin described in Section IX of 17643 (December, 1978) can be used.
  • cellulose a water-soluble cellulose derivative is preferably used. Specifically, for example, carboxymethyl cellulose, carboxyethyl cellulose, methyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, nitrocellulose, cellulose acetate propionate, cellulose acetate, cellulose sulfate and the like can be mentioned.
  • thickening polysaccharides include natural simple polysaccharides, natural complex polysaccharides, synthetic simple polysaccharides, and synthetic complex polysaccharides.
  • galactan such as agarose and agaropectin
  • galactomannoglycan such as locust bean gum and guaran
  • xyloglucan such as tamarind gum
  • glucomannan such as potato mannan
  • Galactoglucomannoglycans such as glycans, conifer-derived glycans, arabinogalactoglycans such as soybean-derived glycans, glycan-derived glycans, glycosaminoglycans such as hyaluronic acid, keratan sulfate, etc.
  • alginic acid alginates, agar, ⁇ -carrageenan, ⁇ -carrageenan, ⁇ -carrageenan, and polysaccharides derived from red algae such as farseleran.
  • a polysaccharide that causes an increase in viscosity at 15 ° C. of 1.0 mPa ⁇ s or more is preferable, and the polysaccharide does not have a carboxylic acid group or a sulfonic acid group. Saccharides are preferred.
  • polymers having reactive functional groups include polyvinylpyrrolidones, polyacrylic acid, acrylic acid-acrylonitrile copolymer, potassium acrylate-acrylonitrile copolymer, vinyl acetate-acrylic ester copolymer, acrylic Acrylic resin such as acid-acrylic acid ester copolymer, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, styrene-methacrylic acid-acrylic acid ester copolymer, styrene- ⁇ -methylstyrene Styrene acrylic acid resin such as acrylic acid copolymer, styrene- ⁇ -methylstyrene-acrylic acid-acrylic acid ester copolymer, styrene-sodium styrenesulfonate copolymer, styrene-2-hydroxyethyl acrylate copolymer , Styrene-2-hydroxyethyl
  • the polymer having a reactive functional group may not correspond to the oxygen-impermeable resin, and has an oxygen permeability coefficient of 1 ⁇ 10 ⁇ 16 (cm 3 (STP) cm / (cm 2 ⁇ sec ⁇ cmHg)) or less.
  • the gas barrier layer mainly has a function of shielding the permeation of oxygen gas existing in the air or the like and isolating the near infrared shielding layer from the oxygen gas. Therefore, for example, the lower surface (surface on the base material side) and the upper surface (surface opposite to the base material) of the near infrared shielding layer so that the gas barrier layer is interposed between the near infrared light shielding layer and the outside world. At least one, preferably only on the upper surface of the near-infrared shielding layer or on both the upper and lower surfaces.
  • the gas barrier layer on both the upper and lower surfaces of the near-infrared shielding layer, the diffusion of oxygen into the near-infrared shielding layer is limited, so that the fluctuation of the oxygen concentration in the near-infrared shielding layer can be made more stable. And photochromism by rutile titanium oxide can be easily controlled.
  • the gas barrier layer contains one or more of the above oxygen-impermeable resins, and preferably consists of the above-mentioned oxygen-impermeable resin.
  • the gas barrier layer is preferably a layer having an oxygen-impermeable resin as a main composition and substantially not containing metal oxide particles such as rutile-type titanium oxide.
  • the oxygen permeability coefficient is 1 ⁇ 10 ⁇ 16 (cm 3 (STP) cm / (cm 2 ⁇ sec ⁇ cmHg)) or less
  • a particularly preferable embodiment is one containing only an oxygen-impermeable resin as the resin component.
  • the visible light transmittance of the gas barrier layer is preferably 80% or more, more preferably 85% or more, and further preferably 90% or more.
  • the transmittance can be measured according to the method defined in JIS R3106: 1998, and can be obtained by averaging the transmittance in the wavelength region of 380 nm to 780 nm.
  • the thickness of the gas barrier layer is preferably 0.5 ⁇ m or more and 5.0 ⁇ m or less. If thickness is 0.5 micrometer or more, it will be easy to ensure the oxygen impermeability required in order to prevent rapid oxidation of a rutile type titanium oxide. On the other hand, if the thickness is 5.0 ⁇ m or less, it is relatively easy to ensure the transmittance of visible light. In addition, since the oxygen permeability is too low, there is a low possibility that the re-oxidation of rutile titanium oxide will be hindered. .
  • the content of the oxygen-impermeable resin in the gas barrier layer is preferably 1% by mass or more and 99.9% by mass or less, and preferably 50% by mass or more and 99.9% by mass or less per dry mass of the gas barrier layer. More preferably, it is more preferably 70% by mass or more and 99.9% by mass or less, and particularly preferably 90% by mass or more and 99.9% by mass or less.
  • the substrate is mainly composed of an article or a substrate that supports the layers constituting the near-infrared shield. That is, a near-infrared shielding body is formed by laminating layers such as a near-infrared shielding layer and a gas barrier layer on the surface of the substrate.
  • Examples of articles constituting the substrate include window glass, wall materials, laying materials, other exterior materials, optical devices, imaging devices, drawing devices, and the like.
  • Examples of the material of the article include glass, polycarbonate resin, polysulfone resin, acrylic resin, polyolefin resin, polyether resin, polyester resin, polyamide resin, polysulfide resin, unsaturated polyester resin, epoxy resin, melamine resin, phenol resin, diallyl Examples thereof include phthalate resin, polyimide resin, urethane resin, polyvinyl acetate resin, polyvinyl alcohol resin, styrene resin, vinyl chloride resin, metal, and ceramic.
  • the substrate constituting the substrate examples include materials molded into appropriate shapes such as a plate shape, a rectangular parallelepiped shape, a sheet shape, a film shape, a lens shape, a columnar shape, and a spherical shape according to various purposes.
  • the substrate may be composed of a single substrate or may be formed by laminating or joining a plurality of the same or different substrates.
  • the base material which has any of flexibility and rigidity may be sufficient.
  • a form of the substrate a sheet form or a film form is preferable, and a stretched film subjected to a stretching process is more preferable.
  • a near-infrared shield is manufactured by laminating
  • a near-infrared shielding film is provided by forming the said base
  • the visible light transmittance of the substrate is preferably 85% or more, and more preferably 90% or more.
  • the transmittance can be measured according to the method defined in JIS R3106: 1998.
  • the thickness of the substrate is preferably 5 ⁇ m or more and 300 ⁇ m or less, and more preferably 15 ⁇ m or more and 150 ⁇ m or less with respect to the light transmission region. If thickness is 5 micrometers or more, it will be easy to support the layer formed on a base material. Moreover, if the thickness is 300 ⁇ m or less, it is relatively easy to ensure the transmittance of visible light.
  • polyolefin such as polyethylene and polypropylene
  • polyester such as polyethylene terephthalate and polyethylene naphthalate
  • acrylic resin such as polymethyl methacrylate, polyvinyl chloride, acetylcellulose, polycarbonate, polyarylate, polystyrene, Aromatic polyamide, polyetheretherketone, polysulfone, polyethersulfone, polyimide, polyetherimide and the like can be mentioned, and polyester is particularly preferable.
  • the dicarboxylic acid component constituting the polyester includes terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenylsulfone dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenylethanedicarboxylic acid, cyclohexane Examples include dicarboxylic acid, diphenyldicarboxylic acid, diphenylthioether dicarboxylic acid, diphenylketone dicarboxylic acid, and phenylindane dicarboxylic acid. Among these, terephthalic acid or 2,6-naphthalenedicarboxylic acid is preferable as the dicarboxylic acid component.
  • diol component constituting the polyester examples include ethylene glycol, propylene glycol, tetramethylene glycol, 1,4-cyclohexanedimethanol, 2,2-bis (4-hydroxyphenyl) propane, and 2,2-bis (4-hydroxyethoxy).
  • ethylene glycol or 1,4-cyclohexanedimethanol is preferable as the diol component.
  • the substrate can be produced by a conventionally known general method.
  • the production of a film-like substrate can be performed by extruding or casting a heat-melted resin into a plate shape and then cooling it while forming it into an appropriate shape.
  • the mechanical strength and light transmission can be increased by stretching the cooled unstretched substrate in an appropriate direction using a uniaxial stretching machine or a biaxial stretching machine.
