WO2013183544A1 - Film d'écrantage vis-à-vis de l'infrarouge et corps d'écrantage vis-à-vis de l'infrarouge - Google Patents

Film d'écrantage vis-à-vis de l'infrarouge et corps d'écrantage vis-à-vis de l'infrarouge Download PDF

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Publication number
WO2013183544A1
WO2013183544A1 PCT/JP2013/065086 JP2013065086W WO2013183544A1 WO 2013183544 A1 WO2013183544 A1 WO 2013183544A1 JP 2013065086 W JP2013065086 W JP 2013065086W WO 2013183544 A1 WO2013183544 A1 WO 2013183544A1
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refractive index
index layer
layer
low refractive
high refractive
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PCT/JP2013/065086
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English (en)
Japanese (ja)
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友香子 高
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コニカミノルタ株式会社
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Priority to JP2014519959A priority Critical patent/JP6146410B2/ja
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/28—Interference filters
    • G02B5/281—Interference filters designed for the infrared light
    • G02B5/282—Interference filters designed for the infrared light reflecting for infrared and transparent for visible light, e.g. heat reflectors, laser protection

Definitions

  • the present invention relates to an infrared shielding film and an infrared shielding body.
  • infrared shielding films infrared light reflecting films
  • an infrared shielding film it has been proposed to produce a laminated film in which a high refractive index layer and a low refractive index layer are alternately laminated by a dry film forming method such as vapor deposition or sputtering. 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 infrared light.
  • the dry film forming method has problems such as high manufacturing cost, difficulty in increasing the area, and being limited to heat-resistant materials.
  • Patent Document 1 a method using a thermosetting resin
  • Patent Document 2 a method using a UV curable resin
  • an aqueous coating solution using a water-soluble polymer there are few known examples using an aqueous coating solution using a water-soluble polymer.
  • aqueous solution does not contain inorganic oxide particles (particularly metal oxide particles).
  • the high refractive index layer is formed by spin-coating an organic solvent (PGMEA; Propylene Glycol Monoethyl Ether Acetate) solution containing TiO 2 , a dispersant, and a UV curable resin, and is formed using an aqueous coating solution. Not a thing.
  • PMEA Propylene Glycol Monoethyl Ether Acetate
  • Patent Document 4 there is a water and ethanol (20:80) mixed solvent and a ZnO 2 and polyvinylpyrrolidone was spin-coated description that the formation of the high refractive index layer.
  • Polyvinyl pyrrolidone is a water-soluble polymer, but uses a mixed solvent of water and ethanol (20:80) as a solvent, and it is difficult to say that it is an aqueous coating solution.
  • sequential coating includes spin coating, bar coating, blade coating, gravure coating, etc., but when producing a multilayer film such as an infrared shielding film, productivity is low because the number of coating and drying increases.
  • simultaneous multilayer coating there is a method using curtain coating, slide bead coating or the like, and a plurality of layers can be formed at the same time, so that productivity is high.
  • the present invention comprises an infrared shielding film with reduced coating unevenness, high film thickness uniformity and excellent infrared shielding properties, an infrared shielding body provided with the infrared shielding film, and the infrared shielding film.
  • An object of the present invention is to provide a coating solution for forming a low refractive index layer or a high refractive index layer.
  • the present inventor has intensively studied in view of the above problems. As a result, it has been found that the above problem can be solved by including an amphoteric surfactant in at least one of the low refractive index layer and the high refractive index layer, and the present invention has been completed.
  • At least one or more laminates in which low refractive index layers and high refractive index layers having different refractive indexes are alternately laminated On a substrate, at least one or more laminates in which low refractive index layers and high refractive index layers having different refractive indexes are alternately laminated, An infrared shielding film in which at least one of the low refractive index layer and the high refractive index layer contains metal oxide particles, a water-soluble resin, and an amphoteric surfactant.
  • An infrared shielding body comprising the infrared shielding film according to any one of the above 1 to 6 on at least one surface of a substrate.
  • the present inventors have at least one laminated body in which low refractive index layers and high refractive index layers having different refractive indexes are alternately laminated on a base material.
  • the infrared shielding film at least one of the low refractive index layer and the high refractive index layer contains an amphoteric surfactant, so that there is little coating unevenness and an infrared shielding property with excellent film surface uniformity.
  • the present invention has been achieved.
  • amphoteric surfactant when used in at least one of the low refractive index layer and the high refractive index layer, the surfactant is adsorbed on the metal oxide particles, and the surface tension is lowered to form a simultaneous multilayer. Is difficult to mix with adjacent layers having different compositions, and the coating unevenness is considered to be improved.
  • the amphoteric surfactant is fluorine-based, it will be oriented on the surface and will be post-processed as a reflective layer (a laminate in which low refractive index layers and high refractive index layers are alternately laminated; reference numeral 13 in FIGS.
  • sulfonic acid-based surfactants have better mixing properties with the low refractive index layer and / or high refractive index layer, and the film thickness uniformity (haze) is improved.
  • coating properties other than coating unevenness (muscles, etc.) are improved, and film thickness uniformity (haze) is further improved. It has been found.
  • the unevenness of coating is reduced, the film thickness uniformity is high, the infrared shielding film excellent in infrared shielding properties, the infrared shielding body provided with the infrared shielding film, and the A coating liquid for forming a low refractive index layer or a high refractive index layer constituting an infrared shielding film is provided.
  • the infrared shielding film of this embodiment includes a base material and a laminate in which at least one low refractive index layer and high refractive index layer are alternately laminated, and the low refractive index layer and the high refractive index layer At least one of the layers includes an amphoteric surfactant. Moreover, it is preferable that the infrared shielding film of this invention has the form of the alternately laminated body by which the low refractive index layer and the high refractive index layer were laminated
  • a refractive index layer having a higher refractive index than the other is referred to as a high refractive index layer
  • a refractive index layer having a lower refractive index than the other is referred to as a low refractive index layer.
  • the terms “high refractive index layer” and “low refractive index layer” refer to a refractive index layer having a higher refractive index when comparing the refractive index difference between two adjacent layers. It means that the lower refractive index layer is a low refractive index layer.
  • high refractive index layer and “low refractive index layer” are used when the refractive index layers constituting the infrared shielding film (optical reflection film) are focused on two adjacent refractive index layers.
  • Each refractive index layer includes all forms other than those having the same refractive index.
  • FIG. 1 is a schematic cross-sectional view showing a general configuration of an infrared shielding film used in one embodiment of the present invention.
  • the infrared shielding film 1 of this embodiment is formed on the base material 11, the undercoat layer 12 formed on both surfaces of the base material 11, and the undercoat layer 12 on both surfaces of the base material 11.
  • the laminated unit 13 formed on both surfaces of the base material 11 is configured to have at least one laminated body in which low refractive index layers 14 and high refractive index layers 15 are alternately laminated. .
  • the number of stacked bodies is 4.5, and the low refractive index layer 14 is disposed on the lowermost layer and the uppermost layer on the base material side.
  • a 9-layer multi-layered product (laminated unit 13) in which five low-refractive index layers 14 and four high-refractive index layers 15 are alternately stacked is formed on both surfaces of the substrate 11, respectively. (See Examples 1-11).
  • the upper surface of the low-refractive index layer 14 of the nine-layer multilayer product (laminated unit 13) on one surface of the base material 11 for example, the surface on the indoor side opposite to the side into which sunlight L is inserted.
  • a transparent hard coat layer (HC layer) 16 is formed, and a nine-layer multilayer product (laminated unit 13) on the other surface of the substrate 11 (for example, a surface to be attached to a substrate 18 such as an automobile window).
  • a transparent adhesive layer 17 is formed on the uppermost low refractive index layer 14.
  • the infrared shielding film 1 may be attached to the inside (inside or inside the vehicle) side of the base 18 such as an automobile window or a glass window of a building (in FIG. 1, the infrared shielding film 1 is attached to the base 18 in FIG. 1). Represents the later state).
  • stacking unit 13 was formed directly on the base material 11 without forming the undercoat layer 12. FIG. Also good.
  • the hard coat layer (HC layer) 16 and the transparent adhesive layer 17 are not necessarily required, and a configuration in which these layers are not provided may be employed.
  • the transparent adhesive layer 17 may be formed on the hard coat layer (HC layer) 16.
  • a release layer (not shown) may be provided on the adhesive layer 17, and the release layer may be peeled off when being attached to the substrate 18.
  • a release layer (not shown) may be provided on the hard coat layer (HC layer) 16, and the release layer may be peeled off after being attached to the substrate 18.
  • HC layer 16 and the transparent adhesive layer 17 other layers (for example, conductive layer, antistatic layer, gas barrier layer, easy adhesion layer, antifouling layer, deodorant layer, droplet) Layer, slippery layer, abrasion resistant layer, antireflection layer, electromagnetic wave shielding layer, ultraviolet absorbing layer, infrared absorbing layer, printed layer, fluorescent light emitting layer, hologram layer, release layer, adhesive layer, adhesive layer, high of the present invention Infrared cut layer (metal layer, liquid crystal layer) other than refractive index layer and low refractive index layer, colored layer (visible light absorbing layer), one or more functional layers such as an intermediate film layer used for laminated glass) alone Or you may use it combining suitably.
  • layers for example, conductive layer, antistatic layer, gas barrier layer, easy adhesion layer, antifouling layer, deodorant layer, droplet
  • slippery layer for example, slippery layer, abrasion resistant layer, antireflection layer, electromagnetic wave shielding layer, ultraviolet absorbing layer, infrare
  • the low refractive index layer 14 is formed from an aqueous coating solution for forming a low refractive index layer, and includes first metal oxide particles (for example, colloidal silica particles) and a water-soluble resin (binder resin; for example, a polymerization degree of 1000).
  • first metal oxide particles for example, colloidal silica particles
  • water-soluble resin binder resin; for example, a polymerization degree of 1000
  • the above polyvinyl alcohol resin) and an aqueous solvent are included.
  • the high refractive index layer 15 is formed from an aqueous coating liquid for forming a high refractive index layer, and includes second metal oxide particles (for example, titanium oxide particles) and a water-soluble resin (binder resin; for example, a polymerization degree of 1000).
  • second metal oxide particles for example, titanium oxide particles
  • a water-soluble resin binder resin; for example, a polymerization degree of 1000
  • the present embodiment is characterized in that an amphoteric surfactant is contained in the coating liquid for forming at least one layer of the laminated unit 13 composed of the low refractive index layer 14 and the high refractive index layer 15.
