WO2013099877A1 - Film de protection contre les infrarouges, méthode de fabrication d'un film de protection contre les infrarouges et protection contre les infrarouges - Google Patents

Film de protection contre les infrarouges, méthode de fabrication d'un film de protection contre les infrarouges et protection contre les infrarouges Download PDF

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Publication number
WO2013099877A1
WO2013099877A1 PCT/JP2012/083513 JP2012083513W WO2013099877A1 WO 2013099877 A1 WO2013099877 A1 WO 2013099877A1 JP 2012083513 W JP2012083513 W JP 2012083513W WO 2013099877 A1 WO2013099877 A1 WO 2013099877A1
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Prior art keywords
refractive index
layer
index layer
coating
shielding film
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PCT/JP2012/083513
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English (en)
Japanese (ja)
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聡史 久光
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コニカミノルタ株式会社
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Publication of WO2013099877A1 publication Critical patent/WO2013099877A1/fr

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Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/26—Reflecting filters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/263—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer having non-uniform thickness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/28—Interference filters
    • G02B5/285—Interference filters comprising deposited thin solid films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/418—Refractive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/71—Resistive to light or to UV

Definitions

  • the present invention relates to an infrared shielding film, an infrared shielding film, and an infrared shielding body that can increase the area at a low cost and are particularly excellent in optical properties with little color unevenness.
  • an infrared shielding film a method of producing a laminated film in which high refractive index layers and low refractive index layers are alternately laminated by a dry film forming method such as vapor deposition or sputtering has been proposed. Further, it is also known that the optical film thickness of the laminated film laminated alternately can be adjusted so as to reflect visible light instead of near infrared light.
  • the dry film forming method has a problem that the manufacturing cost is high, it is difficult to increase the area, and usable materials are limited to heat-resistant materials.
  • thermosetting resin Japanese Patent Laid-Open No. 8-110401
  • UV curable resin Japanese Patent Laid-Open No. 2004-123766
  • the interface between the high-refractive index layer and the low-refractive index layer alternately laminated using these methods is flat and clear. If the wavelength is divided into two, unnecessary reflection is likely to occur other than the wavelength set as the wavelength to be reflected. In particular, in the infrared shielding film, when unnecessary reflection occurs in the visible light region, a phenomenon occurs in which the film appears to be colored. This coloring is known to change in color tone depending on the viewing angle. For example, when a film is formed in a large area such as a window of a building, there is an inconvenience that it is recognized as color unevenness.
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to increase the area at a low cost, and to reduce color tone variation even when the viewing angle changes.
  • the present inventor has found that the object of the present invention can be achieved by adopting the following configuration.
  • the infrared shielding film of the present invention is an infrared shielding film including at least one unit obtained by laminating a high refractive index layer and a low refractive index layer on a substrate, the high refractive index layer and the above Among the low refractive index layers, at least one layer is formed with non-uniform thickness.
  • the layer with non-uniform thickness when the standard deviation of thickness is ⁇ and the average thickness is ⁇ , The variation rate (V) of the thickness represented by Formula 1 is 1% or more and 50% or less.
  • the method for producing an infrared shielding film of the present invention includes a coating step of coating a coating material for a high refractive index layer and a coating solution for a low refractive index layer on a substrate, In this method, coating is performed while varying the thickness of at least one of the coating liquid for the high refractive index layer or the coating liquid for the low refractive index layer.
  • film thickness refers to the “thickness” described in the claims.
  • an infrared shielding film including at least one unit in which a high refractive index layer and a low refractive index layer are laminated on a base material, the high refractive index layer and the low refractive index layer.
  • the refractive index layers at least one layer is formed with non-uniform thickness.
  • V thickness variation rate
  • the infrared shielding film having a standard deviation ratio of 1% or more and 50% or less can realize an infrared shielding film with little change in color tone and little color unevenness even when the viewing angle is different. It is up to the headline and the present invention.
  • the infrared shielding film targeted by the present invention is typically composed of a laminated film in which high refractive index layers and low refractive index layers are alternately laminated, and in the visible light region (wavelength 380 to 780 nm). It has high transmittance and optical characteristics with high reflectance in the near-infrared light region (780 to 2500 nm).
  • the infrared shielding film made of such a laminated film has a wavelength of light to be reflected when the angle viewed is oblique to the film, compared to the case where the angle observed is the vertical direction. Is known to shift to shorter wavelengths. This wavelength shift is caused by interference of light reflected at the interface of each layer, as will be described below.
  • the optical path length difference between the light reflected at one interface and the light reflected at another interface is cos ⁇ times ( ⁇ is the incident angle). This is because, when the light is incident obliquely (that is, when the incident angle is large), the wavelength to be strengthened is shortened.
  • the color tone hardly changes depending on the viewing angle.
  • the refractive index difference between the high refractive index layer and the low refractive index layer is relatively large and the high refractive index layer and the low refractive index layer are separated without interfacial mixing, and the interface is flat, 370 nm to 900 nm.
  • the film may appear colored with unnecessary reflection peaks in the wavelength range. In such a case, since the wavelength of the reflection peak shifts depending on the angle at which the film is viewed, it is recognized as color unevenness.
  • the interface angle varies, A film thickness variation portion is formed.
  • the angle of incident light varies due to the effects of refraction, scattering, and diffraction, thereby reflecting light of a wider wavelength range.
  • the portion where the film thickness is varied has an angle perpendicular to the film surface (that is, unevenness having a plane along the direction perpendicular to the film surface). It is preferable to change the film thickness more smoothly than to form the film.
  • the above mechanism is estimation and does not limit the scope of the present invention.
  • an infrared shielding film and an infrared shielding film can be manufactured at a low cost, with little change in color tone and little color unevenness even when the viewing angle changes.
  • Methods and infrared shields can be provided.
  • the variation rate (V) of the film thickness is preferably 1% or more and 50% or less. Further, the variation rate (V) of the film thickness is more preferably 2% or more and 10% or less. When the variation rate (V) of the film thickness is less than 1%, it is difficult to obtain the effect of the present invention (that is, the effect of preventing color unevenness). On the other hand, when the variation rate (V) of the film thickness is larger than 50%, the haze of the infrared shielding film becomes high and the transparency is lowered, which is unsuitable for practical use.
  • V fluctuation rate
  • V variation rate
  • the average value ( ⁇ ) and standard deviation ( ⁇ ) of the film thickness are multiple points in the cross-sectional image of the layer formed so that the film thickness is non-uniform (the number of measurement points that can ensure statistical reliability) , For example, 1000 locations). At this time, the measurement of the film thickness is not performed locally, but is performed over the entire surface of the film to be measured, and the measurement points are distributed so as to have substantially uniform intervals.
  • the average value ( ⁇ ) of the film thickness and the standard deviation ( ⁇ ) of the film thickness are measured along a plurality of directions in the plane of the film to be measured (that is, a layer having a non-uniform film thickness). You may go.
  • the variation rate (V) of the film thickness to be evaluated in the present invention is the value obtained for the cross-sectional image along the direction with the largest unevenness, that is, the direction with the largest standard deviation ( ⁇ ).
  • ⁇ standard deviation
  • the variation rate (V) of the film thickness in the direction with the largest deviation ( ⁇ ) is calculated.
  • the fluctuation rate (V) of the film thickness obtained in this manner is essential to be 1% or more and 50% or less, and more preferably 2% or more and 10% or less.
  • the average value ( ⁇ ) and standard deviation ( ⁇ ) of the film thickness are expressed as the fluctuation rate (V) of the film thickness in the direction in which the standard deviation ( ⁇ ) is the largest in the plane of the layer having a non-uniform film thickness.
  • the outermost layer that is, the layer farthest from the base material
  • the lowermost layer that is, the closest to the base material
  • the lowermost layer is a layer in contact with the substrate.