  • a stretched film with improved properties can be obtained.
  • the stretched film may be further subjected to a relaxation treatment.
  • the relaxation treatment can be performed, for example, by heating to about 80 ° C. or more and 200 ° C. or less and then cooling. By performing the relaxation treatment, the internal stress and thermal shrinkage of the base material are reduced, so that the light transmittance and the shape accuracy can be improved.
  • An undercoat layer can be formed on the substrate.
  • the resin for forming the undercoat layer include polyester resin, acrylic modified polyester resin, polyurethane resin, acrylic resin, vinyl resin, vinylidene chloride resin, polyethyleneimine vinylidene resin, polyethyleneimine resin, polyvinyl alcohol resin, and modified polyvinyl alcohol resin.
  • Etc. The undercoat layer can be formed by a general coating method, for example, roll coating, gravure coating, knife coating, dip coating, spray coating or the like.
  • the thickness of the undercoat layer is preferably about 0.01 g / m 2 or more and 2.00 g / m 2 or less.
  • the near-infrared shield according to the present embodiment may be configured to include other functional layers employed in general functional films, in addition to the base, the near-infrared shield layer, and the gas barrier layer.
  • Other functional layers include an optical reflective laminate composed of a plurality of layers having different refractive indexes, an infrared shielding layer (metal layer, liquid crystal layer), a conductive layer, an antistatic layer, an easy-adhesion layer (adhesion layer), a protective layer.
  • These functional layers are preferably provided between the base and the near-infrared shielding layer.
  • the functional layer is provided between the base and the gas barrier layer.
  • the near-infrared shielding layer and the optionally formed gas barrier layer are preferably arranged on the outermost surface side in the near-infrared shielding body.
  • optical reflective laminate near infrared reflective laminate
  • a high reflectance in the near infrared region in particular, from the viewpoint of improving the near infrared shielding performance. Therefore, the configuration of the near-infrared reflective laminate will be described below.
  • the near-infrared reflective laminate has a structure in which high refractive index layers and low refractive index layers are alternately laminated. It is a functional layer that exhibits visible light shielding performance by selectively reflecting near infrared rays while transmitting visible light by a structure in which a large number of high refractive index layers and low refractive index layers are laminated.
  • the near-infrared reflective laminate has a near-infrared shielding performance that has a region where the reflectance exceeds 50% in a wavelength region of a wavelength of 900 nm to 1400 nm.
  • the layer arranged closest to the near-infrared shielding layer may be either a high refractive index layer or a low refractive index layer.
  • the high refractive index layer, the low refractive index layer, the near-infrared shielding layer, and the gas barrier layer do not require that the refractive indexes have optical continuity and regularity.
  • the near-infrared reflective laminate has a high refractive index layer and a low refractive index layer having a predetermined refractive index
  • a partition layer and an adhesive layer are provided between the high refractive index layer and the low refractive index layer.
  • the partition layer has a function of suppressing interlayer aggregation and interlayer diffusion of the metal oxide particles generated between the high refractive index layer and the low refractive index layer, and reducing interlayer mixing between the high refractive index layer and the low refractive index layer. Specifically, it can be provided according to the method disclosed in Japanese Patent Application Laid-Open No. 2013-125076.
  • the adhesive layer is a layer interposed for the purpose of improving the adhesiveness between the layers such as the high refractive index layer, the low refractive index layer, and the partition layer.
  • the total number of high refractive index layers and low refractive index layers in the near-infrared reflective laminate is preferably 10 or more and 50 or less, more preferably 10 or more and 30 or less, and more preferably 10 or more and 20 or less. Further preferred. As the total number of these layers is smaller, the number of man-hours during production can be reduced, and the shape accuracy of the produced near-infrared reflective laminate can be easily improved. Further, the smaller the total number of these layers, the easier it is to ensure the visible light transmittance in the near-infrared reflective laminate.
  • the difference in refractive index between the high refractive index layer and the low refractive index layer is 0.10 or more, preferably 0.30 or more, more preferably 0.35 or more, and particularly preferably 0.40 or more. As the refractive index difference is larger, a higher near-infrared reflectance can be achieved with a smaller total number of layers.
  • the visible light transmittance of the near-infrared reflective laminate is preferably 50% or more, more preferably 75% or more, and even more preferably 85% or more.
  • the transmittance can be measured according to the method defined in JIS R3106: 1998.
  • the high refractive index layer mainly includes metal oxide particles and a binder resin.
  • the metal oxide particles are dispersed in a monodisperse manner in the binder resin.
  • the refractive index of the high refractive index layer is preferably 1.60 or more and 2.50 or less, and more preferably 1.80 or more and 2.20 or less.
  • the thickness of the high refractive index layer is preferably 20 nm or more and 800 nm or less, and more preferably 50 nm or more and 350 nm or less.
  • the metal oxide particles in the high refractive index layer are preferably metal oxide particles having a refractive index of 2.0 or more and 3.0 or less.
  • the metal oxide include titanium dioxide, zirconium oxide, zinc oxide, synthetic amorphous silica, colloidal silica, alumina, colloidal alumina, lead titanate, red lead, yellow lead, zinc yellow, and oxidation.
  • examples thereof include chromium, ferric oxide, iron black, copper oxide, magnesium oxide, magnesium hydroxide, strontium titanate, yttrium oxide, niobium oxide, europium oxide, lanthanum oxide, zircon, and tin oxide.
  • titanium oxide particles and zirconium oxide particles are preferable, titanium oxide particles are more preferable, and rutile type titanium oxide particles are further preferable.
  • the metal oxide particles in the high refractive index layer may be any one of particles composed of a single metal oxide and composite oxide particles composed of a plurality of metal oxides, and a composite oxide particle having a core-shell structure, It is good also as a porous hollow particle.
  • the volume average particle diameter of the metal oxide particles in the high refractive index layer is preferably 100 nm or less, more preferably 1 nm or more and 50 nm or less, and further preferably 1 nm or more and 20 nm or less.
  • the volume average particle diameter is a weighted average particle diameter based on a volume reference frequency, and the particles are observed using a scanning electron microscope or a transmission electron microscope, and the total particle diameter of 1000 particles is measured. Desired.
  • the particle diameter is defined as the diameter of the area equivalent circle of the particle in the electron microscope image.
  • the content of the metal oxide particles in the high refractive index layer is preferably 15% by mass to 70% by mass, and more preferably 20% by mass to 65% by mass, based on the dry mass of the high refractive index layer. Preferably, it is more preferably 30% by mass or more and 60% by mass or less.
  • the binder resin in the high refractive index layer any kind of resin can be used as long as the resin is excellent in mechanical strength and visible light transmittance.
  • the binder resin can be selected from the kinds that can be used as the binder resin in the near-infrared shielding layer. Can do.
  • the binder resin in the high refractive index layer does not need to have oxygen impermeability.
  • the weight average molecular weight of the binder resin in the high refractive index layer is preferably 1000 or more and 200000 or less, and more preferably 3000 or more and 40000 or less.
  • the content of the binder resin in the high refractive index layer is preferably 5% by mass or more and 50% by mass or less, and more preferably 10% by mass or more and 40% by mass or less per dry mass of the high refractive index layer. If the content of the binder resin is 5% by mass or more, the surface of the film after drying becomes relatively smooth, and thus the light transmittance of the high refractive index layer tends to be easily secured. Moreover, if content of binder resin is 50 mass% or less, since content of a metal oxide particle can be made relatively high, there exists a tendency for a refractive index to increase easily.
