JP2016118632A - Method for manufacturing optical control film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing an optical control film capable of improving durability.SOLUTION: A method for manufacturing an optical control film containing at least one unit in which high refractive index layers and low refractive index layers are alternately laminated on a substrate includes forming a high refractive index layer (A) or a low refractive index layer (A') which is closest to the substrate using a coating liquid containing a resin, metal oxide particles and a hydrophilic organic solvent having a concentration of 0.1-8 mass%.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing an optical control film.

  In recent years, as part of energy conservation measures, from the viewpoint of reducing the load on cooling equipment, there has been an increasing demand for a near-infrared shielding film that can be attached to a window glass of a building or vehicle to shield the transmission of solar heat rays. Yes.

  As a method for forming a near-infrared shielding film, a laminate unit composed of a structure in which a high refractive index layer and a low refractive index layer are alternately laminated is used as a dry film forming method such as a vapor deposition method or a sputtering method. There has been proposed a method of forming the film by using. However, in the dry film forming method, the vacuum apparatus used for the formation becomes large, the manufacturing cost increases, the enlargement of the area is difficult, and the applicable base material is limited to a heat resistant material. I have a problem.

  In recent years, in place of the dry film forming method having the above-mentioned problems, a method for forming a near infrared shielding film using a wet coating method has been actively studied.

  As a technique of the wet coating method, for example, Patent Document 1 discloses metal oxide particles in which titanium oxide particles are coated with a silicon-containing hydrated oxide, water-soluble polymer and water or water and a small amount of an organic solvent. Are mixed to prepare a high refractive index layer coating liquid and a low refractive index layer coating liquid, and these coating liquids are simultaneously coated and dried to form a high refractive index layer and a low refractive index layer. A method of forming a near infrared shielding film is disclosed.

International Publication No. 2013/054912

  The infrared shielding film obtained by the manufacturing method disclosed in Patent Document 1 exhibits high visible light transmittance and infrared reflectivity, and is excellent in excellent durability. However, in view of an increase in load on cooling facilities due to recent warming and a rise in utility costs, further improvements in durability are required. Moreover, the further improvement of the high visible-light transmittance and infrared reflectivity of an infrared shielding film is also calculated | required.

  Therefore, this invention is made | formed in view of the said situation, and it aims at providing the manufacturing method of the optical control film which can improve durability.

  Another object of the present invention is to provide a method for producing an optical control film capable of improving visible light transmittance and infrared reflectivity.

  As a result of intensive studies to solve the above problems, the present inventors have found that the refractive index closest to the base material (the lowermost layer) among the high refractive index layer and the low refractive index layer constituting the optical reflective layer. It has been found that the above problem can be solved by forming the rate layer using a coating solution containing a hydrophilic organic solvent having a specific concentration, and the present invention has been completed.

  That is, the above-mentioned objects are a method for producing an optical control film including at least one unit in which a high refractive index layer and a low refractive index layer are alternately laminated on a base material, and the high refractive index closest to the base material. Forming the refractive index layer (A) or the low refractive index layer (A ′) using a coating liquid containing a resin, metal oxide particles, and a hydrophilic organic solvent having a concentration of 0.1 to 8% by mass. This can be achieved by the control film manufacturing method.

  According to the method of the present invention, an optical control film with improved durability can be provided. Moreover, the optical control film of the present invention can provide an optical control film exhibiting high visible light transparency and infrared reflectivity.

  The method for producing an optical control film of the present invention is a method for producing an optical control film comprising at least one unit in which a high refractive index layer and a low refractive index layer are alternately laminated on a base material. The closest high refractive index layer (A) or low refractive index layer (A ′) is formed using a coating solution containing a resin, metal oxide particles and a hydrophilic organic solvent having a concentration of 0.1 to 8% by mass. Have In the present specification, the “layer closest to the substrate” is also referred to as the “lowermost layer”. For this reason, the “high refractive index layer (A) or low refractive index layer (A ′) closest to the substrate” is positioned as the “lowermost layer (lowermost layer) high refractive index layer (A) or low refractive index layer. (A ′) ”or simply“ high refractive index layer (A) or low refractive index layer (A ′) ”. Further, “a unit in which high refractive index layers and low refractive index layers are alternately laminated” is also referred to as “optical reflection layer”. In the present specification, a high refractive index layer and a low refractive index layer other than the high refractive index layer (A) or the low refractive index layer (A ′) located in the lowermost layer are simply referred to as “high refractive index layer ( B) ”and“ low refractive index layer (B ′) ”.

  According to Patent Document 1, by using an aqueous coating liquid containing a water-soluble polymer and metal oxide particles in at least one of a high refractive index layer and a low refractive index layer, infrared reflection is performed at a lower cost. It is possible to obtain a film. However, in recent years, despite the increased load on cooling equipment due to global warming, the cost of utilities has soared, and the burden on households continues to increase. For this reason, the infrared reflective film which is more excellent in durability is calculated | required. Further, further energy saving is desired, and further improvement in transparency and reflectance is also required. Further, when the film is used for a long period of time, cracking of the reflective layer or peeling of the film may occur due to repeated expansion and contraction of the film due to moisture or heat, and further improvement in weather resistance is also demanded. In order to improve productivity, there was a tendency for the frequency of coating failures to increase with continuous coating and high-speed coating. For this reason, there is also a need for stable production of films with reduced frequency of coating failures.

  The present invention includes at least a high refractive index layer (A) or a low refractive index layer (A ′) located in the lowermost layer, a resin, metal oxide particles, and a hydrophilic organic solvent having a concentration of 0.1 to 8% by mass. It is formed using a coating liquid. By taking the said structure, durability of an optical control film can be improved. Moreover, the visible light transmittance and infrared reflectivity of the optical control film can also be improved. Although the detailed mechanism by which the optical control film according to the present invention exhibits the above-mentioned effects is unknown, it is presumed as follows. In addition, this invention is not restrained by the following mechanism at all.

  That is, as a result of intensive studies on the above problems, the present inventors have found that the network is formed by the interaction between the resin and the metal oxide particles contained in the coating liquid (hydrogen bonding between the respective hydroxyl groups (OH)). This causes aggregation of resin and metal oxide particles and thickening of the coating liquid, thereby increasing the non-uniformity of the coating liquid and causing coating unevenness, resulting in durability, visible light transmittance and redness. It was noted that a decrease in external (particularly near infrared) reflectance was induced. On the other hand, according to the present invention, when the lowermost layer is formed in the presence of a hydrophilic organic solvent having a specific concentration, the surface tension of the aqueous coating liquid is lowered and the hydrophilic organic solvent is added to the surface of the metal oxide particles. Coordinating to cleave the interaction (hydrogen bond) between the resin and the metal oxide particles to suppress the formation of aggregates by the resin and the metal oxide particles in the coating solution. For this reason, the liquid landing property to a base material improves, it can suppress the viscosity raise of a coating liquid, and can suppress a coating nonuniformity (a smooth coating film can be formed stably). Therefore, the optical control film manufactured by the method of the present invention can improve visible light transmittance, infrared (particularly near infrared) reflectivity, and durability. In addition, the said effect is especially remarkable when C2-C4 alcohol is used as a hydrophilic solvent.

  As described above, according to the method of the present invention, the weather resistance of the optical control film can be improved (the quality can be maintained for a long time), and the quality (transparency, near infrared reflectance) can be improved. In addition, according to the method of the present invention, applicability is improved and application failure can be reduced.

  Therefore, the optical control film produced by the method of the present invention has high visible light transmittance and infrared reflectivity, and is excellent in weather resistance. Therefore, the optical control film according to the present invention can be particularly suitably used as a heat ray shielding film (infrared shielding film or near-infrared shielding film) installed on a building window, a vehicle member, or the like. In this specification, “near infrared” means near infrared having a wavelength of about 750 nm to 2500 nm. Therefore, the “near infrared shielding film” is a film that can block all or part of the near infrared rays by reflecting or absorbing the near infrared rays.

  Embodiments of the present invention will be described below. In addition, this invention is not limited only to the following embodiment. In this specification, “X to Y” indicating a range means “X or more and Y or less”. Unless otherwise specified, measurement of operation and physical properties is performed under conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50%.

  In the present invention, the optical control film has an optical reflection layer including at least one unit in which high refractive index layers and low refractive index layers are alternately laminated. Here, the high refractive index layer and the low refractive index layer include a resin and metal oxide particles. The optical reflection layer is not particularly limited as long as it can prevent intrusion of heat rays (infrared rays) (that is, functions as a heat ray reflection layer). The optical reflective layer is a laminate of layers having different refractive indexes, that is, a laminate in which high refractive index layers and low refractive index layers are alternately laminated. In this specification, 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. Therefore, the terms “high refractive index layer” and “low refractive index layer” mean that each refractive index layer has the same refractive index when attention is paid to two adjacent refractive index layers. All forms other than the forms having the above are included.

  The high refractive index layer and the low refractive index layer are considered as follows. For example, 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. In this case, in the mixed layer, 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, and a set of portions where the low refractive index layer component exceeds 50% by mass is defined as a low refractive index layer. . Specifically, when the low refractive index layer contains, for example, a first metal oxide as a low refractive index component, and 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. In addition, a laminate in which metal oxide particles are not contained in the low refractive index component or the high refractive index component, and one of the high refractive index layer or the low refractive index layer is formed only from a water-soluble resin (organic binder). Similarly, in the 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. Thus, each layer etched by sputtering can be regarded as a high refractive index layer or a low refractive index layer.

  In the method of the present invention, among the layers constituting the optical reflection layer (laminated body), the high refractive index layer (A) or the low refractive index layer (A ′) closest to the substrate is replaced with resin, metal oxide particles. And a coating solution containing a hydrophilic organic solvent having a concentration of 0.1 to 8% by mass. The hydrophilic organic solvent with the above concentration lowers the surface tension of the aqueous coating solution and coordinates with the surface of the metal oxide particles in the coating solution to break the interaction (hydrogen bonding) between the resin and the metal oxide particles. Thus, formation of aggregates by the resin and metal oxide particles is suppressed. For this reason, the coating liquid containing the hydrophilic organic solvent of the said density | concentration is excellent in the liquid landing property to a base material, can suppress the raise of the viscosity of a coating liquid, and can suppress generation | occurrence | production of coating unevenness effectively. Therefore, an optical control film having a lowermost layer formed by using a coating liquid containing a hydrophilic organic solvent having the above-mentioned concentration, and further having a high refractive index layer (B) and a low refractive index layer (B ′) is capable of transmitting visible light. , Infrared (particularly near infrared) reflectivity and durability can be improved.

  Here, the method for forming the optical reflective layer (laminate) according to the present invention is not particularly limited, but the coating liquid for the low refractive index layer and the coating liquid for the high refractive index layer, or the high refractive index layer are formed on the substrate. A coating solution for coating and a coating solution for low refractive index layer are coated. In the above method, the lowermost layer-forming coating solution closest to the substrate contains a resin, metal oxide particles, and a hydrophilic organic solvent having a specific concentration. The coating method is not particularly limited, and for example, roll coating method, rod bar coating method, air knife coating method, spray coating method, slide curtain coating method, or U.S. Pat. No. 2,761,419, U.S. Pat. Examples thereof include a slide hopper coating method and an extrusion coating method described in Japanese Patent No. 2,761,791. In addition, as a method of applying a plurality of layers in a multilayer manner, sequential multilayer coating or simultaneous multilayer coating may be used.

  Below, the simultaneous multilayer application | coating by the slide hopper application | coating method which is a preferable manufacturing method (application | coating method) of this invention is demonstrated in detail. Note that the present invention is not limited to the following method. Hereinafter, unless otherwise specified, the coating liquid for the low refractive index layer and the coating liquid for the high refractive index layer are also collectively referred to as “coating liquid”.

  The coating solution for forming the lowermost layer closest to the substrate contains a resin, metal oxide particles, and a hydrophilic organic solvent having a specific concentration. The hydrophilic organic solvent constituting the coating solution is not particularly limited as long as it exhibits the above effects. In the present specification, “hydrophilic” means that 5 g or more is dissolved in 100 g of water. For this reason, the “hydrophilic organic solvent” intends an organic solvent that dissolves 5 g or more in 100 g of water. Preferably, 6 g or more of the hydrophilic organic solvent is dissolved in 100 g of water. In consideration of the formability of the coating film, the boiling point is preferably 70 to 300 ° C, more preferably 70 to 250 ° C. Specifically, examples of the hydrophilic solvent include alcohols such as methanol, ethanol, 2-propanol and 1-butanol, esters such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate, Examples include ethers such as diethyl ether, propylene glycol monomethyl ether, and ethylene glycol monoethyl ether; amides such as dimethylformamide and N-methylpyrrolidone; and ketones such as acetone, methyl ethyl ketone, acetylacetone, and cyclohexanone. Of these, monohydric alcohols having 2 to 4 carbon atoms and glycol ethers are preferable in consideration of the effect of improving transparency (visible light transmittance), coating properties, layer flexibility, and weather resistance. That is, the hydrophilic organic solvent is preferably a monohydric alcohol or glycol ether having 2 to 4 carbon atoms.

