WO2016017604A1 - 光学フィルム及び光学フィルムの製造方法 - Google Patents
光学フィルム及び光学フィルムの製造方法 Download PDFInfo
- Publication number
- WO2016017604A1 WO2016017604A1 PCT/JP2015/071303 JP2015071303W WO2016017604A1 WO 2016017604 A1 WO2016017604 A1 WO 2016017604A1 JP 2015071303 W JP2015071303 W JP 2015071303W WO 2016017604 A1 WO2016017604 A1 WO 2016017604A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- binder resin
- optical film
- layer
- particles
- vanadium dioxide
- Prior art date
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- HGPXWXLYXNVULB-UHFFFAOYSA-M lithium stearate Chemical compound [Li+].CCCCCCCCCCCCCCCCCC([O-])=O HGPXWXLYXNVULB-UHFFFAOYSA-M 0.000 description 1
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- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
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- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- WPUMVKJOWWJPRK-UHFFFAOYSA-N naphthalene-2,7-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 WPUMVKJOWWJPRK-UHFFFAOYSA-N 0.000 description 1
- LKKPNUDVOYAOBB-UHFFFAOYSA-N naphthalocyanine Chemical compound N1C(N=C2C3=CC4=CC=CC=C4C=C3C(N=C3C4=CC5=CC=CC=C5C=C4C(=N4)N3)=N2)=C(C=C2C(C=CC=C2)=C2)C2=C1N=C1C2=CC3=CC=CC=C3C=C2C4=N1 LKKPNUDVOYAOBB-UHFFFAOYSA-N 0.000 description 1
- 150000002791 naphthoquinones Chemical class 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
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- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
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- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
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- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
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- QFZSBPSUWOMMEC-UHFFFAOYSA-M potassium;prop-2-enenitrile;prop-2-enoate Chemical compound [K+].C=CC#N.[O-]C(=O)C=C QFZSBPSUWOMMEC-UHFFFAOYSA-M 0.000 description 1
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- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- 238000000790 scattering method Methods 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
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- 238000005477 sputtering target Methods 0.000 description 1
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- 239000007858 starting material Substances 0.000 description 1
- 229920005792 styrene-acrylic resin Polymers 0.000 description 1
- 125000001424 substituent group Chemical class 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 235000013706 tagetes lucida Nutrition 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 235000010491 tara gum Nutrition 0.000 description 1
- 239000000213 tara gum Substances 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- 238000009283 thermal hydrolysis Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- SOLUNJPVPZJLOM-UHFFFAOYSA-N trizinc;distiborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-][Sb]([O-])([O-])=O.[O-][Sb]([O-])([O-])=O SOLUNJPVPZJLOM-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
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- 239000002023 wood Substances 0.000 description 1
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- 239000010457 zeolite Substances 0.000 description 1
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Images
Classifications
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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- B05D1/00—Processes for applying liquids or other fluent materials
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- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/40—Distributing applied liquids or other fluent materials by members moving relatively to surface
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- B32B23/04—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B23/08—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B32B23/22—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising ethers
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-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
- C09D101/02—Cellulose; Modified cellulose
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
- C09D129/02—Homopolymers or copolymers of unsaturated alcohols
- C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/004—Reflecting paints; Signal paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/32—Radiation-absorbing paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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- G—PHYSICS
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- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
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- G—PHYSICS
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- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
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- G02B5/08—Mirrors
- G02B5/0816—Multilayer mirrors, i.e. having two or more reflecting layers
- G02B5/085—Multilayer mirrors, i.e. having two or more reflecting layers at least one of the reflecting layers comprising metal
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- G—PHYSICS
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- 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
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Definitions
- the present invention relates to an optical film for shielding near infrared light and a method for producing the same. More specifically, the present invention relates to an optical film having thermochromic properties, low haze, excellent crack resistance and adhesion, and a method for producing the same.
- Near-infrared light shielding film is an effective means for energy saving because it can reduce the load on cooling equipment such as air conditioners in the car by applying it to the window glass of car bodies and buildings.
- an optical film containing a conductor such as ITO (tin-doped indium oxide) as an infrared absorbing substance is disclosed.
- Japanese Patent Application Laid-Open No. 2010-222233 discloses a near-infrared light shielding film including a functional plastic film having an infrared reflection layer and an infrared absorption layer.
- the near-infrared light shielding film having such a structure is preferably used due to its high near-infrared light shielding effect in a low-latitude zone near the equator where the illuminance of sunlight is high.
- the problem is that even if you want to capture sunlight as much as possible in the car or in the room, the light is uniformly shielded, so the car and the room do not warm in winter. .
- thermochromic material capable of controlling the optical properties of near-infrared light shielding and transmission by temperature
- a typical material is vanadium dioxide (hereinafter referred to as VO 2 ).
- VO 2 is known to undergo a phase transition in a temperature range of around 60 ° C. and exhibit thermochromic properties. That is, the optical film using the characteristics of VO 2 can shield near-infrared light that causes heat at a high temperature, and can exhibit characteristics that transmit near-infrared light in a low temperature range. .
- the summertime is hot, near-infrared light is shielded to suppress the temperature rise in the room, and when the wintertime is cold, external light energy can be taken in.
- VO 2 vanadium dioxide
- a method of obtaining vanadium dioxide (VO 2 ) nanoparticles by hydrothermal synthesis from vanadium and hydrazine or a hydrate thereof is disclosed (for example, , See Patent Document 2).
- VO 2 vanadium dioxide
- a possible method is disclosed (for example, see Patent Document 3).
- VO 2 -containing fine particles form an optical functional film that exhibits thermochromic properties when the particles are synthesized and then filtered and dried, or by using a solvent-based coating solution prepared with a binder insoluble in an aqueous solvent.
- the primary particles of the VO 2 -containing fine particles are likely to aggregate to form massive secondary particles.
- the secondary particles of VO 2 -containing fine particles prepared through a drying process once are difficult to completely unravel and become primary particles even if they are subjected to a general dispersion treatment, and are aggregated in the formed optical functional film. Often present as secondary particles in a state.
- the present invention has been made in view of the above-mentioned problems, and its problem is that it has thermochromic properties capable of adjusting the near-infrared shielding rate and near-infrared transmittance according to the temperature environment, has a low haze, and is long.
- An object of the present invention is to provide an optical film having excellent crack resistance and adhesion even during use over a period of time, and a method for producing the same.
- vanadium dioxide-containing fine particles (hereinafter referred to as “vanilladium dioxide”) having a number average particle size of less than 200 nm on the transparent substrate including at least primary particles and secondary particles. , also referred to as VO 2 containing microparticles.) and the optical film comprising an optical functional layer containing a binder resin, has a thermochromic with adjustable infrared shielding factor according to the temperature environment, haze Therefore, the present inventors have found that an optical film having excellent crack resistance and adhesion can be obtained even when used for a long period of time.
- An optical film having an optical functional layer containing at least vanadium dioxide-containing fine particles and a binder resin on a transparent substrate, The optical film, wherein the number average particle diameter of all particles including primary particles and secondary particles of the vanadium dioxide-containing fine particles in the optical functional layer is less than 200 nm.
- the vanadium dioxide-containing fine particles are vanadium dioxide-containing fine particles prepared by an aqueous synthesis method
- the binder resin is an aqueous binder resin
- aqueous binder resin is a polymer containing 50 mol% or more of repeating units having a hydroxy group.
- aqueous binder resin is a polyvinyl alcohol resin or a cellulose resin.
- the surfaces of the fine particles containing vanadium dioxide prepared by the aqueous synthesis method before mixing with the aqueous binder resin are coated with the same or the same kind of resin as the aqueous binder resin.
- the optical film as described in any one of the items up to.
- the near-infrared light shielding layer comprises a high refractive index reflective layer containing a first water-soluble binder resin and first metal oxide particles, a second water-soluble binder resin and second metal oxide particles.
- the water-based binder resin constituting the optical functional layer and the first water-soluble binder resin or the second water-soluble binder resin constituting the reflective layer laminate are the same kind of binder resin. 8.
- the number ratio of primary particles of the vanadium dioxide-containing fine particles in the optical functional layer is 30% by number or more of the total number of particles, according to any one of items 1 to 8, Optical film.
- a method for producing an optical film which is produced by forming an optical functional layer containing at least vanadium dioxide-containing fine particles and a binder resin on a transparent substrate, A method for producing an optical film, comprising adjusting the number average particle size of all particles including primary particles and secondary particles of the vanadium dioxide-containing fine particles to be less than 200 nm.
- the vanadium dioxide-containing fine particles are prepared as an aqueous dispersion containing vanadium dioxide-containing fine particles by the aqueous synthesis method, and the aqueous dispersion is an aqueous system in which at least the aqueous binder resin is dissolved in an aqueous solvent without passing through a dry state.
- An aqueous optical functional layer forming coating solution is prepared by mixing with a binder resin solution, and the optical functional layer forming coating solution is applied onto the transparent substrate by a wet coating method and dried to form an optical film.
- Item 12 The method for producing an optical film according to Item 11, which is produced.
- the aqueous dispersion containing the vanadium dioxide-containing fine particles is subjected to an ultrafiltration treatment before being mixed with the aqueous binder resin solution.
- the near-infrared light shielding layer comprises a high refractive index reflective layer containing a first water-soluble binder resin and first metal oxide particles, a second water-soluble binder resin and second metal oxide particles.
- Item 16 The method for producing an optical film according to Item 15, wherein the low-refractive-index reflective layer contained is alternately laminated to form a reflective layer laminate that selectively reflects light of a specific wavelength.
- the aqueous binder resin contained in the optical functional layer and the first water-soluble binder resin or the second water-soluble binder resin used for forming the near-infrared shielding layer are composed of the same kind of binder resin, and a transparent group 17.
- an optical film having a thermochromic property capable of adjusting the near-infrared shielding rate according to the temperature environment, having a low haze, and having excellent crack resistance and adhesion even when used over a long period of time.
- the manufacturing method can be provided.
- a method for preparing VO 2 -containing fine particles there are a method of pulverizing a VO 2 crystal mass synthesized by a baking treatment and a method of obtaining a VO 2 dispersion by an aqueous synthesis method.
- the method of pulverizing the VO 2 crystal mass it is difficult to make fine particles having a number average particle diameter of 100 nm or less, and the primary particle diameter of the VO 2 particles is large at present.
- Examples of the aqueous synthesis method for preparing VO 2 -containing fine particles in an aqueous system include a synthesis method using a hydrothermal method. According to hydrothermal synthesis, fine particles having a number average particle diameter of 100 nm or less can be synthesized as the primary particle diameter.
- the synthesized VO 2 -containing fine particles are once dried and then the solvent-based binder resin
- the VO 2 -containing fine particles are secondary particles having a number average particle diameter exceeding 200 nm. It was found that only the particle dispersion state in which aggregation occurred can be realized. This is by going through the step of drying the VO 2 containing microparticles, the surface of the VO 2 containing microparticles aqueous synthesis increases the hydrophilic surface energy has been discovered that a strong aggregated secondary particles . Even if the secondary particles thus formed were subjected to a normal dispersion treatment, it was difficult to redisperse the number average particle size to a level of 200 nm or less.
- the secondary agglomerated particle region and the binder resin have different thermal expansion coefficients and hygroscopic expansion coefficients, so that a difference occurs in the stretched state of the layer every time the environment changes, and the binder resin in the secondary agglomerated particle part is damaged. Furthermore, it is considered that moisture and low molecular components in the layer are adsorbed in the gaps between the secondary particles to promote the deterioration of the binder resin in the secondary aggregated particle portion.
- the number average particle size of all particles including the primary particles and secondary particles of the VO 2 -containing fine particles in the optical functional layer is less than 200 nm, the temperature and humidity conditions in the environment in which the optical film is used vary greatly. In the present invention, even when used for a long period of time, it was found that neither cracking nor film peeling occurred.
- a specific reason for achieving the above-mentioned problem is that the number average particle size of all particles including primary particles and secondary particles of VO 2 -containing fine particles is less than 200 nm, thereby changing the environment in which the optical film is used.
- the difference in expansion and contraction characteristics between the VO 2 -containing fine particle part and the binder resin can be suppressed to a level at which no film alteration occurs, and since there are few voids in the secondary particles, the secondary particles enter the secondary particles. It is presumed that the deterioration of the binder resin component in the vicinity of the secondary agglomerated particle part is not particularly advanced because the moisture and low molecular components are less taken up.
- the VO 2 -containing fine particles prepared by the aqueous synthesis method have a strong interaction with the aqueous binder resin.
- the VO 2 -containing fine particles and the binder resin are firmly bonded to each other so that cracking and film peeling are less likely to occur.
- the binder resin enters between the secondary particles, moisture and low-molecular components are less likely to be incorporated into the secondary particles. As a result, the binder resin is less likely to deteriorate. I think that works effectively.
- the binder resin easily enters between the secondary agglomerated particles, it was proved to be effective for the redispersibility of the secondary agglomerated particles, and the thermochromic property that can adjust the near-infrared shielding rate according to the temperature environment. It has a low haze, and an optical film having excellent crack resistance and adhesiveness even when used for a long period of time can be realized.
- Schematic sectional view showing an example of the basic configuration of the optical film of the present embodiment Schematic sectional view showing an example of the layer arrangement of an optical film having a near infrared light shielding layer
- Schematic sectional view showing another example of layer arrangement of an optical film having a near infrared light shielding layer Schematic sectional view showing another example of layer arrangement of an optical film having a near infrared light shielding layer
- Schematic sectional view showing an example of the configuration of an optical film having a near infrared light shielding layer Schematic sectional view showing another example of the configuration of an optical film having a near infrared light shielding layer
- Schematic sectional view showing another example of the configuration of an optical film having a near infrared light shielding layer Schematic sectional view showing an example of the configuration of an optical film having a near infrared light shielding layer on both surfaces of a transparent substrate
- the optical film of the present invention has an optical functional layer containing at least vanadium dioxide-containing fine particles and a binder resin on a transparent substrate, and the primary particles and secondary particles of the vanadium dioxide-containing fine particles in the optical functional layer.
- the number average particle diameter of all the contained particles is less than 200 nm.
- the vanadium dioxide-containing fine particles are vanadium dioxide-containing fine particles prepared by an aqueous synthesis method, and the binder resin is an aqueous binder resin, from the viewpoint that the intended effect of the present invention can be further expressed. It is preferable from a viewpoint which can improve a crack tolerance and adhesiveness more.
- the aqueous binder resin is a polymer containing 50 mol% or more of repeating units having a hydroxy group, has high affinity with vanadium dioxide-containing fine particles, and in the drying process during the formation of the optical functional layer, Aggregation due to the close distance between the particles of the vanadium dioxide-containing fine particles can be effectively prevented, and the number average particle size of all particles including the primary particles and secondary particles of the vanadium dioxide-containing fine particles defined in the present invention. Is one of the methods that can reduce the thickness to less than 200 nm.
- the water-based binder resin is a polyvinyl alcohol-based resin or a cellulose-based resin from the viewpoint of obtaining excellent crack resistance and adhesion in addition to the above effects.
- the surface of the vanadium dioxide-containing fine particles prepared by the water-based synthesis method before mixing with the water-based binder resin may be coated with the same or the same kind of resin as the water-based binder resin, so that the vanadium dioxide-containing fine particles are coated with the water-based binder resin.
- generation of particle aggregates can be prevented, and the number average particle diameter can be made less than 200 nm, which is preferable.
- the optical functional layer has a near-infrared light shielding layer having a function of shielding at least a part of the light wavelength range of 700 to 1000 nm.
- a high refractive index reflective layer containing a water-soluble binder resin and first metal oxide particles, and a low refractive index reflective layer containing a second water-soluble binder resin and second metal oxide particles are alternately laminated.
- the light reflection effect by the reflecting layer laminate can be imparted by making the reflective layer laminate to selectively reflect light of a specific wavelength. And a higher near-infrared shielding effect can be obtained.
- the water-based binder resin constituting the optical functional layer and the first water-soluble binder resin or the second water-soluble binder resin constituting the reflective layer laminate are the same kind of binder resin. It is preferable at the point which can improve the adhesiveness of the reflection function laminated body which is an optical functional layer and a near-infrared-light shielding layer on a base material.
- the ratio of the number of primary particles of the vanadium dioxide-containing fine particles in the optical functional layer is 30% by number or more of the total number of particles.
- the method for producing an optical film of the present invention is a method for producing an optical functional layer containing at least vanadium dioxide-containing fine particles and a binder resin on a transparent substrate, wherein the primary film contains the vanadium dioxide-containing fine particles.
- the optical functional layer is formed so that the number average particle size of all particles including particles and secondary particles is less than 200 nm.
- the vanadium dioxide-containing fine particles prepared by the aqueous synthesis method are used as the vanadium dioxide-containing fine particles, and the water-based binder resin is applied as the binder resin.
- An aqueous optical functional layer forming coating solution is prepared by mixing with a resin solution, and the optical functional layer forming coating solution is applied onto the transparent substrate by a wet coating method and dried to produce an optical film.
- Does not produce aggregates of vanadium dioxide-containing fine particles It is possible to achieve the condition that the number average particle size of all particles including the primary and secondary particles of vanadium dioxide-containing fine particles to be defined is less than 200 nm, and to obtain an optical film excellent in crack resistance and adhesion. It is preferable from the viewpoint that can be achieved.
- the aqueous dispersion containing the vanadium dioxide-containing fine particles may be subjected to an ultrafiltration treatment before being mixed with the aqueous binder resin solution. It is preferable from the viewpoint that it is possible to prevent contamination of foreign matters and coarse secondary particle masses, to obtain an optical film having high coating film uniformity, excellent crack resistance and adhesion.
- the water-based binder resin contained in the optical functional layer and the first water-soluble binder resin or the second water-soluble binder resin used for forming the near-infrared shielding layer are composed of the same kind of binder resin, and On the transparent substrate, the optical functional layer and the near-infrared shielding layer are coated simultaneously to produce an optical film, which improves the interface uniformity between the optical functional layer and the near-infrared shielding layer, and haze Is preferable in that an optical film with reduced can be obtained.
- ⁇ is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
- the optical film of the present invention comprises an optical functional layer containing vanadium dioxide-containing fine particles and a binder resin, on which a number average particle size of all particles including at least primary particles and secondary particles is less than 200 nm on a transparent substrate. It is characterized by having.
- FIG. 1 is a schematic cross-sectional view showing an example of a basic structure of an optical film having an optical functional layer containing vanadium dioxide-containing fine particles and a binder resin.
- An optical film 1 shown in FIG. 1 has a configuration in which an optical functional layer 3 is laminated on a transparent substrate 2.
- the optical functional layer 3 is present in a state where the vanadium dioxide-containing fine particles are dispersed in the binder resin B.
- the vanadium dioxide-containing fine particles constitutes the primary particles VO S of vanadium dioxide vanadium-containing particles dioxide are present independently, an aggregate of two or more vanadium-containing microparticles dioxide (also referred to as aggregates) there, there is a secondary particle VO M of vanadium dioxide.
- an aggregate of two or more vanadium dioxide-containing fine particles is collectively referred to as secondary particles. It is also called secondary particle aggregate or secondary aggregate particle.
- the number average particle size by all particles including primary particles V0 S and secondary particles VO M of vanadium dioxide-containing fine particles in the optical functional layer 3, and less than 200 nm.
- the average particle size of the vanadium dioxide-containing fine particles in the optical functional layer can be determined according to the following method.
- the side surface of the optical functional layer 3 constituting the optical film 1 is trimmed by a microtome to expose a cross section as shown in FIG.
- the exposed cross section is photographed at 10,000 to 100,000 times using a transmission electron microscope (TEM).
- the secondary particles VO M of all of the primary particles of the vanadium dioxide VO S vanadium dioxide dioxide vanadium-containing particles are present in the captured predetermined area of the cross section, measuring the particle size.
- the number of vanadium dioxide-containing fine particles to be measured is preferably in the range of 50 to 100.
- the shot particles are included a primary particle VO S is a single particle, as shown in FIG. 1, the secondary particle VO M is a more aggregate 2 particles.
- the particle size measurement of each particle the particle size of the primary particles VO S vanadium dioxide, measuring the diameter of particles in the state of being independently apart from. If it is not spherical, the projected area of the particle is converted into a circle, and its diameter is taken as the particle size.
- the secondary particles VO M vanadium dioxide 2 or more particles are present in aggregate, after seeking projected area of the entire aggregates, it converted into yen projected area, the particle size with a diameter To do.
- the number average diameter is obtained for the diameters of all the primary particles and secondary particles obtained as described above. Since the cut-out cross-sectional portion has a variation in particle distribution, such measurement is performed for 10 different cross-sectional areas, and the total number of particles is measured from 500 to 1000 to obtain the total number average diameter. Is the “number average particle size (nm) of primary particles and secondary particles of vanadium dioxide-containing fine particles” in the present invention.
- the particle size of the primary particles is in the range of 10 to 100 nm. Accordingly, the particle size of the secondary particles varies depending on the number of aggregated particles, but is roughly in the range of 50 to 500 nm.
- the optical film of the present invention has a function of shielding at least part of the light wavelength range of 700 to 1000 nm. It is preferable to have a near-infrared light shielding layer, and more preferably, the near-infrared light shielding layer includes a high-refractive index reflective layer containing a first water-soluble binder resin and first metal oxide particles, In this configuration, the water-soluble binder resin 2 and the low-refractive index reflective layer containing the second metal oxide particles are alternately laminated to selectively reflect light having a specific wavelength.
