JP2008114413A - Particle laminated film laminate, method for producing the laminate, and optical member using the laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a particle laminated film laminate which is excellent in surface hardness and/or adhesion. <P>SOLUTION: In the particle laminated film laminate, particles having an average partiucle size of 1-23 nm and an electrolyte polymer are adsorbed alternately on the surface of a solid substrate having polar groups in the surface. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a fine particle laminated film laminate, a method for producing the same, and a practically useful optical member using the same.

  As a method for forming a nanometer-scale thin film from a solution, an alternate lamination method has been proposed (see Non-Patent Document 1). A method of laminating fine particles such as silica, titania and ceria by an alternate laminating method has also been reported (see Non-Patent Document 2). The film in which the fine particles are laminated (fine particle laminated film) reflects the optical characteristics of the fine particles. For example, the silica fine particle laminated film has a low refractive index, and the titania fine particle laminated film has a high refractive index.

  However, when the fine particle laminated film is used as a part of a member for optical use, practical adhesion is required. The antireflection film located on the outermost surface of the display is required to have a higher surface hardness, and even the optical member inside the display is required to have a surface hardness that does not cause scratches during assembly. Patent Document 1 describes that a fine particle laminated film is sealed by application of a transparent sealing material and cured to ensure strength and prevent deformation. Patent Document 2 describes that the scratches of the fine particle laminated film are improved by filling the voids in the fine particle laminated film with an actinic radiation reactive monomer and a polymerization initiator and curing them. Patent Document 3 discloses an antireflection method by immersing a photoelectric conversion element having an antireflection film made of a fine particle laminated film in a trimethoxymethylsilane solution and condensing trimethoxymethylsilane with ammonia vapor or hydrochloric acid vapor. It describes that the adhesion of the film is improved. In Patent Document 4 and Patent Document 5, a graft polymer chain having a polar group is introduced onto a substrate by a surface graft polymerization method, and the substrate is formed by immersing the substrate once in a fine particle dispersion solution. It is described that the adsorption between the fine particle single layer film or the fine particle laminated film and the base material becomes strong. In Patent Document 6, a functional group in which an ester bond, a urethane bond, an amide bond, an ether bond, or the like occurs is introduced into each of the transparent substrate surface and the fine particle surface to form a chemical and irreversible bond. It is described that adhesion on a transparent substrate is improved.

JP 2002-361767 A JP 2003-205568 A JP 2003-332604 A JP 2003-112379 A JP 2004-114339 A Japanese Patent Laid-Open No. 2002-6108 Thin Solid Films, 210/211, p831 (1992) Langmuir, Vol. 13, (1997) p6195-6203

  As is clear from the foregoing, the fine particle laminated film is insufficient in surface hardness and adhesion to a substrate in practical use such as optical applications using the fine particle laminated film at least in part. . Then, an object of this invention is to provide the fine particle laminated film laminated body which is excellent in surface hardness and / or adhesiveness, its manufacturing method, and an optical member using the same.

The present invention relates to the following.
1. A fine particle laminated film laminate in which fine particles having an average primary particle size of 1 nm to 23 nm and an electrolyte polymer are alternately adsorbed on the surface of a solid substrate having a polar group on the surface.
2. The fine particles are any of fine particles of oxides of lithium, sodium, magnesium, aluminum, zinc, indium, silicon, tin, titanium, zirconium, yttrium, bismuth, niobium, cerium, cobalt, copper, iron, holmium, and manganese. Item 2. The fine particle laminated film laminate according to Item 1, comprising fine particles.
3. Item 3. The fine particle multilayer film laminate according to Item 1 or 2, wherein the solid substrate having a polar group on the surface has an intermediate layer containing the polar group formed on the surface.
4). The polar group is an epoxy group, a styryl group, a methacryloxy group, an acryloxy group, an amino group, a ureido group, a chloropropyl group, a mercapto group, a sulfide group, an isocyanate group, a carboxyl group, a silanol group, or a hydroxyl group. Item 4. The fine particle multilayer film laminate according to any one of Items 1 to 3, which is a group.
5. Item 5. The fine particle laminated film laminate according to any one of Items 1 to 4, wherein the solid substrate includes a hard coat layer.
6). Item 6. The fine particle laminate film laminate according to any one of Items 1 to 5, wherein the fine particle laminate film has a turbidity of 0.001% to 4%.
7). Item 7. The fine particle multilayer film laminate according to any one of Items 1 to 6, wherein the fine particle multilayer film contains fine particles and an electrolyte polymer of 0.1% by mass to 40% by mass with respect to the fine particles.
8). Item 8. The fine particle multilayer film laminate according to any one of Items 1 to 7, wherein the fine particles are in a bead-like shape.
9. Item 9. The fine particle multilayer film laminate (antireflection film) according to any one of Items 1 to 8, wherein the minimum value of the surface reflectance in the fine particle multilayer film is 3% or less.
10. Item 10. The fine particle multilayer film laminate (semi-transmissive semi-reflective film) according to any one of Items 1 to 9, wherein the fine particle multilayer film has a reflectance of 15% to 50% and a transmittance of 50% to 85%.
11. A step of immersing a solid substrate having a polar group on the surface in a dispersion or electrolyte polymer solution of fine particles having a charge opposite to the charge on the surface; and a fine particle having a charge opposite in sign to the fine particles or the electrolyte polymer Item 11. The method for producing a multilayer laminated film laminate according to any one of Items 1 to 10, comprising a step of immersing in a dispersion or an electrolyte polymer.
12 Item 11. An optical member comprising the particulate multilayer film laminate according to any one of Items 1 to 10.
13. Item 10. An optical member having an antireflection function, comprising the particulate multilayer film laminate according to Item 9.
14 Item 11. An optical member having a semi-transmissive / semi-reflective function, comprising the particulate laminated film laminate according to Item 10.

  In the fine particle laminate film according to the present invention, the fine particle laminate film has excellent adhesion because the solid substrate has a polar group on the surface and fine particles having an average primary particle diameter of 1 nm to 23 nm. It is excellent in practicality.

  When the type of fine particles is metal oxide fine particles, the surface hardness of the fine particle laminated film can be obtained more reliably. Furthermore, by using metal oxide fine particles, the refractive index of the fine particle multilayer film can be changed from a low value to a high value.

  In the fine particle laminated film laminate according to the present invention, the fine particle laminated film may not scatter visible light. In particular, by defining the size of the average primary particle diameter of the fine particles to be smaller than the wavelength of light, a fine particle laminated film that does not scatter visible light can be obtained more reliably. Thereby, the fine particle multilayer film laminate can be usefully used for an optical member that requires transparency.

  By defining the mass ratio of the electrolyte polymer contained in the fine particle laminate film with respect to the fine particles contained in the fine particle laminate film, a fine particle laminate film having a low refractive index can be obtained more reliably. Accordingly, the optical member including the fine particle laminated film can improve the optical characteristics, and the number of laminated multilayer film structures can be reduced.

  By using beaded particles in which primary particles are covalently bonded, steric hindrance occurs when fine particles are alternately laminated, and a fine particle laminated film having a low refractive index can be obtained more reliably. Accordingly, the optical member including the fine particle laminated film can improve the optical characteristics, and the number of laminated multilayer film structures can be reduced.

By defining the solid substrate as a transparent substrate, it is useful for applications utilizing transmitted light.
By defining the minimum value of the surface reflectance of the fine particle laminate film, a high performance antireflection function can be imparted to the fine particle laminate film laminate. Further, by defining the reflectance and transmittance of the fine particle laminated film, a high performance semi-transmissive semi-reflective film function can be imparted to the fine particle laminated film laminate.

According to the method for producing a fine particle laminated film laminate of the present invention, a fine particle laminated film laminate having a fine particle laminated film exhibiting excellent adhesion can be produced. Further, at this time, the fine particle laminated film has high film thickness uniformity, and a normal temperature and wet process is possible as a manufacturing method thereof.
The fine particle multilayer film laminate in the present invention can be usefully used as an optical member as appropriate.

  In the present invention, the fine particle laminated film that can be formed by using the alternating lamination method is laminated on a solid substrate having a polar group on the surface, whereby fine particles having an average primary particle diameter of 1 nm to 23 nm. By using the fine particle laminated film, practical adhesion can be obtained. As a result, the solid substrate on which the fine particle laminated film is laminated can be used for an optical member that requires adhesion.

(1) Solid substrate In order to form an alternately laminated film on a substrate, the substrate preferably has a charge on its surface. In order for the fine particle laminated film formed using the alternating lamination method and the solid substrate to be in close contact with each other, it is desirable that the polar group has a charge on the surface of the substrate. Since the polar group has a charge bias (intramolecular polarization) in the molecule or becomes an ion by dissociation, it has a positive or negative charge locally. A substance having a charge opposite to that of the polar group is adsorbed. As the polar group, vinyl group, epoxy group, styryl group, methacryloxy group, acryloxy group, amino group, ureido group, chloropropyl group, mercapto group, sulfide group, sulfonic acid group, phosphoric acid group, isocyanate group, carboxyl group, It is desirable that it is one or more of functional groups such as an ester group, a carbonyl group, a hydroxyl group, and a silanol group.

  As a result of the solid substrate having a polar group on the surface, the absolute value of the zeta potential is preferably 1 to 100 mV, more preferably 5 to 90 mV, and even more preferably 10 to 80 mV. Moreover, it is preferable that the density | concentration of a polar group is 0.1-30 mol% in a solid base material, it is more preferable that it is 0.2-20 mol%, and it is 0.5-15 mol%. Further preferred. In order to obtain practical adhesion between the fine particle laminated film and the solid substrate, the solid substrate preferably has a polar group to the extent that these conditions are satisfied.

  Examples of the material for the solid substrate include resins, semiconductors such as silicon, metals, and inorganic compounds. Moreover, the shape is arbitrary, such as a shape which has a film, a sheet | seat, a board, and a curved surface. If a part or the whole of the solid substrate can be immersed in a solution such as a cylinder, a thread, a fiber, or a foam, the fine particle laminated film is formed on the surface and can be used. Moreover, even if the cross section of the solid substrate has an uneven shape, the fine particle laminated film can be formed following the surface structure. Even if the surface of the solid substrate has a nanometer scale or submicron scale structure, the fine particle multilayer film can be formed following the structure.

  Examples of the metal include iron, copper, white copper, tinplate, and the like, and are subjected to treatment such as forming an oxide film so that electric charges exist on the surface. Examples of the inorganic compound include glass and ceramics, and have a polar group on the surface.

  Examples of the resin include polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, which have a hydroxyl group or a carboxyl group, a polyamide having a carboxyl group or an amino group, a polyvinyl alcohol, a polymer of acrylic acid or methacrylic acid, or There are copolymers and the like.

  Polar surfaces may be introduced by subjecting these substrate surfaces to corona discharge treatment, glow discharge treatment, plasma treatment, ultraviolet irradiation, ozone treatment, chemical etching treatment with alkali, acid, or the like. You may use resin which introduce | transduced the polar group by such a process. Examples of such a resin include polyethylene, polypropylene, polystyrene, triacetyl cellulose, diacetyl cellulose, acetate butyrate cellulose, polyether sulfone, polyimide, polymethylpentene, polyvinyl chloride, polyvinyl acetal, in addition to the resins exemplified above. Polymethyl methacrylate, polycarbonate, polyurethane and the like can also be used.

  As the solid substrate in the present invention, a substrate in which an intermediate layer having a polar group is formed on the substrate is preferable. In this case, as described above, a resin, a semiconductor such as silicon, a metal, an inorganic compound, or the like can be used as the base material, but the surface does not necessarily have a polar group. As the base material, all of those exemplified above can be used. Examples of forming the intermediate layer include silane coupling agents, resins, and the like. Here, as a resin, naturally, a resin having a polar group is selectively used.

  When the fine particle multilayer film laminate is used as an optical member, the solid substrate (or substrate) may or may not have translucency. Here, the translucent state refers to a state of transmitting light, and does not depend on whether or not light is scattered. The state that does not transmit light means a state that does not transmit light by absorption or reflection, and does not depend on whether or not light is scattered. As a solid substrate (or substrate) having translucency itself, for example, polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, polystyrene, triacetyl cellulose, diacetyl cellulose, acetate butyrate A thermoplastic resin such as cellulose, polyethersulfone, polyamide, polyimide, polymethylpentene, polyvinyl chloride, polyvinyl alcohol, polyvinyl acetal, polymethyl methacrylate, polycarbonate, polyurethane, a glass substrate, or the like is used. As a solid base material (or base material) that does not itself transmit light, a silicon-based or gallium-based semiconductor wafer, a metal, or the like can be used.

  On the surface of a solid substrate where formation of a fine particle laminated film is not desired, the fine particle dispersion such as an adhesive film is adhered to the solid substrate to prevent contact with the solid substrate. Can be prevented.

  The solid substrate of the present invention includes those in which a resin film, an inorganic film, or a film containing both an organic material and an inorganic material is laminated on the substrate. These resin film layer, inorganic film layer, and organic-inorganic film may be located anywhere on the solid substrate, and need not have a polar group when not located on the outermost surface of the solid substrate. The resin film layer, the inorganic film layer, and the organic-inorganic film may or may not be provided with a function of improving the optical function and mechanical characteristics of the solid substrate. An example of a layer that improves the mechanical properties of the solid substrate is a hard coat layer.

  Examples of films for imparting optical functions include antireflection films, reflective films, semi-transmissive and semi-reflective films, visible light reflective infrared transmissive films, infrared reflective visible light transmissive films, blue reflective films, green reflective or red reflective films , An optical function film including at least one bright line cut filter and a color tone correction film. Further optical functions can be imparted by forming a fine particle laminate film on a solid substrate having these optical function films.

  For example, when a multilayer film is formed on a solid substrate having one or more of an antireflection function, a bright line cut filter function, a near infrared cut filter function, and a color tone correction function, the antireflection function and the bright line cut filter function Among the near-infrared cut filter function and the color tone correction function, one or more functions not provided in the solid base material can be given, and an optical suitable for an optical filter for a display such as a plasma display panel or a liquid crystal display device. A member is obtained. In addition, an optical filter obtained by forming an antireflection film including a fine particle laminated film using an optical film such as a light guide plate, a diffusion film, a prism film, a brightness enhancement film, and a polarizing plate as a solid substrate is an optical film interface. Reflection at is suppressed. For this reason, the brightness of a liquid crystal display device incorporating such an optical filter is improved. A transflective liquid crystal display device incorporating an optical filter obtained by using a light diffusing film as a solid substrate and forming a transflective film layer including a fine particle laminated film on the solid substrate Brightness due to reflection is improved. In this way, by forming a fine particle laminated film on a filter member for a display such as a flat panel display, it is possible to achieve high functionality of those members.

(2) Hard coat layer A solid substrate on which a hard coat film is laminated is excellent in mechanical properties. Examples of the material for the hard coat film include crosslinked bodies of polymerizable unsaturated double bond-containing compounds such as acrylic resins, urethane resins, and melamine resins, organic silicate compounds, silicone resins, and metal oxides. It is done. As the polymerizable unsaturated double bond-containing compound, a curable resin such as a thermosetting resin or a radiation curable resin can be used, and it is particularly preferable to use a polyfunctional polymerizable unsaturated double bond-containing compound. .

  Polyfunctional polymerizable unsaturated double bond-containing compounds include esters of polyhydric alcohols and methacrylic acid or acrylic acid (eg, ethylene glycol di- (meth) acrylate, 1,4-dichlorohexane diacrylate, pentaerythritol tetra -(Meth) acrylate, pentaerythritol tri- (meth) acrylate, trimethylolpropane tri- (meth) acrylate, trimethylolethane tri- (meth) acrylate, dipentaerythritol tetra- (meth) acrylate, dipentaerythritol penta- (Meth) acrylate, dipentaerythritol hexa- (meth) acrylate, 1,3,5-cyclohexanetriol trimethacrylate, polyurethane polyacrylate, polyester polyacrylate), vinyl base Zen derivatives (eg, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone), vinylsulfone compounds (eg, divinylsulfone), acrylamide compounds (eg, methylenebis) Acrylamide) and methacrylamide are examples, but not limited thereto. In the above, (meth) acrylate means "methacrylate or acrylate".

  Examples of commercially available polyfunctional polymerizable unsaturated double bond-containing compounds include Mitsubishi Rayon Co., Ltd. polyfunctional acrylic cured paints (Diabeam series, etc.), Nagase Sangyo Co., Ltd. polyfunctional acrylic cured Paint (Denacol series, etc.), Shin-Nakamura Chemical Co., Ltd. polyfunctional acrylic cured paint (NK ester series, etc.), Dainippon Ink Chemical Industries, Ltd. polyfunctional acrylic cured paint (UNIDIC series, etc.), Multifunctional acrylic curable paint (Aronix series, etc.) manufactured by Toa Synthetic Chemical Industry Co., Ltd. Multifunctional acrylic curable paint (Blenmer series, etc.) manufactured by NOF Corporation, Multifunctional acrylic manufactured by Nippon Kayaku Co., Ltd. -Based cured paints (KAYARAD series, etc.), Kyoeisha Chemical Co., Ltd. polyfunctional acrylic cured paints (light ester series, light acrylate series, etc.) And the like.