  In the above preferred examples, the monohydric alcohol having 2 to 4 carbon atoms includes ethanol, 1-propanol, 2-propanol, 1-butanol (n-butyl alcohol, normal butanol), 2-methyl-1-propanol (isobutyl alcohol). ), 2-butanol (sec-butyl alcohol), 2-methyl-2-propanol (tert-butyl alcohol). Among the above alcohols, considering the haze improvement effect, monovalent alcohols having 3 or 4 carbon atoms are preferable, and 1-propanol, 2-propanol, and 1-butanol are more preferable. By using an alcohol having a long carbon number, the coating property can be further improved even with a small addition amount.

  Preferred examples of the glycol ether include ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol ethyl ether acetate, ethylene glycol butyl ether, ethylene glycol butyl ether acetate, ethylene glycol isopropyl ether, ethylene glycol dimethyl ether, ethylene glycol hexyl ether, ethylene Ethylene glycol ethers such as glycol 2-ethyl hexyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate; propylene glycol methyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether, propylene glycol n Propyl ether, propylene glycol n- butyl ether, dipropylene glycol methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol n- propyl ether, propylene glycol ethers such as dipropylene glycol n-butyl ether. Among these, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol ethyl ether acetate, ethylene glycol butyl ether, propylene glycol methyl ether, propylene glycol n-propyl ether, propylene glycol methyl ether acetate, dipropylene glycol n-propyl ether, Propylene glycol n-butyl ether and dipropylene glycol dimethyl ether are preferred, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol ethyl ether acetate, ethylene glycol butyl ether, propylene glycol methyl ether, propylene glycol n-propyl ether, propylene glycol methyl Ether acetate, dipropylene glycol n- propyl ether, propylene glycol n- butyl ether, dipropylene glycol dimethyl ether are more preferable.

  The hydrophilic organic solvent may be used alone or in the form of a mixture of two or more.

  In the present invention, the hydrophilic organic solvent is present in the coating solution at a concentration of 0.1 to 8% by mass. Here, when the concentration is less than 0.1% by mass, the surface tension of the coating liquid is not sufficiently lowered, and the hydrophilic organic solvent is not sufficiently coordinated to the surface of the metal oxide particles. Interactions with particles (hydrogen bonds) cannot be broken sufficiently. For this reason, formation of the aggregate by resin and a metal oxide particle cannot be suppressed, liquid landing property is bad, and the coating nonuniformity will generate | occur | produce. On the other hand, when the concentration exceeds 8% by mass, the liquid landing property is improved, but the transparency (visible light transmittance) is excessively lowered. Moreover, after application | coating, drying and winding up cause blocking, and a weather resistance (especially film | membrane crack) will fall by moisture absorption. In addition, in order to improve productivity, the frequency of occurrence of coating failures tends to increase due to continuous coating and high-speed coating. Considering the effect of improving the liquid landing property, transparency, infrared reflectivity and weather resistance, and further the effect of further suppressing coating unevenness, the concentration of the hydrophilic organic solvent in the coating solution is preferably 0.1 to 4. It is mass%, More preferably, it is 0.1-2 mass%.

  In the method of the present invention, the high refractive index layer (A) or the low refractive index layer (A ′) in the lowermost layer (closest to the base material) is at least a resin, metal oxide particles, and 0.1 to 8% by mass. It forms using the coating liquid containing the hydrophilic organic solvent of density | concentration. Here, when alcohol is used as the hydrophilic organic solvent, the liquid landing property of the coating liquid can be improved. For this reason, it is preferable to form the lowermost layer using an alcohol, particularly a monohydric alcohol having 2 to 4 carbon atoms. On the other hand, when glycol ether is used as the hydrophilic organic solvent, since the boiling point is higher than that of alcohol, the coating film drying rate is slowed, and the leveling property can be improved (improved film smoothing and more uneven coating). Can be reduced). Moreover, although it is trace amount in a coating film (refractive-index layer), glycol ether remains. For this reason, since the softness | flexibility of a coating film is improved and the stress at the time of expansion | swelling of a film by humidity etc. or shrinkage | contraction at the time of drying is improved, a weather resistance (durability) can be improved more. Moreover, the crack (film | membrane crack) of a coating film can be suppressed effectively. Therefore, it is preferable to form the high refractive index layer (B) and / or the low refractive index layer (B ′) other than the lowest layer using glycol ether, and the high refractive index layer (B) and the low refractive index other than the lowermost layer. It is more preferable to form both the rate layers (B ′) using glycol ether. That is, the high refractive index layer (A) or the low refractive index layer (A ′) closest to the substrate is replaced with a resin, metal oxide particles, and a monohydric alcohol having 2 to 4 carbon atoms and having a concentration of 0.1 to 8% by mass. Formed using a coating solution containing a resin, metal oxide particles, and at least one of a high refractive index layer and a low refractive index layer other than the high refractive index layer (A) or the low refractive index layer (A ′) And a coating solution containing glycol ether having a concentration of 0.1 to 8% by mass is preferable.

  As described above, the coating solution for forming the lowermost layer closest to the substrate contains a resin, metal oxide particles, and a hydrophilic organic solvent having a specific concentration, but a high refractive index layer (B) other than the lowermost layer. Further, the low refractive index layer (B ′) may be formed using a coating liquid deviating from the form according to the present invention. The solvent constituting the coating liquid in this case is not particularly limited, but water, an organic solvent, or a mixed solvent thereof is preferable. Examples of the organic solvent include alcohols such as methanol, ethanol, 2-propanol and 1-butanol, esters such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate, diethyl ether, Examples thereof include ethers such as propylene glycol monomethyl ether and ethylene glycol monoethyl ether, amides such as dimethylformamide and N-methylpyrrolidone, and ketones such as acetone, methyl ethyl ketone, acetylacetone and cyclohexanone. These organic solvents may be used alone or in combination of two or more.

  Preferably, the high refractive index layer (B) and the low refractive index layer (B ′) other than the lowermost layer also contain a resin, metal oxide particles, and a hydrophilic organic solvent having a specific concentration, as in the lowermost layer.

  In the present invention, at least the lowermost layer contains a resin, and preferably the high refractive index layer and the low refractive index layer constituting the optical reflection layer contain a resin. By using the resin in this manner, the flexibility of the layer is improved as compared with the optical reflective layer of the inorganic film formed only of the metal oxide material, and thus the film cracking can be effectively prevented. Moreover, the adhesiveness between each layer can be improved. Furthermore, since the optical reflection layer can be formed by coating or the like, uniform and large-area film formation is easy. Moreover, since the film forming speed can be increased, it is preferable from the viewpoint of manufacturing cost and mass production. In addition, since it is not necessary to form a film at a high temperature, the selection range of the substrate is wide, and the optical reflection layer between the optical reflection layer and another layer (for example, the substrate) due to temperature change or the optical reflection layer (in the case of a laminated form) ) Can be effectively prevented from peeling off due to the difference in shrinkage ratio between the two. Furthermore, since the optical reflection layer containing resin is excellent in flexibility as described above, it can be applied to a flexible substrate and can suppress the occurrence of cracks and scratches in a bent portion.

  The resin used in the low refractive index layer and the high refractive index layer is not particularly limited. Each refractive index layer can be formed using a resin by a film forming method such as coating or spin coating. Since these methods are simple and do not ask the heat resistance of a base material, there are many choices, and it can be said that it is an effective film forming method particularly for a resin base material. For example, a mass production method such as a roll-to-roll method can be adopted for the coating type, which is advantageous in terms of cost and process time. Moreover, since the film | membrane containing a resin material is highly flexible, even if it winds up at the time of production or conveyance, these defects do not generate easily and there exists an advantage that it is excellent in handleability.

  The resin contained in the high refractive index layer and the low refractive index layer is preferably a water-soluble polymer that functions as a binder. By including a water-soluble polymer in the high-refractive index layer and the low-refractive index layer, a layer formation method that suppresses the use of an organic solvent can be adopted, so that environmental problems due to the organic solvent can be solved. Moreover, since the softness | flexibility of a coating film can also be achieved, it is preferable. The resins contained in the high refractive index layer and the low refractive index layer may be the same component or different components, but are preferably different. Examples of the water-soluble polymer include polyvinyl alcohol or a derivative thereof (polyvinyl alcohol-based resin), gelatin, cellulose, or a thickening polysaccharide. However, the water-soluble polymer is effective in improving coating unevenness and film thickness uniformity (haze). From the viewpoint, the refractive index layer preferably contains polyvinyl alcohol or a derivative thereof as a resin. Resin may be used independently and may be used in combination of 2 or more type. Moreover, a synthetic product may be used for resin and a commercial item may be used.

  The resin is not particularly limited, and known resins used for the high refractive index layer and the low refractive index layer, such as WO 2012/128109, JP2013-121567A, JP2013-148849A, and the like are the same. Can be used. Specifically, the polyvinyl alcohol-based resin includes various modified polyvinyl alcohols in addition to ordinary polyvinyl alcohol obtained by hydrolyzing polyvinyl acetate.

  The polyvinyl alcohol obtained by hydrolyzing vinyl acetate preferably has an average degree of polymerization of 200 or more, and particularly preferably has an average degree of polymerization of 300 to 5,000. Moreover, it is preferable that it is 70-100 mol%, and, as for saponification degree, it is especially preferable that it is 80-99.9 mol%.

  Examples of the modified polyvinyl alcohol include cation modified polyvinyl alcohol, anion modified polyvinyl alcohol, nonionic modified polyvinyl alcohol, ethylene modified polyvinyl alcohol, and vinyl alcohol resin. Also, vinyl acetate resins (for example, “Exeval” manufactured by Kuraray Co., Ltd.), polyvinyl acetal resins obtained by reacting polyvinyl alcohol with aldehydes (for example, “ESREC” manufactured by Sekisui Chemical Co., Ltd.), silanols having silanol groups Modified polyvinyl alcohol (for example, “R-1130” manufactured by Kuraray Co., Ltd.), modified polyvinyl alcohol resin having an acetoacetyl group in the molecule (for example, “Gosefimer (registered trademark) Z / manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) WR series ") and the like are also included in the polyvinyl alcohol resin.

  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 such a 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 as described in JP-A-7-9758 is added to a part of vinyl alcohol, and JP-A-8-25795. Block copolymer of vinyl compound having hydrophobic group and vinyl alcohol as described, silanol modified polyvinyl alcohol having silanol group, reactivity having reactive group such as acetoacetyl group, carbonyl group, carboxyl group Examples thereof include group-modified polyvinyl alcohol.

  Examples of the cation-modified polyvinyl alcohol include primary to tertiary amino groups and quaternary ammonium groups as described in JP-A No. 61-10383. Polyvinyl alcohol contained therein and 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. N-vinylimidazole, N-vinyl-2-methylimidazole, N- (3-dimethylaminopropyl) methacrylamide, hydroxylethyltrimethylammonium chloride, trimethyl- (2-methacrylamidopropyl) ammonium chloride, N- (1, 1-dimethyl-3-dimethylaminopropyl) acrylamide and the like. The ratio of the cation-modified group-containing monomer of the cation-modified polyvinyl alcohol is preferably 0.1 to 10 mol%, more preferably 0.2 to 5 mol% with respect to vinyl acetate.

  As ethylene modified polyvinyl alcohol, what is described in Unexamined-Japanese-Patent No. 2009-107324, Unexamined-Japanese-Patent No. 2003-248123, Unexamined-Japanese-Patent No. 2003-342322, Japanese Patent Application No. 2013-206913, etc. can be used, for example. Alternatively, commercially available products such as EXEVAL (trade name: manufactured by Kuraray Co., Ltd.) may be used.

  Examples of the vinyl alcohol-based resin include EXEVAL (trade name: manufactured by Kuraray Co., Ltd.) and Nichigo G resin (trade name: manufactured by Nippon Synthetic Chemical Industry Co., Ltd.).

  In addition, the above-mentioned polyvinyl alcohol may be used independently or may be used in combination of 2 or more type. Polyvinyl alcohol may be a synthetic product or a commercial product.