  • the amphoteric surfactant is desirably contained in at least the low refractive index layer 14, and more preferably, the amphoteric surfactant comprises all layers of the low refractive index layer 14 and the high refractive index layer 15 (laminated unit 13). In all layers).
  • the first metal oxide particles for example, colloidal silica particles
  • the second metal oxide particles for example, titanium oxide particles
  • the low refractive index layer 14 from the aqueous coating liquid A containing a water-soluble resin (binder resin) and more preferably an amphoteric surfactant, a second metal oxide particle as a high refractive index material, and a water-soluble resin ( A high refractive index layer 15 is formed from a coating liquid B containing a binder resin) and more preferably an amphoteric surfactant.
  • the laminated unit 13 (9-layer multilayer product) can be formed.
  • the coating liquid A and the coating liquid B are simultaneously coated on one side of the substrate 11 and dried to form a laminated unit 13 (9-layered product).
  • the coating liquid A and the coating liquid B may be simultaneously applied in layers and dried to form the laminated unit 13 (9-layer multilayer product).
  • FIG. 2 is a schematic cross-sectional view showing a general configuration of an infrared shielding film used in another embodiment of the present invention.
  • the infrared shielding film 1 ′ of this embodiment includes a base material 11, an undercoat layer 12 formed on the base material 11, and a laminated unit 13 formed on the undercoat layer 12.
  • the laminated unit 13 is configured to include at least one laminated body in which the low refractive index layers 14 and the high refractive index layers 15 are alternately laminated.
  • the number of laminated bodies is 4.5, and the low refractive index layer 14 is disposed on the lowermost layer and the uppermost layer on the base material side.
  • a nine-layer multi-layer product in which five low refractive index layers 14 and four high refractive index layers 15 are alternately laminated is formed, and further, a five-layer structure is formed on the same structure. It has a configuration of a single-sided 18-layer multilayer product (lamination unit 13) in which a 9-layer multilayer product in which low refractive index layers 14 and four high refractive index layers 15 are alternately stacked is formed (see Example 12). ).
  • laminate unit 13 in which a 9-layer multilayer product in which low refractive index layers 14 and four high refractive index layers 15 are alternately stacked is formed (see Example 12).
  • the uppermost low refractive index layer 14 of the 18-layer multilayer product (laminated unit 13) on one side of the base material 11 (for example, the surface on the indoor side opposite to the side where the sunlight L is inserted).
  • a transparent hard coat layer (HC layer) 16 is formed, and a transparent adhesive layer 17 is formed on the other surface of the base material 11 (for example, a surface attached to a substrate 18 such as an automobile window).
  • the infrared shielding film 1 ′ may be attached to the interior (in the vehicle or the interior) of the base 18 such as an automobile window or a glass window of a building (also in FIG. 2, the infrared shielding film 1 ′ is attached to the base 18. Shows the state after pasting.)
  • the undercoat layer 12 is formed on one surface of the base material 11 is shown. However, even if the laminated unit 13 is formed directly on the base material 11 without forming the undercoat layer 12. Good.
  • the hard coat layer (HC layer) 16 and the transparent adhesive layer 17 are not necessarily required, and a configuration in which these layers are not provided may be employed.
  • the transparent adhesive layer 17 may be formed on the hard coat layer (HC layer) 16.
  • a release layer (not shown) may be provided on the adhesive layer 17, and the release layer may be peeled off when being attached to the substrate 18.
  • a release layer (not shown) may be provided on the hard coat layer (HC layer) 16, and the release layer may be peeled off after being attached to the substrate 18.
  • HC layer 16 and the transparent adhesive layer 17 other layers (for example, conductive layer, antistatic layer, gas barrier layer, easy adhesion layer, antifouling layer, deodorant layer, droplet) Layer, slippery layer, abrasion resistant layer, antireflection layer, electromagnetic wave shielding layer, ultraviolet absorbing layer, infrared absorbing layer, printed layer, fluorescent light emitting layer, hologram layer, release layer, adhesive layer, adhesive layer, high of the present invention Infrared cut layer (metal layer, liquid crystal layer) other than refractive index layer and low refractive index layer, colored layer (visible light absorbing layer), one or more functional layers such as an intermediate film layer used for laminated glass) alone Or you may use it combining suitably.
  • layers for example, conductive layer, antistatic layer, gas barrier layer, easy adhesion layer, antifouling layer, deodorant layer, droplet
  • slippery layer for example, slippery layer, abrasion resistant layer, antireflection layer, electromagnetic wave shielding layer, ultraviolet absorbing layer, infrare
  • the low refractive index layer 14 is formed from an aqueous coating solution for forming a low refractive index layer, and includes first metal oxide particles (for example, colloidal silica particles) and a water-soluble resin (binder resin; for example, a polymerization degree of 1000).
  • first metal oxide particles for example, colloidal silica particles
  • binder resin for example, a polymerization degree of 1000
  • the above polyvinyl alcohol resin) and an aqueous solvent are included.
  • the high refractive index layer 15 is formed from an aqueous coating liquid for forming a high refractive index layer, and includes first metal oxide particles (for example, titanium oxide particles) and a water-soluble resin (binder resin; for example, a polymerization degree of 1000).
  • the above polyvinyl alcohol resin) and an aqueous solvent are included.
  • the coating liquid for forming at least one layer of the laminated unit 13 composed of the low refractive index layer 14 and the high refractive index layer 15 contains an amphoteric surfactant.
  • the amphoteric surfactant is desirably contained in at least the low refractive index layer 14, and more preferably, the amphoteric surfactant comprises all layers of the low refractive index layer 14 and the high refractive index layer 15 (laminated unit 13). In all layers).
  • the first metal oxide particles for example, colloidal silica particles
  • the second metal oxide particles for example, titanium oxide particles
  • the low refractive index layer 14 from the aqueous coating liquid A containing a water-soluble resin (binder resin) and more preferably an amphoteric surfactant, a second metal oxide particle as a high refractive index material, and a water-soluble resin ( A high refractive index layer 15 is formed from a coating liquid B containing a binder resin) and more preferably an amphoteric surfactant.
  • the laminated unit 13 (9-layer multilayer product) can be formed.
  • the coating liquid A and the coating liquid B are simultaneously coated on one side of the substrate 11 and dried to form a nine-layer multilayered product, and the coating liquid A and the coating liquid B are simultaneously coated thereon.
  • the multilayer unit 13 single-sided 18-layer multilayer product may be formed by applying multiple layers and drying to form a 9-layer multilayer product.
  • the infrared shielding film includes at least one laminate (unit) composed of two layers having different refractive indexes, that is, a high refractive index layer and a low refractive index layer.
  • the refractive index layer and the low refractive index layer are considered as follows.
  • a component that constitutes a high refractive index layer (hereinafter referred to as a high refractive index layer component) and a component that constitutes a low refractive index layer (hereinafter referred to as a low refractive index layer component) are mixed at the interface between the two layers.
  • a layer (mixed layer) including a refractive index layer component and a low refractive index layer component may be formed.
  • a set of portions where the high refractive index layer component is 50% by mass or more is defined as a high refractive index layer
  • a set of portions where the low refractive index layer component exceeds 50% by mass is defined as a low refractive index layer.
  • the low refractive index layer contains, for example, a first metal oxide as a low refractive index component
  • the high refractive index layer contains a second metal oxide as a high refractive index component
  • the metal oxide concentration profile in the film thickness direction in these laminated films is measured, and can be regarded as a high refractive index layer or a low refractive index layer depending on the composition.
  • the metal oxide concentration profile of the laminated film is sputtered from the surface in the depth direction using a sputtering method, and is sputtered at a rate of 0.5 nm / min using the XPS surface analyzer with the outermost surface being 0 nm. It can be observed by measuring the atomic composition ratio.
  • a water-soluble resin (organic binder) concentration profile for example, the carbon concentration in the film thickness direction is measured to confirm that the mixed region exists, and the composition is further changed to EDX.
  • each layer etched by sputtering can be regarded as a high refractive index layer or a low refractive index layer.
  • the XPS surface analyzer is not particularly limited, and any model can be used, but ESCALAB-200R manufactured by VG Scientific Fix Co. was 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 difference in refractive index between the adjacent low refractive index layer and high refractive index layer is 0.1 or more.
  • it is 0.3 or more, more preferably 0.35 or more, and particularly preferably more than 0.4.
  • the refractive index difference between the high refractive index layer and the low refractive index layer in all the laminates (units) is It is preferable that it exists in the said suitable range.
  • the outermost layer and the lowermost layer a configuration outside the above preferred range may be used.
  • the preferred refractive index of the low refractive index layer is 1.10 to 1.60, more preferably 1.30 to 1.50.
  • the preferable refractive index of the high refractive index layer is 1.80 to 2.50, more preferably 1.90 to 2.20.
  • the measurement of a refractive index can be performed by the method as described in an Example.
  • 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 an 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.
  • 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 transmittance in the visible light region can be measured according to JIS R3106-1998. Specifically, the infrared transmittance and the infrared reflectance can be measured in addition to the visible light transmittance of the infrared shielding film (sample) using the spectrophotometer described in the examples.
  • the infrared shielding film of the present embodiment may have any structure including at least one laminate (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 infrared shielding film of the present invention may have a configuration in which at least one of the above units is laminated. It may be a membrane.
  • the infrared shielding film of the present invention preferably has a layer structure in which the lowermost layer adjacent to the substrate is a low refractive index layer and the outermost layer is also a low refractive index layer. Adopting a layer structure in which the low refractive index layer is located in the lowermost layer (adhesive surface with the base material) and the uppermost layer (contact surface such as the overcoat layer), the adhesion to the lowermost base material, Blowing resistance and excellent coating properties and adhesion such as hard coat layer on top layer.
  • 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 thickness of the entire infrared shielding film, one layer of the low refractive index layer and one layer of the high refractive index layer can be obtained by measuring the cut surface of the infrared shielding film with a scanning electron microscope (SEM). it can.
  • the layer (mixed layer) containing a high refractive index layer component and a low refractive index layer component when the layer (mixed layer) containing a high refractive index layer component and a low refractive index layer component is formed, it can obtain
  • the thickness of one layer of the low refractive index layer and the thickness of one layer of the high refractive index layer can be designed (set) in advance by simulation calculation so as not to differ greatly from the actual measurement value.
  • 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.
  • amphoteric surfactant examples include a carboxybetaine type, a sulfobetaine type, and an imidazolium type. Specific examples of the amphoteric surfactant preferably used in the present invention are shown below.
  • the sulfobetaine type is preferable from the viewpoint of coating unevenness, and examples of the product include LSB-R, LSB (manufactured by Kawaken Fine Chemical Co., Ltd.), and Amphitol 20HD (manufactured by Kao).