  It is particularly effective to add a polymerization initiator for the purpose of efficiently initiating the polymerization of these polyfunctional polymerizable unsaturated double bond-containing compounds. As the polymerization initiator, acetophenones, benzophenones, Michler's benzoyl are used. Benzoates, α-amyloxime esters, tetramethylthiuram monosulfide and thioxanthones are preferred. In addition to a polymerization initiator, a sensitizer may be used for the purpose of promoting polymerization. Furthermore, a leveling agent and a filler may be added, and additives are added to these compounds as necessary to form a coating material.

  The coating material is coated using, for example, a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, a gravure coating method, etc. to form a coating film, and after drying, a thermosetting resin composition When using a product, the coating is cured by heating. When using an ionizing radiation curable resin composition, the coating is cured by irradiating with ionizing radiation. A layer may be formed. Examples of the ionizing radiation include radiation, electron beams, particle beams, gamma rays, ultraviolet rays, and the like, and ultraviolet rays are particularly preferable. The light source can be from near ultraviolet rays using a mercury lamp to vacuum ultraviolet rays using an excimer laser.

  A commercial product of a solid base material on which a hard coat film is formed may be used. As such a commercial product, Kimoto hard coat PET (KB film), Toray hard coat PET (Tough Top N-TOP), Toyo Examples thereof include a hard coat film made of packaging material, and a hard coat polycarbonate made by Nisshin Kasei (Lexan Margard, Lexan CTG AF).

(3) Intermediate layer In order to reliably introduce a polar group into a solid substrate, an intermediate layer can be laminated on the substrate to form a solid substrate. In this case, the intermediate layer is a surface layer of the solid substrate. The intermediate layer is provided between the solid base material and the fine particle multilayer film, and the intermediate layer has a polar group to improve the adhesion between the solid base material and the fine particle multilayer film. It is considered that the surface hardness of the fine particle laminated film on the solid substrate is improved because the fine particle laminated film having a sufficiently high strength of the film itself is firmly bonded to the solid substrate through the intermediate layer.

  Further, as a method for improving both the strength of the fine particle laminated film itself and the adhesion between the film and the solid substrate (intermediate layer), for example, application of a resin to the fine particle laminated film or application of a reactive monomer to the fine particle laminated film As described above, the fine particle laminate film on the solid substrate is practically sufficiently excellent by interposing the intermediate layer without performing processing such as filling and curing, or immersion of the fine particle laminate film in the silane solution. Can be obtained.

  The polar group contained in the intermediate layer is vinyl group, epoxy group, styryl group, methacryloxy group, acryloxy group, amino group, ureido group, chloropropyl group, mercapto group, sulfide group, sulfonic acid group, phosphoric acid group, isocyanate group. And one or more functional groups among a carboxyl group, an ester group, a carbonyl group, a hydroxyl group, and a silanol group are desirable. As the material for the intermediate layer, resins having these groups, silane coupling agents, and the like can be used.

  Examples of the resin as the material for the intermediate layer include polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, which have a hydroxyl group or a carboxyl group, a polyamide having a carboxyl group or an amino group, polyvinyl alcohol, acrylic acid, or methacrylic acid. Examples include acid polymers or copolymers.

  The intermediate layer is laminated on the resin base material by, for example, a method in which a resin having a polar group is dissolved in a solvent and applied and dried, and a resin having a polar group is applied to a heat resistant resin base material. As a method of melt casting, a method of applying a monomer or oligomer (including a monomer or oligomer having a polar group) as a raw material for a resin of an intermediate layer to a resin base material, reaction curing, and an intermediate layer A raw material monomer or oligomer of the resin can be mixed with a silane coupling agent, applied, and reacted and cured.

You may manufacture the coating liquid of the polyester-type resin to which the polar group was provided as follows. Hereinafter, “parts” means “parts by weight” unless otherwise specified.
117 parts of dimethyl terephthalate, 117 parts of dimethyl isophthalate, 103 parts of ethylene glycol, 58 parts of diethylene glycol, 0.08 part of zinc acetate and 0.08 part of antimony trioxide are heated to 40-220 ° C. in a reaction vessel, Transesterification was performed for a time to obtain a polyester-forming component. Subsequently, 9 parts of 5-sodiumsulfoisophthalic acid was added and subjected to esterification reaction at 220 to 260 ° C. for 1 hour, and further polycondensation reaction was performed under reduced pressure (10 to 0.2 mmHg) for 2 hours. The average molecular weight was 18000 and the softening point was 140. A polyester copolymer provided with a sulfonic acid group at 0 ° C. was obtained. 300 parts of the polyester copolymer provided with the sulfonic acid group and 140 parts of n-butyl cellosolve are stirred at 150 to 170 ° C. for 3 hours to obtain a uniform viscous melt, and 560 parts of water is gradually added to the melt. Thus, a polyester resin aqueous dispersion can be obtained (see Japanese Patent No. 2560754).
You may utilize the water-dispersed polyester resin (For example, Bironal MD-1200, the Toyobo Co., Ltd. product) to which the sulfonic acid which is a commercial item was provided.

  In the above procedure, a metal salt such as sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid and their ester-forming derivatives may be used instead of 5-sodium sulfoisophthalic acid. A polyester copolymer provided with an acid group can be obtained. Examples of the metal in the metal salt include sodium, lithium, potassium, magnesium and the like. Moreover, the polyester copolymer provided with the amino group can be obtained by using 5-aminoisophthalic acid or the like instead of 5-sodium sulfoisophthalic acid.

You may manufacture the polyurethane-type resin to which the polar group was provided as follows.
192 parts of a polyether containing sodium sulfonate obtained by sulfonating a polyether of ethylene oxide starting from allyl alcohol with sodium metabisulfite (SO3 content: 8.3% by weight, polyethylene oxide content: 83% by weight), polytetramethylene 1013 parts of adipate and 248 parts of polypropylene oxide polyether initiated with bisphenol A were mixed and dehydrated at 100 ° C. under reduced pressure (10 to 0.2 mmHg) to obtain 70 ° C., and 178 parts of isophorone diisocyanate and hexamethylene were added. A mixture with 244 parts of -1,6-diisocyanate was added and the resulting mixture was then stirred in the range of 80 ° C. to 90 ° C. until the isocyanate content was 5.6% by weight. The obtained prepolymer was cooled to 60 ° C., and 56 parts of biuret polyisocyanate obtained from 3 moles of hexamethylenediocyanate and 1 mole of water, and 173 parts of bisketimine obtained from isophoronediamine and acetone were sequentially added. Next, a 50 ° C. aqueous solution in which 15 parts of hydrazine hydrate is dissolved can be added to this mixture with vigorous stirring to obtain an aqueous polyurethane resin dispersion.

  Examples of the resin prepared so that a functional group is imparted include organic solvent-soluble amorphous polyester resins, and commercially available products include Byron (103, 200, 220, 226, Toyobo Co., Ltd.). 240, 245, 270, 280, 290, 296, 300, 500, 516, 530, 550, 560, 600, 630, 650, 660, 670, 885, GK110, GK130, GK140, GK150, GK180, GK190, GK250, GK330, GK360, GK590, GK640, GK680, GK780, GK810, GK880, GK890, BX1001) and water-dispersed polyester resins are exemplified, and commercial products thereof are Bayonal (MD-1100) manufactured by Toyobo Co., Ltd. MD-1200, MD-122 MD-1245, MD-1250, MD-1335, MD-1400, MD-1480, MD-1500, MD-1930, MD-1985), and polyester urethane resins. By Toyobo Co., Ltd. byron (UR-1350, UR-1400, UR-2300, UR-3200, UR-3210, UR-3500, UR-4125, UR-5537, UR-8200, UR-8300, UR -8700, UR-9500).

  In the present invention, silane coupling agents include those represented by the following formula (I).

（ただし、式中、Ｒ^１は非加水分解性基であって、ビニルアルキル基、エポキシアルキル基、スチリルアルキル基、メタクリロキシアルキル基、アクリロキシアルキル基、アミノアルキル基、ウレイドアルキル基、クロロプロピルアルキル基やスルフィドアルキル基等のハロゲンアルキル基、メルカプトアルキル基、イソシアネートアルキル基またはヒドロキシアルキル基である。Ｒ^２は加水分解性基であって炭素数が１〜６のアルキル基、ｎは１〜３の整数を示し、Ｒ^１が複数ある場合、各Ｒ^１は互いに同一であっても異なっていてもよく、ＯＲ^２が複数ある場合、各ＯＲ^２は互いに同一であっても異なっていてもよい。）

(In the formula, R ¹ is a non-hydrolyzable group, which is a vinylalkyl group, an epoxyalkyl group, a styrylalkyl group, a methacryloxyalkyl group, an acryloxyalkyl group, an aminoalkyl group, a ureidoalkyl group, a chloropropyl group, A halogen alkyl group such as an alkyl group or a sulfide alkyl group, a mercaptoalkyl group, an isocyanate alkyl group or a hydroxyalkyl group, R ² is a hydrolyzable group having 1 to 6 carbon atoms, and n is 1 to 1 3 of an integer, when R ¹ are a plurality, each R ¹ may be the being the same or different, when OR ² is more, even if each OR ² is not being the same or different Good.)

  As an example of the silane coupling agent treatment of the substrate, first, the silane coupling agent is hydrolyzed into silanol groups by hydrolyzing alkoxy groups in an aqueous medium in the presence or absence of an acid, and the resulting silane solution By contacting the substrate with the hydroxyl group present on the substrate surface, the silanol group can be adsorbed in a hydrogen bond, and then the substrate can be dried by treatment, thereby causing a dehydration condensation reaction, Non-hydrolyzable groups can be imparted to the substrate surface. The silanol group that has not reacted with the non-hydrolyzable group or the glass substrate functions as a polar group in the present invention, and interacts with the fine particle multilayer film, whereby adhesion between the base material and the fine particle multilayer film is obtained. Although details are not clear, it is considered that one or more of covalent bonds, intermolecular forces, and van der Waals forces contribute to the interaction. In the above, the concentration of the silane coupling agent added to the aqueous medium is preferably 0.1 to 3% by weight, and the acid to be present is particularly preferably acetic acid, and the concentration is 0.1 to 3% by weight. % Is preferred.

Specific examples of the silane coupling agent include vinyl trichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinylphenyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, and other vinyl group functional silanes, Alkyl group or aryl group functional silane such as methoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltri Epoxy functional groups such as methoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldiisopropenoxysilane, methyltriglycidoxysilane, γ-glycidoxypropyltriethoxysilane Functional silane, styryl group functional silane such as p-styryltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, methyltri (methacryloxyethoxy) silane, γ-methacryloxypropylmethyldi Methacryloxy group functional silanes such as ethoxysilane, γ-methacryloxypropyltriethoxysilane, acryloxy group functional silanes such as γ-acryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane , Γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopro Rumethyldimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldiethoxysilane, N-β- (N-vinylbenzylamino) Ethyl) -γ-aminopropyltrimethoxysilane, γ-anilinopropyltrimethoxysilane, γ-triethoxysilyl-N- (1,3-dimethyl-butylidene) -propylamine, N-phenyl-3-aminopropyltri Amino group functional silane such as methoxysilane, ureido group functional silane such as γ-ureidopropyltriethoxysilane, chloropropyl group functional silane such as γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ -Mercaptopropyltriethoxysilane, γ-mercaptopropi Mercapto group functional silanes such as methyldimethoxysilane, sulfide group functional silanes such as bis (triethoxysilylpropyl) tetrasulfide, γ-isocyanatopropyltriethoxysilane, trimethylsilyl isocyanate, dimethylsilyl isocyanate, phenylsilyl triisocyanate, tetra There are isocyanate group functional silanes such as isocyanate silane, methylsilyl triisocyanate, vinylsilyl triisocyanate, ethoxysilane triisocyanate and the like.
These silane coupling agents may be used to impart functional groups to the surfaces of the fine particles. As a result, at least one of attractive forces among the covalent bonds, intermolecular forces, and van der Waals forces between the fine particles and between the fine particles and the substrate can be reliably applied.

  Examples of commercially available silane coupling agents include KA-1003, KBM-1003, KBE-1003, KBM-303, KBM-403, KBE-402, KBE-403, and styryl groups having a vinyl group. KBM-1403 having a methacryloxy group, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103 having an acryloxy group, KBM-602 having an amino group, KBM-603, KBE-603, KBM-903, KBE-903, KBE-9103, KBM-573, KBM-575, KBM-6123, KBE-585 having a ureido group, KBM-703 having a chloropropyl group, KBM-802 having a mercapto group, KBM -803, with sulfide group That KBE-846, KBE-9007 having isocyanate groups (manufactured by Shin-Etsu Chemical Co.) and the like. Alternatively, the intermediate layer may be formed using a primer in which the silane coupling agent is already diluted in a solvent or water. Commercially available primers include, for example, KBP-40, KBP-41, KBP-43, KBP-90 diluted with an amino group-containing silane coupling agent, and KBP-44 diluted with an isocyanate group-containing silane coupling agent. And X-12-414 (manufactured by Shin-Etsu Chemical Co., Ltd.) diluted with a silane coupling agent having a mercapto group.

  When the substrate is a resin, it is preferable to use a resin having a polar group for the intermediate layer in order to obtain adhesion between the substrate and the intermediate layer. In addition, when the substrate is an inorganic material substrate such as glass or aluminum, a silane coupling agent is particularly preferable for the intermediate layer.

  When forming a silane coupling agent or a resin as an intermediate layer on a substrate, a coating method that can be employed can be performed by a well-known method, for example, reverse roll coating method, gravure coating method, A kiss coating method, a roll brush method, a spray coating method, an air knife coating method, a wire barber coating method, a pipe doctor method and a curtain coating method, a spin coating method, a dip coating method, an alternating lamination method, and the like can be employed. These methods can be performed alone or in combination.

  Corona discharge treatment, glow discharge treatment, plasma treatment, ultraviolet irradiation, ozone treatment, chemical etching treatment with alkali or acid, etc. to make the adhesion between the substrate and the intermediate layer more reliable May be applied.

  A strong electrolyte polymer layer may be formed for the purpose of making the charge density of the surface of the solid substrate (including the intermediate layer) uniform and adsorbing the fine particles uniformly. For the strong electrolyte polymer, polydiallyldimethylammonium chloride (PDDA) having a positive charge, polyethyleneimine (PEI), or sodium polystyrene sulfonate (PSS) having a negative charge is preferable. By using an alternate lamination method, an alternate lamination film of two types of strong electrolyte polymers having different charge signs may be formed on a solid substrate (including an intermediate layer) [Advanced Material 13 Vol. 52-54 Page (issued in 2001)]. Since the alternating laminated film of strong electrolyte polymer having an alternating lamination number of 10 or less does not disturb the interaction between the polar group on the surface of the solid substrate and the fine particle laminated film, the alternating laminated film of the strong electrolyte polymer is a solid substrate (intermediate layer) Including) is not necessarily strongly in close contact. In order not to prevent the interaction between the solid substrate (including the intermediate layer) and the fine particle laminated film, the number of alternating laminations is more preferably 5 times, and even more preferably 2 times.

  When these strong electrolyte polymer layers are formed on the substrate surface as an intermediate layer, it is desirable that the strong electrolyte polymer layer is in close contact with the substrate. As a method for adhesion, when the substrate or the substrate surface layer is a polymer, a method of bonding a strong electrolyte polymer or the like to the polymer on the substrate surface by a conventionally known method such as heat, light, electron beam, or γ-ray Is mentioned. Moreover, you may graft the monomer which has a polar group on a base material using this method. Examples of the monomer having a polar group include acrylic acid or methacrylic acid or an alkali metal salt or amine salt thereof, itaconic acid or an alkali metal salt or amine acid salt thereof, allylamine or a hydrogen halide acid salt thereof, or 3-vinyl propionic acid. Or alkali metal salt or amine salt thereof, vinyl sulfonic acid or alkali metal salt or amine salt thereof, vinyl styrene sulfonic acid or alkali metal salt or amine salt thereof, 2-sulfoethylene acrylate, 2-sulfoethylene methacrylate, 3-sulfopropylene Acrylate, 3-sulfopropylene methacrylate or alkali metal salt or amine salt thereof, 2-acrylamido-2-methylpropanesulfonic acid or alkali metal salt or amine salt thereof, mono (2-acrylic acid) Yl oxy-ethyl) acid phosphate, mono (2-methacryloyloxyethyl) acid phosphate, phosphoric acid monomer or an alkali metal salt or amine salt thereof, such as acidphosphoxyethyl polyethylene glycol mono (meth) acrylate and the like.

  A solid substrate on which an intermediate layer having a polar group has already been formed can also be obtained as a commercial product. For example, PET film with an easy adhesion layer (A4100, A4300, A7300, A7810, A6340, K1531, K1564) manufactured by Toyobo Co., Ltd., PET (545, 746, 540) manufactured by Teijin DuPont Films, Inc. 709, 705, 707, 399, 330, 534), PEN (Q51DW) with an easy-adhesion layer made by Teijin DuPont Films, and PET with an easy-adhesion layer made by Toray Industries, Inc. (U10, U12, T11, U426) U34, T83, U94, E22, E63), an adhesive polyolefin (Admer) manufactured by Mitsui Chemicals, Inc. and a solid base material in which a polyolefin is multilayered.