  The weight average molecular weight of polyvinyl alcohol is preferably 1,000 to 200,000, and more preferably 3,000 to 60,000. In this specification, the value measured by a static light scattering method, gel permeation chromatography (GPC), TOFMASS, or the like is adopted as the value of “weight average molecular weight”. It is preferable that the weight average molecular weight of the resin (water-soluble polymer) is in the above range because application in a wet film forming method is possible and productivity can be improved.

  As the gelatin applicable to the present invention, various gelatins that have been widely used in the field of silver halide photographic light-sensitive materials can be applied. For example, in addition to acid-processed gelatin and alkali-processed gelatin, production of gelatin is possible. Enzyme-treated gelatin and gelatin derivatives that undergo enzyme treatment in the process, that is, modified with a reagent that has an amino group, imino group, hydroxyl group, carboxyl group as a functional group in the molecule and a group obtained by reaction with it. It may be quality. Well-known methods for producing gelatin are well known. H. James: The Theory of Photographic Process 4th. ed. Reference can be made to descriptions such as 1977 (Macmillan) 55, Science Photo Handbook (above) 72-75 (Maruzen), Fundamentals of Photographic Engineering-Silver Salt Photo Hen 119-124 (Corona). Also, Research Disclosure Magazine Vol. 176, No. And gelatin described in Section IX of 17643 (December, 1978).

  When gelatin is used, a gelatin hardener can be added as necessary. As the hardener that can be used, known compounds that are used as hardeners for ordinary photographic emulsion layers can be used. For example, vinylsulfone compounds, urea-formalin condensates, melanin-formalin condensates, epoxy compounds And organic hardeners such as aziridine compounds, active olefins and isocyanate compounds, and inorganic polyvalent metal salts such as chromium, aluminum and zirconium.

  As the cellulose that can be used in the present invention, a water-soluble cellulose derivative can be preferably used. For example, water-soluble cellulose such as carboxymethyl cellulose (cellulose carboxymethyl ether), methyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and the like. Derivatives, carboxymethyl cellulose (cellulose carboxymethyl ether) and carboxyethyl cellulose, which are carboxylic acid group-containing celluloses, can be mentioned. Other examples include cellulose derivatives such as nitrocellulose, cellulose acetate propionate, cellulose acetate, and cellulose sulfate.

  The thickening polysaccharide that can be used in the present invention is not particularly limited, and examples thereof include generally known natural simple polysaccharides, natural complex polysaccharides, synthetic simple polysaccharides, and synthetic complex polysaccharides. The details of these polysaccharides can be referred to “Biochemical Encyclopedia (2nd edition), Tokyo Chemical Doujinshi”, “Food Industry”, Vol. 31 (1988), p.

  The thickening polysaccharide referred to in the present invention is a polymer of saccharides and has many hydrogen bonding groups in the molecule, and the viscosity at low temperature and the viscosity at high temperature due to the difference in hydrogen bonding force between molecules depending on the temperature. It is a polysaccharide with 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.

  Examples of the thickening polysaccharide applicable to the present invention include galactan (eg, agarose, agaropectin, etc.), galactomannoglycan (eg, locust bean gum, guaran, etc.), xyloglucan (eg, tamarind gum, etc.), 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, κ-carrageenan, λ-carrageenan, ι-carrageenan Derived from Such as natural polymer polysaccharides. From the viewpoint of not lowering the dispersion stability of the metal oxide particles coexisting in the coating solution, it is preferable that the structural unit does not have a carboxylic acid group or a sulfonic acid group. Examples of such thickening polysaccharides include 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. It is preferable that it is a polysaccharide which consists only of. Specifically, 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, tara gum, and arabinogalactan whose main chain is galactose and whose side chain is arabinose can be preferably used. In the present invention, tamarind, guar gum, cationized guar gum, and hydroxypropyl guar gum are particularly preferable.

The resin content in the refractive index layer is preferably 5 to 50 mass%, more preferably 10 to 40 mass%, based on the total solid content of the refractive index layer. When the refractive index layer is formed by a wet film-forming method, the resin content is 5% by mass or more, and when the coating film obtained by coating is dried, the film surface is prevented from being deteriorated due to disturbance. It is preferable because it is possible. On the other hand, if the content of the resin is 50% by mass or less, it becomes a suitable content when metal oxide particles are contained in the low refractive index layer, and the refractive index difference between the low refractive index layer and the high refractive index layer. Is preferable because it can be increased. In addition, in this specification, content of resin is calculated | required from the residual solid content of the evaporation-drying method. Specifically, the optical control film is immersed in hot water at 95 ° C. for 2 hours, the remaining film is removed, the hot water is evaporated, and the amount of the obtained solid matter is defined as the resin amount. In this case, IR (infrared spectroscopy) 1700～1800Cm ^-1 in the spectrum, 900～1000Cm ^-1, and when the peak one each in the region of 800～900Cm ^-1 is observed, the resin (water-soluble polymer) Can be determined to be polyvinyl alcohol.

  In the present invention, at least the lowermost layer contains metal oxide particles, and preferably, the high refractive index layer and the low refractive index layer constituting the optical reflection layer contain metal oxide particles. By containing metal oxide particles, the refractive index difference between the refractive index layers can be increased, and the reflection characteristics are improved. When both the low refractive index layer and the high refractive index layer contain metal oxide particles, the refractive index difference can be further increased. By including metal oxide particles, the number of stacked layers can be reduced and a thin film can be obtained. By reducing the number of layers, productivity can be improved and a decrease in transparency due to scattering at the lamination interface can be suppressed.

  As the metal oxide particles, the metal constituting the metal oxide is Li, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Rb, Sr, Y, Nb, Zr, Mo, Ag, Cd, In, Sn, Sb, Cs, Ba, La, Ta, Hf, W, Ir, Tl, Pb, Bi and a rare earth metal A metal oxide which is one kind or two or more kinds of metals can be used.

Examples of the metal oxide particles used in the high refractive index layer include titanium dioxide, zirconium oxide, zinc oxide, alumina, colloidal alumina, lead titanate, red lead, yellow lead, zinc yellow, chromium oxide, ferric oxide, Iron black, copper oxide, magnesium oxide, magnesium hydroxide, strontium titanate, yttrium oxide, hafnium oxide, niobium oxide, tantalum oxide, barium oxide, indium oxide, europium oxide, lanthanum oxide, zircon, tin oxide, lead oxide, and Examples thereof include lithium niobate, potassium niobate, lithium tantalate, and aluminum / magnesium oxide (MgAl ₂ O ₄ ), which are double oxides composed of these oxides.

  In addition, rare earth oxides can also be used as the metal oxide particles. Specifically, scandium oxide, yttrium oxide, lanthanum oxide, cerium oxide, praseodymium oxide, neodymium oxide, samarium oxide, europium oxide, gadolinium oxide, and oxidation. Examples also include terbium, dysprosium oxide, holmium oxide, erbium oxide, thulium oxide, ytterbium oxide, and lutetium oxide.

  The metal oxide particles used in the high refractive index layer are preferably metal oxide particles having a refractive index of 1.90 or more, and examples thereof include zirconium oxide, cerium oxide, titanium oxide, and zinc oxide. Among them, titanium dioxide is preferable because it can form a transparent and higher refractive index layer having a higher refractive index, and it is particularly preferable to use rutile (tetragonal) titanium oxide particles. The metal oxide particles used for the high refractive index layer may be used singly or in combination of two or more.

  In the present invention, titanium oxide is preferred as the metal oxide of the high refractive index layer, but the titanium oxide may be in the form of core-shell particles coated with a silicon-containing hydrated oxide. The core-shell particles have a structure in which the surface of the titanium oxide particles is coated with a shell made of a silicon-containing hydrated oxide on a titanium oxide serving as a core. By including such core-shell particles in the high refractive index layer, the intermixing of the low refractive index layer and the high refractive index layer is achieved by the interaction between the silicon-containing hydrated oxide of the shell layer and the water-soluble resin. Can be suppressed. Here, the “coating” means a state in which a silicon-containing hydrated oxide is attached to at least a part of the surface of the titanium oxide particles. That is, the surface of the titanium oxide particles used as the metal oxide particles may be completely covered with a silicon-containing hydrated oxide, and a part of the surface of the titanium oxide particles is a silicon-containing hydrated oxide. It may be coated. From the viewpoint that the refractive index of the coated titanium oxide particles is controlled by the coating amount of the silicon-containing hydrated oxide, it is preferable that a part of the surface of the titanium oxide particles is coated with the silicon-containing hydrated oxide. . Hereinafter, such coated titanium oxide particles are also referred to as “silica-attached titanium dioxide sol”. As a method of coating the titanium oxide particles with a silicon-containing hydrated oxide, it can be produced by a conventionally known method. For example, JP-A-10-158015, JP-A-2000-204301, JP-A-2007 Reference can be made to the matters described in JP-A-246351.

  The volume average particle size of the metal oxide particles used in the high refractive index layer is preferably 100 nm or less, more preferably 80 nm or less, and 1 to 70 nm from the viewpoint of a low haze value and excellent visible light transmittance. It is more preferable that it is 10 to 50 nm. Here, the volume average particle diameter means a method of observing the particle itself using a laser diffraction scattering method, a dynamic light scattering method, or an electron microscope, or a particle image appearing on the cross section or surface of the refractive index layer. The particle diameter of 1,000 arbitrary particles is measured by a method of observing with a microscope, and particles having particle diameters of d1, d2,. .. nk number of particulate metal oxides, where volume per particle is vi, volume average particle size mv = {Σ (vi · di)} / {Σ (vi)} The average particle diameter weighted by the volume represented by

  The content of the metal oxide particles in the high refractive index layer is 100% by mass of the solid content of the high refractive index layer, from the viewpoint of heat ray shielding and from the viewpoint of reducing color unevenness when a film is applied to curved glass. Therefore, it is preferable that it is 30-85 mass%, and it is more preferable that it is 40-80 mass%.

  Moreover, as a metal oxide particle used for a low refractive index layer, it is preferable to use silicon dioxide, and it is especially preferable to use colloidal silica. The metal oxide particles (preferably silicon dioxide) contained in the low refractive index layer preferably have an average particle size of 3 to 100 nm. The average particle size of primary particles of silicon dioxide dispersed in a primary particle state (particle size in a dispersion state before coating) is more preferably 3 to 50 nm, and further preferably 3 to 40 nm. 3 to 20 nm is particularly preferable, and 4 to 10 nm is most preferable. Moreover, as an average particle diameter of secondary particle | grains, it is preferable from a viewpoint with few hazes and excellent visible light transmittance | permeability that it is 30 nm or less. The average particle size of the metal oxide in the low refractive index layer is determined by observing the particles themselves or the cross section or surface of the refractive index layer with an electron microscope and measuring the particle size of 1,000 arbitrary particles. The simple average value (number average) is obtained. Here, the particle diameter of each particle is represented by a diameter assuming a circle equal to the projected area.

  As content of the metal oxide particle in a low-refractive-index layer, it is preferable that it is 30-85 mass% with respect to solid content of a low-refractive-index layer from a refractive index viewpoint, and it is 40-80 mass%. More preferably.

  Colloidal silica is obtained by heating and aging a silica sol obtained by metathesis of sodium silicate with an acid or the like or passing through an ion exchange resin layer. For example, JP-A-57-14091 and JP-A-60- No. 219083, JP-A-60-218904, JP-A-61-20792, JP-A-61-188183, JP-A-63-17807, JP-A-4-93284, JP-A-5-278324, JP-A-6-92011, JP-A-6-183134, JP-A-6-297830, JP-A-7-81214, JP-A-7-101142, JP-A-7- 179029, JP-A-7-137431, and WO94 / 26530 pamphlet. That. Such colloidal silica may be a synthetic product or a commercially available product. The surface of the colloidal silica may be cation-modified, or may be treated with Al, Ca, Mg, Ba or the like.

  Such 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.

  In addition to the above, each refractive index layer is composed of, for example, ultraviolet absorbers described in JP-A-57-74193, JP-A-57-87988, and JP-A-62-261476, and JP-A-57-74192. No. 57-87989, No. 60-72785, No. 61-146591, No. 1-95091, No. 3-13376, etc. No. 42993, 59-52689, 62-280069, 61-242871, and JP-A 4-219266, etc., whitening agent, sulfuric acid, phosphoric acid, acetic acid PH adjusters such as citric acid, sodium hydroxide, potassium hydroxide, potassium carbonate, antifoaming agents, lubricants such as diethylene glycol, preservatives, antistatic agents, Various known additives such as DOO agent may contain. The content of these additives is preferably 0.1 to 10% by mass with respect to the solid content of the refractive index layer.