  • the binder resin in the high refractive index layer can be used in combination with a curing agent.
  • curing agent in a high refractive index layer it can select from the seed
  • the content of the curing agent in the high refractive index layer is preferably 0.1% by mass or more and 60% by mass or less, and more preferably 10% by mass or more and 60% by mass or less per mass of the binder resin.
  • amino acids amino acids, emulsion resins, ultraviolet absorbers, anti-fading agents, surfactants, fluorescent brighteners, pH adjusters, antifoaming agents, lubricants, antiseptics, antistatic agents, matting agents, etc.
  • one or more of these additives may be contained.
  • the content of the additive is preferably 20% by mass or less per dry mass of the high refractive index layer.
  • amino acid an amino acid having an isoelectric point of 6.5 or less is used. Specific examples include aspartic acid, glutamic acid, glycine, serine, and the like, and glycine or serine is particularly preferable.
  • amino acid one or more optical isomers may be added alone, or a racemate may be added. By adding such an amino acid, the dispersibility of the metal oxide particles can be improved.
  • a resin in which fine particles of a water-insoluble resin having an average particle size of about 0.01 ⁇ m or more and 2.0 ⁇ m or less is dispersed in an aqueous medium is used.
  • a single polymer obtained by polymerizing one or more ethylene monomers such as acrylic acid esters, methacrylic acid esters, vinyl compounds, and styrene compounds, and diene monomers such as butadiene and isoprene.
  • ethylene monomers such as acrylic acid esters, methacrylic acid esters, vinyl compounds, and styrene compounds, and diene monomers such as butadiene and isoprene.
  • examples thereof include a polymer or a copolymer. That is, acrylic resins, styrene-butadiene resins, ethylene-vinyl acetate resins and the like.
  • the emulsion resin can be prepared, for example, by subjecting a water-insoluble monomer to emulsion polymerization in the form of an emulsion using a hydrophilic dispersant.
  • hydrophilic dispersants include alkyl sulfonates, alkyl benzene sulfonates, diethylamine, ethylenediamine, quaternary ammonium salts, polyoxyethylene nonylphenyl ether, polyethylene ethylene laurate, hydroxyethyl cellulose, polyvinyl pyrrolidone, polyvinyl Alcohol etc. are mentioned.
  • the ultraviolet absorber for example, known additives as described in JP-A-57-74193, JP-A-57-87988, and JP-A-62-261476 can be used.
  • the anti-fading agent include, for example, JP-A-57-74192, JP-A-57-87989, JP-A-60-72785, JP-A-61-146591, JP-A-1-14659.
  • Known additives such as those described in JP95091A and JP-A-3-13376 can be used.
  • the surfactant any of conventionally known anionic surfactants, cationic surfactants, nonionic surfactants and amphoteric surfactants can be used.
  • fluorescent brighteners examples include, for example, JP-A-59-42993, JP-A-59-52689, JP-A-62-280069, JP-A-61-228771, and JP-A-4.
  • Known additives as described in JP-A-219266 can be used.
  • species such as a sulfuric acid, phosphoric acid, an acetic acid, a citric acid, sodium hydroxide, potassium hydroxide, potassium carbonate, can be used.
  • the low refractive index layer mainly includes metal oxide particles and a binder resin.
  • the metal oxide particles are dispersed in a monodisperse manner in the binder resin.
  • the refractive index of the low refractive index layer is preferably 1.60 or less, more preferably 1.10 or more and 1.60 or less, and further preferably 1.30 or more and 1.50 or less.
  • the thickness of the low refractive index layer is preferably 20 nm or more and 800 nm or less, and more preferably 50 nm or more and 350 nm or less.
  • the metal oxide particles in the low refractive index layer are preferably metal oxide particles having a refractive index of 1.0 to 1.7.
  • Specific examples of the metal oxide include synthetic amorphous silica and colloidal silica. In preparing these metal oxides, it is particularly preferable to use an acidic colloidal silica sol, and it is more preferable to use a colloidal silica sol dispersed in an organic solvent.
  • the metal oxide particles in the low refractive index layer may be porous hollow particles.
  • colloidal silica is disclosed in, for example, JP-A-57-14091, JP-A-60-219083, JP-A-60-219084, JP-A-61-20792, JP-A-61-188183. JP-A-63-17807, JP-A-4-93284, JP-A-5-278324, JP-A-6-92011, JP-A-6-183134, JP-A-6-297830, It can be prepared with reference to JP-A-7-81214, JP-A-7-101142, JP-A-7-179029, JP-A-7-137431, and International Publication No. 94/26530. .
  • the volume average particle diameter of the metal oxide particles contained in the low refractive index layer is preferably 100 nm or less, more preferably 3 nm or more and 50 nm or less, further preferably 3 nm or more and 20 nm or less, and further preferably 4 nm or more. Particularly preferably, it is 10 nm or less.
  • the volume average particle diameter is a weighted average particle diameter with a volume reference frequency.
  • the particle diameter of the metal oxide particles is defined as the diameter of the area equivalent circle of the particles observed using a scanning electron microscope or a transmission electron microscope.
  • the content of the metal oxide particles in the low refractive index layer is preferably 0.1% by mass or more and 50% by mass or less, and 0.5% by mass or more and 45% by mass or less per dry mass of the low refractive index layer. More preferably, it is more preferably 1% by mass to 40% by mass, and particularly preferably 5% by mass to 30% by mass.
  • any species can be used as long as it is a resin excellent in mechanical strength and visible light transmittance.
  • it is selected from the species that can be used as the binder resin in the near-infrared shielding layer. Can do.
  • the binder resin in the low refractive index layer does not need to have oxygen impermeability.
  • the weight average molecular weight of the binder resin in the low refractive index layer is preferably 1000 or more and 200000 or less, and more preferably 3000 or more and 40000 or less.
  • the content of the binder resin in the low refractive index layer is preferably 1% by mass or more and 99.9% by mass or less, and more preferably 1% by mass or more and 50% by mass or less per dry mass of the low refractive index layer. preferable.
  • the binder resin in the low refractive index layer can be used in combination with a curing agent.
  • curing agent in a low refractive index layer it can select from the seed
  • the content of the curing agent in the low refractive index layer is preferably 1% by mass or more and 10% by mass or less, and more preferably 2% by mass or more and 6% by mass or less per mass of the binder resin.
  • amino acids amino acids, emulsion resins, UV absorbers, anti-fading agents, surfactants, fluorescent brighteners, pH adjusters, antifoaming agents, lubricants, antiseptics, antistatic agents, matting agents, etc.
  • One or more of these additives may be contained.
  • the content of the additive is preferably 20% by mass or less per dry mass of the low refractive index layer.
  • the near-infrared shield according to the present embodiment can be manufactured according to a conventionally known method for manufacturing a laminated film.
  • the method for producing a near-infrared shield includes, for example, a step of applying a coating solution for forming a near-infrared shielding layer comprising rutile titanium oxide particles and a binder resin, A step of drying to form a near-infrared shielding layer, a step of applying a coating solution for forming a gas barrier layer containing an oxygen-impermeable resin, and a drying of the applied coating solution for forming a gas barrier layer to form a gas barrier layer Comprising the steps.
  • each coating solution is applied on a substrate or a layer already formed on the substrate.
  • the step of applying the coating solution may be performed sequentially from the lower layer side (substrate side) according to the laminated structure of the near-infrared shield to be manufactured, or may be performed simultaneously by overlaying a plurality of coating solutions. .
  • the step of drying the coating solution may be performed each time each coating solution is sequentially applied, or may be collectively performed for a plurality of layers after a plurality of coating solutions are stacked.
  • the coating solution used for the production of the near-infrared shield is obtained by dissolving the binder resin in an appropriate solvent, adding necessary additives, etc., and adding the rutile-type titanium oxide for the coating solution for forming the near-infrared shielding layer. What is necessary is just to prepare by homogenizing.