  • at least the outermost layer located farthest from the base material among the high refractive index layer and the low refractive index layer has a non-uniform thickness.
  • the thickness of the lowermost layer located at least closest to the base material among the high refractive index layer and the low refractive index layer is formed unevenly.
  • the outermost layer is a layer with varying thickness
  • the surface of the outermost layer faces in various directions, so that incident light can take various angles due to refraction, and the color tone hardly changes over a wide angle. (That is, color unevenness is prevented).
  • the layer whose thickness has been changed is used as the lowermost layer
  • the entire laminated film formed thereon is not flat and faces in various directions, so that the color tone hardly changes with a wide angle.
  • the infrared shielding film of this embodiment includes a base material and at least one of units composed of a high refractive index layer and a low refractive index layer.
  • the terms “high refractive index layer” and “low refractive index layer” refer to the refractive index layer having a higher refractive index when the refractive index difference between two adjacent layers is compared. This means that the lower refractive index layer is the lower refractive index layer. Therefore, the infrared shielding film of the present embodiment has all the forms other than the form in which each refractive index layer has the same refractive index when attention is paid to two adjacent refractive index layers in each refractive index layer constituting the film. Is included.
  • the refractive index difference between the adjacent high refractive index layer and the low refractive index layer may be 0.1 or more. More preferably, it is 0.3 or more, More preferably, it is 0.35 or more, Especially preferably, it is 0.4 or more.
  • the upper limit is not particularly limited but is usually 1.4 or less.
  • the refractive index difference between the high refractive index layer and the low refractive index layer in all the units is within the preferred range. Is preferred. However, regarding the outermost layer and the lowermost layer, a configuration outside the above preferred range may be used.
  • the high refractive index layer preferably has a refractive index of 1.80 to 2.50, more preferably 1.90 to 2.20.
  • the preferred refractive index of the low refractive index layer is 1.10 to 1.60, more preferably 1.30 to 1.50.
  • the reflectance in a specific wavelength region is determined by the difference in refractive index between two adjacent layers and the number of layers, and the larger the difference in refractive index, the same reflectance can be obtained with a smaller number of layers.
  • the refractive index difference and the required number of layers can be calculated using commercially available optical design software. For example, in order to obtain a near-infrared reflectance of 90% or more, if the difference in refractive index is smaller than 0.1, it is necessary to laminate 200 layers or more, which not only reduces productivity, but also at the lamination interface. Scattering increases, transparency decreases, and it becomes very difficult to manufacture without failure. From the standpoint of improving reflectivity and reducing the number of layers, there is no upper limit to the difference in refractive index, but practically about 1.4 is the limit.
  • the transmittance in the visible light region shown in JIS R3106-1998 is preferably 50% or more, preferably 75% or more, more preferably 85% or more.
  • the region having a wavelength of 900 nm to 1400 nm has a region with a reflectance exceeding 50%.
  • the infrared shielding film of the present embodiment may have any structure including at least one unit composed of a high refractive index layer and a low refractive index layer on a base material.
  • the range of the total number of layers is 100 layers or less, that is, 50 units or less, more preferably 40 layers (20 units) or less. More preferably, it is 20 layers (10 units) or less.
  • the total thickness of the infrared shielding film of this embodiment is preferably 12 ⁇ m to 315 ⁇ m, more preferably 15 ⁇ m to 200 ⁇ m, and still more preferably 20 ⁇ m to 100 ⁇ m.
  • the thickness per layer of the low refractive index layer is preferably 20 to 800 nm, and more preferably 50 to 350 nm.
  • the thickness per layer of the high refractive index layer is preferably 20 to 800 nm, and more preferably 50 to 350 nm.
  • the present invention is characterized in that the film thickness of at least one of the high refractive index layer and the low refractive index layer varies in the plane while adopting such a basic configuration. Thereby, even if the angle seen visually changes, the change of the color tone in an infrared shielding film can be reduced.
  • the resin binder used in the low refractive index layer and the high refractive index layer is not particularly limited, and examples thereof include polyvinyl alcohol.
  • polyvinyl alcohol in addition to ordinary polyvinyl alcohol obtained by hydrolyzing polyvinyl acetate, polyvinyl alcohol includes cation-modified polyvinyl alcohol, anion-modified polyvinyl alcohol having an anionic group such as a carboxyl group, and nonion having a nonionic group. Modified polyvinyl alcohols such as modified polyvinyl alcohol and silyl-modified polyvinyl alcohol having a silyl group are also included.
  • the polyvinyl alcohol obtained by hydrolyzing vinyl acetate preferably has an average degree of polymerization of 1,000 or more, particularly preferably an average degree of polymerization of 1,500 to 5,000. 1,000 is more preferably used. This is because when the polymerization degree of polyvinyl alcohol is 1,000 or more, there is no cracking of the coating film, and when it is 5,000 or less, the coating solution is stable. In addition, that the coating solution is stable means that the coating solution is stabilized over time. The same applies hereinafter.
  • the saponification degree is preferably 70 to 100%, more preferably 80 to 99.5% in view of solubility in water.
  • a low polymerization degree highly saponified polyvinyl alcohol having a polymerization degree of 100 to 500 and a saponification degree of 95 mol% or more is added to at least one of the refractive index layers. It is preferable to include. When such a low degree of polymerization and high saponified polyvinyl alcohol is contained, the stability of the coating solution is improved.
  • each refractive index layer may contain, in addition to ordinary polyvinyl alcohol obtained by hydrolyzing polyvinyl acetate, partially modified polyvinyl alcohol.
  • modified polyvinyl alcohol include cation-modified polyvinyl alcohol, anion-modified polyvinyl alcohol, nonionic-modified polyvinyl alcohol, and vinyl alcohol polymers.
  • Examples of the cation-modified polyvinyl alcohol include primary to tertiary amino groups and quaternary ammonium groups in the main chain or side chain of the polyvinyl alcohol as described in, for example, JP-A-61-110483. It is obtained by saponifying a copolymer of an ethylenically unsaturated monomer having a cationic group and vinyl acetate.
  • Examples of the ethylenically unsaturated monomer having a cationic group include trimethyl- (2-acrylamido-2,2-dimethylethyl) ammonium chloride and trimethyl- (3-acrylamido-3,3-dimethylpropyl) ammonium chloride.
  • the ratio of the cation-modified group-containing monomer in the cation-modified polyvinyl alcohol is 0.1 to 10 mol%, preferably 0.2 to 5 mol%, relative to vinyl acetate.
  • Anion-modified polyvinyl alcohol is described in, for example, polyvinyl alcohol having an anionic group as described in JP-A-1-206088, JP-A-61-237681 and JP-A-63-307979.
  • examples thereof include a copolymer of vinyl alcohol and a vinyl compound having a water-soluble group, and a modified polyvinyl alcohol having a water-soluble group as described in JP-A-7-285265.
  • Nonionic modified polyvinyl alcohol includes, for example, a polyvinyl alcohol derivative in which a polyalkylene oxide group is added to a part of vinyl alcohol as described in JP-A-7-9758, and JP-A-8-25795.
  • Block copolymer of vinyl compound having a hydrophobic group and vinyl alcohol, silanol-modified polyvinyl alcohol having silanol group, reactive group modification having reactive group such as acetoacetyl group, carbonyl group, carboxyl group Polyvinyl alcohol etc. are mentioned.
  • vinyl alcohol polymers examples include Exeval (trade name: manufactured by Kuraray Co., Ltd.) and Nichigo G polymer (trade name: manufactured by Nippon Synthetic Chemical Industry Co., Ltd.).
  • Modified polyvinyl alcohol can be used in combination of two or more, such as the degree of polymerization and the type of modification.
  • the curing agent that can be used together with polyvinyl alcohol is not particularly limited as long as it causes a curing reaction with polyvinyl alcohol, but boric acid and salts thereof are preferable.