  • Fluorine-based amphoteric surfactants are also included in the present invention. However, when a hard coat layer (HC layer) or the like is applied on the reflective layer later, the coating property deteriorates if it is fluorine-based. From the viewpoint, the fluorine type is not preferable.
  • amphoteric surfactant per layer of low refractive index layer or high refractive index layer
  • the amount is preferably 0.05% by mass or more and 2% by mass or less, and more preferably 0.1% by mass or more and 1.0% by mass or less.
  • the amphoteric surfactant is obtained by cutting the infrared shielding film into a predetermined size (for example, 1 cm ⁇ 1 cm square), and setting the outermost surface of the laminated film in which the low refractive index layer and the high refractive index layer are alternately laminated to 0 nm.
  • the chemical structure can also be specified by the concentration and LC-MS (LC apparatus: Agilent 1100 manufactured by Agilent, MS apparatus: LCQ series manufactured by Thermo Fisher Scientific). Sputtering is performed in the same manner as described above, so that only two layers (one low refractive index layer and one high refractive index layer) remain on the surface of the substrate, soak in water (preferably warm water), and chemistry is performed by LC-MS. Identify the structure.
  • the surfactant is added to the low refractive index layer side, the high refractive index layer side, or both the low refractive index layer and the high refractive index layer can be specified including its chemical structure. .
  • the surfactant is added to only a part (one layer or more) of the laminated film in which the low refractive index layer and the high refractive index layer are alternately laminated, the above operation is repeated ( That is, 1 layer, 2 layers, 3 layers, 4 layers,..., N layers remain from the surface of the base material) and water (preferably warm water), and the surfactant is eluted. Whether or not is determined.
  • This also applies to nonionic surfactants and anionic surfactants, which will be described later, in the same manner as amphoteric surfactants, in any part of a laminated film in which low refractive index layers and high refractive index layers are alternately laminated.
  • the content of the nonionic surfactant or the anionic surfactant per layer of the refractive index layer or the high refractive index layer can be specified.
  • the amount of the amphoteric surfactant with respect to the total amount of the aqueous coating liquid for forming the low refractive index layer or the high refractive index layer is preferably 0.0001 to 0.20 mass%, more preferably 0.001 to 0.05 mass%. If the amount is less than 0.0001% by mass, the effect of lowering the surface tension cannot be obtained, and if it exceeds 0.20% by mass, the mixing with the coating solution is slightly deteriorated and the solution becomes slightly cloudy.
  • the amphoteric surfactant added to the present invention is highly effective in reducing the surface tension and has as high a water solubility as possible.
  • the static surface tension of each layer is preferably 45 mN / m or less from the viewpoint of applicability.
  • a static surface tension meter for example, a static surface tension meter TD manufactured by Lauda
  • the static surface tension of the sample can be measured.
  • the amount of the amphoteric surfactant added to the total amount of the coating solution should be adjusted so that the content of the amphoteric surfactant per layer of the low refractive index layer or the high refractive index layer described above after diffusion. That's fine.
  • Nonionic surfactants, anionic surfactants In the infrared shielding film of the present invention, from the viewpoint of further improving and improving coating unevenness, film thickness uniformity (haze), etc., at least one layer of the low refractive index layer and the high refractive index layer is nonionic and anionic. It is desirable to further contain at least one selected from the group consisting of surfactants. In particular, it is particularly preferable to use at least one selected from the group consisting of nonionic surfactants and anionic surfactants in the low refractive index layer to the high refractive index layer in which the amphoteric surfactant is used. It is effective.
  • nonionic (nonionic) surfactants examples include silicon surfactants, acetylene surfactants, polyoxyethylene surfactants, and the like.
  • Silicon-based surfactants are those in which the side chain or terminal of dimethylpolysiloxy acid has been polyether-modified. Has been.
  • the acetylene-based surfactant can be obtained as a commercial product, and examples thereof include Surfinol and Olphine manufactured by Nissin Chemical Industry Co., Ltd. and acetylenol manufactured by Kawaken Fine Chemical Co., Ltd.
  • polyoxyethylene surfactants include polyoxyethylene alkyl ethers and polyoxyalkylene derivatives, such as Kao-made Emulgen.
  • nonionic (nonionic) surfactants it is possible to use a combination of at least one of a silicon-based or polyoxyethylene-based surfactant and an amphoteric surfactant (particularly a sulfonic acid-based surfactant). From the viewpoint of
  • examples of the anionic surfactant that can be used in the present invention include sulfate ester salts, sulfonate salts, carboxylate salts, and phosphate ester salts.
  • sulfate ester salts include Kao-made Emar
  • sulfonates include Kao-made Neo-Perex and Pelex.
  • carboxylate include neohytenol manufactured by Daiichi Kogyo Seiyaku
  • examples of the phosphate ester salt include Prisurf manufactured by Daiichi Kogyo Seiyaku.
  • a sulfate ester salt or a sulfonate salt is preferable from the viewpoint of miscibility with the liquid.
  • nonionic surfactants and anionic surfactants are used in combination with amphoteric surfactants (especially sulfonic acid surfactants), the above-mentioned nonionic surfactants and anionic surfactants
  • the nonionic (nonionic) surfactant is preferably a silicon-based or polyoxyethylene-based surfactant, and the anionic surfactant is preferably a sulfate ester salt or sulfonic acid.
  • a combination of salts selected from salts is excellent in that a synergistic effect can be exhibited without impairing both effects (see Example 10).
  • the total amount of the nonionic surfactant or the anionic surfactant per layer of the low refractive index layer is preferably 5 to 50% by mass of the content of the amphoteric surfactant described above.
  • the combined amount of the nonionic surfactant or anionic surfactant per layer of the high refractive index layer is 5 to 50% by mass of the content of the amphoteric surfactant described above. Is preferred.
  • the surfactant used in combination with the amphoteric surfactant preferably has an HLB value of 10 to 15 from the viewpoint of surface tension reducing ability and water solubility.
  • the HLB value can be calculated using an existing calculation method (for example, an atlas method, a Griffin method, a Davis method, a Kawakami method, a method for determining from a retention time in high performance liquid chromatography, or the like).
  • the HLB value of the surfactant mixture is a weighted average of the HLB values of the respective components.
  • the addition of the nonionic surfactant or the anionic surfactant is preferably 0.0001 to 0.10% by mass with respect to the total amount of the coating solution in each layer. Further, for the amphoteric surfactant in the coating solution of each layer, the combined amount of the nonionic surfactant or the anionic surfactant is 5 to 50% by mass of the amount of the amphoteric surfactant in the coating solution. It is preferable from the viewpoint of applicability.
  • the binder resin is preferably composed of a water-soluble resin. This is because the use of a water-soluble resin makes it possible to form a refractive index layer without using an organic solvent, which is environmentally preferable.
  • a water-soluble resin polyvinyl alcohol resin, gelatin, celluloses, polysaccharide thickeners, and polymers having reactive functional groups are preferable, but the performance of the infrared shielding film (coating unevenness and film thickness uniformity (haze))
  • These water-soluble resins may be used alone or in combination of two or more.
  • the polyvinyl alcohol resin (PVA) used as the water-soluble resin of the present invention preferably has a polymerization degree (average polymerization degree) of 1500 to 7000, more preferably 2000 to 6000, and further preferably 2300 to 7000. 4500. It is because the cracking resistance of the coating film is improved when it is 1500 or more, and the coating solution is stabilized when it is 7000 or less.
  • the degree of polymerization refers to the viscosity average degree of polymerization, which is measured according to JIS-K6726 (1994). After the polyvinyl alcohol resin (PVA) is completely re-saponified and purified, From the intrinsic viscosity [ ⁇ ] (dl / g) measured in water, it is obtained by the following formula.
  • the low-polymerization degree polyvinyl alcohol-type resin whose polymerization degree is less than 1000 is excluded from calculation of the said polymerization degree.
  • the modified polyvinyl alcohol resin is included in the calculation of the degree of polymerization.
  • the low-polymerization degree polyvinyl alcohol resin having a polymerization degree of less than 1000 was excluded from the calculation of the polymerization degree.
  • a water-soluble resin (polyvinyl alcohol-type resin) used as a binder resin and a protective agent described later are used. This is to distinguish the water-soluble resin (polyvinyl alcohol-based resin) used as.
  • a water-soluble resin (polyvinyl alcohol resin) used as a binder resin and a water-soluble resin (polyvinyl alcohol resin) used as a protective agent to be described later are not distinguished from each other, and the binder resin has a function as a protective agent. It can also be considered that a water-soluble resin (polyvinyl alcohol resin) can be applied. In this case, in order to effectively express the function as a protective agent, it is desirable to contain a water-soluble resin (polyvinyl alcohol-based resin) having a low polymerization degree of less than 1000 at a predetermined ratio.
  • a water-soluble resin polyvinyl alcohol resin
  • a low degree of polymerization highly saponified polyvinyl alcohol having a degree of polymerization of 100 to 700 and a degree of saponification of 95 mol% or more in a predetermined ratio. Containing such a low degree of polymerization and highly saponified polyvinyl alcohol improves the stability of the coating solution, reduces coating unevenness, improves coating properties, and increases the film thickness uniformity (haze) of the infrared shielding film. it can.
  • the infrared shielding film of the present invention preferably contains polyvinyl alcohol resins having different saponification degrees in the high refractive index layer and the low refractive index layer.
  • polyvinyl alcohol resins having different saponification degrees in the high refractive index layer and the low refractive index layer mixing at the interface is suppressed, the infrared reflectance (infrared shielding ratio) is improved, and the haze is increased. Since it becomes low, it is preferable.
  • Either the high refractive index layer or the low refractive index layer may have a higher saponification degree, but the polyvinyl alcohol contained in the high refractive index layer has a higher saponification degree than the polyvinyl alcohol contained in the low refractive index layer. Is more preferable. This is because the metal oxide particles contained in the high refractive index layer can be protected by polyvinyl alcohol having a high degree of saponification.
  • the difference in absolute value of the saponification degree between the polyvinyl alcohol resin contained in the low refractive index layer and the polyvinyl alcohol resin contained in the high refractive index layer is preferably 3 mol% or more. More preferably, it is 5 mol% or more. If it is such a range, it is preferable in order to make the interlayer mixing state of a high refractive index layer and a low refractive index layer into a preferable level.
  • the difference in the degree of saponification between the polyvinyl alcohol contained in the low refractive index layer and the polyvinyl alcohol contained in the high refractive index layer is preferably as far as possible, but 20 mol from the viewpoint of solubility of polyvinyl alcohol in water. % Or less is preferable.
