JP2009175672A - Low refractive index film, method for manufacturing the same, and antireflection film containing low refractive index film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a low refractive index film and a method for manufacturing the film, by which a low refractive index film can be manufactured at a normal temperature and normal pressure, and a particulate layered film includes followability to a microstructure and does not degrade optical performances such as diffusion property and condensing property given by the microstructure, and to provide an antireflection film containing a low refractive index film. <P>SOLUTION: The low refractive index film includes a particulate layered film formed by alternately depositing an electrolyte polymer and fine particles on a microstructure surface, wherein the refractive index of the particulate layered film ranges from 1.10 to 1.21. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a low refractive index film used for an optical member and the like, a manufacturing method thereof, and an antireflection film including the low refractive index film.

  Low refractive index film is anti-reflection 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 or red reflection film, bright line cut filter, color correction An optical functional film included in the film is formed on the optical member.

  Not only optical members with a flat surface shape, but also optical function members such as brightness enhancement lens films and diffusion films for liquid crystal backlights, Fresnel lenses, lenticular lenses, and microlenses used for video projection television screens are all made of resin. The desired geometrical optical performance is obtained because the material has a microstructure. An optical functional film including a low refractive index film is also required on the surface of these fine structures.

  When a low refractive index film is used as an antireflection film, the low refractive index film having a single layer structure becomes an antireflection film as it is. The antireflection film having a single layer structure exhibits antireflection performance in a wider wavelength range, and the cost is reduced by reducing the number of layers. As the refractive index of the antireflection film having a single-layer structure, a low refractive index in the range of 1.2 to 1.3 is desired when the substrate is a transparent material such as a resin material.

Examples of the method for forming the low refractive index film include vapor phase methods such as vapor deposition and sputtering, and coating methods such as dipping and spin coating.
However, typical low-refractive-index thin films obtained by the vapor phase method are MgF ₂ having a refractive index of 1.38 and LiF having 1.39, and the performance of these thin films as a single-layer antireflection film is low. .

  In addition, as a typical material of the low refractive index film obtained by the coating method, a fluorine-based polymer material having a refractive index of 1.35 to 1.4, or fluorine having a refractive index of 1.37 to 1.46 Although there is a porous material in which fine particles made of a monomer polymer are fused (see, for example, Patent Document 1), a fluorine-based polymer material having a refractive index of 1.3 or less has not been obtained.

On the other hand, examples of the porous structure film obtained by firing becoming a low refractive index film include porous films of porous SOG and magnesium fluoride (see, for example, Patent Documents 2 and 3).
However, the porous SOG requires a baking treatment of 200 ° C. or more in order to make the refractive index 1.3 or less, and the magnesium fluoride porous film needs a heat treatment of 150 ° C. for 1 hour. Therefore, from the viewpoint of heat resistance of the resin material and maintaining the structure of the fine structure, a low refractive index film that requires firing is not suitable as an antireflection film for a resin substrate.

  Even when the solid substrate has a fine structure such as a Fresnel lens or a lenticular lens, the low refractive index film with a single layer structure suppresses the reflected light on the lens surface and prevents the ghost of the image projected on a video projection screen or the like. It is effective for suppression. Also in other optical function members, the antireflection film can increase transmitted light.

In the vapor phase method, a thin film can be formed by following the shape of the microstructure.
However, since the vapor phase method requires a vacuum apparatus, the manufacturing cost becomes expensive.
Furthermore, the film formed on the inner wall of the vacuum apparatus peels off and remains as a foreign substance on the low refractive index film.
Moreover, the substrate heating generally performed in order to acquire the adhesiveness of a low refractive index film | membrane produces a crack in the resin-made fine structure with a thermal stress (for example, refer patent document 4).

The coating method does not require a vacuum device, and does not generate foreign matters derived from the vacuum device.
However, in the spin coating method, it is inevitable that the coating material remains in the concave portion of the fine structure, and the low refractive index film becomes thick in the concave portion. When the low refractive index film does not follow the fine structure in this way, geometric optical performance such as diffusibility and light condensing property provided by the fine structure is impaired.

On the other hand, in the dip coating method or the like, the film thickness can be controlled by the pulling speed, so that the coating material can follow the microstructure.
However, it is necessary to slow the pulling speed up to several tens of μm / second, and the manufacturing cost becomes extremely high (for example, see Patent Document 5).

  As a method for forming a nanometer-scale thin film from a solution, an alternate lamination method has been proposed (for example, see Non-Patent Document 1). In the alternate lamination method, since a thin film is formed by electrostatic adsorption in a liquid, it is possible to obtain a thin film that closely follows the microstructure. Moreover, since it is a normal temperature process, the resin material is not thermally damaged.

  A thin film in which an electrolyte polymer having a positive charge and an electrolyte polymer having a negative charge are alternately laminated is a low refractive index film having a refractive index of about 1.2 by generating voids in the thin film by hydrochloric acid treatment (for example, And Patent Documents 6 and 7).

  On the other hand, a fine particle monolayer film in which fine particles are electrostatically adsorbed on an electrolyte polymer layer becomes a low refractive index film without the need for acid treatment or the like (see, for example, Patent Documents 8 and 9). The reason why the fine particle single layer film is a low refractive index film is that the surface irregularity shape by fine particles having a diameter of 100 nm or more continuously changes the refractive index, and voids between the fine particles lower the average refractive index.

However, a fine particle monolayer film using fine particles having a diameter exceeding 100 nm scatters and diffuses visible light, and thus is not suitable for an optical member requiring transparency.
In addition, when the optical member surface has a fine structure, for example, when the fine structure is a lens, when the low refractive index film on the lens surface scatters or diffuses light, the geometrical optical means that the light does not collect at the focal point. Cause a significant decrease in performance.

On the other hand, when fine particles having a diameter of 100 nm or less are used, a transparent fine particle laminated film is easily obtained.
However, the refractive index reduction effect derived from the surface irregularity shape cannot be obtained. For this reason, it has been attempted to reduce the average refractive index of the fine particle multilayer film by increasing the density of voids between the fine particles (see, for example, Patent Documents 10 to 12).

Japanese Patent No. 3718031 JP 2003-158125 A JP 2004-302112 A JP 2000-156486 A Japanese Patent No. 2905712 JP 2004-109624 A JP 2005-266252 A JP 2002-006108 A JP 2006-208726 A JP 2006-297680 A JP 2006-301124 A JP 2006-301125 A Thin Solid Films, 210/211, p831 (1992)

  In the present invention, a low refractive index film can be formed at room temperature and normal pressure, and even if the solid substrate has a fine structure, the fine particle laminated film in the low refractive index film follows the fine structure. An object of the present invention is to provide a low refractive index film, a method for manufacturing the same, and an antireflection film including the low refractive index film without impairing the geometric optical performance such as diffusibility and light condensing property.

The present invention relates to the following matters.
(1) It is composed of a fine particle laminated film formed by alternately laminating electrolyte polymer and fine particles on the surface of a solid substrate, and the refractive index of the fine particle laminated film is 1.10 or more and 1.21 or less. Low refractive index film.

(2) The low refractive index film according to (1), wherein the fine particle laminated film is formed by alternately adsorbing an electrolyte polymer and fine particles on the surface of a solid substrate.

(3) The fine particles in the fine particle laminated film include one or more of porous silica fine particles, hollow silica fine particles, and silica fine particles having a shape in which primary particles are connected to each other (1) or The low refractive index film according to (2).

(4) The low refractive index film according to any one of (1) to (3), wherein an average primary particle diameter of the fine particles in the fine particle laminated film is 1 nm or more and 40 nm or less.

(5) The fine particle multilayer film further contains an electrolyte polymer, and the content of the electrolyte polymer is 0.01% by mass or more and 10% by mass or less based on the fine particles. ). The low refractive index film according to any one of the above.

(6) The solid substrate surface has any one of a lenticular lens, a Fresnel lens, a prism, a microlens array, a light guiding fine structure, a light diffusing fine structure, and a fine structure for obtaining a hologram. The low refractive index film according to any one of (1) to (5), wherein the low refractive index film is provided.

(7) An antireflection film comprising the low refractive index film according to any one of (1) to (6).

(8) A method for producing a low refractive index film comprising a fine particle laminated film having a refractive index of 1.10 or more and 1.21 or less formed on the surface of a solid substrate,
(I) a step of bringing the electrolyte polymer solution (liquid A) or the fine particle dispersion (liquid B) into contact with the solid substrate surface, and then a rinsing step;
(Ii) A step of bringing a dispersion of fine particles having a charge opposite to that of the electrolyte polymer of the liquid A into contact with the surface of the solid base after the liquid A is contacted, or the surface of the solid base after the liquid B is contacted A step of contacting a solution of an electrolyte polymer having an opposite charge with the fine particles of the liquid B, followed by a rinsing step, and (iii) a step of alternately repeating (i) and (ii),
A method for producing a low refractive index film, comprising:

(9) The above (8) is characterized in that the fine particles in the fine particle laminated film include one or more of porous silica fine particles, hollow silica fine particles, and silica fine particles having a shape in which primary particles are connected. The manufacturing method of the low-refractive-index film of description.

(10) The method for producing a low refractive index film according to (8) or (9), wherein the average primary particle diameter of the fine particles in the fine particle dispersion is 1 nm or more and 40 nm or less.

(11) In any one of (8) to (10), the fine particle multilayer film is formed so that the content of the electrolyte polymer with respect to the fine particles is 0.01% by mass or more and 10% by mass or less. The manufacturing method of the low-refractive-index film of description.

(12) The method for producing a low refractive index film according to any one of (8) to (11), wherein fine particles and an electrolyte polymer are alternately adsorbed on the surface of a solid substrate to form a fine particle laminated film. .

(13) The surface of the solid substrate has any one of a lenticular lens, a Fresnel lens, a prism, a microlens array, a light guiding fine structure, a light diffusing fine structure, and a fine structure for obtaining a hologram. The method for producing a low refractive index film according to any one of (8) to (12), wherein:

(14) The method for producing a low refractive index film according to any one of (8) to (13), wherein the low refractive index film is an antireflection film.