  • boric acid and its salts known ones can be used, generally compounds having a group capable of reacting with polyvinyl alcohol or compounds that promote the reaction between different groups possessed by polyvinyl alcohol, selected as appropriate Used.
  • the curing agent include, for example, epoxy curing agents (diglycidyl ethyl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-diglycidyl cyclohexane, N, N-diglycidyl- 4-glycidyloxyaniline, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, etc.), aldehyde curing agents (formaldehyde, glioxal, etc.), active halogen curing agents (2,4-dichloro-4-hydroxy-1,3,5) , -S-triazine, etc.), active vinyl compounds (1,3,5-trisacryloyl-hexahydro-s-triazine, bisvinylsulfonylmethyl ether, etc.), aluminum alum and the like.
  • epoxy curing agents diglycidyl ethyl
  • Boric acid or a salt thereof refers to an oxygen acid having a boron atom as a central atom and a salt thereof, 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 a mixture of two or more. Particularly preferred is a mixed aqueous solution of boric acid and borax.
  • aqueous solutions of boric acid and borax can be added only in relatively dilute aqueous solutions, respectively, but by mixing them both can be made into a concentrated aqueous solution and the coating solution can be concentrated. Further, 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 and / or borax from the viewpoint of further suppressing interlayer mixing.
  • boric acid salt and / or borax the metal oxide particles and the OH group of polyvinyl alcohol, which is a water-soluble binder resin, form a hydrogen bond network, resulting in a high refractive index layer. It is considered that the interlayer mixing between the low refractive index layer and the low refractive index layer is suppressed, and preferable near-infrared shielding characteristics are achieved.
  • the film surface temperature of the coating film is once cooled to about 15 ° C., and then the set surface coating process is used to dry the film surface.
  • the set surface coating process is used to dry the film surface.
  • the total amount of the curing agent used is preferably 1 to 600 mg per gram of polyvinyl alcohol, and preferably 100 to 600 mg per gram of polyvinyl alcohol.
  • 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 of the present invention is a temperature at which the water-soluble polymer is most dissolved, and when it is dissolved in water at a concentration of 0.5% by mass, it is filtered through a G2 glass filter (maximum pores 40 to 50 ⁇ m). In this case, the mass of the insoluble matter filtered out is within 50% by mass of the added water-soluble polymer.
  • water-soluble polymers other than polyvinyl alcohol can be contained.
  • a water-soluble polymer gelatin, celluloses, thickening polysaccharides, and polymers having reactive functional groups are particularly preferable. These water-soluble polymers may be used alone or in combination of two or more.
  • 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, imino group, hydroxyl group, carboxyl group as a functional group in the molecule and a group obtained by reaction with it. You may have done. The general method for producing gelatin is well known, see for example T.W. H. James: The Theory of Photographic Process 4th. ed.
  • gelatin hardener When gelatin is used, a gelatin hardener may be added as necessary.
  • hardener known compounds that are used as hardeners for ordinary photographic emulsion layers can be used.
  • vinylsulfone compounds urea-formalin condensates, melanin-formalin condensates, epoxy Organic hardeners such as benzene compounds, aziridine compounds, active olefins and isocyanate compounds, and inorganic polyvalent metal salts such as chromium, aluminum and zirconium.
  • a water-soluble cellulose derivative can be preferably used.
  • water-soluble cellulose derivatives such as carboxymethyl cellulose (cellulose carboxymethyl ether), methyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose.
  • examples thereof include cellulose derivatives, carboxymethyl cellulose (cellulose carboxymethyl ether) and carboxyethyl cellulose which are carboxylic acid group-containing celluloses.
  • 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 many hydrogen bonding groups in the molecule, and the viscosity at low temperature and the viscosity at high temperature due to the difference in hydrogen bonding force between molecules depending on the temperature. It is a polysaccharide with significant differences. More preferably, when the metal oxide fine particles are added, the viscosity is increased due to hydrogen bonding with the metal oxide fine particles at a low temperature.
  • Polysaccharides that cause an increase of 1.0 mPa ⁇ s or more are preferable, more preferably 5.0 mPa ⁇ s or more, and even more preferably a polysaccharide having a viscosity increasing ability of 10.0 mPa ⁇ s or more.
  • thickening polysaccharides include, for example, galactan (eg, agarose, agaropectin, etc.), galactomannoglycan (eg, locust bean gum, guaran, etc.), xyloglucan (eg, tamarind gum, etc.), Glucomannoglycan (eg, salmon mannan, wood-derived glucomannan, xanthan gum, etc.), galactoglucomannoglycan (eg, softwood-derived glycan), arabinogalactoglycan (eg, soybean-derived glycan, microorganism-derived glycan, etc.), Red algae such as glucuronoglycan (eg, gellan gum), glycosaminoglycan (eg, hyaluronic acid, keratan sulfate, etc.), alginic acid and alginate, agar, ⁇ -carrageenan, ⁇ -car
  • 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.
  • water-soluble polymer examples include polymers having a reactive functional group, such as polyvinylpyrrolidones, polyacrylic acid, acrylic acid-acrylonitrile copolymer, 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 -Styrene acrylic resins such as acrylate copolymer, styrene- ⁇ -methylstyrene-acrylic acid copolymer, or styrene- ⁇ -methylstyrene-acrylic acid-acrylic acid ester copolymer, styrene-styrene sulfonic acid Sodium copolymer, styrene-2-hydroxyethyl Acrylate copolymer, styrene-2-hydroxyethyl acrylate-potassium styrene sulfonate copolymer, styrene-maleic acid copoly
  • the high refractive index layer and / or the low refractive index layer according to the present invention desirably contains metal oxide particles.
  • Metal oxide in the low refractive index layer In the low refractive index layer, it is preferable to use silicon dioxide as a metal oxide, and it is particularly preferable to use colloidal silica.
  • the average particle diameter of the metal oxide in the low refractive index layer according to the present invention is such that the particles themselves or particles appearing on the cross section or surface of the refractive index layer are observed with an electron microscope, and 1,000 arbitrary particles are formed. The diameter is 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 metal oxide particles (preferably silicon dioxide) contained in the low refractive index layer preferably have an average particle size of 3 to 100 nm.
  • the average particle size of primary particles of silicon dioxide dispersed in a primary particle state is more preferably 3 to 50 nm, and further preferably 3 to 40 nm.
  • 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.
  • 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.
  • the content of the metal oxide particles in the low refractive index layer is preferably 20 to 70% by mass and more preferably 30 to 70% by mass with respect to 100% by mass of the solid content of the low refractive index layer. More preferably, it is 40 to 60% by mass. When the content is 20% by mass or more, a desired refractive index is obtained, and when it is 70% by mass or less, the coating property is improved, which is preferable.
  • Metal oxide in the high refractive index layer for example, titanium dioxide, zirconium oxide, zinc oxide, alumina, colloidal alumina, lead titanate, red lead, yellow lead, zinc yellow, chromium oxide, oxidized oxide
  • metal oxide particles of the high refractive index layer according to the present invention for example, titanium dioxide, zirconium oxide, zinc oxide, alumina, colloidal alumina, lead titanate, red lead, yellow lead, zinc yellow, chromium oxide, oxidized oxide
  • the high refractive index layer contains high refractive index metal oxide fine particles such as titanium and zirconia, that is, titanium oxide fine particles and zirconia oxide fine particles. It is preferable to do. In that case, it is preferable to contain rutile (tetragonal) titanium oxide particles having a volume average particle diameter of 100 nm or less.
  • titanium oxide particles of the present invention those obtained by modifying the surface of an aqueous titanium oxide sol so as to be dispersible in an organic solvent or the like are preferably used.
  • any conventionally known method can be used.