  • the degree of saponification is the ratio of hydroxyl groups to the total number of acetyloxy groups (derived from the starting vinyl acetate) and hydroxyl groups in the polyvinyl alcohol resin.
  • the polyvinyl alcohol resin for which the difference in the saponification degree in each refractive index layer is compared When each refractive index layer contains a plurality of polyvinyl alcohol resins (different saponification degrees), the content is the highest in the refractive index layer. It is a high polyvinyl alcohol resin. This is because the saponification degree of the main resin is important.
  • the term “polyvinyl alcohol resin having the highest content in the refractive index layer” it is assumed that the polyvinyl alcohol resins having a difference in saponification degree of 3 mol% or less are the same polyvinyl alcohol resin. Is calculated.
  • a low polymerization degree polyvinyl alcohol resin having a polymerization degree of less than 1000 is a different polyvinyl alcohol resin (even if there is a polyvinyl alcohol resin having a saponification difference of 3 mol% or less, the same polyvinyl alcohol resin is used. do not do).
  • polyvinyl alcohol resins having a saponification degree of 90 mol%, a saponification degree of 91 mol%, and a saponification degree of 93 mol% are respectively contained in the same layer by 10 mass%, 40 mass%, and 50 mass%.
  • These three polyvinyl alcohol resins are the same polyvinyl alcohol resin, and these three mixtures are polyvinyl alcohol resins contained in the low refractive index layer or the high refractive index layer.
  • polyvinyl alcohol-based resin having a difference in saponification degree of 3 mol% or less is sufficient if it is within 3 mol% when attention is paid to any polyvinyl alcohol resin, for example, 90, 91, 92, 94 mol. % Vinyl alcohol-based resin, when paying attention to 91 mol% vinyl alcohol-based resin, since all polyvinyl alcohol-based resins are within 3 mol%, the same polyvinyl alcohol-based resin is obtained.
  • PVA203 5% by mass
  • PVA117 25% by mass
  • PVA217 10% by mass
  • PVA220 10% by mass
  • PVA224 10% by mass
  • PVA235 20% by mass
  • PVA245 20% by mass
  • most contained A large amount of PVA is a mixture of PVA 217 to 245 (the difference in the degree of saponification of PVA 217 to 245 is within 3 mol%, so they are the same polyvinyl alcohol resin.
  • the number at the beginning of the brand represents the classification of the degree of saponification, and the next two numbers multiplied by 100 represent the standard of the degree of polymerization.
  • This mixture becomes a polyvinyl alcohol resin contained in the low refractive index layer or the high refractive index layer.
  • the saponification degree is 88 mol% (both are the first number of the brand, so the saponification degree is 2). 88 mol% (average value)). Further, the modified polyvinyl alcohol resin is included in the calculation of the saponification degree.
  • the saponification degree of the polyvinyl alcohol resin contained in the low refractive index layer and the polyvinyl alcohol resin contained in the high refractive index layer is preferably 75 mol% or more from the viewpoint of solubility in water. Further, one of the polyvinyl alcohol resin contained in the low refractive index layer and the polyvinyl alcohol resin contained in the high refractive index layer has a saponification degree of 90 mol% or more and the other is less than 90 mol%. This is preferable in order to bring the interlayer mixing state with the low refractive index layer to a preferable level.
  • one of the polyvinyl alcohol resin contained in the low refractive index layer and the polyvinyl alcohol resin contained in the high refractive index layer has a saponification degree of 95 mol% or more and the other is 90 mol% or less.
  • the saponification degree of the polyvinyl alcohol resin contained in the low refractive index layer is more preferably 90 mol% or less, and the saponification degree of the polyvinyl alcohol resin contained in the high refractive index layer is more preferably 95 mol% or more.
  • the coating liquid for forming the high refractive index layer and the low refractive index layer is excellently stabilized, and mixing of the interface between the high refractive index layer and the low refractive index layer obtained by coating the coating liquid is suppressed.
  • Infrared reflectivity infrared shielding rate
  • haze can be reduced
  • metal oxide particles contained in the high refractive index layer can be protected by polyvinyl alcohol having a high degree of saponification. is there.
  • the upper limit of the saponification degree of the polyvinyl alcohol-based resin is not particularly limited, but is usually less than 100 mol% and about 99.9 mol% or less.
  • Polyvinyl alcohol resins preferably used in the present invention include, in addition to ordinary polyvinyl alcohol obtained by hydrolyzing polyvinyl acetate (unmodified polyvinyl alcohol), cation-modified polyvinyl alcohol having a terminal cation-modified, anionic group Also included are anion-modified polyvinyl alcohol, nonionic-modified polyvinyl alcohol, modified polyvinyl alcohol modified with acrylic, and vinyl acetate resin (vinyl alcohol polymer) (for example, “Exeval” manufactured by Kuraray).
  • polyvinyl acetal resins obtained by reacting aldehyde with polyvinyl alcohol (for example, “S-LEC” manufactured by Sekisui Chemical), silanol-modified polyvinyl alcohols having a silanol group (for example, “R-1130” manufactured by Kuraray), and the like.
  • S-LEC polyvinyl alcohol
  • silanol-modified polyvinyl alcohols having a silanol group for example, “R-1130” manufactured by Kuraray
  • These polyvinyl alcohol resins can be used in combination of two or more, such as the degree of polymerization and the type of modification.
  • water-soluble means a compound that dissolves 1% by mass or more in an aqueous medium, preferably 3% by mass or more.
  • 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.
  • 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, such as the degree of polymerization and the type of modification.
  • vinyl acetate resin examples include EXVAL (trade name: manufactured by Kuraray Co., Ltd.), and Nichigo G polymer (trade name: manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) as a modified polyvinyl alcohol. Etc.
  • Silanol-modified polyvinyl alcohol is not particularly limited, and may be synthesized by a known method or may be a commercially available product.
  • the modification rate of the silanol-modified polyvinyl alcohol is usually 0.01 to 5 mol%, preferably 0.1 to 1 mol%. If the modification rate is less than 0.01 mol%, the water resistance may deteriorate, and if it exceeds 5 mol%, the solubility in water may deteriorate.
  • the silanol-modified polyvinyl alcohol preferably has a saponification degree of 95 mol% or more, more preferably 95.0 to 99.5 mol%, from the viewpoint of scratch resistance and gloss marks.
  • Silanol-modified polyvinyl alcohol has a degree of polymerization of usually 300 to 2,500, preferably 500 to 1,700.
  • the degree of polymerization is 300 or more, the strength of the coating layer is high, and when the degree of polymerization is 2,500 or less, the viscosity of the coating solution does not become excessively high and is suitable for process.
  • silanol-modified polyvinyl alcohol is contained in a coating solution for forming a refractive index layer because the coating solution is stabilized and, as a result, the coating properties of the resulting coating film are improved.
  • that the coating solution is stable means that the coating solution is stabilized over time.
  • the high refractive index layer preferably contains silanol-modified polyvinyl alcohol. This is because when silanol-modified polyvinyl alcohol is used, the haze is improved and the transparency of the film is increased.
  • silanol-modified polyvinyl alcohol is contained in the high refractive index layer, the content thereof is preferably 1 to 40% by mass with respect to 100% by mass of the total solid content of the high refractive index layer, and 2 to 30% by mass. More preferably, the content is 3 to 25% by mass.
  • the content is 1% by mass or more, setability is improved, the film is hardly disturbed and haze is improved, and when it is 40% by mass or less, the stability of the liquid is good.
  • the polyvinyl alcohol-based resin (total polyvinyl alcohol-based resin) is preferably contained in the range of 5 to 50% by mass with respect to 100% by mass of the total mass (solid content) of each refractive index layer. It is more preferably ⁇ 40% by mass, and further preferably 14-30% by mass.
  • the polyvinyl alcohol-based resin is 5.0% by mass or more, the film surface becomes uniform and the tendency to improve transparency becomes large during drying after coating the refractive index layer.
  • the content is 50% by mass or less, the relative content of the metal oxide becomes appropriate, and it becomes easy to increase the difference in refractive index between the high refractive index layer and the low refractive index layer.
  • the “film surface” means the surface of the coating film and may also be referred to as “surface”.
  • the total polyvinyl alcohol resin means the total amount of polyvinyl alcohol resin contained in each refractive index layer.
  • a low polymerization degree polyvinyl alcohol resin having a polymerization degree of less than 1000 is also included in the content of the total polyvinyl alcohol resin.
  • gelatin As gelatin that can be used as the water-soluble resin of the present invention, various types of gelatin that have been widely used in the field of silver halide photographic materials can be applied.
  • Enzyme-treated gelatin and gelatin derivatives that perform enzyme treatment in the gelatin production process that is, reagents having amino groups, imino groups, hydroxyl groups, carboxyl groups as functional groups in the molecule, and groups obtained by reaction with them It may be processed and modified.
  • 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 can 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.
  • carboxymethyl cellulose cellulose carboxymethyl ether
  • methyl cellulose hydroxymethyl cellulose
  • hydroxyethyl cellulose hydroxypropyl cellulose
  • 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 thickening polysaccharide applicable as the water-soluble resin of 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 a large difference in characteristics, and when adding metal oxide fine particles, it causes a viscosity increase that seems to be due to hydrogen bonding with the metal oxide fine particles at a low temperature. When added, it 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. Polysaccharides.
  • 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 alginates, agar, ⁇ -carrageenan, ⁇ -carrageenan
  • 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.
  • two or more thickening polysaccharides can be used in combination.
  • water-soluble resins examples include polymers having reactive functional groups, such as polyvinylpyrrolidones, polyacrylic acid, acrylic acid-acrylonitrile copolymer, potassium acrylate-acrylonitrile copolymer.
  • Acrylic resins such as polymers, vinyl acetate-acrylic acid ester copolymers, or acrylic acid-acrylic acid ester copolymers, styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, styrene-methacrylic acid- Acrylic ester copolymer, styrene- ⁇ -methylstyrene-acrylic acid copolymer, styrene- ⁇ -methylstyrene-acrylic acid-acrylic ester copolymer, or other styrene acrylic resin, styrene-sodium styrenesulfonate Copolymer, styrene-2-hydroxyethyl Acrylate copolymer, styrene-2-hydroxyethyl acrylate-potassium styrene sulfonate copolymer, styrene-maleic acid copolymer, s
  • the low refractive index layer and / or the high refractive index layer preferably contains a water-soluble resin that covers (protects) the metal oxide particles.