  Examples of the PET film with an easy adhesion layer include Japanese Patent No. 2560754, Japanese Patent No. 3632044, Japanese Patent Application Laid-Open No. Sho 61-270153, Japanese Patent Application Laid-Open No. Sho 62-162540, Japanese Patent Application Laid-Open No. Sho 63-286346, and Japanese Patent Laid-Open No. Sho 63. JP-A-288750, JP-A-1-139259, JP-B-4-55215, JP-B-5-54493, JP-B-5-88190, JP-A-11-125926, JP-A-2005-97571. The one disclosed in the publication is preferred.

(4) Formation method of fine particle laminated film On a solid substrate by a method of alternately immersing a solid substrate in an electrolyte polymer solution and a step of immersing in a fine particle dispersion (dispersion solution) (alternate lamination method). A fine particle laminated film can be formed. Although there is no restriction | limiting in particular in the frequency | count of repeating, The film thickness of a thin film is controllable by the frequency | count (Langmuir, Vol.13, pp.6195-6203, (1997)). In the above alternating lamination method, the number of times of repeating alternately is preferably 1 to several tens of times in order to ensure transparency. Further, in the above alternate lamination method, it is preferable to end with the step of immersing in the fine particle dispersion solution rather than ending with the step of immersing in the electrolyte polymer solution.
When the adsorption progresses in each step and the surface charge is reversed, no further electrostatic adsorption occurs, so that the thickness of the film formed by one immersion can be controlled. Further, the material that has been physically adsorbed excessively can be removed by rinsing the adsorption surface after immersion. Furthermore, as long as the surface charge is reversed, the film formation can be continued. Therefore, the film thickness uniformity of the thin film formed by the alternating lamination method is higher and the film thickness controllability is higher than the normal dip coating method.
High film thickness controllability is important for the fine particle laminated film to exhibit a desired optical function. In addition, high film thickness uniformity not only does not cause uneven appearance, but in a multilayer film structure in which thin films having different refractive indexes are multilayered, the interface between the thin films is not disturbed, that is, the optical function is manifested by thin film interference. It is important not to damage.

  As an apparatus for forming a fine particle laminated film, an arm called a dipper (J. Appl. Phys., Vol. 79) which automatically moves an arm to which a solid base material is fixed and immerses the solid base material in a fine particle dispersion according to a program. , Pp. 7501-7509, (1996), Japanese Patent Application No. 2000-568599). Moreover, you may use the continuous film formation process which takes out a film from the film currently wound up in roll shape, is immersed in fine particle dispersion as it is, is dried, and winds up a film in roll shape.

(5) Fine particle dispersion The fine particle dispersion used in the present invention is obtained by dispersing the above-described fine particles in a medium (liquid) that is a mixed solvent such as water, an organic solvent, or water and a water-soluble organic solvent. It is. Examples of the water-soluble organic solvent include methanol, ethanol, propanol, acetone, dimethylformamide, acetonitrile and the like. The proportion of fine particles in the fine particle dispersion is usually preferably about 0.001 to 30% (weight), and the fine particles can be dispersed by a known method. When the dispersibility of the fine particles is low, a so-called dispersant can be used when preparing the fine particle dispersion in order to improve the dispersibility. As such a dispersant, a surfactant, an electrolyte polymer, a nonionic polymer, or the like can be used. The amount of these dispersants to be used varies depending on the type of the dispersant to be used, but generally 0.00001 to 0.1% (weight) is preferable. If too much, gelation / separation occurs, The fine particles become electrically neutral in the dispersion, and the fine particle laminated film cannot be obtained.

  The pH of the fine particle dispersion can be adjusted in the range of 1 to 13 with an alkaline aqueous solution such as sodium hydroxide or potassium hydroxide or an acidic aqueous solution such as hydrochloric acid or sulfuric acid, and the pH can also be adjusted with a dispersant. . As the pH of the fine particle dispersion deviates from the equipotential point, the electrostatic attractive force with the solid substrate or the electrolyte polymer tends to increase. The equipotential point is a pH value at which the surface potential of the fine particles becomes 0 and the electrostatic repulsion force disappears, so that the particles aggregate. However, the equipotential point varies depending on the number of surface hydroxyl groups and the crystal structure. It depends on the material.

(6) Fine particle material The average primary particle diameter of the fine particles dispersed in the fine particle dispersed aqueous solution used in the present invention is 1 to 23 nm. In addition, in order to obtain a high-hardness fine particle laminated film and from the viewpoint of securing the optical function of the fine particle laminated film, 1 to 20 nm is preferable, 1 to 15 nm is more preferable, and 1 to 10 nm is most preferable. Fine particles having an average primary particle diameter of less than 1 nm are difficult to form. When the average primary particle diameter is larger than 23 nm, it becomes difficult to obtain a high-hardness fine particle laminated film.
The average primary particle diameter of the fine particles is 1 to 23 nm. Thereby, the transparency of the fine particle laminate film is obtained, and the optical function of the fine particle laminate film is ensured. When the average primary particle diameter is larger than 100 nm, it becomes easy to scatter visible light, and the transparency of the fine particle multilayer film tends to be impaired.
In addition, when the fine particle laminated film is formed by the alternating lamination method, the amount of change in the film thickness of the fine particle laminated film per one alternate lamination is usually about the same as the average primary particle diameter of the fine particles. Therefore, if the average primary particle size is too large, the accuracy of film thickness control is lowered, and it is difficult to obtain a film thickness with high accuracy in terms of optical function expression. As long as the film thickness controllability is not impaired, the fine particles are primary particles or secondary particles of the type in which the primary particles are aggregated. Also good.

The film thickness d ₁ required for the optical function expression of the fine particle laminated film is expressed by the following formula (1)

（但し、式中、λは光学的機能を発現したい波長、ｎは膜の屈折率、ｘは通常２〜８である）で求められる（光学薄膜技術、日本オプトメカトロニクス協会、岡本幹夫著、ｐｐ．７−４５、２００２年１月１５日発行、参照）。

Where λ is the wavelength at which the optical function is desired, n is the refractive index of the film, and x is usually 2 to 8 (optical thin film technology, Japan Opto-Mechatronics Association, Mikio Okamoto, pp 7-45, issued January 15, 2002, see).

  In the present invention, the average primary particle diameter, average secondary particle diameter, and bead-shaped particle diameter of fine particles can be measured using a known method. When primary particles are not aggregated but are dispersed in the fine particle dispersion, the average primary particle diameter can be measured by a dynamic scattering method. However, in the case of secondary particles in which primary particles are aggregated or beaded particles in which primary particles are covalently bonded, it is not the average primary particles that are measured by the dynamic scattering method. This is the particle size of the beaded particles. The average primary particle diameter in secondary particles or beaded particles can be measured by the BET method or electron microscopy. In the BET method, molecules with an occupied area such as nitrogen gas are adsorbed on the particle surface, the specific surface area is obtained from the relationship between the adsorbed amount and the pressure, and the specific surface area is converted from the conversion table into the particle diameter. The average primary particle size can be determined.

  In electron microscopy, first, fine particles are scooped from a fine particle dispersion on a copper mesh on which an amorphous carbon film having a thickness of several tens of nanometers is formed, or fine particles are adsorbed on the amorphous carbon film. These fine particles are observed with a transmission electron microscope, then the lengths of all the fine particles in the photographed image are measured, and the arithmetic average thereof is obtained as the average primary particle diameter. Note that the number of fine particles for measuring the length is desirably 100 or more, and when the number of fine particles in one photographed image is less than 100, it is set to 100 or more using a plurality of photographed images. When the axial ratios of the particles are greatly different as in the case of columnar particles, the length of the minor axis is generally measured, and the arithmetic average is taken as the average primary particle diameter.

  Further, the fine particles in the above particle diameter measurement may be obtained not only from the fine particle dispersion for preparing the fine particle laminated film but also from the fine particle laminated film. As a method for obtaining from the fine particle laminated film, the fine particle aggregate on the solid substrate is polished by steel wool (manufactured by Nippon Steel Wool Co., Ltd., # 0000) or a cutter, and the fine particle aggregate is peeled off. An example is a method in which the aggregate is subjected to ultrasonic waves in a solvent. As a result, fine particle aggregates and monodispersed fine particles having a reduced size can be obtained. As the solvent, water, an organic solvent, or a mixed solvent such as water and a water-soluble organic solvent can be used.

  In electron microscopy, the shape of the fine particles can be observed simultaneously with the particle size. It can be distinguished whether the particles are spherical or beaded. As shown in FIG. 1, the bead-like particles have primary particles connected in a bead shape, and each primary particle is covalently bonded. In the fine particle film using beaded particles, due to the steric hindrance caused by the beaded shape, other beaded particles and the electrolyte polymer having the opposite charge cannot occupy the space closely, resulting in spherical particles. It has a higher porosity and a lower refractive index than the fine particle film using.

The fine particles in the present invention include inorganic fine particles. Specifically, lithium, sodium, magnesium, aluminum, zinc, indium, silicon, tin, titanium, zirconium, yttrium, bismuth, niobium, cerium, cobalt, copper, iron , Holmium, manganese and other halides and oxides are used. More specifically, lithium fluoride (LiF), sodium fluoride (NaF), magnesium fluoride (MgF ₂ ), aluminum fluoride ( AlF ₃ ), aluminum oxide (Al ₂ O ₃ ), zinc oxide (ZnO), indium tin oxide (ITO), silica (SiO ₂ ), tin oxide (SnO ₂ ), titanium oxide (TiO ₂ ), zirconium oxide ( ZrO _2), yttrium oxide _{(Y 2 O} 3), bismuth oxide (Bi O _3), niobium oxide _{(Nb 2 O} 5), ceria _(CeO 2), cobalt oxide (CoO), copper (CuO), iron _{(Fe 2 O} 3), holmium _{(Ho 2 O} 3), manganese (Mn ₃ O _4), and the like. these may be used alone or in combination of two or more. The fine particles may be indefinite, and there is no particular limitation on the crystal form that can be taken. For example, TiO ₂ may be rutile or anatase. Commercially available products of such inorganic fine particles include, for example, titania fine particle aqueous dispersion (Tainock M-6) manufactured by Taki Chemical Co., Ltd., and zinc oxide fine particle aqueous dispersion (ZnO-) manufactured by Sumitomo Osaka Cement Co., Ltd. 350), Ceria fine particle aqueous dispersion (Nydral P10) manufactured by Taki Chemical Co., Ltd., Tin oxide fine particle aqueous dispersion (Cerames S-8) manufactured by Taki Chemical Co., Ltd., manufactured by Taki Chemical Co., Ltd. Niobium oxide fine particle aqueous dispersion (Vilaral NB-X10), Alumina fine particle aqueous dispersion (Alumina sol-5) manufactured by Nissan Chemical Industries, Ltd., Silica fine particle aqueous dispersion (Snowtex (manufactured by Nissan Chemical Industries, Ltd.)) ST) 20) etc. can be used.

Among the above inorganic fine particles, silica (SiO ₂ ) is preferable in that a thin film having a low refractive index required for an antireflection film can be obtained, and water-dispersed colloidal silica (average primary particle diameter controlled from 1 nm to 23 nm) ( Most preferred is SiO ₂ ). Examples of such commercially available inorganic fine particles include Snowtex (manufactured by Nissan Chemical Industries). In order to obtain a lower refractive index, it is more preferable that the basic fine particles contain a bead-shaped particle shape as shown in FIG. Examples of commercially available products include Snowtex UP or Snowtex OUP series (manufactured by Nissan Chemical Industries, Ltd.) and Fine Cataloid F120 (manufactured by Catalyst Chemical Industries, Ltd.), and pearl necklace-like silica sol.

  As the fine particles in the present invention, polymer fine particles can also be used. For example, polyethylene, polystyrene, acrylic polymer, silicon polymer, phenol resin, polyamide, natural polymer can be mentioned, and these can be used alone or in combination of two or more. Can be used as a mixture. From liquid phase to solution spray method, solvent removal method, aqueous solution reaction method, emulsion method, suspension polymerization method, dispersion polymerization method, alkoxide hydrolysis method (sol-gel method), hydrothermal reaction method, chemical reduction method, liquid It is synthesized by a manufacturing method such as medium pulse laser ablation. Examples of commercially available polymer fine particles include Mist Pearl (manufactured by Arakawa Chemical Industries, Ltd.).

  In addition, an ionic functional group may be added to the surface of these fine particles for the purpose of applying at least one of at least one of a covalent bond, an intermolecular force, and a van der Waals force between the fine particles and between the fine particles and the substrate. good. The functional group can be imparted to the surface of the fine particles by subjecting the silane coupling agent represented by the chemical formula (I) to a condensation reaction with the hydroxyl groups of the fine particles. Examples of the functional group imparted to the surface of the fine particles include the above-described vinyl group, epoxy group, styryl group, methacryloxy group, acryloxy group, amino group, ureido group, chloropropyl group, sulfide group, mercapto group, and isocyanate group. Can do. Examples of commercially available silane couplings include KBM series and KBE series manufactured by Shin-Etsu Chemical. In addition, a carboxyl group, a carbonyl group, a phenol group or the like may be imparted to the surface of the fine particles, and as a commercially available fine particle having such a functional group imparted to the surface, for example, Mist Pearl (manufactured by Arakawa Chemical Industries) Etc.

  The fine particles dispersed in the medium are electrically negatively or positively charged because a diffusion electric double layer is generated due to dissociation of surface polar groups and adsorption of ions. The thickness (1 / κ) of the diffusion electric double layer on the surface of the fine particle is a distance where the attractive force between the surface charge and the counter ion (electrolyte ion) balances with the force due to thermal motion. Here, κ is called a Debye-Huckel parameter and expressed as the following equation (Hiroyuki Oshima, “Dispersion stability / aggregation control of nanoparticle and measurement evaluation of zeta potential”, Technical Information Association).

（式中、ｋはＢｏｌｔｚｍａｎｎ定数、ε_０は真空の誘電率、ε_ｒは媒体（液）の比誘電率、Ｔは絶対温度、Ｚは価数、ｅは単位電荷、Ｎ_Ａはアボガドロ数、Ｃは電解質濃度で単位はＭ（＝ｍｏｌ／リットル）である。）

(Wherein, k is Boltzmann constant, epsilon ₀ is the vacuum dielectric constant, epsilon _r is the relative dielectric constant of the medium (liquid), T is an absolute temperature, Z is valence, e is the unit charge, _{N A} is Avogadro's number, C is the electrolyte concentration, and the unit is M (= mol / liter).)

The surface potential (φ ₀ ) of the fine particles is the product of the electric field (σ / ε _r ε ₀ ) and the electric double layer (1 / κ) due to the surface charge density (σ), and is represented by the following equation.

この式から、微粒子の表面電位（φ_０）は、表面電荷密度（σ）や電解質濃度（Ｃ）により制御できることが分かる。

From this equation, it can be seen that the surface potential (φ ₀ ) of the fine particles can be controlled by the surface charge density (σ) and the electrolyte concentration (C).

The electrolyte added to increase the electrolyte concentration is not limited as long as it dissolves in water or water, an alcohol mixed solvent, etc., but alkali metals and alkaline earth metals, quaternary ammonium ions, and halogen elements And salts such as LiCl, KCl, NaCl, MgCl ₂ and CaCl ₂ are used. The surface charge density (σ) can be controlled by pH. This is because the degree of dissociation (ionization) of the dissociating group on the particle surface is affected by pH. For example, when there are carboxyl groups (—COOH) or surface hydroxyl groups (—OH) on the surface of the fine particles, ionization occurs as carboxylate anions (—COO ⁻ ) or hydroxide ions (—O ⁻ ) when the pH is raised. Therefore, the charge density σ increases. On the other hand, when there is an amino group (—NH ₂ ), when the pH is lowered, ammonium ions (—NH ₃ ⁺ ) are formed and the charge density is increased. That is, there is an increase in charge density in the high pH region and the low pH region.

The fine particles dispersed in the solution are electrically negatively or positively charged due to dissociation of surface polar groups and adsorption of ions. The fine particles having the same sign on the surface potential repel each other and stably disperse in the medium without aggregation. The zeta potential reflects the surface charge of the fine particles and is used as an indicator of the dispersion stability of the fine particles (Fumio Kitahara, Kunio Furusawa, Masataka Ozaki, Hiroyuki Oshima, “Zeta Potential Zeta Potential: Physical Chemistry of Fine Particle Interface”, Scientist Issued in January 1995). If the absolute value of the zeta potential increases, the repulsive force between the fine particles becomes strong and the stability of the particles becomes high. Conversely, when the zeta potential approaches zero, the fine particles tend to aggregate.
This zeta potential can be measured, for example, by an electrophoretic light scattering measurement method (also called a laser Doppler method). Irradiate fine particles migrating with an external electric field (E) with laser light of wavelength (λ), measure the frequency change (Doppler shift amount Δν) of the light scattered at the scattering angle (θ), (V) is obtained.

ただし、ｎは媒体（液）の屈折率である。ここで得られた泳動速度（Ｖ）と外部電場（Ｅ）から電気移動度（Ｕ）が次式より求められる。

Here, n is the refractive index of the medium (liquid). From the migration velocity (V) and the external electric field (E) obtained here, the electric mobility (U) is obtained from the following equation.