  • JP-A-63-17221, JP-A-7-819, JP-A-9-165218 See the matters described in Kaihei 11-43327, JP-A-63-17221, JP-A-7-819, JP-A-9-165218, JP-A-11-43327, etc. Can do.
  • titanium oxide—physical properties and applied technology Kiyono Manabu, p. 255 to 258 (2000), Gihodo Publishing Co., Ltd., or paragraph number 0011 to WO2007 / 039953.
  • the method of the step (2) described in 0023 can be referred to.
  • titanium dioxide hydrate is treated with at least one basic compound selected from the group consisting of alkali metal hydroxides or alkaline earth metal hydroxides.
  • the titanium dioxide dispersion obtained comprises a step (2) of treating with a carboxylic acid group-containing compound and an inorganic acid.
  • JP-A-2000-053421 comprising alkyl silicate as a dispersion stabilizer, and silicon in the alkyl silicate is changed to SiO 2.
  • the titanium oxide particles may be coated with a silicon-containing hydrated oxide.
  • the coating amount of the silicon-containing hydrated compound is 3 to 30% by mass, preferably 3 to 10% by mass, more preferably 3 to 8% by mass. This is because when the coating amount is 30% by mass or less, the desired refractive index of the high refractive index layer can be obtained, and when the coating amount is 3% or more, particles can be stably formed.
  • titanium oxide particles with a silicon-containing hydrated oxide it can be produced by a conventionally known method.
  • JP-A-10-158015 Si / Al hydration to rutile titanium oxide) Oxide treatment
  • a method for producing a titanium oxide sol in which a hydrous oxide of silicon and / or aluminum is deposited on the surface of titanium oxide after peptization in the alkali region of the titanate cake JP 2000-204301 A (A sol in which a rutile-type titanium oxide is coated with a complex oxide of Si and Zr and / or Al.
  • JP 2007-246351 Oxidation obtained by peptizing hydrous titanium oxide
  • titanium to hydrosol
  • R 1 n SiX 4-n wherein R 1 as stabilizer C 1 -C 8 alkyl group, glycidyloxy substituted C 1 -C Alkyl or C 2 -C 8 alkenyl group, X is an alkoxy group, n is 1 or 2.
  • the volume average particle size of the metal oxide particles used in the present invention is preferably 30 nm or less, more preferably 1 to 30 nm, and even more preferably 5 to 15 nm.
  • a volume average particle size of 30 nm or less is preferable from the viewpoint of low haze and excellent visible light transmittance.
  • the volume average particle diameter is a volume average particle diameter of primary particles or secondary particles dispersed in a medium, and can be measured by a laser diffraction / scattering method, a dynamic light scattering method, or the like.
  • the particles themselves or the particles appearing on the cross section or surface of the refractive index layer are observed with an electron microscope, and the particle diameters of 1,000 arbitrary particles are measured, and d1, d2,. ...
  • Nk particles each having a particle size of dk the volume average particle size when the volume per particle is vi
  • the metal oxide particles used in 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 0.1 to 20%.
  • the content of the metal oxide particles in the high refractive index layer is preferably 15 to 70% by mass and more preferably 20 to 65% by mass with respect to 100% by mass of the solid content of the high refractive index layer. 30 to 60% by mass is more preferable from the viewpoint of near-infrared shielding.
  • the high refractive index layer or the low refractive index layer may further contain an emulsion resin.
  • the emulsion resin By including the emulsion resin, the flexibility of the film is increased and the workability such as sticking to glass is improved.
  • An emulsion resin is a resin in which fine resin particles having an average particle diameter of about 0.01 to 2.0 ⁇ m, for example, are dispersed in an emulsion state in an aqueous medium. Obtained by emulsion polymerization using a molecular dispersant. There is no fundamental difference in the polymer component of the resulting emulsion resin depending on the type of dispersant used.
  • the dispersant used in the polymerization of the emulsion 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 a hydroxyl group, the presence of hydroxyl groups is estimated on at least the surface of fine particles, and the emulsion resin polymerized using other dispersants has chemical and physical properties of the emulsion. Different.
  • the polymer dispersant containing a hydroxyl group is a polymer dispersant having a weight average molecular weight of 10,000 or more, and has a hydroxyl group substituted at the side chain or terminal.
  • an acrylic polymer such as sodium polyacrylate or polyacrylamide is used.
  • examples of such polymers include 2-ethylhexyl acrylate copolymer, polyethers such as polyethylene glycol and polypropylene glycol, and polyvinyl alcohol. Polyvinyl alcohol is particularly preferable.
  • Polyvinyl alcohol used as a polymer dispersant is an anion-modified polyvinyl alcohol having an anionic group such as a cation-modified polyvinyl alcohol or a carboxyl group in addition to ordinary polyvinyl alcohol obtained by hydrolysis of polyvinyl acetate. Further, modified polyvinyl alcohol such as silyl-modified polyvinyl alcohol having a silyl group is also included. Polyvinyl alcohol has a higher effect of suppressing the occurrence of cracks when forming the ink absorbing layer when the average degree of polymerization is higher, but when the average degree of polymerization is within 5000, the viscosity of the emulsion resin is not high, and at the time of production Easy to handle.
  • the average degree of polymerization is preferably 300 to 5000, more preferably 1500 to 5000, and particularly preferably 3000 to 4500.
  • the saponification degree of polyvinyl alcohol is preferably 70 to 100 mol%, more preferably 80 to 99.5 mol%.
  • Examples of the resin that is emulsion-polymerized with the above polymer dispersant include homopolymers or copolymers of ethylene monomers such as acrylic acid esters, methacrylic acid esters, vinyl compounds, and styrene compounds, and diene compounds such as butadiene and isoprene.
  • Examples of the polymer include acrylic resins, styrene-butadiene resins, and ethylene-vinyl acetate resins.
  • the high refractive index layer and the low refractive index layer according to the present invention can contain various additives as required.
  • optical brighteners sulfuric acid, phosphoric acid, acetic acid , PH adjusters such as citric acid, sodium hydroxide, potassium hydroxide and potassium carbonate, antifoaming agents, lubricants such as diethylene glycol Preservatives, anti-static agents may also contain various known additives such as a matting agent.
  • the infrared shielding film is a conductive layer, an antistatic layer, a gas barrier layer, an easy adhesion layer (adhesion layer) for the purpose of adding further functions under the base material or on the outermost surface layer opposite to the base material.
  • One or more functional layers such as an intermediate film layer may be included.
  • ⁇ Base material As the base material of the infrared shielding film, various resin films can be used, such as polyolefin films (polyethylene, polypropylene, etc.), polyester films (polyethylene terephthalate, polyethylene naphthalate, etc.), polyvinyl chloride, cellulose acetate, etc.
  • a polyester film can be used. Although it does not specifically limit as a polyester film (henceforth polyester), It is preferable that it is polyester which has the film formation property which has a dicarboxylic acid component and a diol component as main structural components.
  • the main component dicarboxylic acid component includes terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenylsulfone dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenylethanedicarboxylic acid, Examples thereof include cyclohexane dicarboxylic acid, diphenyl dicarboxylic acid, diphenyl thioether dicarboxylic acid, diphenyl ketone dicarboxylic acid, and phenylindane dicarboxylic acid.
  • diol component examples include ethylene glycol, propylene glycol, tetramethylene glycol, cyclohexanedimethanol, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyethoxyphenyl) propane, bis ( 4-Hydroxyphenyl) sulfone, bisphenol fluorene hydroxyethyl ether, diethylene glycol, neopentyl glycol, hydroquinone, cyclohexanediol and the like.
  • polyesters having these as main components from the viewpoints of transparency, mechanical strength, dimensional stability, etc., dicarboxylic acid components such as terephthalic acid, 2,6-naphthalenedicarboxylic acid, diol components such as ethylene glycol and 1 Polyester having 1,4-cyclohexanedimethanol as the main constituent is preferred.