  • covers (protects) a metal oxide particle is demonstrated.
  • the water-soluble resin has a role for facilitating dispersion of the metal oxide particles in a solvent, and is hereinafter referred to as a “protecting agent”.
  • the protective agent is preferably a water-soluble resin having a degree of polymerization of preferably 100 to 700, more preferably 200 to 500, from the viewpoint of stabilizing the metal oxide fine particles.
  • a polyvinyl alcohol-type resin is preferable from an adsorptive viewpoint, it is still more preferable that it is a modified polyvinyl alcohol from a viewpoint of transparency and stabilization.
  • the saponification degree of polyvinyl alcohol is preferably 95% mol or more, more preferably 98 to 99.5 mol%, the adsorptivity to particles is strong and preferable.
  • the polyvinyl alcohol resin is omitted because it is described in the column of the polyvinyl alcohol resin.
  • the protective agent is preferably contained in the range of 0.1 to 30% by mass, more preferably 0.5 to 20% by mass with respect to 100% by mass of the metal oxide particles, and 1 to 10% by mass. % Is more preferable. Including the protective agent in the above range is preferable because the liquid stability of the low refractive index layer and / or the coating liquid for high refractive index is excellent and the coating property is stable.
  • the low refractive index layer and / or the high refractive index layer of the present invention may contain a curing agent. This is because the curing agent can react with the polyvinyl alcohol-based resin to form a hydrogen bond network. Moreover, when a polyvinyl alcohol-type resin is used as a binder resin, the effect can be exhibited especially.
  • the curing agent that can be used together with the polyvinyl alcohol-based resin is not particularly limited as long as it causes a curing reaction with the polyvinyl alcohol-based resin, but a group consisting of boric acid, borate, and borax. Is preferably selected.
  • boric acid, borate, and borax known materials can be used, and in general, a compound having a group capable of reacting with a polyvinyl alcohol resin or a reaction between different groups of a polyvinyl alcohol resin is promoted. And are appropriately selected and 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 ether
  • Boric acid or borate refers to oxyacids and salts thereof having a boron atom as a central atom, and specifically, orthoboric acid, diboric acid, metaboric acid, tetraboric acid, pentaboric acid, and octaborate. Boric acid and their salts.
  • Borax is a mineral represented by Na 2 B 4 O 5 (OH) 4 .8H 2 O (decahydrate of sodium tetraborate Na 2 B 4 O 7 ).
  • Boric acid having a boron atom, borate, and borax as a curing agent may be used alone or as 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 it is preferable to use boric acid and a salt thereof and / or borax in order to obtain the effects of the present invention.
  • boric acid and its salt and / or borax are used, the metal oxide particles and the OH group of the polyvinyl alcohol resin form a hydrogen bond network, and as a result, the high refractive index layer and the low refractive index layer It is considered that the interlayer mixing is suppressed and preferable infrared shielding properties 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. Can express an effect more preferably.
  • the total amount of the curing agent used is preferably 1 to 600 mg, more preferably 100 to 600 mg, per 1 g of binder resin (polyvinyl alcohol resin). From the viewpoint of effectively expressing the effects described above as the curing agent, the total amount of the curing agent described above is the optimum amount for the binder resin (polyvinyl alcohol resin).
  • the high refractive index layer and / or the low refractive index layer preferably contains metal oxide particles.
  • first metal oxide particles examples include silicon dioxide such as zinc oxide, synthetic amorphous silica, and colloidal silica, alumina, and colloidal alumina.
  • the first metal oxide particles may be used alone or in combination of two or more.
  • the low refractive index layer it is preferable to use silicon dioxide as the first metal oxide particles from the viewpoint of a low refractive index and a small particle size, and a low refractive index and a small particle size. Further, it is particularly preferable to use colloidal silica from the viewpoint of high transparency and easy handling without forming secondary particles.
  • the average particle diameter (number average) of the first metal oxide particles (preferably silicon dioxide) contained in the low refractive index layer of the present invention is preferably 1 to 100 nm, and preferably 3 to 50 nm. More preferred. This is because the film thickness of the low refractive index layer is particularly preferably about 120 to 150 nm. Therefore, the smaller the average particle diameter (number average) of the first metal oxide particles (preferably silicon dioxide) is, the smaller the one is. preferable. However, 1 nm or more is desirable from the viewpoint of technical production. From the same viewpoint, the average particle diameter (number average) of the first metal oxide particles (preferably silicon dioxide) is 100 nm or less, preferably 50 nm or less, particularly preferably 30 nm or less.
  • the average particle diameter (number average) of the metal oxide fine particles is determined by observing the particles themselves or the particles appearing on the cross section or surface of the refractive index layer with an electron microscope, and 1,000 arbitrary particles. The particle size is measured 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.
  • colloidal silica may be a synthetic product or a commercially available product.
  • examples of commercially available products include the Snowtex series (Snowtex OS, OXS, S, OS, 20, 30, 40, O, N, C, etc.) sold by Nissan Chemical Industries.
  • 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 first metal oxide particles in the low refractive index layer is preferably 20 to 75% by mass, and preferably 30 to 70% by mass with respect to 100% by mass of the total solid content of the low refractive index layer. More preferably, the content is 35 to 69% by mass, still more preferably 40 to 68% by mass. When it is 20% by mass or more, a desired refractive index is obtained, and when it is 75% by mass or less, the coatability is good, which is preferable.
  • the high refractive index layer of the present invention preferably contains second metal oxide particles.
  • the second metal oxide particles that can be contained in the high refractive index layer are preferably metal oxide particles different from the low refractive index layer from the viewpoint of making the refractive index different.
  • Examples of the metal oxide particles used in the high refractive index layer according to the present invention include titanium oxide, zirconium oxide, zinc oxide, alumina, colloidal alumina, niobium oxide, europium oxide, and zircon.
  • the second metal oxide in order to adjust the refractive index, may be used alone or in combination of two or more.
  • the high refractive index layer is made of metal oxide particles having a high refractive index such as titanium and zirconia, that is, titanium oxide particles and zirconia oxide. It is preferable to contain particles.
  • rutile (tetragonal) titanium oxide particles having a volume average particle size of 100 nm or less is easier to reduce the particle size than the anatase type, and reacts by a photocatalytic action as in the anatase type and has a high refractive index. It is more preferable from the viewpoint that the layer is not colored.
  • a plurality of types of titanium oxide particles may be mixed.
  • the first metal oxide particles contained in the low refractive index layer and the second metal oxide particles contained in the high refractive index layer are in a state of having ionicity (that is, the electric charges have the same sign). It is preferable. For example, in the case of simultaneous multilayer coating, if the ionicity is different, it reacts at the interface to form aggregates and haze deteriorates.
  • silicon dioxide anion
  • titanium oxide cation
  • titanium oxide can be anionized by treatment with a silicon-containing hydrated oxide.
  • the average particle diameter (number average) of the second metal oxide particles contained in the high refractive index layer of the present invention is preferably 3 to 100 nm, and more preferably 3 to 50 nm.
  • the second metal oxide particles contained in the high refractive index layer preferably have a volume average particle size of 50 nm or less, more preferably 1 to 45 nm, and further preferably 5 to 40 nm. preferable.
  • a volume average particle size of 50 nm or less is preferable from the viewpoint of low visible light transmittance and low haze.
  • the volume average particle 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. This is because, in polydispersion, large particle diameters are mixed and haze increases (thickness uniformity and transparency decrease).
  • the monodispersion here means that the monodispersity obtained by the following formula is 40% or less. This monodispersity is more preferably 30% or less, and particularly preferably 0.1 to 20%.
  • the average value of the particle diameters in the following monodispersity formula refers to the volume average value of the particles.
  • the content of the metal oxide particles in the high refractive index layer is preferably 15 to 85% by mass, and preferably 20 to 80% by mass with respect to 100% by mass of the total solid content of the high refractive index layer. More preferred is 30 to 75% by mass. By setting it as the said range, a thing with favorable infrared shielding property can be performed.
  • the titanium oxide particles preferably used as the second metal oxide particles of the present invention are preferably those obtained by modifying the surface of the titanium oxide sol so that it can be dispersed in water or an organic solvent.
  • Examples of the method for preparing an aqueous titanium oxide sol include the matters described in JP-A-63-17221, JP-A-7-819, JP-A-9-165218, JP-A-11-43327, and the like. Can be referred to.
  • titanium oxide particles are used as the second metal oxide particles, for example, “Titanium oxide—physical properties and applied technology” Manabu Seino, p. 255-258 (2000) Gihodo Publishing Co., Ltd.
  • the method of step (2) described in paragraph numbers 0011 to 0023 of WO2007 / 039953 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.
  • the second metal oxide particles of the present invention are preferably in the form of core-shell particles in which titanium oxide particles are coated with a silicon-containing hydrated oxide.
  • the volume average particle diameter of the titanium oxide particles as the core part is preferably more than 1 nm and less than 30 nm, more preferably 4 nm or more and less than 30 nm, and the surface of the titanium oxide particles is used as the core titanium oxide.
  • This is a structure in which a shell made of silicon-containing hydrated oxide is coated so that the coating amount of silicon-containing hydrated oxide is 3 to 30% by mass as SiO 2 with respect to 100% by mass.
  • the interaction between the silicon-containing hydrated oxide of the shell layer and the binder resin causes the high-refractive index layer and the low-refractive index layer to There is an effect that mixing between layers is suppressed.
  • the silicon-containing hydrated oxide may be any of a hydrate of an inorganic silicon compound, a hydrolyzate and / or a condensate of an organic silicon compound, and in order to obtain the effects of the present invention, a silanol group is used. More preferably. Therefore, in the present invention, the second metal oxide particles are preferably silica-modified (silanol-modified) titanium oxide particles in which the titanium oxide particles are silica-modified.
  • the coating amount of the silicon-containing hydrated compound of titanium oxide is 3 to 30% by mass, preferably 3 to 10% by mass, more preferably 3 to 8% by mass as SiO 2 with respect to 100% by mass of titanium oxide. . 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.
  • the second metal oxide particles of the present invention core-shell particles produced by a known method can be used.
  • core-shell particles produced by a known method can be used.
  • the following (i) to (iv); (i) an aqueous solution containing titanium oxide particles is heated and hydrolyzed, or an aqueous solution containing titanium oxide particles is neutralized by adding an alkali to obtain an average particle size.
  • the titanium oxide particles and the mineral acid were mixed so that the molar ratio of titanium oxide particles / mineral acid was in the range of 1 / 0.5 to 1/2.