電気移動度（Ｕ）からゼータ電位（ζ）は、次式のＳｍｏｌｕｃｈｏｗｓｋｉの式を用いて求められる。

From the electric mobility (U), the zeta potential (ζ) is obtained using the following Smoluchowski equation.

ただし、ηは媒体（液）の粘度、εは媒体（液）の誘電率である（北原文雄、古澤邦夫、尾崎正孝、大島広行、「Ｚｅｔａ Ｐｏｔｅｎｔｉａｌゼータ電位：微粒子界面の物理化学」、サイエンティスト社、１９９５年１月発行）。
無機酸化物の粒子では分散溶液のｐＨが変わるとゼータ電位が大きく変化する。例えば、チタニア粒子（日本アエロジル社製）が分散する溶液のｐＨを３、７．５、１１と変化させると、ゼータ電位は＋４０ｍＶ、０ｍＶ、−２０ｍＶと変化し、粒子径は４００ｎｍ、１６００ｎｍ、９００ｎｍと変化する。すなわちゼータ電位が０ｍＶになると粒子は凝集することがわかる（大塚電子（株）、アプリケーションノート、ゼータ電位「無機物のゼータ電位測定」、ｐ．ＬＳ−Ｎ００２−６、２００２年９月１日発行）。このことから、溶液中の微粒子を安定に分散させるために、微粒子のゼータ電位の絶対値を数ｍＶ〜数十ｍＶの範囲に制御することが望ましい。

Where η is the viscosity of the medium (liquid), and ε is the dielectric constant of the medium (liquid) (Fumio Kitahara, Kunio Furusawa, Masataka Ozaki, Hiroyuki Oshima, “Zeta Potential Zeta Potential: Physical Chemistry of Fine Particle Interface”, Scientist Issued in January 1995).
In inorganic oxide particles, the zeta potential changes greatly when the pH of the dispersion changes. For example, when the pH of the solution in which titania particles (Nippon Aerosil Co., Ltd.) are dispersed is changed to 3, 7.5, and 11, the zeta potential changes to +40 mV, 0 mV, and −20 mV, and the particle sizes are 400 nm, 1600 nm, and 900 nm. And change. That is, it can be seen that the particles aggregate when the zeta potential becomes 0 mV (Otsuka Electronics Co., Ltd., application note, zeta potential “measurement of zeta potential of inorganic substances”, p. LS-N002-6, issued on September 1, 2002). . Therefore, in order to stably disperse the fine particles in the solution, it is desirable to control the absolute value of the zeta potential of the fine particles in the range of several mV to several tens of mV.

The silica fine particle aqueous dispersion (Snowtex (ST) 20) manufactured by Nissan Chemical Co., Ltd. adjusted to 1% by weight had a pH of 10, and the zeta potential of the fine silica particles was −48 mV. When the pH of the silica fine particle dispersion was adjusted to 9, the zeta potential of the silica fine particles became −45 mV. Further, when sodium chloride was added to the silica fine particle aqueous dispersion having a pH of 10 to adjust the silica fine particle aqueous dispersion having a sodium chloride concentration of 0.25 mol / liter, the zeta potential of the silica fine particles became −40 mV. .
In a silica fine particle laminated film produced by an alternate lamination method using a silica fine particle aqueous dispersion and a 0.3% by weight aqueous solution of polydiallyldimethylammonium chloride (PDDA), when the zeta potential is −48 mV, While the refractive index was 1.31, the refractive index was 1.29 when the zeta potential was −45 mV and −40 mV. When the fine particle volume ratio is obtained from the refractive index of 1.31, 60% is obtained, and when the fine particle volume ratio is obtained from the refractive index of 1.29, it is 56%. From this, the decrease in the refractive index is considered to be due to the decrease in the porosity due to the decrease in the zeta potential of the fine particles. In this way, the refractive index of the fine particle multilayer film can be controlled by controlling the zeta potential of the fine particles.

The kind of fine particles contained in the fine particle laminated film is not limited to one. For example, two or more kinds of fine particles adsorbed in one immersion of the fine particle dispersion solution may be used, and the kind of fine particles may be different for each immersion of the fine particle dispersion solution.
Note that fine particles of titanium oxide, cerium oxide, niobium oxide, tin oxide, aluminum oxide, and silicon oxide are preferable in terms of increasing the surface hardness of the fine particle laminated film.

(7) Electrolyte polymer solution The electrolyte polymer solution is required when the fine particle laminated film is produced using the alternating lamination method. This electrolyte polymer solution is obtained by dissolving an electrolyte polymer having a charge opposite to or having the same sign as the surface charge of fine particles in water, an organic solvent or a mixed solvent of water-soluble organic solvent and water. Examples of water-soluble organic solvents that can be used include methanol, ethanol, propanol, acetone, dimethylformamide, and acetonitrile. This electrolyte polymer solution is used to form a fine particle laminated film.

  As the electrolyte polymer, a polymer having a charged functional group in the main chain or side chain can be used. In this case, the polyanion generally has a negatively charged functional group such as sulfonic acid, sulfuric acid, and carboxylic acid. For example, polystyrene sulfonic acid (PSS), polyvinyl sulfate (PVS), dextran, and the like. Sulfuric acid, chondroitin sulfate, polyacrylic acid (PAA), polymethacrylic acid (PMA), polymaleic acid, polyfumaric acid, and a copolymer containing at least one of them can be used. The polycation generally has a positively charged functional group such as quaternary ammonium group or amino group, such as polyethyleneimine (PEI), polyallylamine hydrochloride (PAH), polydiallyldimethyl. Ammonium chloride (PDDA), polyvinyl pyridine (PVP), polylysine, polyacrylamide, and a copolymer containing at least one of them can be used. These electrolyte polymers are both water-soluble or soluble in a mixture of water and an organic solvent, and the weight average molecular weight of the electrolyte polymer (measured using a standard polystyrene calibration curve by gel permeation chromatography). However, it is generally preferred to have a value of about 400 to 300,000, depending on the type of electrolyte polymer used. In general, the concentration of the electrolyte polymer in the solution is preferably about 0.0001 to 30% (weight). Further, the pH of the electrolyte polymer solution is not particularly limited.

  By using polydiallyldimethylammonium chloride (PDDA), which is a polycation, and polystyrene sulfonic acid (PSS), which is a polyanion, a (PDDA / PSS) multilayer film can be produced by an alternate lamination method. The thickness of the 45-layer structure film (PDDA / PSS) formed on the silicon wafer with 45 times of alternate lamination is 60 nm, and the thickness of the PDDA / PSS film per alternate lamination is about 1.3 nm. it can. From this, it can be seen that the PDDA layer and the PSS layer are formed with a molecular order thinness. In addition, the monomolecular layer of PDDA and PSS is considered to be several tens from the molecular structure.

(8) Fine particle laminated film The refractive index of the fine particle laminated film can be controlled by selecting the fine particle material. The refractive index of the fine particle laminated film can be obtained by analysis from polarization characteristics measured by ellipsometry, or analysis from reflection spectrum or transmission spectrum measured by a spectrophotometer. The advantage of these methods is that the film thickness of the fine particle laminated film can be evaluated simultaneously. Other methods for determining the film thickness of the fine particle laminated film include a method of observing a film such as SEM (scanning electron microscope), TEM (transmission electron microscope), or AFM (atomic force microscope). It is also possible to form a film on the quartz resonator and obtain the film thickness from the frequency change amount and the density of the film material.
When polydiallyldimethylammonium chloride (PDDA) is used as the electrolyte polymer having a different charge from that of the fine particles, as described above, the PDDA layer has a molecular order thinness of less than 1.3 nm. Therefore, it is considered that the PDDA layer covers the intermediate layer surface and the fine particle surface while following the planar shape and the spherical shape. The thin layer functions as an electrostatic bonding material between the intermediate layer and the fine particles and between the fine particles and the fine particles.

The refractive index of the fine particle laminated film is lower than the bulk of the fine particle material because a gap is formed between the fine particles in the fine particle laminated film. In particle laminated film of the present invention the gap between the particles is almost air, the refractive index n _c of the particle laminated film can be determined from the following equation.

（ただし、式中、ρ_ｐは微粒子積層膜中の微粒子の体積密度、ｎ_Ｐは微粒子を構成する物質の屈折率、ｎ_０は空気の屈折率＝１．０を示す。）（薄膜・光デバイス、吉田貞史、矢嶋弘義著、東京大学出版会、ｐｐ．３４−３７、１９９４年９月２０日発行、参照）。例えば、バルクの屈折率ｎ_Ｐが２．３のチタニア微粒子を用いた微粒子積層膜の屈折率ｎ_ｃは１．８となり、バルクの屈折率ｎ_Ｐが１．４８のシリカ微粒子を用いた微粒子積層膜の屈折率ｎ_ｃは１．３となる。このように、微粒子積層膜は微粒子材料のバルクより低い屈折率を示すため、光学的な設計において屈折率の選択範囲を広げる。

(Wherein ρ _p represents the volume density of the fine particles in the fine particle laminated film, n _P represents the refractive index of the substance constituting the fine particles, and n ₀ represents the refractive index of air = 1.0) (Thin Film / Light Device, Sadayoshi Yoshida, Hiroyoshi Yajima, The University of Tokyo Press, pp. 34-37, published September 20, 1994). For example, the refractive index n _c is 1.8 next to the particle laminated film in which the refractive index n _P of the bulk is used titania fine particles of 2.3, particle laminated with silica particles having a refractive index n _P of the bulk 1.48 refractive index _{n c} of the film becomes 1.3. Thus, the fine particle laminated film exhibits a refractive index lower than that of the bulk of the fine particle material, and thus widens the selection range of the refractive index in optical design.

In the fine particle laminated film of the present invention, since the gap between the fine particles is almost air, the volume density ρ _{P of the} fine particles can also be obtained from the refractive index of the fine particle laminated film from the following equation.

例えば、屈折率ｎ_ｃが１．８のチタニア微粒子積層膜中のチタニア微粒子の体積密度ρ_Ｐは５２％となり、屈折率ｎ_ｃが１．３のシリカ微粒子積層膜中のシリカ微粒子の体積密度ρ_Ｐは５８％となる。

For example, the volume density [rho _P titania fine titania particle laminated film having a refractive index n _c is 1.8 becomes 52%, the volume density of the silica particles of the silica fine particles laminated film having a refractive index n _c is 1.3 [rho _P is 58%.

On the other hand, the refractive index n _c ′ of the fine particle laminate film when filled with a resin having a refractive index n _r so as to completely fill the voids of the fine particle laminate film is expressed by the following equation.

同じ微粒子の体積密度の場合、空隙を樹脂で完全に充填した微粒子積層膜の屈折率ｎ_ｃ’よりも、空隙を有する微粒子積層膜の屈折率ｎ_ｃのほうが屈折率は低くなる。そのため、空隙を樹脂で完全に充填した微粒子積層膜よりも空隙を有する微粒子積層膜のほうがバルクより低い屈折率を示し、光学的な設計において屈折率の選択範囲を広げる。

If the volume density of the same particles, than the refractive index n _{c 'of} particle laminated film was completely filled with resin voids, the refractive index towards the refractive index n _c of the particle laminated film having pores is low. Therefore, the fine particle laminate film having voids has a lower refractive index than the bulk than the fine particle laminate film in which the voids are completely filled with resin, and widens the selection range of the refractive index in optical design.

The fine particle laminated film desirably has a small turbidity in order to exhibit an optical function. When the solid substrate has translucency like glass, the solid substrate having translucency from the haze value (JIS K 7361-1-1997) of the translucent solid substrate on which the fine particle laminated film is formed. The value obtained by subtracting the haze was defined as the turbidity of the fine particle laminated film. Here, the translucent state refers to a state of transmitting light, and does not depend on whether or not light is scattered. On the other hand, when the solid substrate does not have translucency like a silicon wafer, the solid substrate does not have translucency from the reflection turbidity of the non-translucent solid substrate on which the fine particle laminated film is formed. The value obtained by subtracting the reflection turbidity of was used as the turbidity of the fine particle laminated film. Here, the state having no translucency means a state where light is not transmitted by absorption or reflection, and does not depend on whether light is scattered. The reflection turbidity is a value obtained by dividing the diffuse reflectance by the total reflectance. The diffuse reflectance is a value obtained by subtracting the specular reflectance obtained by measuring the specularly reflected light from the total reflectance. The total reflectance is a reflectance obtained by measuring light reflected in all directions.

  From the viewpoint that it is desirable that the turbidity of the fine particle laminated film is small, the turbidity of the fine particle laminated film is preferably 0.001% to 4%, more preferably 0.001% to 2%, and 0.001% to 1%. Is most preferred. Speaking structurally that no visible light is scattered, it means that the voids and fine particles inside the fine particle laminated film have a size not exceeding 100 nm. In order to reduce the increase in the haze value and the increase in diffuse reflectance described above to 4% or less, it is desirable that the size of the voids and fine particles be within 100 nm.

  In the fine particle laminated film of the present invention, when the particle diameter of the fine particles is reduced, the refractive index tends to increase, that is, the fine particle volume fraction in the fine particle laminated film tends to increase. This is because the fine particle laminate film is densified because the cohesive force of the fine particles is increased by the reduction of the particle diameter. Densification of the fine particle laminated film increases the number of fine particles capable of bonding between fine particles in order to increase the number of adjacent fine particles in the fine particle laminated film. Therefore, it can be said that the increase in the number of fine particles that can be combined is one of the factors for improving the hardness of the fine particle laminated film by densification of the fine particle laminated film.

  When the particle shape is beaded, the refractive index of the fine particle laminated film is reduced due to steric hindrance, which indicates that the densification is inhibited and the volume fraction of fine particles in the fine particle laminated film is reduced. On the other hand, since the bead-like particles are in a state where the primary particles are covalently bonded, the bead-like particles themselves are strong. Therefore, it is considered that the fine particle laminated film produced using bead-like particles has a higher strength than the fine particle laminated film produced using spherical particles, although the densification is inhibited.

  In the present invention, since the solid substrate has a polar group on the surface, the fine particle laminated film formed thereon can obtain practical adhesion.

  An example of a method for evaluating the surface hardness of a film on a solid substrate is a pencil hardness test. An apparatus that evaluates the hardness of the thin film itself without depending on the hardness of the solid substrate includes a nanoindenter. Moreover, a tape peeling test is mentioned as a method of evaluating adhesiveness. In the present invention, a pencil hardness test is used as a method for evaluating the surface hardness of the film. Practical surface hardness of the film is preferably a pencil hardness of a density symbol of 6B or more, more preferably a pencil hardness of a density symbol of HB or more, more preferably a pencil hardness of a density symbol of H or more, and a density symbol of 3H or more. Pencil hardness is most preferred.

  In the present invention, a tape peeling test was used as a method for evaluating the adhesion of an actual film. However, the adhesive tape used for the test does not necessarily have an adhesive strength of 2.94 N / 10 mm or more as defined in JIS Z 1522, and may be tested using an adhesive tape having a lower adhesive strength. The above adhesive tape with low adhesive strength has a surface protection during processing, transportation, assembly and storage of various optical films and optical members having optical performance such as antireflection performance and light diffusion performance, such as protective film. Adhesive tape used for contamination prevention and fixing can be mentioned. Practical film adhesion is preferably such that the film remains intact as a result of the tape peel test using the adhesive tape. In addition, when the fine particle laminated film of the present invention remains without being damaged in a tape peeling test using an adhesive tape having a certain adhesive strength, the film is not damaged even when an adhesive tape having an adhesive strength lower than that is used. It is known that it remains. For example, the titania fine particle laminated film on the glass remaining without damage in the tape peeling test using an adhesive tape (31B, manufactured by Nitto Denko Corporation) having an adhesive strength of 3.11 N / 10 mm has an adhesive strength of 0.1. Even if 72N / 10mm adhesive tape (Mitsui Chemicals' cross tape SB-135S-BN) is used, the film remains intact and adhesive strength is 0.16N / 10mm adhesive tape (Hitalex manufactured by Hitachi Chemical Co., Ltd.). Even when P-3010) was used, the film remained without being damaged.

The fact that the solid substrate is exposed after the tape peeling test can be judged from the fact that the exposed portion has the same reflectance as the solid substrate. However, when the solid substrate is not exposed, the film is coherently broken by the adhesive tape, and there is a residue of the film, so that the reflectance is not necessarily the same as that of the solid substrate. Therefore, the presence or absence of damage to the film was evaluated from the surface reflection spectrum as follows. The surface opposite to the test surface on which the tape peeling test was performed was polished with steel wool (manufactured by Nippon Steel Wool Co., Ltd., # 0000) until the solid substrate surface was exposed, and the laminated film was removed. A black adhesive tape (VT-196, manufactured by Nichiban Co., Ltd.) was attached to the exposed solid substrate surface so that no bubbles remained, and the surface reflectance spectrum of one side on which the fine particle multilayer film was formed was measured with visible ultraviolet spectrophotometry. It was measured with a meter (manufactured by JASCO Corporation, V-570). When the reflectance is lower than that of the solid substrate, the wavelength at which the surface reflectance takes a minimum value at a wavelength of 400 to 800 nm is λ _min, and when the reflectance is higher than that of the solid substrate, the surface reflectance is at a wavelength of 400 to 800 nm. The wavelength at which the maximum value was obtained was defined as λ _max . When the film is damaged, λ _min or λ _max decreases (wavelength shift toward the short wavelength side). Therefore, it was defined that the film was damaged when λ _min or λ _max decreased by 30 nm or more after peeling of the adhesive tape (when the wavelength shifted by 30 nm or more to the short wavelength side).