  • polyesters mainly composed of polyethylene terephthalate and polyethylene naphthalate, copolymerized polyesters composed of terephthalic acid, 2,6-naphthalenedicarboxylic acid and ethylene glycol, and mixtures of two or more of these polyesters are mainly used. Polyester as a constituent component is preferable.
  • the thickness of the film substrate used in the present invention is preferably 10 to 300 ⁇ m, particularly 20 to 150 ⁇ m.
  • the film base material of this invention may be what overlap
  • a unit composed of a high refractive index layer and a low refractive index layer is laminated on a substrate, and specifically, a coating for a high refractive index layer. It is preferable to form a laminate by alternately applying and drying the solution and the coating solution for the low refractive index layer.
  • the coating method By using the coating method, the manufacturing cost can be reduced as compared with the dry film forming method, and an infrared shielding film having a larger area can be provided.
  • Specific examples include the following: (1) A high refractive index layer coating solution is applied onto a substrate and dried to form a high refractive index layer, and then a low refractive index layer coating solution is applied and dried.
  • the method (4) is preferable because it is a simpler manufacturing process and the interface of each layer is not easily separated. That is, it is preferable that the coating step is performed by
  • Examples of the coating method include a roll coating method, a rod bar coating method, an air knife coating method, a spray coating method, a curtain coating method, or US Pat. Nos. 2,761,419 and 2,761,791.
  • a slide bead coating method using an hopper, an extrusion coating method, or the like is preferably used.
  • the viscosity of the high refractive index layer coating solution and the low refractive index layer coating solution in the simultaneous multilayer coating is preferably in the range of 5 to 100 mPa ⁇ s, more preferably 10 to The range is 50 mPa ⁇ s.
  • the range of 5 to 1200 mPa ⁇ s is preferable, and the range of 25 to 500 mPa ⁇ s is more preferable.
  • the viscosity of the coating solution at 15 ° C. is preferably 100 mPa ⁇ s or more, more preferably 100 to 30,000 mPa ⁇ s, still more preferably 3,000 to 30,000 mPa ⁇ s, and most preferably 10 , 30,000 to 30,000 mPa ⁇ s.
  • the high refractive index layer coating solution and the low refractive index layer coating solution are heated to 30 ° C. or more, and after coating, the temperature of the formed coating film is once cooled to 1 to 15 ° C.
  • the drying is preferably performed at 10 ° C. or more, and more preferably, the drying conditions are wet bulb temperature 5 to 50 ° C. and film surface temperature 10 to 50 ° C.
  • the cooling method immediately after coating is preferably performed by the horizontal set method because the formed film thickness can be easily controlled and the film thickness can be precisely controlled.
  • the present invention is characterized in that the film thickness of at least one of the high refractive index layer and the low refractive index layer varies in the plane (that is, the film thickness is formed nonuniformly).
  • the film thickness As described above, as means for changing the film thickness, there are a method of applying a coating solution on a substrate on which irregularities are formed, a method of forming a film by pressing a mold, and the like. It is convenient and desirable to change the film thickness at the time of application.
  • the method of changing the film thickness at the time of coating by simultaneous multilayer coating is a method of changing the flow rate of the coating solution supplied to the coater, a method of changing the film transport speed, applying vibration to the coating film before drying or blowing air
  • the method of changing the flow rate of the coating solution is preferable because it can easily control the fluctuation amount of the film thickness.
  • it includes a coating step of applying a coating solution for a high refractive index layer and a coating solution for a low refractive index layer on a substrate, and in the coating step, at least one coating solution for a high refractive index layer or Preferably, the coating method is performed while varying the thickness of the coating solution for the low refractive index layer.
  • the coating solution when applying the coating solution onto the substrate, the coating solution is fed to the coater by a material supply device (ie, gear pump, tube pump, etc.), and the coating solution is applied onto the continuously conveyed substrate.
  • a material supply device ie, gear pump, tube pump, etc.
  • variations in coating amount are generated by controlling the continuous weak vibration (pulsation) generated in the pump, the degree of sealing of the flow part of the coating liquid, the substrate conveyance speed (coating speed), etc. It becomes possible to make it.
  • a pressure gauge in the vicinity of the coater (for example, between the liquid feeding tank and the coater, etc.), it is possible to measure the pressure when the coating liquid is discharged and when it is not discharged due to the pulsation of the pump. it can. Therefore, by selecting an appropriate pump and controlling the substrate conveyance speed and the pressure at which the coating liquid is discharged within an appropriate range, the flow rate fluctuations are periodically changed with respect to the average flow rate of the coating liquid on the substrate. (That is, the amount of coating liquid discharged in the coater is adjusted), and as a result, the amount of variation in the thickness of the coating film can be controlled.
  • the flow rate change due to pump pulsation is ⁇ 2% to ⁇ 50% with respect to the average flow rate (that is, 2% to 50% in absolute value). % Or less) is preferably adjusted so that periodic flow rate fluctuations occur. That is, in the coating step, the flow rate of at least one of the high refractive index layer coating solution or the low refractive index layer coating solution is periodically changed in a range of ⁇ 2% to ⁇ 50% with respect to the average flow rate. It is preferable to vary the thickness of the layer by making the above. More preferably, it is in the range of ⁇ 4% to ⁇ 15% (that is, an absolute value of 4% to 15%).
  • a technique may be adopted in which a groove is provided in the coater slit and the discharge portion of the coating liquid is made non-uniform. .
  • the solvent for preparing the high refractive index layer coating solution and the low refractive index layer coating solution is not particularly limited, but water, an organic solvent, or a mixed solvent thereof is preferable.
  • the organic solvent examples include alcohols such as methanol, ethanol, 2-propanol and 1-butanol, esters such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate, diethyl ether, Examples thereof include ethers such as propylene glycol monomethyl ether and ethylene glycol monoethyl ether, amides such as dimethylformamide and N-methylpyrrolidone, and ketones such as acetone, methyl ethyl ketone, acetylacetone and cyclohexanone. These organic solvents may be used alone or in combination of two or more. From the viewpoint of environment and simplicity of operation, the solvent of the coating solution is preferably water or a mixed solvent of water and methanol, ethanol, or ethyl acetate, and more preferably water.
  • the concentration of the resin binder in the high refractive index layer coating solution is preferably 0.5 to 10% by mass.
  • concentration of the metal oxide particles in the high refractive index layer coating solution is preferably 1 to 50% by mass.
  • the concentration of the water-soluble polymer in the low refractive index layer coating solution is preferably 1 to 10% by mass.
  • concentration of the metal oxide particles in the low refractive index layer coating solution is preferably 1 to 50% by mass.
  • the method for preparing the high refractive index layer coating solution and the low refractive index layer coating solution is not particularly limited.
  • metal oxide particles, a resin binder, and other additives that are added as necessary are added and stirred.
  • the method of mixing is mentioned.
  • the order of addition of the respective components is not particularly limited, and the respective components may be sequentially added and mixed while stirring, or may be added and mixed at one time while stirring. If necessary, it is further adjusted to an appropriate viscosity using a solvent.
  • the high refractive index layer using an aqueous high refractive index coating solution prepared by adding and dispersing rutile type titanium oxide having a volume average particle size of 100 nm or less.
  • the infrared shielding film of the present invention can be applied to a wide range of fields. Therefore, this invention relates also to the infrared shielding body by which the said infrared shielding film or the infrared shielding film obtained by said manufacturing method is provided in the at least one surface of the base material.
  • film for window pasting such as heat ray reflecting film that gives heat ray reflection effect, film for agricultural greenhouses, etc. Etc., mainly for the purpose of improving the weather resistance.
  • the infrared light shielding film according to the present invention is suitable for a member that is bonded to a substrate such as glass or a glass substitute resin directly or via an adhesive.