  • the slurry is heat-treated at a temperature not lower than the boiling point of the slurry and not higher than the boiling point of the slurry, and then a silicon compound (for example, an aqueous sodium silicate solution) is added to the obtained slurry containing the titanium oxide particles.
  • a silicon compound for example, an aqueous sodium silicate solution
  • a method of neutralizing by mixing a titanium oxide sol stabilized at a pH in an acidic range obtained by peptizing a monobasic acid or a salt thereof with an alkyl silicate as a dispersion stabilizer by a conventional method (Iii) Hydrogen peroxide and metallic tin, while maintaining a molar ratio of H 2 O 2 / Sn of 2 to 3, simultaneously or alternately, such as a titanium salt (for example, titanium tetrachloride), etc.
  • the mixture is added to the aqueous solution to form a basic salt aqueous solution containing titanium, and the basic salt aqueous solution is kept at a temperature of 50 to 100 ° C.
  • a stable aqueous sol of composite colloidal particles containing silicon dioxide is produced by preparing an aqueous solution containing silicate (eg, sodium silicate aqueous solution) and removing cations present in the aqueous solution. Is done.
  • silicate eg, sodium silicate aqueous solution
  • the obtained composite aqueous sol containing titanium oxide is 100 parts by mass in terms of metal oxide TiO 2
  • the obtained composite aqueous sol containing silicon dioxide is 2 to 100 in terms of metal oxide SiO 2.
  • Titanium oxide hydrosol obtained by peptizing titanium hydroxide, organoalkoxysilane (R 1 nSiX 4-n ) as a stabilizer or a compound selected from hydrogen peroxide and aliphatic or aromatic hydroxycarboxylic acid
  • organoalkoxysilane R 1 nSiX 4-n
  • the core-shell particles produced by the method of performing desalting after adjusting the pH of the solution to 3 to less than 9 and aging (Patent No. 4550753).
  • the high refractive index layer and the low refractive index layer according to the present invention can contain various additives as necessary.
  • Fluorescent brighteners sulfuric acid, phosphoric acid, acetic acid, citric acid, sodium hydroxide, potassium hydroxide described in JP-A-62-280069, JP-A-61-228771 and JP-A-4-219266
  • pH adjusters such as potassium carbonate, antifoaming agents, lubricants such as diethylene glycol, preservatives, antistatic agents and matting agents It may contain.
  • the base material used for the infrared shielding film of the present invention is not particularly limited as long as it is formed of a transparent organic material.
  • Examples of such a substrate include methacrylic acid ester, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), polyarylate, polystyrene (PS), aromatic polyamide, polyether ether ketone, polysulfone. , A film made of a resin such as polyethersulfone, polyimide, or polyetherimide, and a resin film obtained by laminating two or more layers of the resin. From the viewpoint of cost and availability, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC) and the like are preferably used.
  • the thickness of the substrate is preferably about 5 to 200 ⁇ m, more preferably 15 to 150 ⁇ m, particularly from the viewpoint of ease of attaching an infrared shielding film to the substrate side such as a window glass, an automobile windshield and a rear window.
  • the thickness is preferably 50 to 100 ⁇ m. If the thickness of the substrate is too thick, it becomes difficult to wind up the infrared shielding film, and if it is too thin, it becomes difficult to handle (the film loses its waist).
  • Two or more substrates may be stacked, and in this case, the types of the substrates may be the same or different.
  • the base material preferably has a visible light transmittance of 85% or more shown in JIS R3106-1998, and more preferably 90% or more. It is advantageous and preferable in that the transmittance of the visible light region shown in JIS R3106-1998 when the substrate is an infrared shielding film is 50% or more when the substrate has the above transmittance.
  • the base material using the resin or the like may be an unstretched film or a stretched film.
  • a stretched film is preferable from the viewpoint of strength improvement and thermal expansion suppression.
  • the base material can be manufactured by a conventionally known general method.
  • an unstretched substrate that is substantially amorphous and not oriented can be produced by melting a resin as a material with an extruder, extruding it with an annular die or a T-die, and quenching.
  • the unstretched base material is subjected to a known method such as uniaxial stretching, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular-type simultaneous biaxial stretching, or the flow direction of the base material (vertical axis), or A stretched substrate can be produced by stretching in the direction perpendicular to the flow direction of the substrate (horizontal axis).
  • the draw ratio in this case can be appropriately selected according to the resin as the raw material of the base material, but is preferably 2 to 10 times in each of the vertical axis direction and the horizontal axis direction.
  • the base material may be subjected to relaxation treatment or offline heat treatment in terms of dimensional stability.
  • the relaxation treatment is preferably carried out in the process from the heat setting in the stretching film forming process of the polyester film (for example, PET, PEN, etc.) to the winding after the tenter is taken out in the transverse stretching. .
  • the relaxation treatment is preferably performed at a treatment temperature of 80 to 200 ° C., more preferably at a treatment temperature of 100 to 180 ° C., from the viewpoint of ease of production (for example, applicability of the subsequent coating solution). is there.
  • the relaxation rate is preferably in the range of 0.1 to 10% in both the longitudinal direction and the width direction. 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 substrate is preferably coated with the undercoat layer coating solution inline on one or both sides in the film forming process.
  • 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 to these undercoat layers.
  • the undercoat layer 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 is preferably about 0.01 to 2 g / m 2 (dry state). This is because, when the coating amount of the undercoat layer is 0.01 g / m 2 or more, the adhesion effect is sufficient, and when it is 2 g / m 2 or less, the transparency is improved.
  • a laminate composed of a high refractive index layer and a low refractive index layer is laminated on a substrate, for example, a coating for a high refractive index layer.
  • the laminate and the coating solution for the low refractive index layer are alternately applied and dried to form a laminate.
  • a coating solution for a low refractive index layer containing first metal oxide particles, a water-soluble resin (preferably, a first polyvinyl alcohol resin), an amphoteric surfactant, and an aqueous solvent
  • a coating solution for a high refractive index layer comprising: 2 metal oxide particles; a water-soluble resin that is a binder resin (preferably a second polyvinyl alcohol-based resin); an amphoteric surfactant; and an aqueous solvent; It is obtained by the manufacturing method of the infrared shielding film including the process of apply
  • a high refractive index layer and a low refractive index layer are alternately applied and dried to form a laminate.
  • Specific examples include: (1) A high refractive index layer coating solution is applied on a substrate and dried to form a high refractive index layer, and then a low refractive index layer coating solution is applied.
  • the method (4) which is a simpler manufacturing process, is preferable.
  • simultaneous multi-layer coating usually interfacial mixing is more likely to occur.
  • an amphoteric surfactant interfacial mixing is suppressed and coating unevenness and haze are improved. Therefore, the effect is more easily exhibited when manufacturing by simultaneous multilayer coating.
  • the coating liquid for the low refractive index layer or the high refractive index layer used in the present invention is not particularly limited as long as it is an aqueous coating liquid.
  • a coating liquid used for forming at least one layer of a low refractive index layer or a high refractive index layer containing metal oxide particles a water-soluble resin (binder resin), and an amphoteric surfactant.
  • the aqueous coating solution contains metal oxide particles, a water-soluble resin (binder resin), an amphoteric surfactant, and an aqueous solvent.
  • the content of the amphoteric surfactant in the aqueous coating solution is preferably 0.001 to 0.05% by mass with respect to the total amount of the aqueous coating solution.
  • amount of the amphoteric surfactant added is 0.001% by mass or more, the effect of improving the coating unevenness is good, and when it is 0.05% by mass or less, the transparency is also good.
  • metal oxide particles in addition to the metal oxide particles and the water-soluble resin (binder resin), at least one low refractive index layer or high refractive index layer (preferably at least all of the low refractive index layer) further containing an amphoteric surfactant.
  • metal oxide particles may be used as a method for preparing an aqueous coating solution for a high refractive index layer or a low refractive index layer used for forming a layer, more preferably a whole layer of a low refractive index layer or a high refractive index layer).
  • Water-soluble resins binder resins; especially polyvinyl alcohol resins, other binder resins
  • amphoteric surfactants e.g., sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate
  • the method for preparing a coating solution for a high refractive index layer or a low refractive index layer not containing an amphoteric surfactant is not particularly limited.
  • metal oxide particles metal oxide particles, water-soluble resin (binder resin; particularly polyvinyl Alcohol-based resins, other binder resins), and other additives that are added as necessary, and a method of stirring and mixing.
  • the order of addition of the respective components is not particularly limited, and the respective components may be sequentially added and mixed while stirring, or may be added and mixed at one time while stirring. If necessary, the viscosity is adjusted to an appropriate viscosity using a solvent (in particular, water or an aqueous solvent containing water).
  • the second metal oxide particles contained in the coating solution for the high refractive index layer are preferably prepared separately in a dispersion state before preparing the coating solution. That is, it is preferable to form 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. Furthermore, in the present invention, a high refractive index layer is formed using an aqueous high refractive index layer coating solution prepared by adding and dispersing titanium oxide particles coated with a silicon-containing hydrated oxide by the method described above. More preferably, it is formed. In the case of using a dispersion liquid, the dispersion liquid may be appropriately added so as to have an arbitrary concentration in each layer.
  • the solvent for preparing the coating solution for the high refractive index layer and the coating solution for the low refractive index layer is not particularly limited, but an aqueous solvent (particularly water or an aqueous solvent containing water) is preferable.
  • an aqueous solvent particularly water or an aqueous solvent containing water
  • a water-soluble resin binder resin
  • an aqueous solvent can be suitably used.
  • the aqueous solvent does not require a large-scale production facility, so that it is preferable in terms of productivity and also in terms of environmental conservation.
  • an organic solvent may be included, 10 mass% or less is preferable with respect to the coating liquid whole quantity, Most preferably, it shall be 5 mass% or less. However, it is desirable from the viewpoint that the above effect can be effectively expressed.
  • aqueous solvent examples include water; alcohols such as methanol, ethanol, 2-propanol, and 1-butanol; These aqueous solvents may be used alone or in admixture of two or more.
  • organic solvent used within a range not impairing the effects of the present invention include esters such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethyl ether, propylene glycol monomethyl ether, Examples include ethers such as ethylene glycol monoethyl ether, amides such as dimethylformamide and N-methylpyrrolidone, and ketones such as acetone, methyl ethyl ketone, acetylacetone and cyclohexanone.
  • the solvent of the coating solution is particularly preferably water or a mixed solvent of water and methanol, ethanol, or ethyl acetate, and water or an aqueous solvent containing water (particularly water and water).
  • a mixed solvent with methanol or ethanol) is more preferable, and water is most preferable.