  • the rutile-type titanium oxide to be added may be either a dry powder form or a sol form. When using a sol-form rutile-type titanium oxide, the sol medium may be replaced with the solvent of the coating solution as necessary. .
  • rutile titanium oxide particles are coated with an oxygen-impermeable resin and dispersed in a binder resin, the particles are obtained by immersing in an oxygen-impermeable resin solution and drying. Further, rutile-type titanium oxide coated particles can be used for preparing the coating solution.
  • the solvent examples include water, alcohols such as methanol, ethanol, propanol, and butanol, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, depending on the type of binder resin to be dissolved.
  • Esters such as diethyl ether, tetrahydrofuran, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, acetone, methyl ethyl ketone, acetylacetone, cyclohexanone And appropriate species such as dimethyl sulfoxide and acetonitrile.
  • the coating solution is preferably applied after heating to a temperature range of 30 ° C. or more and 60 ° C. or less.
  • a coating method of the coating liquid a general coating method can be used.
  • a coating method such as a bar coater, a comma coater, a roll coater, a blade coater, a gravure coater, a slot die coater, an air knife coater, or a dip coater is used. The method to use is mentioned.
  • the coating solution As a method for drying the coating solution, a method in which constant rate drying at a low temperature and reduced rate drying performed by raising the temperature is preferable.
  • the coating solution is set at a cold temperature of about 1 ° C to 15 ° C. Thereafter, a method of drying by heating is preferred.
  • the temperature in the heat drying is preferably a temperature at which the wet bulb temperature is 5 ° C. or higher and 50 ° C. or lower and the film surface temperature is 30 ° C. or higher and 100 ° C. or lower.
  • the near-infrared shielding body according to the present invention described above can be applied as a lighting window for various buildings, vehicles, railways, ships, and the like.
  • Such near-infrared shields show near-infrared impermeability under sunlight, reducing the temperature rise of the space, but when there is no solar radiation, visible light transmission is restored, and dark and rainbow colors This is useful in that glare due to coloring and irregular reflection is reduced and a good design property is exhibited.
  • the photochromism shown by the near-infrared shield is rutile titanium oxide, so it has durability against repeated temperature, humidity, color change, etc. A shield is obtained.
  • the near-infrared shield according to the present invention is applied as a light transmitting member including an optical element provided in an optical device, an imaging device, a drawing device, and the like, a wall material of various structures, a laying material, and other exterior materials. can do.
  • a near-infrared shield is useful in that the near-infrared impermeability and visible light transmissivity can be changed by adjusting the amount of ultraviolet rays.
  • a near-infrared shielding body (near-infrared shielding film) having a near-infrared shielding layer comprising rutile-type titanium oxide particles was produced, and the absorption in the near-infrared region and the transmittance in the visible light region were evaluated. .
  • Example 1 As Example 1, the near-infrared shielding film of the single layer structure in which the near-infrared shielding layer formed on the base material contains an oxygen-impermeable resin was produced.
  • the base material made from a polyethylene terephthalate (PET) with a thickness of 50 micrometers was used.
  • PET polyethylene terephthalate
  • rutile titanium oxide an aqueous titanium oxide solution “SRD-W” (manufactured by Sakai Chemical Industry Co., Ltd.) was used. “SRD-W” is an aqueous solution having a titanium oxide particle diameter of 5 nm and a titanium oxide concentration of 15 mass%.
  • polyvinyl alcohol “PVA124” manufactured by Kuraray Co., Ltd.
  • the oxygen permeability coefficient of polyvinyl alcohol “PVA124” at 20 ° C. was 4.0 ⁇ 10 ⁇ 18 (cm 3 ⁇ cm / (cm 2 ⁇ sec ⁇ cmHg)).
  • the oxygen permeability coefficient of the resin used was prepared by using a disk-shaped resin film having a thickness of 100 ⁇ m and a diameter of 5 cm as a test piece, and using a gas permeability measuring device “Gasperm-100” (manufactured by JASCO Corporation). And measured.
  • the oxygen transmission coefficient (P) [cm 3 ⁇ cm / (cm 2 ⁇ sec ⁇ cmHg)] is the oxygen transmission rate (q) [cm 3 ], the average thickness (L) [ ⁇ m] of the test piece, and the oxygen supply pressure (p) [kg / cm 2 ], permeation area of the specimen (a) [cm 2], with a measurement time (t) [min], can be calculated according to the following equation 1.
  • the near-infrared shielding film according to Example 1 was manufactured according to the following procedure. First, the pH was adjusted to 4 by adding 3% citric acid to the titanium oxide aqueous solution. Next, an aqueous resin solution having an oxygen-impermeable resin concentration of 4% by mass was added to the aqueous titanium oxide solution to prepare a coating solution having a titanium oxide particle content of 45% by mass. And the prepared coating liquid was apply
  • the formed coating film was exposed to cold air and set and dried, and then subjected to hot air drying to form a near-infrared shielding layer having a film thickness of 1.0 ⁇ m, and the near-infrared shielding film according to Example 1 did.
  • the absorptance in the near-infrared region and the transmittance in the visible light region of the manufactured near-infrared shielding film according to Example 1 were measured.
  • the transmittance and absorption rate of the near-infrared shielding film were determined for each before ultraviolet irradiation and after ultraviolet irradiation, and the near-infrared shielding performance and visible light transmission performance along the change in the redox state of rutile titanium oxide were confirmed.
  • Measurement of light transmittance and absorptance before and after ultraviolet irradiation was carried out in a wavelength region of 300 to 2000 nm using an integrating sphere spectrophotometer “U-4000” (Hitachi, Ltd.). The measured value at a wavelength of 1200 nm was used for the absorptance in the near infrared region, and the measured value at a wavelength of 550 nm was used for the transmittance in the visible light region.
  • a weather resistance tester “xenon weather meter” manufactured by Suga Test Instruments Co., Ltd.
  • xenon lamp as a light source was used for ultraviolet irradiation.
  • the light transmittance / absorbance was measured according to the following procedure. First, the manufactured near-infrared shielding film was attached to blue glass having a thickness of 3 mm to prepare a sample. Then, the light transmittance and absorptivity of the sample were measured using a spectrophotometer, and the absorptivity in the near infrared region and the transmittance in the visible light region before ultraviolet irradiation were obtained. Subsequently, the sample was exposed to xenon light having an intensity of 160 W / m 2 for 30 minutes under the conditions of a temperature of 30 ° C. and a humidity of 60%.
  • the light transmittance and absorptivity of the sample were measured again using a spectrophotometer, and the absorptance in the near-infrared region and the transmittance in the visible light region after ultraviolet irradiation were determined.
  • the absorption rate in the near-infrared region was 3% and the transmittance in the visible region was 90% before ultraviolet irradiation, whereas after the ultraviolet irradiation, The absorptance in the near infrared region was 72%, and the transmittance in the visible light region was 81%.
  • Example 2 As Example 2, the near-infrared shielding film of the single layer structure in which the near-infrared shielding layer formed on the base material contains an oxygen-impermeable resin was produced.
  • the near-infrared shielding film which concerns on Example 2 was manufactured according to the procedure similar to Example 1 except the point which used ethylene modified polyvinyl alcohol "RS2117” (made by Kuraray Co., Ltd.) as oxygen-impermeable resin. .
  • the oxygen permeability coefficient of ethylene-modified polyvinyl alcohol “RS2117” at 20 ° C. was 5.0 ⁇ 10 ⁇ 18 (cm 3 ⁇ cm / (cm 2 ⁇ sec ⁇ cmHg)).
  • the absorption rate in the near-infrared region and the transmittance in the visible light region of the manufactured near-infrared shielding film according to Example 2 were measured in the same manner as in Example 1.
  • the absorption rate in the near-infrared region was 3% and the transmittance in the visible region was 90% before ultraviolet irradiation, whereas after the ultraviolet irradiation,