- FIGS. 2A to 2C are schematic cross-sectional views showing typical layer arrangements of an optical film having a near infrared light shielding layer together with an optical functional layer according to the present invention on a transparent substrate.
- the optical film 1 shown in FIG. 2A has a configuration in which the optical functional layer 3, the near-infrared light shielding layer 4, and the transparent substrate 2 are arranged in this order from the light incident side L.
- the optical film 1 shown in FIG. 2B is an example in which the optical functional layer 3 according to the present invention is disposed between the transparent substrate 2 and the near-infrared light shielding layer 4, and FIG.
- the near-infrared light shielding layer 4 is disposed on the light incident side L
- the optical functional layer 3 according to the present invention is disposed on the back surface side of the transparent substrate 2.
- These layer configurations in the present invention are not particularly limited as long as at least the transparent base material and the optical functional layer 3 are provided, and the layer configuration can be selected according to each purpose.
- FIGS. 2A to 2C are cross-sectional views showing in detail the configuration of the near-infrared light shielding layer 4 in the optical film 1 whose schematic layer configuration is shown in FIGS. 2A to 2C.
- a high refractive index reflective layer containing a first water-soluble binder resin and first metal oxide particles, a second water-soluble binder resin, and a second metal
- a preferred embodiment is a reflective layer laminate in which low refractive index reflective layers containing oxide particles are alternately laminated to selectively reflect light having a specific wavelength.
- FIG. 3 is a configuration diagram showing in detail the configuration of the near-infrared light shielding layer 4 in the optical film 1 shown in FIG. 2A.
- the optical film 1 of the present invention has a high refractive index containing a first water-soluble binder resin and first metal oxide particles as a near infrared light shielding layer 4 on a transparent substrate 2. It has a reflection layer laminate ML1 in which an infrared reflection layer, and a low refractive index infrared reflection layer containing a second water-soluble binder resin and second metal oxide particles are alternately laminated, on which an optical The functional layer 3 is provided.
- the reflective layer laminate ML1 is composed of n layers of infrared reflective layers T 1 to T n from the transparent substrate 2 side.
- T n-1 are refractive indexes of 1.80 to 2.
- An example of the configuration is a high refractive index layer in the range of .50.
- the refractive index as used in the field of this invention is the value measured in the environment of 25 degreeC.
- FIG. 4 is a configuration diagram showing in detail a specific configuration of the near-infrared light shielding layer 4 in the layer arrangement of the optical film 1 shown in FIG. 2B.
- FIG. It is the block diagram which showed in detail the specific structure of the near-infrared-light shielding layer 4 in the layer arrangement
- FIG. 6 shows an optical film 1 of the present invention, in which a reflective layer laminate ML1a and a reflective layer laminate ML1b containing metal oxide particles are arranged on both sides of a transparent substrate 2, and the optical functional layer 3A and the optical layer are arranged on the respective upper surfaces.
- the functional layer 3B is arranged.
- the optical functional layer 3B can be omitted.
- FIG. 7 is a schematic cross-sectional view showing an example of a configuration having a near-infrared shielding layer composed of a polymer layer laminate in the optical film of the present invention.
- a polymer layer laminate ML2 (2) that also serves as a transparent base material as a near infrared light shielding layer is configured by laminating two types of polymer films that are different from each other. Yes.
- PEN 1 formed from a polyethylene naphthalate (PEN) film from the lower surface side
- PMMA 1 , PEN 2 , PMMA 2 , PEN 3 PMMA formed from a polymethyl methacrylate (PMMA) film.
- PMMA polymethyl methacrylate
- the total number of laminated films is preferably in the range of 150 to 1000 layers.
- the optical functional layer 3 is disposed on the polymer layer laminate ML2.
- FIG. 2A It is not necessary to newly provide the transparent substrate 2 as shown in FIG. 2C.
- these polymer layer laminates for example, the contents described in US Pat. No. 6,049,419 can be referred to.
- optical film of the present invention various functional layers may be provided as necessary in addition to the constituent layers described above.
- the total thickness of the optical film of the present invention is not particularly limited, but is in the range of 250 to 1500 ⁇ m, preferably in the range of 400 to 1200 ⁇ m, more preferably in the range of 600 to 1000 ⁇ m. Preferably, it is in the range of 750 to 900 ⁇ m.
- visible light transmittance measured by a method according to JIS R 3106 (1998) “Testing method of transmittance, reflectance, emissivity, and solar heat gain of plate glass” Is preferably 20% or more, more preferably 30% or more, and still more preferably 50% or more.
- the optical film of the present invention has an optical functional layer containing at least vanadium dioxide-containing fine particles and a binder resin on a transparent substrate, and the number average of primary particles and secondary particles of vanadium dioxide-containing fine particles in the optical functional layer.
- the particle size is less than 200 nm.
- a near-infrared light shielding layer having a function of shielding at least part of the light wavelength range of 700 to 1000 nm.
- the transparent substrate applicable to the present invention is not particularly limited as long as it is transparent, and examples thereof include glass, quartz, and a transparent resin film. However, from the viewpoint of imparting flexibility and suitability for production (manufacturing process suitability). Is preferably a transparent resin film. “Transparent” in the present invention means that the average light transmittance in the visible light region is 20% or more, preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more.
- the thickness of the transparent substrate according to the present invention is preferably in the range of 30 to 200 ⁇ m, more preferably in the range of 30 to 100 ⁇ m, and still more preferably in the range of 35 to 70 ⁇ m. If the thickness of the transparent substrate is 30 ⁇ m or more, wrinkles and the like are less likely to occur during handling, and if the thickness is 200 ⁇ m or less, when producing laminated glass, to the curved glass surface when bonding to the glass substrate The follow-up performance is improved.
- the transparent substrate according to the present invention is preferably a biaxially oriented polyester film, but an unstretched or at least one stretched polyester film can also be used.
- a stretched film is preferable from the viewpoint of strength improvement and thermal expansion suppression.
- a stretched film is more preferable.
- the transparent substrate according to the present invention has a thermal shrinkage within a range of 0.1 to 3.0% at a temperature of 150 ° C. from the viewpoint of preventing generation of wrinkles of the optical film and cracking of the infrared reflective layer. Is more preferable, being in the range of 1.5 to 3.0%, more preferably 1.9 to 2.7%.
- the transparent substrate applicable to the optical film of the present invention is not particularly limited as long as it is transparent, but various transparent resin films are preferably used.
- polyolefin films for example, polyethylene, polypropylene, etc.
- Polyester films for example, polyethylene terephthalate, polyethylene naphthalate, etc.
- polyvinyl chloride for example, polyethylene terephthalate, polyethylene naphthalate, etc.
- triacetyl cellulose films and the like, preferably polyester films and triacetyl cellulose films.
- the polyester film (hereinafter simply referred to as “polyester”) is not particularly limited, but is preferably a polyester having a film-forming property having a dicarboxylic acid component and a diol component as main components.
- the main dicarboxylic acid component include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenylsulfone dicarboxylic acid, diphenyl ether dicarboxylic acid, and diphenylethanedicarboxylic acid.
- Examples include acids, cyclohexane dicarboxylic acid, diphenyl dicarboxylic acid, diphenyl thioether dicarboxylic acid, diphenyl ketone dicarboxylic acid, and phenylindane dicarboxylic acid.
- diol component examples include ethylene glycol, propylene glycol, tetramethylene glycol, cyclohexanedimethanol, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyethoxyphenyl) propane, Examples thereof include bis (4-hydroxyphenyl) sulfone, bisphenol full orange hydroxyethyl ether, diethylene glycol, neopentyl glycol, hydroquinone, and cyclohexanediol.
- polyesters having these as main components from the viewpoints of transparency, mechanical strength, dimensional stability, etc., dicarboxylic acid components such as terephthalic acid, 2,6-naphthalenedicarboxylic acid, diol components such as ethylene glycol and 1 Polyester having 1,4-cyclohexanedimethanol as the main constituent is preferred. Furthermore, polyesters mainly composed of polyethylene terephthalate and polyethylene naphthalate, copolymerized polyesters composed of terephthalic acid, 2,6-naphthalenedicarboxylic acid and ethylene glycol, and mixtures of two or more of these polyesters are mainly used. Polyester as a constituent component is preferable.
- fine particles may be contained within a range that does not impair transparency in order to facilitate handling.
- the fine particles used in the present invention include inorganic fine particles such as calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and crosslinked polymers. Examples thereof include organic particles such as particles and calcium oxalate.
- the method of adding fine particles include a method of adding fine particles in the raw material polyester, a method of adding directly to an extruder, and the like, and any one of these methods may be adopted.
- additives may be added in addition to the fine particles as necessary.
- additives include stabilizers, lubricants, cross-linking agents, anti-blocking agents, antioxidants, dyes, pigments, and ultraviolet absorbers.
- the transparent resin film that is a transparent substrate can be produced by a conventionally known general film forming method.
- an unstretched transparent resin film that is substantially amorphous and not oriented can be produced by melting a resin as a material with an extruder, extruding it with an annular die or a T-die, and quenching.
- the unstretched transparent resin film is uniaxially stretched, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular simultaneous biaxial stretching, and other known methods such as transparent resin film flow (vertical axis) direction.
- a stretched transparent resin film can be produced by stretching in the direction perpendicular to the flow direction of the transparent resin film (horizontal axis).
- the draw ratio in this case can be appropriately selected according to the resin that is the raw material of the transparent resin film, but is preferably 2 to 10 times in the vertical axis direction and the horizontal axis direction.
- the transparent resin film may be subjected to relaxation treatment or offline heat treatment from the viewpoint of dimensional stability.
- the relaxation treatment is performed in a process from the heat setting in the stretching process of the polyester film to the winding in the transversely stretched tenter or after exiting the tenter.
- the relaxation treatment is preferably performed as a treatment temperature within a temperature range of 80 to 200 ° C., and more preferably within a temperature range of 100 to 180 ° C.
- the relaxation rate is preferably in the range of 0.1 to 10% in both the longitudinal direction and the width direction, and more preferably, the relaxation rate is 2 to 6%.
- the relaxed substrate is subjected to off-line heat treatment to improve heat resistance and to improve dimensional stability.
- the transparent resin film is preferably formed by applying the undercoat layer coating solution in-line on one or both sides in the film forming process to form the undercoat layer.
- undercoating during the film forming process is referred to as in-line undercoating.
- resins used in the undercoat layer coating solution useful in the present invention include polyester resins, acrylic-modified polyester resins, polyurethane resins, acrylic resins, vinyl resins, vinylidene chloride resins, polyethyleneimine vinylidene resins, polyethyleneimine resins, and polyvinyl alcohol resins. , Modified polyvinyl alcohol resin, gelatin and the like, and any of them can be preferably used.
- a conventionally well-known additive can also be added in these undercoat layer coating liquids.
- the undercoat layer coating solution can be coated by a known method such as roll coating, gravure coating, knife coating, dip coating, or spray coating.
- the coating amount of the undercoat layer coating solution is preferably in the range of 0.01 to 2.0 g / m 2 (dry state).
- Optical function layer [Vanadium dioxide-containing fine particles]
- vanadium dioxide-containing fine particles having a number average particle size of less than 200 nm of all particles including primary particles and secondary particles are present in a binder resin in a dispersed state.
- the crystal form of the vanadium dioxide-containing fine particles according to the present invention is not particularly limited, but from the viewpoint of efficiently expressing thermochromic properties (automatic light control), rutile vanadium dioxide-containing fine particles (VO 2 -containing fine particles) are used. It is particularly preferable to use it.
- the vanadium dioxide-containing fine particles according to the present invention may contain other crystal-type VO 2 -containing fine particles such as A-type or B-type within a range that does not impair the purpose.
- the number average particle size of all particles including primary particles and secondary particles of vanadium dioxide-containing fine particles in the optical functional layer is less than 200 nm.
- the average particle size of the vanadium dioxide-containing fine particles in the optical functional layer can be determined according to the following method.
- the side surface of the optical functional layer containing vanadium dioxide-containing fine particles is trimmed using a microtome or the like to expose the cross section of the optical functional layer as shown in FIG.
- the exposed cross section is photographed at a magnification of 10,000 to 100,000 times using a transmission electron microscope (TEM).
- TEM transmission electron microscope
- the particle size of all the vanadium dioxide-containing fine particles present in a certain region of the photographed cross section is measured.
- the vanadium dioxide-containing fine particles to be measured are preferably in the range of 50 to 100 particles.
- primary particles and secondary particles are mixed as shown in FIG. 1, and the particle size of the primary particles of vanadium dioxide is the diameter of each independent particle. .
- the projected area of the particle is converted into a circle, and its diameter is taken as the particle size.
- the secondary particles of vanadium dioxide in which two or more particles are aggregated after determining the projected area of the entire aggregate, the projected area is converted into a circle, and the diameter is calculated as the The aggregated secondary particles are defined as one particle.
- the number average diameter is obtained for each diameter of the primary particles and secondary particles obtained as described above. Since the cut-out cross section has a variation in particle distribution, the number average diameter is measured for 10 cross-sectional areas of different scenes, and the total number of particles is measured for 500 to 1000 particles. The average diameter was determined and used as the number average particle diameter referred to in the present invention.
- the number average particle size of all particles including the primary particles and secondary particles according to the present invention is characterized by being less than 200 nm, preferably in the range of 1 to 180 nm, more preferably 5 to It is in the range of 100 nm, more preferably in the range of 10 to 80 nm.
- the primary particle size of the vanadium dioxide-containing fine particles is preferably in the range of 1 to 150 nm, more preferably in the range of 5 to 100 nm, and most preferably in the range of 10 to 50 nm. .
- the primary particle number ratio of the vanadium dioxide-containing fine particles in the optical functional layer which can be determined by the above measurement method, is 30% by number or more of the total number of primary particles and secondary particles. It is preferably at least 60% by number, more preferably at least 80% by number. The ideal upper limit is 100% by number, but the current maximum value is 95% by number or less.
- the aspect ratio of the vanadium dioxide-containing fine particles is preferably within the range of 1.0 to 3.0.
- the vanadium dioxide-containing fine particles having such characteristics have a sufficiently small aspect ratio and close to a spherical shape and an isotropic shape, the dispersibility when added to a solution is good.
- the particle size in the single crystal state is sufficiently small, it is possible to exhibit better thermochromic properties as compared with conventional fine particles.
- vanadium dioxide-containing fine particles in addition to vanadium dioxide (VO 2 ), for example, tungsten (W), molybdenum (Mo), niobium (Nb), tantalum (Ta), tin (Sn), rhenium (Re) ), Iridium (Ir), osmium (Os), ruthenium (Ru), germanium (Ge), chromium (Cr), iron (Fe), gallium (Ga), aluminum (Al), fluorine (F) and phosphorus (P It may contain at least one element selected from the group consisting of By adding such an element, it becomes possible to control the phase transition characteristics (particularly the light control temperature) of the vanadium dioxide-containing fine particles.
- the total amount of such additives (dopants) with respect to the finally obtained vanadium dioxide-containing fine particles is sufficient to be about 0.1 to 5.0 atomic% with respect to vanadium (V) atoms.
- the concentration of the vanadium dioxide-containing fine particles in the optical functional layer according to the present invention is not particularly limited, but is generally preferably in the range of 5 to 60% by mass with respect to the total mass of the optical functional layer, more preferably. Is in the range of 5 to 40% by mass, more preferably in the range of 5 to 30% by mass.
- Method for producing vanadium dioxide-containing fine particles In general, the production method of vanadium dioxide-containing fine particles, a method of pulverizing the VO 2 sintered body synthesized by the solid phase method, vanadium pentoxide and (V 2 O 5) as a starting material, synthesis of VO 2 in the liquid phase A water-based synthesis method in which particles are grown while being grown.
- vanadium dioxide-containing fine particles As a method for producing vanadium dioxide-containing fine particles according to the present invention has an average primary particle size is small, in that it is possible to suppress the variation in particle size, the V 2 O 5 as raw materials, the VO 2 containing microparticles in a liquid phase An aqueous synthesis method in which particles are grown while being synthesized is preferred.
- examples of the aqueous synthesis method include a hydrothermal synthesis method and an aqueous synthesis method using a supercritical state. Details of the hydrothermal synthesis method will be described later. Details of the aqueous synthesis method using a supercritical state (also referred to as supercritical hydrothermal synthesis method) are disclosed in, for example, paragraph numbers (0011) and (0015) to (0018) of JP-A-2010-58984. Reference can be made to the production methods described.
- the hydrothermal synthesis method is applied, and the aqueous synthesis method is used to prepare an aqueous dispersion containing vanadium dioxide-containing fine particles, and the vanadium dioxide-containing fine particles in the aqueous dispersion are dried.
- a coating solution for forming an optical functional layer is prepared by mixing with a water-based binder resin solution in a dispersed state constituting primary particles in which vanadium dioxide-containing fine particles are separated, and forming an optical functional layer in this state
- An optical functional layer according to the present invention in which the number average particle size of all particles including the primary and secondary particles of vanadium dioxide-containing fine particles is less than 200 nm by forming an optical functional layer using the coating liquid for coating. can be formed.
- fine TiO 2 fine particles that serve as the core of particle growth are added as core particles, and the core particles are grown to produce vanadium dioxide-containing fine particles. You can also
- the following shows the production process of vanadium dioxide-containing fine particles by a typical hydrothermal synthesis method.
- a substance (I) containing vanadium (V), hydrazine (N 2 H 4 ) or a hydrate thereof (N 2 H 4 .nH 2 O), and water are mixed to prepare a solution (A).
- the solution (A) may be an aqueous solution in which the substance (I) is dissolved in water, or may be a suspension in which the substance (I) is dispersed in water.
- the substance (I) examples include divanadium pentoxide (V 2 O 5 ), ammonium vanadate (NH 4 VO 3 ), vanadium trichloride (VOCl 3 ), sodium metavanadate (NaVO 3 ), and the like. .
- the substance (I) is not particularly limited as long as it is a compound containing pentavalent vanadium (V). Hydrazine (N 2 H 4 ) and its hydrate (N 2 H 4 .nH 2 O) function as a reducing agent for the substance (I) and have a property of being easily dissolved in water.
- the solution (A) may further contain a substance (II) containing the element to be added.
- the element to be added include tungsten (W), molybdenum (Mo), niobium (Nb), tantalum (Ta), tin (Sn), rhenium (Re), iridium (Ir), osmium (Os), ruthenium ( Ru), germanium (Ge), chromium (Cr), iron (Fe), gallium (Ga), aluminum (Al), fluorine (F), or phosphorus (P).
- thermochromic properties of the vanadium dioxide-containing fine particles in particular, the transition temperature can be controlled.
- the solution (A) may further contain an oxidizing or reducing substance (III).
- the substance (III) include hydrogen peroxide (H 2 O 2 ).
- hydrothermal reaction treatment is performed using the prepared solution (A).
- “hydrothermal reaction” means a chemical reaction that occurs in hot water (subcritical water) whose temperature and pressure are lower than the critical point of water (374 ° C., 22 MPa).
- the hydrothermal reaction treatment is performed, for example, in an autoclave apparatus.
- Single crystal fine particles containing vanadium dioxide (VO 2 ) are obtained by the hydrothermal reaction treatment.
- the conditions of the hydrothermal reaction treatment are set as appropriate, but the temperature of the hydrothermal reaction treatment is, for example, within the range of 250 to 350 ° C. Preferably, it is in the range of 250 to 300 ° C, more preferably in the range of 250 to 280 ° C.
- the hydrothermal reaction treatment time is preferably in the range of 1 hour to 5 days, for example. Increasing the time can control the particle size and the like of the obtained single crystal fine particles, but an excessively long processing time increases the energy consumption.
- the surface of the obtained vanadium dioxide-containing fine particles may be subjected to a coating treatment or a surface modification treatment with a resin. Thereby, the surface of the vanadium dioxide-containing fine particles is protected, and surface-modified single crystal fine particles can be obtained.
- the surface of the vanadium dioxide-containing fine particles is coated with the same or the same kind of resin as the aqueous binder resin.
- the “coating” as used in the present invention is a state where the entire surface of the particle is completely covered with the resin with respect to the vanadium dioxide-containing fine particles, or a part of the particle surface is covered with the resin. It may be in a state.
- the particle surface is coated with the same or the same kind of resin as the aqueous binder resin. It is preferable.
- the same resin means “the same basic skeleton of the resin”, “the same constituent components of the resin”, “the same constituent components and their ratio”, “the same degree of polymerization or molecular weight” and “ken It meets all the requirements of “the same degree of conversion”.
- the “same kind of resin” means that the basic skeleton of the resin is the same.
- the surface of the vanadium dioxide-containing fine particles is coated with the same or the same kind of resin as the water-based binder resin, so that aggregation of the vanadium dioxide-containing fine particles when mixed with the water-based binder resin solution can be prevented.
- the vanadium dioxide-containing fine particles may crosslink the aqueous binder resin to form a gel, and the surface of the vanadium dioxide-containing fine particles is formed by the aqueous binder resin. By coating, such gelation can also be prevented.
- Examples include a method of adding an aqueous binder resin before performing ultrafiltration treatment, or a method of adding a resin component to a dispersion containing vanadium dioxide-containing fine particles before mixing with an aqueous binder resin solution. .