According to the low refractive index film of the present invention, it can be used for a wide range of applications as an optical functional film because of its low refractive index. When the low refractive index film is used as an antireflection film having a single layer structure, reflected light and transmitted light can be achromatic in addition to suppressing reflected light and improving transmitted light.
In addition, the low refractive index film of the present invention can exhibit excellent antireflection performance more reliably by defining the refractive index of the low refractive index film and the volume ratio of the voids.

In the low refractive index film of the present invention, the refractive index of the low refractive index film can be more reliably lowered by limiting the material of the fine particles to the material having a low refractive index and the shape of the fine particles.
In the low refractive index film of the present invention, by defining the average primary particle diameter of the fine particles, the transparency of the low refractive index film can be improved, and even if the solid substrate has a fine structure, the geometric optical Performance is not impaired.

In the low refractive index film of the present invention, the refractive index of the low refractive index film can be more reliably reduced by defining the amount of electrolyte polymer contained in the low refractive index film.
In the low refractive index film of the present invention, the volume ratio of voids contained in the low refractive index film can be increased by forming the fine particle laminated film by the alternating lamination method, and the refractive index of the low refractive index film can be more reliably increased. Can be reduced.
On the other hand, the above-described low refractive index film of the present invention can be manufactured by the low refractive index film manufacturing method of the present invention. In particular, since a low refractive index film can be formed at room temperature and normal pressure, a vacuum device or the like is not required, and cracks due to thermal stress do not occur in the resinous solid substrate.

In addition, when the solid substrate has a fine structure, fine particles and electrolyte polymer are alternately adsorbed on the surface of the fine structure to form a low refractive index film. It does not impair geometric optical performance such as diffusibility and light condensing property provided by the structure.
In the low refractive index film of the present invention, by defining the fine structure, the performance of the optical functional member by the low refractive index film can be improved more reliably.

The low refractive index film of the present invention comprises a fine particle laminate film formed by alternately laminating electrolyte polymer and fine particles on the surface of a solid substrate, and the refractive index of the fine particle laminate film is 1.10 or more and 1.21 or less. It is characterized by being.
Further, the method for producing a low refractive index film of the present invention is a method for producing a low refractive index film having a refractive index of 1.10 or more and 1.21 or less and comprising a fine particle laminated film,
Formation of the fine particle laminated film,
(I) a step of bringing the electrolyte polymer solution (liquid A) or the fine particle dispersion (liquid B) into contact with the solid substrate surface, and then a rinsing step;
(Ii) A step of bringing a dispersion of fine particles having a charge opposite to that of the electrolyte polymer of the liquid A into contact with the surface of the solid base after the liquid A is contacted, or the surface of the solid base after the liquid B is contacted A step of contacting a solution of an electrolyte polymer having an opposite charge with the fine particles of the liquid B, followed by a rinsing step, and (iii) a step of alternately repeating (i) and (ii),
It is characterized by being performed by a series of steps including
Hereinafter, the antireflection film for a fine structure according to the present invention and the respective embodiments of the manufacturing method thereof will be described together.

  The low refractive index film of the present invention is formed on a solid substrate such as an optical member, so that it is 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. It functions as an optical functional film included in the film, the green reflection or red reflection film, the bright line cut filter, and the color tone correction film.

  In addition, for microscopic structures having geometric optical performance such as optical function members such as brightness enhancement lens films and diffusion films for liquid crystal backlights, Fresnel lenses, lenticular lenses, and microlenses used in video projection television screens. However, the low refractive index film of the present invention follows well. As a result, the low refractive index film of the present invention functions as an optical functional film without impairing the geometric optical performance of the fine structure.

(A) Solid substrate The solid substrate may be flat or have other shapes. The shape may be a fine structure having geometric optical performance. Examples of the fine structure include a lenticular lens sheet, a Fresnel lens sheet, a prism sheet, a microlens array sheet, an on-chip microlens array, a light guide sheet, a diffusion sheet, a hologram sheet, and a solar cell.

  Therefore, examples of the fine structure include a lenticular lens, a Fresnel lens, a prism, a microlens array, a light guiding fine structure, a light diffusing fine structure, and a fine structure for obtaining a hologram.

(B) Solid substrate material In order to form a fine particle laminate film on a solid substrate by an alternate lamination method, the solid substrate needs to have a charge on its surface. In order for the fine particle laminated film formed using the alternating lamination method to adhere to the solid substrate, it is desirable that the polar group has a charge on the surface of the solid substrate. The polar group has a positive or negative charge locally because it has a charge bias (intramolecular polarization) in the molecule or becomes an ion by dissociation.

  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.

Examples of the material for the solid substrate include resins, semiconductors such as silicone, metals, inorganic compounds, and the like.
Moreover, the shape is arbitrary, such as a shape which has a film, a sheet | seat, a board, and a curved surface. If the solid substrate can be partly or wholly immersed, such as a cylinder, thread, fiber, foam, etc., and the solution can enter, it can be used because a fine particle laminated film is formed on the surface. it can.

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.
Furthermore, even if the solid substrate surface has a nanometer-scale or sub-micron-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 a 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 polymer of polyvinyl alcohol, acrylic acid, or methacrylic acid, or A copolymer etc. are mentioned.

  Also, polyethylene, polypropylene, polystyrene, triacetyl cellulose, diacetyl cellulose, acetate butyrate cellulose, polyethersulfone, polyimide, polymethylpentene, polyvinyl chloride, polyvinyl acetal, polymethyl methacrylate, polycarbonate, polyurethane, etc. are used. You can also

  The surface of the solid substrate may be subjected to corona discharge treatment, glow discharge treatment, plasma treatment, ultraviolet irradiation, ozone treatment, chemical etching treatment with alkali or acid, etc. to introduce polar groups. You may use resin which introduce | transduced the polar group by such a process.

  In the present invention, the solid substrate 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 properties 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 substrate can be given, and it is suitable for an optical filter for a display such as a plasma display panel or a liquid crystal display device. An optical 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. As described above, 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.

  Forming a fine particle laminate film by preventing contact between the fine particle dispersion and the solid substrate, such as attaching an adhesive film, to the front or back surface of the solid substrate where formation of the fine particle laminate film is not desired Can be prevented.

(C) Hard coat material By laminating a hard coat film, the mechanical properties of the solid substrate are improved. Examples of materials for the hard coat film include cross-linked products 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 polyfunctional acrylic cured paints (Diabeam series, etc.) manufactured by Mitsubishi Rayon Co., Ltd., and polyfunctional acrylics manufactured by Nagase Sangyo Co., Ltd. -Based cured paint (Denacol series, etc.), Shin-Nakamura Chemical Co., Ltd. polyfunctional acrylic cured paint (NK ester series, etc.), Dainippon Ink & Chemicals Co., Ltd. multifunctional acrylic cured paint (UNIDIC) Series), multifunctional acrylic cured paints made by Toa Gosei Chemical Industry Co., Ltd. (Aronix series, etc.), multifunctional acrylic cured paints made by NOF Corporation (Blenmer series, etc.), Nippon Kayaku ( Co., Ltd. polyfunctional acrylic curable paint (KAYARAD series, etc.), Kyoeisha Chemical Co., Ltd. polyfunctional acrylic curable paint (light ester series, Ito acrylate series, etc.).

  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 substrate formed with a hard coat film may be used, and as such a commercial product, hard coat PET (KB film) manufactured by Kimoto, hard coat PET manufactured by Toray (Tough Top N-TOP) Examples thereof include a hard coat film made by Toyo Packaging Co., Ltd., and a hard coat polycarbonate (Lexan Margard, Lexan CTG AF) made by Nisshin Kasei.

(D) Intermediate layer In order to reliably introduce a polar group into a solid substrate, an intermediate layer can be laminated on the solid substrate to form a solid substrate. In this case, the intermediate layer is a surface layer of the solid substrate. Alternatively, the intermediate layer material may form a fine structure.

  The intermediate layer is provided between the solid base material and the fine particle laminated film, and the intermediate layer has a polar group to improve the adhesion between the solid base material and the fine particle laminated 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 is firmly bonded to the solid substrate through the intermediate layer.

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. , A carboxyl group, an ester group, a carbonyl group, a hydroxyl group, or a silanol group, preferably one or more functional groups.
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. There are acid polymers or copolymers.

  The intermediate layer is laminated on the solid substrate by, for example, a method in which a resin having a polar group is dissolved in a solid substrate and applied and dried. (Including monomers and oligomers having polar groups) are applied to a solid substrate and reacted and cured, and a silane coupling agent is mixed and applied to a resin raw material monomer and oligomer as an intermediate layer and cured. It can be performed by a method or the like. In addition to the method for forming the intermediate layer described above, the intermediate layer material may be used as a solid substrate, for example, by transferring the intermediate layer material to a mold.

You may manufacture the coating liquid of the polyester-type resin to which the polar group was provided as follows.
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 were heated to 40-220 ° C. in a reaction vessel, and 3 Transesterification is performed for a time to obtain a polyester-forming component.

  Next, 9 parts of 5-sodium sulfoisophthalic acid was added, and the esterification reaction was carried out at 220 to 260 ° C. for 1 hour, followed by a polycondensation reaction under reduced pressure (10 to 0.2 mmHg) for 2 hours, with an average molecular weight of 18000, softening A polyester copolymer having a sulfonic acid group having a point of 140 ° C. is 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, an aqueous polyester resin dispersion can be obtained.
A commercially available water-dispersed polyester resin to which a sulfonic acid is added (for example, Vylonal MD-1200, manufactured by Toyobo Co., Ltd., trade name) may be used.

  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.
Polyethylene containing sodium sulfonate obtained by sulfonating a polyether of ethylene oxide starting from allyl alcohol with sodium metabisulfite (SO ₃ -content: 8.3% by weight, polyethylene oxide content: 83% by weight), 192 parts, polytetra 1013 parts of methylene adipate and 248 parts of polypropylene oxide polyether initiated with bisphenol A were mixed and dehydrated under reduced pressure (10-0.2 mmHg) at 100 ° C. to 70 ° C., to which 178 parts of isophorone diisocyanate and A mixture with 244 parts of hexamethylene-1,6-diisocyanate is added and the resulting mixture is further stirred in the range of 80 ° C. to 90 ° C. until the isocyanate content is 5.6% by weight.