  • the absorptance in the near infrared region was 65%, and the transmittance in the visible light region was 80%.
  • Example 3 As Example 3, the near-infrared shielding film of the single layer structure in which the near-infrared shielding layer formed on the base material contains an oxygen-impermeable resin was produced. In addition, the near-infrared shielding film which concerns on Example 3 was manufactured according to the procedure similar to Example 1 except the point which prepared and used the coating liquid whose particle content rate of a titanium oxide is 30 mass%.
  • the absorbance in the near infrared region and the transmittance in the visible light region of the produced near infrared shielding film according to Example 3 were measured in the same manner as in Example 1.
  • the absorption rate in the near-infrared region was 3% and the transmittance in the visible light region was 90% before ultraviolet irradiation, whereas after the ultraviolet irradiation, The absorptance in the near infrared region was 45%, and the transmittance in the visible light region was 83%.
  • Example 4 As Example 4, the near-infrared shielding film of the single layer structure in which the near-infrared shielding layer formed on the base material contains an oxygen-impermeable resin was produced.
  • the near-infrared shielding film according to Example 4 was manufactured according to the same procedure as in Example 1 except that titanium oxide “TTO-55” (manufactured by Ishihara Sangyo Co., Ltd.) was used as the rutile titanium oxide. .
  • “TTO-55” is titanium oxide having a particle diameter of 50 nm, prepared by a solid phase method and surface-treated with Al (OH) 3 .
  • the absorbance in the near infrared region and the transmittance in the visible light region of the manufactured near infrared shielding film according to Example 4 were measured in the same manner as in Example 1.
  • the absorption rate in the near-infrared region was 3% and the transmittance in the visible light region was 84% before the ultraviolet irradiation, whereas after the ultraviolet irradiation, The absorptance in the near infrared region was 52%, and the transmittance in the visible light region was 78%.
  • Example 5 As Example 5, the near-infrared shielding film of the single layer structure in which the near-infrared shielding layer formed on the base material contains an oxygen-impermeable resin was produced.
  • the near-infrared shielding film which concerns on Example 5 is Example 1 except the point which prepared and used the titanium oxide (silica coat titanium oxide) by which the surface was coat
  • Titanium oxide having a surface coated with silicon oxide was prepared according to the following procedure. First, after adding 2 parts by mass of pure water to 0.5 parts by mass of 15.0% by mass titanium oxide sol “SRD-W” (rutile-type titanium dioxide particles, volume average particle size 5 nm, manufactured by Sakai Chemical Industry Co., Ltd.) Heated to 90 ° C. Subsequently, 0.45 parts by mass of an aqueous silicic acid solution (an aqueous solution obtained by diluting “sodium silicate 4” (manufactured by Nippon Chemical Industry Co., Ltd.) with pure water so that the SiO 2 equivalent concentration becomes 0.5%) Then, heat treatment was performed at 175 ° C. for 18 hours in an autoclave.
  • SRD-W rutile-type titanium dioxide particles, volume average particle size 5 nm, manufactured by Sakai Chemical Industry Co., Ltd.
  • silica deposited oxide sol solid content of 20 wt% of silicon oxide (SiO 2) titanium oxide sol attached to the surface.
  • the absorption rate in the near-infrared region and the transmittance in the visible light region of the manufactured near-infrared shielding film according to Example 5 were measured in the same manner as in Example 1.
  • the absorption rate in the near-infrared region was 3% and the transmittance in the visible light region was 92% before ultraviolet irradiation, whereas after the ultraviolet irradiation, The absorptance in the near infrared region was 77%, and the transmittance in the visible light region was 82%.
  • Example 6 As Example 6, the near-infrared shielding film of the single layer structure in which the near-infrared shielding layer formed on the base material contains an oxygen-impermeable resin was produced.
  • the near-infrared shielding film which concerns on Example 6 was manufactured according to the procedure similar to Example 5 except the point which coat
  • Titanium oxide having a surface coated with silicon oxide was prepared according to the following procedure. First, after adding 2 parts by mass of pure water to 0.5 parts by mass of 15.0% by mass titanium oxide sol “SRD-W” (rutile-type titanium dioxide particles, volume average particle size 5 nm, manufactured by Sakai Chemical Industry Co., Ltd.) And heated to 90 ° C. Subsequently, 0.6 parts by mass of an aqueous silicic acid solution (an aqueous solution obtained by diluting “sodium silicate 4” (manufactured by Nippon Chemical Industry Co., Ltd.) with pure water so that the SiO 2 equivalent concentration is 0.6%) is gradually added. Then, heat treatment was performed at 175 ° C. for 18 hours in an autoclave.
  • SRD-W rutile-type titanium dioxide particles, volume average particle size 5 nm, manufactured by Sakai Chemical Industry Co., Ltd.
  • titanium oxide sol solid component concentration 20 wt% of silicon oxide (SiO 2) on the surface.
  • SiO 2 silicon oxide
  • the absorption rate in the near infrared region and the transmittance in the visible light region of the manufactured near infrared shielding film according to Example 6 were measured in the same manner as in Example 1.
  • the absorption rate in the near-infrared region was 3% and the transmittance in the visible light region was 92% before ultraviolet irradiation, whereas after the ultraviolet irradiation, The absorptance in the near infrared region was 85%, and the transmittance in the visible light region was 82%.
  • Example 7 As Example 7, the near-infrared shielding film of the single layer structure in which the near-infrared shielding layer formed on the base material contains oxygen-impermeable resin was manufactured. In addition, the near-infrared shielding film which concerns on Example 7 was manufactured according to the procedure similar to Example 5 or Example 6 except the point which coat
  • Titanium oxide having a surface coated with silicon oxide was prepared according to the following procedure. First, after adding 2 parts by mass of pure water to 0.5 parts by mass of 15.0% by mass titanium oxide sol “SRD-W” (rutile-type titanium dioxide particles, volume average particle size 5 nm, manufactured by Sakai Chemical Industry Co., Ltd.) And heated to 90 ° C. Subsequently, 1.5 parts by mass of an aqueous silicic acid solution (an aqueous solution obtained by diluting “sodium silicate 4” (manufactured by Nippon Chemical Industry Co., Ltd.) with pure water so that the SiO 2 equivalent concentration becomes 0.6%) Then, heat treatment was performed at 175 ° C. for 18 hours in an autoclave.
  • SRD-W rutile-type titanium dioxide particles, volume average particle size 5 nm, manufactured by Sakai Chemical Industry Co., Ltd.
  • titanium oxide sol solid component concentration 20 wt% of silicon oxide (SiO 2) on the surface.
  • the coating amount of silicon oxide was 10% by mass with respect to titanium oxide.
  • the absorption rate in the near-infrared region and the transmittance in the visible light region of the manufactured near-infrared shielding film according to Example 7 were measured in the same manner as in Example 1.
  • the absorption rate in the near-infrared region was 3% and the transmittance in the visible light region was 92% before ultraviolet irradiation, whereas after the ultraviolet irradiation,
  • the absorptivity in the near infrared region was 84%, and the transmittance in the visible light region was 82%.
  • Example 8 the near-infrared shielding film of the single layer structure in which the near-infrared shielding layer formed on the base material contains an oxygen-impermeable resin was produced.
  • the base material made from a polyethylene terephthalate (PET) with a thickness of 50 micrometers was used.
  • the rutile titanium oxide an aqueous titanium oxide solution “SRD-W” (manufactured by Sakai Chemical Industry Co., Ltd.) was used.
  • the oxygen-impermeable resin polyacrylonitrile “Zeklon (registered trademark)” (manufactured by Mitsui Chemicals, Inc.) was used.
  • the oxygen permeability coefficient of polyacrylonitrile “Zeklon” at 20 ° C. was 1.5 ⁇ 10 ⁇ 17 (cm 3 ⁇ cm / (cm 2 ⁇ sec ⁇ cmHg)).