- the vanadium dioxide-containing fine particles can be made more fine, the monodispersity of the vanadium dioxide-containing fine particles is improved, and the generation of secondary particles at the synthesis stage of the vanadium dioxide-containing fine particles.
- the amount of the resin component to be added is preferably in the range of 0.1 to 50% by mass, more preferably in the range of 0.3 to 10% by mass, based on the total mass of the vanadium dioxide-containing fine particles. Most preferably, it is in the range of 5% by weight.
- the resin component that covers the surface of the vanadium dioxide-containing fine particles is the same or the same type of resin as the aqueous binder resin, but a relatively low molecular weight resin can be preferably used.
- the resin component is not limited as long as it is the same as or similar to the resin applied as the aqueous binder resin.
- celluloses include, for example, Metrols 60SH-03, SM-4 (above, manufactured by Shin-Etsu Chemical Co., Ltd., Non-ionic cellulose ethers), and for polyvinyl alcohols, resin materials having a polymerization degree of 500 or less can be preferably used.
- Kuraray Poval PVA102 (polymerization degree 200), PVA103 (polymerization degree 300) PVA105 (degree of polymerization 500), PVA203 (degree of polymerization 300), PVA205 (degree of polymerization 500), PVA403 (degree of polymerization 300), PVA405 (degree of polymerization 500), EXEVAL RS-4104 (degree of polymerization 400) Manufactured).
- the dispersion liquid of vanadium dioxide-containing fine particles is dried, and a transmission electron microscope or a scanning type is used. This can be confirmed by observing with an electron microscope.
- the coating treatment or the surface modification treatment may be performed with a silane coupling agent, for example.
- thermochromic vanadium dioxide VO 2
- the dispersion of vanadium dioxide-containing fine particles prepared by the above aqueous synthesis method contains impurities such as residues generated in the synthesis process, and secondary aggregated particles are generated when the optical functional layer is formed. Since it becomes a trigger and may cause deterioration of the optical functional layer during long-term storage, it is preferable to remove impurities in advance at the stage of the dispersion.
- the vanadium dioxide-containing fine particle dispersion As a method for removing impurities in the vanadium dioxide-containing fine particle dispersion, conventionally known means for separating foreign substances and impurities can be applied.
- the vanadium dioxide-containing fine particle dispersion is subjected to centrifugation, and vanadium dioxide-containing A method of precipitating fine particles, removing impurities in the supernatant, adding and dispersing the dispersion medium again, or removing impurities out of the system using an exchange membrane such as an ultrafiltration membrane may be used. From the viewpoint of preventing aggregation of vanadium-containing fine particles, a method using an ultrafiltration membrane is most preferable.
- Examples of the material for the ultrafiltration membrane include cellulose, polyethersulfone, and polytetrafluoroethylene (abbreviation: PTFE). Among these, polyethersulfone and PTFE are preferably used.
- Binder resin used for forming the optical functional layer according to the present invention will be described.
- the binder resin applicable to the formation of the optical functional layer according to the present invention is not particularly limited, but is preferably a water-based binder resin.
- the aqueous binder resin referred to in the present invention represents a resin material having a solubility of 0.5 g or more with respect to 100 g of water at 20 ° C., more preferably a resin having a solubility of 1.0 g or more. Moreover, after making it melt
- Sugar derivatives such as dextrin, dextran and dextran sulfate; natural materials such as thickening polysaccharides; polyvinyl alcohols, polyvinylpyrrolidones, polyacrylic acid, acrylic acid-acrylonitrile copolymers, potassium acrylate-acrylonitrile
- Acrylic resins such as copolymers, vinyl acetate-acrylic acid ester copolymers, or acrylic acid-acrylic acid ester copolymers; styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, styrene-methacrylic acid -Acrylate ester Styrene acrylic resin such as styrene- ⁇ -methylstyrene-acrylic acid copolymer, styrene- ⁇ -methylstyrene-acrylic acid-acrylic acid ester copolymer; styrene-sodium styrenesulfon
- a polymer containing 50 mol% or more of repeating unit components having a hydroxy group which has a high affinity with vanadium dioxide-containing fine particles and has a high effect of preventing particle aggregation even during drying of film formation, is preferable.
- examples thereof include celluloses, polyvinyl alcohols, and acrylic resins having a hydroxy group.
- polyvinyl alcohols and celluloses can be most preferably used.
- the water-based binder resin constituting the optical functional layer and the first water-soluble binder resin or the second water-soluble binder resin constituting the reflective layer laminate described later are the same kind of binder resin. It is a preferable aspect.
- polyvinyl alcohols As the polyvinyl alcohol preferably used in the present invention, ordinary polyvinyl alcohol obtained by hydrolyzing polyvinyl acetate can be used. In addition, about polyvinyl alcohol, it describes in detail by description of the 1st water-soluble binder resin or 2nd water-soluble binder resin which comprises the reflection layer laminated body mentioned later.
- Polyvinyl alcohols include, in addition to ordinary polyvinyl alcohol, modified polyvinyl alcohols such as polyvinyl alcohol having a cation-modified terminal and anion-modified polyvinyl alcohol having an anionic group.
- Examples of the cation-modified polyvinyl alcohol include primary to tertiary amino groups and quaternary ammonium groups as described in JP-A No. 61-10383.
- Examples of the ethylenically unsaturated monomer having a cationic group include trimethyl- (2-acrylamido-2,2-dimethylethyl) ammonium chloride and trimethyl- (3-acrylamido-3,3-dimethylpropyl) ammonium chloride.
- the ratio of the cation-modified group-containing monomer in the cation-modified polyvinyl alcohol is 0.1 to 10 mol%, preferably 0.2 to 5 mol%, relative to vinyl acetate.
- Anion-modified polyvinyl alcohol is described in, for example, polyvinyl alcohol having an anionic group as described in JP-A-1-206088, JP-A-61-237681 and JP-A-63-307979.
- examples thereof include a copolymer of vinyl alcohol and a vinyl compound having a water-soluble group, and a modified polyvinyl alcohol having a water-soluble group as described in JP-A-7-285265.
- Nonionic modified polyvinyl alcohol includes, for example, a polyvinyl alcohol derivative in which a polyalkylene oxide group is added to a part of vinyl alcohol as described in JP-A-7-9758, and JP-A-8-25795.
- the block copolymer of the vinyl compound and vinyl alcohol which have the described hydrophobic group is mentioned.
- Polyvinyl alcohol can be used in combination of two or more different degrees of polymerization and different types of modification.
- polyvinyl alcohol used in the present invention a synthetic product or a commercially available product may be used.
- commercially available products used as polyvinyl alcohol include, for example, PVA-102, PVA-103, PVA-105, PVA-110, PVA-117, PVA-120, PVA-124, PVA-203, PVA-205, PVA-210, PVA-217, PVA-220, PVA-224, PVA-235 (above, manufactured by Kuraray Co., Ltd.), JC-25, JC-33, JF-03, JF-04, JF-05, JP- 03, JP-04JP-05, JP-45 (above, manufactured by Nippon Vinegar Poval Co., Ltd.) and the like.
- the cellulose that can be used for forming the optical functional layer according to the present invention is preferably a water-soluble cellulose derivative, such as carboxymethyl cellulose (cellulose carboxymethyl ether), methyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, and the like.
- Water-soluble cellulose derivatives, carboxymethyl cellulose (cellulose carboxymethyl ether), carboxyethyl cellulose and the like which are carboxylic acid group-containing celluloses.
- Other examples include cellulose derivatives such as nitrocellulose, cellulose acetate propionate, cellulose acetate, and cellulose sulfate.
- the aqueous binder resin is a polymer containing 50 mol% or more of repeating units having a hydroxy group.
- the repeating unit component is originally composed of three components. It has a hydroxy group, and some of these three hydroxy groups are substituted. “Containing 50 mol% or more of a repeating unit component having a hydroxy group” means that the repeating unit component having a hydroxy group in this substituent or a repeating unit component in which one or more unsubstituted hydroxy groups remain is contained in an amount of 50 mol% or more. Represents that.
- gelatin As the gelatin applicable to the present invention, various gelatins that have been widely used in the field of silver halide photographic light-sensitive materials can be applied. For example, in addition to acid-processed gelatin and alkali-processed gelatin, production of gelatin is possible. Enzyme-treated gelatin and gelatin derivatives that undergo enzyme treatment in the process, that is, modified with a reagent that has an amino group, an imino group, a hydroxy group, or a carboxy group as functional groups in the molecule and has groups obtained by reaction with them. It may be quality. General methods for producing gelatin are well known and are described, for example, in T.W. H. James: The Theory of Photographic Process 4th. ed.
- a gelatin hardener can be added as necessary.
- Organic hardeners such as organic compounds, active olefins and isocyanate compounds, and inorganic polyvalent metal salts such as chromium, aluminum and zirconium.
- the thickening polysaccharide that can be used in the present invention is not particularly limited, and examples thereof include generally known natural simple polysaccharides, natural complex polysaccharides, synthetic simple polysaccharides, and synthetic complex polysaccharides. The details of these polysaccharides can be referred to “Biochemical Encyclopedia (2nd edition), Tokyo Chemical Doujinshi”, “Food Industry”, Vol. 31 (1988), p.
- the thickening polysaccharide referred to in the present invention is a polymer of saccharides and has a number of hydrogen bonding groups in the molecule. Due to the difference in hydrogen bonding strength between molecules depending on the temperature, the viscosity at low temperature and the viscosity at high temperature. It is a polysaccharide with a large difference in characteristics. When metal oxide fine particles are added, the viscosity rises due to hydrogen bonding with the metal oxide fine particles at low temperatures. Is a polysaccharide that increases its viscosity at 15 ° C. by 1.0 mPa ⁇ s or more, preferably 5.0 mPa ⁇ s or more, more preferably 10.0 mPa ⁇ s or more. .
- Examples of the thickening polysaccharide applicable to the present invention include galactan (eg, agarose, agaropectin, etc.), galactomannoglycan (eg, locust bean gum, guaran, etc.), xyloglucan (eg, tamarind gum, etc.), Glucomanoglycans (eg, salmon mannan, wood-derived glucomannan, xanthan gum, etc.), galactoglucomannoglicans (eg, softwood-derived glycans, etc.), arabinogalactoglycans (eg, soybean-derived glycans, microorganism-derived glycans, etc.) , Glucoraminoglycans (eg, gellan gum), glycosaminoglycans (eg, hyaluronic acid, keratan sulfate, etc.), alginic acid and alginate, agar, ⁇ -car
- the structural unit preferably contains a carboxylic acid group or a sulfonic acid group. What it does not have is preferable.
- Such polysaccharides include, for example, pentoses such as L-arabitose, D-ribose, 2-deoxyribose, and D-xylose, and hexoses such as D-glucose, D-fructose, D-mannose, and D-galactose only. It is preferable that it is a polysaccharide.
- tamarind seed gum known as xyloglucan whose main chain is glucose and side chain is glucose
- guar gum known as galactomannan whose main chain is mannose and side chain is glucose
- cationized guar gum Hydroxypropyl guar gum
- locust bean gum locust bean gum
- tara gum arabinogalactan whose main chain is galactose and whose side chain is arabinose
- tamarind, guar gum, cationized guar gum, and hydroxypropyl guar gum are particularly preferable.
- aqueous binder resin examples include polymers having a reactive functional group.
- polyvinylpyrrolidones polyacrylic acid, acrylic acid-acrylonitrile copolymer, potassium acrylate-acrylonitrile copolymer, vinyl acetate-acrylic ester copolymer, or acrylic acid-acrylic ester copolymer
- Acrylic resin styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, styrene-methacrylic acid-acrylic acid ester copolymer, styrene- ⁇ -methylstyrene-acrylic acid copolymer, or styrene- ⁇ -Styrene acrylate resin such as methylstyrene-acrylic acid-acrylic ester copolymer, styrene-sodium styrenesulfonate copolymer,
- ultraviolet absorbers described in JP-A-57-74193, JP-A-57-87988, JP-A-62-261476, etc. JP-A-57-74192, JP-A-57- No. 878989, JP-A-60-72785, JP-A-61-146591, JP-A-1-95091, JP-A-3-13376, etc.
- surfactants such as cation or nonion, JP-A-59-42993, JP-A-59-52689, JP-A-62-280069, JP-A-61-242871, and JP-A-4-242 209266, etc.
- optical brighteners sulfuric acid, phosphoric acid, acetic acid, citric acid, sodium hydroxide, potassium hydroxide, potassium carbonate and other pH adjusters
- antifoaming agents Lubricants such as diethylene glycol, antiseptics, antifungal agents, antistatic agents, matting agents, heat stabilizers, antioxidants, flame retardants, crystal nucleating agents, inorganic particles, organic particles, viscosity reducing agents, lubricants, infrared absorbers
- additives such as pigments and pigments.
- the method for forming the optical functional layer according to the present invention is not particularly limited, but in the present invention, after preparing vanadium dioxide-containing fine particles from the aqueous synthesis method by the above method, without undergoing a drying step, Forming an aqueous optical functional layer by mixing a dispersion liquid in which vanadium dioxide-containing fine particles are separated without being associated with an aqueous binder resin solution prepared by dissolving the aqueous binder resin in an aqueous solvent.
- a method of forming an optical functional layer by preparing a coating liquid for coating and applying the coating liquid on a transparent substrate by a wet coating method using the coating liquid for forming an optical functional layer and drying it.
- the “aqueous solvent” used for the preparation of the optical functional layer coating solution refers to a solvent in which 50% by mass or more of the components are composed of water. Of course, 100% by mass containing no other solvent may be pure water, and considering the dispersion stability of the vanadium dioxide-containing fine particles, it is preferable that the content of the other organic solvent is small.
- the solvent constituting the aqueous solvent is not particularly limited as long as it is a solvent compatible with water as a component other than water, but an alcohol solvent can be preferably used, and the boiling point thereof is relatively close to water. Isopropyl alcohol is preferred.
- the wet coating method used for forming the optical functional layer is not particularly limited, and for example, a roll coating method, a rod bar coating method, an air knife coating method, a spray coating method, a slide curtain coating method, or US Pat. No. 2,761,419. Examples thereof include a slide hopper coating method and an extrusion coating method described in the specification, US Pat. No. 2,761791.
- a preferred embodiment is a configuration in which a near infrared light shielding layer having a function of shielding at least part of the light wavelength range of 700 to 1000 nm is provided.
- Examples of the near-infrared shielding layer in the present invention include a layer containing an inorganic or organic infrared absorber, a metal thin film layer, a dielectric multilayer laminate, and the like.
- the body is preferred.
- Examples of the inorganic infrared absorber include tin-doped indium oxide (abbreviation: ITO), antimony-doped tin oxide (abbreviation: ATO), zinc antimonate, lanthanum hexaboride (LaB 6 ), and cesium-containing tungsten oxide (Cs 0). .33 WO 3 ) and the like.
- Examples of organic infrared absorbers include polymethine, phthalocyanine, naphthalocyanine, metal complex, aminium, imonium, diimonium, anthraquinone, dithiol metal complex, naphthoquinone, indolephenol, azo And triallylmethane-based compounds.
- the metal thin film layer is preferably composed mainly of silver having excellent infrared reflectivity.
- gold or palladium is contained in an amount of 2 to 5% by mass as a total of gold atoms and palladium atoms.
- a reflective layer laminate ML1 in which an infrared reflective layer containing a water-soluble binder resin and metal oxide particles described with reference to FIGS. ML1a, ML1b, or a polymer layer laminate ML2 in which the polymer layers described with reference to FIG. 7 are laminated, and particularly a reflective layer laminate in which a refractive index containing a water-soluble binder resin and metal oxide particles is laminated.
- a reflective layer laminate in which an infrared reflective layer containing a water-soluble binder resin and metal oxide particles described with reference to FIGS. ML1a, ML1b, or a polymer layer laminate ML2 in which the polymer layers described with reference to FIG. 7 are laminated, and particularly a reflective layer laminate in which a refractive index containing a water-soluble binder resin and metal oxide particles is laminated.
- the polymer layer laminate that is one of the near-infrared shielding layers according to the present invention is configured by laminating a large number of first polymer layers having a first refractive index and second polymer layers having a second refractive index.
- the first polymer layer and the second polymer layer are laminated on top of each other to form a polymer layer laminate.
- the polymer material constituting the first and second polymer layers include polyester, acrylic, a blend or copolymer of polyester acrylic, and examples thereof include polyethylene-2,6-naphthalate (PEN) and naphthalene dicarboxylic copolyester (coPEN).
- PEN polyethylene-2,6-naphthalate
- coPEN naphthalene dicarboxylic copolyester
- PMMA Polymethyl methacrylate
- PBN polybutylene-2,6-naphthalate
- PET polyethylene terephthalate
- naphthalene dicarboxylic acid derivative diol copolymer
- polyether ether ketone syndiotc polystyrene resin (SPS), etc.
- Specific combinations of the first polymer layer and the second polymer layer include combinations of PEN / PMMA, PET / PMMA, PEN /
- PEN and PMMA polymer films having different materials are laminated.
- PEN 1 formed of a polyethylene naphthalate (PEN) film
- PMMA 1 PEN 2 formed of a polymethyl methacrylate (PMMA) film
- PMMA 2 PMMA 2 , PEN 3 , PMMA 3 , (omitted)
- PEN n ⁇ 1 , PMMA n , PEN n are laminated to form a polymer layer laminate ML2.
- the polymer layer laminate also serves as the transparent substrate according to the present invention.
- the total number of films to be laminated is not particularly limited, but is preferably in the range of about 150 to 1000 layers.
- Reflective layer laminate As the near-infrared shielding layer applied to the optical film of the present invention, a reflective layer laminate as exemplified in FIGS. 3 to 6 is a particularly preferable embodiment.
- the reflective layer laminate according to the present invention includes the first water-soluble binder resin and the first metal oxide particles on at least one surface side on the transparent substrate constituting the optical film of the present invention described above.
- An infrared reflective layer having a high refractive index hereinafter also referred to as a high refractive index layer
- an infrared reflective layer having a low refractive index containing a second water-soluble binder resin and second metal oxide particles hereinafter referred to as “high refractive index layer”.
- Also referred to as a low-refractive index layer.
- the water-based binder resin constituting the optical functional layer and the first water-soluble binder resin or the second water-soluble binder resin constituting the reflective layer laminate are the same type of binder. It is preferably a resin, and more preferably polyvinyl alcohol.
- the thickness per layer of the high refractive index layer is preferably in the range of 20 to 800 nm, and more preferably in the range of 50 to 350 nm. Further, the thickness per layer of the low refractive index layer is preferably in the range of 20 to 800 nm, and more preferably in the range of 50 to 350 nm.
- the high-refractive index layer and the low-refractive index layer may have a clear interface between them or a structure that gradually changes. Good.
- the maximum refractive index ⁇ minimum refractive index ⁇ n, two layers The point of the minimum refractive index + ⁇ n / 2 is regarded as the layer interface.
- the metal oxide concentration profile of the reflective layer laminate formed by alternately laminating the high refractive index layer and the low refractive index layer is etched from the surface to the depth direction using a sputtering method, Using an XPS surface analyzer, the atomic composition ratio can be measured by sputtering at a rate of 0.5 nm / min with the outermost surface being 0 nm. Moreover, it is also possible to obtain
- TEM electron microscope
- the XPS surface analyzer is not particularly limited, and any model can be used.
- ESCALAB-200R manufactured by VG Scientific, Inc. can be used.
- Mg is used for the X-ray anode, and measurement is performed at an output of 600 W (acceleration voltage: 15 kV, emission current: 40 mA).
- the range of the total number of the high refractive index layer and the low refractive index layer is preferably in the range of 6 to 100 layers, more preferably in the range of 8 to 100, from the viewpoint of productivity. It is within the range of 40 layers, more preferably within the range of 9 to 30 layers.
- the difference in refractive index between the adjacent high refractive index layer and low refractive index layer is preferably 0.1 or more, more preferably 0.3 or more, and further preferably 0.35 or more. Yes, particularly preferably 0.4 or more.
- the outermost layer and the lowermost layer may be configured outside the range of the refractive index difference defined above.
- the reflectance in a specific wavelength region is determined by the difference in refractive index between two adjacent layers and the number of layers, and the larger the difference in refractive index, the same reflectance can be obtained with a smaller number of layers.
- the refractive index difference and the required number of layers can be calculated using commercially available optical design software. For example, in order to obtain a near-infrared reflectance of 90% or more, if the difference in refractive index is less than 0.1, it is necessary to laminate 200 layers or more, which not only decreases productivity but also scattering at the interface of the layers. Becomes larger, the transparency is lowered, and it becomes very difficult to manufacture without failure. From the standpoint of improving reflectivity and reducing the number of layers, there is no upper limit to the difference in refractive index, but practically about 1.4 is the limit.
- a layer structure in which the lowermost layer adjacent to the transparent substrate is a low refractive index layer is preferable from the viewpoint of adhesion to the transparent substrate.
- the layer adjacent to the optical functional layer according to the present invention is also preferably a low refractive index layer containing silicon dioxide as metal oxide particles in a range of 10 to 60% by mass.
- the first and second water-soluble binder resins contained in the high refractive index layer or the low refractive index layer are preferably polyvinyl alcohol. Moreover, it is preferable that the saponification degree of the polyvinyl alcohol contained in the high refractive index layer is different from the saponification degree of the polyvinyl alcohol contained in the low refractive index layer. Furthermore, the first metal oxide particles contained in the high refractive index layer are preferably titanium oxide particles, and more preferably titanium oxide particles surface-treated with a silicon-containing hydrated oxide. . Moreover, it is preferable to use silica (silicon dioxide) as the second metal oxide particles contained in the low refractive index layer.