  • the adhesive so that the infrared shielding film is on the sunlight (heat ray) incident surface side when it is bonded to a window glass. Further, when the infrared shielding film is sandwiched between the window glass and the base material, it can be sealed from moisture and the surrounding gas, which is preferable from the viewpoint of durability. Even if the infrared shielding film of the present invention is installed outdoors or on the outside of a vehicle (for external application), it is preferable because of environmental durability.
  • an adhesive mainly composed of a photocurable or thermosetting resin can be used.
  • the adhesive preferably has durability against ultraviolet rays, and is preferably an acrylic adhesive or a silicone adhesive. Furthermore, an acrylic adhesive is preferable from the viewpoint of adhesive properties and cost. In particular, since the peel strength can be easily controlled, a solvent system is preferable among the solvent system and the emulsion system in the acrylic adhesive. When a solution polymerization polymer is used as the acrylic solvent-based pressure-sensitive adhesive, known monomers can be used as the monomer.
  • a polyvinyl butyral resin or an ethylene-vinyl acetate copolymer resin used as an intermediate layer of laminated glass may be used.
  • plastic polyvinyl butyral manufactured by Sekisui Chemical Co., Ltd., Mitsubishi Monsanto, etc.
  • ethylene-vinyl acetate copolymer manufactured by Takeda Pharmaceutical Co., Ltd., duramin
  • modified ethylene-vinyl acetate copolymer [Mersen G manufactured by Tosoh Corporation].
  • polyvinyl alcohol PVA-117, polymerization degree 1700, saponification degree 98.5 mol%, Kuraray Co., Ltd.
  • PVA-117 polyvinyl alcohol
  • a surfactant Lapisol A30, manufactured by NOF Corporation
  • a coating solution L1 for low refractive index was prepared.
  • silica-attached titanium dioxide sol After adding 2 parts by mass of pure water to 0.5 parts by mass of 15.0% by mass titanium oxide sol (SRD-W, volume average particle size 5 nm, rutile type titanium dioxide particles, manufactured by Sakai Chemical Co., Ltd.), the mixture was heated to 90 ° C. . Subsequently, 1.3 parts by mass of an aqueous silicic acid solution (sodium silicate 4 (manufactured by Nippon Chemical Co., Ltd.) diluted with pure water so that the SiO 2 concentration becomes 2.0% by mass) was gradually added. A heat treatment at 175 ° C. for 18 hours in an autoclave, followed by cooling and concentration with an ultrafiltration membrane, so that a titanium dioxide sol having a solid content of 20% by mass of SiO 2 on the surface (hereinafter, silica adhesion) Titanium dioxide sol) was obtained.
  • SRD-W volume average particle size 5 nm, rutile type titanium dioxide particles, manufactured by Sakai Chemical Co., Ltd
  • Example Preparation of sample 1
  • a slide hopper coating apparatus capable of coating 9 layers.
  • On the film (A4300 manufactured by Toyobo Co., Ltd .: double-sided easy-adhesive layer), a total of 9 layers are alternately formed so that the average film thickness during drying is 150 nm for each low refractive index layer and 150 nm for each high refractive index layer. Multi-layer coating was performed.
  • the first layer (lowermost layer), the second layer, the third layer, the fourth layer, the fifth layer, the sixth layer, the seventh layer, the eighth layer, and the ninth layer are formed from the base material side.
  • the coating solution was fed to the slide hopper coating device, and the first to ninth layers were fed by pressurizing the feeding tank.
  • a flow meter (FD-SS2A, manufactured by Keyence Corporation) provided between the liquid feed tank and the slide hopper coating device, there was almost no fluctuation in the flow rate in the liquid feed flow path from the first layer to the ninth layer. It was confirmed that there was no (less than ⁇ 1% of the average flow rate).
  • the slide hopper coating apparatus is formed by forming grooves of 0.1 mm width and 0.1 mm depth at a 0.3 mm pitch in the width direction in the coater slit of the ninth layer in order to form a film thickness nonuniformly in the ninth layer.
  • the 9-layer multilayer coating was further performed twice on the 9-layer multilayer coating product. At this time, the one having no groove of the coater slit was used, and all layers were fed by pressurizing the liquid feeding tank. In this way, Sample 1 having a total of 27 layers was produced.
  • the variation rate (V) of the film thickness of the ninth layer in which the film thickness was formed nonuniformly was 33%.
  • Example 2 Preparation of sample 2
  • On the film (A4300 manufactured by Toyobo Co., Ltd .: double-sided easy-adhesive layer), a total of 9 layers are alternately formed so that the average film thickness during drying is 150 nm for each low refractive index layer and 150 nm for each high refractive index layer.
  • Multi-layer coating was performed at a coating speed of 30 m / min.
  • the first layer (lowermost layer), the second layer, the third layer, the fourth layer, the fifth layer, the sixth layer, the seventh layer, the eighth layer, and the ninth layer are formed from the base material side.
  • the coating solution was fed to the slide hopper coating device.
  • the ninth layer was fed by a gear pump (GX-12, manufactured by Iwaki), and the first to eighth layers were fed by pressurizing the feeding tank. It was.
  • the flow rate was confirmed by a flow meter (FD-SS2A, manufactured by Keyence Corporation) provided between the liquid feed tank and the slide hopper coating device, the flow rate to the ninth layer was ⁇ 4% of the average flow rate.
  • Example 3 Polyethylene terephthalate with a thickness of 50 ⁇ m heated to 45 ° C. while keeping the coating liquid L1 for the low refractive index layer and the coating solution H1 for the high refractive index layer at 45 ° C. using a slide hopper coating apparatus capable of coating 9 layers.
  • a slide hopper coating apparatus capable of coating 9 layers.
  • On the film (A4300 manufactured by Toyobo Co., Ltd .: double-sided easy-adhesive layer), a total of 9 layers are alternately formed so that the average film thickness during drying is 150 nm for each low refractive index layer and 150 nm for each high refractive index layer. Multi-layer coating was performed at a coating speed of 30 m / min.
  • the first layer (lowermost layer), the second layer, the third layer, the fourth layer, the fifth layer, the sixth layer, the seventh layer, the eighth layer, and the ninth layer are formed from the base material side.
  • the 9th layer prepared two liquid supply tanks, one was a gear pump (GX-12, manufactured by Iwaki Co.) and the other was a liquid supply tank. The liquid was fed by pressing, and the liquid was fed in front of the flowmeter.
  • the flow meter (FD-SS2A, manufactured by Keyence Corporation) provided between the liquid feed tank and the slide hopper coating device is used to adjust the mixing amount of the gear pump liquid feed and the pressurized liquid feed while confirming the flow rate.
  • Adjustment was made so that a periodic flow rate fluctuation of about ⁇ 2% with respect to the average flow rate occurred in the liquid flow path.
  • the 1st to 8th layers perform liquid transfer by pressurizing the liquid supply tank, and there is almost no fluctuation in the flow rate in the flow path to the 1st to 8th layers (less than ⁇ 1% of the average flow rate) )It was confirmed.
  • the 9-layer multilayer coating was further performed twice on the 9-layer multilayer coating product. At this time, all the layers were fed by pressurizing the feeding tank. In this way, Sample 3 consisting of a total of 27 layers was produced. Although the evaluation of the film thickness will be described in detail later, in Sample 3, the variation rate (V) of the film thickness of the ninth layer in which the film thickness was formed nonuniformly was 1%.
  • Example 4 Polyethylene terephthalate with a thickness of 50 ⁇ m heated to 45 ° C. while keeping the coating liquid L1 for the low refractive index layer and the coating solution H1 for the high refractive index layer at 45 ° C. using a slide hopper coating apparatus capable of coating 9 layers.
  • a slide hopper coating apparatus capable of coating 9 layers.