(9) Optical Member Since the fine particle laminated film in the present invention is obtained by an alternating lamination method, the film thickness uniformity is high, and therefore the fine particle laminated film can be suitably used for an optical member. The fine particle laminated film is, for example, an antireflection film, a reflection film, a semi-transmission semi-reflection film, a visible light reflection infrared transmission film, an infrared reflection visible light transmission film, a blue reflection film, a green reflection film, a red reflection film, a bright line cut filter film, It can function as a film having a structure in which two or more color correction films are added.
Therefore, the solid base material on which the fine particle laminated film is formed includes, for example, a base material with an antireflection film, a base material with a reflection film (mirror), a base material with a semi-transmissive semi-reflective film (half mirror), and a visible light reflecting infrared transmissive film Base material (cold mirror), base material with infrared reflective visible light transmission film (hot mirror), base material with blue reflective film, base material with green reflective film or base material with red reflective film (dichroic mirror), bright line cut filter It can be used as a substrate with a film or a substrate with a color tone correction film.

The above functions can be created separately by selecting fine particles and adjusting the refractive index of the fine particle laminated film. In many cases, the above-described function is expressed by a fine particle laminated film composed of a multilayer structure film formed by laminating a low refractive index film and a high refractive index film on a solid substrate while controlling the film thickness.
The range of refractive index required for optical function expression is generally 1.3 to 1.5 for a low refractive index film and 1.6 to 2.4 for a high refractive index film. The lower the refractive index, the better. The higher the refractive index, the better. In addition, the film thickness required for optical function expression can be calculated | required by said Formula (1). The refractive index can be adjusted by selecting fine particles as described above.

An example of a multi-layer structure of the antireflection film has a high refractive index film and a low refractive index film was sequentially 2-layer structure on a solid substrate, it respectively the thickness close to the thickness d ₂ shown by the following formula Is desired.

（ただし、式中、λは波長、ｎは膜の屈折率を示す。）

(In the formula, λ is the wavelength, and n is the refractive index of the film.)

  If the square of the refractive index of the high refractive index film is equal to the product of the square of the refractive index of the low refractive index film and the refractive index of the solid substrate, the surface reflectance at the wavelength λ can be reduced to 0%. Therefore, if the refractive index of the high refractive index film can be increased to 1.85, the surface reflectance can be brought close to 0% even if the refractive index of the low refractive index film is 1.50. In the case of an antireflection film having a single layer structure, if the film thickness of the single layer film satisfies the formula (5) and the refractive index of the film is equal to the square root of the refractive index of the solid substrate, surface reflection at the wavelength λ The rate can be 0%. From the viewpoint of use in an actual antireflection film, the minimum value of the surface reflectance of the fine particle multilayer film in the visible light wavelength region is preferably 3% or less, more preferably 2% or less, and more preferably 1%. Or less, and most preferably 0.5% or less.

The basic multilayer structure of the semi-transmissive / semi-reflective film is generally a four-layer structure in which two layers of a high refractive index film and a low refractive index film are sequentially laminated on a solid substrate and repeated twice. The thickness of each layer of the high refractive index film and the low refractive index film is basically close to the thickness d _2. In order to reduce the wavelength dependency of the transmittance, it may be slightly increased or decreased. Note that even a single layer film of a high refractive index film exhibits a semi-transmissive / semi-reflective function in a wavelength region centered on the wavelength λ by making the film thickness close to d ₂ . From the viewpoint of use in an actual semi-transmissive / semi-reflective film, the average value of the reflectance in the visible light wavelength region of the fine particle laminated film is 15% to 50% and the average value of the transmittance is 50% to 85%. More preferably, the average value of the reflectance is 15% to 40% and the average value of the transmittance is 60% to 85%, and the average value of the reflectance is 15% to 30%. The average transmittance is most preferably 70% or more and 85% or less.

The basic multilayer structure of the reflective film is a two-layer structure in which two layers of a high refractive index film and a low refractive index film are sequentially laminated on a solid substrate. Although the film has an alternately laminated structure, the lowermost layer on the solid substrate side and the outermost surface layer are high refractive index films. The film thickness is determined by d ₂ of essentially each of the above formula (5). The higher the number of repetitions of the two-layer structure of the high refractive index film and the low refractive index film, the higher the reflectance. Further, the greater the difference in refractive index between the low refractive index film and the high refractive index film, the higher the reflectance even if the number of repetitions of the two-layer structure is the same. Therefore, by increasing the difference in refractive index between the low refractive index film and the high refractive index film, the number of repetitions of the two-layer structure necessary for obtaining a high reflectance can be reduced.

  A visible light reflecting infrared transmission film, an infrared reflection visible light transmission film, a blue reflection film, a green reflection film, a red reflection film, a bright line cut filter film, and a color tone correction film are characterized by high reflectivity at a specific wavelength. Therefore, the basic film structure is a multilayer structure such as a reflective film.

  As can be seen from the equation (2), the refractive index of the fine particle laminated film can be controlled by changing the fine particle material or controlling the fine particle volume density, and a fine refractive index laminated film having a high refractive index or a low refractive index can be obtained. For example, if the volume density of fine particles is controlled to 60% by using fine particles of titanium oxide having a bulk refractive index of 2.3, ceria of 2.2, and tin oxide of 1.9, a refractive index of 1.89. A high refractive index film such as a titania fine particle laminated film, a ceria fine particle laminated film having a refractive index of 1.82 or a tin oxide fine particle laminated film having a refractive index of 1.60 is obtained. On the other hand, if the volume density of the fine particles is controlled to 50% using aluminum oxide having a bulk refractive index of 1.6 and silica fine particles of 1.48, a refractive index of 1.33 is obtained. A low refractive index film such as a silica fine particle laminated film having a rate of 1.26 is obtained. It is considered that the fine particle volume density can be controlled by the zeta potential of the fine particles.

(10) Drying treatment The drying treatment may be performed by heating the fine particle laminated film formed on the surface of the solid substrate as described above. The water contained in the fine particle laminated film is removed by the drying treatment, and more van der Waals force, intermolecular force, coulomb attractive force and covalent bond between the fine particles are generated, and the film hardness is improved. The heating temperature should be lower than the melting point, glass transition temperature, softening temperature, etc. of the base material. When a plastic base material is used for the solid base material, the temperature at which the optical function such as transparency and no coloring of the solid base material is maintained. Is good. The heating temperature may exceed the melting point or boiling point of the electrolyte polymer in the fine particle laminated film. Since the electrolyte polymer in the fine particle laminated film in the present invention is extremely small, even if it is evaporated by heating and removed from the fine particle laminated film, the optical function and mechanical properties are maintained. In addition, the electrolyte polymer is necessary as an electrostatic binder for the formation of the fine particle laminate film, but after the fine particle laminate film is formed, the electrolyte polymer exists because the fine particle laminate film is retained by the attractive force between fine particles. May or may not exist.
The heating time is preferably about 1 minute to 1 hour. Of course, the relationship between the heating temperature and the heating time is relative, and when the processing temperature is lowered, it goes without saying that the object can be achieved by continuing the processing for a longer time. The atmosphere for the heat treatment is not limited, and may be an oxidizing atmosphere such as air, an inert atmosphere such as nitrogen, or a reducing atmosphere including hydrogen. There is no restriction | limiting also in the heating method, It can carry out using heating means thru | or a heating apparatus like an oven, an induction heating apparatus, and an infrared heater.

(11) Sealing material / overcoat material When the optical member containing the fine particle laminated film laminate of the present invention is located on the outermost surface of the display, its antifouling property and very high surface hardness are required. The fine particle laminated film may be sealed or overcoated in order to impart or improve surface hardness.

  Many fine voids exist in the fine particle laminated film obtained by the present invention. Therefore, the film strength is further improved by immersing the fine particle laminated film in the resin, filling the voids with the resin, and then curing. Examples of such resin materials include resin compositions such as ionizing radiation curable resins, thermosetting resins, thermoplastic resins, and reactive silicone oils. Alternatively, after immersing in a metal alkoxide solution, the voids can be filled with a converted silica by dipping into a solution of polysilazane by drying and filling the voids with a cured metal oxide. Further, these resin compositions and metal oxides may coat the fine particle laminated film, and this overcoat further improves the film strength. The resin composition or metal oxide may be overcoated without filling the voids in the fine particle laminated film.

An antifouling agent coating may be applied to the surface of the fine particle laminated film to prevent dirt such as water and oil and fat components. As the antifouling agent, there are typically surface coating agents such as a silane compound, a perfluorosilane compound having an alkoxy group (fluorine silane coupling agent), and a fluorine compound. As in the sol-gel reaction, the silane compound is networked by hydrolysis and polycondensation due to dehydration and dealcoholization. When a metal oxide is used for the fine particles, a hydroxyl group exists on the surface, so intermolecular bonding occurs even when the silane compound is directly coated. First, the alkoxy group reacts with the hydroxyl group on the surface to dealcoholize and immobilize, and then the hydrolysis proceeds with moisture in the air, resulting in the formation of a three-dimensionally bonded siloxane bond by condensation. As a result, it has excellent durability against mechanical wear and deterioration due to surface friction and wear. Examples of the silane compound include perhydropolysilazane. By applying this organic solvent solution of perhydropolysilazane and baking in the air, it reacts with moisture and oxygen, and a dense high-purity silica (amorphous SiO ₂ ) film is obtained at about 450 ° C.
Further, the surface coating agent containing fluorine is preferable because it exhibits high water repellency because of the presence of a hydrophobic group mainly composed of fluorine on the surface. A fluororesin layer can be obtained by applying a solution obtained by diluting a fluororesin such as perfluororesin with a fluorine-based solvent such as methylnonafluoroisobutyl ether or methylnonafluorobutyl ether, and performing a heat treatment at about 50 to 130 ° C. Representative examples of such a coating agent include OPTOOL DSX (manufactured by Daikin), Durasurf DS5000 (manufactured by Harves), Novec EGC-1720 (manufactured by Sumitomo 3M), and the like.

Optical function of a multilayer laminated film structure in which a particulate multilayer film is formed on a solid substrate if it is a monomolecular layer formed with a fluorine-based silane coupling agent or an overcoat with a thickness of up to about 20 nm There is no effect. The fluorine-based silane coupling agent is a silane coupling agent in which the non-hydrolyzable group in the chemical formula (I) is a fluoroalkyl group or a perfluoropolyether group. However, when an overcoat exceeding 20 nm is applied, the film thickness of this overcoat must be controlled in order for the solid substrate on which the fine particle laminated film is formed to exhibit an optical function as a member for optical applications. Don't be. Film thickness required in the optical function expression is determined in the d _1. As a method for forming an overcoat film that can control the film thickness within such a range, any known method can be used. For example, a wet process such as a roll coating method, a spin coating method, a dip coating method, a gravure coating method, and an alternating lamination method, a dry process such as a vapor deposition method and a sputtering method, and a method in which these are combined.

As an example of an optical member using a multilayer film of an overcoat and a fine particle laminate film, a fine particle laminate film having a high refractive index n _H is formed on a solid substrate with a thickness (d ₃ ) with respect to the wavelength λ of light.

になるように形成し、その上に微粒子積層膜よりも低い屈折率ｎ_Ｌのオーバーコート膜を光の波長λに対して、厚さ（ｄ_４）が

An overcoat film having a refractive index n _L lower than that of the fine particle laminated film is formed thereon with a thickness (d ₄ ) with respect to the light wavelength λ.

になるように形成した反射防止膜付き基材が挙げられ、波長λで基材よりも反射率が低減する。

And a substrate with an antireflection film formed so that the reflectance is lower than that of the substrate at the wavelength λ.

(12) Mass measurement using a crystal resonator A crystal resonator is used as a mass sensor for measuring a very small amount of mass change. When a substance adheres to the electrode surface of the crystal resonator, the mass of the entire crystal resonator increases, and the resonance frequency of the crystal resonator decreases. (See Surface Technology, Akihiro Seo, “Crystal Microvibration Microbalance”, Vol. 45, No. 10, pp. 1003-1008, 1994) The mass increase (Δm) of this crystal resonator is an attached substance. And is related to the decrease (ΔF) in the resonance frequency of the crystal resonator by the Sauerbrey equation shown below.

ただし、Ａは電極面積、μは水晶のせん断応力（２．９４７×１０^１０ｋｇ・ｍ・ｓ）、ｐは水晶の比重（２６４８ｋｇ／ｍ^３）、Ｆ_０はセンサーの共振基本周波数である。（Ｚ．Ｐｈｙｓ．，Ｇ．Ｓａｕｅｒｂｒｅｙ著，Ｖｏｌ．１５５，ｐ．２０６，１９５９年）

Where A is the electrode area, μ is the shear stress of the crystal (2.947 × 10 ¹⁰ kg · m · s), p is the specific gravity of the crystal (2648 kg / m ³ ), and F ₀ is the resonance fundamental frequency of the sensor. (Z. Phys., G. Sauerbrey, Vol. 155, p. 206, 1959)

In the formation of the fine particle laminated film by the alternating lamination method, the mass of the fine particles adsorbed on the substrate can be evaluated by immersing the quartz crystal in the fine particle dispersion and adsorbing the fine particles on the quartz crystal resonator. . Moreover, the mass of the electrolyte polymer adsorbed on the substrate can be evaluated by immersing the same crystal oscillator in an electrolyte polymer solution and adsorbing the electrolyte polymer on the crystal oscillator.
The fine particle laminated film formed by the alternating lamination method is almost composed of fine particles, and the composition ratio of the electrolyte polymer is small. By mass evaluation using a crystal resonator, the mass ratio of the electrolyte polymer to the fine particles in the fine particle laminated film can be evaluated.
If fine particles and the electrolyte polymer is adsorbed on the electrode surface of the same crystal oscillator, the ratio of the mass of the electrolyte polymer to the mass of particulates _{(Δm p) (Δm e)} (Δm e / Δm p) , the following formulas (A) Guided by the formula.

However, ΔF _e is a decrease in the resonance frequency due to adsorption of the electrolyte polymer, and ΔF _p is a decrease in the resonance frequency due to adsorption of the fine particles. That is, the mass ratio (Δm _e / Δm _p ) of the electrolyte polymer to the fine particles can be obtained as the ratio (ΔF _e / ΔF _p ) of the decrease in the resonance frequency due to the adsorption of the electrolyte polymer to the fine particles.

In order to form the fine particle laminated film in the present invention, the step (A) of immersing the solid substrate in an electrolyte polymer solution and then immersing in ultrapure water for rinsing, immersing in a fine particle dispersion, and then rinsing The step (B) of immersing in ultrapure water is performed in this order. The step of sequentially performing the step (A) once and the step (B) once is defined as one cycle of the fine particle laminated film forming step, and is repeated up to the number of cycles (N _max ) at which the fine particle laminated film has a thickness that exhibits the optical function. . When the quartz crystal unit is immersed together with the base material in the order of electrolyte polymer solution, ultrapure water, fine particle dispersion, and ultrapure water, the adsorption and rinsing of the electrolyte polymer, and the change in resonance frequency accompanying the adsorption and rinsing of the fine particles are as shown in FIG. Can be measured. Here, an aqueous dispersion of silica fine particles (Snowtex (ST) 20) was used as the fine particle dispersion, and PDDA was used as the electrolyte polymer solution.

The frequency decrease (ΔF _e ) is a frequency decrease due to the mass of the electrolyte polymer remaining on the quartz resonator and the solid substrate through the adsorption and rinsing of the electrolyte polymer. This ΔF _e is measured between the first to N _max times in the fine particle laminated film forming step, and the average value thereof is taken as ΔF _e ^av . The frequency decrease (ΔF _P ) is a frequency decrease due to the mass of the fine particles remaining on the quartz vibrator and the base material after the adsorption and rinsing of the fine particles. The [Delta] F _P a particle laminated film forming step is measured between 1 and _{N max,} and the average value and [Delta] F _P ^av. Using these, the mass ratio (me _{/ P} ) of the electrolyte polymer with respect to the fine particles in the fine particle laminated film can be obtained by the following equation.

In the fine particle laminated film formed in the present invention, the mass ratio ( _{me / p} ) of the electrolyte polymer to the fine particles is usually as small as 0.1% to 40%. When the volume ratio of the fine particles are the same, the refractive index of the particle laminated film that completely fills the voids in the resin n _c '(formula (4) see) the particle laminated film having pores than the refractive index n _{c (formula} (3) See) is lower. From this, the smaller the volume ratio of the electrolyte polymer to the fine particles contained in the fine particle laminated film, that is, the smaller the mass ratio ( _{me / P} ) of the electrolyte polymer to the fine particles contained in the fine particle laminated film, the more the refractive index of the fine particle laminated film. It can be seen that the rate is low. In the same fine particle volume density (filling rate), the mass ratio (me _{/ P} ) of the electrolyte polymer to the fine particles is 0.1% to 40%, which is smaller than that of the film in which the fine particles are dispersed in the resin. The refractive index is lowered. That is, in order to lower the refractive index of the fine particle multilayer film, the electrolyte polymer mass ratio ( _{me / P} ) is preferably 0.1% to 40%, more preferably 0.1% to 20%, % To 5% is most preferred.