  • the near-infrared shielding film according to Example 8 was manufactured according to the following procedure. First, the titanium oxide aqueous solution is concentrated using an ultrafiltration membrane to reduce the volume to 50%, and then a series of operations to return to 100% volume by adding acetonitrile is repeated. To acetonitrile. Subsequently, a dimethyl sulfoxide solution in which the concentration of the oxygen-impermeable resin was 4% by mass was added to the titanium oxide solution to prepare a coating solution having a titanium oxide particle content of 45% by mass. And the near-infrared shielding layer was formed in accordance with the procedure similar to Example 1 after that using this coating liquid, and it was set as the near-infrared shielding film which concerns on Example 8. FIG.
  • the absorption rate in the near-infrared region and the transmittance in the visible light region of the manufactured near-infrared shielding film according to Example 8 were measured in the same manner as in Example 1.
  • the absorption rate in the near-infrared region was 3% and the transmittance in the visible light region was 90% before the ultraviolet irradiation, whereas after the ultraviolet irradiation,
  • the absorptance in the near infrared region was 40%, and the transmittance in the visible light region was 83%.
  • Example 9 As Example 9, the near-infrared shielding film of the single layer structure in which the near-infrared shielding layer formed on the base material contains an oxygen-impermeable resin was produced.
  • the near-infrared shielding film according to Example 9 uses a near-infrared reflective laminate in which a high refractive index layer and a low refractive index layer are alternately laminated as a base material. 5 was prepared according to the same procedure as in Example 1 except that titanium oxide (silica-coated titanium oxide) whose surface was coated with silicon oxide was used.
  • the high refractive index layer and the low refractive index layer in the near-infrared reflective laminate are each composed of a polymethyl methacrylate copolymer, and are formed by coextrusion on polyethylene terephthalate.
  • the thickness of the near-infrared reflective laminate is 65 ⁇ m
  • the refractive index of the high refractive index layer is 1.65
  • the refractive index of the low refractive index layer is 1.49.
  • the absorption rate in the near-infrared region and the transmittance in the visible light region of the manufactured near-infrared shielding film according to Example 9 were measured in the same manner as in Example 1.
  • the absorption rate here was calculated
  • the absorption rate in the near-infrared region was 50% and the transmittance in the visible light region was 83% before the ultraviolet irradiation, whereas after the ultraviolet irradiation, The absorptivity in the near infrared region was 81%, and the transmittance in the visible light region was 76%.
  • Example 10 a near-infrared shielding film having a laminated structure in which a near-infrared shielding layer formed on a substrate was sandwiched between two gas barrier layers containing an oxygen-impermeable resin was produced.
  • the base material made from a polyethylene terephthalate (PET) with a thickness of 50 micrometers was used.
  • the rutile titanium oxide an aqueous titanium oxide solution “SRD-W” (manufactured by Sakai Chemical Industry Co., Ltd.) was used.
  • the oxygen-impermeable resin polyvinyl alcohol “PVA124” (manufactured by Kuraray Co., Ltd.) was used.
  • the near-infrared shielding film according to Example 10 was manufactured according to the following procedure. First, the pH was adjusted to 4 by adding 3% citric acid to the titanium oxide aqueous solution. Next, an aqueous resin solution having an oxygen-impermeable resin concentration of 4% by mass was added to the aqueous titanium oxide solution to prepare a coating solution having a titanium oxide particle content of 45% by mass. And the resin aqueous solution which does not contain titanium oxide was apply
  • the prepared coating liquid was applied onto the formed gas barrier layer using a slide coater to form a coating film.
  • the formed coating film was exposed to cold air of 5 ° C. and set and dried, and then 80 ° C.
  • a near-infrared shielding layer having a film thickness of 1.0 ⁇ m was formed.
  • a resin aqueous solution not containing titanium oxide is further applied onto the formed near-infrared shielding layer using a slide coater to form a coating film, and the formed coating film is exposed to 5 ° C. cold air. After being set and dried, it was subjected to hot air drying at 80 ° C. to form a gas barrier layer having a film thickness of 1 ⁇ m, and the near-infrared shielding film according to Example 10 was obtained.
  • the absorption rate in the near-infrared region and the transmittance in the visible light region of the manufactured near-infrared shielding film according to Example 10 were measured in the same manner as in Example 1.
  • the absorption rate in the near-infrared region was 3% and the transmittance in the visible light region was 90% before ultraviolet irradiation, whereas after the ultraviolet irradiation,
  • the absorptance in the near infrared region was 70%, and the transmittance in the visible light region was 80%.
  • Example 11 As Example 11, a near-infrared shielding film having a laminated structure in which a near-infrared shielding layer formed on a substrate was sandwiched between two gas barrier layers containing an oxygen-impermeable resin was produced.
  • the near-infrared shielding film which concerns on Example 11 was manufactured according to the procedure similar to Example 10 except the point which used ethylene modified polyvinyl alcohol "RS2117" (made by Kuraray Co., Ltd.) as oxygen-impermeable resin. .
  • the absorption in the near infrared region and the transmittance in the visible light region of the manufactured near infrared shielding film according to Example 11 were measured in the same manner as in Example 1.
  • the absorption rate in the near-infrared region was 3% and the transmittance in the visible light region was 90% before the ultraviolet irradiation, whereas after the ultraviolet irradiation, The absorptance in the near infrared region was 62%, and the transmittance in the visible light region was 79%.
  • Example 12 As Example 12, a near-infrared shielding film having a laminated structure in which a near-infrared shielding layer formed on a substrate was sandwiched between two gas barrier layers containing an oxygen-impermeable resin was produced.
  • the near-infrared shielding film which concerns on Example 12 is the procedure similar to Example 10 except the point which used polyacrylonitrile "Zeklon (trademark)" (made by Mitsui Chemicals, Inc.) as oxygen-impermeable resin.
  • the absorption rate in the near-infrared region and the transmittance in the visible light region of the manufactured near-infrared shielding film according to Example 12 were measured in the same manner as in Example 1.
  • the absorption rate in the near-infrared region was 3% and the transmittance in the visible region was 90% before ultraviolet irradiation, whereas after the ultraviolet irradiation, The absorptance in the near infrared region was 39%, and the transmittance in the visible light region was 83%.
  • Example 13 As Example 13, a near-infrared shielding film having a laminated structure in which a near-infrared shielding layer formed on a substrate was sandwiched between two gas barrier layers containing an oxygen-impermeable resin was produced.
  • the near-infrared shielding film which concerns on Example 13 uses the titanium oxide (silica coat titanium oxide) by which the surface was coat
  • the absorption in the near infrared region and the transmittance in the visible light region of the manufactured near infrared shielding film according to Example 13 were measured in the same manner as in Example 1.
  • the absorption rate in the near-infrared region was 3% and the transmittance in the visible light region was 92% before the ultraviolet irradiation, whereas after the ultraviolet irradiation, The absorptance in the near infrared region was 77%, and the transmittance in the visible light region was 82%.
  • Example 14 As Example 14, a near-infrared shielding film having a laminated structure in which a near-infrared shielding layer formed on a substrate was sandwiched between two gas barrier layers containing an oxygen-impermeable resin was produced. Note that the near-infrared shielding film according to Example 14 uses a near-infrared reflective laminate in which high-refractive index layers and low-refractive index layers similar to those in Example 9 are alternately laminated as a base material.
  • ethylene modified polyvinyl alcohol “RS2117” manufactured by Kuraray Co., Ltd.
  • rutile titanium oxide titanium oxide (silica coated titanium oxide) whose surface was coated with silicon oxide was used as Example 5.
  • the absorbance in the near infrared region and the transmittance in the visible light region of the manufactured near infrared shielding film according to Example 14 were measured in the same manner as in Example 1.