  • the coating liquid for the low refractive index layer and the coating liquid for the high refractive index layer include a water-soluble resin such as polyvinyl alcohol and water or water from the viewpoint that the coating film can be set after coating and mixing between layers can be suppressed. It is preferable to use an aqueous coating solution containing an aqueous solvent containing a main component.
  • the concentration of the binder resin (including polyvinyl alcohol resin) in the coating solution for the high refractive index layer is preferably 0.5 to 10% by mass.
  • the concentration of the metal oxide particles in the coating solution for the high refractive index layer is preferably 1 to 50% by mass.
  • the concentration of the amphoteric surfactant in the coating solution for the high refractive index layer is 0.001 to 0.05% by mass. Is preferred.
  • the concentration of the binder resin (including polyvinyl alcohol resin) in the coating solution for the low refractive index layer is preferably 0.5 to 10% by mass.
  • the concentration of the metal oxide particles in the coating solution for the low refractive index layer is preferably 1 to 50% by mass.
  • the concentration of the amphoteric surfactant in the coating solution for the low refractive index layer is 0.001 to 0.05% by mass. Is preferred.
  • the viscosity of the coating solution for the high refractive index layer and the coating solution for the low refractive index layer at the time of simultaneous multilayer coating is in the range of 5 to 100 mPa ⁇ s when the slide bead coating method is used. Is more preferable, and the range of 10 to 50 mPa ⁇ s is more preferable.
  • the viscosity at 45 ° C. is preferably in the range of 5 to 1200 mPa ⁇ s, more preferably in the range of 25 to 500 mPa ⁇ s.
  • 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 coating solution for high refractive index layer and the coating solution for low refractive index layer are heated to 30 ° C. or more, and after coating, the temperature of the formed coating film is set to 1 to 15 ° C. It is preferably cooled once and dried at 10 ° C. or higher, and more preferably, the drying conditions are wet bulb temperature 5 to 50 ° C. and film surface temperature 10 to 50 ° C. Moreover, as a cooling method immediately after application
  • 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 conditions for the coating and drying method are not particularly limited.
  • One is coated on a substrate and dried to form a layer, and then the other coating solution is coated on this layer and dried to form a laminated film precursor (unit).
  • the number of units necessary for expressing the desired infrared shielding performance is sequentially applied and dried by the above method to obtain a laminated film precursor.
  • drying it is preferable to dry the formed coating film at 30 ° C. or higher.
  • drying is preferably performed in the range of a wet bulb temperature of 5 to 50 ° C.
  • a film surface temperature of 5 to 100 ° C. preferably 10 to 50 ° C.
  • hot air of 40 to 60 ° C. is blown for 1 to 5 seconds. dry.
  • warm air drying, infrared drying, and microwave drying are used.
  • drying in a multi-stage process is preferable to drying in a single process, and it is more preferable to set the temperature of the constant rate drying section ⁇ the temperature of the decremental drying section.
  • the temperature range of the constant rate drying section is preferably 30 to 60 ° C.
  • the temperature range of the decreasing rate drying section is preferably 50 to 100 ° C.
  • the conditions of the coating and drying method when performing simultaneous multilayer coating are as follows.
  • the coating solution for the high refractive index layer and the coating solution for the low refractive index layer are heated to 30 to 60 ° C., and the high refractive index is applied onto the substrate.
  • the temperature of the formed coating film is preferably cooled (set) preferably to 1 to 15 ° C., and then dried at 10 ° C. or higher.
  • More preferable drying conditions are a wet bulb temperature of 5 to 50 ° C. and a film surface temperature of 10 to 50 ° C. For example, it is dried by blowing warm air at 80 ° C. for 1 to 5 seconds.
  • coating it is preferable to carry out by a horizontal set system from a viewpoint of the uniformity improvement of the formed coating film.
  • the set means that the viscosity of the coating composition is increased by means such as lowering the temperature by applying cold air or the like to the coating film, the fluidity of the substances in each layer and in each layer is reduced, or the gel It means the process of converting.
  • a state in which the cold air is applied to the coating film from the surface and the finger is pressed against the surface of the coating film is defined as a set completion state.
  • the time (setting time) from the time of application until the setting is completed by applying cold air is preferably within 5 minutes, and more preferably within 2 minutes. Further, the lower limit time is not particularly limited, but it is preferable to take 45 seconds or more. If the set time is too short, mixing of the components in the layer may be insufficient. On the other hand, if the set time is too long, the interlayer diffusion of the metal oxide fine particles proceeds, and the refractive index difference between the high refractive index layer and the low refractive index layer may be insufficient. If the intermediate layer between the high-refractive index layer and the low-refractive index layer is highly elastic, the setting step may not be provided.
  • the set time can be adjusted by adjusting the concentration of water-soluble resin and metal oxide particles, or by adding other components such as gelatin, pectin, agar, carrageenan, gellan gum and other known gelling agents. Can be adjusted.
  • the temperature of the cold air is preferably 0 to 25 ° C, more preferably 5 to 10 ° C.
  • the time for which the coating film is exposed to cold air is preferably 10 to 360 seconds, more preferably 10 to 300 seconds, and further preferably 10 to 120 seconds, although it depends on the transport speed of the coating film.
  • the infrared shielding film provided by the present invention can be applied to a wide range of fields. For example, pasting to facilities exposed to sunlight for a long time, such as outdoor windows of buildings and automobile windows, films for window pasting such as infrared shielding films that give an infrared shielding effect, films for agricultural greenhouses, etc. As, it is mainly used for the purpose of improving the weather resistance.
  • the infrared shielding film according to the present invention is bonded to a substrate such as glass or a glass substitute resin directly or via an adhesive.
  • an infrared shielding body in which the infrared shielding film according to the present invention is provided on at least one surface of a substrate.
  • the substrate include, for example, glass, polycarbonate resin, polysulfone resin, acrylic resin, polyolefin resin, polyether resin, polyester resin, polyamide resin, polysulfide resin, unsaturated polyester resin, epoxy resin, melamine resin, Examples thereof include phenol resin, diallyl phthalate resin, polyimide resin, urethane resin, polyvinyl acetate resin, polyvinyl alcohol resin, styrene resin, vinyl chloride resin, metal plate, ceramic and the like.
  • the type of resin may be any of a thermoplastic resin, a thermosetting resin, and an ionizing radiation curable resin, and two or more of these may be used in combination.
  • the substrate that can be used in the present invention can be produced by a known method such as extrusion molding, calendar molding, injection molding, hollow molding, compression molding and the like.
  • the thickness of the substrate is not particularly limited, but is usually 0.1 mm to 5 cm.
  • the adhesive layer or adhesive layer that bonds the infrared shielding film and the substrate is preferably provided with the infrared shielding film on the sunlight (heat ray) incident surface side.
  • 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, a solvent system is preferable in the acrylic pressure-sensitive adhesive because the peel strength can be easily controlled. 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 Co., Ltd.
  • ethylene-vinyl acetate copolymer manufactured by DuPont, Takeda Pharmaceutical Co., Ltd., duramin
  • modified ethylene-vinyl acetate copolymer (Mersen G, manufactured by Tosoh Corporation).
  • Insulation performance and solar heat shielding performance of infrared shielding films or infrared shields are generally JIS R 3209-1998 (multi-layer glass), JIS R 3106-1998 (transmittance / reflectance / emissivity of sheet glass) ⁇ Test method for solar heat acquisition rate), JIS R 3107-1998 (Method for calculating thermal resistance of plate glass and heat transmissivity in architecture).
  • Measure solar transmittance, solar reflectance, emissivity, and visible light transmittance (1) Using a spectrophotometer with a wavelength (300 to 2500 nm), measure the spectral transmittance and spectral reflectance of various single glass plates. The emissivity is measured using a spectrophotometer having a wavelength of 5.5 to 50 ⁇ m. In addition, a predetermined value is used for the emissivity of float plate glass, polished plate glass, mold plate glass, and heat ray absorbing plate glass. (2) The solar transmittance, solar reflectance, solar absorption rate, and modified emissivity are calculated in accordance with JIS R 3106-1998 by calculating solar transmittance, solar reflectance, solar absorption rate, and vertical emissivity.
  • the corrected emissivity is obtained by multiplying the vertical emissivity by the coefficient shown in JIS R 3107-1998.
  • the heat insulation and solar heat shielding properties are calculated by (1) calculating the thermal resistance of the multi-layer glass according to JIS R 3209-1998 using the measured thickness value and the corrected emissivity. However, when the hollow layer exceeds 2 mm, the gas thermal conductance of the hollow layer is obtained according to JIS R 3107-1998.
  • the heat insulation is obtained by adding a heat transfer resistance to the heat resistance of the double-glazed glass and calculating the heat flow resistance.
  • Solar heat shielding properties are calculated by calculating the solar heat acquisition rate according to JIS R 3106-1998 and subtracting from 1.
  • Example 1 Preparation of coating liquid L1 for low refractive index layer 650 parts of a 10% by weight aqueous solution of colloidal silica (manufactured by Nissan Chemical Co., Ltd .; Snowtex OXS), 30 parts of a 4.0% by weight aqueous solution of polyvinyl alcohol (PVA103, polymerization degree 300, saponification degree 99 mol%, manufactured by Kuraray Co., Ltd.), After mixing 150 parts of a 3.0% by weight aqueous solution of acid and finishing with 1000 parts of pure water, a silicon oxide dispersion L1 was prepared.
  • PVA103 polyvinyl alcohol
  • the base-treated titanium compound was suspended in pure water so as to have a TiO 2 concentration of 20 g / L, and citric acid was added in an amount of 0.4 mol% with respect to the amount of TiO 2 with stirring, and the temperature was raised.
  • citric acid was added in an amount of 0.4 mol% with respect to the amount of TiO 2 with stirring, and the temperature was raised.
  • concentrated hydrochloric acid was added to a hydrochloric acid concentration of 30 g / L, and the mixture was stirred for 3 hours while maintaining the liquid temperature.
  • the pH and zeta potential of the obtained titanium oxide sol aqueous dispersion were measured, the pH was 1.4 and the zeta potential was +40 mV. Furthermore, when the particle size was measured by Zetasizer Nano manufactured by Malvern, the volume average particle size was 35 nm, and the monodispersity was 16%.
  • silica-modified titanium oxide particles 2 kg of pure water was added to 0.5 kg of the 10.0 mass% titanium oxide sol aqueous dispersion described above, and then heated to 90 ° C. Thereafter, 1.3 kg of a 2.0 mass% aqueous silicic acid solution was gradually added, and then the obtained dispersion was subjected to heat treatment at 175 ° C. for 18 hours in an autoclave and further concentrated to obtain a rutile structure. A sol aqueous dispersion of 20% by mass of silica-modified titanium oxide particles having a titanium oxide layer and a coating layer of SiO 2 was obtained.