The obtained prepolymer is cooled to 60 ° C., and 56 parts of biuret polyisocyanate obtained from 3 moles of hexamethylenedisocyanate and 1 mole of water, and 173 parts of bisketimine obtained from isophoronediamine and acetone are 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 the functional group is imparted include organic solvent-soluble amorphous polyester resins. Examples of commercially available products include BYRON (103, 200, 220, manufactured by Toyobo Co., Ltd.). 226, 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, trade names).

  Moreover, water-dispersed polyester resin is mentioned, As a commercial item, Toyobo Co., Ltd. product, Bironal (MD-1100, MD-1200, MD-1220, MD-1245, MD-1250, MD-1335, MD -1400, MD-1480, MD-1500, MD-1930, MD-1985, trade names).

  Moreover, a polyester urethane resin is mentioned, As a commercial item, Toyobo Co., Ltd. make, 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, trade names).

  In the present invention, examples of the silane coupling agent include those represented by the following chemical 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又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 a silane coupling agent treatment of a solid substrate, first, a silane coupling agent is hydrolyzed to an silanol group by hydrolyzing an alkoxy group in an aqueous medium in the presence or absence of an acid. By bringing the solid substrate into contact with the solution, silanol groups can be adsorbed by hydrogen bonding to the hydroxyl groups present on the surface of the solid substrate, and then the solid substrate can be dried, thereby performing dehydration condensation. A reaction takes place and a non-hydrolyzable group can be imparted to the surface of the solid substrate.

  The silanol group that has not reacted with the non-hydrolyzable group also functions as a polar group in the present invention, and the solid substrate and the fine particle laminated film can be adhered by interacting with the fine particle laminated film. 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.

  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 silane such as methyldimethoxysilane, sulfide group functional silane 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, and ethoxysilane triisocyanate.

  A functional group may be imparted to the surface of the fine particles using these silane coupling agents. Accordingly, at least one of attractive forces among the covalent bonds, the intermolecular forces, and the 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 having a vinyl group, KBM-1003, KBE-1003, KBM-303 having an epoxy group, KBM-403, KBE-402, KBE-403, and a styryl 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 (Shin-Etsu Chemical none Co., Ltd., trade name) having an isocyanate group 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. Examples of commercially available primers include KBP-40, KBP-41, KBP-43, KBP-90 diluted with a silane coupling agent having an amino group, and KBP-44 diluted with a silane coupling agent having an isocyanate group. And X-12-414 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) diluted with a silane coupling agent having a mercapto group.

  A resin having a polar group is preferably used for the intermediate layer in order to obtain adhesion between the solid substrate and the intermediate layer. As a coating method that can be adopted when forming a silane coupling agent or resin as an intermediate layer on a solid substrate, it can be performed by a well-known method, for example, reverse roll coating method, gravure coating method, etc. Kiss coating method, roll brushing method, spray coating method, air knife coating method, wire barber coating method, pipe doctor method and curtain coating method, spin coating method, dip coating method, alternating lamination method, etc. can be adopted . These methods can be performed alone or in combination. In any coating method, it is desirable to dilute the concentration of the coating solution so that the intermediate layer follows the fine structure.

  In order to ensure adhesion between the solid substrate and the intermediate layer, the solid substrate is subjected to corona discharge treatment, glow discharge treatment, plasma treatment, ultraviolet irradiation, ozone treatment, chemical etching treatment with alkali or acid, etc. Also good.

  An electrolyte polymer layer may be formed for the purpose of making the charge density of the surface of the solid substrate (which may include an intermediate layer) uniform and adsorbing fine particles evenly. For the electrolyte polymer, polydiallyldimethylammonium chloride (PDDA) having a positive charge, polyethyleneimine (PEI), or sodium polystyrene sulfonate (PSS) having a negative charge is preferable.

  In addition, as shown in Advanced Material, Vol. 13, pp. 52-54 (issued in 2001), an alternating lamination method is used to form an alternating laminated film of two types of electrolyte polymers with different charge signs. (It may include an intermediate layer).

  When these electrolyte polymer layers are formed on the surface of the solid substrate as an intermediate layer, it is desirable that the electrolyte polymer layer is in close contact with the solid substrate. When the solid substrate or the solid substrate surface layer is a polymer, the electrolyte polymer or the like is bonded to the polymer on the surface of the solid substrate by a conventionally known method such as heat, light, electron beam, or γ ray. The method of letting it be mentioned.

  Moreover, you may graft the monomer which has a polar group on a solid 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 hydrohalic acid salt thereof, or 3-vinyl propionic acid. Or its alkali metal salt or amine salt, vinyl sulfonic acid or its alkali metal salt or amine salt, vinyl styrene sulfonic acid or its alkali metal salt or amine salt, 2-sulfoethylene acrylate, 2-sulfoethylene methacrylate, 3-sulfopropylene Acrylate, 3-sulfopropylene methacrylate or an alkali metal salt or amine salt thereof, 2-acrylamido-2-methylpropanesulfonic acid or an alkali metal salt or amine salt thereof, mono (2-acryloyl) Oxyethyl) 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.

(E) Formation method of fine particle laminated film Langmuir, Vol. 13, pp. 6195-6203, (1997), a method of alternately repeating the step of contacting the electrolyte polymer solution (liquid A) and the step of contacting the fine particle dispersion (liquid B) with the solid substrate (alternate lamination method) ) To form a fine particle laminated film on the solid substrate. More specifically, it is formed by the following steps (i) to (iii).
(I) a step of bringing the electrolyte polymer solution (liquid A) or the fine particle dispersion (liquid B) into contact with the solid substrate surface, and then a rinsing step;
(Ii) A step of bringing a dispersion of fine particles having a charge opposite to that of the electrolyte polymer of the liquid A into contact with the surface of the solid base after the liquid A is contacted, or the surface of the solid base after the liquid B is contacted A step of contacting a solution of an electrolyte polymer having the opposite charge with the fine particles of the liquid B, a step of rinsing, and a step of alternately repeating (iii), (i) and (ii) And the fine particle dispersion come into contact with each other, whereby the electrolyte polymer and the fine particles are alternately adsorbed to form a fine particle laminated film. The number of repetitions is not particularly limited, but the thickness of the thin film can be controlled by the number of repetitions. In the above alternate lamination method, the number of times of repeating alternately is preferably 1 to 100 times in order to ensure transparency. Moreover, in said alternating lamination method, it is preferable to complete | finish in the process contacted with a fine particle dispersion solution rather than the process contacted with an electrolyte polymer solution.

  When adsorption progresses in each step and the surface charge is reversed, further electrostatic adsorption does not occur. Therefore, the thickness of the film formed by one contact of the electrolyte polymer solution or the fine particle dispersion solution can be controlled. Further, the material that has been physically adsorbed excessively can be removed by rinsing the adsorption surface.

  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 by the optical interference effect. The rinsing liquid is preferably water, an organic solvent, or a mixed solvent such as water and a water-soluble organic solvent. Examples of the water-soluble organic solvent include methanol, ethanol, propanol, acetone, dimethylformamide, acetonitrile and the like.

  As an apparatus for forming a fine particle laminated film, J.A. Appl. Phys. , Vol. 79, pp. As shown in 7501-7509, (1996) and Japanese Patent Application No. 2000-568599, the arm to which the solid substrate is fixed automatically moves, and the solid substrate is moved into the electrolyte polymer solution, the fine particle dispersion or the rinse according to the program. You may use the apparatus called a dipper to immerse in a liquid.

  Further, the fine particle laminated film may be formed by dropping or spraying an electrolyte polymer solution or a fine particle dispersion on a solid substrate. At that time, the rinsing liquid may be supplied by any of dripping, spraying, showering, or a combined method. Further, the solid substrate may perform movement such as conveyance and rotation.

(F) Fine particle dispersion The fine particle dispersion used in the present invention is obtained by dispersing fine particles described later in a medium (liquid) that is a mixed solvent such as water, an organic solvent, or water and a water-soluble organic solvent. . 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 0.005 to 15% by weight, more preferably about 0.001 to 10% by weight, and further preferably about 0.01 to 5% by weight. If the proportion of the fine particles is too low, a fine particle laminated film cannot be formed, and if it is too high, the fine particle laminated film impairs transparency and flatness due to aggregation of fine particles. 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. In general, the amount of the dispersant with respect to the fine particles is preferably about 0.001 to 100% by weight. Separation occurs, or the fine particles become electrically neutral in the dispersion, making it difficult to obtain a fine particle laminated film.

  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. Can do. 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.

(G) 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 nm or more and 40 nm or less, and the fine particle laminated film has high transparency. It is preferable in order not to impair the geometric optical performance of the body, more preferably 2 nm to 30 nm, and still more preferably 3 nm to 20 nm. Fine particles having an average primary particle diameter of less than 1 nm are difficult to form. When the average primary particle diameter exceeds 40 nm, it becomes difficult to form a transparent fine particle laminated film on the fine structure, and the geometric optical performance of the fine structure is 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.

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

（ただし、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 to be developed, 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, the average secondary particle diameter, and the particle diameter of particles having a shape in which primary particles are connected can be measured using a known method. In the present invention, particles having a shape in which primary particles are connected may be expressed as beaded particles.

  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 nm 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.

  The fine particles in the above-mentioned 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 of 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. A method of dispersing the aggregate in a solvent can be mentioned.

The method and apparatus for dispersing the fine particle aggregate is not particularly limited, and examples thereof include a method of applying ultrasonic waves, a method of dispersing by a roll, a Banbury mixer, a kneader, a single screw extruder, a twin screw extruder, and the like.
Thereby, 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 primary particle has a porous structure, is hollow, or has a shape in which the primary particles are connected. The primary particles connected to each other have a shape as shown in FIG. 1 and may be called beaded particles in the present invention.