  Such a refractive index different from that of the bulk broadens the selection range of the refractive index in the optical design, so that the fine particle laminated film is useful for developing optical functionality. For example, antireflection film, reflection film, semi-transmission semi-reflection film, visible light reflection infrared transmission film, infrared reflection visible light transmission film, blue reflection film, green reflection film, red reflection film, bright line cut filter film, color tone correction film When the fine particle laminated film is included as a low refractive index film, the lower the refractive index of the fine particle laminated film, the more the optical characteristics can be improved and the number of layers of the multilayer structure film can be reduced.

  The fine particle multilayer film laminate in the present invention is an optical member having either or both of a low refractive index thin film and a high refractive index thin film, for example, a substrate with an antireflection film, a substrate with a reflection film (mirror), a semi-transmissive semi-transparent Base material with reflective film (half mirror), Base material with visible light reflecting infrared transmissive film (cold mirror), Base material with infrared reflective visible light transmissive film (hot mirror), Base material with blue reflective film and base with green reflective film It is useful as a material and a base material (dichroic mirror) with a red reflecting film. If a lens, a glass substrate, or the like is used as a base material (or a solid base material), a film or the like is used as a base material (or a solid material). When used as a base material), a polarizing plate, a diffusion sheet, a lens sheet, etc. are used as a base material (or a solid substrate) for an antireflection film or a near-infrared cut film for displays such as plasma display panels and liquid crystal display devices. By using the) it can be suitably used for an optical member for liquid crystal display device.

1. Base material PET film with a resin layer provided with polar groups called easy-adhesion layers on both sides as a base material (A4300, manufactured by Toyobo Co., Ltd., refractive index 1.65, 100 mm × 100 mm × 125 μm thickness), BK A −5 glass substrate (manufactured by Matsunami, 25 mm × 75 mm × 0.7 mm thick) and a polycarbonate substrate (Polycaace EC100C, manufactured by Tsutsuchusha, refractive index 1.59, 100 mm × 100 mm × 0.5 mm thick) were used.
2. Formation of fine particle laminated film (Film fine particle film forming process)
A silica aqueous dispersion (Snowtex (ST) 20, manufactured by Nissan Chemical Industries, Ltd., silica sol) in which silica fine particles having an average primary particle size of 15 nm measured by the BET method are dispersed is used as the fine particle dispersion, and PDDA is used as an electrolyte polymer. Used as.
As a solution, a 0.3 wt% PDDA aqueous solution and a 1.0 wt% fine particle dispersion were prepared. The pH of the fine particle dispersion was unadjusted to 9.5, and the pH of the PDDA aqueous solution was adjusted to 9. Step (a) of immersing the solid substrate and the crystal resonator in a PDDA aqueous solution for 1 minute and immersing in ultra pure water for rinsing for 3 minutes, immersing in a fine particle dispersion for 1 minute, and then rinsing ultra pure The step (a) of immersing in water for 3 minutes was performed in this order. This step (a) once and step (b) once are sequentially performed as one cycle, and this cycle is repeated 11 times (the number of times of fine particle alternate lamination), and the fine particle laminated film is formed on the surface of the solid substrate and the crystal resonator. Formed. By monitoring the resonance frequency of the crystal resonator in the step (a), the frequency decrease (ΔF _e ) due to the mass of the electrolyte polymer remaining on the crystal resonator and the solid substrate can be evaluated. By repeating this evaluation of ΔF _e for 11 cycles and averaging, an average value (ΔF _e ^av ) of frequency decrease due to the mass of the electrolyte polymer can be obtained. By monitoring the resonance frequency of the crystal unit in the step (A), it is possible to evaluate the amount of frequency decrease (ΔF _p ) due to the mass of the fine particles remaining on the crystal unit and the solid substrate. By repeating this evaluation of ΔF _p for 11 cycles and averaging, the average value (ΔF _p ^av ) of the frequency decrease due to the mass of the fine particles can be obtained. As a ratio of ΔF _e ^av and ΔF _p ^av , the mass ratio (me _{/ p} ) of the electrolyte polymer to the fine particles in the fine particle laminated film can be obtained (see formula (8)).
A solid substrate (fine particle laminated film laminated body) on which a fine particle laminated film is laminated is placed on a slide stand (150 mm × 82 mm × 22 mm) made of stainless steel having a thickness of 0.5 mm, and 110 ° C. by a dryer (manufactured by Yamato Kagaku). Was subjected to a heat treatment for 1 hour to obtain an optical member having a silica fine particle laminated film.

(Measurement of haze value)
The result of having measured the haze value of the BK-5 glass substrate in which the fine particle laminated film obtained above was formed on both surfaces in accordance with JIS K 7361-1-1997 with a turbidimeter (manufactured by Nippon Denshoku Industries Co., Ltd.). 0.4%. The haze value of only the BK-5 glass substrate was measured in the same manner, and as a result, it was 0.1%. The turbidity of the fine particle laminate film was determined by subtracting the haze value of only the solid substrate from the haze value of the solid substrate on which the fine particle laminate film was formed on both surfaces. As a result, the turbidity of the fine particle laminate film was 0.3%, and it was found that the transparency of the fine particle laminate film was very high.
(Measurement of transmittance and surface reflectance)
When the transmission spectrum of this fine particle laminate film (BK-5 glass substrate having a silica fine particle laminate film formed on both surfaces) was measured with a visible ultraviolet spectrophotometer (manufactured by JASCO Corporation, V-570), The maximum transmittance at a wavelength of 400 to 800 nm was 98%. Further, one side of the BK-5 glass substrate on which the silica fine particle laminated film was formed was polished with steel wool (manufactured by Nippon Steel Wool Co., Ltd., # 0000) until the glass surface was exposed to remove the laminated film. A black adhesive tape (VT-196, manufactured by Nichiban Co., Ltd.) was attached to the exposed glass surface so that no bubbles remained, and the surface reflectance spectrum of one surface on which the fine particle multilayer film was formed was measured with a visible ultraviolet spectrophotometer ( It was measured by JASCO Corporation V-570). The minimum surface reflectance at a wavelength of 400 to 800 nm of the BK-5 glass substrate on which the silica fine particle laminated film was formed was 0.5%.
Since the transmittance of the BK-5 glass substrate was 91% and the surface reflectance was 4.5%, it was found that an antireflection film having excellent characteristics was formed and contributed to the improvement of the transmittance.
The mass ratio (me _{/ p} ) of the electrolyte polymer to the fine particles in the fine particle laminated film evaluated from the change in the resonance frequency of the crystal resonator was 3%. From this, it is understood that the fine particle laminated film is composed of almost only fine particles.

(Evaluation of adhesion of fine particle laminated film)
The adhesion between the particle laminate film on the BK-5 glass substrate and the particle laminate film on the polycarbonate substrate was evaluated by performing a tape peeling test as follows. An adhesive tape (Hitalex P-3010 manufactured by Hitachi Chemical Co., Ltd.) having an adhesive strength of 39 cN / 25 mm and a width of 25 mm was used as the adhesive tape. Using a roll laminator (LMP-350EX manufactured by Lamy Corporation), an adhesive tape was attached to the fine particle laminate film under the conditions of a roll load of 0.3 MPa, a feed rate of 0.3 m / min, and a temperature of 20 ° C. One minute after the tape was brought into close contact, one end of the tape was lifted at a right angle to the substrate surface and peeled off instantaneously. It was judged from the surface reflection spectrum whether the fine particle laminated film remained without being damaged. When the minimum value of the surface reflectance of the solid base material formed with the fine particle laminate film at a wavelength of 400 to 800 nm is λ _min, and the decrease amount of λ _min before and after the adhesive tape is applied is greater than 30 nm, the fine particle laminate The membrane was defined as damaged. The fine particle laminated film on the BK-5 glass substrate remained without being damaged, and the fine particle laminated film on the polycarbonate substrate was also left without being damaged (described as film remaining in Table 1).

(Measurement of pencil hardness of fine particle laminated film)
The pencil hardness of the particle laminated film on the PET film having the easy adhesion layer was evaluated as follows based on JIS K 5400-1990.
An optical X-axis movable stage is fixed on an electronic balance (manufactured by Kensei Kogyo Co., Ltd.), a stainless steel plate having a thickness of 3 mm is placed on the X-axis movable stage, and a fine particle laminated film is placed on the stainless steel plate. The formed solid substrate was fixed. This electronic balance was fixed on a lab jack. A pencil was inserted into a plastic hose cut to about 5 cm, the plastic hose into which the pencil was inserted was sandwiched with a lamp clamp or the like, and the lamp clamp or the like was fixed to a stand with a muff or the like. The lab jack was extended so that the solid substrate on which the fine particle laminated film was formed was pressed against a pencil, and the lab jack was extended so that the weight of the electronic balance was increased by 1.00 ± 0.05 kg. At this time, the tip of the pencil core is sharpened by polishing paper No. 400 so that the corner is flat and sharp, and the pencil makes an angle of 45 degrees with respect to the solid substrate surface on which the fine particle laminated film is formed. It is fixed to keep. The X-axis movable stage was moved so that the solid substrate moved in the direction opposite to the direction of the pencil lead. At this time, the moving speed of the X-axis movable stage is about 1 cm / s, and the distance is about 1 cm. The pencil powder remaining on the surface of the fine particle laminate film after being pulled is blown off with an air blow, and then the pencil powder is pressed against the lump of the remaining pencil powder without rubbing a plastic eraser (made by dragonfly pencil, PE01). Was removed as much as possible. Each time I scratched the pencil, the pencil was sharpened with # 400 abrasive paper.
Light is applied to the layered particulate film from a 45 degree angle to the solid substrate surface at a right angle to the scratched direction, and the light reflected from the 45 degree angle (specular reflection light) is visually observed. When a slight bite was seen, it was determined that there was a scratch. If there is no scratch on the membrane more than once in 5 tests, replace the pencil with the higher density symbol and perform the same test to find a pencil with more than 2 scratches on the membrane. The density symbol that is one step lower than the density symbol of No. was defined as pencil hardness by scratch evaluation. The pencil hardness of the fine particle multilayer film formed on the PET film with an easy adhesion layer was H.

Silica aqueous dispersion (Snowtex (ST) O, manufactured by Nissan Chemical Industries, Ltd., silica sol) in which silica fine particles having an average primary particle diameter of 15 nm measured by the BET method are dispersed is used as the fine particle dispersion, alternating fine particles A fine-particle laminated film laminate was produced according to Example 1 except that the number of laminations was three.
When the transmission spectrum of this fine particle laminate film laminate (BK-5 glass substrate having a silica fine particle laminate film formed on both sides) was measured in the same manner as in Example 1, the maximum transmittance at a wavelength of 400 to 800 nm was 98%. Met. When the surface reflection spectrum of one surface on which the fine particle film was formed was measured in the same manner as in Example 1, the minimum surface reflectance at a wavelength of 400 to 800 nm was 0.5%.
The turbidity of the fine particle laminated film evaluated in the same manner as in Example 1 was 0.3%.
As a result of evaluating the adhesiveness in the same manner as in Example 1, the fine particle laminated film on the BK-5 glass substrate remained without being damaged, and the fine particle laminated film on the polycarbonate substrate remained without being damaged.

Silica aqueous dispersion (Snowtex (ST) N, manufactured by Nissan Chemical Industries, Ltd., silica sol) in which silica fine particles having an average primary particle diameter of 15 nm measured by the BET method are dispersed is used as the fine particle dispersion, alternating fine particles A fine particle laminated film laminate was produced in the same manner as in Example 1 except that the number of times of lamination was 12 and the fine particle laminated film laminate was not heat-treated at 110 ° C. for 1 hour. When the transmission spectrum of this fine particle laminate film laminate (BK-5 glass substrate having a silica fine particle laminate film formed on both sides) was measured in the same manner as in Example 1, the maximum transmittance at a wavelength of 400 to 800 nm was 98%. Met. When the surface reflection spectrum of one surface on which the fine particle film was formed was measured in the same manner as in Example 1, the minimum surface reflectance at a wavelength of 400 to 800 nm was 0.8%.
The turbidity of the fine particle laminated film evaluated in the same manner as in Example 1 was 0.3%. As a result of evaluating the adhesiveness in the same manner as in Example 1, the fine particle laminated film on the BK-5 glass substrate remained without being damaged, and the fine particle laminated film on the polycarbonate substrate remained without being damaged.

Silica aqueous dispersion (Snowtex (ST) S, manufactured by Nissan Chemical Industries, Ltd., silica sol) in which silica fine particles having an average primary particle diameter of 10 nm measured by the BET method are dispersed is used as the fine particle dispersion. A fine particle laminated film laminate was produced in the same manner as in Example 1 except that the number of times of lamination was 18 and the fine particle laminated film laminated body was not heat-treated at 110 ° C. for 1 hour. When the transmission spectrum of this fine particle laminated film laminate (BK-5 glass substrate having a silica fine particle laminated film formed on both surfaces) was measured in the same manner as in Example 1, the maximum transmittance at a wavelength of 400 to 800 nm was 97%. Met. When the surface reflection spectrum of one surface on which the fine particle film was formed was measured in the same manner as in Example 1, the minimum surface reflectance at a wavelength of 400 to 800 nm was 1.1%.
The turbidity of the fine particle laminated film evaluated in the same manner as in Example 1 was 0.3%. As a result of evaluating the adhesiveness in the same manner as in Example 1, the fine particle laminated film on the BK-5 glass substrate remained without being damaged, and the fine particle laminated film on the polycarbonate substrate remained without being damaged.

Silica aqueous dispersion (Snowtex (ST) OS, manufactured by Nissan Chemical Industries, Ltd., silica sol) in which silica fine particles having an average primary particle diameter of 10 nm measured by the BET method are dispersed is used as the fine particle dispersion, alternating fine particles A fine-particle laminated film laminate was produced according to Example 1 except that the number of laminations was three. When the transmission spectrum of this fine particle laminate film laminate (BK-5 glass substrate having a silica fine particle laminate film formed on both sides) was measured in the same manner as in Example 1, the maximum transmittance at a wavelength of 400 to 800 nm was 98%. Met. When the surface reflection spectrum of one surface on which the fine particle film was formed was measured in the same manner as in Example 1, the minimum surface reflectance at a wavelength of 400 to 800 nm was 0.7%.
The turbidity of the fine particle laminated film evaluated in the same manner as in Example 1 was 0.3%. As a result of evaluating the adhesiveness in the same manner as in Example 1, the fine particle laminated film on the BK-5 glass substrate remained without being damaged, and the fine particle laminated film on the polycarbonate substrate remained without being damaged.

A silica aqueous dispersion (Snowtex (ST) NS, manufactured by Nissan Chemical Industries, Ltd., silica sol) in which silica fine particles having an average primary particle diameter of 10 nm measured by the BET method are dispersed is used as the fine particle dispersion. A fine particle laminated film laminate was produced in the same manner as in Example 1 except that the number of times of lamination was 16 and the fine particle laminated film laminate was not heat-treated at 110 ° C. for 1 hour. When the transmission spectrum of this fine particle laminated film laminate (BK-5 glass substrate having a silica fine particle laminated film formed on both surfaces) was measured in the same manner as in Example 1, the maximum transmittance at a wavelength of 400 to 800 nm was 97%. Met. When the surface reflection spectrum of one surface on which the fine particle film was formed was measured in the same manner as in Example 1, the minimum surface reflectance at a wavelength of 400 to 800 nm was 1.2%.
The turbidity of the fine particle laminated film evaluated in the same manner as in Example 1 was 0.3%. As a result of evaluating the adhesiveness in the same manner as in Example 1, the fine particle laminated film on the BK-5 glass substrate remained without being damaged, and the fine particle laminated film on the polycarbonate substrate remained without being damaged.

Silica aqueous dispersion (Snowtex (ST) XS, manufactured by Nissan Chemical Industries, Ltd., silica sol) in which silica fine particles having an average primary particle diameter of 5 nm measured by the Sears method are dispersed are used as the fine particle dispersion. A fine particle laminated film laminate was produced in the same manner as in Example 1 except that the number of laminations was 22 and the fine particle laminated film laminated body was not heat-treated at 110 ° C. for 1 hour. When the transmission spectrum of this fine particle laminated film laminate (BK-5 glass substrate having a silica fine particle laminated film formed on both surfaces) was measured in the same manner as in Example 1, the maximum transmittance at a wavelength of 400 to 800 nm was 97%. Met. When the surface reflection spectrum of one surface on which the fine particle film was formed was measured in the same manner as in Example 1, the minimum surface reflectance at a wavelength of 400 to 800 nm was 1.3%.
The turbidity of the fine particle laminated film evaluated in the same manner as in Example 1 was 0.3%. Adhesiveness was evaluated in the same manner as in Example 1 except that an adhesive tape having an adhesive strength of 180 cN / 25 mm and a width of 25 mm was used as the adhesive tape (Icross Tape SB-135S-BN manufactured by Mitsui Chemicals, Inc.). As a result, the fine particle laminated film on the BK-5 glass substrate remained without being damaged, and the fine particle laminated film on the polycarbonate substrate remained without being damaged.