  • a silica-modified titanium oxide particle dispersion H1 was prepared by mixing 20 parts of an aqueous solution (with a saponification degree of 99 mol%, manufactured by Kuraray Co., Ltd.) and 90 parts of a 3% by mass boric acid aqueous solution.
  • the confirmation of the mixed region (mixed layer) between layers and the measurement (confirmation) of the film thickness were performed by cutting the laminated film (infrared shielding film sample) and cutting the cut surface with a high refractive index material (TiO 2 ) using an XPS surface analyzer. ) And a low refractive index material (SiO 2 ) were measured, and it was confirmed that the film thicknesses of the respective layers were ensured.
  • Example 2 The infrared shielding film was the same as in Example 1 except that the amphoteric surfactant of the coating liquid L1 for the low refractive index layer was changed to Kao Amphital 20HD and 8 parts were added with a 5% aqueous solution to prepare the coating liquid L2. Sample 2 was prepared.
  • Example 3 From Example 2, except for adding amphotol 20HD made by Kao as an amphoteric surfactant to the coating solution H1 for the high refractive index layer and adding 1.5 parts of 5% aqueous solution to prepare the coating solution H3. Similarly, an infrared shielding film sample 3 was produced.
  • Example 4 Infrared shielding film in the same manner as in Example 1 except that the amphoteric surfactant of the coating liquid L1 for the low refractive index layer was changed to Kaoh's Amphital 20AB and 8 parts were added with a 5% aqueous solution to prepare the coating liquid L4. Sample 4 was prepared.
  • Example 5 The amphoteric surfactant in the coating solution L2 for the low refractive index layer of Example 3 was changed to SOFTAZOLIN LSB-R (manufactured by Kawaken Fine Chemical Co., Ltd.), and 5 nonionic surfactants (manufactured by Big Chemie; BYK-348) were used.
  • An infrared shielding film sample 5 was prepared in the same manner as in Example 3 except that 0.8 part of an aqueous solution of 0.8% was added and the coating liquid L5 was prepared.
  • An infrared shielding film sample 6 was prepared in the same manner as in Example 3 except that the coating liquid L6 was added.
  • Example 7 In Example 3, the amphoteric surfactant in the coating solution L2 for the low refractive index layer was changed from 8 parts to 0.32 part, and the amphoteric surfactant in the coating solution for the high refractive index was 0.20 with a 5% aqueous solution.
  • the infrared shielding film sample 7 was produced like Example 3 except having changed into the part and producing the coating liquid L7.
  • Example 8 The infrared shielding film sample 8 was prepared in the same manner as in Example 3 except that the amphoteric surfactant in the coating liquid L2 for the low refractive index layer was changed from 8 parts to 24 parts from Example 3 to prepare the coating liquid L8. Produced.
  • Example 9 An infrared shielding film sample 9 was prepared in the same manner as in Example 5 except that the nonionic surfactant in the coating liquid L5 for the low refractive index layer was removed from Example 5 to prepare the coating liquid L9.
  • Example 10 0.8 parts of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .; Hightenol NF0825) was further added to the coating liquid L5 for the low refractive index layer of Example 5 as a 5% aqueous solution to prepare a coating liquid L10.
  • An infrared shielding film sample 10 was produced in the same manner as in Example 5 except that.
  • Example 11 The fluorine surfactant was removed from the coating liquid L1 for the low refractive index layer of Example 1 to prepare a coating liquid L11, and 5% of Softazoline LSB-R (manufactured by Kawaken Fine Chemical) was used as the coating liquid H1 for the high refractive index layer.
  • An infrared shielding film sample 11 was produced in the same manner as in Example 1 except that 4 parts were added with an aqueous solution to produce the coating liquid H11.
  • Example 12 The configuration of the infrared shielding film sample of Example 9 was not formed by forming a multilayer coating product consisting of 9 layers on both sides of the base material (polyethylene terephthalate film), but after applying the 9-layer multilayer coating on one side of the base material, An infrared shielding film sample 12 was produced in the same manner as in Example 9 except that 9 layers were applied in a multilayer manner to obtain a multilayer coated product consisting of 18 layers on one side (see FIG. 2).
  • the infrared shielding film sample 13 was produced like Example 1 except having changed into the part and producing the coating liquid L13.
  • Example 2 The surfactant in the low refractive index layer coating solution L1 was changed from Example 1 to 8 parts of a nonionic surfactant (manufactured by Big Chemie; BYK-348) with a 5% aqueous solution except that the coating solution L14 was prepared. Similarly, an infrared shielding film sample 14 was produced.
  • a nonionic surfactant manufactured by Big Chemie; BYK-3448
  • Example 3 The same procedure as in Example 1 except that the surfactant in the low refractive index layer coating solution L1 was changed to 8 parts with a 5% aqueous solution of a cationic surfactant (manufactured by Kao Corp .; Cotamine 24P) was carried out. In the same manner as in Example 1, an infrared shielding film sample 15 was produced.
  • a cationic surfactant manufactured by Kao Corp .; Cotamine 24P
  • Example 4 An infrared shielding film sample 16 was prepared in the same manner as in Example 1 except that the surfactant in the low refractive index layer coating liquid L1 was removed from Example 1 to prepare the coating liquid L16.
  • the content of the amphoteric surfactant in each layer can be determined from the solid content of the coating solution.
  • Samples are prepared by coating the target layers (high refractive index layer and low refractive index layer) whose refractive index is measured on the base material as single layers, and according to the following method, each of the high refractive index layer and the low refractive index layer The refractive index of was determined.
  • 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 difference between the high refractive index layer and the low refractive index layer of each of Samples 1 to 16 in Examples 1 to 12 and Comparative Examples 1 to 4 was 0.3 or more. It was confirmed that.
  • haze value Measurement of film surface uniformity (haze value)
  • NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd.
  • a streak No streak is observed.
  • ⁇ A streak is observed toward the end.
  • ⁇ A streak is observed at other than the end.
  • ⁇ A streak is observed on the entire surface.
  • the irradiance of the irradiated part is 100 mW / cm 2 using an ultraviolet lamp while purging with nitrogen so that the atmosphere has an oxygen concentration of 1.0% by volume or less. Then, the coating layer was cured with an irradiation dose of 0.2 J / cm 2 to form a hard coat layer (HC layer) having a dry film thickness of 3 ⁇ m.
  • HC layer hard coat layer
  • the composition of the hard coat coating composition 1 is as follows.
  • ⁇ The hard coat coating composition 1 can be applied without any problem and a good HC layer can be formed.
  • ⁇ Coating unevenness is observed when the hard coat coating composition 1 is applied.

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

Abstract

La présente invention vise à proposer un film d'écrantage vis-à-vis de l'infrarouge pour rendre minimaux des défauts de revêtement, le film d'écrantage vis-à-vis de l'infrarouge ayant une uniformité d'épaisseur de film élevée et des propriétés d'écrantage vis-à-vis de l'infrarouge exceptionnelles. A cet effet, selon la présente invention, au moins un corps stratifié dans lequel une couche de réfraction faible et une couche de réfraction élevée ayant un taux de réfraction différent sont stratifiées est disposé sur un substrat, au moins une couche de la couche de réfraction faible et de la couche de réfraction élevée étant configurée à partir d'un film d'écrantage vis-à-vis de l'infrarouge contenant des particules d'oxyde métallique, une résine aqueuse et un agent tensio-actif ampholytique.
PCT/JP2013/065086 2012-06-06 2013-05-30 Film d'écrantage vis-à-vis de l'infrarouge et corps d'écrantage vis-à-vis de l'infrarouge WO2013183544A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015093413A1 (fr) * 2013-12-18 2015-06-25 コニカミノルタ株式会社 Film réfléchissant la lumière et réflecteur de lumière l'utilisant
JP2015125168A (ja) * 2013-12-25 2015-07-06 コニカミノルタ株式会社 誘電体多層膜フィルム
JPWO2015056752A1 (ja) * 2013-10-17 2017-03-09 コニカミノルタ株式会社 赤外遮蔽フィルムおよびこれを用いた赤外遮蔽体および熱線反射合わせガラス
WO2017043288A1 (fr) * 2015-09-09 2017-03-16 コニカミノルタ株式会社 Film de réflexion optique
JP2018076418A (ja) * 2016-11-08 2018-05-17 株式会社パイロットコーポレーション ボールペン用水性インキ組成物及びそれを内蔵したボールペン

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JP2007155782A (ja) * 2005-11-30 2007-06-21 Toyo Ink Mfg Co Ltd 着色組成物の製造方法、着色組成物及びカラーフィルタ
JP2011053710A (ja) * 2010-11-25 2011-03-17 Toyo Ink Mfg Co Ltd カラーフィルタ用着色組成物
JP2012027287A (ja) * 2010-07-24 2012-02-09 Konica Minolta Holdings Inc 近赤外反射フィルム及びそれを設けた近赤外反射体

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007155782A (ja) * 2005-11-30 2007-06-21 Toyo Ink Mfg Co Ltd 着色組成物の製造方法、着色組成物及びカラーフィルタ
JP2012027287A (ja) * 2010-07-24 2012-02-09 Konica Minolta Holdings Inc 近赤外反射フィルム及びそれを設けた近赤外反射体
JP2011053710A (ja) * 2010-11-25 2011-03-17 Toyo Ink Mfg Co Ltd カラーフィルタ用着色組成物

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2015056752A1 (ja) * 2013-10-17 2017-03-09 コニカミノルタ株式会社 赤外遮蔽フィルムおよびこれを用いた赤外遮蔽体および熱線反射合わせガラス
WO2015093413A1 (fr) * 2013-12-18 2015-06-25 コニカミノルタ株式会社 Film réfléchissant la lumière et réflecteur de lumière l'utilisant
JPWO2015093413A1 (ja) * 2013-12-18 2017-03-16 コニカミノルタ株式会社 光反射フィルムおよびこれを用いた光反射体
JP2015125168A (ja) * 2013-12-25 2015-07-06 コニカミノルタ株式会社 誘電体多層膜フィルム
WO2017043288A1 (fr) * 2015-09-09 2017-03-16 コニカミノルタ株式会社 Film de réflexion optique
JP2018076418A (ja) * 2016-11-08 2018-05-17 株式会社パイロットコーポレーション ボールペン用水性インキ組成物及びそれを内蔵したボールペン

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