  In addition, the numerical value of the average primary particle diameter prescribed | regulated in this invention is a numerical value obtained by BET method. However, the hollow fine particles and the porous fine particles described later are values obtained by (transmission type) electron microscopy.

  In order to improve the strength of the fine particle laminated film, it is preferable that the primary particles are covalently bonded to each other. In the fine particle film using beaded particles, the steric hindrance caused by the beaded shape prevents other beaded particles or the electrolyte polymer having the opposite charge from occupying a dense space, resulting in spherical particles. It has a higher porosity and a lower refractive index than the fine particle film using.

  In the bead-like particles as shown in FIG. 1, more than half of the bead-like particles dispersed in the solution are composed of four or more primary particles. Further, in the case of beaded particles, primary particles are not aggregated on a three-dimensional dumpling, and the number of particles adjacent to one primary particle often does not exceed 10. In the closest packing, the number of particles adjacent to one primary particle is 16.

  The arrangement of primary particles in the bead-shaped particles is characterized in that the portion where the number of particles adjacent to one primary particle is 1 or more occupies more than half. For this reason, the bead-like particles are easy to take a two-dimensionally expanded shape when adsorbed on the base material, and contribute to the improvement of the film forming property. Furthermore, when the primary particles are covalently bonded, the strength of the fine particle laminated film is also improved.

The fine particles in the present invention include inorganic fine particles. Specifically, lithium, sodium, magnesium, aluminum, zinc, indium, silicone, 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 (B ₂ 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, and these can be used alone or in admixture of two or more. The fine particles may be indefinite, and there are no particular limitations on the crystal form that can be obtained.

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 having an average primary particle diameter controlled to 1 nm to 40 nm ( Most preferred is SiO ₂ ). Examples of such commercially available inorganic fine particles include Snowtex (manufactured by Nissan Chemical Industries).

Furthermore, in terms of shape, it is preferable to use one or more of porous silica fine particles, hollow silica fine particles, and silica fine particles having a shape in which primary particles are connected. This is because when the fine particle laminated film is formed using particles having a shape in which the primary particles are connected, densification is inhibited by steric hindrance, so that the refractive index of the fine particle laminated film is lowered. Further, when the fine particle laminated film is formed using porous particles and hollow particles, voids on the surface of the porous particles and voids inside the hollow particles are introduced, and the refractive index of the fine particle laminated film is lowered.
The porous silica fine particles preferably have a porosity of 10 to 70% and preferably have pores having an inner diameter of 1 to 25 nm. As an example of the production method, 1 mmol of hydrochloric acid and 40 mL of water are added to 0.1 mol of tetraethoxysilane, and 10 wt% of gelatin is further added, followed by hydrolysis at room temperature for 1 hour, followed by drying at 50 ° C., air The temperature is raised to 600 ° C. at a rate of 1 ° C./min to obtain a silica-based porous body having pores generated by removing gelatin. Furthermore, an aqueous dispersion of porous silica fine particles having a diameter of several tens of nm can be obtained by pulverizing the porous body in water by a bead mill or the like. Examples of commercially available products include Nipsil and Nipgel manufactured by Nippon Silica Kogyo.
As the hollow silica fine particles, those having a void ratio of 10 to 50% with respect to the fine particles are preferable, and examples of commercially available ones include Suriria manufactured by Catalyst 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. Commercially available products include Snowtex UP, Snowtex PS-S, Snowtex PS-M (Nissan Chemical Industries, trade name) and Fine Catalloy F120 (Catalyst Chemical Industries, trade name). There is a pearl necklace-like silica sol.

  As the fine particles in the present invention, polymer fine particles can also be used, and examples thereof include polyethylene, polystyrene, acrylic polymer, silicone polymer, phenol resin, polyamide, natural polymer, 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. Further, a carboxyl group, a carbonyl group, a phenol group or the like may be imparted to the surface of the fine particles,
Examples of commercially available fine particles having such functional groups on the surface include Mist Pearl (trade name, manufactured by Arakawa Chemical Industries, Ltd.).

  The fine particles dispersed in the medium are electrically negatively or positively charged because a diffusion electric double layer is generated by 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 particles expressed by the following formula 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 is 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, a mixed solvent of alcohol, etc., but is a salt of an alkali metal and alkaline earth metal, a quaternary ammonium ion, etc. and a halogen element. LiCl, KCl, NaCl, MgCl ₂ , CaCl ₂ or the like is 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 having the same sign on the surface potential repel each other and stably disperse in the medium without agglomeration. The zeta potential reflects the surface charge of fine particles and is used as an indicator of the dispersion stability of fine particles (Fumio Kitahara, Kunio Furusawa, Masataka Ozaki, Hiroyuki Oshima, “Zeta Potential Zeta Potential: Physical Chemistry of Fine Particle Interfaces”, 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。）

(Where n is the refractive index of the medium (liquid). The electromobility (U) is obtained from the following equation from the migration velocity (V) and the external electric field (E) obtained here.)

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。

The zeta potential (ζ) can be obtained from the electric mobility (U) 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））。

(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)).

  As a relatively new method for measuring the zeta potential, an ultrasonic method or a colloid oscillating current method can also be mentioned. Examples of the measuring apparatus include trade names DT-200, DT-1200, and DT-300 manufactured by Dispersion Technology. Since the fine particles in the solvent irradiated with ultrasonic waves vibrate relatively due to the density difference between the solvent and the fine particles, an electric field called a colloid vibration potential is generated by the polarization of the charged fine particles and the surrounding counter ions. The zeta potential can be measured by detecting and analyzing this electric field.

  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 diameters 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 has a pH of 10, and the zeta potential of the silica fine particles is -48 mV. When the pH of the silica fine particle dispersion is adjusted to 9, the zeta potential of the silica fine particles becomes −45 mV. Further, when sodium chloride is added to a silica fine particle aqueous dispersion having a pH of 10 to prepare a silica fine particle aqueous dispersion having a sodium chloride concentration of 0.25 mol / liter, the zeta potential of the silica fine particles becomes −40 mV.

  In a silica fine particle laminated film produced by an alternating 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, the silica fine particle laminated film The refractive index is 1.31, whereas the refractive index is 1.29 when the zeta potential is −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 volume fraction of the fine particles due to the decrease in the zeta potential of the fine particles. That is, 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 may be adsorbed in one contact of the fine particle dispersion solution, and the kind of fine particles may be different for each contact 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.

(H) 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, acetonitrile, and the like.

  As the electrolyte polymer, a polymer having a charged functional group in the main chain or side chain can be used.

  The polyanion generally has a functional group that can be negatively charged, such as sulfonic acid, sulfuric acid, carboxylic acid, etc., for example, polystyrene sulfonic acid (PSS), polyvinyl sulfate (PVS), dextran sulfate, Chondroitin sulfate, polyacrylic acid (PAA), polymethacrylic acid (PMA), polymaleic acid, polyfumaric acid, polyparaphenylene (−), polythiophene-3-acetic acid, polyamic acid, and a co-polymer containing at least one of them A polymer etc. can be used. Also, charged living organisms such as functional polymer ions such as poly (aniline-N-propanesulfonic acid) (PAN), various deoxyribonucleic acid (DNA), ribonucleic acid (RNA), and charged polysaccharides such as pectin. Polymers can also be used.

  For example, polyethyleneimine (PEI and its quaternized product), polyallylamine and its quaternized product, polyallylamine hydrochloride (PAH), polydiallyldimethylammonium chloride (PDDA), polyvinylpyridine (PVP), polylysine, polyacrylamide, polypyrrole Polyaniline, polyparaphenylene (+), polyparaphenylene vinylene, polyethylimine, a copolymer containing at least one of them, or a salt whose type is changed can be used.

For example, polyallylamine amide sulfate, copolymer of allylamine hydrochloride and diallylamine hydrochloride, copolymer of allylamine hydrochloride and dimethylallylamine hydrochloride, allylamine hydrochloride and other copolymers, partially methoxycarbonylated allylamine polymer Partially methylcarbonylated allylamine acetate polymer, diallylamine hydrochloride polymer, methyldiallylamine hydrochloride polymer, methyldiallylamine amide sulfate polymer, methyldiallylamine acetate polymer, copolymer of diallylamine hydrochloride and sulfur dioxide, Copolymer of diallylamine acetate and ion dioxide, copolymer of diallylmethylethylammonium ethyl sulfate and sulfur dioxide, copolymer of methyldiallylamine hydrochloride and sulfur dioxide, diallyldimethylammonium Copolymer of loride and sulfur dioxide, copolymer of diallyldimethylammonium chloride and acrylamide, copolymer of diallyldimethylammonium chloride and diallylamine hydrochloride derivative, copolymer of dimethylamine and epichlorohydrin, dimethyl Examples thereof include a copolymer of amine, ethylenediamine, and epichlorohydrin, and a copolymer of polyamide polyamine and epichlorohydrin.
The polycation is preferably a primary to tertiary amino group or a quaternary ammonium group. Although details are unknown, the surface hydroxyl group of silica and amino group or ammonium group are relatively strongly bonded.

  These electrolyte polymers are either water-soluble or soluble in a mixed solution of water and an organic solvent, and the weight average molecular weight of the electrolyte polymer (measured by gel permeation chromatography using a standard polystyrene calibration curve). 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 0.0003 to 3% by weight, more preferably about 0.001 to 1% by weight, and further preferably about 0.01 to 1% by weight. If the concentration of the electrolyte polymer is too low, a fine particle laminate film cannot be formed, and if it is too high, removal of excess electrolyte polymer in the washing process becomes insufficient, and the fine particle laminate film becomes transparent and flat in order to produce aggregates. Damage. The pH of the electrolyte polymer solution is preferably 5 or more and 12 or less, more preferably 6 or more and 11.5 or less, and further preferably 7 or more and 11 or less. If the pH is too low, the hydroxyl groups of the metal oxide fine particles cannot be activated, the amount of adsorption of the electrolyte polymer becomes nonuniform, and the film thickness of the fine particle multilayer film becomes nonuniform. If the pH is too high, the metal oxide is dissolved, so that the fine particle laminated film impairs transparency and flatness.