Silica aqueous dispersion (Snowtex (ST) OXS, manufactured by Nissan Chemical Industries, Ltd., silica sol) in which silica fine particles having an average primary particle diameter of 5 nm measured by the Sears method are dispersed are used as the fine particle dispersion. A fine particle laminated film laminate was produced in the same manner as in Example 1 except that the number of laminations was five and that the heat treatment of the fine particle laminated film laminate was not performed at 110 ° C. for 1 hour. When the transmission spectrum of this fine particle laminate film laminate (BK-5 glass substrate having a silica fine particle laminate film formed on both sides) was measured in the same manner as in Example 1, the maximum transmittance at a wavelength of 400 to 800 nm was 98%. Met. When the surface reflection spectrum of one surface on which the fine particle film was formed was measured in the same manner as in Example 1, the minimum surface reflectance at a wavelength of 400 to 800 nm was 0.9%.
The turbidity of the fine particle laminated film evaluated in the same manner as in Example 1 was 0.3%.
As a result of evaluating the adhesiveness in the same manner as in Example 7, the fine particle laminated film on the BK-5 glass substrate remained without being damaged, and the fine particle laminated film on the polycarbonate substrate remained without being damaged.

A silica aqueous dispersion (Snowtex (ST) NXS, manufactured by Nissan Chemical Industries, Ltd., silica sol) in which silica fine particles having an average primary particle diameter of 5 nm measured by the Sears method are dispersed is used as the fine particle dispersion, and the alternating fine particles A fine particle laminated film laminate was produced in the same manner as in Example 1 except that the number of laminations was 18 and the fine particle laminated film laminated body was not heat-treated at 110 ° C. for 1 hour. When the transmission spectrum of this fine particle laminate film (BK-5 glass substrate having a silica fine particle laminate film formed on both sides) was measured in the same manner as in Example 1, the maximum transmittance at a wavelength of 400 to 800 nm was 96%. Met. When the surface reflection spectrum of one surface on which the fine particle film was formed was measured in the same manner as in Example 1, the minimum surface reflectance at a wavelength of 400 to 800 nm was 1.9%.
The turbidity of the fine particle laminated film evaluated in the same manner as in Example 1 was 0.3%.
As a result of evaluating the adhesiveness in the same manner as in Example 7, the fine particle laminated film on the BK-5 glass substrate remained without being damaged, and the fine particle laminated film on the polycarbonate substrate remained without being damaged.

A silica aqueous dispersion (Snowtex (ST) PSS, manufactured by Nissan Chemical Industries, Ltd., silica sol) in which bead-like silica fine particles having an average primary particle size of 14 nm measured by the BET method are dispersed is used as the fine particle dispersion. A fine particle laminated film laminate was produced in the same manner as in Example 1 except that the number of fine particle alternating laminations was nine and that the fine particle laminated film laminate was heat-treated at 130 ° C. for 2 hours. When the transmission spectrum of this fine particle laminate film laminate (BK-5 glass substrate having a silica fine particle laminate film formed on both sides) was measured in the same manner as in Example 1, the maximum transmittance at a wavelength of 400 to 800 nm was 99%. Met. When the surface reflection spectrum of one surface on which the fine particle film was formed was measured in the same manner as in Example 1, the minimum surface reflectance at a wavelength of 400 to 800 nm was 0.2%.
The turbidity of the fine particle laminated film evaluated in the same manner as in Example 1 was 0.3%.
As a result of evaluating the adhesiveness in the same manner as in Example 1, the fine particle laminated film on the BK-5 glass substrate remained without being damaged, and the fine particle laminated film on the polycarbonate substrate remained without being damaged.

A silica aqueous dispersion (Snowtex (ST) PSSO, manufactured by Nissan Chemical Industries, Ltd., silica sol) in which bead-like silica fine particles having an average primary particle size of 14 nm measured by the BET method are dispersed is used as the fine particle dispersion. A fine particle laminated film laminate was produced in the same manner as in Example 1 except that the number of fine particle alternating laminations was set to 3 and the fine particle laminated film laminate was heat-treated at 130 ° C. for 2 hours. When the transmission spectrum of this fine particle laminate film (BK-5 glass substrate having a silica fine particle laminate film formed on both sides) was measured in the same manner as in Example 1, the maximum transmittance at a wavelength of 400 to 800 nm was 96%. Met. When the surface reflection spectrum of one surface on which the fine particle film was formed was measured in the same manner as in Example 1, the minimum surface reflectance at a wavelength of 400 to 800 nm was 0.7%.
The turbidity of the fine particle laminated film evaluated in the same manner as in Example 1 was 1.9%.
As a result of evaluating the adhesiveness in the same manner as in Example 1, the fine particle laminated film on the BK-5 glass substrate remained without being damaged, and the fine particle laminated film on the polycarbonate substrate remained without being damaged.

A silica aqueous dispersion (Snowtex (ST) UP, manufactured by Nissan Chemical Industries, Ltd., silica sol) in which bead-like silica fine particles having an average primary particle diameter of 8 nm measured by the BET method are dispersed is used as the fine particle dispersion. A fine particle laminated film laminate was produced in the same manner as in Example 1 except that the number of alternating fine particle lamination was set to 11 and that the fine particle laminated film laminated body was heat-treated at 130 ° C. for 2 hours. When the transmission spectrum of this fine particle laminate film laminate (BK-5 glass substrate having a silica fine particle laminate film formed on both sides) was measured in the same manner as in Example 1, the maximum transmittance at a wavelength of 400 to 800 nm was 99%. Met. When the surface reflection spectrum of one surface on which the fine particle film was formed was measured in the same manner as in Example 1, the minimum surface reflectance at a wavelength of 400 to 800 nm was 0.3%.
The turbidity of the fine particle laminated film evaluated in the same manner as in Example 1 was 0.3%.
As a result of evaluating the adhesiveness in the same manner as in Example 1, the fine particle laminated film on the BK-5 glass substrate remained without being damaged, and the fine particle laminated film on the polycarbonate substrate remained without being damaged.

A silica aqueous dispersion (Snowtex (ST) OUP, manufactured by Nissan Chemical Industries, Ltd., silica sol) in which bead-like silica fine particles having an average primary particle size of 8 nm measured by the BET method are dispersed was used as a fine particle dispersion. A fine particle laminated film laminate was produced in accordance with Example 1 except that the number of fine particle alternating laminations was three. When the transmission spectrum of this fine particle laminate film laminate (BK-5 glass substrate having a silica fine particle laminate film formed on both sides) was measured in the same manner as in Example 1, the maximum transmittance at a wavelength of 400 to 800 nm was 99%. Met. When the surface reflection spectrum of one surface on which the fine particle film was formed was measured in the same manner as in Example 1, the minimum surface reflectance at a wavelength of 400 to 800 nm was 0.05%.
The turbidity of the fine particle laminated film evaluated in the same manner as in Example 1 was 0.3%.
As a result of evaluating the adhesiveness in the same manner as in Example 1, the fine particle laminated film on the BK-5 glass substrate remained without being damaged, and the fine particle laminated film on the polycarbonate substrate remained without being damaged.

(Comparative Example 1)
Silica aqueous dispersion (Snowtex (ST) 50, manufactured by Nissan Chemical Industries, Ltd., silica sol) in which silica fine particles having an average primary particle size of 25 nm measured by the BET method are dispersed is used as the fine particle dispersion. A fine-particle multilayer film laminate was produced in accordance with Example 1 except that the number of laminations was seven. When the transmission spectrum of this fine particle laminate film laminate (BK-5 glass substrate having a silica fine particle laminate film formed on both sides) was measured in the same manner as in Example 1, the maximum transmittance at a wavelength of 400 to 800 nm was 99%. Met. When the surface reflection spectrum of one surface on which the fine particle film was formed was measured in the same manner as in Example 1, the minimum surface reflectance at a wavelength of 400 to 800 nm was 0.05%.
The turbidity of the fine particle laminated film evaluated in the same manner as in Example 1 was 0.3%.
As a result of evaluating adhesion in the same manner as in Example 1, the fine particle laminated film on the BK-5 glass substrate was peeled off, and the fine particle laminated film on the polycarbonate substrate was also peeled off (described as film peeling in Table 1).

(Comparative Example 2)
A silica aqueous dispersion (Snowtex (ST) 20L, manufactured by Nissan Chemical Industries, Ltd., silica sol) in which silica fine particles having an average primary particle diameter of 45 nm measured by the BET method are dispersed is used as the fine particle dispersion. A fine-particle multilayer film laminate was produced in accordance with Example 1 except that the number of laminations was seven. When the transmission spectrum of this fine particle laminate film laminate (BK-5 glass substrate having a silica fine particle laminate film formed on both sides) was measured in the same manner as in Example 1, the maximum transmittance at a wavelength of 400 to 800 nm was 99%. Met. When the surface reflection spectrum of one surface on which the fine particle film was formed was measured in the same manner as in Example 1, the minimum surface reflectance at a wavelength of 400 to 800 nm was 0.05%.
The turbidity of the fine particle laminated film evaluated in the same manner as in Example 1 was 0.5%.
As a result of evaluating adhesion in the same manner as in Example 1, the fine particle laminated film on the BK-5 glass substrate was peeled off, and the fine particle laminated film on the polycarbonate substrate was also peeled off.

(Comparative Example 3)
A silica aqueous dispersion (Snowtex (ST) XL, manufactured by Nissan Chemical Industries, Ltd., silica sol) in which silica fine particles having an average primary particle diameter of 50 nm measured by the BET method are dispersed is used as the fine particle dispersion. A fine particle laminated film laminate was produced in the same manner as in Example 1 except that the number of laminations was six. When the transmission spectrum of this fine particle laminate film laminate (BK-5 glass substrate having a silica fine particle laminate film formed on both sides) was measured in the same manner as in Example 1, the maximum transmittance at a wavelength of 400 to 800 nm was 99%. Met. When the surface reflection spectrum of one surface on which the fine particle film was formed was measured in the same manner as in Example 1, the minimum surface reflectance at a wavelength of 400 to 800 nm was 0.05%.
The turbidity of the fine particle laminated film evaluated in the same manner as in Example 1 was 0.7%.
As a result of evaluating adhesion in the same manner as in Example 1, the fine particle laminated film on the BK-5 glass substrate was peeled off, and the fine particle laminated film on the polycarbonate substrate was also peeled off.

(Comparative Example 4)
Silica aqueous dispersion (Snowtex (ST) YL, manufactured by Nissan Chemical Industries, Ltd., silica sol) in which silica fine particles having an average primary particle diameter of 65 nm measured by the BET method are dispersed is used as the fine particle dispersion, alternating fine particles A fine particle laminated film laminate was produced in the same manner as in Example 1 except that the number of laminations was 5. When the transmission spectrum of this fine particle laminate film laminate (BK-5 glass substrate having a silica fine particle laminate film formed on both sides) was measured in the same manner as in Example 1, the maximum transmittance at a wavelength of 400 to 800 nm was 99%. Met. When the surface reflection spectrum of one surface on which the fine particle film was formed was measured in the same manner as in Example 1, the minimum surface reflectance at a wavelength of 400 to 800 nm was 0.1%.
The turbidity of the fine particle laminated film evaluated in the same manner as in Example 1 was 1.0%.
As a result of evaluating adhesion in the same manner as in Example 1, the fine particle laminated film on the BK-5 glass substrate was peeled off, and the fine particle laminated film on the polycarbonate substrate was also peeled off.

(Comparative Example 5)
A silica aqueous dispersion (Snowtex (ST) ZL, manufactured by Nissan Chemical Industries, Ltd., silica sol) in which silica fine particles having an average primary particle diameter of 85 nm measured by the BET method are dispersed is used as the fine particle dispersion. A fine-particle laminated film laminate was produced according to Example 1 except that the number of laminations was four. When the transmission spectrum of this fine particle laminate film laminate (BK-5 glass substrate having a silica fine particle laminate film formed on both sides) was measured in the same manner as in Example 1, the maximum transmittance at a wavelength of 400 to 800 nm was 99%. Met. When the surface reflection spectrum of one surface on which the fine particle film was formed was measured in the same manner as in Example 1, the minimum surface reflectance at a wavelength of 400 to 800 nm was 0.3%.
The turbidity of the fine particle laminated film evaluated in the same manner as in Example 1 was 2.2%.
As a result of evaluating adhesion in the same manner as in Example 1, the fine particle laminated film on the BK-5 glass substrate was peeled off, and the fine particle laminated film on the polycarbonate substrate was also peeled off.

(Comparative Example 6)
A silica aqueous dispersion (Snowtex (ST) PSM, manufactured by Nissan Chemical Industries, Ltd., silica sol) in which beaded silica fine particles having an average primary particle size of 24 nm measured by the BET method are dispersed is used as the fine particle dispersion. A fine particle laminated film laminate was produced in accordance with Example 1 except that the number of fine particle alternating laminations was nine. When the transmission spectrum of this fine particle laminate film laminate (BK-5 glass substrate having a silica fine particle laminate film formed on both sides) was measured in the same manner as in Example 1, the maximum transmittance at a wavelength of 400 to 800 nm was 99%. Met. When the surface reflection spectrum of one surface on which the fine particle film was formed was measured in the same manner as in Example 1, the minimum surface reflectance at a wavelength of 400 to 800 nm was 0.1%.
The turbidity of the fine particle laminated film evaluated in the same manner as in Example 1 was 0.8%.
As a result of evaluating adhesion in the same manner as in Example 1, the fine particle laminated film on the BK-5 glass substrate was peeled off, and the fine particle laminated film on the polycarbonate substrate was also peeled off.

(Comparative Example 7)
A silica aqueous dispersion (Snowtex (ST) PSMO, manufactured by Nissan Chemical Industries, Ltd., silica sol) in which bead-like silica fine particles having an average primary particle size of 24 nm measured by the BET method are dispersed was used as a fine particle dispersion. A fine particle laminated film laminate was produced in accordance with Example 1 except that the number of fine particle alternating laminations was three. When the transmission spectrum of this fine particle laminate film (BK-5 glass substrate having a silica fine particle laminate film formed on both sides) was measured in the same manner as in Example 1, the maximum transmittance at a wavelength of 400 to 800 nm was 96%. Met. When the surface reflection spectrum of one surface on which the fine particle film was formed was measured in the same manner as in Example 1, the minimum surface reflectance at a wavelength of 400 to 800 nm was 0.8%.
The turbidity of the fine particle laminated film evaluated in the same manner as in Example 1 was 2.5%.
As a result of evaluating adhesion in the same manner as in Example 1, the fine particle laminated film on the BK-5 glass substrate was peeled off, and the fine particle laminated film on the polycarbonate substrate was also peeled off.

  Table 1 summarizes the particle diameters and shapes of the silica fine particles in Examples 1 to 13 and Comparative Examples 1 to 7 and the characteristics of the fine particle film.

A PET film (A4100, manufactured by Toyobo Co., Ltd., refractive index 1.58, 100 mm × 100 mm × 125 μm thickness) having a resin layer provided with a polar group called an easy adhesion layer on one side was used as a substrate.
The substrate is immersed for 1 minute in an aqueous polyester resin dispersion in which water-dispersed polyester resin (Vylonal MD-1245, manufactured by Toyobo Co., Ltd.) is diluted 10 times with ultrapure water, and then dried at room temperature. A polyester resin layer was formed as an intermediate layer to prepare a solid substrate (substrate with an intermediate layer). This base material with an intermediate layer was placed on a slide stand (150 mm × 82 mm × 22 mm) made of stainless steel having a thickness of 0.5 mm, and heat-treated at 110 ° C. for 10 minutes with a dryer (manufactured by Yamato Kagaku).
Using this substrate with an intermediate layer, a fine particle laminated film was formed according to Example 1 to produce a fine particle laminated film laminate.
As a result of conducting the pencil hardness test of the fine particle laminated film in the same manner as in Example 1, the pencil hardness was H.

  Except that a hard coat PET film (KB film G01H, manufactured by Kimoto Co., Ltd., 100 mm × 100 mm × 125 μm thickness, hard coat surface used by UV ozone treatment) was used as the base material, the same procedure as in Example 14 was performed. A fine particle laminated film laminate was prepared. As a result of the pencil hardness test of the fine particle multilayer film performed in the same manner as in Example 1, the pencil hardness was 3H.

PET film (A4300, manufactured by Toyobo Co., Ltd., refractive index 1.65, 100 mm × 100 mm × 125 μm thickness) and BK-5 having a resin layer to which a polar group called an easy-adhesion layer is provided on both sides as a base material A glass substrate (manufactured by Matsunami Co., Ltd., 25 mm × 75 mm × 0.7 mm thickness) was used, and an alumina aqueous dispersion (alumina sol-520, Nissan Chemical Industries, Ltd.) in which alumina fine particles having an average primary particle diameter of 15 nm measured by the BET method were dispersed. Co., Ltd., aluminum oxide sol) was used as the fine particle dispersion, the fine particle concentration of the fine particle dispersion was adjusted to 1% by weight, the number of fine particle alternating laminations was set to 40 times, and the fine particle laminated film laminate. A fine particle laminated film laminate was prepared according to Example 1 except that the heat treatment at 110 ° C. for 1 hour was not performed. When the transmission spectrum of this fine particle laminated film laminate (BK-5 glass substrate having a silica fine particle laminated film formed on both sides) was measured in the same manner as in Example 1, the minimum transmittance at a wavelength of 400 to 800 nm was 91%. Met. When the reflection spectrum of the BK-5 glass substrate having the silica fine particle laminated film formed on both sides was measured with a visible ultraviolet spectrophotometer (manufactured by JASCO Corporation, V-570), the maximum at a wavelength of 400 to 800 nm was obtained. The reflectance of was 8%. When the surface reflection spectrum of one surface on which the fine particle film was formed was measured in the same manner as in Example 1, the maximum surface reflectance at a wavelength of 400 to 800 nm was 4.0%.
The turbidity of the fine particle laminated film evaluated in the same manner as in Example 1 was 0.3%.
As a result of evaluating the adhesiveness in the same manner as in Example 1 except that an adhesive tape having a width of 776 cN / 25 mm and a width of 30 mm (No. 31B, manufactured by Nitto Denko Corporation) was used for the adhesive tape, As for eyes, the fine particle laminated film on the BK-5 glass substrate remained without being damaged.