- silica silicon dioxide
- the high refractive index layer according to the present invention contains a first water-soluble binder resin and first metal oxide particles, and if necessary, a curing agent, other binder resin, a surfactant, and various additives. Etc. may be included.
- the refractive index of the high refractive index layer according to the present invention is preferably 1.80 to 2.50, more preferably 1.90 to 2.20.
- the first water-soluble binder resin according to the present invention is a temperature at which the water-soluble binder resin is most dissolved, and when dissolved in water at a concentration of 0.5% by mass (maximum pores 40 to 40). 50 mass), the mass of the insoluble matter that is filtered off when it is filtered is within 50 mass% of the added water-soluble binder resin.
- the weight average molecular weight of the first water-soluble binder resin according to the present invention is preferably in the range of 1,000 to 200,000. Further, it is more preferably within the range of 3000 to 40000.
- the weight average molecular weight as used in the present invention can be measured by a known method, for example, static light scattering, gel permeation chromatography (GPC), time-of-flight mass spectrometry (TOF-MASS), etc.
- GPC gel permeation chromatography
- TOF-MASS time-of-flight mass spectrometry
- a value measured by gel permeation chromatography which is a widely used method, is employed.
- the content of the first water-soluble binder resin in the high refractive index layer is preferably within the range of 5 to 50% by mass with respect to the solid content of 100% by mass of the high refractive index layer. It is more preferable to be within the range.
- water-soluble binder resin applied to a high refractive index layer It is especially preferable that it is polyvinyl alcohol.
- the water-soluble binder resin applied to the low refractive index layer described later is also preferably polyvinyl alcohol.
- Polyvinyl alcohol having a different saponification degree between the respective refractive index layers in the high refractive index layer and the low refractive index layer.
- the polyvinyl alcohol used in the high refractive index layer is polyvinyl alcohol (A)
- the polyvinyl alcohol used in the low refractive index layer is polyvinyl alcohol (B ).
- each refractive index layer contains a plurality of polyvinyl alcohols having different saponification degrees and polymerization degrees
- the polyvinyl alcohol having the highest content in each refractive index layer is changed to polyvinyl alcohol (A ) And polyvinyl alcohol (B) in the low refractive index layer.
- the “degree of saponification” is the ratio of hydroxy groups to the total number of acetyloxy groups (derived from the starting vinyl acetate) and hydroxy groups in polyvinyl alcohol.
- the degree of polymerization is calculated assuming that the polyvinyl alcohol having a saponification degree difference of 3 mol% or less is the same polyvinyl alcohol. .
- a low polymerization degree polyvinyl alcohol having a polymerization degree of 1000 or less is a different polyvinyl alcohol (even if there is a polyvinyl alcohol having a saponification degree difference of 3 mol% or less, it is not regarded as the same polyvinyl alcohol).
- polyvinyl alcohol having a saponification degree of 90 mol%, a saponification degree of 91 mol%, and a saponification degree of 93 mol% is contained in the same layer by 10 mass%, 40 mass%, and 50 mass%, respectively.
- These three polyvinyl alcohols are the same polyvinyl alcohol, and the mixture of these three is polyvinyl alcohol (A) or (B).
- the above-mentioned “polyvinyl alcohol having a saponification degree difference of 3 mol% or less” suffices to be within 3 mol% when attention is paid to any polyvinyl alcohol.
- the difference in the absolute value of the saponification degree between the polyvinyl alcohol (A) and the polyvinyl alcohol (B) is preferably 3 mol% or more, and more preferably 5 mol% or more. If it is such a range, since the interlayer mixing state of a high refractive index layer and a low refractive index layer will become a preferable level, it is preferable. Moreover, although the difference of the saponification degree of polyvinyl alcohol (A) and polyvinyl alcohol (B) is so preferable that it is separated, it is 20 mol% or less from the viewpoint of the solubility to water of polyvinyl alcohol. It is preferable.
- the saponification degree of polyvinyl alcohol (A) and polyvinyl alcohol (B) is preferably 75 mol% or more from the viewpoint of solubility in water. Furthermore, the intermixed state of the high refractive index layer and the low refractive index layer is that one of the polyvinyl alcohol (A) and the polyvinyl alcohol (B) has a saponification degree of 90 mol% or more and the other is 90 mol% or less. Is preferable from the viewpoint of maintaining a preferable level. It is more preferable that one of the polyvinyl alcohol (A) and the polyvinyl alcohol (B) has a saponification degree of 95 mol% or more and the other is 90 mol% or less. In addition, although the upper limit of the saponification degree of polyvinyl alcohol is not specifically limited, Usually, it is less than 100 mol% and is about 99.9 mol% or less.
- the polymerization degree of the two types of polyvinyl alcohols having different saponification degrees is preferably 1000 or more, particularly preferably those having a polymerization degree in the range of 1500 to 5000, more preferably in the range of 2000 to 5000. Those are more preferably used. If the polymerization degree of polyvinyl alcohol is 1000 or more, there is no crack of the coating film, and if it is 5000 or less, it is preferable from the viewpoint of stabilizing the coating liquid properties.
- “the coating liquid physical properties are stable” means that the coating liquid physical properties, for example, the coating liquid viscosity and the like are stabilized over time.
- the degree of polymerization of at least one of polyvinyl alcohol (A) and polyvinyl alcohol (B) is in the range of 2000 to 5000, it is preferable because cracks in the coating film are reduced and the reflectance at a specific wavelength is improved.
- the polymerization degree of both the polyvinyl alcohol (A) and the polyvinyl alcohol (B) is 2000 to 5000, it is preferable in that the above effect can be exhibited more remarkably.
- “Degree of polymerization” as used herein refers to the viscosity average degree of polymerization, measured according to JIS K 6726 (1994), and measured in water at 30 ° C. after completely re-saponifying and purifying polyvinyl alcohol.
- the degree of polymerization P determined by the following formula (1) from the intrinsic viscosity [ ⁇ ] (cm 3 / g).
- the polyvinyl alcohol (B) contained in the low refractive index layer preferably has a saponification degree in the range of 75 to 90 mol% and a polymerization degree in the range of 2000 to 5000.
- polyvinyl alcohol having such characteristics is contained in the low refractive index layer, it is preferable in that interfacial mixing is further suppressed. This is considered to be because there are few cracks of a coating film and set property improves.
- the polyvinyl alcohol (A) and (B) used in the present invention may be a synthetic product or a commercially available product.
- Examples of commercially available products used as polyvinyl alcohol (A) and (B) include, for example, PVA-102, PVA-103, PVA-105, PVA-110, PVA-117, and PVA-120 manufactured by Kuraray Co., Ltd.
- the first water-soluble binder resin according to the present invention is a modified polyvinyl alcohol partially modified in addition to normal polyvinyl alcohol obtained by hydrolyzing polyvinyl acetate within the range not impairing the effects of the present invention. May be included.
- modified polyvinyl alcohol By including such modified polyvinyl alcohol, the adhesion, water resistance, and flexibility of the formed refractive index layer may be improved.
- modified polyvinyl alcohol include cation-modified polyvinyl alcohol, anion-modified polyvinyl alcohol, nonion-modified polyvinyl alcohol, and vinyl alcohol-based polymers.
- Examples of the cation-modified polyvinyl alcohol include primary to tertiary amino groups and quaternary ammonium groups as described in JP-A No. 61-10383.
- Examples of the ethylenically unsaturated monomer having a cationic group include trimethyl- (2-acrylamido-2,2-dimethylethyl) ammonium chloride and trimethyl- (3-acrylamido-3,3-dimethylpropyl) ammonium chloride.
- the ratio of the cation-modified group-containing monomer in the cation-modified polyvinyl alcohol is 0.1 to 10 mol%, preferably 0.2 to 5 mol%, relative to vinyl acetate.
- Anion-modified polyvinyl alcohol is described in, for example, polyvinyl alcohol having an anionic group as described in JP-A-1-206088, JP-A-61-237681 and JP-A-63-307979.
- examples thereof include a copolymer of vinyl alcohol and a vinyl compound having a water-soluble group, and a modified polyvinyl alcohol having a water-soluble group as described in JP-A-7-285265.
- Nonionic modified polyvinyl alcohol includes, for example, a polyvinyl alcohol derivative in which a polyalkylene oxide group is added to a part of vinyl alcohol as described in JP-A-7-9758, and JP-A-8-25795.
- Block copolymer of vinyl compound having hydrophobic group and vinyl alcohol, silanol-modified polyvinyl alcohol having silanol group, reactive group modification having reactive group such as acetoacetyl group, carbonyl group and carboxy group Polyvinyl alcohol etc. are mentioned.
- vinyl alcohol polymers examples include EXEVAL (registered trademark, manufactured by Kuraray Co., Ltd.) and Nichigo G polymer (registered trademark, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.).
- Two or more kinds of modified polyvinyl alcohol can be used in combination, such as the degree of polymerization and the type of modification.
- the content of the modified polyvinyl alcohol is not particularly limited, but is preferably in the range of 1 to 30% by mass with respect to the total mass (solid content) of each refractive index. If it is in such a range, the said effect will be exhibited more.
- the polyvinyl alcohol (A) having a low saponification degree is used for the high refractive index layer and polyvinyl alcohol (B) having a high saponification degree is used for the low refractive index layer
- the polyvinyl alcohol ( A) is preferably contained in the range of 40 to 100% by mass, more preferably in the range of 60 to 95% by mass, based on the total mass of all polyvinyl alcohols in the layer.
- the polyvinyl alcohol (B) is preferably contained in the range of 40 to 100% by mass, more preferably in the range of 60 to 95% by mass with respect to the total mass of all polyvinyl alcohols in the low refractive index layer.
- the polyvinyl alcohol (A) is preferably contained in the range of 40 to 100% by mass, more preferably in the range of 60 to 95% by mass, based on the total mass of all polyvinyl alcohols in the layer.
- the polyvinyl alcohol (B) is preferably contained in the range of 40 to 100% by mass, more preferably in the range of 60 to 95% by mass with respect to the total mass of all polyvinyl alcohols in the low refractive index layer.
- any binder in the high refractive index layer, as the first water-soluble binder resin other than polyvinyl alcohol, any binder can be used as long as the high refractive index layer containing the first metal oxide particles can form a coating film. Even components can be used without limitation.
- the second water-soluble binder resin other than the polyvinyl alcohol (B) the low refractive index layer containing the second metal oxide particles is coated as described above. Any device can be used without limitation as long as it can be formed.
- water-soluble polymers such as gelatins, celluloses, thickening polysaccharides and polymers having reactive functional groups described as the aqueous binder resin of the optical functional layer. Is preferred.
- the content of other binder resin used together with polyvinyl alcohol preferably used as the water-soluble binder resin is in the range of 5 to 50% by mass with respect to 100% by mass of the solid content of the high refractive index layer. It can also be used within.
- the binder resin is preferably composed of a water-soluble polymer. That is, in the present invention, a water-soluble polymer other than polyvinyl alcohol and modified polyvinyl alcohol may be used as the binder resin in addition to the polyvinyl alcohol and modified polyvinyl alcohol as long as the effect is not impaired.
- the water-soluble polymer referred to in the present invention is a temperature at which the water-soluble polymer is most dissolved, and when dissolved in water at a concentration of 0.5% by mass, a G2 glass filter (maximum pores 40-50 ⁇ m) is used.
- the mass of the insoluble matter (residue) that is filtered off when filtered is within 50 mass% of the added water-soluble polymer.
- water-soluble polymers the aforementioned gelatins, celluloses, thickening polysaccharides, or polymers having reactive functional groups are preferred. These water-soluble polymers may be used alone or in combination of two or more.
- binder resins such as gelatins, celluloses, polysaccharide thickeners, and polymers having reactive functional groups are the same as those described as the aqueous binder resin for the optical functional layer. be able to.
- the first metal oxide particles applicable to the high refractive index layer are preferably metal oxide particles having a refractive index in the range of 2.0 to 3.0. More specifically, for example, titanium oxide, zirconium oxide, zinc oxide, synthetic amorphous silica, colloidal silica, alumina, colloidal alumina, lead titanate, red lead, yellow lead, zinc yellow, chromium oxide, second oxide Examples include iron, iron black, copper oxide, magnesium oxide, magnesium hydroxide, strontium titanate, yttrium oxide, niobium oxide, europium oxide, lanthanum oxide, zircon, and tin oxide. In addition, composite oxide particles composed of a plurality of metals, core / shell particles whose metal structure changes into a core / shell shape, and the like can also be used.
- a metal oxide fine particle having a high refractive index such as titanium or zirconium, specifically, a titanium oxide fine particle or a zirconia oxide is formed on the high refractive index layer. It is preferable to contain fine particles. Among these, titanium oxide particles are more preferable from the viewpoint of the stability of the coating solution used for forming the high refractive index layer.
- the rutile type tetragonal type
- the weather resistance of the high refractive index layer and the adjacent layer is higher, and the refractive index is higher. To preferred.
- core / shell particles are used as the first metal oxide particles in the high refractive index layer, due to the interaction between the silicon-containing hydrated oxide of the shell layer and the first water-soluble binder resin, From the viewpoint of suppressing interlayer mixing between the high refractive index layer and the adjacent layer, core / shell particles in which titanium oxide particles are coated with a silicon-containing hydrated oxide are more preferable.
- the aqueous solution containing titanium oxide particles used for the core of the core-shell particles according to the present invention has a pH measured in the range of 1.0 to 3.0 measured at 25 ° C., and the zeta potential of the titanium oxide particles is It is preferable to use a positive aqueous titanium oxide sol whose surface is hydrophobized so that it can be dispersed in an organic solvent.
- the content of the first metal oxide particles according to the present invention is in the range of 15 to 80% by mass with respect to 100% by mass of the solid content of the high refractive index layer, the refractive index difference from the low refractive index layer Is preferable from the viewpoint of imparting. Further, it is preferably in the range of 20 to 77% by mass, particularly preferably in the range of 30 to 75% by mass.
- content in case metal oxide particles other than the said core-shell particle are contained in a high refractive index layer will not be specifically limited if it is a range which can have the effect of this invention.
- the volume average particle size of the first metal oxide particles applied to the high refractive index layer is preferably in the range of 1 to 30 nm, and more preferably in the range of 5 to 15 nm. .
- a volume average particle size in the range of 1 to 30 nm is preferable from the viewpoint of low visible light transmittance and low haze.
- the first metal oxide particles according to the present invention are preferably monodispersed.
- the monodispersion here means that the monodispersity obtained by the following formula (2) is 40% or less. This monodispersity is more preferably 30% or less, and particularly preferably in the range of 0.1 to 20%.
- titanium oxide particles surface-treated with a silicon-containing hydrated oxide is preferably used.
- the titanium particles may be referred to as “core / shell particles” or “Si-coated TiO 2 ”.
- the titanium oxide particles constituting the core portion are coated with the silicon-containing hydrated oxide constituting the shell portion, and preferably the average particle size of the titanium oxide particles as the core portion
- the coating amount of the silicon-containing hydrated oxide is based on the total mass of the titanium oxide particles. This is a structure in which a shell made of a silicon-containing hydrated oxide is coated so as to be within a range of 3 to 30% by mass as SiO 2 .
- the interaction between the silicon-containing hydrated oxide of the shell layer and the first water-soluble binder resin causes the high refractive index layer and the low refractive index layer to The effect of suppressing the intermixing between the layers and the effect of preventing the deterioration of the binder and choking due to the photocatalytic activity of titanium oxide when titanium oxide is used as the core are exhibited.
- Choking is a phenomenon in which particulate powder or the like adheres when the surface of a formation layer is struck.
- the core-shell particles relative to the titanium oxide core, the coating amount of hydrated oxides of silicon-containing to form the shell, when the titanium oxide is 100 mass%, as SiO 2 3 ⁇ It is preferably in the range of 30% by mass, more preferably in the range of 3 to 10% by mass, and still more preferably in the range of 3 to 8% by mass.
- the coating amount of the shell is 30% by mass or less, it is possible to achieve a high refractive index of the high refractive index layer, and when the coating amount of the shell is 3% by mass or more, the particles of the core / shell particles Can be formed stably.
- the average particle diameter of the core / shell particles is preferably in the range of 1 to 30 nm, more preferably in the range of 5 to 20 nm, and still more preferably in the range of 5 to 15 nm.
- optical properties such as near infrared reflectance, transparency, and haze can be further improved.
- the average particle diameter as used in the field of this invention means a primary average particle diameter, and can be measured from the electron micrograph by a transmission electron microscope (TEM) etc. of a core shell particle. Further, it may be measured by a particle size distribution meter using a dynamic light scattering method or a static light scattering method.
- TEM transmission electron microscope
- the average particle diameter of the primary particles is the particle itself, or the core-shell particles appearing on the cross section or surface of the refractive index layer are observed with an electron microscope,
- the particle diameter of 1000 arbitrary particles is measured, and it is determined as a simple average value (number average).
- the particle diameter of each particle is represented by a diameter assuming a circle equal to the projected area.
- a known preparation method can be employed as a method for preparing the core / shell particles applicable to the present invention.
- a known preparation method can be employed.
- the silicon-containing hydrated oxide applied to the core / shell particles may be either an inorganic silicon compound hydrate, an organosilicon compound hydrolyzate or a condensate thereof.
- a compound having a silanol group is preferred.
- core / shell particles when core / shell particles are applied as the first metal oxide particles, other metal oxide particles may be included in addition to the core / shell particles.
- various ionic dispersants and protective agents can be used so that the core and shell particles described above do not aggregate in a chargeable manner.
- metal oxide particles that can be used in addition to the core / shell particles include titanium dioxide, zirconium oxide, zinc oxide, synthetic amorphous silica, colloidal silica, alumina, colloidal alumina, lead titanate, red lead, and yellow lead.
- Zinc yellow Zinc yellow, chromium oxide, ferric oxide, iron black, copper oxide, magnesium oxide, magnesium hydroxide, strontium titanate, yttrium oxide, niobium oxide, europium oxide, lanthanum oxide, zircon, tin oxide and the like.
- the core / shell particles according to the present invention may be those in which the entire surface of the titanium oxide particles as the core is coated with a silicon-containing hydrated oxide, and a part of the surface of the titanium oxide particles as the core is silicon-containing. It may be coated with a hydrated oxide.
- a curing agent can also be used to cure the first water-soluble binder resin applied to the high refractive index layer.
- the curing agent that can be used together with the first water-soluble binder resin is not particularly limited as long as it causes a curing reaction with the water-soluble binder resin.
- boric acid and its salt are preferable as the curing agent.
- known ones can be used, and in general, a compound having a group capable of reacting with polyvinyl alcohol, or a compound that accelerates the reaction between different groups possessed by polyvinyl alcohol, etc. It can be selected and used.
- curing agents applicable to the present invention include epoxy curing agents (for example, diglycidyl ethyl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-diglycidyl cyclohexane, N , N-diglycidyl-4-glycidyloxyaniline, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, etc.), aldehyde-based curing agents (for example, formaldehyde, glioxal, etc.), active halogen-based curing agents (for example, 2,4-dichloro- 4-hydroxy-1,3,5, -s-triazine, etc.), active vinyl compounds (for example, 1,3,5-trisacryloyl-hexahydro-s-triazine, bisvinylsulfonylmethyl ether, etc.), aluminum alum, etc. Mention
- Boric acid and salts thereof refer to oxygen acids and salts thereof having a boron atom as a central atom, specifically, orthoboric acid, diboric acid, metaboric acid, tetraboric acid, pentaboric acid, and octaboron. Examples include acids and their salts.
- Boric acid having a boron atom and a salt thereof as a curing agent may be used alone or in combination of two or more. Particularly preferred is a mixed aqueous solution of boric acid and borax.
- Boric acid and borax can each be prepared only in a relatively dilute aqueous solution, but by mixing them both can be prepared as a concentrated aqueous solution, allowing the coating solution to be concentrated. Moreover, there is an advantage that the pH of the aqueous solution to be added can be controlled relatively freely.
- boric acid and a salt thereof, or borax as the curing agent from the viewpoint of more reliably obtaining the object effect of the present invention.
- boric acid and its salts or borax metal oxide particles and the hydroxy group of polyvinyl alcohol, which is a water-soluble binder resin, can more easily form a hydrogen bond network, resulting in high refraction. It is thought that interlayer mixing between the refractive index layer and the low refractive index layer is suppressed, and a preferable near-infrared blocking characteristic is achieved.
- the film surface temperature of the formed coating film is cooled to about 15 ° C., and then the coating film surface is dried.
- the above effect can be expressed more preferably.
- the content of the curing agent in the high refractive index layer is preferably in the range of 1 to 10% by mass and more preferably in the range of 2 to 6% by mass with respect to 100% by mass of the solid content of the high refractive index layer. preferable.
- the total amount of the curing agent is preferably in the range of 1 to 600 mg per 1 g of polyvinyl alcohol, and 100 to 600 mg per 1 g of polyvinyl alcohol. More preferably within the range.
- the low refractive index layer according to the present invention contains a second water-soluble binder resin and second metal oxide particles, and further includes a curing agent, a surface coating component, a particle surface protective agent, a binder resin, a surfactant, and the like. These various additives may be included.