  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.

(I) Fine Particle Laminate Film The fine particle laminate film according to the present invention is a low refractive index fine particle laminate film having a refractive index of 1.10 or more and 1.21 or less as described above, and has excellent antireflection performance. It can be demonstrated. In addition, by being a porous layer, the internal voids contribute to the reduction of the refractive index, and by defining the volume ratio of the voids of the fine particle multilayer film, it is possible to more reliably exhibit excellent antireflection performance. .
The fine particle laminated film will be described in detail below.

  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 and 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), and 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 an electrolyte polymer having a different charge from fine particles, the PDDA layer has a molecular order thickness of less than 1.3 nm as described above. Therefore, the PDDA layer is considered to cover the surface of the solid substrate or fine particles while following the surface shape. The thin substrate functions as an electrostatic binding material between the solid substrate 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）。

(In the formula, 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.

  The refractive index of the fine particle laminated film according to the present invention is 1.10 or more and 1.21 or less, but if it is less than 1.10, it is difficult to form a fine particle laminated film having the refractive index. When the refractive index is increased by a contaminating material or an adsorbing material, the antireflection function is easily lowered. The refractive index is preferably 1.14 or more and 1.20 or less, and more preferably 1.14 or more and 1.19 or less.

In the fine particle laminated film of the present invention, since the gap between the fine particles is almost air, the volume ratio of air in the fine particle laminated film (porosity ρ ₀ ) can also be obtained from the refractive index of the fine particle laminated film from the following equation.

For example, becomes 48% porosity [rho ₀ is in the titania particle laminated film having a refractive index _{n c} is 1.8, the porosity [rho ₀ of the silica particle laminated film having a refractive index _{n c} is 1.3 becomes 42% .
The porosity ρ ₀ of the fine particle multilayer film according to the present invention is preferably 61.0% or more and 82.4% or less, more preferably 63.0% or more and 74.8% or less, and 63.0% or more and 74.8%. % Or less is most preferable. When the porosity ρ ₀ is 61.0% or more and 82.4% or less, the refractive index of the fine particle laminated film can be set to the predetermined numerical value described above.

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

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. For this reason, the fine particle laminated film having voids exhibits a lower refractive index than the fine particle laminated film in which the voids are completely filled with resin, and the refractive index selection range is widened in optical design.

Although particle laminated film has voids in the film, because the size of the particles and the gap is sufficiently smaller than the wavelength of light (visible light), with an average refractive index n _c. In addition, when a material other than fine particles is filled in the voids of the fine particle laminated film for some reason, the size of the voids of the fine particle laminated film becomes small, and even in that case, an average refractive index is exhibited. The antireflection film including these fine particle multilayer films or the antireflection film including the fine particle multilayer film containing a material other than the fine particles in the gap has an average refractive index and optically functions as a single layer film. .

  In the fine particle laminated film formed using particles having a shape in which primary particles are connected as shown in FIG. 1, densification is hindered by steric hindrance between the particles, so that the refractive index of the fine particle laminated film is lowered. In that case, since voids larger than the particle diameter of the primary particles exist in the inside and surface of the fine particle laminated film, the internal voids are obtained by TEM (transmission electron microscope), and the surface voids are obtained by SEM (scanning electron microscope) or AFM. It can be observed with an atomic force microscope.

When the low refractive index film on the surface of the solid substrate having a refractive index n _s with the refractive index n _AR and the thickness d _AR as of the formula: is formed, the surface reflectance of the solid substrate at a wavelength λ 0 %.

For example, in order to set the surface reflectance of a transparent solid base material having a wavelength of 550 nm of n _S = 1.54 to 0%, a low refractive index film of n _AR = 1.241 and d _AR = 111 nm is used as a solid base. It is necessary to form on the surface of the material. FIG. 2 shows the relationship between the surface reflectance when an antireflection film is formed on a transparent solid substrate with n _S = 1.54 and the refractive index of the low refractive index film. Even if the refractive index of the low refractive index film is smaller or larger than n _AR, surface reflectivity of the solid substrate with a low refractive index film is increased from 0%.

On the other hand, in order to make the surface reflectance of a transparent solid substrate of n _S = 1.54 at a wavelength of 550 nm 0.1% or less, the n _C of the low refractive index film is 1.203 or more and 1.281. The following is sufficient. Moreover, in order to make the surface reflectance of a transparent solid base material of n _S = 1.54 at a wavelength of 550 nm 1.0% or less, n _C of the low refractive index film is 1.123 or more and 1.372 or less. If it is. In the absence of a low refractive index film, the surface reflectance of a transparent solid substrate with n _S = 1.54 is 4.5%. Therefore, if a low refractive index film having a refractive index of 1.123 or more and 1.372 or less is formed on the surface of the solid substrate, the low refractive index film functions as an antireflection film.

The refractive index of the fine particle laminated film according to the present invention is smaller than the refractive index n _AR (see formula (5)) that makes the surface reflectance of the solid substrate 0%. Thereby, even if the refractive index of the fine particle laminated film increases for some reason, it continues to function as an antireflection film. For example, when the refractive index of the fine particle laminated film which was 1.372 is increased to 1.490 for some reason, the surface reflectance of the solid base material is increased from 1.0% to 3.3%. It is no longer an antireflection film.

However, when the refractive index of the fine particle laminated film that was 1.123 increases to 1.241 for some reason, the surface reflectance of the solid substrate decreases from 1.0% to 0.0%, and the fine particle laminated film becomes It becomes an optimal antireflection film. From this, it can be said that the fine particle laminated film having a refractive index smaller than n _AR (see formula (5)) is an excellent low refractive index film from the viewpoint of maintaining the antireflection function even if the refractive index increases for some reason.

  The reason why the refractive index of the fine particle laminated film increases includes contamination of the fine particle laminated film, moisture absorption, reinforcement and the like. The fine particle laminated film has voids in the film, and the voids are connected to the film surface. For this reason, infiltration of contaminating materials and adsorption of water, solvents and low molecular weight substances can occur. In that case, cleaning is required to remove the contaminating material and the adsorbing material.

However, it is possible to maintain the anti-reflection function without the removal of contaminating material and adsorbent material by using a refractive index n _AR smaller particle laminated film as described above.
Further, in order to adhere the fine particle laminated film to the solid substrate, to improve the strength of the fine particle laminated film itself, or to obtain both of them, a reinforcing agent may be infused into the fine particle laminated film and cured.

  The adhesion and film strength of the fine particle film can be improved by bringing the fine particle laminated film into contact with the curable resin, filling the voids with the resin to some extent, and then curing. Examples of such a resin material include resin compositions such as ionizing radiation curable resins, thermosetting resins, thermoplastic resins, and reactive silicone oils.

  Alternatively, after contact with the metal alkoxide solution, the void can be filled to some extent with a method of drying and filling the void to some extent with a hardened metal oxide, or by dipping in a solution of polysilazane and converted silica.

Further, these resin compositions and metal oxides may coat the fine particle laminated film, and this overcoat further improves the film strength. If these materials are filled to some extent voids particle laminated film increases the refractive index slightly, but it is possible to maintain the anti-reflection function by using a refractive index n _AR smaller particle laminated film as described above. The resin composition or metal oxide may be overcoated without filling the voids in the fine particle laminated film.

  In addition, for use as an optical functional thin film other than the antireflection film, the fine particle laminated film having a low refractive index as in the present invention is useful for improving the optical performance and maintaining the optical function.

(J) Optical Member Since the fine particle laminated film according to the present invention is obtained by an alternating lamination method, the film thickness uniformity is high. 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 transflective 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 reflective film (mirror), a base material with a semi-transmissive semi-reflective film (half mirror), and a visible light reflecting infrared transmissive film. Substrate with 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 It can be used as a substrate with a filter film or a substrate with a color tone correction 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 the refractive index required for the expression of the optical function 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 of the low refractive index film, the better, and the higher the refractive index of the high refractive film, 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 antireflection film having a multilayer structure includes an antireflection film having four or more layers in which a high refractive index film and a low refractive index film are alternately laminated on a solid substrate, and exhibits an antireflection function in a wide wavelength region. In this case, the greater the difference in refractive index between the low refractive index film and the high refractive index film, the better the antireflection performance. 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, more 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 above formula (1), but in order to flatten the reflection spectrum and the transmission spectrum in the target wavelength region, that is, the reflectance. In order to reduce the wavelength dependence 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 being close to the equation (1). 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%. It is preferable that the average reflectance is 15% to 40% and the average transmittance is 60% to 85%, and the average reflectance is 15% to 30%. Further, the average value of the transmittance is more 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, and the high refractive index film and the low refractive index are laminated. 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 basically determined by the equation (1). 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. The fine particle volume density can be controlled by the fine particle zeta potential and the fine particle shape.

  In a fine structure whose fine structure is highly controlled and has high geometric optical performance, it is not desirable for the antireflection film or low refractive index film on the surface of the fine structure to scatter and diffuse visible light. This is because an antireflection film or a low refractive index film that scatters or diffuses light even slightly increases the degree of light scattering / diffusion when light is incident obliquely.

  In many cases, light is incident on the antireflection film on the surface of the fine structure not only from the normal direction but also at an oblique incidence. Therefore, for example, when an antireflection film or a low refractive index film that scatters and diffuses light is formed on the surface of the lens-shaped object, geometric optical performance degradation occurs such that the light does not collect at the focal point. That is, it is desirable that the antireflection film and the low refractive index film are transparent so that the antireflection film does not impair the geometric optical performance of the microstructure. In the present invention, by measuring the turbidity of the antireflection film or the low refractive index film, it can be evaluated that the antireflection film or the low refractive index film of the present invention does not impair the geometric optical performance of the microstructure.

  In a fine structure having a highly controlled fine structure and high geometric optical performance, it is desirable that the antireflection film on the surface of the fine structure be formed following the shape of the fine structure. When the antireflection film does not follow the shape of the fine structure, the geometric optical performance of the fine structure is impaired. Taking the lens-like microstructure as an example, if the antireflection film on the surface of the on-chip microlens array used in the solid-state imaging device does not follow the microlens, the amount of light collected will be reduced in order to impair the light collection performance of the lens. The sensitivity decreases due to the decrease, and the light irradiated to the part other than the photodiode becomes stray light, causing flare and contrast reduction.