  Alternatively, when each refractive index layer contains a water-soluble polymer, a curing agent can be used to cure the water-soluble polymer. Curing agents include boric acid and its salts, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-diglycidylcyclohexane, N, N-diglycidyl-4-glycidyloxyaniline, sorbitol polyglycidyl Ether, glycerol polyglycidyl ether, etc.), aldehyde-based curing agents (formaldehyde, glyoxal, etc.), active halogen-based curing agents (2,4-dichloro-4-hydroxy-1,3,5, -s-triazine, etc.), active Examples thereof include vinyl compounds (1,3,5-trisacryloyl-hexahydro-s-triazine, bisvinylsulfonylmethyl ether, etc.), aluminum alum, borax and the like. It is preferable that content of the hardening | curing agent in a refractive index layer is 1-10 mass% with respect to solid content of a refractive index layer.

  Alternatively, each refractive index layer may contain a surfactant for adjusting the surface tension at the time of application. Here, an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, and the like can be used as the surfactant, and an anionic surfactant is more preferable. Preferred compounds include those containing a hydrophobic group having 8 to 30 carbon atoms and a sulfonic acid group or a salt thereof in one molecule. The content of the surfactant in each refractive index layer is preferably 0.01 to 5% by mass with respect to the solid content of the refractive index layer.

  The method for preparing the coating liquid is not particularly limited, and examples thereof include a method in which a resin, metal oxide particles, a hydrophilic organic solvent, and other additives that are added as necessary are added and stirred. At this time, the order of addition of the respective components is not particularly limited, and the respective components may be sequentially added and mixed while stirring, or may be added and mixed at one time while stirring. If necessary, it is further adjusted to an appropriate viscosity using a solvent.

  In addition, the temperature of the coating solution when applying the coating solution to the substrate (for example, simultaneous multi-layer coating) is preferably 25 to 60 ° C., and 30 to 45 ° C. when using the slide bead coating method. A range is more preferred. Moreover, when using a curtain application | coating system, the temperature range of 25-60 degreeC is preferable, and the temperature range of 30-45 degreeC is more preferable.

  The viscosity of the coating solution at the time of coating (for example, simultaneous multilayer coating) is not particularly limited. However, when the slide bead coating method is used, it is preferably in the range of 5 to 100 mPa · s and more preferably in the range of 10 to 50 mPa · s in the preferable temperature range of the coating solution. Moreover, when using a curtain application | coating system, it is preferable that it is the range of 5-1200 mPa * s in the range of the preferable temperature of said coating liquid, and it is more preferable that it is the range of 25-500 mPa * s. If it is the range of such a viscosity, simultaneous multilayer coating can be performed efficiently. Further, the viscosity at 15 ° C. of the coating solution is preferably 100 mPa · s or more, more preferably 100 to 30,000 mPa · s, further preferably 3,000 to 30,000 mPa · s, and most preferably 10 , 30,000 to 30,000 mPa · s.

  As a coating and drying method, it is preferable that the coating liquid is heated to a desired temperature and coated, and then the temperature of the formed coating film is once cooled to 1 to 15 ° C and dried at 10 ° C or higher. More preferably, the drying is performed at a temperature of 50 to 90 ° C. Moreover, as a cooling method immediately after application | coating, it is preferable to carry out by a horizontal set system from a viewpoint of the formed coating-film uniformity.

  As described above, the optical reflection layer is formed on the substrate. Here, the optical reflection layer may be configured to have at least one unit (stacked body) in which high refractive index layers and low refractive index layers are alternately stacked. The number of layers (total number of refractive index layers) is not particularly limited, but is preferably 6 to 2000 (that is, 3 to 1000 units), more preferably 10 to 1000 (that is, 5 to 500 units), More preferably, it is 10-500 (namely, 5-250 units). If the number of layers exceeds 2000, haze increases, and if it is less than 6, the desired reflectance may not be achieved. Moreover, the optical control film of this invention should just be a structure which has at least 1 or more units on the said base material. For example, the lowermost layer and the outermost layer of the laminated film may be either a high refractive index layer or a low refractive index layer. However, by adopting a layer configuration in which the low refractive index layer is located in the lowermost layer and the outermost layer, the viewpoint that the adhesion to the lowermost adjacent layer (for example, the substrate, the optical reflection layer) and the durability of the uppermost layer are excellent. Therefore, a layer configuration in which the lowermost layer and the outermost layer are low refractive index layers (that is, the total number of refractive index layers is an odd number) is preferable.

  In the optical reflection layer, the high refractive index layer preferably has a higher refractive index, but the refractive index is preferably 1.70 to 2.50, more preferably 1.80 to 2.20. The low refractive index layer preferably has a lower refractive index, but preferably has a refractive index of 1.10 to 1.60, more preferably 1.30 to 1.55, and even more preferably 1. 30 to 1.50.

  In the optical reflection layer, it is preferable to design a large difference in refractive index between the high refractive index layer and the low refractive index layer from the viewpoint of increasing the heat ray reflectance with a small number of layers. In at least one of the units composed of the high refractive index layer and the low refractive index layer, the difference in refractive index between the adjacent high refractive index layer and low refractive index layer is preferably 0.1 or more, more preferably Is 0.2 or more, more preferably 0.25 or more. When the optical reflective layer has a plurality of units of the low refractive index layer and the high refractive index layer, the refractive index difference between the low refractive index layer and the high refractive index layer in all the units may be within the preferred range. preferable. However, the outermost layer and the lowermost layer of the optical reflection layer may have a configuration outside the above preferred range.

  The reflectance in a specific wavelength region is determined by the difference in refractive index between two adjacent layers (high refractive index layer and low refractive index layer) and the number of layers, and the larger the refractive index difference, 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 reflectivity (infrared shielding rate) of 90% or more, if the difference in refractive index is smaller than 0.1, a laminate exceeding 100 layers is required, which not only reduces productivity. , Scattering at the laminated interface increases and transparency decreases. From the viewpoint of improving the reflectance and reducing the number of layers, there is no upper limit to the difference in refractive index, but it is substantially about 1.4.

  The refractive index is obtained as the difference between the refractive indexes of the high refractive index layer and the low refractive index layer according to the following method. That is, each refractive index layer is formed as a single layer (using a base material if necessary), and after cutting this sample into 10 cm × 10 cm, the refractive index is obtained according to the following method. Using a U-4000 type (manufactured by Hitachi, Ltd.) as a spectrophotometer, the surface opposite to the measurement surface (back surface) of each sample is roughened, and then light absorption is performed with a black spray. Then, the reflection of light on the back surface is prevented, and the reflectance in the visible light region (400 nm to 700 nm) is measured at 25 points under the condition of regular reflection at 5 degrees to obtain an average value, and the average refractive index is determined from the measurement result. Ask.

  In addition, when the optical path difference between the reflected light on the surface of the layer and the reflected light on the bottom of the layer is a relationship expressed by n · d = wavelength / 4 when viewed as a single layer film, the reflected light is controlled to be strengthened by the phase difference. And reflectivity can be increased. Here, n is the refractive index, d is the physical film thickness of the layer, and n · d is the optical film thickness. By using this optical path difference, reflection can be controlled. Using this relationship, the refractive index and film thickness of each layer are controlled to control the reflection of visible light and near infrared light. That is, the reflectance in a specific wavelength region can be increased by the refractive index of each layer, the film thickness of each layer, and the way of stacking each layer.

  The thickness (thickness after drying) of the low refractive index layer and the high refractive index layer is preferably 20 to 1000 nm, more preferably 50 to 500 nm, and further preferably 100 to 300 nm. More preferably, the thickness is particularly preferably 100 to 200 nm. The thickness of the low refractive index layer and the high refractive index layer may be the same or different. The thickness per layer of each refractive index layer can be adjusted by changing the width in the film thickness direction at the die extrusion port and / or by stretching conditions. In addition, when extending | stretching a laminated body, the said film thickness shows the thickness after extending | stretching.

  In the present invention, the substrate is not particularly limited and is preferably a film support. The film support may be transparent or opaque, and various substrates can be used.

  For example, polyolefin films (polyethylene, polypropylene, etc.), polyester films (polyethylene terephthalate, polyethylene naphthalate, etc.), polyvinyl chloride, cellulose acetate, etc. can be used, and polyester films are preferred. Although it does not specifically limit as a polyester film (henceforth polyester), It is preferable that it is polyester which has the film formation property which has a dicarboxylic acid component and a diol component as main structural components.

  The thickness of the base material used in the present invention is preferably 10 to 300 μm, particularly 20 to 150 μm. Two or more substrates may be stacked, and in this case, each substrate may be the same or different. Furthermore, when a base material is arrange | positioned at both surfaces of an optical reflection layer, each base material may be the same or different.

  By the above method, an optical control film having high visible light transmittance and infrared reflectivity and excellent weather resistance can be produced.

  The optical control film according to the present invention can be made into a visible light reflection film or a near-infrared reflection film by changing a specific wavelength region for increasing the reflectance. That is, if the specific wavelength region for increasing the reflectance is set to the visible light region, the visible light reflecting film is obtained, and if the specific wavelength region is set to the near infrared region, the near infrared reflecting film is obtained. In the case of a near-infrared reflective film, the transmittance at 550 nm in the visible light region shown in JIS R3106: 1998 is preferably 50% or more, more preferably 70% or more, and 75% or more. Is more preferable. Further, the transmittance at 1200 nm is preferably 35% or less, more preferably 25% or less, and further preferably 20% or less. It is preferable to design the optical film thickness and unit so as to be in such a suitable range. Moreover, it is preferable to have the area | region which has a reflectance exceeding 50% in the area | region of wavelength 900nm-1400nm.

  Since the infrared region of the incident spectrum of sunlight is particularly related to the increase in indoor temperature, shielding near infrared light is particularly effective for suppressing the increase in indoor temperature. Looking at the cumulative energy ratio from the shortest infrared wavelength (760 nm) to the longest wavelength 3200 nm based on the weight coefficient described in Japanese Industrial Standard JIS R3106: 1998, the infrared from the wavelength 760 nm to the longest wavelength 3200 nm Looking at the cumulative energy from 760 nm to each wavelength when the total energy of the entire region is 100, the total energy from 760 to 1300 nm occupies about 75% of the entire infrared region. Therefore, shielding the wavelength region up to 1300 nm is efficient in energy saving effect by heat ray shielding.

  The total thickness of the optical control film according to the present invention is preferably 12 to 315 μm, more preferably 15 to 200 μm, and still more preferably 20 to 100 μm.

  The optical control film according to the present invention essentially includes a base material and an optical reflection layer, but may have other constituent members. For example, the optical control film according to the present invention may have a hard coat layer on the optical reflective layer or on the opposite side of the optical reflective layer via the substrate. The hard coat layer functions as a surface protective layer for enhancing the scratch resistance of the optical control film. In the present specification, the “hard coat layer” is a layer having a pencil hardness of H or more according to JIS K 5600-5-4: 1999.

  The hard coat layer may be a single layer or a laminate of two or more layers. When the optical control film has two or more hard coat layers, the configuration of each hard coat layer may be the same or different.

  When the optical control film has a hard coat layer, the hard coat material constituting the hard coat layer is not particularly limited, but is an inorganic represented by active energy ray curable resin, thermosetting resin, and polysiloxane. A material (polysiloxane hard coat material) or the like is preferably used. The hard coat material may be used alone or in the form of a mixture of two or more.

  The active energy ray curable resin is not particularly limited, but preferably contains a monomer having an ethylenically unsaturated double bond, and more preferably an ultraviolet curable resin. The ultraviolet curable resin is not particularly limited, but is an ultraviolet curable urethane (meth) acrylate resin, an ultraviolet curable polyester (meth) acrylate resin, an ultraviolet curable epoxy (meth) acrylate resin, an ultraviolet curable polyol (meth) acrylate. Examples thereof include resins. Among these, it is preferable to use an ultraviolet curable (meth) acrylate resin.

  The ultraviolet curable urethane (meth) acrylate resin is obtained by reacting a polyester polyol with an isocyanate monomer or a prepolymer, and further adding 2-hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2 It can be easily obtained by reacting a (meth) acrylate monomer having a hydroxy group such as hydroxypropyl (meth) acrylate. For example, a mixture of 100 parts of Unidic 17-806 (manufactured by DIC Corporation) and 1 part of Coronate L (manufactured by Nippon Polyurethane Industry Co., Ltd.) described in JP-A-59-151110 is preferably used.