- the refractive index of the low refractive index layer according to the present invention is preferably in the range of 1.10 to 1.60, more preferably 1.30 to 1.50 at 23 ° C. and 55% RH.
- Polyvinyl alcohol is preferably used as the second water-soluble binder resin applied to the low refractive index layer according to the present invention. Furthermore, it is more preferable to use polyvinyl alcohol (B) having a saponification degree different from that of the polyvinyl alcohol (A) applied to the high refractive index layer in the low refractive index layer according to the present invention.
- description about the preferable weight average molecular weight etc. of 2nd water-soluble binder resin here is demonstrated in detail in the water-soluble binder resin of the said high refractive index layer, The description is abbreviate
- the content of the second water-soluble binder resin in the low refractive index layer is preferably in the range of 20 to 99.9% by mass with respect to 100% by mass of the solid content of the low refractive index layer, and 25 to 80 More preferably, it is in the range of mass%.
- any method can be used as long as the low refractive index layer containing the second metal oxide particles can form a coating film. Anything can be used without limitation.
- water-soluble polymers particularly gelatin, thickening polysaccharides, polymers having reactive functional groups
- These water-soluble polymers may be used alone or in combination of two or more.
- the content of the other binder resin used together with polyvinyl alcohol preferably used as the second water-soluble binder resin is 0 to 10 mass with respect to 100 mass% of the solid content of the low refractive index layer. % Can also be used.
- the low refractive index layer of the reflective layer laminate it is a preferable aspect to contain water-soluble polymers such as celluloses, thickening polysaccharides and polymers having reactive functional groups. Since the same polymer as the water-soluble polymer described in the above-described high refractive index layer is used, the description thereof is omitted here.
- silica As the second metal oxide particles applied to the low refractive index layer according to the present invention, silica (silicon dioxide) is preferably used, and specific examples thereof include synthetic amorphous silica and colloidal silica. Of these, acidic colloidal silica sol is more preferably used, and colloidal silica sol dispersed in an organic solvent is more preferably used. Further, in order to further reduce the refractive index, hollow fine particles having pores inside the particles can be used as the second metal oxide particles applied to the low refractive index layer, particularly silica (silicon dioxide). The hollow fine particles are preferred.
- the average particle diameter of the second metal oxide particles (preferably silicon dioxide) applied to the low refractive index layer is generally in the range of 3 to 100 nm.
- the average particle size of primary particles of silicon dioxide dispersed in a primary particle state is more preferably in the range of 3 to 50 nm, and in the range of 3 to 40 nm. Is more preferably 3 to 20 nm, and most preferably in the range of 4 to 10 nm.
- the average particle diameter of the secondary particles of the second metal oxide particles is in the range of 2 to 3 times the average average particle diameter of the primary particles described above, so that the haze and the like can be set low. From the viewpoint of being able to.
- the average particle size of the metal oxide particles applied to the low refractive index layer is determined by observing the particles themselves or particles appearing on the cross section or surface of the refractive index layer with an electron microscope, and determining the particle size of 1000 arbitrarily selected particles. Measured and obtained as a simple average value (number average).
- the particle diameter of each particle is represented by a diameter assuming a circle equal to the projected area.
- the colloidal silica used in the present invention is obtained by heating and aging a silica sol obtained by metathesis with an acid of sodium silicate or the like and passing through an ion exchange resin layer.
- a silica sol obtained by metathesis JP-A-61-20792, JP-A-61-188183, JP-A-63-17807, JP-A-4-93284 JP-A-5-278324, JP-A-6-92011, JP-A-6-183134, JP-A-6-297830, JP-A-7-81214, JP-A-7-101142 JP-A-7-179029, JP-A-7-137431, and International Publication No. 1994/26530. It is intended.
- colloidal silica may be a synthetic product or a commercially available product.
- the surface of the colloidal silica may be cation-modified, or may be treated with Al, Ca, Mg, Ba or the like.
- Hollow particles can also be used as the second metal oxide particles applied to the low refractive index layer.
- the average particle pore diameter is preferably within the range of 3 to 70 nm, more preferably within the range of 5 to 50 nm, and even more preferably within the range of 5 to 45 nm.
- the average particle pore diameter of the hollow particles is the average value of the inner diameters of the hollow particles.
- the refractive index of the low refractive index layer is sufficiently lowered.
- the average particle pore diameter is 50, or more, randomly observed as an electron microscope, circular, elliptical, or substantially circular or elliptical, and the pore diameter of each particle is determined.
- the pore diameter of the particle means the minimum distance among the distances between the two parallel lines that surround the outer edge of the pore that can be observed as a circle, an ellipse, or a substantially circle or ellipse. To do.
- the surface of the second metal oxide particles according to the present invention may be coated with a surface coating component.
- a surface coating component such as polyaluminum chloride. This makes it difficult to aggregate with the first metal oxide particles.
- the content of the second metal oxide particles in the low refractive index layer is preferably within the range of 0.1 to 70% by mass with respect to 100% by mass of the solid content of the low refractive index layer, and preferably 30 to 70%. It is more preferably in the range of mass%, more preferably in the range of 45 to 65 mass%.
- the low refractive index layer according to the present invention may contain a curing agent, similar to the high refractive index layer.
- the curing agent is not particularly limited as long as it causes a curing reaction with the second water-soluble binder resin contained in the low refractive index layer.
- boric acid and salts thereof, or borax are preferred as the curing agent when polyvinyl alcohol is used as the second water-soluble binder resin applied to the low refractive index layer.
- boric acid and its salts known ones can be used.
- the content of the curing agent in the low refractive index layer is preferably in the range of 1 to 10% by mass and preferably in the range of 2 to 6% by mass with respect to 100% by mass of the solid content of the low refractive index layer. It is more preferable.
- the total amount of the curing agent used is preferably in the range of 1 to 600 mg per gram of polyvinyl alcohol, and in the range of 100 to 600 mg per gram of polyvinyl alcohol. More preferred.
- curing agent applicable to the formation of the low refractive index layer can include the same compounds as the curing agent exemplified in the above-described high refractive index layer, and description thereof is omitted here.
- additives for each refractive index layer In the high refractive index layer and the low refractive index layer according to the present invention, various additives can be used as necessary.
- the content of the additive in the high refractive index layer and the low refractive index layer is in the range of 0 to 20% by mass with respect to 100% by mass of the solid content of the high refractive index layer and the low refractive index layer. preferable. Representative additives applicable to the present invention are described below.
- At least one of the high refractive index layer and the low refractive index layer may further contain a surfactant.
- a surfactant any of zwitterionic, cationic, anionic, and nonionic types can be used. More preferably, a betaine zwitterionic surfactant, a quaternary ammonium salt cationic surfactant, a dialkylsulfosuccinate anionic surfactant, an acetylene glycol nonionic surfactant, or a fluorine cationic interface It is an activator.
- the addition amount of the surfactant is in the range of 0.005 to 0.30% by mass when the total mass of the coating solution for the high refractive index layer or the coating solution for the low refractive index layer is 100% by mass. Is preferably within the range of 0.01 to 0.10% by mass.
- the high refractive index layer or the low refractive index layer may contain an amino acid having an isoelectric point of 6.5 or less.
- amino acid By including the amino acid, the dispersibility of the metal oxide particles in the high refractive index layer or the low refractive index layer can be improved.
- an amino acid is a compound having an amino group and a carboxyl group in the same molecule, and may be any type of amino acid such as ⁇ -, ⁇ -, and ⁇ -.
- Some amino acids have optical isomers, but in the present invention, there is no difference in effect due to optical isomers, and any isomer can be used alone or in racemic form.
- preferred amino acids include aspartic acid, glutamic acid, glycine, serine and the like, and glycine and serine are particularly preferred.
- the isoelectric point of an amino acid is a pH value where there is a region where the positive and negative charges in the molecule are balanced at a specific pH and the overall charge is zero.
- the isoelectric point of each amino acid can be determined by isoelectric focusing at a low ionic strength.
- the high refractive index layer or the low refractive index layer according to the present invention may further contain an emulsion resin.
- an emulsion resin By including the emulsion resin, the flexibility of the film is increased, and the processability at the time of attaching the glass is improved.
- the emulsion resin referred to in the present invention is a resin dispersion in which fine, for example, resin particles having an average particle diameter of about 0.01 to 2.0 ⁇ m are dispersed in an aqueous medium in an emulsion state.
- the monomer is obtained by emulsion polymerization using a polymer dispersant having a hydroxy group. There is no fundamental difference in the polymer component of the resulting emulsion resin depending on the type of dispersant used.
- dispersant used in the polymerization of the emulsion examples include polyoxyethylene nonylphenyl ether in addition to low molecular weight dispersants such as alkylsulfonate, alkylbenzenesulfonate, diethylamine, ethylenediamine, and quaternary ammonium salt.
- Polymer dispersing agents such as polyoxyethylene lauryl ether, hydroxyethyl cellulose, and polyvinylpyrrolidone.
- emulsion polymerization is performed using a polymer dispersant having hydroxy groups
- the presence of hydroxy groups is estimated on at least the surface of fine particles
- emulsion resins polymerized using other dispersants are the chemical and physical properties of emulsions. The nature is different.
- the polymer dispersant having a hydroxy group is a polymer dispersant having a weight average molecular weight of 10,000 or more, and having a hydroxy group substituted on the side chain or terminal.
- polyacrylic acid soda polyacrylamide
- acrylic polymer examples include those obtained by copolymerization of 2-ethylhexyl acrylate, polyethers such as polyethylene glycol and polypropylene glycol, and the like.
- At least one of the high refractive index layer and the low refractive index layer may further contain a lithium compound.
- the coating solution for the high refractive index layer or the coating solution for the low refractive index layer containing the lithium compound makes it easier to control the viscosity of the coating solution, and as a result, production stability when the optical film of the present invention is applied to glass. Will be improved.
- the lithium compound applicable to the present invention is not particularly limited.
- lithium lithium hypochlorite, lithium oxide, lithium carbide, lithium nitride, lithium niobate, lithium sulfide, lithium borate, LiBF 4 , LiClO 4 , LiPF 4 , LiCF 3 SO 3 and the like.
- These lithium compounds can be used alone or in combination of two or more.
- lithium hydroxide is preferable from the viewpoint of sufficiently exerting the effects of the present invention.
- the amount of lithium compound added is preferably in the range of 0.005 to 0.05 g, more preferably 0.01 to 0.03 g, per gram of metal oxide particles present in each refractive index layer.
- Additives other than those described above applicable to the high refractive index layer and the low refractive index layer according to the present invention are listed below.
- ultraviolet absorbers described in JP-A-57-74193, JP-A-57-87988, and JP-A-62-261476, JP-A-57-74192, and JP-A-57-87989 are listed below.
- nonionic surfactants JP-A-59-42993, JP-A-59-52689, JP-A-62-280069, JP-A-61-242871, and JP-A-4-219266.
- Optical brighteners sulfuric acid, phosphoric acid, acetic acid, citric acid, sodium hydroxide, potassium hydroxide, potassium carbonate, etc.
- Lubricants such as tylene glycol, antiseptics, antifungal agents, antistatic agents, matting agents, heat stabilizers, antioxidants, flame retardants, crystal nucleating agents, inorganic particles, organic particles, thickeners, lubricants, infrared absorption Examples include various known additives such as agents, dyes, and pigments.
- the method for forming a reflective layer laminate according to the present invention is preferably formed by applying a wet coating method. Furthermore, the first water-soluble binder resin and the first metal oxide particles are formed on the transparent substrate.
- a manufacturing method including a step of wet-coating a coating liquid for a high refractive index layer containing a coating liquid for a low refractive index layer containing a second water-soluble binder resin and second metal oxide particles. preferable.
- the optical functional layer and the near-infrared shielding layer according to the present invention can be simultaneously coated on the transparent substrate by a wet coating method to manufacture an optical film. This is a preferred embodiment.
- the wet coating method is not particularly limited.
- roll coating method for example, roll coating method, rod bar coating method, air knife coating method, spray coating method, slide curtain coating method, US Pat. No. 2,761,419, US Pat. No. 2,761791 And a slide hopper coating method, an extrusion coating method and the like described in a book.
- the optical film of the present invention can be sandwiched between a pair of glass constituent members to form a laminated glass, and this laminated glass can be used for automobiles, railway vehicles, aircraft, ships, buildings, and the like. Laminated glass can be used for other purposes.
- the laminated glass is preferably laminated glass for buildings or vehicles.
- the laminated glass can be used for an automobile windshield, side glass, rear glass, roof glass, or the like.
- the glass member examples include inorganic glass and organic glass (resin glazing).
- the inorganic glass examples include float plate glass, heat ray absorbing plate glass, polished plate glass, mold plate glass, netted plate glass, lined plate glass, and colored glass such as green glass.
- the organic glass is a synthetic resin glass substituted for inorganic glass.
- the organic glass (resin glazing) examples include a polycarbonate plate and a poly (meth) acrylic resin plate.
- the poly (meth) acrylic resin plate examples include a polymethyl (meth) acrylate plate.
- inorganic glass is preferred from the viewpoint of safety when it is damaged by an external impact.
- the prepared solution 1 is placed in a commercially available autoclave for hydrothermal reaction treatment (HU-25 type, manufactured by Sanai Kagaku Co., which is provided with a 25 ml Teflon (registered trademark) inner cylinder in a SUS body) at 100 ° C. For 8 hours, followed by hydrothermal reaction at 270 ° C. for 24 hours.
- a commercially available autoclave for hydrothermal reaction treatment (HU-25 type, manufactured by Sanai Kagaku Co., which is provided with a 25 ml Teflon (registered trademark) inner cylinder in a SUS body) at 100 ° C. For 8 hours, followed by hydrothermal reaction at 270 ° C. for 24 hours.
- reaction product was filtered, and the filtration residue was filtered and washed with water and ethanol. Furthermore, this reaction product was dried at 60 ° C. for 10 hours using a constant temperature dryer to obtain vanadium dioxide-containing fine particles.
- the obtained vanadium dioxide-containing fine particle powder was added to pure water so as to have a concentration of 3.0% by mass to prepare a mixed solution, and an ultrasonic disperser (UH-300 manufactured by SMT) was used. An ultrasonic dispersion treatment was performed for 5 minutes to redisperse, and a vanadium dioxide-containing fine particle dispersion 1 was prepared.
- an ultrasonic disperser UH-300 manufactured by SMT
- PVA-124 which is a polyvinyl alcohol
- optical functional layer (layer A)
- a polyethylene terephthalate film (Toyobo A4300, double-sided easy-adhesion layer, abbreviated as PET in Table 1) having a thickness of 50 ⁇ m
- the above-prepared coating solution for forming an optical functional layer was prepared using an extrusion coater. 1 is wet-coated under the condition that the layer thickness after drying is 1.5 ⁇ m, and then dried by blowing hot air at 110 ° C. for 2 minutes to form an optical functional layer (layer A). Film 101 was produced.
- the prepared solution 1 is placed in a commercially available autoclave for hydrothermal reaction treatment (HU-25 type, manufactured by Sanai Kagaku Co., which is provided with a 25 ml Teflon (registered trademark) inner cylinder in a SUS body) at 100 ° C.
- a hydrothermal reaction treatment at 270 ° C. for 24 hours to prepare vanadium dioxide-containing fine particle dispersion 2 in which vanadium dioxide-containing fine particles were dispersed at a concentration of 3.0% by mass.
- optical film 103 Preparation of optical film 103
- polyvinyl alcohol (PVA-124) which is a water-based binder resin used for the preparation of the coating solution 2 for forming an optical functional layer
- PVP polyvinyl pyrrolidone
- Polyvinylpyrrolidone K-85 is a polymer having a hydroxy group-containing repeating unit ratio of less than 50 mol%.
- polyvinyl alcohol (PVA-124) which is an aqueous binder resin used for the preparation of the coating solution 2 for forming an optical functional layer, is 45 mol% of the same amount of hydroxyethyl acrylate (abbreviation: HEA).
- HEA hydroxyethyl acrylate
- An optical film 104 was produced in the same manner except that the optical functional layer (layer A) was formed using the coating solution 4 for forming an optical functional layer prepared by changing to the aqueous mixed solvent.
- optical film 105 In the production of the optical film 102, polyvinyl alcohol (PVA-124), which is an aqueous binder resin used in the preparation of the coating solution 2 for forming an optical functional layer, was changed to the same amount of polyhydroxyethyl acrylate (abbreviation: PHEA).
- PVA-124 polyvinyl alcohol
- PHEA polyhydroxyethyl acrylate
- the optical film 105 was produced in the same manner except that the optical functional layer (layer A) was formed using the optical functional layer-forming coating solution 5 prepared above.
- a vanadium dioxide-containing fine particle dispersion prepared by subjecting the vanadium dioxide-containing fine particle dispersion 2 used for the preparation of the coating solution 2 for forming an optical functional layer to ultrafiltration according to the following method.
- the optical film 106 was produced in the same manner except that the coating solution 6 for forming an optical functional layer was prepared using No. 3, and the optical functional layer (layer A) was formed using this.
- optical film 107 In the production of the optical film 106, instead of the vanadium dioxide-containing fine particle dispersion 3 used for the preparation of the coating solution 6 for forming an optical functional layer, polyvinyl alcohol (PVA-103) is used during the growth of vanadium dioxide-containing fine particles according to the following method. In this manner, a coating solution 7 for forming an optical functional layer is prepared using a vanadium dioxide-containing fine particle dispersion 4 prepared by coating the particle surface with PVA, and an optical functional layer (layer A) is formed using the coating solution 7. An optical film 107 was produced in the same manner except that.
- PVA-103 polyvinyl alcohol
- a 5% by weight aqueous solution of polyvinyl alcohol (PVA-103) was added to the prepared solution 1, and this solution was added to a commercially available autoclave for hydrothermal reaction treatment (HU-25 type, manufactured by Sanai Kagaku Co., Ltd., SUS body). And a 25 ml volume Teflon (registered trademark) inner cylinder), and subjected to a hydrothermal reaction treatment at 100 ° C. for 8 hours and subsequently at 270 ° C. for 24 hours, and the surface is coated with PVA-103.
- a vanadium dioxide-containing fine particle dispersion 4 in which the vanadium dioxide-containing fine particles were dispersed at a concentration of 3.0% by mass was prepared.
- the polyvinyl alcohol (PVA-124) which is a water-based binder resin used for the preparation of the coating solution 2 for forming an optical functional layer, is changed to the same amount of polyvinyl alcohol (PVA-217).
- An optical film 108 was produced in the same manner except that a functional layer forming coating solution 8 was prepared and an optical functional layer (layer A) was formed using the functional layer forming coating solution 8.
- the polyvinyl alcohol which is an aqueous binder resin used in the preparation of the coating solution 7 for forming the optical functional layer, is changed from PVA-124 to PVA-217, and further coated on the surface of the vanadium dioxide-containing fine particles.
- the optical film 109 was prepared in the same manner except that the PVA-103 was changed from PVA-103 to PVA-203 to prepare an optical functional layer forming coating solution 9, and the optical functional layer (layer A) was formed using the coating liquid 9 did.
- the coating time of the PVA-203 on the surface of the vanadium dioxide-containing fine particles was changed from the time of particle growth to before the ultrafiltration treatment for the vanadium dioxide-containing fine particle dispersion, and the vanadium dioxide-containing fine particle dispersion Then, 10 parts by mass of PVA-203 is added to 100 parts by mass of the vanadium dioxide-containing fine particles, subjected to a shelling treatment at 60 ° C. for 1 hour, and the surface of the vanadium dioxide-containing fine particles is coated.
- the optical film 110 was prepared in the same manner except that the coating solution 10 for forming an optical functional layer was prepared using the vanadium dioxide-containing fine particle dispersion prepared and the optical functional layer (layer A) was formed using it. Produced.
- optical film 111 In the production of the optical film 109, the coating time of the PVA-203 on the surface of the vanadium dioxide-containing fine particles was subjected to ultrafiltration treatment on the vanadium dioxide-containing fine particle dispersion from the time of particle growth, and then 100 parts by mass of the vanadium dioxide-containing fine particles.
- an optical functional layer using a vanadium dioxide-containing fine particle dispersion prepared by adding PVA-203 corresponding to 10 parts by mass, performing a shelling treatment at 60 ° C. for 1 hour, and coating the surface of the vanadium dioxide-containing fine particles.
- An optical film 111 was produced in the same manner except that a forming coating solution 11 was prepared and an optical functional layer (layer A) was formed using the coating solution 11.
- optical film 112 In the production of the optical film 109, a vanadium dioxide-containing fine particle dispersion prepared by changing the coating resin on the surface of the vanadium dioxide-containing fine particles from PVA-203 to PVA-217 of the same type as the aqueous binder resin used for forming the optical functional layer.
- An optical film 112 was prepared in the same manner as above except that the coating solution 12 for forming an optical functional layer was prepared and an optical functional layer (layer A) was formed using the coating solution 12.
- optical film 113 In the production of the optical film 110, the vanadium dioxide-containing fine particle dispersion prepared by changing the coating resin on the surface of the vanadium dioxide-containing fine particles from PVA-203 to PVA-217 of the same type as the water-based binder resin used for forming the optical functional layer.
- An optical film 113 was prepared in the same manner except that the coating solution 13 for forming an optical functional layer was prepared and an optical functional layer (layer A) was formed using the coating solution 13.