  In the present invention, the cross section of the fine structure formed by the fine particle laminated film is observed with a scanning electron microscope or the like, and the thickness of the fine particle laminated film with respect to the normal direction from the fine structure surface is measured. The followability to the structure can be evaluated. Further, the fine structure can be observed from an oblique direction with a scanning electron microscope or the like, and the followability of the fine particle laminated film to the fine structure can be evaluated from the shape of the projected fine structure.

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.

  The tape peeling test does not necessarily have an adhesive strength of 2.94 N / 10 mm or more as defined in JIS Z 1522, and the test may be performed using an adhesive tape used in a more actual process. In the manufacturing process of a semiconductor such as a photoelectric conversion element, a protective tape such as an adhesive tape used in the back grinding process corresponds to it.

  In addition, for optical function members such as Fresnel lenses and lenticular lenses used in LCD backlight brightness enhancement lens films, diffusion films, and video projection television screens, surface protection, contamination prevention, etc. Adhesive tape to be fixed to fix it.

(K) Mass measurement 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, so that the resonance frequency of the crystal resonator decreases. (Refer to 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) of 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 solid substrate can be evaluated by bringing the quartz crystal into contact with the fine particle dispersion and adsorbing the fine particles on the quartz crystal vibrator. it can.
Further, as shown in Japanese Patent Application No. 2000-568599, the mass of the electrolyte polymer adsorbed on the substrate is evaluated by bringing the same crystal resonator into contact with the electrolyte polymer solution and adsorbing the electrolyte polymer on the crystal resonator. can do.

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.

（ただし、ΔＦ_ｅは電解質ポリマーの吸着による共振周波数の減少分であり、ΔＦ_ｐは微粒子の吸着による共振周波数の減少分である。すなわち、微粒子に対する電解質ポリマーの質量比（Δｍ_ｅ／Δｍ_ｐ）は、微粒子に対する電解質ポリマーの吸着による共振周波数の減少分の比（ΔＦ_ｅ／ΔＦ_ｐ）として求めることができる。）

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

In order to form the fine particle laminated film in the present invention, a step (A) in which the solid substrate is brought into contact with the electrolyte polymer solution and then in contact with ultrapure water for rinsing, and in contact with the fine particle dispersion, and then in the rinsing The process (B) which contacts ultrapure water is performed in this order. The step of performing this step (A) once and step (B) once as one cycle of the fine particle laminated film forming step is repeated up to the number of cycles (N _max ) at which the fine particle laminated film has a thickness that exhibits an optical function. .

  When the quartz crystal resonator is brought into contact with the solid base material in the order of the electrolyte polymer solution, the ultrapure water, the fine particle dispersion, and the ultrapure water, the adsorption and rinsing of the electrolyte polymer and the change in the resonance frequency accompanying the adsorption and rinsing of the fine particles are shown in FIG. Can be measured as follows. Here, an aqueous dispersion of silica fine particles (Snowtex (ST) 20) is used as the fine particle dispersion, and PDDA is used as the electrolyte polymer solution.

The frequency decrease (ΔF _e ) is the 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 during the first to N _max times in the fine particle laminated film forming step, and the average value thereof is taken as ΔF _ee ^av .

The frequency decrease (ΔF _P ) is the frequency decrease due to the mass of the fine particles remaining on the quartz vibrator and the solid substrate through 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 according to the present invention, the mass ratio (me _{/ p} ) of the electrolyte polymer to the fine particles is preferably 0.01% by mass or more and 10% by mass or less. When the volume ratio of the fine particles are the same, the refractive index n _c of the particle laminated film that completely fills the voids in the resin '(Equation (4) see) the refractive index of the particle laminated film having pores than n _{c (formula} (2) 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 0.01% to 10%, 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 laminated film, it is preferable to contain 0.01% by mass or more and 10% by mass or less of the electrolyte polymer, and more preferably 0.1% by mass or more and 5% by mass or less. .

  The mass of the electrolyte polymer in the fine particle laminated film may be evaluated as a mass decrease when heated to the boiling point of the electrolyte polymer or higher with a differential thermobalance. In this case, the fine particle laminated film formed on a high hardness substrate such as a silicone wafer or glass may be peeled off from the substrate with a cutter or the like, and the powder fine particle laminated film may be used as a sample.

  Further, the mass decrease of the electrolyte polymer in the fine particle laminated film on the substrate after high-temperature firing may be measured by a high sensitivity electronic balance, and the mass of the electrolyte polymer in the fine particle laminated film may be evaluated. In this case, a high melting point base material such as a silicone wafer or glass may be used, and a sufficient time should be allowed to elapse after baking at a high temperature so as not to give a difference in the moisture absorption amount of the fine particle laminated film.

(L) 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 is preferably lower than the melting point, glass transition temperature, softening temperature, etc. of the solid substrate, and is preferably a temperature at which the optical function such as transparency and non-coloring of the solid substrate is maintained. 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. It 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, the purpose 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.

EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not restrict | limited at all by these Examples.
[Example 1]
1. Formation of fine particle laminated film (low refractive index film) (film production process of fine particle laminated film)
The pH of the silica aqueous dispersion (manufactured by Nissan Chemical Industries, Ltd., trade name: SNOWTEX (ST) OUP, 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 not adjusted. As an electrolyte polymer aqueous solution, an aqueous solution adjusted to 0.001% by weight of polydiallyldimethylammonium chloride (PDDA, manufactured by Aldrich) and a pH of 10 is used as an electrolyte polymer. It was.

  Microlens array sheet as a substrate, silicon wafer (SUMPCO, 6PW-A1, 6 inch Φ, 625 μm thickness), glass substrate (Matsunami Glass, product name: S1111, 25 mm × 75 mm × 0.7 mm thickness) The refractive index at a wavelength of 550 nm is 1.54), a step of dropping an electrolyte polymer aqueous solution and showering for 1 minute after rinsing ultrapure water for 1 minute, and a fine particle dispersion being dropped. After the elapse of 1 minute, the step (a) of showering ultrapure water for rinsing for 1 minute was performed in this order. Performing the step (a) once and the step (b) once in order was defined as one cycle, and this cycle number was defined as the number of fine particle alternating laminations. The number of times the fine particles were alternately laminated was 21 times, and a fine particle laminated film (low refractive index film) was formed on the surface of the solid substrate.

A method for measuring the mass ratio of the electrolyte polymer to the fine particles in the fine particle laminated film will be described below.
A step of immersing the quartz crystal in an electrolyte polymer aqueous solution for 1 minute, immersing in ultra pure water for rinsing for 3 minutes (A '), a step of immersing in silica sol for 1 minute, and then immersing in ultra pure water for rinsing for 3 minutes (I ') was applied in this order. 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 by} the number of times of alternate lamination of fine particles and averaging, the average value (ΔF _e ^av ) of the frequency decrease due to the mass of the electrolyte polymer can be obtained. By monitoring the resonance frequency of the crystal resonator in the step (A ′), it is possible to evaluate the frequency decrease (ΔF _p ) due to the mass of the fine particles remaining on the crystal resonator and the solid substrate.

By repeating this evaluation of ΔF _{p by} the number of times of fine particle alternate lamination 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 (9)). 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 quartz resonator was 3%. From this, it can be seen that the fine particle laminated film is substantially composed only of fine particles.

2. Evaluation of transparency of fine particle laminated film The haze value of the glass substrate on which the fine particle laminated film obtained above was formed was measured with a turbidimeter (manufactured by Nippon Denshoku Industries Co., Ltd.) according to JIS K 7361-1-1997. As a result, it was 0.4%. The haze value of the glass substrate alone was measured in the same manner and was found to be 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. As a result, it was found that the turbidity of the fine particle laminated film was 0.3%, and the transparency of the fine particle laminated film was very high.

3. Evaluation of antireflection performance of fine particle laminated film When the transmission spectrum of the glass substrate on which the fine particle laminated film is formed was measured with a visible ultraviolet spectrophotometer (trade name: V-570, manufactured by JASCO Corporation), the wavelength was 400 to 400. The maximum transmittance at 800 nm was 94.4%.

Also, a black adhesive tape (manufactured by Nichiban Co., Ltd., trade name: VT-196) is attached to the opposite surface of the glass substrate on which the fine particle laminated film is formed so that no bubbles remain, and one side on which the fine particle laminated film is formed The surface reflectance spectrum was measured with a visible ultraviolet spectrophotometer (trade name: V-570, manufactured by JASCO Corporation). The minimum surface reflectance at a wavelength of 400 to 800 nm of the glass substrate on which the fine particle laminated film was formed was 0.8%.
Since the transmittance of the glass substrate was 91% and the surface reflectance was 4.5%, it was found that an antireflection film having excellent characteristics was formed and the transmittance was also improved.

4). Evaluation of Refractive Index of Fine Particle Layered Film As a result of evaluating the refractive index and film thickness of the fine particle layered film on the silicon wafer with an automatic ellipsometer (manufactured by Fibrabo Co., Ltd., trade name: MARY-102, laser wavelength 632.8 nm), The fine particle laminated film had a refractive index of 1.138 and a thickness of 121 nm.

[Example 2]
A fine particle laminated film (low refractive index film) was produced on the substrate in accordance with Example 1 except that the fine particle dispersion was adjusted to 0.3% by weight and that the number of alternating fine particle laminations was six. .
When the transmission spectrum of the glass substrate on which the fine particle laminated film was formed was measured in the same manner as in Example 1, the maximum transmittance at a wavelength of 400 to 800 nm was 95.1%.

When the surface reflection spectrum of the glass substrate on which the fine particle laminated 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%.
Further, the refractive index of the fine particle laminated film evaluated in the same manner as in Example 1 is 1.204, the thickness is 114 nm, and the turbidity of the fine particle laminated film evaluated in the same manner as in Example 1 is 0.3%. The mass ratio (me _{/ p} ) of the electrolyte polymer to the fine particles in the fine particle laminated film evaluated in the same manner as in Example 1 was 3%.