  • On the film (A4300 manufactured by Toyobo Co., Ltd .: double-sided easy-adhesive layer), a total of 9 layers are alternately formed so that the average film thickness during drying is 150 nm for each low refractive index layer and 150 nm for each high refractive index layer. Multi-layer coating was performed at a coating speed of 30 m / min.
  • the first layer (lowermost layer), the second layer, the third layer, the fourth layer, the fifth layer, the sixth layer, the seventh layer, the eighth layer, and the ninth layer are formed from the base material side.
  • the coating solution was fed to the slide hopper coating device.
  • two solution feeding tanks were prepared, one with a tube pump (WM-520, manufactured by Iwaki), and the other with a solution feeding tank.
  • the liquid was fed by pressurization, and the liquid was fed in front of the flowmeter.
  • the flow meter (FD-SS2A, manufactured by Keyence Corporation) provided between the liquid feed tank and the slide hopper coating device is used to adjust the mixing amount of the gear pump liquid feed and the pressurized liquid feed while confirming the flow rate.
  • the flow rate was adjusted so that a periodic flow rate fluctuation of about ⁇ 15% with respect to the average flow rate occurred in the liquid feeding channel.
  • the 1st to 8th layers perform liquid transfer by pressurizing the liquid supply tank, and there is almost no fluctuation in the flow rate in the flow path to the 1st to 8th layers (less than ⁇ 1% of the average flow rate) )It was confirmed.
  • the 9-layer multilayer coating was further performed twice on the 9-layer multilayer coating product. At this time, all the layers were fed by pressurizing the feeding tank. In this way, Sample 4 having a total of 27 layers was produced. Although the evaluation of the film thickness will be described in detail later, in Sample 4, the variation rate (V) of the film thickness of the ninth layer in which the film thickness was formed nonuniformly was 8%.
  • Example 5 Polyethylene terephthalate with a thickness of 50 ⁇ m heated to 45 ° C. while keeping the coating liquid L1 for the low refractive index layer and the coating solution H1 for the high refractive index layer at 45 ° C. using a slide hopper coating apparatus capable of coating 9 layers.
  • a slide hopper coating apparatus capable of coating 9 layers.
  • On the film (A4300 manufactured by Toyobo Co., Ltd .: double-sided easy-adhesion layer), a total of 9 layers are alternately formed so that the average film thickness during drying is 150 nm for each low refractive index layer and 150 nm for each high refractive index layer. Multi-layer coating was performed at a coating speed of 30 m / min.
  • the first layer (lowermost layer), the second layer, the third layer, the fourth layer, the fifth layer, the sixth layer, the seventh layer, the eighth layer, and the ninth layer are formed from the base material side.
  • the coating solution was fed to the slide hopper coating device.
  • two solution feeding tanks were prepared, one with a tube pump (WM-520, manufactured by Iwaki), and the other with a solution feeding tank.
  • the liquid was fed by pressurization, and the liquid was fed in front of the flowmeter.
  • the flow meter (FD-SS2A, manufactured by Keyence Corporation) provided between the liquid feed tank and the slide hopper coating device is used to adjust the mixing amount of the gear pump liquid feed and the pressurized liquid feed while confirming the flow rate.
  • Adjustment was made so that a periodic flow rate fluctuation of about ⁇ 30% with respect to the average flow rate occurred in the liquid flow path.
  • the 1st to 8th layers perform liquid transfer by pressurizing the liquid supply tank, and there is almost no fluctuation in the flow rate in the flow path to the 1st to 8th layers (less than ⁇ 1% of the average flow rate) )It was confirmed.
  • the 9-layer multilayer coating was further performed twice on the 9-layer multilayer coating product. At this time, all the layers were fed by pressurizing the feeding tank. In this way, Sample 5 having a total of 27 layers was produced. Although the evaluation of the film thickness will be described in detail later, in Sample 5, the variation rate (V) of the film thickness of the ninth layer in which the film thickness was formed nonuniformly was 20%.
  • Example 6 Preparation of sample 6
  • On the film (A4300 manufactured by Toyobo Co., Ltd .: double-sided easy-adhesive layer), a total of 9 layers are alternately formed so that the average film thickness during drying is 150 nm for each low refractive index layer and 150 nm for each high refractive index layer.
  • Multi-layer coating was performed at a coating speed of 30 m / min.
  • the first layer (lowermost layer), the second layer, the third layer, the fourth layer, the fifth layer, the sixth layer, the seventh layer, the eighth layer, and the ninth layer are formed from the base material side.
  • the coating solution was fed to the slide hopper coating device.
  • two solution feeding tanks were prepared, one with a tube pump (WM-520, manufactured by Iwaki), and the other with a solution feeding tank.
  • the liquid was fed by pressurization, and the liquid was fed in front of the flowmeter.
  • the flow meter (FD-SS2A, manufactured by Keyence Corporation) provided between the liquid feed tank and the slide hopper coating device is used to adjust the mixing amount of the gear pump liquid feed and the pressurized liquid feed while confirming the flow rate.
  • the flow rate was adjusted so that a periodic flow rate fluctuation of about ⁇ 50% with respect to the average flow rate occurred in the liquid feeding channel.
  • the 1st to 8th layers perform liquid transfer by pressurizing the liquid supply tank, and there is almost no fluctuation in the flow rate in the flow path to the 1st to 8th layers (less than ⁇ 1% of the average flow rate) )It was confirmed.
  • the 9-layer multilayer coating was further performed twice on the 9-layer multilayer coating product. At this time, all the layers were fed by pressurizing the feeding tank. In this way, Sample 6 consisting of a total of 27 layers was produced. Although the evaluation of the film thickness will be described in detail later, in Sample 6, the variation rate (V) of the film thickness of the ninth layer in which the film thickness was formed nonuniformly was 41%.
  • Example 7 Polyethylene terephthalate with a thickness of 50 ⁇ m heated to 45 ° C. while keeping the coating liquid L1 for the low refractive index layer and the coating solution H1 for the high refractive index layer at 45 ° C. using a slide hopper coating apparatus capable of coating 9 layers.
  • a slide hopper coating apparatus capable of coating 9 layers.
  • On the film (A4300 manufactured by Toyobo Co., Ltd .: double-sided easy-adhesive layer), a total of 9 layers are alternately formed so that the average film thickness during drying is 150 nm for each low refractive index layer and 150 nm for each high refractive index layer. Multi-layer coating was performed at a coating speed of 30 m / min.
  • the first layer (lowermost layer), the second layer, the third layer, the fourth layer, the fifth layer, the sixth layer, the seventh layer, the eighth layer, and the ninth layer are formed from the base material side.
  • the coating solution was fed to the slide hopper coating device, and the first to ninth layers were fed by pressurizing the feeding tank. It was confirmed that there was almost no flow rate fluctuation (less than ⁇ 1%) in the liquid flow path from the first layer to the ninth layer.
  • a 9-layer multi-layer coating was performed in the same manner to form 10th to 18th layers.
  • 9-layer multilayer coating was further carried out to form the 19th to 27th layers.
  • the 27th layer was transferred to the 19th layer by a gear pump (GX-12, manufactured by Iwaki).
  • the 26th layer was fed by pressurizing the feeding tank.
  • the flow rate was confirmed by a flow meter (FD-SS2A, manufactured by Keyence Corporation) provided between the liquid feed tank and the slide hopper coating device, the flow rate to the 27th layer was ⁇ 4% of the average flow rate. It was confirmed that there was a periodic flow rate fluctuation, and there was almost no flow rate fluctuation (less than ⁇ 1% with respect to the average flow rate) in the liquid flow path from the 19th layer to the 26th layer. In this way, Sample 7 having a total of 27 layers was produced. Although the evaluation of the film thickness will be described in detail later, in Sample 7, the variation rate (V) of the film thickness of the 27th layer in which the film thickness was formed nonuniformly was 2%.