- a vanadium dioxide-containing fine particle dispersion prepared by changing the coating resin on the surface of the vanadium dioxide-containing fine particles from PVA-203 to PVA-217 of the same type as the aqueous binder resin used for forming the optical functional layer in the production of the optical film 111.
- An optical film 114 was prepared in the same manner except that the coating solution 14 for forming an optical functional layer was prepared and an optical functional layer (layer A) was formed using the coating solution 14.
- PVA-124 polyvinyl alcohol
- Metalroze 60SH hydroxypropyl methylcellulose
- An optical film 115 was produced in the same manner except that.
- PVA-124 polyvinyl alcohol
- Metalroze 60SH hydroxypropyl methylcellulose
- An optical film 116 was produced in the same manner except that it was formed.
- optical film 117 In the production of the optical film 109, after forming the following near-infrared light shielding layer 1 (polymer layer laminate) which also serves as a transparent substrate as the layer B, using the extrusion coater, the optical functional layer prepared above is formed.
- the coating liquid 9 is wet-coated under the condition that the layer thickness after drying is 1.5 ⁇ m, and then dried by blowing hot air of 110 ° C. for 2 minutes to form the optical functional layer 9 (layer A of the optical film 109).
- optical film 118 In the production of the optical film 109, the following near-infrared light shielding layer 2 (undercoat layer / silver near-infrared light reflection layer / hard coat layer) was formed as the layer B on the transparent substrate, and then an extrusion coater.
- the optical functional layer-forming coating solution 9 prepared above is wet-coated under the condition that the layer thickness after drying is 1.5 ⁇ m, and then dried by blowing hot air at 110 ° C. for 2 minutes. Then, an optical functional layer 9 (layer A of the optical film 109) was formed, and an optical film 118 having a configuration in which the near-infrared light shielding layer 2 and the optical functional layer 9 were laminated on a transparent substrate was produced.
- the undercoat layer coating solution 1 was added to the transparent substrate (thickness: 50 ⁇ m, polyethylene terephthalate film, (Toyobo A4300, double-sided easy-adhesion layer) using a micro gravure coater, drying at 90 ° C., and using an ultraviolet lamp, the illuminance of the irradiated part is 100 mW / cm 2 and the irradiation amount is 100 mJ / cm
- the coating film was cured as 2 , and an undercoat layer having a thickness of 1 ⁇ m was formed.
- a silver thin film layer (silver near-infrared light reflection layer) having a thickness of 15 nm was formed on the formed undercoat layer by vacuum deposition using silver containing 2% by mass of gold as a sputtering target material.
- an acrylic resin (OPSTAR Z7535, manufactured by JSR) was applied on the silver thin film layer using a micro gravure coater, dried at 90 ° C., and then irradiated with an ultraviolet lamp at an illuminance of 100 mW / cm 2 .
- the coating layer is cured with an irradiation amount of 100 mJ / cm 2 to form a hard coat layer having a thickness of 0.8 ⁇ m, and the near-infrared light shielding layer 2 (undercoat layer / silver near-infrared light reflection layer) as layer B / Hard coat layer).
- the undercoat layer coating solution 1 was prepared by sequentially adding, stirring, and mixing the following constituent materials.
- Acrylic monomer KAYARAD DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.) 200 parts by mass Irgacure 184 (manufactured by BASF Japan Ltd.) 20 parts by mass Propylene glycol monomethyl ether 110 parts by mass Ethyl acetate 110 parts by mass [of optical film 119 Production)
- the optical film 109 After forming the following near-infrared light shielding layer 3 (reflection layer laminate) as the layer B on the transparent substrate, the above-prepared optical functional layer was formed using an extrusion coater.
- the coating liquid 9 is wet-coated under the condition that the layer thickness after drying is 1.5 ⁇ m, and then dried by blowing hot air of 110 ° C. for 2 minutes to sequentially form the optical functional layer 9,
- An optical film 119 having the configuration shown in FIG. 3 in which the near-infrared light shielding layer 3 and the optical functional layer 9 were laminated on a transparent substrate was produced.
- coating liquid L1 for low refractive index layer 680 parts of 10% by mass of colloidal silica (silicon dioxide, manufactured by Nissan Chemical Industries, Ltd., Snowtex (registered trademark) OXS) as second metal oxide particles And 30 parts by weight of 4.0% by weight polyvinyl alcohol (manufactured by Kuraray Co., Ltd., PVA-103: polymerization degree 300, saponification degree 98.5 mol%) and 150 parts by weight of 3.0% by weight boric acid aqueous solution. Mixed and dispersed. Pure water was added to prepare 1000 parts of colloidal silica dispersion L1 as a whole.
- the obtained colloidal silica dispersion L1 was heated to 45 ° C., and 4.0% by mass of the second water-soluble binder resin was polyvinyl alcohol (manufactured by Nihon Acetate / Poval, JP-45: 760 parts of an aqueous solution were sequentially added with stirring.
- the polymerization degree was 4500 and the saponification degree was 86.5 to 89.5 mol%.
- 40 parts of a 1% by weight betaine surfactant manufactured by Kawaken Fine Chemical Co., Ltd., Sofazoline (registered trademark) LSB-R
- aqueous solution was added to prepare a coating solution L1 for a low refractive index layer.
- coating liquid L2 for low refractive index layer In preparation of the coating liquid L1 for low refractive index layer, the solid content of silicon dioxide (colloidal silica) as the second metal oxide particles was changed to 50% by mass. In the same manner as described above, a coating solution L2 for a low refractive index layer used for forming the outermost layer of the reflective layer laminate was prepared.
- the raw material titanium oxide hydrate is obtained by thermal hydrolysis of an aqueous titanium sulfate solution according to a known method.
- the base-treated titanium compound was suspended in pure water so that the concentration when converted to TiO 2 was 20 g / L. Therein, the 0.4 mol% of citric acid was added with stirring to TiO 2 weight. After that, when the temperature of the mixed sol solution reaches 95 ° C., concentrated hydrochloric acid is added so that the hydrochloric acid concentration becomes 30 g / L. The mixture is stirred for 3 hours while maintaining the liquid temperature at 95 ° C. A liquid was prepared.
- the pH at 25 ° C. was 1.4
- the zeta potential was +40 mV.
- the particle size was measured with a Zetasizer Nano manufactured by Malvern, the monodispersity was 16%.
- titanium oxide sol solution was dried at 105 ° C. for 3 hours to obtain titanium oxide powder fine particles.
- the powder fine particles were subjected to X-ray diffraction measurement using JDX-3530 type manufactured by JEOL Datum Co., Ltd. and confirmed to be rutile titanium oxide fine particles.
- the volume average particle diameter of the fine particles was 10 nm.
- a 20.0 mass% titanium oxide sol aqueous dispersion containing rutile-type titanium oxide fine particles having a volume average particle diameter of 10 nm was added to 4 kg of pure water to obtain a sol solution serving as core particles.
- a reflective layer laminate ML1 having the configuration shown in FIG. 3 was produced according to the following method.
- a transparent substrate A high refractive index layer H1 is formed on one side of a polyethylene terephthalate film (Toyobo Co., Ltd., Cosmo Shine A4300, double-sided adhesive bonding treatment, abbreviated as PET) heated to 45 ° C. which is the material (2). And it apply
- a polyethylene terephthalate film Toyobo Co., Ltd., Cosmo Shine A4300, double-sided adhesive bonding treatment, abbreviated as PET
- the low refractive index layer L1 (T 1 ) is formed on one surface of the transparent substrate (2), and the high refractive index layer H1 (T 2 ) is laminated thereon.
- a total of 16 layers are laminated one by one, and a low refractive index layer L2 (T n ) having a silicon dioxide content of 50 mass% is formed on the 16th high refractive index layer H1, and 17 layers are simultaneously formed. Multi-layer coating was performed.
- ML1 reflective layer laminate
- the prepared coating solution 9 for forming an optical functional layer was prepared using an extrusion coater. Then, wet coating is performed under the condition that the layer thickness after drying is 1.5 ⁇ m, and then dried by blowing hot air at 110 ° C. for 2 minutes to sequentially form the optical functional layer 9 on the transparent substrate. An optical film 120 in which the near infrared light shielding layer 4 and the optical functional layer 9 were laminated was produced.
- the following near-infrared light shielding layer 4 coating solution was applied on the transparent substrate with a wire bar so that the (average) film thickness after drying was 4 ⁇ m, and then manufactured by Eye Graphics Co., Ltd. in an air atmosphere.
- a UV curing device using a high-pressure mercury lamp
- curing conditions 400 mJ / cm 2
- drying conditions drying at 80 ° C. for 3 minutes to form a near-infrared light shielding layer 4 (layer B) ITO thin film
- ⁇ Preparation of coating solution for near infrared light shielding layer 4 100 parts of V-7600B (UV curable hard coat material) manufactured by Nippon Synthetic Chemical Co., Ltd., 5 parts of Irgacure 184 (manufactured by BASF Japan) as a photopolymerization initiator, ITO powder (super fine particle ITO manufactured by Sumitomo Metal Mining) ) 100 parts were added and diluted with methyl ethyl ketone as a solvent to prepare a coating solution for near infrared light shielding layer 4 having a solid content of 30% by mass.
- V-7600B UV curable hard coat material
- Irgacure 184 manufactured by BASF Japan
- ITO powder super fine particle ITO manufactured by Sumitomo Metal Mining
- optical film 121 In the production of the optical film 119, the optical functional layer forming coating solution 9 (surface coating during particle formation) used for forming the optical functional layer was used for forming the optical functional layer of the optical film 110.
- An optical film 121 was produced in the same manner except that the coating solution was changed to the coating solution 10 (surface coating before ultrafiltration treatment).
- optical film 122 In the production of the optical film 119, the optical functional layer forming coating solution 9 (surface coating during particle formation) used for forming the optical functional layer is used for forming the optical functional layer of the optical film 111.
- An optical film 122 was produced in the same manner except that the coating liquid 11 (surface coating after ultrafiltration treatment) was changed.
- optical film 123 In the production of the optical film 119, the optical functional layer forming coating solution 9 (surface coating during particle formation) used for forming the optical functional layer was used for forming the optical functional layer of the optical film 115.
- An optical film 123 was produced in the same manner except that the coating liquid 15 was changed.
- optical film 124 In the production of the optical film 119, the optical functional layer forming coating solution 9 (surface coating during particle formation) used for forming the optical functional layer was used for forming the optical functional layer of the optical film 116.
- An optical film 124 was produced in the same manner except that the coating liquid 16 was changed.
- optical films 125 to 127 were produced in the same manner except that the near-infrared light shielding layer and the optical functional layer were formed on the transparent substrate by the simultaneous multilayer coating method. did.
- optical film 128 In the formation of the optical functional layer of the optical film 101, the aqueous binder PVA-124 used for the preparation of the optical functional layer forming coating solution 1 was changed to a non-aqueous Byron 200 (ester resin, manufactured by Toyobo Co., Ltd.) And the optical film 128 was produced similarly except having formed the optical function layer (layer A) using the coating liquid 17 for optical function layer formation prepared by changing the solvent into methyl ethyl ketone.
- aqueous binder PVA-124 used for the preparation of the optical functional layer forming coating solution 1 was changed to a non-aqueous Byron 200 (ester resin, manufactured by Toyobo Co., Ltd.)
- the optical film 128 was produced similarly except having formed the optical function layer (layer A) using the coating liquid 17 for optical function layer formation prepared by changing the solvent into methyl ethyl ketone.
- PET Polyethylene terephthalate (binder resin)
- PVA-103 polyvinyl alcohol, Kuraray Poval PVA-103, manufactured by Kuraray Co., Ltd.
- PVA-124 polyvinyl alcohol, Kuraray Poval PVA-124, manufactured by Kuraray Co., Ltd.
- PVA-203 polyvinyl alcohol, Kuraray Poval PVA-203, manufactured by Kuraray Co., Ltd.
- PVA- 217 Polyvinyl alcohol, Kuraray Poval PVA-217, Kuraray Co., Ltd.
- PVP Polyvinylpyrrolidone, K-85, Nippon Shokubai Co., Ltd.
- HEA Hydroxyethyl acrylate
- AAm Acrylamide 60SH-50: Hydroxypropyl methylcellulose (cellulose-based resin), Shin-Etsu Byron 200 manufactured by Chemical Industry Co., Ltd .: ester resin, manufactured by Toyobo Co., Ltd.
- optical film laminated glass [Production of Optical Film Laminated Glass 101-129]
- the above-prepared optical films 101 to 129 are formed on a transparent adhesive sheet (manufactured by Nitto Denko Corporation) on a glass plate having a thickness of 1.3 mm and a size of 15 cm ⁇ 20 cm (manufactured by Matsunami Glass Kogyo Co., Ltd., “slide glass white edge polishing”). , LUCIACS CS9621T) to produce optical film laminated glasses 101 to 129.
- optical film laminated glass 130 Without providing an optical film, it was composed only of the glass plate having a thickness of 1.3 mm and a size of 15 cm ⁇ 20 cm, and this was designated as an optical film-laminated glass 130.
- ⁇ Size in 5 optical films The total number of occurrences of cracks and film peeling of 0.5 mm or more and less than 3 mm is 11 or more, or the total number of cracks and film peeling of 3 mm or more is 1 or more [Evaluation of heat shielding properties] Using the produced optical film-bonded glasses 101 to 130, the following heat-insulating properties assumed in summer and winter were evaluated, and the thermochromic properties of the optical films were determined.
- Measurement environment An environmental room was used in which an optical film-laminated glass was placed on the window frame of an environmental test room having a room temperature of 28 ° C. so that the inside would be an optical film, and a Japanese Cool Biz room was assumed.
- a 150 W halogen lamp was turned on from the position 50 cm away from the outside of the environmental test room where the optical film-laminated glass was placed, assuming the summer sun.
- the laminated glass was heated to 70 ° C. with a thermocouple.
- thermometer was installed at a position 1 m away from the optical film-laminated glass in the environmental test chamber, the temperature after 1 hour was measured under the above conditions, and the heat shielding property was evaluated according to the following criteria.
- a 100 W halogen lamp was lit from a position 50 cm away from the outside of the environment test room where the optical film-laminated glass was placed, assuming the winter sun.
- thermometer was installed at a position 1 m away from the optical film-laminated glass in the environmental test chamber, the temperature after 1 hour was measured under the above conditions, and the heat shielding property was evaluated according to the following criteria.
- ⁇ Temperature after 1 hour is 26 ° C or higher, and heat energy from external light has entered moderately.
- ⁇ Temperature after 24 hours is more than 24 ° C and less than 26 ° C. Later temperature is 22 ° C. or more and 24 ° C. or less.
- ⁇ Temperature after 21 hours is 21 ° C. or more and 22 ° C. or less.
- X Many near infrared light is unconditionally shielded and after 1 hour. Is less than 21 ° C. [Evaluation of haze] About each produced said optical film bonding glass, haze (%) was measured using the haze meter- (Nippon Denshoku Industries Co., Ltd. make, NDH2000), and the haze was evaluated according to the following reference
- the optical film of the present invention has thermochromic properties capable of adjusting the near-infrared shielding rate depending on the temperature environment, has a low haze, and can be used over a long period of time. It turns out that the outstanding crack tolerance and adhesiveness are favorable.
- the optical film of the present invention is an optical film having thermochromic properties, low haze, excellent crack resistance and adhesion, and is sandwiched between a pair of glass constituent members to constitute a laminated glass.
- This laminated glass can be suitably used as a window glass member for automobiles, railway vehicles, aircraft, ships and buildings.