[Example 3]
It was used as a fine particle dispersion adjusted to 1% by weight, an electrolyte polymer aqueous solution adjusted to 0.1% by weight of polydiallyldimethylammonium chloride (PDDA) and pH 10, and the number of alternating fine particle laminations was set to 2 times. Except for this, a fine particle laminated film (low refractive index film) was produced on a substrate in accordance with Example 1.

When the transmission spectrum of the glass substrate on which the fine particle laminated film was formed was measured in the same manner as in Example 1, the maximum transmittance at a wavelength of 400 to 800 nm was 95.0%.
When the surface reflection spectrum of the glass substrate on which the fine particle laminated 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%.
Further, the refractive index of the fine particle laminated film evaluated in the same manner as in Example 1 is 1.199, the thickness is 115 nm, and the turbidity of the fine particle laminated film evaluated in the same manner as in Example 1 is 0.3%. The mass ratio (me _{/ p} ) of the electrolyte polymer to the fine particles in the fine particle laminated film evaluated in the same manner as in Example 1 was 3%.

[Example 4]
Used as a fine particle dispersion adjusted to 0.1% by weight, adjusted to 0.01% by weight of polyethyleneimine (PEI), used an aqueous electrolyte polymer solution without adjusting pH, and repeated the number of times of alternating fine particle lamination three times. Except for the above, a fine particle laminated film (low refractive index film) was produced on the substrate according to Example 1.

When the transmission spectrum of the glass substrate on which the fine particle laminated film was formed was measured in the same manner as in Example 1, the maximum transmittance at a wavelength of 400 to 800 nm was 94.7%.
When the surface reflection spectrum of the glass substrate on which the fine particle laminated 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%.
Further, the refractive index of the fine particle laminated film evaluated in the same manner as in Example 1 is 1.167, the thickness is 118 nm, and the turbidity of the fine particle laminated film evaluated in the same manner as in Example 1 is 0.3%. The mass ratio (me _{/ p} ) of the electrolyte polymer to the fine particles in the fine particle laminated film evaluated in the same manner as in Example 1 was 3%.

[Example 5]
The pH of the silica aqueous dispersion (manufactured by Nissan Chemical Industries, Ltd., trade name: Snowtex (ST) PSS, silica sol) in which bead-like silica fine particles having an average primary particle diameter of 15 nm measured by the BET method are dispersed is not adjusted. Used as a fine particle dispersion whose concentration was adjusted to 10% by weight, polyethyleneimine (PEI) was adjusted to 1% by weight, an electrolyte polymer aqueous solution without adjusting the pH was used, and the number of times of fine particle alternate lamination was 10 times. Except for the above, a fine particle laminated film (low refractive index film) was produced on a substrate according to Example 1.

When the transmission spectrum of the glass substrate on which the fine particle laminated film was formed was measured in the same manner as in Example 1, the maximum transmittance at a wavelength of 400 to 800 nm was 95.0%.
When the surface reflection spectrum of the glass substrate on which the fine particle laminated 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 refractive index of the fine particle laminated film evaluated in the same manner as in Example 1 was 1.195, the thickness was 115 nm, and the turbidity of the fine particle laminated film evaluated in the same manner as in Example 1 was 0.3%. .

[Example 6]
The pH of a silica aqueous dispersion (manufactured by Nissan Chemical Industries, Ltd., trade name: Snowtex (ST) PSM, silica sol) in which beaded silica fine particles having an average primary particle diameter of 20 nm measured by the BET method are dispersed is not adjusted. Used as a fine particle dispersion whose concentration was adjusted to 1% by weight, polyethyleneimine (PEI) was adjusted to 0.1% by weight, an aqueous electrolyte polymer solution was used without adjusting the pH, and the number of times of fine particle alternate lamination was 15. A fine particle laminated film (low refractive index film) was produced on the base material in the same manner as in Example 1 except that the process was repeated.

When the transmission spectrum of the glass substrate on which the fine particle multilayer film was formed was measured in the same manner as in Example 1, the maximum transmittance at a wavelength of 400 to 800 nm was 94.9%.
When the surface reflection spectrum of the glass substrate on which the fine particle laminated 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%.
Further, the refractive index of the fine particle laminated film evaluated in the same manner as in Example 1 was 1.180, the thickness was 117 nm, and the turbidity of the fine particle laminated film evaluated in the same manner as in Example 1 was 0.3%. .

[Example 7]
A fine particle laminated film on the substrate according to Example 1 except that a microlens array sheet having a microlens (photocurable resin, width 9 μm, height 1.5 μm) as a fine structure is used as the substrate. Was made. A protective tape was applied to a part of the microlens array sheet to provide a portion where the fine particle laminated film was not formed.

The microlens array sheet on which the fine particle multilayer film was formed was observed with a scanning electron microscope (manufactured by Philips, trade name: XL30ESEM) from an angle of 75 ° from the normal direction of the sheet surface. The shape of the lens was observed.
Similarly, the shape of the microlens where the fine particle laminated film was not formed was also observed. The outline of the observation image of the microlens formed with the fine particle laminated film is shown by a broken line in FIG.

  Further, the outline of the observation image of the microlens in which the fine particle laminated film is not formed is also shown by a solid line in FIG. Assuming that the thickness of the fine particle laminated film is 0.1 μm, the outline of the microlens formed by the fine particle laminated film is shifted from the outline of the microlens not formed by the fine particle laminated film by 0.1 μm. As a result, it was confirmed that the fine particle laminated film on the microlens had a uniform thickness with respect to the normal direction of the microlens, and that the fine particle laminated film satisfactorily followed the shape of the microlens.

[Example 8]
Fine particle laminated film on the substrate according to Example 4 except that a microlens array sheet having a microlens (photocurable resin, width 9 μm, height 1.5 μm) as a microstructure is used as the substrate. Was made. A protective tape was applied to a part of the microlens array sheet to provide a portion where the fine particle laminated film was not formed.

  As in Example 7, the microlens formed with the fine particle laminate film and the microlens without the fine particle laminate film were observed with a scanning electron microscope and the contours of the observed images were compared. It was confirmed that the thickness with respect to the normal direction was uniform and the shape followability of the fine particle laminated film was good.

[Example 9]
Fine particle laminated film on the substrate according to Example 6 except that a microlens array sheet having a microlens (photocurable resin, width 9 μm, height 1.5 μm) as a fine structure is used as the substrate. Was made. A protective tape was applied to a part of the microlens array sheet to provide a portion where the fine particle laminated film was not formed.

  As in Example 7, the microlens formed with the fine particle laminate film and the microlens without the fine particle laminate film were observed with a scanning electron microscope and the contours of the observed images were compared. It was confirmed that the thickness with respect to the normal direction was uniform and the shape followability of the fine particle laminated film was good.

[Example 10]
The silica isopropanol dispersion (catalyst chemical industry Co., Ltd., trade name: sulria, silica sol) in which hollow silica fine particles having an average primary particle size of 40 nm measured by transmission electron microscopy are dispersed is ultra-adjusted without adjusting the pH. Used as a fine particle dispersion whose concentration was adjusted to 0.1% by dilution with pure water, and an electrolyte polymer aqueous solution adjusted to 0.3% by weight of polydiallyldimethylammonium chloride (PDDA) and pH 10. A fine particle laminated film (low refractive index film) was produced on the base material in the same manner as in Example 1 except that the number of alternating fine particle laminations was five.

When the transmission spectrum of the glass substrate on which the fine particle laminated film was formed was measured in the same manner as in Example 1, the maximum transmittance at a wavelength of 400 to 800 nm was 94.9%.
When the surface reflection spectrum of the glass substrate on which the fine particle laminated 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%.
Further, the refractive index of the fine particle laminated film evaluated in the same manner as in Example 1 is 1.180, the thickness is 117 nm, and the turbidity of the fine particle laminated film evaluated in the same manner as in Example 1 is 0.3%. The mass ratio (me _{/ p} ) of the electrolyte polymer to the fine particles in the fine particle laminated film evaluated in the same manner as in Example 1 was 3%.

[Comparative Example 1]
Silica aqueous dispersion (manufactured by Nissan Chemical Industries, Ltd., trade name: Snowtex (ST) O, silica sol) in which spherical silica fine particles having an average primary particle diameter of 15 nm measured by the BET method are dispersed is 0.1% by weight. Except for using as an adjusted fine particle dispersion, using polydiallyldimethylammonium chloride (PDDA) as an electrolyte polymer aqueous solution adjusted to 0.1% by weight, pH 10, and changing the number of times of fine particle alternate lamination to 3 times. A fine particle laminated film was produced on the substrate according to Example 1.

When the transmission spectrum of the glass substrate on which the fine particle laminated film was formed was measured in the same manner as in Example 1, the maximum transmittance at a wavelength of 400 to 800 nm was 95.1%.
When the surface reflection spectrum of the glass substrate on which the fine particle laminated 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%.
Further, the refractive index of the fine particle laminated film evaluated in the same manner as in Example 1 is 1.268, the thickness is 108 nm, and the turbidity of the fine particle laminated film evaluated in the same manner as in Example 1 is 0.3%. The mass ratio (me _{/ p} ) of the electrolyte polymer to the fine particles in the fine particle laminated film evaluated in the same manner as in Example 1 was 3%.

[Comparative Example 2]
A silica water dispersion (manufactured by Nissan Chemical Industries, Ltd., trade name: Snowtex (ST) XL, silica sol) in which spherical silica fine particles having an average primary particle size of 50 nm measured by the BET method are dispersed was adjusted to 1% by weight. Example 1 except that it was used as a fine particle dispersion, polyethyleneimine (PEI) was adjusted to 0.1% by weight, an electrolyte polymer aqueous solution without adjusting the pH was used, and the number of times of fine particle alternating lamination was 23 times. In accordance with the above, a fine particle laminated film was prepared on a substrate.