  UV curable polyester (meth) acrylate resin is easy by reacting monomers such as 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, and (meth) acrylic acid to the hydroxyl or carboxy group at the end of the polyester. (For example, JP-A-59-151112).

  The ultraviolet curable epoxy (meth) acrylate resin can be obtained by reacting a terminal hydroxyl group of the epoxy resin with a monomer such as (meth) acrylic acid, (meth) acrylic acid chloride, or glycidyl (meth) acrylate. . For example, Unidic V-5500 (manufactured by DIC Corporation) can be used.

  The ultraviolet curable polyol (meth) acrylate resin is not particularly limited, but ethylene glycol (meth) acrylate, polyethylene glycol di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol. Examples include tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and alkyl-modified dipentaerythritol penta (meth) acrylate.

  Moreover, as a polysiloxane type | system | group hard-coat material applicable to formation of a hard-coat layer, the compound represented by following General formula (1) is preferable.

In the general formula (1), R and R ₁ each independently represent a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, and m and n are m + n = 4. An integer that satisfies the relationship.

  Specific compounds include tetramethoxysilane, tetraethoxysilane, tetra-iso-propoxysilane, tetra-n-popropoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, tera Pentaethoxysilane, tetrapenta-iso-propoxysilane, tetrapenta-n-propoxysilane, tetrapenta-n-butoxysilane, tetrapenta-sec-butoxysilane, tetrapenta-tert-butoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyl Tributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethylethoxysilane, dimethylmethoxysilane, dimethylpropoxysilane, dimethylbutoxy Emissions, dimethyldimethoxysilane, dimethyldiethoxysilane, hexyl trimethoxysilane. In addition, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-β- ( N-aminobenzylaminoethyl) -γ-aminopropylmethoxysilane / hydrochloride, γ-glycidoxypropyltrimethoxysilane, aminosilane, methylmethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloro Mention may be made of propyltrilimethoxysilane, hexamethyldisilazane, vinyltris (β-methoxyethoxy) silane, octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride. Those having a hydrolyzable group such as methoxy group or ethoxy group substituted with a hydroxy group are generally referred to as polyorganosiloxane hard coat materials.

  Specifically, the polyorganosiloxane-based hard coat material is Surcoat series, BP-16N (manufactured by Doken Co., Ltd.), SR2441 (manufactured by Toray Dow Corning Co., Ltd.), Perma-New 6000 (California Hardcoating Company) ) Etc. can be used.

  Among these, it is preferable to use an active energy ray-curable resin in consideration of hardness after curing, shrinkage stress, and the like. That is, the hard coat layer preferably contains an active energy ray curable resin.

  The amount of the hard coat material in the hard coat layer is not particularly limited, but is preferably 20 to 100% by mass and more preferably 30 to 99.9% by mass with respect to the solid content of the hard coat layer. .

  Moreover, it is desirable that the hard coat layer has a configuration that does not promote shrinkage even under sunlight exposure conditions. In order to suppress or prevent such shrinkage, the hard coat layer may contain an ultraviolet absorber and / or an antioxidant. The ultraviolet absorber and / or antioxidant that can be used when the hard coat layer contains an ultraviolet absorber or an antioxidant is not particularly limited, and known ultraviolet absorbers and antioxidants can be used. Specifically, as the antioxidant, 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 2,2′-methylenebis (4-ethyl-6-t) -Butylphenol), tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] phenolic antioxidants such as methane; distearyl-3,3′-thio Thiol antioxidants such as dipropionate, pentaerythritol-tetrakis- (β-lauryl-thiopropionate); tris (2,4-di-t-butylphenyl) phosphite, distearyl pentaerythritol diphosphite Phosphite antioxidants such as di (2,6-di-t-butylphenyl) pentaerythritol diphosphite; bis (2,2 6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) hindered amine antioxidants such sebacate; and the like. In addition, you may use antioxidant alone or in mixture of 2 or more types. As the antioxidant, a synthetic product or a commercially available product may be used. Examples of commercially available products include, for example, NOCRACK (registered trademark) series (manufactured by Ouchi Shinsei Chemical Co., Ltd.), ADK STAB (registered trademark) series (manufactured by ADEKA Corporation), IRGANOX (registered trademark) series, IRGAFOS ( (Registered trademark) series (all of which are manufactured by Ciba Specialty Chemicals) and Sumilizer (registered trademark) series (which are manufactured by Sumitomo Chemical Co., Ltd.).

  Moreover, as an ultraviolet absorber, the same thing as described in the following adhesion layer can be used.

  When the hard coat layer contains an ultraviolet absorber or an antioxidant, the content thereof is preferably 0.05 to 10% by mass with respect to the total mass of the hard coat layer, and 0.1 to 5 It is more preferable that the amount is not more than mass%. This is because when the hard coat layer is irradiated with ultraviolet rays, the reaction in the hard coat layer is accelerated and the shrinkage stress is increased. In addition, a phenomenon in which the hard coat layer itself becomes brittle due to decomposition of the resin in the hard coat layer may occur. Therefore, by including an ultraviolet absorber or an antioxidant in the hard coat layer, shrinkage and decomposition of the hard coat layer can be suppressed, so that weather resistance adhesion can be improved. In addition, the said content intends these total amounts, when a hard-coat layer contains both a ultraviolet absorber and antioxidant.

  Alternatively, the hard coat layer may contain inorganic fine particles. Preferable inorganic fine particles include fine particles of an inorganic compound containing a metal such as titanium, silica, zirconium, aluminum, magnesium, antimony, zinc or tin. The average particle size of the inorganic fine particles is preferably 1000 nm or less, and more preferably in the range of 10 to 500 nm, in order to ensure visible light transmittance. In addition, since inorganic fine particles have a higher bonding strength with the curable resin forming the hard coat layer, they can be prevented from falling out of the hard coat layer, so that a photopolymerization reactivity such as monofunctional or polyfunctional acrylate is present. Those having a functional group introduced on the surface are preferred.

  Alternatively, the hue can be adjusted by adding a dye or a pigment to the hard coat layer. For example, cadmium red, molybdenum red, chromium permillion, chromium oxide, viridian, titanium cobalt green, cobalt green, cobalt chrome green, Victoria green, ultramarine blue, ultramarine blue, bitumen, Berlin blue, miloli blue, cobalt blue, cerulean blue, Colored inorganic pigments such as cobalt silica blue, cobalt zinc blue, manganese violet, mineral violet, and cobalt violet, organic pigments such as phthalocyanine pigments, and anthraquinone dyes are preferably used.

  The layer thickness of the hard coat layer is preferably 0.1 to 50 μm, more preferably 0.5 to 20 μm, and still more preferably 1 to 10 μm. If it is 0.1 μm or more, the hard coat property tends to be improved. Conversely, if it is 50 μm or less, the transparency of the optical control film can be improved.

As a method of forming a hard coat layer on the reflective layer film, a coating liquid for hard coat layer is applied by coating with a wire bar, spin coating, dip coating, etc. on an optical reflective layer composed of a high refractive index layer and a low refractive index layer. The film can be formed by a dry film forming method such as vapor deposition. Moreover, it is possible to apply and form a film using a continuous coating apparatus such as a die coater, a gravure coater, or a comma coater. For example, in the case of a polysiloxane-based hard coat material, after coating, after drying the solvent, heat treatment for 30 minutes to several days in a temperature range of 50 to 150 ° C. in order to promote curing and crosslinking of the hard coat material It is preferable to carry out. In consideration of the heat resistance of the coated substrate and the stability of the substrate when it is formed into a laminated roll, it is preferable to perform the treatment for 2 days or more within the range of 40 to 80 ° C. When an active energy ray curable resin is used, the reactivity varies depending on the irradiation wavelength, the illuminance, and the light amount of the active energy ray, and therefore it is necessary to select optimum conditions depending on the resin to be used. However, for example, when an ultraviolet lamp is used as the active energy ray, the illuminance is preferably 50 to 1500 mW / cm ² and the irradiation energy amount is preferably 50 to 1500 mJ / cm ² .

  The solvent used when the hard coat layer is formed by a coating method is not particularly limited, and examples thereof include toluene, xylene, cyclohexane, methanol, ethanol, isopropanol, butanol, cyclohexanol, acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, Examples include diisobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, tetrahydrofuran, ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (ethyl cellosolve), methyl acetate, ethyl acetate, and methyl lactate. . These solvents can be used alone or in combination.

  The coating liquid for forming the hard coat layer may contain a surfactant. When a coating film is formed with a coating liquid for forming a hard coat layer containing a surfactant, it becomes a highly leveled coating film, thus preventing the formation of parts with a high or low residual solvent amount. In addition, it can be expected that the adhesion of the hard coat layer is improved. Moreover, water repellency, slipperiness, etc. can be provided to the hard coat layer. There is no restriction | limiting in particular as a kind of surfactant, A fluorine-type surfactant, an acrylic surfactant, a silicone-type surfactant, etc. can be used. In particular, a fluorosurfactant is preferably used from the viewpoint of leveling properties, water repellency, and slipperiness of the coating solution. As examples of these surfactants, those described above for the optical reflection layer can be used.

  The amount of the surfactant in the hard coat layer can be adjusted by changing the blending amount of the surfactant in the hard coat coating solution, and the mass of the surfactant per dry mass of the hard coat layer is 0.01-5. It is preferable that it is mass%.

  Moreover, the optical control film according to the present invention may further have an adhesive layer on the substrate, the optical reflection layer, or the hard coat layer.

  The adhesive layer preferably has an immediate adhesive force of 2 to 8 N / 25 mm at the time of application to the substrate (for example, glass), and the immediate adhesive force is 4 to 8 N / 25 mm. Immediate adhesive strength means the adhesive strength of the adhesive layer measured 24 hours after sticking the optical control film on glass. The adhesive strength of the adhesive layer can be adjusted by appropriately selecting the material constituting the adhesive layer.

  Moreover, the immediate adhesive force of the said adhesion layer and glass at the time of affixing is 4-8N / 25mm, and the adhesion layer and glass at the time of being left for one week on 30 degreeC and 60% of humidity with a sticking state remain | survived. The adhesive strength with time is preferably 7 to 15 N / 25 mm from the viewpoint of curved surface adhesion. Furthermore, it is more preferable that the adhesive strength with time is 10 to 15 N / 25 mm from the viewpoint of improving durability and reducing adhesive residue. The adhesive strength with time indicates the adhesive strength of the adhesive layer measured after a certain period of time after the optical control film was attached to glass.

  When the optical control film according to the present invention is attached to a window glass, water is sprayed on the window, and the attachment method of attaching the adhesive layer of the optical control film to the wet glass surface, the so-called water application method is re-adjusted and repositioned. Etc. from the viewpoint of the above. For this reason, a pressure-sensitive adhesive having a low adhesive strength in the presence of water is preferable.

  The adhesive which comprises an adhesion layer is not specifically limited, A well-known adhesive can be used similarly. Specific examples include acrylic adhesives, silicon adhesives, urethane adhesives, polyvinyl butyral adhesives, ethylene-vinyl acetate adhesives, and the like. Among these, acrylic pressure-sensitive adhesives are preferable from the viewpoints of durability, transparency, and ease of adjustment of adhesive properties. The acrylic pressure-sensitive adhesive uses an acrylic resin that is mainly composed of alkyl acrylate and copolymerized with a polar monomer component. The alkyl acrylate ester is an alkyl ester of acrylic acid or methacrylic acid and is not particularly limited. For example, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, (meth ) Pentyl acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, and the like. Commercially available products may be used as the pressure-sensitive adhesive, specifically, Toyo Ink BPS5978, Nippon Synthetic Chemical Coponil (for example, N-2147, 5697, 5698, 5705L) and the like can be used.

  Moreover, when forming an adhesive layer with an acrylic adhesive, the hardening | curing agent of an acrylic adhesive can be used. The curing agent for the acrylic pressure-sensitive adhesive is not particularly limited, and for example, an isocyanate-based, epoxy-based, or alidiline-based curing agent can be used. As the isocyanate curing agent, an aromatic type such as tonoleylene diisocyanate (TDI) can be preferably used in order to obtain a stable adhesive force even after long-term storage and to form a harder adhesive layer. Specifically, Toyo Ink BXX5134 can be used.

  It is preferable that the addition amount (solid content conversion) of a hardening | curing agent is 2-9 mass% with respect to an adhesive, More preferably, it is 3-7 mass%. If it is such a range, an adhesive will not remain easily and sufficient adhesive force can also be ensured.