Abstract
Description
前記光学機能層中における前記二酸化バナジウム含有微粒子の一次粒子及び二次粒子を含めた全粒子の数平均粒径が、200nm未満であることを特徴とする光学フィルム。
前記二酸化バナジウム含有微粒子の一次粒子及び二次粒子を含めた全粒子の数平均粒径が、200nm未満となるように調整することを特徴とする光学フィルムの製造方法。
本発明の光学フィルムは、透明基材上に、少なくとも一次粒子及び二次粒子を含めた全粒子の数平均粒径が、200nm未満である二酸化バナジウム含有微粒子とバインダー樹脂を含有する光学機能層を有することを特徴とする。
本発明の光学フィルムは、透明基材上に、少なくとも二酸化バナジウム含有微粒子とバインダー樹脂を含有する光学機能層を有し、光学機能層中における二酸化バナジウム含有微粒子の一次粒子及び二次粒子の数平均粒径が、200nm未満であることを特徴とする。
本発明に適用可能な透明基材としては、透明であれば特に制限はなく、ガラス、石英、透明樹脂フィルム等を挙げることができるが、フレキシブル性の付与及び生産適性(製造工程適性)の観点からは、透明樹脂フィルムであることが好ましい。本発明でいう「透明」とは、可視光領域における平均光線透過率が20%以上であることをいい、好ましくは30%以上、より好ましくは50%以上、特に好ましくは70%以上である。
〔二酸化バナジウム含有微粒子〕
本発明に係る光学機能層では、バインダー樹脂中に、一次粒子及び二次粒子を含めた全粒子の数平均粒径が200nm未満である二酸化バナジウム含有微粒子が分散されて存在していることを特徴とする。
一般に、二酸化バナジウム含有微粒子の製造方法は、固相法により合成されたVO2焼結体を粉砕する方法と、五酸化二バナジウム(V2O5)を原料として、液相でVO2を合成しながら粒子成長させる水系合成法が挙げられる。
バナジウム(V)を含む物質(I)と、ヒドラジン(N2H4)またはその水和物(N2H4・nH2O)と、水とを混ぜて溶液(A)を調製する。この溶液(A)は、物質(I)が水中に溶解した水溶液であっても良いし、物質(I)が水中に分散した懸濁液であっても良い。
次に、調製した溶液(A)を用いて、水熱反応処理を行う。ここで、「水熱反応」とは、温度と圧力が、水の臨界点(374℃、22MPa)よりも低い熱水(亜臨界水)中において生じる化学反応を意味する。水熱反応処理は、例えば、オートクレーブ装置内で行われる。水熱反応処理により、二酸化バナジウム(VO2)含有の単結晶微粒子が得られる。
必要に応じて、得られた二酸化バナジウム含有微粒子の表面に対し、樹脂によるコーティング処理または表面改質処理を行っても良い。これにより、二酸化バナジウム含有微粒子の表面が保護され、表面改質された単結晶微粒子を得ることができる。本発明では、その中でも、二酸化バナジウム含有微粒子の表面を水系バインダー樹脂と同じ又は同種の樹脂により被覆されていることが好ましい態様である。なお、本発明でいう「被覆」とは、二酸化バナジウム含有微粒子に対し、当該樹脂により粒子全面が完全に覆われている状態であっても、あるいは、粒子表面の一部が樹脂により覆われている状態であってもよい。
本発明に係る二酸化バナジウム含有微粒子においては、微粒子を調製し、光学機能層の形成に用いる水系のバインダー樹脂溶液と混合する前に、その粒子表面を水系バインダー樹脂と同じ又は同種の樹脂により被覆されていることが好ましい。
上記水系合成法により調製された二酸化バナジウム含有微粒子の分散液中には、合成過程での生じた残渣などの不純物が含まれており、光学機能層を形成する際に、二次凝集粒子発生の引き金となり、光学機能層の長期保存での劣化要因となることがあるため、予め分散液の段階で不純物を除去することが好ましい。
次いで、本発明に係る光学機能層の形成に用いるバインダー樹脂について説明する。
本発明で好ましく用いられるポリビニルアルコール類には、ポリ酢酸ビニルを加水分解して得られる通常のポリビニルアルコールを用いることができる。なお、ポリビニルアルコール類については、後述する反射層積層体を構成する第1の水溶性バインダー樹脂又は第2の水溶性バインダー樹脂の説明で、詳細に記載する。
本発明に係る光学機能層の形成に用いることのできるセルロース類としては、水溶性のセルロース誘導体が好ましく、例えば、カルボキシメチルセルロース(セルロースカルボキシメチルエーテル)、メチルセルロース、ヒドロキシメチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース等の水溶性セルロース誘導体や、カルボン酸基含有セルロース類であるカルボキシメチルセルロース(セルロースカルボキシメチルエーテル)、カルボキシエチルセルロース等を挙げることができる。その他には、ニトロセルロース、セルロースアセテートプロピオネート、酢酸セルロース、セルロース硫酸エステル等のセルロース誘導体を挙げることができる。
本発明に適用可能なゼラチンとしては、従来、ハロゲン化銀写真感光材料分野で広く用いられてきた各種ゼラチンを適用することができ、例えば、酸処理ゼラチン、アルカリ処理ゼラチンの他に、ゼラチンの製造過程で酵素処理をする酵素処理ゼラチン及びゼラチン誘導体、すなわち分子中に官能基としてのアミノ基、イミノ基、ヒドロキシ基、カルボキシ基を有し、それと反応して得る基を持った試薬で処理し改質したものでもよい。ゼラチンの一般的な製造法はよく知られており、例えば、T.H.James:The Theory of Photographic Process 4th. ed. 1977(Macmillan)55項、科学写真便覧(上)72~75項(丸善)、写真工学の基礎-銀塩写真編119~124頁(コロナ社)等の記載を参考にすることができる。また、リサーチ・ディスクロージャー誌第176巻、No.17643(1978年12月)のIX項に記載されているゼラチンを挙げることができる。
本発明で用いることのできる増粘多糖類としては、特に制限はなく、例えば、一般に知られている天然単純多糖類、天然複合多糖類、合成単純多糖類及び合成複合多糖類に挙げることができ、これら多糖類の詳細については、「生化学事典(第2版),東京化学同人出版」、「食品工業」第31巻(1988)21頁等を参照することができる。
本発明に適用可能な水系バインダー樹脂として、反応性官能基を有するポリマー類が挙げられる。例えば、ポリビニルピロリドン類、ポリアクリル酸、アクリル酸-アクリルニトリル共重合体、アクリル酸カリウム-アクリルニトリル共重合体、酢酸ビニル-アクリル酸エステル共重合体、若しくはアクリル酸-アクリル酸エステル共重合体などのアクリル系樹脂、スチレン-アクリル酸共重合体、スチレン-メタクリル酸共重合体、スチレン-メタクリル酸-アクリル酸エステル共重合体、スチレン-α-メチルスチレン-アクリル酸共重合体、若しくはスチレン-α-メチルスチレン-アクリル酸-アクリル酸エステル共重合体などのスチレンアクリル酸樹脂、スチレン-スチレンスルホン酸ナトリウム共重合体、スチレン-2-ヒドロキシエチルアクリレート共重合体、スチレン-2-ヒドロキシエチルアクリレート-スチレンスルホン酸カリウム共重合体、スチレン-マレイン酸共重合体、スチレン-無水マレイン酸共重合体、ビニルナフタレン-アクリル酸共重合体、ビニルナフタレン-マレイン酸共重合体、酢酸ビニル-マレイン酸エステル共重合体、酢酸ビニル-クロトン酸共重合体、酢酸ビニル-アクリル酸共重合体などの酢酸ビニル系共重合体及びそれらの塩が挙げられる。これらの中で、特に好ましい例としては、ポリビニルピロリドン類及びこれを含有する共重合体が挙げられる。
本発明に係る光学機能層には、本発明の目的効果を損なわない範囲で各種の添加剤を添加することができ、それらの添加剤を以下に列挙する。
本発明に係る光学機能層の形成方法としては、特に制限はないが、本発明においては、前記方法により、水系合成法より二酸化バナジウム含有微粒子を調製した後、乾燥させる工程を経ることがなく、二酸化バナジウム含有微粒子が会合せずに離間している状態で存在する分散液と、上記水系バインダー樹脂を水系溶媒に溶解して調製した水系バインダー樹脂溶液と混合することにより、水系の光学機能層形成用塗布液を調製し、この光学機能層形成用塗布液を用いて、湿式塗布方式により透明基材上に当該塗布液を塗布、乾燥して光学機能層を形成する方法が好ましい。
本発明の光学フィルにおいては、光学機能層に加え、700~1000nmの光波長範囲内の少なくとも一部を遮蔽する機能を有する近赤外光遮蔽層を設ける構成であることが好ましい態様である。
本発明に係る近赤外遮蔽層の一つであるポリマー層積層体は、第1屈折率を有する第1ポリマー層と、第2屈折率を有する第2ポリマー層とを多数積層して構成される。
本発明の光学フィルムに適用する近赤外遮蔽層としては、図3~図6で例示したような反射層積層体であることが、特に好ましい態様である。
本発明に係る高屈折率層は、第1の水溶性バインダー樹脂及び第1の金属酸化物粒子を含有し、必要に応じて、硬化剤、その他のバインダー樹脂、界面活性剤、及び各種添加剤等を含んでもよい。
本発明に係る第1の水溶性バインダー樹脂とは、該水溶性バインダー樹脂が最も溶解する温度で、0.5質量%の濃度に水に溶解させた際、G2グラスフィルタ(最大細孔40~50μm)で濾過した場合に濾別される不溶物の質量が、加えた該水溶性バインダー樹脂の50質量%以内であるものをいう。
本発明において、高屈折率層及び低屈折率層においては、それぞれの屈折率層間でケン化度の異なるポリビニルアルコールを適用することが好ましい。
重合度P=(〔η〕×103/8.29)(1/0.62)
低屈折率層に含まれるポリビニルアルコール(B)は、ケン化度が75~90mol%の範囲内で、かつ重合度が2000~5000の範囲内であることが好ましい。このような特性を備えたポリビニルアルコールを低屈折率層に含有させると、界面混合がより抑制される点で好ましい。これは、塗膜のひび割れが少なく、かつセット性が向上するためであると考えられる。
本発明において、高屈折率層では、ポリビニルアルコール以外の第1の水溶性バインダー樹脂としては、第1の金属酸化物粒子を含有した高屈折率層が塗膜を形成することができれば、いかなるバインダー成分でも制限なく使用可能である。また、後述する低屈折率層においても、ポリビニルアルコール(B)以外の第2の水溶性バインダー樹脂としては、前記と同様に、第2の金属酸化物粒子を含有した低屈折率層が塗膜を形成することができれば、どのようなものでも制限なく使用可能である。ただし、環境の問題や塗膜の柔軟性を考慮すると、前記光学機能層の水系バインダー樹脂として説明したゼラチン類、セルロース類、増粘多糖類、反応性官能基を有するポリマー等の水溶性高分子が好ましい。
本発明において、高屈折率層に適用可能な第1の金属酸化物粒子としては、屈折率が2.0~3.0の範囲内にある金属酸化物粒子が好ましい。さらに具体的には、例えば、酸化チタン、酸化ジルコニウム、酸化亜鉛、合成非晶質シリカ、コロイダルシリカ、アルミナ、コロイダルアルミナ、チタン酸鉛、鉛丹、黄鉛、亜鉛黄、酸化クロム、酸化第二鉄、鉄黒、酸化銅、酸化マグネシウム、水酸化マグネシウム、チタン酸ストロンチウム、酸化イットリウム、酸化ニオブ、酸化ユーロピウム、酸化ランタン、ジルコン、酸化スズなどが挙げられる。また、複数の金属で構成された複合酸化物粒子やコア・シェル状に金属構成が変化するコア・シェル粒子等を用いることもできる。
単分散度=(粒径の標準偏差)/(粒径の平均値)×100(%)
〈コア・シェル粒子〉
本発明に係る高屈折率層に適用する第1の金属酸化物粒子としては、「含ケイ素の水和酸化物で表面処理された酸化チタン粒子」を用いることが好ましく、このような形態の酸化チタン粒子を「コア・シェル粒子」、あるいは「Si被覆TiO2」と称する場合もある。
本発明においては、高屈折率層に適用する第1の水溶性バインダー樹脂を硬化させるため、硬化剤を使用することもできる。
本発明に係る低屈折率層は、第2の水溶性バインダー樹脂及び第2の金属酸化物粒子を含有し、更に、硬化剤、表面被覆成分、粒子表面保護剤、バインダー樹脂、界面活性剤等の各種添加剤を含んでもよい。
本発明に係る低屈折率層に適用する第2の水溶性バインダー樹脂として、ポリビニルアルコールが好ましく用いられる。さらに、前記高屈折率層に適用するポリビニルアルコール(A)のケン化度とは、ケン化度が異なるポリビニルアルコール(B)を、本発明に係る低屈折率層に用いることがより好ましい。なお、ここでの第2の水溶性バインダー樹脂の好ましい重量平均分子量等についての説明は、上記高屈折率層の水溶性バインダー樹脂において詳細に説明されており、ここではその説明を省略する。
本発明に係る低屈折率層に適用する第2の金属酸化物粒子としては、シリカ(二酸化ケイ素)を用いることが好ましく、具体的な例として合成非晶質シリカ、コロイダルシリカ等が挙げられる。これらのうち、酸性のコロイダルシリカゾルを用いることがより好ましく、有機溶媒に分散させたコロイダルシリカゾルを用いることがさらに好ましい。また、屈折率をより低減させるためには、低屈折率層に適用する第2の金属酸化物粒子として、粒子の内部に空孔を有する中空微粒子を用いることができ、特にシリカ(二酸化ケイ素)の中空微粒子が好ましい。
本発明に係る低屈折率層において、前記高屈折率層と同様に、硬化剤を含むことができる。硬化剤としては、低屈折率層に含まれる第2の水溶性バインダー樹脂と硬化反応を起こすものであれば、特に制限されない。特に、低屈折率層に適用する第2の水溶性バインダー樹脂としてポリビニルアルコールを用いた場合の硬化剤としては、ホウ酸及びその塩、又はホウ砂が好ましい。また、ホウ酸及びその塩以外にも公知のものが使用できる。
本発明に係る高屈折率層及び低屈折率層には、必要に応じて各種の添加剤を用いることができる。また、高屈折率層及び低屈折率層における添加剤の含有量は、高屈折率層及び低屈折率層の固形分100質量%に対して、0~20質量%の範囲内であることが好ましい。本発明に適用可能な代表的な添加剤を以下に記載する。
本発明においては、高屈折率層及び低屈折率層の少なくとも1層が、さらに界面活性剤を含有してもよい。界面活性剤としては、両性イオン系、カチオン系、アニオン系、ノニオン系のいずれの種類も使用することができる。より好ましくは、ベタイン系両性イオン性界面活性剤、4級アンモニウム塩系カチオン性界面活性剤、ジアルキルスルホコハク酸塩系アニオン性界面活性剤、アセチレングリコール系ノニオン性界面活性剤、又はフッ素系カチオン性界面活性剤である。
本発明において、高屈折率層又は低屈折率層は、等電点が6.5以下のアミノ酸を含有していてもよい。当該アミノ酸を含むことにより、高屈折率層又は低屈折率層中の金属酸化物粒子の分散性を向上させることができる。
本発明に係る高屈折率層又は低屈折率層は、エマルジョン樹脂をさらに含有していてもよい。エマルジョン樹脂を含むことにより、膜の柔軟性が高くなり、ガラス貼付時の加工性が向上する。
本発明においては、高屈折率層及び低屈折率層の少なくとも1層が、さらにリチウム化合物を含有してもよい。該リチウム化合物を含む高屈折率層用塗布液又は低屈折率層用塗布液は、塗布液の粘度制御がより容易となり、その結果、ガラスに本発明の光学フィルムを貼付する際の製造安定性がより向上する。
本発明に係る高屈折率層及び低屈折率層に適用可能な上記で説明した以外の添加剤を、以下に列挙する。例えば、特開昭57-74193号公報、特開昭57-87988号公報、及び特開昭62-261476号公報に記載の紫外線吸収剤、特開昭57-74192号、特開昭57-87989号公報、特開昭60-72785号公報、特開昭61-146591号公報、特開平1-95091号公報、及び特開平3-13376号公報等に記載されている退色防止剤、アニオン、カチオン又はノニオンの各種界面活性剤、特開昭59-42993号公報、特開昭59-52689号公報、特開昭62-280069号公報、特開昭61-242871号公報、及び特開平4-219266号公報等に記載されている蛍光増白剤、硫酸、リン酸、酢酸、クエン酸、水酸化ナトリウム、水酸化カリウム、炭酸カリウム等のpH調整剤、消泡剤、ジエチレングリコール等の潤滑剤、防腐剤、防黴剤、帯電防止剤、マット剤、熱安定剤、酸化防止剤、難燃剤、結晶核剤、無機粒子、有機粒子、減粘剤、滑剤、赤外線吸収剤、色素、顔料等の公知の各種添加剤などが挙げられる。
本発明に係る反射層積層体の形成方法は、湿式塗布方式を適用して形成することが好ましく、更には、透明基材上に、第1の水溶性バインダー樹脂及び第1の金属酸化物粒子を含む高屈折率層用塗布液と、第2の水溶性バインダー樹脂及び第2の金属酸化物粒子を含む低屈折率層用塗布液とを、積層しながら湿式塗布する工程を含む製造方法が好ましい。
本発明の光学フィルムは、1対のガラス構成部材で挟持させて、合わせガラスを構成することができ、この合わせガラスは、自動車、鉄道車両、航空機、船舶及び建築物等に使用できる。合わせガラスは、これらの用途以外にも使用できる。上記合わせガラスは、建築用又は車両用の合わせガラスであることが好ましい。上記合わせガラスは、自動車のフロントガラス、サイドガラス、リアガラス又はルーフガラス等に使用できる。
〔光学フィルム101の作製〕
(二酸化バナジウム含有微粒子分散液1の調製:粒子乾燥工程あり)
純水10mLに、バナジン酸アンモニウム(NH4VO3、和光純薬社製、特級)0.433gを混合し、更に、ヒドラジン水和物(N2H4・H2O、和光純薬社製、特級)の5質量%水溶液をゆっくり滴下し、23℃、55%RHにけるpH値が9.2の溶液1を調製した。調製した溶液1を、市販の水熱反応処理用オートクレーブ(三愛科学社製 HU-25型、SUS製本体に25ml容積のテフロン(登録商標)製内筒を備える構成。)内に入れ、100℃で8時間、引き続き270℃で24時間、水熱反応処理を行った。
下記の各構成材料を順次添加、混合及び溶解して水系の光学機能層形成用塗布液1を調製した。
3質量%のホウ酸水溶液 10質量部
5質量%のポリビニルアルコール(5質量%水溶液、PVA-124;重合度:2400、ケン化度:98~99mol%;クラレ株式会社製)
60質量部
5質量%の界面活性剤水溶液(ソフタゾリンLSB-R、川研ファインケミカル株式会社製) 2質量部
なお、ポリビニルアルコールであるPVA-124は、ヒドロキシ基含有の繰り返し単位の比率が50モル%以上のポリマーである。
厚さが50μmのポリエチレンテレフタレートフィルム(東洋紡製A4300、両面易接着層、表1にはPETと略記。)の透明基材上に、押出コーターを用いて、上記調製した光学機能層形成用塗布液1を、乾燥後の層厚が1.5μmとなる条件で湿式塗布を行い、次いで110℃の温風を2分間吹きつけて乾燥させて、光学機能層(層A)を形成して、光学フィルム101を作製した。
(二酸化バナジウム含有微粒子分散液2の調製:粒子乾燥工程なし)
純水10mLに、バナジン酸アンモニウム(NH4VO3、和光純薬社製、特級)0.433gを混合し、更に、ヒドラジン水和物(N2H4・H2O、和光純薬社製、特級)の5質量%水溶液をゆっくり滴下し、23℃、55%RHにけるpH値が9.2の溶液1を調製した。調製した溶液1を、市販の水熱反応処理用オートクレーブ(三愛科学社製 HU-25型、SUS製本体に25ml容積のテフロン(登録商標)製内筒を備える構成。)内に入れ、100℃で8時間、引き続き270℃で24時間、水熱反応処理を施して、二酸化バナジウム含有微粒子が3.0質量%の濃度で分散されている二酸化バナジウム含有微粒子分散液2を調製した。
下記の各構成材料を順次添加、混合及び溶解して水系の光学機能層形成用塗布液2を調製した。
3質量%のホウ酸水溶液 10質量部
5質量%のポリビニルアルコール(5質量%水溶液、PVA-124;重合度:2400、ケン化度:98~99mol%;クラレ株式会社製)
60質量部
5質量%の界面活性剤水溶液(ソフタゾリンLSB-R、川研ファインケミカル株式会社製) 2質量部
(光学機能層の形成)
厚さが50μmのポリエチレンテレフタレートフィルム(東洋紡製A4300、両面易接着層、略称:PET)上に、押出コーターを用いて、上記調製した光学機能層形成用塗布液2を、乾燥後の層厚が1.5μmとなる条件で湿式塗布を行い、次いで110℃の温風を2分間吹きつけて乾燥させて、光学機能層(層A)を形成して、光学フィルム102を作製した。
上記光学フィルム102の作製において、光学機能層形成用塗布液2の調製に用いた水系バインダー樹脂であるポリビニルアルコール(PVA-124)を、同量のポリビニルピロリドン(略称:PVP、日本触媒社製、K-85、K値=85)に変更して調製した光学機能層形成用塗布液3を用いて光学機能層(層A)を形成した以外は同様にして、光学フィルム103を作製した。
上記光学フィルム102の作製において、光学機能層形成用塗布液2の調製に用いた水系バインダー樹脂であるポリビニルアルコール(PVA-124)を、同量のヒドロキシエチルアクリレート(略称:HEA)が45mol%で、アクリルアミド(略称:AAm)が55mol%の共重合体ポリマーに変更し、更に、各添加剤の溶媒を、水から、H2O/イソプロピルアルコール(略称:IPA)=7/3(質量比)の水系混合溶媒に変更して調製した光学機能層形成用塗布液4を用いて光学機能層(層A)を形成した以外は同様にして、光学フィルム104を作製した。
上記光学フィルム102の作製において、光学機能層形成用塗布液2の調製に用いた水系バインダー樹脂であるポリビニルアルコール(PVA-124)を、同量のポリヒドロキシエチルアクリレート(略称:PHEA)に変更して調製した光学機能層形成用塗布液5を用いて、光学機能層(層A)を形成した以外は同様にして、光学フィルム105を作製した。
上記光学フィルム102の作製において、光学機能層形成用塗布液2の調製に用いた二酸化バナジウム含有微粒子分散液2に対し、下記の方法に従って限外濾過処理を施して調製した二酸化バナジウム含有微粒子分散液3を用いて光学機能層形成用塗布液6を調製し、これを用いて光学機能層(層A)を形成した以外は同様にして、光学フィルム106を作製した。
前記調製した二酸化バナジウム含有微粒子分散液2を20℃に保った状態で、系内循環させる形で接続したポリエーテルスルホン製で分画分子量が30万の濾過膜を有する限外濾過装置(日本ミリポア株式会社製 ペリコン2カセット)を用いて濃縮操作を行い、初期二酸化バナジウム含有微粒子分散液2の体積に対し、10%まで濃縮した後、水を足して、100%とし、この濃縮と希釈操作を3回繰り返して、粒子濃度が3質量%の限外濾過処理済みの二酸化バナジウム含有微粒子分散液3を調製した。
上記光学フィルム106の作製において、光学機能層形成用塗布液6の調製に用いた二酸化バナジウム含有微粒子分散液3に代えて、下記の方法に従って二酸化バナジウム含有微粒子の成長時にポリビニルアルコール(PVA-103)を共存させて、粒子表面をPVAで被覆して調製した二酸化バナジウム含有微粒子分散液4を用いて光学機能層形成用塗布液7を調製し、それを用いて光学機能層(層A)を形成した以外は同様にして、光学フィルム107を作製した。