When the transmission spectrum of the glass substrate on which the fine particle laminated film was formed was measured in the same manner as in Example 1, the maximum transmittance at a wavelength of 400 to 800 nm was 94.8%.
When the surface reflection spectrum of the glass substrate on which the fine particle laminated 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%.
Further, the refractive index of the fine particle laminated film evaluated in the same manner as in Example 1 is 1.223, the thickness is 112 nm, and the turbidity of the fine particle laminated film evaluated in the same manner as in Example 1 is 0.6%. The mass ratio (me _{/ p} ) of the electrolyte polymer to the fine particles in the fine particle laminated film evaluated in the same manner as in Example 1 was 3%.

[Comparative Example 3]
A silica water dispersion (manufactured by Nissan Chemical Industries, Ltd., trade name: Snowtex (ST) ZL, silica sol) in which spherical silica fine particles having an average primary particle diameter of 85 nm measured by the BET method are dispersed was adjusted to 1% by weight. According to Example 1, except that it was used as a fine particle dispersion, polyethyleneimine (PEI) was adjusted to 1% by weight, an electrolyte polymer aqueous solution not adjusting pH was used, and the number of fine particle alternate laminations was set to 16. Thus, a fine particle laminated film was produced on the substrate.

When the transmission spectrum of the glass substrate on which the fine particle laminated film was formed was measured in the same manner as in Example 1, the maximum transmittance at a wavelength of 400 to 800 nm was 93.6%.
When the surface reflection spectrum of the glass substrate on which the fine particle laminated 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%.
Further, the refractive index of the fine particle laminated film evaluated in the same manner as in Example 1 is 1.241, the thickness is 111 nm, and the turbidity of the fine particle laminated film evaluated in the same manner as in Example 1 is 1.8%. The mass ratio (me _{/ p} ) of the electrolyte polymer to the fine particles in the fine particle laminated film evaluated in the same manner as in Example 1 was 3%.

[Comparative Example 4]
Silica fine particle methyl ethyl ketone dispersion (manufactured by Nissan Chemical Industries, Ltd., trade name: MEK-ST, organosilica sol) in which spherical silica fine particles having an average primary particle size of 15 nm measured by the BET method are dispersed is adjusted to 1.5% by weight. The fine particle dispersion was used.

The above-mentioned microlens array sheet as a base material, silicon wafer (SUMPCO 6PW-A1, 6 inch Φ, 625 μm thickness), glass base material (Matsunami Glass, S1111, 25 mm × 75 mm × 0.7 mm thickness, wavelength The fine particle dispersion was dropped into the refractive index at 550 nm of 1.54), and developed and dried at a rotation speed of 1000 min ⁻¹ to form a fine particle laminated film on the substrate.

When the transmission spectrum of the glass substrate on which the fine particle laminated film was formed was measured in the same manner as in Example 1, the maximum transmittance at a wavelength of 400 to 800 nm was 94.8%.
When the surface reflection spectrum of the glass substrate on which the fine particle laminated 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 0.4%.
Further, the refractive index of the fine particle laminated film evaluated in the same manner as in Example 1 was 1.315, the thickness was 105 nm, and the turbidity of the fine particle laminated film evaluated in the same manner as in Example 1 was 0.3%. .

[Comparative Example 5]
1.5 weight silica fine particle isopropanol dispersion (manufactured by Nissan Chemical Industries, Ltd., trade name: IPA-ST-UP, organosilica sol) in which bead-like silica fine particles having an average primary particle diameter of 8 nm measured by the BET method are dispersed. A fine particle laminated film was produced on a substrate according to Comparative Example 4 except that a fine particle dispersion adjusted to% was used.

When the transmission spectrum of the glass substrate on which the fine particle laminated film was formed was measured in the same manner as in Example 1, the maximum transmittance at a wavelength of 400 to 800 nm was 95.1%.
When the surface reflection spectrum of the glass substrate on which the fine particle laminated 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 refractive index of the fine particle laminated film evaluated in the same manner as in Example 1 was 1.232, the thickness was 112 nm, and the turbidity of the fine particle laminated film evaluated in the same manner as in Example 1 was 0.3%. .

[Comparative Example 6]
Fine particle laminated film on the substrate according to Comparative Example 1 except that a microlens array sheet having a microlens (photocurable resin, width 9 μm, height 1.5 μm) as a microstructure is used as the substrate. Was made. A protective tape was applied to a part of the microlens array sheet to provide a portion where the fine particle laminated film was not formed.

  As in Example 7, the microlens formed with the fine particle laminate film and the microlens without the fine particle laminate film were observed with a scanning electron microscope and the contours of the observed images were compared. It was confirmed that the thickness with respect to the normal direction was uniform and the shape followability of the fine particle laminated film was good.

[Comparative Example 7]
Fine particle laminated film on the substrate according to Comparative Example 5 except that a microlens array sheet having a microlens (photocurable resin, width 9 μm, height 1.5 μm) as a fine structure is used as the substrate. Was made. A protective tape was applied to a part of the microlens array sheet to provide a portion where the fine particle laminated film was not formed.

  As in Example 7, the microlens formed with the fine particle laminate film and the microlens without the fine particle laminate film were observed with a scanning electron microscope and the contours of the observed images were compared. As a result, as shown in FIG. The fine particle laminated film had a non-uniform thickness in the normal direction of the microlens, and became thicker as it approached the valley portion of the microlens. Thereby, it turns out that a fine particle lamination film changes the shape of a micro lens, and it is guessed that condensing performance falls.

  The results of the above Examples and Comparative Examples are shown in Tables 1 and 2.

  From Tables 1 and 2, in Examples 1 to 6, it can be seen that the refractive index of the fine particle multilayer film can be lowered to 1.138 to 1.204, and the antireflection function can be obtained with those refractive indexes. Further, for example, it can be seen that the fine particle laminated film of Example 4 can maintain the antireflection function with the minimum surface reflectance of 0.5% even if the refractive index increases by 0.15 due to contamination or the like (see FIG. 2). On the other hand, in Comparative Examples 1 to 5, the refractive index is in the range of 1.223 to 1.315, and the current minimum surface reflectance is lower than that of the example, but the refractive index is increased due to contamination or the like. As shown in FIG. 2, there is a problem that the surface reflectance increases and the antireflection function cannot be maintained.

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 relationship between the refractive index of an antireflection film, and the surface reflectance of a solid base material (refractive index 1.54) with an antireflection film. 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 are rinsed. The contour of an image obtained by observing the microlens formed with the fine particle multilayer film of Example 7 with an SEM (broken line in the figure) and the contour of the image obtained by SEM observation of the microlens before forming the fine particle laminated film (solid line in the figure) FIG. The contour of an image obtained by observing the microlens formed with the fine particle laminated film of Comparative Example 7 with an SEM (broken line in the figure) and the outline of the image obtained by SEM observing the microlens before forming the fine particle laminated film (solid line in the figure) FIG.

Claims (14)

  A low refractive index characterized by comprising a fine particle laminate film formed by alternately laminating electrolyte polymer and fine particles on the surface of a solid substrate, the refractive index of the fine particle laminate film being 1.10 or more and 1.21 or less film.   The low refractive index film according to claim 1, wherein the fine particle laminated film is formed by alternately adsorbing an electrolyte polymer and fine particles on the surface of a solid substrate.   The fine particles in the fine particle laminated film include one or more of porous silica fine particles, hollow silica fine particles, and silica fine particles having a shape in which primary particles are connected to each other. Low refractive index film.   4. The low refractive index film according to claim 1, wherein an average primary particle diameter of the fine particles in the fine particle laminated film is 1 nm or more and 40 nm or less.   The said fine particle laminated film contains electrolyte polymer further, The content rate of this electrolyte polymer is 0.01 mass% or more and 10 mass% or less with respect to microparticles | fine-particles, The any one of Claims 1-4 characterized by the above-mentioned. 2. A low refractive index film according to 1.   The solid substrate surface has a fine structure of any one of a lenticular lens, a Fresnel lens, a prism, a microlens array, a light guiding fine structure, a light diffusing fine structure, and a fine structure for obtaining a hologram. The low refractive index film according to any one of claims 1 to 5, wherein   An antireflection film comprising the low refractive index film according to claim 1. A method for producing a low refractive index film comprising a fine particle laminated film having a refractive index of 1.10 or more and 1.21 or less formed on the surface of a solid substrate,
(I) a step of bringing the electrolyte polymer solution (liquid A) or the fine particle dispersion (liquid B) into contact with the solid substrate surface, and then a rinsing step;
(Ii) A step of bringing a dispersion of fine particles having a charge opposite to that of the electrolyte polymer of the liquid A into contact with the surface of the solid base after the liquid A is contacted, or the surface of the solid base after the liquid B is contacted A step of contacting a solution of an electrolyte polymer having an opposite charge with the fine particles of the liquid B, followed by a rinsing step, and (iii) a step of alternately repeating (i) and (ii),
A method for producing a low refractive index film, comprising:   The low refraction according to claim 8, wherein the fine particles in the fine particle laminated film include one or more of porous silica fine particles, hollow silica fine particles, and silica fine particles having a shape in which primary particles are connected. Manufacturing method of rate membrane.   The method for producing a low refractive index film according to claim 8 or 9, wherein an average primary particle diameter of the fine particles in the fine particle dispersion is 1 nm or more and 40 nm or less.   The low refractive index according to any one of claims 8 to 10, wherein the fine particle laminated film is formed so that the content of the electrolyte polymer with respect to the fine particles is 0.01 mass% or more and 10 mass% or less. Manufacturing method of rate membrane.   The method for producing a low refractive index film according to any one of claims 8 to 11, wherein fine particle and electrolyte polymer are alternately adsorbed on the surface of the solid substrate to form a fine particle laminated film.   The solid substrate surface has a fine structure of any one of a lenticular lens, a Fresnel lens, a prism, a microlens array, a light guiding fine structure, a light diffusing fine structure, and a fine structure for obtaining a hologram. The method for producing a low refractive index film according to any one of claims 8 to 12.   The method for producing a low refractive index film according to any one of claims 8 to 13, wherein the low refractive index film is an antireflection film.

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