  The pressure-sensitive adhesive layer may contain an additive in addition to the pressure-sensitive adhesive. Here, the additive is not particularly limited. For example, a stabilizer, a surfactant, an ultraviolet absorber, a silane coupling agent, a flame retardant, an antistatic agent, an antioxidant (antioxidant), and a heat stabilizer. , Lubricants, fillers, coloring, adhesion regulators and the like. Among these, it is preferable that an adhesion layer contains a ultraviolet absorber. By providing an adhesive layer containing an ultraviolet absorber on the incident side of sunlight with respect to the optical reflection layer, the amount of sunlight (particularly infrared light) entering the optical reflection layer (the amount of sunlight absorbed by the optical reflection layer) is Reduce more. Moreover, when using the optical control film which concerns on this invention for window sticking, degradation of the light reflection film by an ultraviolet-ray can be suppressed.

  Here, it does not restrict | limit especially as an ultraviolet absorber, A well-known ultraviolet absorber can be used. For example, benzophenone ultraviolet absorbers such as 2,4-dihydroxy-benzophenone and 2-hydroxy-4-methoxy-benzophenone; 2- (2′-hydroxy-5-methylphenyl) benzotriazole, 2- (2′-hydroxy -3 ', 5'-di-t-butylphenyl) benzotriazole UV absorbers such as benzotriazole; phenyl salicylate, 2-4-di-t-butylphenyl-3,5-di-t-butyl Phenyl salicylate UV absorbers such as -4-hydroxybenzoate; hindered amine UV absorbers such as bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate; 2,4-diphenyl-6- ( 2-hydroxy-4-methoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2 Triazine-based UV absorbers such as hydroxy-4-ethoxyphenyl) -1,3,5-triazine; and the like.

  In addition to the above, the ultraviolet absorber includes a compound having a function of converting the energy held by ultraviolet rays into vibrational energy in the molecule and releasing the vibrational energy as thermal energy or the like.

  In addition, you may use a ultraviolet absorber individually or in mixture of 2 or more types. Moreover, as the ultraviolet absorber, a synthetic product or a commercially available product may be used. Examples of commercially available products include, for example, Tinuvin (registered trademark) 320, Tinuvin (registered trademark) 328, Tinuvin (registered trademark) 234, Tinuvin (registered trademark) 477, Tinuvin (registered trademark) 1577, and Tinuvin (registered trademark) 622. (Above, manufactured by BASF Japan Ltd.), ADK STAB (registered trademark) LA-31 (above, manufactured by ADEKA CORPORATION), SESORB (registered trademark) 102, SESORB (registered trademark) 103, SEESORB (registered trademark) 501 (or more, Cipro Kasei Co., Ltd.).

  It is preferable that the addition amount (in solid content conversion) of a ultraviolet absorber is 0.1-10 mass% with respect to an adhesive, More preferably, it is 0.5-5 mass%. If it is such a range, the sunlight absorption amount of an optical reflection layer can be reduced more effectively.

  1-100 micrometers is preferable and, as for the thickness of the adhesion layer, 3-50 micrometers is more preferable. If it is 1 micrometer or more, there exists a tendency for adhesiveness to improve and sufficient adhesive force is acquired. On the contrary, if the thickness is 100 μm or less, not only the transparency of the optical control film is improved, but also when the optical control film is attached to the window glass and then peeled off, no cohesive failure occurs between the adhesive layers, and adhesion to the glass surface There is a tendency that there is no remaining agent.

  The method for forming the adhesive layer is not particularly limited, but separately from the desired component (base material, optical reflection layer or hard coat layer), the adhesive layer coating liquid is applied on the separator and dried to form the adhesive layer. After the formation, a method in which the member and the adhesive layer are bonded together is preferable.

  Examples of the separator used at this time include a silicone-coated release PET film and a silicone-coated PE film. The method of applying the coating solution for the adhesive layer on the separator is not particularly limited, and examples thereof include a method of applying the coating solution by wire bar coating, spin coating, dip coating, etc., and forming a film. It is possible to apply and form a film using a continuous coating apparatus such as a coater or a comma coater.

  In the present specification, “adhesive strength” is determined by measuring according to JIS A 5759: 2008 6.8 adhesive strength test, and more specifically, measured according to the method described in the following examples. Is done.

  Further, the optical control film according to the present invention has other layers (for example, a conductive layer, an antistatic layer, a gas barrier layer, an easy-adhesion layer, an antifouling layer, a deodorant layer, a droplet layer, an easy-slip layer, and wear resistance. 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, infrared cut layer (metal layer, liquid crystal layer), colored layer (visible light) Absorbing layer) and one or more functional layers such as an interlayer film used for laminated glass may be used alone or in appropriate combination.

(Optical control body)
The optical control film provided by the present invention can be applied to a wide range of fields. For example, it can be used as a window pasting film such as an infrared shielding film which is attached to facilities exposed to sunlight for a long period of time such as an outdoor window of a building or an automobile window and imparts an infrared shielding effect.

  That is, according to the further another form of this invention, the optical control body which uses the optical control film which concerns on this invention is provided. Specifically, a light reflector in which the above-described optical control film is attached to a light-transmitting substrate is also provided. The light reflector has a structure in which an optical control film is bonded to a light-transmitting substrate via an adhesive layer.

  Specific examples of the light transmissive 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, Examples include melamine resin, phenol resin, diallyl phthalate resin, polyimide resin, urethane resin, polyvinyl acetate resin, polyvinyl alcohol resin, styrene resin, and vinyl chloride resin. Further, the light-transmitting substrate may have total light transmittance or may have light transmittance for a partial wavelength region.

  The operational effects of the present invention can be expressed more effectively when the light-transmitting substrate is a curved surface. “Curved surface” means a surface having a radius of curvature of 3 m or less. The reason why the radius of curvature is 3 m or less is that when the radius of curvature exceeds 3 m, there is no difference from a planar substrate.

  The effects of the present invention will be described using the following examples and comparative examples. However, the technical scope of the present invention is not limited only to the following examples. In the following examples, the operation was performed at room temperature (25 ° C.) unless otherwise specified. Unless otherwise specified, “%” and “part” mean “% by mass” and “part by mass”, respectively.

<Preparation of coating solution 1 for low refractive index layer>
The following constituent materials were added and mixed in this order at 45 ° C., and then finished with 1000 parts of pure water to prepare a coating solution 1 for a low refractive index layer.

<Preparation of coating solutions 2 to 6 for low refractive index layer>
The ethanol concentration is 0.5 mass% (low refractive index layer coating liquid 2) and 1 mass% (low refractive index layer coating liquid 3) with respect to the low refractive index layer coating liquid 1 prepared above. ) Ethanol was added so as to be 2% by mass (low refractive index layer coating solution 4), 4% by mass (low refractive index layer coating solution 5) and 8% by mass (low refractive index layer coating solution 6). By adding, coating solutions 2 to 6 for the low refractive index layer were prepared.

<Preparation of coating solution 7 for low refractive index layer>
1-propanol was added to the coating solution 1 for the low refractive index layer prepared above so that the concentration of 1-propanol was 2% by mass to prepare a coating solution 7 for the low refractive index layer.

<Preparation of coating liquid 8 for low refractive index layer>
2-Propanol was added to the coating solution 1 for the low refractive index layer prepared above so that the concentration of 2-propanol was 1.5% by mass to prepare a coating solution 8 for the low refractive index layer. .

<Preparation of coating solution 9 for low refractive index layer>
1-butanol was added to the coating solution 1 for the low refractive index layer prepared above so that the concentration of 1-butanol was 1% by mass to prepare a coating solution 9 for the low refractive index layer.

<Preparation of coating solution 10 for low refractive index layer>
Neoethanol AP-11 was added to the coating solution 1 for the low refractive index layer prepared above so that the concentration of Neoethanol AP-11 (manufactured by Daishin Chemical Co., Ltd.) was 3% by mass, A coating solution 10 for a low refractive index layer was prepared. Neoethanol AP-11 is a mixed liquid composed of ethanol 85.5 ± 1.0 vol%, methanol 4.7 ± 0.5 vol%, and 2-propanol 9.8 ± 0.5 vol%.

<Preparation of coating solution 11 for low refractive index layer>
Ethylene glycol butyl ether was added to the low refractive index layer coating solution 1 prepared above so that the concentration of ethylene glycol butyl ether was 1% by mass to prepare a low refractive index layer coating solution 11.

<Preparation of coating solution 12 for low refractive index layer>
Propylene glycol methyl ether was added to the low refractive index layer coating solution 1 prepared above so that the concentration of propylene glycol methyl ether was 1% by mass to prepare a low refractive index layer coating solution 12. .

<Preparation of coating solution 13 for low refractive index layer>
Dipropylene glycol n-propyl ether is added to the coating solution 1 for the low refractive index layer prepared above so that the concentration of dipropylene glycol n-propyl ether is 1% by mass. A coating solution 13 was prepared.

<Preparation of coating solutions 14 to 16 for the low refractive index layer>
The concentration of propylene glycol butyl ether is 1% by mass (low refractive index layer coating solution 14) and 0.5% by mass (low refractive index layer coating) with respect to the low refractive index layer coating solution 1 prepared above. Propylene glycol butyl ether was added so that it might become the liquid 15) and 2 mass% (coating liquid 16 for low refractive index layers), and the coating liquids 14-16 for low refractive index layers were prepared.

<Preparation of coating liquid 17 for low refractive index layer>
1-propanol was added to the coating solution 1 for the low refractive index layer prepared above so that the concentration of ethanol was 10% by mass to prepare a coating solution 17 for the low refractive index layer.

<Preparation of coating liquid 18 for low refractive index layer>
2-Propanol was added to the coating solution 1 for a low refractive index layer prepared above so that the concentration of 2-propanol was 10% by mass to prepare a coating solution 18 for a low refractive index layer.

<Preparation of coating liquid 19 for low refractive index layer>
Propylene glycol butyl ether was added to the low refractive index layer coating solution 1 prepared above so that the concentration of propylene glycol butyl ether was 10% by mass to prepare a low refractive index layer coating solution 19.

<Preparation of high refractive index layer coating solution 1>
(Preparation of silica-modified titanium oxide particle dispersion)
A dispersion of silica-modified titanium oxide particles was prepared as follows.

That is, a titanium sulfate aqueous solution was thermally hydrolyzed by a known method to obtain titanium oxide hydrate. The obtained titanium oxide hydrate was suspended in water to obtain 10 L of an aqueous suspension of titanium oxide hydrate (TiO ₂ concentration: 100 g / L). To this, 30 L of an aqueous sodium hydroxide solution (concentration 10 mol / L) was added with stirring, the temperature was raised to 90 ° C., and the mixture was aged for 5 hours. The obtained solution was neutralized with hydrochloric acid, filtered and washed with water to obtain a base-treated titanium compound.

Next, the base-treated titanium compound was suspended in pure water and stirred so that the TiO ₂ concentration was 20 g / L. Under stirring, it was added citric acid in an amount of 0.4 mol% with respect to TiO ₂ weight. The temperature was raised to 95 ° C., concentrated hydrochloric acid was added so that the hydrochloric acid concentration was 30 g / L, and the solution temperature was maintained, followed by stirring for 3 hours. Here, when the pH and zeta potential of the obtained mixed liquid were measured, the pH at 25 ° C. was 1.4, and the zeta potential was +40 mV. Further, when the particle size was measured by Zetasizer Nano (manufactured by Malvern), the volume average particle size was 20 nm and the monodispersity was 16%.

  1 kg of pure water was added to 1 kg of 20 mass% titanium oxide sol aqueous dispersion containing rutile-type titanium oxide particles prepared as described above to prepare a 10 mass% titanium oxide sol aqueous dispersion.

2 kg of pure water was added to 0.5 kg of the 10 mass% titanium oxide sol aqueous dispersion, and then heated to 90 ° C. Thereafter, 1.3 kg of an aqueous silicic acid solution having a SiO ₂ concentration of 2.0 mass% was gradually added. The obtained dispersion is subjected to heat treatment at 175 ° C. for 18 hours in an autoclave, and further concentrated to contain SiO ₂ coated titanium oxide having a rutile structure and having a solid content concentration of 20% by mass. A dispersion (sol water dispersion) of titanium dioxide sol (hereinafter referred to as silica-modified titanium oxide particles) (volume average particle size: 35 nm) having ₂ attached to the surface was obtained.

(Preparation of coating solution)
The following constituent materials were sequentially added at 45 ° C. to the sol dispersion of silica-modified titanium oxide particles prepared above, and finally finished with 1000 parts of pure water to prepare a coating solution 1 for a high refractive index layer.

<Preparation of coating liquid 2 for high refractive index layer>
Ethanol was added to the coating solution 1 for the high refractive index layer prepared above so that the ethanol concentration was 2% by mass to prepare the coating solution 2 for the high refractive index layer.