  • Example 8 Polyethylene terephthalate with a thickness of 50 ⁇ m heated to 45 ° C. while keeping the coating liquid L1 for the low refractive index layer and the coating solution H1 for the high refractive index layer at 45 ° C. using a slide hopper coating apparatus capable of coating 9 layers.
  • a slide hopper coating apparatus capable of coating 9 layers.
  • On the film (A4300 manufactured by Toyobo Co., Ltd .: double-sided easy-adhesive layer), a total of 9 layers are alternately formed so that the average film thickness during drying is 150 nm for each low refractive index layer and 150 nm for each high refractive index layer. Multi-layer coating was performed at a coating speed of 30 m / min.
  • the first layer (lowermost layer), the second layer, the third layer, the fourth layer, the fifth layer, the sixth layer, the seventh layer, the eighth layer, and the ninth layer are formed from the base material side.
  • the coating solution was fed to the slide hopper coating device.
  • the first layer was fed by a gear pump (GX-12, manufactured by Iwaki), and the second to ninth layers were fed by pressurizing the feeding tank. It was.
  • the flow rate was confirmed by a flow meter (FD-SS2A, manufactured by Keyence Corporation) provided between the liquid feed tank and the slide hopper coating device, the flow rate to the first layer was ⁇ 4% of the average flow rate.
  • the first layer (lowermost layer), the second layer, the third layer, the fourth layer, the fifth layer, the sixth layer, the seventh layer, the eighth layer, and the ninth layer are formed from the base material side.
  • the coating solution was fed to the slide hopper coating device, and the first to ninth layers were fed by pressurizing the feeding tank.
  • a flow meter FD-SS2A, manufactured by Keyence Corporation
  • the 9-layer multilayer coating was further performed twice on the 9-layer multilayer coating product.
  • Sample 9 consisting of a total of 27 layers was produced. Although the evaluation of the film thickness will be described in detail later, in Sample 9, the film thicknesses of all the layers were almost uniform, and the film thickness variation rate (V) was less than 1%.
  • the first layer (lowermost layer), the second layer, the third layer, the fourth layer, the fifth layer, the sixth layer, the seventh layer, the eighth layer, and the ninth layer are formed from the base material side.
  • the coating solution was fed to the slide hopper coating device.
  • the ninth layer was fed by a tube pump (WM-520, manufactured by Iwaki Co.), and the first to eighth layers were fed by pressurizing the feeding tank. I did it.
  • a flow meter FD-SS2A, manufactured by Keyence Corporation
  • the film thickness was measured for cross sections along a plurality of directions (at least two directions orthogonal to each other), and the measured value in the direction with the largest standard deviation ( ⁇ ) of the film thickness was adopted.
  • the film thickness fluctuation rate (V) with respect to the average value of the film thickness was obtained by the following formula 1.
  • Table 1 below shows the film thickness fluctuation rates (V) of Samples 1 to 10.
  • the back side on the measurement side of each sample is roughened, and then light absorption treatment is performed with a black spray to reflect light on the back side.
  • the refractive index was obtained from the measurement result of the reflectance in the visible light region (400 nm to 700 nm) under the condition of regular reflection at 5 degrees.
  • the refractive index of each layer depends on the material even if it is a laminated structure in which a high refractive index layer and a low refractive index layer are laminated. Therefore, it was confirmed that the refractive index difference between the high refractive index layer and the low refractive index layer was 0.1 or more.
  • haze value The haze value was measured with a haze meter (Nippon Denshoku Industries Co., Ltd., NDH2000).
  • Samples 1 to 8 corresponding to the examples of the present invention had good results with good balance between color difference and haze. That is, when the variation rate (V) of the film thickness was 1% or more and 50% or less, values suitable for practical use were obtained for both color difference and haze.
  • Samples 2, 4, 7, and 8 show that an infrared shielding film having a small color difference and haze and in which color unevenness is more difficult to recognize is obtained.
  • the variation rate (V) of the film thickness is 2% or more and 10% or less, the color difference is smaller than 10 and the haze is 1.5% or less, and the infrared shielding is more difficult to recognize color unevenness.
  • a film can be obtained.
  • the film thickness variation layer is the outermost layer (27th layer) or the lowermost layer (first layer)
  • the color difference is extremely small and the haze is also small. Therefore, it was shown that when the film thickness variation layer is the outermost layer or the lowermost layer, a good infrared shielding film with extremely small color unevenness can be obtained.
  • Samples 9 and 10 corresponding to the comparative example had values that were not suitable for practical use in either color difference or haze. That is, when the fluctuation width (V) of the film thickness is less than 1% or greater than 50%, it has been shown that good values cannot be obtained for both color difference and haze.
  • Infrared shielding bodies 1 to 8 were produced using the infrared shielding films 1 to 8 produced as described above. Infrared shielding films 1 to 8 were bonded with an acrylic adhesive on a transparent acrylic resin plate having a thickness of 5 mm and 20 cm ⁇ 20 cm to produce infrared shielding bodies 1 to 8, respectively.
  • the infrared shielding bodies 1 to 8 produced above can be easily used even though they are large in size, and excellent light reflectivity (color unevenness) can be obtained by using the infrared shielding film of the present invention. Reduction).

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

Abstract

La présente invention concerne un film de protection contre les infrarouges qui contient au moins une unité stratifiée constituée d'une couche à indice de réfraction élevé et d'une couche à indice de réfraction faible sur un matériau de base, l'épaisseur d'au moins une des couches à indice de réfraction élevé ou faible étant non uniforme, et dans la couche d'épaisseur non uniforme, la variation (V) de l'épaisseur définie par l'équation 1 est entre 1 et 50 %, σ étant l'écart type de l'épaisseur et µ étant la valeur moyenne de l'épaisseur. Selon la présente invention, on peut augmenter la surface active du film de protection contre les infrarouges à faible coût, film dans lequel les changements de couleur sont petits même si l'angle d'observation change, et les variations de couleur sont petites. V[%] = (σ/µ) x 100 ... (Equation 1)
PCT/JP2012/083513 2011-12-28 2012-12-25 Film de protection contre les infrarouges, méthode de fabrication d'un film de protection contre les infrarouges et protection contre les infrarouges WO2013099877A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000329935A (ja) * 1999-05-24 2000-11-30 Teijin Ltd プラズマディスプレイ前面板用近赤外線反射フィルムおよびそれからなる積層体
JP2002521730A (ja) * 1998-07-31 2002-07-16 ミネソタ マイニング アンド マニュファクチャリング カンパニー 二次成形性多層光学フィルムおよび成形方法
JP2005059331A (ja) * 2003-08-11 2005-03-10 Teijin Ltd 二軸延伸多層積層フィルム、装飾用糸および装飾用粉末
WO2005040868A1 (fr) * 2003-10-27 2005-05-06 Teijin Dupont Films Japan Limited Film de protection contre le rayonnement proche infrarouge
JP2006126315A (ja) * 2004-10-27 2006-05-18 Toray Ind Inc 光学フィルター

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002521730A (ja) * 1998-07-31 2002-07-16 ミネソタ マイニング アンド マニュファクチャリング カンパニー 二次成形性多層光学フィルムおよび成形方法
JP2000329935A (ja) * 1999-05-24 2000-11-30 Teijin Ltd プラズマディスプレイ前面板用近赤外線反射フィルムおよびそれからなる積層体
JP2005059331A (ja) * 2003-08-11 2005-03-10 Teijin Ltd 二軸延伸多層積層フィルム、装飾用糸および装飾用粉末
WO2005040868A1 (fr) * 2003-10-27 2005-05-06 Teijin Dupont Films Japan Limited Film de protection contre le rayonnement proche infrarouge
JP2006126315A (ja) * 2004-10-27 2006-05-18 Toray Ind Inc 光学フィルター

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