  • the absorption rate here was calculated
  • the absorption rate in the near-infrared region was 50% and the transmittance in the visible light region was 82% before ultraviolet irradiation, whereas after the ultraviolet irradiation, The absorptance in the near infrared region was 79%, and the transmittance in the visible light region was 83%.
  • Example 15 As Example 15, the near-infrared shielding film of the single layer structure in which the near-infrared shielding layer formed on the base material contains an oxygen-impermeable resin was produced. In addition, the near-infrared shielding film which concerns on Example 15 was the same procedure as Example 1 except having formed so that the film thickness after drying of the near-infrared shielding layer formed on the base material might be 0.3 micrometer.
  • the absorption in the near infrared region and the transmittance in the visible light region of the manufactured near infrared shielding film according to Example 15 were measured in the same manner as in Example 1.
  • the absorption rate in the near-infrared region was 0.9% and the transmittance in the visible light region was 92% before the ultraviolet irradiation, whereas the ultraviolet irradiation was performed.
  • the absorptance in the near infrared region was 35%, and the transmittance in the visible light region was 87%.
  • Example 16 As Example 16, the near-infrared shielding film of the single layer structure in which the near-infrared shielding layer formed on the base material contains an oxygen-impermeable resin was produced.
  • the near-infrared shielding film according to Example 16 was the same procedure as Example 1 except that the near-infrared shielding layer formed on the substrate was formed such that the film thickness after drying was 0.5 ⁇ m.
  • the absorbance in the near infrared region and the transmittance in the visible light region of the manufactured near infrared shielding film according to Example 16 were measured in the same manner as in Example 1.
  • the absorption rate in the near-infrared region was 1.5% and the transmittance in the visible region was 92% before the ultraviolet irradiation, whereas the ultraviolet irradiation was performed.
  • the absorptivity in the near infrared region was 45%, and the transmittance in the visible light region was 85%.
  • Comparative Example 1 As Comparative Example 1, a near-infrared shielding film having a single layer structure in which the near-infrared shielding layer formed on the substrate did not contain an oxygen-impermeable resin was produced.
  • the near-infrared shielding film which concerns on the comparative example 1 was manufactured according to the procedure similar to Example 1 except the point which replaced with oxygen permeable resin and used the hydroxypropyl methylcellulose (HPMC). Hydroxypropyl methylcellulose had an oxygen permeability coefficient at 20 ° C. of 4.0 ⁇ 10 ⁇ 16 (cm 3 ⁇ cm / (cm 2 ⁇ sec ⁇ cmHg)), and was not equipped with oxygen impermeability.
  • the absorption rate in the near infrared region and the transmittance in the visible light region of the manufactured near infrared shielding film according to Comparative Example 1 were measured in the same manner as in Example 1.
  • the absorption rate in the near-infrared region was 3% and the transmittance in the visible light region was 90% before ultraviolet irradiation, whereas after the ultraviolet irradiation,
  • the absorptivity in the near infrared region was 21%, and the transmittance in the visible light region was 89%.
  • Comparative Example 2 As Comparative Example 2, a near-infrared shielding film having a single layer structure in which the near-infrared shielding layer formed on the substrate did not contain an oxygen-impermeable resin was produced.
  • the near-infrared shielding film which concerns on the comparative example 2 was manufactured according to the procedure similar to Example 1 except the point which replaced with oxygen permeable resin and used polyethyleneglycol (PEO).
  • Polyethylene glycol had an oxygen permeability coefficient at 20 ° C. of 3.0 ⁇ 10 ⁇ 9 (cm 3 ⁇ cm / (cm 2 ⁇ sec ⁇ cmHg)), and was not equipped with oxygen impermeability.
  • the absorption in the near infrared region and the transmittance in the visible light region of the manufactured near infrared shielding film according to Comparative Example 2 were measured in the same manner as in Example 1.
  • the absorption rate in the near-infrared region was 3% and the transmittance in the visible light region was 90% before ultraviolet irradiation, whereas after the ultraviolet irradiation, The absorptance in the near infrared region was 8%, and the transmittance in the visible light region was 90%.
  • Comparative Example 3 As Comparative Example 3, a near-infrared shielding film having a single layer structure in which the near-infrared shielding layer formed on the base material contains an oxygen-impermeable resin but does not have a predetermined thickness was manufactured.
  • the near-infrared shielding film which concerns on the comparative example 3 was the same procedure as Example 1 except having formed so that the film thickness after drying of the near-infrared shielding layer formed on the base material might be set to 0.2 micrometer.
  • the absorbance in the near infrared region and the transmittance in the visible light region of the manufactured near infrared shielding film according to Comparative Example 3 were measured in the same manner as in Example 1.
  • the absorption ratio in the near infrared region was 0.6% and the transmittance in the visible light region was 92%, whereas the ultraviolet irradiation was performed.
  • the absorptance in the near infrared region was 20%, and the transmittance in the visible light region was 87%.
  • Comparative Example 4 As Comparative Example 4, a near-infrared shielding film having a single-layer structure in which a near-infrared shielding layer formed on a substrate contained an oxygen-impermeable resin but did not have a predetermined film thickness was produced.
  • the near-infrared shielding film which concerns on the comparative example 4 was the same procedure as Example 1 except having formed so that the film thickness after drying of the near-infrared shielding layer formed on the base material might be set to 1.1 micrometers.
  • the absorption in the near infrared region and the transmittance in the visible light region of the manufactured near infrared shielding film according to Comparative Example 4 were measured in the same manner as in Example 1.
  • the absorptance in the near infrared region was 3.3% and the transmittance in the visible light region was 83%, whereas the ultraviolet irradiation was performed.
  • the absorptance in the near infrared region was 80%, and the transmittance in the visible light region was 69%.
  • Table 1 shows properties, absorption in the near infrared region, and transmittance in the visible light region of the near infrared shielding films according to Examples 1 to 16 and Comparative Examples 1 to 4.
  • the near-infrared region In contrast, in the near-infrared shielding films according to Examples 1 to 16, in which the rutile-type titanium oxide contained in the near-infrared shielding layer is isolated from the oxygen gas by the oxygen-impermeable resin, the near-infrared region The absorptance in was significantly increased after UV irradiation. Further, the transmittance in the visible light region was at a high level before the ultraviolet irradiation, and a high transmittance was ensured even after the ultraviolet irradiation.
  • the near-infrared shielding performance is effectively exhibited, while under non-irradiation of ultraviolet rays, it exhibits good visible light transmission, and is colored in dark or rainbow colors. It was confirmed that glare due to irregular reflection can be reduced and a near-infrared shielding film exhibiting good design properties can be provided.
  • Example 1 By comparing Example 1 with Examples 5 to 7, the use of titanium oxide having a surface coated with a hydrated oxide of silicon resulted in effective coloration of titanium oxide. There was a tendency to increase the absorption rate in the region. Moreover, by comparing Example 1 and Example 4, it was confirmed that the smaller the titanium oxide particle diameter, the better the absorption in the near infrared region and the transmittance in the visible light region. In addition, by comparing Example 5 and Example 9, by absorbing a near-infrared reflective laminate that reflects near-infrared light between the base material and the near-infrared shielding layer, absorption in the near-infrared region is achieved. It was confirmed that the rate could be further improved.
  • NIR shield 1 Near-infrared shield (single layer structure) 2 Near-infrared shield (laminated structure) 10 Substrate 20 Near-infrared shielding layer 30A Gas barrier layer (lower layer) 30B Gas barrier layer (upper layer)