<Preparation of coating solution 3 for high refractive index layer>
Ethylene glycol butyl ether was added to the coating solution 1 for the high refractive index layer prepared above so that the concentration of ethylene glycol butyl ether was 1% by mass to prepare a coating solution 3 for the high refractive index layer.

<Preparation of coating solution 4 for high refractive index layer>
Propylene glycol methyl ether was added to the coating solution 1 for the high refractive index layer prepared above so that the concentration of propylene glycol methyl ether was 1% by mass to prepare a coating solution 4 for the high refractive index layer. .

<Preparation of coating liquid 5 for high refractive index layer>
Dipropylene glycol n-propyl ether is added to the coating solution 1 for the high refractive index layer prepared above so that the concentration of dipropylene glycol n-propyl ether is 1% by mass. A coating solution 5 was prepared.

<Preparation of coating solutions 6 and 7 for the high refractive index layer>
The concentration of propylene glycol butyl ether is 1% by mass (high refractive index layer coating solution 6) and 2% by mass (high refractive index layer coating solution 7) with respect to the coating solution 1 for high refractive index layer prepared above. ), Propylene glycol butyl ether was added to prepare coating solutions 6 and 7 for the high refractive index layer.

<Preparation of coating liquid 8 for high refractive index layer>
Propylene glycol butyl ether was added to the coating solution 1 for a high refractive index layer prepared above so that the concentration of propylene glycol butyl ether was 10% by mass to prepare a coating solution 8 for a high refractive index layer.

Example 1
<Preparation of transparent substrate>
As a transparent substrate, a polyethylene terephthalate film (A4300, double-sided easy-adhesive layer, thickness: 50 μm, length 200 m × width 210 mm, manufactured by Toyobo Co., Ltd., hereinafter also abbreviated as “PET film”) was prepared.

<Formation of optical reflection layer on substrate>
Using a slide hopper type wet coating apparatus capable of 15-layer coating, the low refractive index layer coating liquid 2, the low refractive index layer coating liquid 1 and the high refractive index layer coating liquid 1 prepared above are kept at 40 ° C. On the other hand, 15 layers were applied on the transparent substrate at a coating speed (support conveyance direction) of 100 m / min. Immediately after coating each refractive index layer coating solution, cold air of 5 ° C. was blown and set. At this time, even if the surface was touched with a finger, the time until the finger was lost (set time) was 1 minute. After completion of the setting, warm air of 80 ° C. was blown and dried to form a 15-layer optical reflection layer on the substrate (laminate 1). At this time, the lowermost layer and the uppermost layer were low refractive index layers, and other than that, the low refractive index layers and the high refractive index layers were alternately laminated. Also, the low refractive index layer coating liquid 2 is used to form the lowest refractive index layer, the low refractive index layer coating liquid 1 is used to form the other low refractive index layers, and the high refractive index layer is formed. A coating solution 1 for a high refractive index layer was used. The coating amount was adjusted such that the film thickness during drying was 150 nm for each low refractive index layer and 130 nm for each high refractive index layer. In addition, the said film thickness was confirmed by cut | disconnecting the manufactured laminated body (a base material and an optical reflection layer), and observing the cut surface with an electron microscope. At this time, when the interface between the two layers could not be clearly observed, the interface was determined by the XPS profile in the thickness direction of TiO ₂ contained in the layer obtained by the XPS surface analyzer.

  About the liquid landing property of the coating head (lowermost layer) and the coating film after coating / drying (coating irregularity) during coating of the coating solution 1 for the low refractive index layer and the coating solution 1 for the high refractive index layer The results of evaluation according to the following evaluation criteria are shown in Table 2 below. In Table 2, “Liquidability” and “Coating unevenness” were evaluated as follows.

<Adhesion layer formation on the base material on which the optical reflection layer is formed>
(Preparation of adhesive layer forming coating solution 1)
100 parts by mass of an acrylic resin having a hydroxy group, 50 parts by mass of MKC methyl silicate MS-56 (Mitsubishi Chemical's tetramethyl silicate partial hydrolyzate condensate, n average value = 10), 1 part by mass of dibutyltin laurate, xylene 700 parts by mass and 150 parts by mass of isopropyl alcohol were mixed and stirred to prepare a resin mixture having a solid content of 10% by mass.

  The obtained resin mixture was mixed with 2.0 parts by mass of Tinuvin 477 (a UV absorber manufactured by BASF Japan Ltd.) to prepare a coating solution 1 for forming an adhesive layer.

  The prepared coating solution 1 for forming an adhesive layer is coated with a wire bar on the optical reflective layer formed as described above so that the dry film thickness is 8 μm, and dried at 80 ° C. for 2 minutes. An adhesive layer was formed. A 25 μm thick polyester film (therapy, manufactured by Toyo Metallizing Co., Ltd.) was bonded as a separator film to the surface of the adhesive layer by a bonding machine. Thus, the optical control film 1 was produced.

<Production of optical control body>
After cutting the optical control film 1 produced above to a width of 10 cm and a length of 10 cm, the adhesive layer side is applied to a commercially available blue plate glass having a thickness of 3 mm, and water is applied to the glass plate surface and bonded together by a water bonding method. A sample was prepared. The sample was placed on a roll with a roller so that only the weight of a steel roller covered with a 6 mm thick rubber was placed on a roll having a diameter of 15.2 cm (6 inches) and a width of 100 mm and covered with rubber having a thickness of 6 mm. Glass was pressure-bonded to produce the optical control body 1.

  About the optical control film 1 or the optical control body 1 produced as described above, visible light transmittance (%) and near-infrared reflectance (%), visible light transmittance (% ) And near-infrared reflectance (%), and cracks after the weather resistance test were evaluated. The results are shown in Table 2 below.

<Measurement of visible light transmittance and near infrared reflectance>
About the optical control body 1, using the spectrophotometer (integral sphere use, the Hitachi Ltd. make, U-4000 type | mold), as a visible light transmittance | permeability, the average transmittance | permeability in the area | region of 380 nm-750 nm is set as a near-infrared reflectance. The reflectance at 800 to 1300 nm was measured.

<Haze>
About ten optical control films 1, haze was measured using the haze meter (NDH2000 type | mold, Nippon Denshoku Industries Co., Ltd.), and the average value was computed. The light source of the haze meter was a 5V9W halogen sphere, and a silicon photocell (with a relative visibility filter) was used as the light receiving part. The haze was measured at 23 ° C. and 55% RH.

<Evaluation of weather resistance (visible light transmittance and near infrared reflectance)>
The optical control film 1 was irradiated with a super xenon weather meter (Suga Test Machine SX75) for 300 hours under a cycle condition with a radiation intensity of 180 W / m ² and a rainfall of 18 minutes / 40 minutes to perform a weather resistance test. After the weather resistance test, the visible light transmittance and the near infrared reflectance were measured in the same manner as in the above <Measurement of visible light transmittance and near infrared reflectance>. In Table 2 below, the above results are shown as the visible light transmittance and the near infrared reflectance after the weather resistance test.

<Evaluation of weather resistance (cracking)>
Using a super xenon weather meter (Suga Test Machine SX75), the optical control body 1 was irradiated for 300 hours under a cycle condition with a radiation intensity of 180 W / m ² and a rainfall of 18 minutes / 40 minutes to perform a weather resistance test. The state of film cracking of the optical reflection layer of the optical control body after the weather resistance test was visually observed with a 5-fold magnifier and evaluated according to the following evaluation criteria. Note that “A”, “B”, and “C” are practical. In addition, in the following Table 2, the said result is shown as a crack after a weather resistance test.

(Examples 2 to 14)
In Example 1, instead of the coating solution 2 for the low refractive index layer, the coating solutions 3 to 15 for the low refractive index layer were used for forming the lowermost low refractive index layer, respectively. Then, an optical reflection layer was formed on the substrate (laminates 2 to 14). In addition, the liquid landing property and coating unevenness at this time were evaluated in the same manner as in Example 1, and the results are shown in Table 2.

  Next, in Example 1, optical control films 2 to 14 were produced in the same manner except that the laminates 2 to 14 produced above were used instead of the laminate 1.

  Furthermore, in Example 1, the optical control bodies 2-14 were produced like Example 1 except using the optical control films 2-14 produced above instead of the optical control film 1, respectively.

  About the optical control films 2-14 or the optical control bodies 2-14 produced as described above, in the same manner as in Example 1, the visible light transmittance (%) and the near infrared reflectance (%), the weather resistance test The visible light transmittance (%) and near-infrared reflectance (%) later, and cracks after the weather resistance test were evaluated. The results are shown in Table 2 below.

(Example 15)
In Example 1, the low-refractive-index layer coating liquid 4 is formed to form the lowermost low-refractive-index layer, the low-refractive-index layer coating liquid 4 is formed to form the other low-refractive-index layers, and the high-refractive-index layer. An optical reflective layer was formed on the substrate in the same manner as in Example 1 except that the high refractive index layer coating solution 2 was used instead for forming (Laminate 15). In addition, the liquid landing property and coating unevenness at this time were evaluated in the same manner as in Example 1, and the results are shown in Table 2.

  Next, in Example 1, an optical control film 15 was produced in the same manner except that the laminate 15 produced above was used instead of the laminate 1.

  Furthermore, in Example 1, the optical control body 15 was produced like Example 1 except using the optical control film 15 produced above instead of the optical control film 1. FIG.

  About the optical control film 15 or the optical control body 15 produced as described above, in the same manner as in Example 1, visible light transmittance (%) and near infrared reflectance (%), visible light after a weather resistance test The transmittance (%) and near-infrared reflectance (%), and cracks after the weather resistance test were evaluated. The results are shown in Table 2 below.

(Example 16)
In Example 1, the low-refractive-index layer coating liquid 14 is formed to form the lowermost low-refractive-index layer, the low-refractive-index layer coating liquid 4 is formed to form the other low-refractive-index layers, and the high-refractive-index layer. An optical reflective layer was formed on the base material in the same manner as in Example 1 except that the high refractive index layer coating solution 2 was used instead for forming (Laminate 16). In addition, the liquid landing property and coating unevenness at this time were evaluated in the same manner as in Example 1, and the results are shown in Table 2.

  Next, in Example 1, an optical control film 16 was produced in the same manner except that the laminate 16 produced above was used instead of the laminate 1.

  Further, in Example 1, an optical control body 16 was produced in the same manner as in Example 1 except that the optical control film 16 produced above was used instead of the optical control film 1.

  About the optical control film 16 or the optical control body 16 produced as described above, in the same manner as in Example 1, visible light transmittance (%) and near-infrared reflectance (%), visible light after weathering test The transmittance (%) and near-infrared reflectance (%), and cracks after the weather resistance test were evaluated. The results are shown in Table 2 below.

(Example 17)
In Example 1, the low refractive index layer coating liquid 8 is formed to form the lowermost low refractive index layer, the low refractive index layer coating liquid 11 is formed to form the other low refractive index layers, and the high refractive index layer. An optical reflective layer was formed on the substrate in the same manner as in Example 1 except that the coating solution 3 for the high refractive index layer was used instead for forming (Laminate 17). In addition, the liquid landing property and coating unevenness at this time were evaluated in the same manner as in Example 1, and the results are shown in Table 2.

  Next, in Example 1, an optical control film 17 was produced in the same manner except that the laminate 17 produced above was used instead of the laminate 1.

  Furthermore, in Example 1, the optical control body 17 was produced like Example 1 except using the optical control film 17 produced above instead of the optical control film 1. FIG.

  About the optical control film 17 or the optical control body 17 produced as described above, in the same manner as in Example 1, visible light transmittance (%) and near-infrared reflectance (%), visible light after weathering test The transmittance (%) and near-infrared reflectance (%), and cracks after the weather resistance test were evaluated. The results are shown in Table 2 below.

(Example 18)
In Example 1, the low refractive index layer coating solution 8 is used to form the lowermost low refractive index layer, the low refractive index layer coating solution 12 is used to form the other low refractive index layers, and the high refractive index layer. An optical reflective layer was formed on the substrate in the same manner as in Example 1 except that the coating solution 4 for the high refractive index layer was used in place of each other (Laminate 18). In addition, the liquid landing property and coating unevenness at this time were evaluated in the same manner as in Example 1, and the results are shown in Table 2.

  Next, in Example 1, the optical control film 18 was produced in the same manner except that the laminate 18 produced above was used instead of the laminate 1.

  Further, in Example 1, an optical control body 18 was produced in the same manner as in Example 1 except that the optical control film 18 produced above was used instead of the optical control film 1.