純水10mLに、バナジン酸アンモニウム(NH4VO3、和光純薬社製、特級)0.433gを混合し、更に、ヒドラジン水和物(N2H4・H2O、和光純薬社製、特級)の5質量%水溶液をゆっくり滴下し、pH値が9.2の溶液1を調製した。調製した溶液1にポリビニルアルコール(PVA-103)の5質量%水溶液を0.54g添加し、この溶液を、市販の水熱反応処理用オートクレーブ(三愛科学社製 HU-25型、SUS製本体に25ml容積のテフロン(登録商標)製内筒を備える構成。)内に入れ、100℃で8時間、引き続き270℃で24時間、水熱反応処理を施して、表面がPVA-103で被覆されている二酸化バナジウム含有微粒子が3.0質量%の濃度で分散されている二酸化バナジウム含有微粒子分散液4を調製した。
上記光学フィルム102の作製において、光学機能層形成用塗布液2の調製に用いた水系バインダー樹脂であるポリビニルアルコール(PVA-124)を、同量のポリビニルアルコール(PVA-217)に変更して光学機能層形成用塗布液8を調製し、それを用いて光学機能層(層A)を形成した以外は同様にして、光学フィルム108を作製した。
上記光学フィルム107の作製において、光学機能層形成用塗布液7の調製に用いた水系バインダー樹脂であるポリビニルアルコールを、PVA-124からPVA-217に変更し、更に二酸化バナジウム含有微粒子表面に被覆するPVAをPVA-103からPVA-203に変更して光学機能層形成用塗布液9を調製し、それを用いて光学機能層(層A)を形成した以外は同様にして、光学フィルム109を作製した。
上記光学フィルム109の作製において、二酸化バナジウム含有微粒子表面に対するPVA-203の被覆時期を、粒子成長時から二酸化バナジウム含有微粒子分散液に対する限外濾過処理を行う前に変更し、二酸化バナジウム含有微粒子分散液に、二酸化バナジウム含有微粒子100質量部に対し、10質量部相当分のPVA―203を添加し、60℃で1時間のシェリング処理を施して、二酸化バナジウム含有微粒子表面を被覆した後に限外濾過処理を行って調製した二酸化バナジウム含有微粒子分散液を用いて光学機能層形成用塗布液10を調製し、それを用いて光学機能層(層A)を形成した以外は同様にして、光学フィルム110を作製した。
上記光学フィルム109の作製において、二酸化バナジウム含有微粒子表面に対するPVA-203の被覆時期を、粒子成長時から二酸化バナジウム含有微粒子分散液に対する限外濾過処理を行った後に、二酸化バナジウム含有微粒子100質量部に対し、10質量部相当分のPVA―203を添加し、60℃で1時間のシェリング処理を施して、二酸化バナジウム含有微粒子表面を被覆して調製した二酸化バナジウム含有微粒子分散液を用いて光学機能層形成用塗布液11を調製し、それを用いて光学機能層(層A)を形成した以外は同様にして、光学フィルム111を作製した。
上記光学フィルム109の作製において、二酸化バナジウム含有微粒子表面に対する被覆樹脂を、PVA-203から光学機能層の形成で用いる水系バインダー樹脂と同種のPVA-217に変更して調製した二酸化バナジウム含有微粒子分散液を用いて光学機能層形成用塗布液12を調製し、それを用いて光学機能層(層A)を形成した以外は同様にして、光学フィルム112を作製した。
上記光学フィルム110の作製において、二酸化バナジウム含有微粒子表面に対する被覆樹脂を、PVA-203から光学機能層の形成で用いる水系バインダー樹脂と同種のPVA-217に変更して調製した二酸化バナジウム含有微粒子分散液を用いて光学機能層形成用塗布液13を調製し、それを用いて光学機能層(層A)を形成した以外は同様にして、光学フィルム113を作製した。
上記光学フィルム111の作製において、二酸化バナジウム含有微粒子表面に対する被覆樹脂を、PVA-203から光学機能層の形成で用いる水系バインダー樹脂と同種のPVA-217に変更して調製した二酸化バナジウム含有微粒子分散液を用いて光学機能層形成用塗布液14を調製し、それを用いて光学機能層(層A)を形成した以外は同様にして、光学フィルム114を作製した。
上記光学フィルム102の作製において、光学機能層形成用塗布液2の調製に用いた水系バインダー樹脂であるポリビニルアルコール(PVA-124)に代えて、同量のセルロース樹脂であるヒドロキシプロピルメチルセルロース(メトローズ60SH-50、メトキシ基=28~30%、ヒドロキシプロポキシ基=7.0~12% 信越化学工業社製)を用いて調製した光学機能層形成用塗布液15により光学機能層(層A)を形成した以外は同様にして、光学フィルム115を作製した。
上記光学フィルム106の作製において、光学機能層形成用塗布液3の調製に用いた水系バインダー樹脂であるポリビニルアルコール(PVA-124)に代えて、同量のセルロース樹脂であるヒドロキシプロピルメチルセルロース(メトローズ60SH-50、メトキシ基=28~30%、ヒドロキシプロポキシ基=7.0~12% 信越化学工業社製)を用いて調製した光学機能層形成用塗布液16により、光学機能層(層A)を形成した以外は同様にして、光学フィルム116を作製した。
上記光学フィルム109の作製において、層Bとして透明基材を兼ねた下記近赤外光遮蔽層1(ポリマー層積層体)を形成した後、押出コーターを用いて、上記調製した光学機能層形成用塗布液9を、乾燥後の層厚が1.5μmとなる条件で湿式塗布を行い、次いで110℃の温風を2分間吹きつけて乾燥させて、光学機能層9(光学フィルム109の層A)を形成して、透明基材上に近赤外光遮蔽層1及び光学機能層9を積層した図7に記載の構成からなる光学フィルム117を作製した。
米国特許公報第6049419号明細書の実施例の例3に記載の方法に従って、ポリエチレンナフタレート(PEN)とポリメタクアリレート(PMMA)を交互に積層した総数が112層で、厚さ50μmの図7に記載の構成のポリマー層積層体ML2を作製した。このポリマー層積層体ML2を近赤外光遮蔽層1という。
上記光学フィルム109の作製において、前記透明基材上に、層Bとして下記近赤外光遮蔽層2(下引層/銀近赤外光反射層/ハードコート層)を形成した後、押出コーターを用いて、上記調製した光学機能層形成用塗布液9を、乾燥後の層厚が1.5μmとなる条件で湿式塗布を行い、次いで110℃の温風を2分間吹きつけて乾燥させて、光学機能層9(光学フィルム109の層A)を形成して、透明基材上に近赤外光遮蔽層2及び光学機能層9を積層した構成からなる光学フィルム118を作製した。
下記の方法で下引層塗布液1を調製し、孔径0.4μmのポリプロピレン製フィルターで濾過した後、この下引層塗布液1を、前記透明基材(厚さ:50μm、ポリエチレンテレフタレートフィルム、東洋紡製A4300、両面易接着層)上に、マイクログラビアコーターを用いて塗布し、90℃で乾燥の後、紫外線ランプを用い、照射部の照度が100mW/cm2で、照射量を100mJ/cm2として塗膜を硬化させ、厚さ1μmの下引層を形成した。
下記に示す各構成材料を、順次添加、撹拌、混合して下引層塗布液1を調製した。
イルガキュア184(BASFジャパン(株)製) 20質量部
プロピレングリコールモノメチルエーテル 110質量部
酢酸エチル 110質量部
〔光学フィルム119の作製〕
上記光学フィルム109の作製において、前記透明基材上に、層Bとして下記近赤外光遮蔽層3(反射層積層体)を形成した後、押出コーターを用いて、上記調製した光学機能層形成用塗布液9を、乾燥後の層厚が1.5μmとなる条件で湿式塗布を行い、次いで110℃の温風を2分間吹きつけて乾燥させて、光学機能層9を逐次形成して、透明基材上に近赤外光遮蔽層3及び光学機能層9を積層した図3に記載の構成からなる光学フィルム119を作製した。
〈反射層形成用塗布液の調製〉
〈1〉低屈折率層用塗布液L1の調製
10質量%の第2の金属酸化物粒子としてのコロイダルシリカ(二酸化ケイ素、日産化学工業株式会社製、スノーテックス(登録商標)OXS)水溶液680部と、4.0質量%のポリビニルアルコール(株式会社クラレ製、PVA-103:重合度300、ケン化度98.5mol%)水溶液30部と、3.0質量%のホウ酸水溶液150部とを混合し、分散した。純水を加え、全体として1000部のコロイダルシリカ分散液L1を調製した。
上記低屈折率層用塗布液L1の調製において、第2の金属酸化物粒子である二酸化ケイ素(コロイダルシリカ)の固形分量を50質量%に変更した以外は同様にして、反射層積層体の最表層の形成に用いる低屈折率層用塗布液L2を調製した。
〈3.1〉コア・シェル粒子の調製
〈3.2〉コア部を構成するルチル型酸化チタンの調製
水中に、酸化チタン水和物を懸濁させ、TiO2に換算した時の濃度が100g/Lになるように、酸化チタンの水性懸濁液を調製した。10L(リットル)の該懸濁液に、30Lの水酸化ナトリウム水溶液(濃度10モル/L)を撹拌しながら加えた後、90℃に加熱し、5時間熟成させた。次いで、塩酸を用いて中和し、濾過後水を用いて洗浄した。
2kgの純水に、10.0質量%の酸化チタンゾル水系分散液0.5kgを加え、90℃に加熱した。次いで、SiO2に換算した時の濃度が2.0質量%であるように調製したケイ酸水溶液1.3kgを徐々に添加し、オートクレーブ中、175℃で18時間加熱処理を行い、さらに濃縮して、コア粒子としてはルチル型構造を有する酸化チタンであり、被覆層としてはSiO2であるコア・シェル粒子(平均粒径:10nm)のゾル液(固形分濃度20質量%)を得た。
上記で得られた固形分濃度20.0質量%の第1の金属酸化物粒子としてのコア・シェル粒子を含むゾル液28.9部と、1.92質量%のクエン酸水溶液10.5部と、10質量%のポリビニルアルコール(株式会社クラレ製、PVA-103:重合度300、ケン化度98.5mol%)水溶液2.0部と、3質量%のホウ酸水溶液9.0部とを混合して、コア・シェル粒子分散液H1を調製した。
下記の方法に従って図3に記載の構成からなる反射層積層体ML1を作製した。
上記光学フィルム119の作製において、前記透明基材上に、下記近赤外光遮蔽層4(ITO薄膜)を形成した後、押出コーターを用いて、上記調製した光学機能層形成用塗布液9を、乾燥後の層厚が1.5μmとなる条件で湿式塗布を行い、次いで110℃の温風を2分間吹きつけて乾燥させて、光学機能層9を逐次形成して、透明基材上に近赤外光遮蔽層4及び光学機能層9を積層した光学フィルム120を作製した。
下記近赤外光遮蔽層4用塗布液を、乾燥後の(平均)膜厚が4μmになるように前記透明基材上にワイヤーバーで塗布した後、空気雰囲気下で、アイグラフィックス社製のUV硬化装置(高圧水銀ランプ使用)を用い、硬化条件;400mJ/cm2で硬化を行い、その後乾燥条件;80℃、3分で乾燥して、層Bとして近赤外光遮蔽層4(ITO薄膜)を形成した。
日本合成化学株式会社製のV-7600B(UV硬化型ハードコート材)100部に、光重合開始剤としてイルガキュア184(BASFジャパン(株)製)5部、ITO粉末(住友金属鉱山製 超微粒子ITO)100部を添加して、溶剤としてメチルエチルケトンで希釈して、固形分が30質量%の近赤外光遮蔽層4用塗布液を調製した。
上記光学フィルム119の作製において、光学機能層の形成に用いた光学機能層形成用塗布液9(粒子形成時表面被覆)を、光学フィルム110の光学機能層の形成に用いた光学機能層形成用塗布液10(限外濾過処理前に表面被覆)に変更した以外は同様にして、光学フィルム121を作製した。
上記光学フィルム119の作製において、光学機能層の形成に用いた光学機能層形成用塗布液9(粒子形成時表面被覆)を、光学フィルム111の光学機能層の形成に用いた光学機能層形成用塗布液11(限外濾過処理後に表面被覆)に変更した以外は同様にして、光学フィルム122を作製した。
上記光学フィルム119の作製において、光学機能層の形成に用いた光学機能層形成用塗布液9(粒子形成時表面被覆)を、光学フィルム115の光学機能層の形成に用いた光学機能層形成用塗布液15に変更した以外は同様にして、光学フィルム123を作製した。
上記光学フィルム119の作製において、光学機能層の形成に用いた光学機能層形成用塗布液9(粒子形成時表面被覆)を、光学フィルム116の光学機能層の形成に用いた光学機能層形成用塗布液16に変更した以外は同様にして、光学フィルム124を作製した。
上記光学フィルムフィルム119、121、122の作製において、透明基材上に、近赤外光遮蔽層及び光学機能層を同時重層塗布方式で形成した以外は同様にして、光学フィルム125~127を作製した。
上記光学フィルム101の光学機能層の形成において、光学機能層形成用塗布液1の調製に用いた水系バインダーPVA―124を、非水系のバイロン200(エステル系樹脂、東洋紡社製)に変更し、かつ溶媒をメチルエチルケトンに変更して調製した光学機能層形成用塗布液17を用いて光学機能層(層A)を形成した以外は同様にして、光学フィルム128を作製した。
米国特許公報第6049419号明細書の実施例の例3に記載の方法に従って、ポリエチレンナフタレート(PEN)とポリメタクアリレート(PMMA)を交互に積層した総数が224層で、厚さ100μmのポリマー層積層体MLを作製し、これを光学フィルム129とした。
PET:ポリエチレンテレフタレート
(バインダー樹脂)
PVA-103:ポリビニルアルコール、クラレポバールPVA-103、クラレ社製
PVA-124:ポリビニルアルコール、クラレポバールPVA-124、クラレ社製
PVA-203:ポリビニルアルコール、クラレポバールPVA-203、クラレ社製
PVA-217:ポリビニルアルコール、クラレポバールPVA-217、クラレ社製
PVP:ポリビニピロリドン、K-85、日本触媒社製
HEA:ヒドロキシエチルアクリレート
AAm:アクリルアミド
60SH-50:ヒドロキシプロピルメチルセルロース(セルロース系樹脂)、信越化学工業社製
バイロン200:エステル系樹脂、東洋紡社製
(溶媒)
MEK:メチルエチルケトン
IPA:イソプロピルアルコール
《光学フィルム貼合ガラスの作製》
〔光学フィルム貼合ガラス101~129の作製》
上記作製した光学フィルム101~129を、厚さ1.3mmで、サイズが15cm×20cmのガラス板(松浪硝子工業社製、「スライドガラス白縁磨」)に、透明粘着シート(日東電工社製、LUCIACS CS9621T)を用いて貼り合わせて光学フィルム貼合ガラス101~129を作製した。
光学フィルムを付与せずに、厚さ1.3mmでサイズ15cm×20cmの上記ガラス板のみで構成し、これを光学フィルム貼合ガラス130とした。
〔保存性の評価:光学フィルムの評価〕
得られた各光学フィルムを10cm角のサイズで各5枚ずつ切り出し、保存性の評価として下記の保存加速試験を行い、保存加速試験後のサンプルを作製した。次いで、下記の評価ランクに従って、保存性の評価を行った。
3台の加速試験機を準備し、それぞれを85℃(加湿なし)、-20℃、60℃・相対湿度80%に調整し、各光学フィルムを(85℃:1時間)→(-20℃:1時間)→(60℃・相対湿度80%:1時間)で順次保存し、これを3回繰り返す。なお、各加速試験機間の移動は1分以内とした。その後、メタルハライドランプ式耐候性試験機(スガ試験機製 M6T)を用い、放射照度1kW/m2の光を15時間照射した。これを1サイクルとして、計3サイクルの保存加速試験を行った。
○:5枚の光学フィルムとも、0.5mm以上のひび割れ及び膜剥がれの発生がみられない
○△:5枚の光学フィルムにおいて、サイズが0.5mm以上、3mm未満のひび割れや膜剥れの総発生数が1個以上、2個以下である
△:5枚の光学フィルムにおいて、サイズが0.5mm以上、3mm未満のひび割れや膜剥れの総発生数が3個以上、5個以下である
△×:5枚の光学フィルムにおいて、サイズが0.5mm以上、3mm未満のひび割れや膜剥れの総発生数が6個以上、10個以下である
×:5枚の光学フィルムにおいて、サイズが0.5mm以上、3mm未満のひび割れや膜剥れの総発生数が11個以上、あるいはサイズが3mm以上のひび割れや膜剥れの総発生数が1個以上
〔遮熱性の評価〕
作製した光学フィルム貼合ガラス101~130を用いて、下記の夏場想定の遮熱性及び冬場想定の遮熱性を評価し、光学フィルムのサーモクロミック性を判定した。
〈測定環境〉
・測定環境:室温が28℃の環境試験室の窓枠に、光学フィルム貼合ガラスを、内側が光学フィルムとなるように配置し、日本クールビズ室内を想定した環境室を用いた。
環境試験室内の光学フィルム貼合ガラスより1m離れた位置に温度計を設置し、上記条件で1時間経過後の温度を測定し、下記の基準に従って遮熱性の評価を行った。
○:1時間経過後の温度が29℃以上、32℃以下である
○△:1時間経過後の温度が32℃以上、34℃以下である
△:1時間経過後の温度が34℃以上、36℃以下である
×:1時間経過後の温度が36℃以上であり、過酷な環境である
(冬場想定の遮熱性評価)
〈測定環境〉
・測定環境:室温が20℃の環境試験室の窓枠に、光学フィルム貼合ガラスを、内側が光学フィルムとなるように配置し、日本ウオームビズ室内を想定した環境室を用いた。
環境試験室内の光学フィルム貼合ガラスより1m離れた位置に温度計を設置し、上記条件で1時間経過後の温度を測定し、下記の基準に従って遮熱性の評価を行った。
○:1時間経過後の温度が24℃以上、26℃未満である
○△:1時間経過後の温度が22℃以上、24℃以下である
△:1時間経過後の温度が21℃以上、22℃以下である
×:多くの近赤外光が無条件で遮蔽され、1時間経過後の温度が21℃未満である
〔ヘイズの評価〕
上記作製した各光学フィルム貼合ガラスについて、ヘイズメータ-(日本電色工業社製、NDH2000)を用いて、ヘイズ(%)を測定し、下記の基準に従ってヘイズの評価を行った。
○:ヘイズが、2.0%以上、3.0%未満である
○△:ヘイズが、3.0%以上、5.0%未満である
△:5.0%以上、8.0%未満である
×:8.0%以上である
以上により得られた結果を、表3に示す。
2 透明基材
3、3A、3B 光学機能層
4 近赤外光遮蔽層
B バインダー樹脂
L 光線入射側
ML1、ML1a、ML1b 反射層積層体
ML2 ポリマー層積層体
PEN1~PENn ポリエチレンナフタレートフィルム
PMMA1~PMMAn ポリメチルメタアクリレートフィルム
T1~Tn、Ta1~Tan、Tb1~Tbn 赤外線反射層
VOS 二酸化バナジウム含有微粒子の一次粒子
VOM 二酸化バナジウム含有微粒子の二次粒子
Claims (17)
- 透明基材上に、少なくとも二酸化バナジウム含有微粒子とバインダー樹脂とを含有する光学機能層を有する光学フィルムであって、
前記光学機能層中における前記二酸化バナジウム含有微粒子の一次粒子及び二次粒子を含めた全粒子の数平均粒径が、200nm未満であることを特徴とする光学フィルム。 - 前記二酸化バナジウム含有微粒子が、水系合成法により調製された二酸化バナジウム含有微粒子であり、かつ前記バインダー樹脂が、水系バインダー樹脂であることを特徴とする請求項1に記載の光学フィルム。
- 前記水系バインダー樹脂が、ヒドロキシ基を有する繰り返し単位を50モル%以上含有するポリマーであることを特徴とする請求項2に記載の光学フィルム。
- 前記水系バインダー樹脂が、ポリビニルアルコール系樹脂又はセルロース系樹脂であることを特徴とする請求項2又は請求項3に記載の光学フィルム。
- 前記水系バインダー樹脂と混合する前の前記水系合成法により調製され二酸化バナジウム含有微粒子の表面が、前記水系バインダー樹脂と同じ又は同種の樹脂により被覆されていることを特徴とする請求項2から請求項4までのいずれか一項に記載の光学フィルム。
- 前記光学機能層に加え、700~1000nmの光波長範囲内の少なくとも一部を遮蔽する機能を有する近赤外光遮蔽層を有することを特徴とする請求項1から請求項5までのいずれか一項に記載の光学フィルム。
- 前記近赤外光遮蔽層が、第1の水溶性バインダー樹脂と第1の金属酸化物粒子を含有する高屈折率反射層と、第2の水溶性バインダー樹脂と第2の金属酸化物粒子を含有する低屈折率反射層とを交互に積層し、特定の波長の光を選択的に反射する反射層積層体であることを特徴とする請求項6に記載の光学フィルム。
- 前記光学機能層を構成する水系バインダー樹脂と、前記反射層積層体を構成する前記第1の水溶性バインダー樹脂又は前記第2の水溶性バインダー樹脂とが、同種のバインダー樹脂であることを特徴とする請求項7に記載の光学フィルム。
- 前記光学機能層中における前記二酸化バナジウム含有微粒子の一次粒子の粒子個数比率が、全粒子数の30個数%以上であることを特徴とする請求項1から請求項8までのいずれか一項に記載の光学フィルム。
- 透明基材上に、少なくとも二酸化バナジウム含有微粒子とバインダー樹脂を含有する光学機能層を形成して製造する光学フィルムの製造方法であって、
前記二酸化バナジウム含有微粒子の一次粒子及び二次粒子を含めた全粒子の数平均粒径が、200nm未満となるように調整することを特徴とする光学フィルムの製造方法。 - 前記二酸化バナジウム含有微粒子として、水系合成法により調製した二酸化バナジウム含有微粒子を用い、かつ前記バインダー樹脂が水系バインダー樹脂であることを特徴とする請求項10に記載の光学フィルムの製造方法。
- 前記二酸化バナジウム含有微粒子が、前記水系合成法により二酸化バナジウム含有微粒子を含む水系分散液として調製し、当該水系分散液は、乾燥状態を経ることなく、少なくとも前記水系バインダー樹脂を水系溶媒に溶解した水系バインダー樹脂溶液と混合することにより、水系の光学機能層形成用塗布液を調製し、当該光学機能層形成用塗布液を湿式塗布方式により、前記透明基材上に塗布、乾燥して光学フィルムを製造することを特徴とする請求項11に記載の光学フィルムの製造方法。
- 前記水系の光学機能層形成用塗布液の調製において、前記二酸化バナジウム含有微粒子を含む水系分散液が、前記水系のバインダー樹脂溶液と混合する前に、限外濾過処理が施されていることを特徴とする請求項12に記載の光学フィルムの製造方法。
- 前記二酸化バナジウム含有微粒子の表面を、前記水系バインダー樹脂と同じ又は同種の樹脂で被覆することを特徴とする請求項11から請求項13までのいずれか一項に記載の光学フィルムの製造方法。
- 前記光学機能層に加え、700~1000nmの光波長範囲内の少なくとも一部を遮蔽する機能を有する近赤外光遮蔽層を形成することを特徴とする請求項10から請求項14までのいずれか一項に記載の光学フィルムの製造方法。
- 前記近赤外光遮蔽層が、第1の水溶性バインダー樹脂と第1の金属酸化物粒子を含有する高屈折率反射層と、第2の水溶性バインダー樹脂と第2の金属酸化物粒子を含有する低屈折率反射層とを交互に積層し、特定の波長の光を選択的に反射する反射層積層体を形成することを特徴とする請求項15に記載の光学フィルムの製造方法。
- 前記光学機能層が含有する水系バインダー樹脂と、前記近赤外遮蔽層の形成に用いる第1の水溶性バインダー樹脂又は第2の水溶性バインダー樹脂を、同種のバインダー樹脂で構成し、かつ透明基材上に、前記光学機能層と前記近赤外遮蔽層を同時重層塗布して光学フィルムを製造することを特徴とする請求項16に記載の光学フィルムの製造方法。
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EP3176614A1 (en) | 2017-06-07 |
US20170131445A1 (en) | 2017-05-11 |
EP3176614A4 (en) | 2018-04-25 |
JPWO2016017604A1 (ja) | 2017-04-27 |
CN106575001A (zh) | 2017-04-19 |
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