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Laminated Bodies (AREA)
  • Optical Filters (AREA)

Abstract

L'objet de la présente invention est de pourvoir à un corps de protection contre le proche infrarouge et à un film de protection contre le proche infrarouge qui présentent des propriétés de non-transmission de lumière dans le proche infrarouge résistantes aux intempéries et des propriétés de transmission de lumière visible résistantes aux intempéries. Un corps de protection contre le proche infrarouge selon la présente invention est pourvu d'une base et d'une couche de protection contre le proche infrarouge qui est formée sur la base et qui contient des particules d'oxyde de titane rutile. Ledit corps de protection contre le proche infrarouge est caractérisé en ce que : chaque particule d'oxyde de titane rutile est recouverte d'une résine imperméable à l'oxygène présentant un coefficient de perméation de l'oxygène inférieur ou égal à 1 × 10-16 (cm3(STP)cm/(cm2·sec·cmHg)); et l'épaisseur de film de la couche de protection contre le proche infrarouge après séchage est située dans la plage allant de 0,3 μm à 1,0 μm (inclus). En outre, un film de protection contre le proche infrarouge est obtenu en présentant une base constituée d'un matériau de base de type film flexible.
PCT/JP2014/077960 2013-10-24 2014-10-21 Corps de protection contre le proche infrarouge et film de protection contre le proche infrarouge WO2015060305A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2015543866A JPWO2015060305A1 (ja) 2013-10-24 2014-10-21 近赤外線遮蔽体及び近赤外線遮蔽フィルム

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013-220886 2013-10-24
JP2013220886 2013-10-24

Publications (1)

Publication Number Publication Date
WO2015060305A1 true WO2015060305A1 (fr) 2015-04-30

Family

ID=52992899

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/077960 WO2015060305A1 (fr) 2013-10-24 2014-10-21 Corps de protection contre le proche infrarouge et film de protection contre le proche infrarouge

Country Status (2)

Country Link
JP (1) JPWO2015060305A1 (fr)
WO (1) WO2015060305A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108369303A (zh) * 2015-12-25 2018-08-03 柯尼卡美能达株式会社 光学反射膜

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009086659A (ja) * 2007-09-13 2009-04-23 Mitsubishi Chemicals Corp 熱線遮蔽膜及びその積層体
JP2013148849A (ja) * 2012-01-23 2013-08-01 Konica Minolta Inc 赤外遮蔽フィルムおよび赤外遮蔽体
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

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009086659A (ja) * 2007-09-13 2009-04-23 Mitsubishi Chemicals Corp 熱線遮蔽膜及びその積層体
JP2013148849A (ja) * 2012-01-23 2013-08-01 Konica Minolta Inc 赤外遮蔽フィルムおよび赤外遮蔽体
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

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108369303A (zh) * 2015-12-25 2018-08-03 柯尼卡美能达株式会社 光学反射膜
CN108369303B (zh) * 2015-12-25 2020-10-09 柯尼卡美能达株式会社 光学反射膜

Also Published As

Publication number Publication date
JPWO2015060305A1 (ja) 2017-03-09

Similar Documents

Publication Publication Date Title
JP6115675B2 (ja) 光学反射フィルム及びそれを用いた光学反射体
JP5939257B2 (ja) 近赤外遮蔽フィルムおよび近赤外遮蔽体
WO2015104981A1 (fr) Film réfléchissant le rayonnement infrarouge, procédé de fabrication d'un film réfléchissant le rayonnement infrarouge, et procédé de fabrication d'un verre stratifié
WO2014069507A1 (fr) Film de réflexion optique, film protégeant des infrarouges et processus pour leur production
WO2014199872A1 (fr) Film de protection infrarouge, corps de protection infrarouge l'utilisant et verre stratifié réfléchissant les rayons thermiques
JPWO2015056594A1 (ja) 赤外遮蔽フィルムおよび合わせガラス
JP6428608B2 (ja) 赤外線遮蔽フィルム、赤外線遮蔽フィルムの設置方法及び赤外線遮蔽フィルムの虹彩防止方法
JPWO2016006388A1 (ja) 光学フィルム
US20160062000A1 (en) Optical reflective film, method for manufacturing the same, and optical reflector using the same
JPWO2015056752A1 (ja) 赤外遮蔽フィルムおよびこれを用いた赤外遮蔽体および熱線反射合わせガラス
WO2016017513A1 (fr) Film réfléchissant les infrarouges et verre feuilleté
WO2013183544A1 (fr) Film d'écrantage vis-à-vis de l'infrarouge et corps d'écrantage vis-à-vis de l'infrarouge
WO2015060305A1 (fr) Corps de protection contre le proche infrarouge et film de protection contre le proche infrarouge
JP6176256B2 (ja) 光学反射フィルムおよびそれを用いた光学反射体
WO2017077810A1 (fr) Film réfléchissant la lumière
JP2013080178A (ja) 光遮蔽フィルムおよびそれを用いた赤外遮蔽体
JP2013125076A (ja) 近赤外遮蔽フィルムおよび近赤外遮蔽体
JP5817553B2 (ja) 赤外遮蔽フィルムおよび赤外遮蔽体
WO2014148366A1 (fr) Film réflecteur de lumière et son procédé de fabrication
JP5910274B2 (ja) 熱線遮断フィルムおよびその製造方法
JPWO2015174308A1 (ja) 光学反射フィルム、その製造方法およびそれを用いる光学反射体
JP2014215513A (ja) 赤外遮蔽フィルムおよび赤外遮蔽体
JP2012252107A (ja) 赤外遮蔽フィルム、赤外遮蔽フィルムの製造方法、および赤外遮蔽体
JP2021104637A (ja) 積層体および物品
JP2016114806A (ja) 光学フィルム

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14854994

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2015543866

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14854994

Country of ref document: EP

Kind code of ref document: A1