  About the optical control film 18 or the optical control body 18 produced as described above, in the same manner as in Example 1, visible light transmittance (%) and near-infrared reflectance (%), visible light after a weather resistance test The transmittance (%) and near-infrared reflectance (%), and cracks after the weather resistance test were evaluated. The results are shown in Table 2 below.

(Example 19)
In Example 1, the low-refractive-index layer coating liquid 8 is formed to form the lowermost low-refractive-index layer, the low-refractive-index layer coating liquid 13 is formed to form the other low-refractive-index layers, and the high-refractive-index layer. An optical reflective layer was formed on the substrate in the same manner as in Example 1 except that the high-refractive-index layer coating solution 5 was used instead for forming (Laminated body 19). In addition, the liquid landing property and coating unevenness at this time were evaluated in the same manner as in Example 1, and the results are shown in Table 2.

  Next, in Example 1, an optical control film 19 was produced in the same manner except that the laminate 19 produced above was used instead of the laminate 1.

  Furthermore, in Example 1, the optical control body 19 was produced like Example 1 except using the optical control film 19 produced above instead of the optical control film 1. FIG.

  About the optical control film 19 or the optical control body 19 produced as described above, in the same manner as in Example 1, visible light transmittance (%) and near-infrared reflectance (%), visible light after weathering test The transmittance (%) and near-infrared reflectance (%), and cracks after the weather resistance test were evaluated. The results are shown in Table 2 below.

(Example 20)
In Example 1, the low-refractive-index layer coating liquid 8 is formed to form the lowermost low-refractive-index layer, the low-refractive-index layer coating liquid 14 is formed to form the other low-refractive-index layers, and the high-refractive-index layer. An optical reflective layer was formed on the substrate in the same manner as in Example 1 except that the high-refractive index layer coating solution 6 was used instead for forming (Laminate 20). In addition, the liquid landing property and coating unevenness at this time were evaluated in the same manner as in Example 1, and the results are shown in Table 2.

  Next, in Example 1, an optical control film 20 was produced in the same manner except that the laminate 20 produced above was used instead of the laminate 1.

  Furthermore, in Example 1, the optical control body 20 was produced like Example 1 except using the optical control film 20 produced above instead of the optical control film 1. FIG.

  About the optical control film 20 or the optical control body 20 produced as described above, in the same manner as in Example 1, visible light transmittance (%) and near infrared reflectance (%), visible light after weathering test The transmittance (%) and near-infrared reflectance (%), and cracks after the weather resistance test were evaluated. The results are shown in Table 2 below.

(Example 21)
In Example 1, the low-refractive index layer coating liquid 8 is formed to form the lowermost low-refractive index layer, the low-refractive index layer coating liquid 1 is formed to form the other low-refractive index layers, and the high-refractive index layer. An optical reflective layer was formed on the base material in the same manner as in Example 1 except that the high refractive index layer coating solution 7 was used instead for forming (Laminate 21). In addition, the liquid landing property and coating unevenness at this time were evaluated in the same manner as in Example 1, and the results are shown in Table 2.

  Next, in Example 1, an optical control film 21 was produced in the same manner except that the laminate 21 produced above was used instead of the laminate 1.

  Further, in Example 1, an optical control body 21 was produced in the same manner as in Example 1 except that the optical control film 21 produced above was used instead of the optical control film 1.

  About the optical control film 21 or the optical control body 21 produced as described above, in the same manner as in Example 1, visible light transmittance (%) and near infrared reflectance (%), visible light after weathering test The transmittance (%) and near-infrared reflectance (%), and cracks after the weather resistance test were evaluated. The results are shown in Table 2 below.

(Example 22)
In Example 1, the low-refractive-index layer coating solution 8 is used to form the lowermost low-refractive-index layer, the low-refractive-index layer coating solution 16 is used to form the other low-refractive-index layers, and the high-refractive-index layer. An optical reflective layer was formed on the substrate in the same manner as in Example 1 except that the coating solution 1 for the high refractive index layer was used instead for forming (Laminate 22). In addition, the liquid landing property and coating unevenness at this time were evaluated in the same manner as in Example 1, and the results are shown in Table 2.

  Next, in Example 1, an optical control film 22 was produced in the same manner except that the laminate 22 produced above was used instead of the laminate 1.

  Furthermore, in Example 1, instead of the optical control film 1, an optical control body 22 was produced in the same manner as in Example 1 except that the optical control film 22 produced above was used.

  About the optical control film 22 or the optical control body 22 produced as described above, in the same manner as in Example 1, visible light transmittance (%) and near-infrared reflectance (%), visible light after weathering test The transmittance (%) and near-infrared reflectance (%), and cracks after the weather resistance test were evaluated. The results are shown in Table 2 below.

(Comparative Example 1)
In Example 1, in place of the low refractive index layer coating liquid 2, the low refractive index layer coating liquid 1 was used in the same manner as in Example 1 except that the lower refractive index layer coating liquid 1 was used for forming the lowest refractive index layer. A reflective layer was formed on the substrate (laminate 23). In addition, the liquid landing property and coating unevenness at this time were evaluated in the same manner as in Example 1, and the results are shown in Table 2.

  Next, in Example 1, an optical control film 23 was produced in the same manner except that the laminate 23 produced above was used instead of the laminate 1.

  Further, in Example 1, an optical control body 23 was produced in the same manner as in Example 1 except that the optical control film 23 produced above was used instead of the optical control film 1.

  About the optical control film 23 or the optical control body 23 produced as described above, in the same manner as in Example 1, visible light transmittance (%) and near infrared reflectance (%), visible light after a weather resistance test The transmittance (%) and near-infrared reflectance (%), and cracks after the weather resistance test were evaluated. The results are shown in Table 2 below.

(Comparative Example 2)
In Example 1, except that the low refractive index layer coating liquid 1 was used for forming the lowermost low refractive index layer, and the high refractive index layer coating liquid 2 was used instead for forming the high refractive index layer, respectively. In the same manner as in Example 1, an optical reflective layer was formed on the substrate (laminate 24). In addition, the liquid landing property and coating unevenness at this time were evaluated in the same manner as in Example 1, and the results are shown in Table 2.

  Next, in Example 1, the optical control film 24 was produced in the same manner except that the laminate 24 produced above was used instead of the laminate 1.

  Furthermore, in Example 1, the optical control body 24 was produced like Example 1 except using the optical control film 24 produced above instead of the optical control film 1. FIG.

  About the optical control film 24 or the optical control body 24 produced as described above, in the same manner as in Example 1, visible light transmittance (%) and near infrared reflectance (%), visible light after weathering test The transmittance (%) and near-infrared reflectance (%), and cracks after the weather resistance test were evaluated. The results are shown in Table 2 below.

(Comparative Example 3)
In Example 1, the low-refractive-index layer coating solution 1 is used instead for forming the lowermost low-refractive-index layer, and the low-refractive-index layer coating solution 4 is used instead for forming the other low-refractive-index layers. Except for this, an optical reflective layer was formed on the substrate in the same manner as in Example 1 (laminate 25). In addition, the liquid landing property and coating unevenness at this time were evaluated in the same manner as in Example 1, and the results are shown in Table 2.

  Next, in Example 1, an optical control film 25 was produced in the same manner except that the laminate 25 produced above was used instead of the laminate 1.

  Further, in Example 1, an optical control body 25 was produced in the same manner as in Example 1 except that the optical control film 25 produced above was used instead of the optical control film 1.

  About the optical control film 25 or the optical control body 25 produced as described above, in the same manner as in Example 1, visible light transmittance (%) and near-infrared reflectance (%), visible light after a weather resistance test The transmittance (%) and near-infrared reflectance (%), and cracks after the weather resistance test were evaluated. The results are shown in Table 2 below.

(Comparative Example 4)
In Example 1, the coating solution 1 for the low refractive index layer is formed for forming the lowest refractive index layer, the coating solution 14 for the low refractive index layer is formed for forming the other low refractive index layers, and the high refractive index layer. An optical reflective layer was formed on the substrate in the same manner as in Example 1 except that the high refractive index layer coating solution 6 was used instead for forming (Laminate 26). In addition, the liquid landing property and coating unevenness at this time were evaluated in the same manner as in Example 1, and the results are shown in Table 2.

  Next, in Example 1, an optical control film 26 was produced in the same manner except that the laminate 26 produced above was used instead of the laminate 1.

  Further, in Example 1, an optical control body 26 was produced in the same manner as in Example 1 except that the optical control film 26 produced above was used instead of the optical control film 1.

  About the optical control film 26 or the optical control body 26 manufactured as described above, in the same manner as in Example 1, visible light transmittance (%) and near-infrared reflectance (%), visible light after weathering test The transmittance (%) and near-infrared reflectance (%), and cracks after the weather resistance test were evaluated. The results are shown in Table 2 below.

(Comparative Example 5)
In Example 1, in place of the low refractive index layer coating solution 2, the low refractive index layer coating solution 17 was used in the same manner as in Example 1 except that the lower refractive index layer coating solution 17 was used for forming the lowest refractive index layer. A reflective layer was formed on the substrate (laminate 27). In addition, the liquid landing property and coating unevenness at this time were evaluated in the same manner as in Example 1, and the results are shown in Table 2.

  Next, in Example 1, an optical control film 27 was produced in the same manner except that the laminate 27 produced above was used instead of the laminate 1.

  Furthermore, in Example 1, instead of the optical control film 1, an optical control body 27 was produced in the same manner as in Example 1 except that the optical control film 27 produced above was used.

  About the optical control film 27 or the optical control body 27 manufactured as described above, in the same manner as in Example 1, visible light transmittance (%) and near-infrared reflectance (%), visible light after weathering test The transmittance (%) and near-infrared reflectance (%), and cracks after the weather resistance test were evaluated. The results are shown in Table 2 below.

(Comparative Example 6)
In Example 1, the low-refractive-index layer coating liquid 18 is formed to form the lowermost low-refractive-index layer, the low-refractive-index layer coating liquid 19 is formed to form the other low-refractive-index layers, and the high-refractive-index layer. An optical reflective layer was formed on the substrate in the same manner as in Example 1 except that the high refractive index layer coating solution 8 was used instead for forming (Laminate 28). In addition, the liquid landing property and coating unevenness at this time were evaluated in the same manner as in Example 1, and the results are shown in Table 2. In addition, in this example, many blockings were recognized after drying and winding up the coating film.

  Next, in Example 1, an optical control film 28 was produced in the same manner except that the laminate 28 produced above was used instead of the laminate 1.

  Further, in Example 1, an optical control body 28 was produced in the same manner as in Example 1 except that the optical control film 28 produced above was used instead of the optical control film 1.

  About the optical control film 28 or the optical control body 28 produced as described above, in the same manner as in Example 1, visible light transmittance (%) and near-infrared reflectance (%), visible light after weathering test The transmittance (%) and near-infrared reflectance (%), and cracks after the weather resistance test were evaluated. The results are shown in Table 2 below.

  Table 1 below summarizes the types and amounts of the hydrophilic organic solvents used in Examples 1 to 22 and Comparative Examples 1 to 6 for forming the low refractive index layer and the high refractive index layer.

  From Table 1 above, the optical control film of the present invention improves the liquid landing property of the coating liquid by forming the lowermost layer using a coating liquid containing a hydrophilic organic solvent having a specific concentration, and the occurrence of coating unevenness. It turns out that it can suppress. Moreover, it turns out that the optical control film provided in this way and the optical control body provided with the said optical control film are excellent in weather resistance, maintaining high heat ray shielding property.

Claims (3)

A method for producing an optical control film comprising at least one unit in which a high refractive index layer and a low refractive index layer are alternately laminated on a substrate,
For the high refractive index layer (A) or low refractive index layer (A ′) closest to the substrate, a coating solution containing a resin, metal oxide particles, and a hydrophilic organic solvent having a concentration of 0.1 to 8% by mass is used. A method for producing an optical control film.   The manufacturing method of the optical control film of Claim 1 whose said hydrophilic organic solvent is a C2-C4 monohydric alcohol or glycol ether. A high refractive index layer (A) or a low refractive index layer (A ′) closest to the substrate is made of resin, metal oxide particles and a monohydric alcohol having 2 to 4 carbon atoms and having a concentration of 0.1 to 8% by mass. Formed using a coating solution containing,
At least one of the high refractive index layer and the low refractive index layer other than the high refractive index layer (A) or the low refractive index layer (A ′) is made of resin, metal oxide particles, and 0.1 to 8% by mass concentration. The manufacturing method of the optical control film of Claim 1 or 2 formed using the coating liquid containing glycol ether.