A titania aqueous dispersion (Tynoch M-6, manufactured by Taki Chemical Co., Ltd., titanium oxide sol) in which titania fine particles having an average primary particle diameter of 6 nm measured by a dynamic scattering method are dispersed is used as the fine particle dispersion. A fine particle laminated film laminate was produced in the same manner as in Example 16 except that the fine particle concentration of the dispersion was adjusted to 0.3% by weight and the fine particle alternate lamination number was 12 times. When the transmission spectrum of this fine particle laminated film laminate (BK-5 glass substrate on which both surfaces of the silica fine particle laminated film were formed) was measured in the same manner as in Example 1, the minimum transmittance at a wavelength of 400 to 800 nm was 71%. Met. When the reflection spectrum of the BK-5 glass substrate having the silica fine particle laminated film formed on both surfaces was measured with a visible ultraviolet spectrophotometer (manufactured by JASCO Corporation, V-570), the maximum at a wavelength of 400 to 800 nm was obtained. The reflectance of was 28%. When the surface reflection spectrum of one surface on which the fine particle film was formed was measured in the same manner as in Example 1, the maximum surface reflectance at a wavelength of 400 to 800 nm was 14.3%. Since the transmittance of the BK-5 glass substrate was 91% and the surface reflectance was 4.5%, it was found that a semi-transmissive semi-reflective film was formed and a half mirror function was imparted.
The turbidity of the fine particle laminated film evaluated in the same manner as in Example 1 was 0.3%.
As a result of evaluating the adhesiveness in the same manner as in Example 16, the fine particle laminated film on the BK-5 glass substrate remained without being damaged.

A titania aqueous dispersion (Tynoc AM-15, manufactured by Taki Chemical Co., Ltd., titanium oxide sol) in which titania fine particles having an average primary particle diameter of 20 nm measured by a dynamic scattering method are dispersed is used as the fine particle dispersion. A fine particle laminated film laminate was produced in the same manner as in Example 1 except that the fine particle concentration of the dispersion was adjusted to 0.3% by weight and the number of fine particle alternating laminations was set to 10.
The transmission spectrum of this fine particle laminate film (BK-5 glass substrate having a silica fine particle laminate film formed on both sides) was measured in the same manner as in Example 1. As a result, the minimum transmittance at a wavelength of 400 to 800 nm was 70%. Met. When the reflection spectrum of the BK-5 glass substrate having the silica fine particle laminated film formed on both surfaces was measured with a visible ultraviolet spectrophotometer (manufactured by JASCO Corporation, V-570), the maximum at a wavelength of 400 to 800 nm was obtained. The reflectance was 29%. When the surface reflection spectrum of one surface on which the fine particle film was formed was measured in the same manner as in Example 1, the maximum surface reflectance at a wavelength of 400 to 800 nm was 14.6%.
The turbidity of the fine particle laminated film evaluated in the same manner as in Example 1 was 0.3%.
As a result of evaluating the adhesiveness in the same manner as in Example 16, the fine particle laminated film on the BK-5 glass substrate remained without being damaged.

The use of a ceria aqueous dispersion (Nydral P10, manufactured by Taki Chemical Co., Ltd., cerium oxide sol) in which ceria fine particles having an average primary particle diameter of 8 nm measured by a dynamic scattering method are dispersed, as the fine particle dispersion A fine particle laminated film laminate was produced in the same manner as in Example 1 except that the fine particle concentration was adjusted to 0.2% by weight and the number of fine particle alternate laminations was 20 times. The transmission spectrum of this fine particle laminate film (BK-5 glass substrate having a silica fine particle laminate film formed on both surfaces) was measured in the same manner as in Example 1. As a result, the minimum transmittance at a wavelength of 400 to 800 nm was 73%. Met. When the reflection spectrum of the BK-5 glass substrate on which the silica fine particle laminated film was formed on both sides was measured with a visible ultraviolet spectrophotometer (manufactured by JASCO Corporation, V-570), the maximum at a wavelength of 400 to 800 nm was obtained. The reflectance of was 26%. When the surface reflection spectrum of one surface on which the fine particle film was formed was measured as in Example 1, the maximum surface reflectance at a wavelength of 400 to 800 nm was 13.0%.
The turbidity of the fine particle laminated film evaluated in the same manner as in Example 1 was 0.3%.
As a result of evaluating the adhesiveness in the same manner as in Example 16, the fine particle laminated film on the BK-5 glass substrate remained without being damaged.

A niobium oxide aqueous dispersion (Biral NB-X10, manufactured by Taki Chemical Co., Ltd., niobium oxide sol) in which niobium oxide fine particles having an average primary particle diameter of 5 nm measured by a dynamic scattering method are dispersed was used as a fine particle dispersion. In addition, a fine particle laminated film laminate was produced in accordance with Example 1 except that the fine particle concentration of the fine particle dispersion was adjusted to 0.2% by weight and the number of fine particle alternate laminations was 40 times. When the transmission spectrum of this fine particle multilayer film laminate (BK-5 glass substrate having a silica fine particle multilayer film formed on both surfaces) was measured in the same manner as in Example 1, the minimum transmittance at a wavelength of 400 to 800 nm was 81%. Met. When the reflection spectrum of the BK-5 glass substrate having the silica fine particle laminated film formed on both surfaces was measured with a visible ultraviolet spectrophotometer (manufactured by JASCO Corporation, V-570), the maximum at a wavelength of 400 to 800 nm was obtained. The reflectance of was 18%. When the surface reflection spectrum of one surface on which the fine particle film was formed was measured in the same manner as in Example 1, the maximum surface reflectance at a wavelength of 400 to 800 nm was 8.8%.
The turbidity of the fine particle laminated film evaluated in the same manner as in Example 1 was 0.3%.
As a result of evaluating the adhesiveness in the same manner as in Example 16, the fine particle laminated film on the BK-5 glass substrate remained without being damaged.

An aqueous tin oxide dispersion (Cerames S-8, manufactured by Taki Chemical Co., Ltd., tin oxide sol) in which tin oxide fine particles having an average primary particle diameter of 2 nm measured by a dynamic scattering method were dispersed was used as the fine particle dispersion. In addition, a fine particle laminated film laminate was prepared in accordance with Example 1 except that the fine particle concentration of the fine particle dispersion was adjusted to 0.2% by weight and the number of fine particle alternate laminations was set to 15. When the transmission spectrum of this fine particle laminate film (BK-5 glass substrate having a silica fine particle laminate film formed on both surfaces) was measured in the same manner as in Example 1, the minimum transmittance at a wavelength of 400 to 800 nm was 86%. Met. When the reflection spectrum of the BK-5 glass substrate having the silica fine particle laminated film formed on both surfaces was measured with a visible ultraviolet spectrophotometer (manufactured by JASCO Corporation, V-570), the maximum at a wavelength of 400 to 800 nm was obtained. The reflectance of was 13%. When the surface reflection spectrum of one surface on which the fine particle film was formed was measured in the same manner as in Example 1, the maximum surface reflectance at a wavelength of 400 to 800 nm was 6.6%.
The turbidity of the fine particle laminated film evaluated in the same manner as in Example 1 was 0.3%.
As a result of evaluating the adhesiveness in the same manner as in Example 16, the fine particle laminated film on the BK-5 glass substrate remained without being damaged.

  Table 2 summarizes the particle diameter and shape of the metal oxide fine particles and the characteristics of the fine particle film in Examples 16 to 21.

(Measurement of surface reflectance of glass substrate and evaluation of refractive index)
A black adhesive tape (manufactured by Nichiban Co., Ltd.) is attached to the back so that no bubbles remain so that reflection from the BK-5 glass substrate (Matsunami, 25 mm x 75 mm x 0.7 mm thickness) can be ignored. The reflection spectrum of the surface with respect to 5 ° incidence was measured with an ultraviolet spectrophotometer (manufactured by JASCO Corporation, V-570). However, a silicon wafer was used as the standard mirror. By multiplying the measured surface reflectance spectrum R _obs (λ) of the glass (sample) at the wavelength λ by the surface reflectance R _Si of the silicon wafer at the wavelength λ, the surface reflectance R _sub of the glass (sample) at the wavelength λ ( λ) was determined. R _Si was 55 to 37% at a wavelength of 400 to 800 nm, and R _Si (λ) at a wavelength λ was obtained from the following equation.

（ただし、式中、ｎ_Ｓｉ（λ）は波長λにおけるシリコンウエハの屈折率、ｋ_Ｓ（λ）_ｉは波長λにおけるシリコンウエハの消衰係数を示す。）（薄膜・光デバイス、吉田貞史、矢嶋弘義著、東京大学出版会、ｐｐ．８−１４、１９９４年９月２０日発行、参照）

(Where n _Si (λ) represents the refractive index of the silicon wafer at the wavelength λ, and k _S (λ) _i represents the extinction coefficient of the silicon wafer at the wavelength λ.) (Thin Film / Optical Device, Sadashi Yoshida (See Hiroyoshi Yajima, University of Tokyo Press, pp. 8-14, published on September 20, 1994)

In the above calculation, n _Si (λ) and k _Si (λ) are literature values (D. Aspens and JB Theeten, J. Electrochem. Soc. Vol. 127, p1359 (1980)). Using.
The refractive index n _sub of the glass substrate was determined from the following equation from the surface reflectance R _sub of the glass substrate.

（ただし、式中、ｎ_ｓｕｂ（λ）は、波長λにおけるガラス基板の屈折率を示す。）（薄膜・光デバイス、吉田貞史、矢嶋弘義著、東京大学出版会、ｐｐ．８−１４、１９９４年９月２０日発行、参照）

(In the formula, n _sub (λ) represents the refractive index of the glass substrate at the wavelength λ.) (Thin Film / Optical Device, Sadashi Yoshida, Hiroyoshi Yajima, University of Tokyo Press, pp. 8-14, (See September 20, 1994)

The refractive index (n _sub ) of the BK-5 glass substrate was 1.55 to 1.52 at a wavelength of 400 to 800 nm.

(Measurement of surface reflectance of glass substrate with fine particle laminate film)
As described in Example 1, the glass surface is exposed with steel wool (# 0000, manufactured by Nippon Steel Wool Co., Ltd.) on one side of the obtained optical member (solid substrate is BK-5 glass substrate) having the fine particle laminated film. The laminated film was removed by polishing. A black adhesive tape (manufactured by Nichiban Co., Ltd., VT-196) was attached to the exposed glass surface so that no bubbles remained, and the surface reflectance spectrum of the surface on which the fine particle multilayer film was formed was measured in the same manner as described above. . The minimum value of the surface reflectance at a wavelength of 400 to 800 nm is 0.9% for the silica fine particle laminated film described in Example 8, 0.7% for the silica fine particle laminated film described in Example 5, and the silica fine particle described in Example 13. The laminated film was 0.05%. The maximum value of the surface reflectance at a wavelength of 400 to 800 nm is 14.3% for the titania fine particle laminated film, 13.0% for the ceria fine particle laminated film, 8.8% for the niobium oxide fine particle laminated film, and the oxidation. The tin fine particle laminated film was 6.6%.

(Determination of refractive index of fine particle laminate film)
If the reflectivity is lower than the solid substrate (glass substrate), the minimum value of the surface reflectance at a wavelength 400~800nm and _{R min,} following the refractive index _{n c} of the particle laminated film at a wavelength lambda _min of _{R min} Obtained from the formula.

Also, if the reflectance is higher than a solid substrate (glass substrate), the maximum value of the surface reflectance at a wavelength 400~800nm and _{R max,} the refractive index _{n c} of the particle laminated film at a wavelength of _{R max} lambda _max Is obtained from the following equation.

  As described above, the refractive index of the silica fine particle laminated film described in Example 8 is 1.36, the silica fine particle laminated film described in Example 5 is 1.34, the silica fine particle laminated film described in Example 13 is 1.26, and the titania. It was found that the fine particle laminated film was 1.85, the ceria fine particle laminated film was 1.81, the niobium oxide fine particle laminated film was 1.68, and the tin oxide fine particle laminated film was 1.61.

(Determination of fine particle volume ratio of fine particle laminated film)
In the fine particle laminated film of the present invention, since the gap between the fine particles is almost air, the volume density ρ _{P of the} fine particles can also be obtained from the refractive index of the fine particle laminated film from the following equation.

From this, the volume density ρ _P of the silica fine particles is 72% for the silica fine particle laminated film described in Example 8, 67% for the silica fine particle laminated film described in Example 5, and 49% for the silica fine particle laminated film described in Example 13. I found out.

(Thickness of fine particle laminated film)
If the reflectivity is lower than the solid substrate, the film thickness d _c of the particle laminated film was determined from the following equation.

However, the minimum value of the surface reflectance only one at a wavelength of 400 to 800 nm, when the maximum value is not the long wavelength side sought d _c a m of the above equation as 0.
The reflectance is higher than the solid substrate, the film thickness d _c of the particle laminated film was determined from the following equation.

However, the maximum value of the surface reflectance at a wavelength of 400~800nm is only one, if there is no local minimum long wavelength side was determined d _c a m of the above equation as 0. Further, the maximum value of the surface reflectance only one at a wavelength of 400 to 800 nm, if the minimum value is on the longer wavelength side was determined d _c a m of the above equation as 1. Thus, the film thickness of the silica fine particle laminated film described in Example 8 is 100 nm, the silica fine particle laminated film described in Example 5 is 100 nm, the silica fine particle laminated film described in Example 13 is 110 nm, the titania fine particle laminated film is 72 nm, It was found that the ceria fine particle laminated film was 79 nm, the niobium oxide fine particle laminated film was 101 nm, and the tin oxide fine particle laminated film was 90 nm.

It is a schematic diagram which shows the state of the microparticles which continued in the shape of a bead, and the particle diameter of a primary particle. It is a graph which shows the change of the resonance frequency of a crystal oscillator when electrolyte polymer adsorb | sucks on a crystal oscillator, and it is rinsed, and then microparticles | fine-particles adsorb | suck and rinse.

Claims (14)

  A fine particle laminated film laminate in which fine particles having an average primary particle diameter of 1 nm to 23 nm and an electrolyte polymer are alternately adsorbed on the surface of a solid substrate having a polar group on the surface.   The fine particles are any of fine particles of oxides of lithium, sodium, magnesium, aluminum, zinc, indium, silicon, tin, titanium, zirconium, yttrium, bismuth, niobium, cerium, cobalt, copper, iron, holmium, and manganese. 2. The fine particle laminated film laminate according to claim 1, comprising fine particles.   The fine particle laminated film laminate according to claim 1 or 2, wherein the solid base material having a polar group on the surface thereof has an intermediate layer containing the polar group formed on the surface thereof.   The polar group is an epoxy group, a styryl group, a methacryloxy group, an acryloxy group, an amino group, a ureido group, a chloropropyl group, a mercapto group, a sulfide group, an isocyanate group, a carboxyl group, a silanol group, or a hydroxyl group. The fine particle laminated film laminate according to any one of claims 1 to 3, which is a group.   The fine particle laminated film laminate according to any one of claims 1 to 4, wherein the solid substrate includes a hard coat layer.   The fine particle multilayer film laminate according to any one of claims 1 to 5, wherein the turbidity of the fine particle multilayer film is 0.001% or more and 4% or less.   The fine particle laminate film according to any one of claims 1 to 6, wherein the fine particle laminate film contains fine particles and an electrolyte polymer of 0.1 mass% or more and 40 mass% or less with respect to the fine particles.   The fine particle multilayer film laminate according to any one of claims 1 to 7, which has a shape in which the fine particles are arranged in a bead shape.   The minimum value of the surface reflectance in a fine particle laminated film is 3% or less, The fine particle laminated film laminated body in any one of Claims 1-8.   The fine particle multilayer film laminate according to any one of claims 1 to 9, wherein the fine particle multilayer film has a reflectance of 15% to 50% and a transmittance of 50% to 85%.   A step of immersing a solid substrate having a polar group on the surface in a dispersion of fine particles having a charge opposite to the charge on the surface or an electrolyte polymer solution, and a fine particle having a charge opposite in sign to the fine particles or the electrolyte polymer. The method for producing a multilayer laminated film laminate according to any one of claims 1 to 10, further comprising a step of immersing in a dispersion or an electrolyte polymer.   The optical member containing the fine particle laminated film laminated body in any one of Claims 1-10.   An optical member having an antireflection function, comprising the fine particle multilayer film laminate according to claim 9.   An optical member having a semi-transmissive and semi-reflective function, comprising the fine particle laminated film laminate according to claim 10.

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